Pretreatment and Posttreatment Approaches For Reducing Biomass in

University of Tennessee, Knoxville
TRACE: Tennessee Research and Creative

Exchange
Masters Theses Graduate School
12-2017
Pretreatment and Posttreatment Approaches for Reducing

Biomass Inorganic Impurities during Gasification
Qiaoming Liu
University of Tennessee
Follow this and additional works at: https://trace.tennessee.edu/utk_gradthes
Recommended Citation
Liu, Qiaoming, "Pretreatment and Posttreatment Approaches for Reducing Biomass Inorganic Impurities
during Gasification. " Master's Thesis, University of Tennessee, 2017.
https://trace.tennessee.edu/utk_gradthes/5020
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To the Graduate Council:
I am submitting herewith a thesis written by Qiaoming Liu entitled "Pretreatment and

Posttreatment Approaches for Reducing Biomass Inorganic Impurities during Gasification." I
have examined the final electronic copy of this thesis for form and content and recommend that
it be accepted in partial fulfillment of the requirements for the degree of Master of Science, with
a major in Biosystems Engineering.
Nourredine H. Abdoulmoumine, Stephen C. Chmely, Major Professor
We have read this thesis and recommend its acceptance:
Xiaofei Ye
Accepted for the Council:

Dixie L. Thompson
Vice Provost and Dean of the Graduate School
(Original signatures are on file with official student records.)

Pretreatment and Posttreatment Approaches for Reducing Biomass
Inorganic Impurities during Gasification
A Thesis Presented for the
Master of Science
Degree
The University of Tennessee, Knoxville
Qiaoming Liu
December 2017
Copyright © 2017 by Qiaoming Liu.
All rights reserved.
ii
ACKNOWLEDGEMENTS
I would like to thank my professors, Dr. Nour Abdoulmoumine and Dr. Chmely, for supporting
me, encouraging me, and offering me this great opportunity to participate in the research. I
would like to express my gratitude to my colleagues, Femi Oyedeji and Ross Houston, for being
my support and motivation. I wish to acknowledge Dr. Philip Ye, Dr. Nicole Labbe, and Dr.
Sushil Adhikari, without whose generous help, resources, and insights, the research would not
have been accomplished. I am grateful to the University of Tennessee, Sungrant Southeastern
Regional Center and the Department of Transportation with support for this research.
iii
ABSTRACT
During gasification, biomass can be thermally decomposed into a mixture of combustible

gases known collectively as syngas to produce heat, power, and liquid fuels in downstream
processes. However, inorganic elements, present in biomass and released into syngas as
impurities, are considered one of the main deterrent to the commercial deployment of biomass
gasification technologies and have recently contributed to the failure of a thermochemical
biorefinery. In conventional gasification installations, a syngas cleanup process area, which
comprises a combination of processes, is used to reduce the concentrations of these inorganic
impurities below tolerable limits.
In recent years, several treatment approaches have been explored to reduce the
concentrations of inorganic impurities in syngas and, ultimately, decrease the cost associated
with syngas cleanup. This project is aligned with these recent advancements and seeks to
develop gasification treatments to mitigate the impact of inorganic species. Specifically, the
project objectives are to i) develop a hot water extraction (HWE) based pretreatment approach to
reduce select inorganic elements (N, S, Na, K, Ca, and Mg) relevant to gasification; ii) develop
and evaluate new sorbents for posttreatment and; iii) evaluate the impact of HWE pretreatment
and sorbent posttreatment on the overall economics of the gasification plant.
In the first objective, HWE was carried out at five temperatures (60, 80, 100, 120 and
140 °C) and three soaking times (15, 30, 45 min) and the effect of these two parameters on the
responses (N, S, Na, K, Ca, and Mg reduction) were investigated by a two factor analysis of
variance of an unbalanced, complete factorial design at the 0.05 significance level. It was
observed that the acidity of the extraction liquor increased with both temperature and time with
lower pH resulting in higher total inorganic reduction.
For posttreatment of gas phase inorganics in syngas, layered double hydroxide based
mixed metal sorbent was synthesized, characterized and evaluated against commercial sorbents
on a model syngas mixture. The sorbents were thermally stable in the hot gas cleanup
temperature range (300 - 700 °C). Further, fixed bed experimental evaluation of hydrogen
chloride (HCl) gas removal was conducted on the sorbents.
iv
TABLE OF CONTENTS
INTRODUCTION .......................................................................................................................... 1
CHAPTER I Biomass Treatment Strategies for Thermochemical Conversion .............................. 2

1. ABSTRACT............................................................................................................................ 3
2. INTRODUCTION .................................................................................................................. 4
3. THE ORIGIN, NATURE, AND VARIABILITY OF INORGANICS IN
LIGNOCELLULOSIC BIOMASS ............................................................................................. 5
4. THE EFFECT OF INORGANICS ON BIOMASS THERMOCHEMICAL CONVERSION
PROCESSES .............................................................................................................................. 8
4.1 Pyrolysis............................................................................................................................ 8
4.2 Gasification ....................................................................................................................... 9
4.3 Combustion ..................................................................................................................... 11
5. PRE-TREATMENTS FOR THERMOCHEMICAL CONVERSION OF BIOMASS ........ 12
5.1 Mechanical pre-treatment ............................................................................................... 13
5.2 Thermal pre-treatment .................................................................................................... 14
5.3 Chemical pre-treatment ................................................................................................... 17
5.3.1 Water leaching ......................................................................................................... 17
5.3.2 Acid washing ............................................................................................................ 22
5.3.3 Base washing ........................................................................................................... 24
6. POST-TREATMENTS FOR THE THERMOCHEMICAL CONVERSION OF BIOMASS
24
6.1 Gas product posttreatments ............................................................................................. 25
6.2 Liquid product posttreatments ........................................................................................ 26
6.3 Solid product posttreatments........................................................................................... 26
7. CONCLUSIONS .................................................................................................................. 27
8. ACKNOWLEDGMENTS .................................................................................................... 28
9. REFERENCES ..................................................................................................................... 29
CHAPTER II Hot Water Extraction as a Pretreatment for Reducing Syngas Inorganics Impurities
– A Parametric Investigation on Switchgrass and Loblolly Pine Bark ......................................... 37
v
1. ABSTRACT...................................................................................................................... 38
2. INTRODUCTION ............................................................................................................ 39
3. MATERIALS AND METHODS...................................................................................... 41
3.1 Biomass preparation and characterization ...................................................................... 41
3.2 Hot water extraction ........................................................................................................ 41
3.3 Characterization of hot water extraction products .......................................................... 42
3.4 Statistical analyses .......................................................................................................... 43
4. RESULTS AND DISCUSSION ....................................................................................... 43
4.1 Proximate and ultimate analysis of raw switchgrass and loblolly pine bark samples .... 43
4.2 Effect of hot water extraction ......................................................................................... 45
4.2.1 Effect on nitrogen reduction and its impact on nitrogen contaminants................... 47
4.2.2 Effect on sulfur reduction and its impact on sulfur contaminants ........................... 48
4.2.3 Effect on alkali metal reduction and its impact on syngas metal contaminants ...... 49
4.2.4 Effect on alkaline earth metals reduction and their impact on syngas metal
contaminants ..................................................................................................................... 50
5. CONCLUSIONS .............................................................................................................. 52
6. ACKNOWLEDGMENTS ................................................................................................ 53
7. REFERENCES ................................................................................................................. 54
8. APPENDIX ....................................................................................................................... 58
8.1 Hot water extraction experimental conditions and severities ......................................... 58
8.2 Summary of two-way analysis of variance results ......................................................... 59
8.3 Illustration of extraction severity .................................................................................... 60
CHAPTER III Synthesis and Evaluation of Sorbents for Reducing the Concentrations of
Hydrogen Chloride in Syngas ....................................................................................................... 61
1. ABSTRACT...................................................................................................................... 62
2. INTRODUCTION ............................................................................................................ 63
3.1 Sorbent synthesis and preparation .................................................................................. 64
3.2 Sorbent characterization.................................................................................................. 65
3.3 Sorption study, sampling and analysis procedure ........................................................... 65
3.4 Model of HCl Sorption ................................................................................................... 67
vi
4.1 Characterization of sorbents ........................................................................................... 70
4.1.1 Elemental analysis of synthesized sorbent by ICP-OES .......................................... 70
4.1.2 Thermogravimetric analysis (TGA) ......................................................................... 70
4.1.3 BET analysis ............................................................................................................ 71
4.2 HCl sorption study .......................................................................................................... 72
4.3 Kinetics model fitting of HCl removal reaction ............................................................. 75
5. CONCLUSIONS .............................................................................................................. 75
6. ACKNOWLEDGMENTS ................................................................................................ 76
7. REFERENCES ................................................................................................................. 77
8. APPENDIX ....................................................................................................................... 80
8.1 Reaction temperature ...................................................................................................... 80
8.2 Actual experimental setup............................................................................................... 80
8.3 MATLAB code for kinetics model fitting of HCl removal reaction at 600 °C .............. 81
CHAPTER IV Techno-Economic Analysis of a Conceptual Biorefinery – Hot Water Extraction

Integrated to a Hybrid Biochemical and Thermochemical Conversion Process for High Ash
Lignocellulosic Biomass to Hydrocarbon Fuels and Succinic Acid ............................................. 87
1. ABSTRACT...................................................................................................................... 88
2. INTRODUCTION ............................................................................................................ 89
3.1 Feed handling, hot water extraction, and succinic acid production ................................ 90
3.2 Gasification ..................................................................................................................... 93
3.3 Syngas cleanup and compression.................................................................................... 93
3.4 Methanol synthesis.......................................................................................................... 93
3.5 Methanol conditioning .................................................................................................... 94
3.6 High-octane gasoline synthesis ....................................................................................... 94
4. ECONOMIC ANALYSIS ................................................................................................ 95
4.1 Capital cost estimation .................................................................................................... 95
4.2 Production cost estimation .............................................................................................. 96
4.3 Economic analysis .......................................................................................................... 96
vii
5.1 Process performance of HWE and succinic acid production .......................................... 97
5.2 Total capital investment .................................................................................................. 97
5.3 Operating costs................................................................................................................ 99
5.4 Minimum fuel selling price ........................................................................................... 100
6. REFERENCES ............................................................................................................... 102
CONCLUSIONS AND FUTURE PERSPECTIVES ................................................................. 103

1. CONCLUSIONS ............................................................................................................ 104
2. RECOMMENDATIONS FOR FUTURE WORK ......................................................... 106
VITA ........................................................................................................................................... 107
viii
LIST OF TABLES
Table 1 Origin of inorganic matter in lignocellulosic biomassa ..................................................... 6

Table 2 Common nature of inorganic in lignocellulosic biomass .................................................. 6
Table 3 Typical syngas applications and associated cleaning requirements11 .............................. 10
Table 4 Select indices indicative of slagging, fouling, agglomeration, and corrosiona ................ 12
Table 5 Effect of mechanical sieving on ash content for select lignocellulosic feedstocks ......... 14
Table 6 Summary of thermal pretreatment for inorganic removal from biomass ........................ 18
Table 7 Summary of chemical pretreatment for inorganic removal from biomass ...................... 19
Table 8 Proximate and ultimate analyses of raw switchgrass and loblolly pine bark .................. 44
Table 9 Summary of hot water extraction experimental conditions and severities for switchgrass
............................................................................................................................................... 58
Table 10 Summary of hot water extraction experimental conditions and severities for pine bark
............................................................................................................................................... 58
Table 11 Summary of two-way analysis of variance results for switchgrass and pine bark ........ 59
Table 12 Weight loss (%) of the sorbents during TGA ................................................................ 71
Table 13 Summary of BET analysis results of sorbents calcined at 700 °C ................................ 71
Table 14 Comparison of BET analysis results of MgAlO from literature .................................... 72
Table 15 Summary of 1 ppm HCl breakthrough time of sorbents ................................................ 73
Table 16 Summary surface elemental composition of cLDH and cLDH samples after sorption
tests shown in Figure 15 ....................................................................................................... 74
Table 17 Summary of kinetic model results ................................................................................. 76
Table 18 Summary of Nth Plant Assumptions1 ............................................................................. 91
Table 19 Ultimate analysis of woody biomass and switchgrass after HWE ................................ 91
Table 20 Plant workforce and salary per position ........................................................................ 96
Table 21 Feed and product flow rates for high-octane hydrocarbons and succinic acid production
process................................................................................................................................... 97
Table 22 Capital cost estimates per process area for both scenarios (2017 U.S. dollars) ............ 98
Table 23 Indirect cost factors for both scenarios .......................................................................... 99
Table 24 Summary of the project costs......................................................................................... 99
ix
LIST OF FIGURES
Figure 1 Pathways to aerosols: ejection of biomass inorganics during primary aerosol formation30
................................................................................................................................................. 9
Figure 2 Schematic representation of the hot water extraction experimental setup ..................... 42
Figure 3 Effect of temperature and time of hot water extraction on pH (a), ash reduction (b), and
mass loss (c) for switchgrass, and effect of temperature and time of hot water extraction on
pH (d), ash reduction (e), and mass loss (f) for pine bark. Red dots represent response
means for each condition and surface plot represents best fit of experimental data............. 45
Figure 4 Effect of hot water extraction severity on pH (a and d), ash content reduction (b and e),
and mass loss (c and f) for switchgrass (above) and pine bark (below), respectively .......... 47
Figure 5 The effect of HWE severity on nitrogen (N) content reduction for switchgrass (a) and
pine bark (b ) ......................................................................................................................... 48
Figure 6 The effect of HWE severity on S content reduction for switchgrass (a) and pine bark (b)
............................................................................................................................................... 49
Figure 7 The effect of HWE severity on alkali metals reduction for switchgrass (a) and pine bark
(b) .......................................................................................................................................... 50
Figure 8 The effect of HWE severity on alkaline-earth metals reduction for switchgrass (a) and
pine bark (b) .......................................................................................................................... 51
Figure 9 Illustration of the area under the curve approach used to calculate severity of HWE ... 60
Figure 10 Schematic representation of the fixed bed experimental setup .................................... 66
Figure 11 TGA curves of calcined sorbents ................................................................................. 71
Figure 12 The concentration of in NaOH solution for sorbents at 400, 500, and 600 °C ...... 73
Figure 13 The concentration of outlet HCl gas for sorbents at 400, 500, and 600 °C with grey
line representing 1 ppm breakthrough .................................................................................. 73
Figure 14 SEM micrographs of: (a) cLDH; (b) cLDH after 14 h sorption at 400 °C; (c) cLDH
after 14 h sorption at 500 °C; (d) cLDH after 14 h sorption at 600 °C with 2000 X
magnification, and (e) cLDH; (f) cLDH after 14 h sorption at 400 °C; (g) cLDH after 14 h
sorption at 500 °C; (h) cLDH after 14 h sorption at 600 °C with 500 X magnification ....... 75
Figure 15 PXRD diffractograms of: (a) original LDH sample and references
(((Mg6Al2)(OH)18(H2O)4)0.375, NaNO3, Na2CO3, and Mg36Al61.7), (b) calcined LDH sample
x
and references (Na3.893(CO3)2, NaNO3, Mg2O(OH)2, and Al2O3), and (c) calcined LDH
sample after 28 h of HCl sorption and references (NaCl, Na2CO3, Al2O3·3H2O, MgO, and
Na6MgCl8) ............................................................................................................................. 75
Figure 16 Kinetics model fitting of HCl removal reaction ........................................................... 76
Figure 17 The reactor temperature of 14 h HCl sorption test at 400 °C, 500 °C, and 600 °C,
respectively ........................................................................................................................... 80
Figure 18 Actual experimental setup ............................................................................................ 80
Figure 19 Biomass gasification and the production of high-octane hydrocarbons diagram......... 91
Figure 20 Succinic acid production plant flow diagram ............................................................... 92
Figure 21 Simplified methanol to hydrocarbons flow diagram .................................................... 95
Figure 22 Cost contribution details of the base case scenario .................................................... 101
Figure 23 Cost contribution details of the HWE and SA production scenario ........................... 101
xi
INTRODUCTION
This thesis presents research conducted to develop and evaluate pre and post gasification
treatments to reduce the levels of inorganics in biomass and syngas during gasification. It is
structured in chapters and comprises of five chapters. Chapter I is a reprint of the paper entitled,
“Biomass Treatment Strategies for Thermochemical Conversion,” published in the Journal of
Energy Fuels in March 2017. The paper summarizes pre-treatment and post-treatment techniques
for controlling the inorganic elements during thermochemical conversion processes (pyrolysis,
gasification, and combustion). The paper comprehensively reviews recent work to elucidate the
fate of inorganics during these processes and summarizes pre-treatment and post-treatment
techniques for controlling the inorganic impurities. Chapter II summarizes our investigation of
switchgrass and loblolly pine bark inorganic removal using hot water extraction as a gasification
pretreatment. The findings of this study have compiled into manuscript currently under review in
Fuel in September 2017. Chapter III summarizes our investigation on post gasification treatment
of inorganics using hydrogen chloride as model compound. The findings of this chapter will be
compiled into a manuscript for submission to Applied Catalysis A: General. In Chapter IV, we
carried out a techno-economic analysis of conceptual biorefinery that integrates hot water
extraction to remove inorganics, gasification to produce hydrocarbon fuels and biochemical
conversion to produce succinic acid (SA) from high ash switchgrass. The findings of this chapter
will be compiled into a manuscript for submission to Biofuels, Bioproducts & Biorefining.
Finally, Chapter V presents concluding remarks based on the outcomes of this project and
recommendations for future work.
1
CHAPTER I
BIOMASS TREATMENT STRATEGIES FOR THERMOCHEMICAL
CONVERSION
2
Qiaoming Liua, Stephen C. Chmelyb and Nourredine Abdoulmouminea,b
a
Biosystems Engineering and Soil Science Department, University of Tennessee
b
Center for Renewable Carbon, University of Tennessee
Copyright © 2017 by authors and American Chemical Society
How to cite this paper: Qiaoming Liu, Stephen C. Chmely, and Nourredine Abdoulmoumine.
"Biomass treatment strategies for thermochemical conversion." Energy & Fuels 31.4 (2017):
3525-3536. DOI: 10.1021/acs.energyfuels.7b00258
1. ABSTRACT
Biomass is among the most promising renewable resources to provide a sustainable

solution to meet the world’s increasing usage of it in biochemical and thermochemical
conversion technologies. Thermochemical conversion processes (pyrolysis, gasification, and
combustion) thermally convert biomass into energy-dense intermediates that can be, in turn,
converted to power, liquid fuels, and chemicals. The performance of the processes and quality of
the intermediates are strongly affected by endogenic and technogenic inorganics. This review
highlights investigations on the effect and the fate of inorganics during pyrolysis, gasification,
and combustion of lignocellulosic biomass and critically and comprehensively presents
pretreatment and post-treatment approaches for inorganic removal. During pyrolysis process, the
inorganic contents can have significant catalytic effects and change the thermal degradation rate,
chemical pathway, and bio-oil yield. During combustion process, the inorganic contents can
bring various technological problems, environmental risks, and health concerns. During
gasification process, the inorganic contents cause diversified downstream hazards. In recent
years, several pre-treatment (mechanical, thermal, and chemical pre-treatment) and post-
treatment (gas product and liquid product post-treatment) approaches have been employed to
control and diminish the impact of inorganics during thermochemical conversion. Effective pre-
treatment technologies exist to remove inorganic contaminants to lower concentration limits.
However, the main drawbacks of these pre-treatments are that they (i) reduce the overall
3
efficiency due to the need of further drying process of wet biomass after pre-treatment and (ii)
increase chemicals, facilities, and drying costs. Post-treatment technologies are utilized to meet
the strict levels of cleanup demands for the downstream applications. A great number of
technologies exist to purify the raw synthesis gas stream that is produced by thermochemical
conversion of biomass.
2. INTRODUCTION
The excessive consumption, finite reserves, and established contribution to the

greenhouse effect of fossil fuels is motivating the development of renewable technologies as
sustainable long-term solutions. These technologies rely on biomass, solar, wind, water or
geothermal resources as their primary energy source. Among all these renewable resources,
biomass is the only resource that produces power, liquid fuels, and chemicals, thus making it an
attractive option for countries with abundant biomass resources.1 Biomass can be converted to
intermediates that can be used to produce power, liquid fuels, and chemicals through
biochemical (enzymatic hydrolysis, sugar fermentation) or thermochemical (combustion,
pyrolysis, gasification) routes. The biochemical route seeks to convert carbohydrates in
lignocellulosic biomass to energy carriers for power,2 ethanol and butanol as liquid fuels,3 and
other platform chemicals.4-6 In the thermochemical platform, biomass is converted thermally to
energy-dense intermediates that can be, in turn, converted to power, liquid fuels, and chemicals.7
Specifically, biomass can be converted to thermal energy during direct combustion; into thermal
energy and a mixture of flammable gas known as syngas during gasification; and into mostly an
energy-rich liquid known as bio-oil, as well as a small amount of syngas and solid biochar during
pyrolysis.7 The presence of biomass inorganics is detrimental to processes in both routes. For
example, the presence of inorganic compounds during biochemical conversion has been
associated with many issues that resulted in the inhibition of biological growth or productivity
through the biochemical conversion route.8-10 Issues related to inorganics during thermochemical
conversion include equipment corrosion, fouling of surfaces, catalysts deactivation, and bed
agglomeration in reactors.11-12
In recent years, recognizing the challenges associated with inorganics during biomass
conversion, several review papers attempted to organize the growing body of knowledge on the
fate of inorganics during conversion, their effects on the processes, and pre-treatment and post-
4
treatment strategies to mitigate those effects.13-14 However, past reviews focused on pre-
treatment techniques in the context of biochemical conversion technologies15 and post-treatment
reviews focused solely on gasification.11-12 This review focuses only on the main
thermochemical conversion processesnamely, pyrolysis, gasification, and combustionand
comprehensively reviews recent work to elucidate the fate of inorganics during these processes
and summarizes pre-treatment and post-treatment techniques for controlling these elements.
3. THE ORIGIN, NATURE, AND VARIABILITY OF INORGANICS IN

LIGNOCELLULOSIC BIOMASS
Besides the structural carbohydrates and lignin, lignocellulosic biomass also contains a
small amount of extraneous components that do not serve structural functions. These extraneous
components are present inside and outside the cell wall but are generally not bound to it.16-18
Extraneous components are grouped into extractives and inorganics, the latter being of interest in
this review. Inorganic elements in lignocellulosic biomass have different origins: authigenic,
which is formed in the biomass; detrital, which is formed outside the biomass, but fixed inside or
on the biomass; and technogenic, which is formed outside the biomass (see Table 1).19-20
The type and proportions of inorganics are highly variable and are dependent on several
environmental conditions. For example, plants grown on contaminated groundwater absorbed
more metal contaminants than their counterparts.21 The same species of Syncarpia laurifolia,
commonly known as the turpentine tree, had 0.6% and 0.09% physiological silicon when grown
in Australia and Hawaii, respectively.18 Agricultural crops were reported to have a higher
nitrogen content for a higher total nitrogen supply via fertilizer nitrogen applications.22-23
Natural or physiological inorganics originate from proteins and alkaloids for nitrogen,
sulfate salts of minerals for sulfur and soil nutrients taken up during plant growth for nitrogen,
sulfur, and all other metals, respectively.18 Anthropogenic inorganics are a result of harvest
operations (i.e., type of equipment, harvest techniques) and seasons that result in increases in
inorganic content.
Physiological inorganics are present in lignocellulosic biomass in numerous forms, as
illustrated in Table 2. These elements can be in their organic form when covalently bonded to
organic structures (e.g., proteins) or in their inorganic simplest form as a free ion (e.g., Na+ )
dissolved inside the fluid matter of the plant or as salts (e.g., NaCl).21 The alkali metals (Na and
5
Table 1 Origin of inorganic matter in lignocellulosic biomassa
origin time of formation formation mechanism
Natural Process
authigenic syngenetic inorganics that are the result of biogenic processes
during plant growth (e.g., photosynthesis, diffusion,
adsorption, osmosis, pinocytosis, exocytosis,
endocytosis, hydrolysis, precipitation, etc.)
epigenetic inorganics generated from natural processes after
plants died (evaporation, precipitation)
detrital pre-syngenetic fine (~ 1μm) inorganic particulates suspended in water
and transported into the plant during syngenesis
(endocytosis)
syngenetic, small (<10–100 μm) inorganic particulates deposited
pre-syngenetic on plant surfaces by water and wind, and fixed in
or epigenetic voids and cracks over time during plant growth
Anthropogenic Process
technogenic post-epigenetic none physiological inorganics resulting from harvest
(collection, handling, transportation) and
preprocessing (comminution, separation, etc.)
operations
a
Syngenetic = during plant growth; epigenetic = after plant death; pre-syngenetic = before plant
growth, post-epigenetic = during and after plant collection.
Table 2 Common nature of inorganic in lignocellulosic biomass

(adapted from ref 21)
group examples of examples of inorganic forms dominant forms
organic forms
alkali metals oxalate Na+ and K+ in fluid matter; mostly in ionic salts
KCl, NaCl; forms
NaNO3, KNO3
alkaline earth oxalate; Mg2+ and Ca2+ in fluid matter; form with organic
metals carbonate CaCl2, MgCl2, counter ions to large
Ca3(PO4)2 and Mg3(PO4)2 extent complexes
transition Fe-Chelates; Fe2+, Mn2+ and Cr3+ in fluid often in small (< 2 μm)
metals Mn- matter; crystal structures
Carbohydrate Metallic form; Iron oxide
other metals – aluminum hydroxide mostly in inorganic
(Al, Pb etc.) (Al(OH)3);Kaolinite forms
2− 2−
non-metals covalently sulfate (SO4 ), sulfite (SO3 ) varies with types of
(P, S etc.) bound to and phosphate (PO43 −) anions feedstocks
proteins, amino
acids
6
K) are mostly not metabolized by the plant and remain in the form of ionic salts in
lignocellulosic biomass materials.24 They are often dissolved in the fluid matter are trapped
within the biomass cell structure in free ion form (Na+ , K+ ) with counterions such as chloride
(Cl−) or malate (C4H4O5 2−).21 Alkali metals also appear in solid salt structures fixed on the
biomass cell wall.21 A small amount of Na and K are attached to functional groups in the organic
matrix as carboxylates and phenoxides.25 Alkaline-earth metals (Mg and Ca) exist in different
chemical statuses than alkali metals. In the plants, Mg and Ca are required for plant growth and,
to a large extent, have a tendency to form complexes with organic counterions.25 As such,
alkaline-earth metals do not usually occur in free ionic form.
Besides alkali and alkaline-earth metals, other metals commonly present in
lignocellulosic biomass are Fe, Cu, Ni, Cd, Cr, Co, Mn, Zn, Al, and Pb. When present in
biomass, the concentrations of the transition metals are usually very low. Transition metals
present in biomass can be from the natural environment (for example, when mineral-rich water
or contaminated groundwater is taken up by the roots and transported via the stems to upper
branches and leaves18). The sources of these elements are largely technogenic. For example,
harvesting equipment can transfer metal traces to the biomass material due to natural wear and
tear that occurs as a result of these operations.19 These metals have various forms. They can bond
with organic matter and impurities in the amorphous or crystalline cellulose or defects in the salt
crystal structure.26 In addition, they can exist in ionic form and as impurities in sulfates, nitrates,
etc.26 Cohen and Dunn27 reported these metals to be often included in small (<2 μm) crystal
structures. Fe, Cu, Ni, Cr, Mn, Zn, and Pb were shown to associate primarily with the water-
insoluble portion of the lignocellulosic biomass, while Cd, Co, and Al showed positive
associations with the water-soluble fraction.26 Except for Fe, Cu, and Al, all transition elements
showed a positive association with cellulose. Elements that did not show a positive association
with cellulose (Fe, Cu, and Al) are frequently used as construction metals in processing
equipment, which suggests that these elements may be rather more technogenic than natural.19
Nonmetals such as phosphorus (P) and sulfur (S) can be found in both organic and
inorganic components. The ratio between organic and inorganic sulfur-containing molecules is
largely dependent on the type of biomass, as well as the location. While phosphorus and sulfur
can exist in proteins and amino acids and as sulfate and phosphate anions,21 phosphorus is
predominantly found in its inorganic form. Chlorine is also present in most biomass materials as
7
chlorides, chlorites, and chlorates. Chlorides identified in biomass can be formed in biomass and
from outside resources in origin.19 Elemental nitrogen (N) exists as nitrates, nitrites, and
alkaloids.18
4. THE EFFECT OF INORGANICS ON BIOMASS THERMOCHEMICAL

CONVERSION PROCESSES
Thermochemical conversion technologies (combustion, gasification, and pyrolysis) are

very sensitive to feedstock inorganic content with recommended ash contents of <1 wt %.20 In
the next sections, we discuss the effect and fate of inorganics on pyrolysis, gasification, and
combustion.
4.1 Pyrolysis
Inorganic elements of biomass have been known for some time to have significant and
often undesired consequences on the pyrolysis process.28-29 The presence of these elements in the
pyrolysis vapors occurs by ejection of biomass inorganics during primary aerosol formation, as
illustrated in Figure 1.30 Although biomass inorganics remain predominantly in the biochar, the
fraction ejected as well as fine biochar particles entrained can have drastic impacts on the biooil
properties and product yields.21, 29 Studies have shown negative effects of higher bulk ash content
on the pyrolysis yields with a negative correlation between total ash content and bio-oil yield.31-
32
Biomass feedstocks with low ash content generally result in higher organic bio-oil, compared
to high ash feedstocks. It was reported that bio-oil yields increased by 1%− 5% for each 1% of
ash removed from native biomass.31, 33-34 Silica is relatively inert and typically accumulates in the
product char fraction. However, even trace levels (<0.1%) of catalytically active ash components
can change the thermal degradation rate and chemical pathways during pyrolysis. Alkali metals
(K and Na) and, to a lesser extent, the alkaline-earth metals (Ca and Mg) are known to catalyze
the thermal degradation of biomass. In the case of alkali metals at a lower concentration in
biomass, the extent of transfer from biomass to bio-oil varies, depending on the species: for
sodium, the transfer is high and averages 25% of the original content in biomass, whereas for
potassium, the transfer was moderate and 2.6%.21 For alkaline-earth metals, the concentration
of Ca and Mg in the pyrolysis oil was reported to be within the range of 1%−5% of the original
content in the biomass.21 In addition, a higher water content was observed in the bio-oil with
higher content of alkaline-earth metals.35 For nonmetals, the degree of sulfur transfer varied
8
based on the biomass type. In the woody biomass materials, the extent of sulfur transfer was 36%
or greater, while it was 32%−96% in the agricultural residues. Phosphorus had a low transfer to
pyrolysis oil, with an average of 2%.21 Meanwhile, gas-phase emissions during pyrolysis
contain a certain degree of nitrogenous species (NH3, HNCO, and HCN), chlorine species (HCl
and Cl2), and sulfur species (COS, H2S, and SO2).36 The formation pathways of NH3 are that (i)
proteins and amino acids may release in the form of NH3 in the temperature range of
300−500 °C, (ii) thermal cracking reactions of tar and char can form NH3 by undergoing
secondary reactions, and (iii) hydrogenation and hydrolysis of HCN can introduce NH3 on the
surface of the char.37 As for HCN and HNCO, cracking of the cyclic amides is considered to be
the main reaction leading to their formation.38 NH3, HNCO, and HCN are the precursors of
nitrogen oxides (NOX and N2O), which can cause environmental concerns. Chloric species could
be released to the flue gas as HCl and much lower content of Cl2, which could subsequently
bring corrosion problems.36 For sulfur species, COS and H2S are released from the
decomposition of organically bound sulfur with a lower stability, and SO2 comes from the
evaporation or transformation of inorganic sulfate.36 The SO2 content from the sulfur is also
considered to be an important factor in the corrosion processes.36
Figure 1 Pathways to aerosols: ejection of biomass inorganics during primary aerosol

formation30
4.2 Gasification
Inorganic impurities in gasification producer gas include sulfur compounds, nitrogen
compounds, alkali metals (primarily potassium and sodium), and hydrogen chloride (HCl).12, 39-40
Depending on the downstream applications, each contaminant creates specific challenges
ranging from corrosion and fouling of surfaces to rapid and permanent deactivation of
9
catalysts.39, 41 In the producer gas, the concentrations of contaminants based on biomass-bound
inorganic impurities vary greatly and are positively correlated to inorganic content in the starting
solid feedstocks.42-43 Thus, the cleaning process for syngas is of great importance. The level of
required cleaning varies, depending on the downstream technology and/or emission standards
(see Table 3).11
Table 3 Typical syngas applications and associated cleaning requirements11

application sulfur nitrogen alkali halides
gas turbine <20 μL L−1 <50 μL L−1 <0.024 μL L−1 1 μL L−1
methanol synthesis <1 mg m−3 <0.1 mg m−3 <0.1 mg m−3
FT synthesis <0.01 μL L−1 <0.02 μL L−1 <0.01 μL L−1 <0.01 μL L−1
During gasification, the major nonmetal biomass inorganics are nitrogen, sulfur, and
chlorine, because contaminants derived from these species have been tied to specific challenges
in downstream applications (see Table 3). Typical syngas applications and associated cleaning
requirements are also given in Table 3.11-12, 39, 41 Biomass-bound nitrogen is predominantly
transformed to ammonia (NH3), with smaller amounts of hydrogen cyanide (HCN), in producer
gas. The nitrogen-based contaminants can also be further oxidized to nitrogen oxide (NO) and/or
dioxide (NO2), both of which are environmental pollutants subjected to control under the U.S.
Environmental Protection Agency (USEPA) regulations. Biomass sulfur is converted
predominantly to hydrogen sulfide (H2S), carbonyl sulfide (COS), and other minor sulfur
containing compounds.12, 44 Organically associated S is released during the decomposition of the
organic fuel matrix during devolatilization.45 Through this pathway, the release of S proceeds
through the formation of SH radicals, which come from the thermal decomposition of S-bound
organic compounds.46 These SH radicals, which are highly reactive, could extract H, C, or O
from the char, forming H2S, COS, or SO2.45-46
Their proportions in producer gas are dependent on the sulfur content of the starting
feedstocks, as well as the operating conditions: higher physiological sulfur in biomass results in
higher sulfur-based contaminants in producer gas, while lower equivalence ratios (i.e., lower O2)
result in more reduced forms of sulfur contaminants.39-40 Chloride, which is the most abundant of
the halide-based contaminants in producer gas, is present at relatively lower concentrations in the
form of HCl with concentrations of <100 ppmv for woody biomass.39-40 Despite their low
concentrations, chlorine-based contaminants can cause serious challenges, including fouling and
10
deposition as the producer gas is cooled downstream, as well as corrosion, as a result of the
deposition and catalyst poisoning.47 Moreover, chloride in the producer gas can react with other
contaminants in the gas phase to produce other contaminants such as ammonium chloride
(NH4Cl) and sodium chloride (NaCl). Besides sulfur, nitrogen, and chlorine, trace metals are
important to track throughout the process. Especially, alkali and, to a lesser extent, alkaline-earth
metals are of interest, because they have been associated with hot corrosion of the gasifier.48 In
addition, catalysts are known to be extremely sensitive to alkali metals and can easily be
poisoned by levels found in biomass during in situ catalytic gasification.11 However, since alkali
compounds can leave the reactor as aerosols and vapors and are transported out of the reactor,
normally in the form of hydroxides, chlorides, and sulfates, they still present a challenge for ex-
situ conditioning of syngas or downstream catalytic applications and can cause substantially
fouling and corrosion in downstream processes.48-49
4.3 Combustion
About 95%−97% of the world’s bioenergy is currently produced by direct combustion of
biomass.50 As a result, 480 million tons of biomass ash could be generated worldwide annually
if the burned biomass is assumed to be 7 billion tons.50 The challenges of managing biomass-ash-
derived inorganics during combustion is welldocumented.12, 51-53 Generally, issues related to
these inorganics during combustion are agglomeration,50 alkali deposits,53 slagging,51 fouling, 51-
52
and corrosion.52, 54 The propensity for inorganics to lead to the aforementioned issues are
measured by various indices, as shown in Table 4.
Slagging and fouling propensity are typically determined by similar feedstock
properties.52, 55-56 Slagging is defined as the formation of sintered and molten deposits on
surfaces and refractory lining in the main furnace cavity in regions directly exposed to flame
radiation, while fouling is defined as the formation of sintered, but not molten, deposits on
surfaces in the convective pass of the boiler not directly exposed to flame radiation with flue gas
temperature below the melting temperature of the bulk fuel ash.57 Slagging and fouling deposits
are of great concern to biomass or biomass-coal fired plants. Its primary mechanism consists of
the condensation of devolatilized inorganic species on the refractory lining, heat exchangers,
superheaters, reheaters, and other surfaces in the furnace and on the path of hot flue gases.58 The
transformation of inorganic components with chemical reactions occurring could cause the
formation of chemical compounds and complexes with extremely low melting point and/or very
11
Table 4 Select indices indicative of slagging, fouling, agglomeration, and corrosiona
indicesb empirical formula indicator of propensity
Low Medium High
base/Acid slagging < 0.4 0.4 - 0.7 >0.7

Ratio
fouling

fouling Index fouling < 0.6 0.6 - 40 > 40

slagging slagging <0.6 0.6 - 2.0 > 2.0

factor
alkali index fouling < 0.17 0.17 - 0.34 > 0.34

(kg/GJ) slagging
Cl content corrosion < 0.1 > 0.1
(wt.% dry)
S content corrosion < 0.1 > 0.1
(wt.% dry)
bed agglomeration > 2.5 0.1 - 2.5 < 0.1

agglomeration
a
Data taken from ref 55-58. bIndices for which units are not specified are unitless.
high adhesion force.55 For example, Na2S2O7 melts by 401 °C, K2S2O7 melts by 325 °C,
Na3K3Fe2(SO4)6 melts by 552 °C, Na2SO4−NaCl melts by 625 °C, Na2S−FeS melts by 640 °C,
and eutectic mixture CaSO4−CaS melts by 850 °C.55 The low melting points can be expected by
combustion of fuels with high sodium and potassium contents.55 The mechanism typically begins
with the condensation of alkali salt vapors on exposed surfaces, thus creating sticky anchors that
assist in binding other inorganics and particulates.59 The result of this process is the formation of
a hard and fused glassy layered deposit structure on these surfaces and the loss of functional
purpose (i.e., loss heat transfer potential, loss of integrity, etc.).50-51 Among the inorganic
elements, K, Na, Cl, and S are thought to be the root causes of slagging/fouling, agglomeration,
and corrosion during the combustion of biomass-based fuels.60-61
5. PRE-TREATMENTS FOR THERMOCHEMICAL CONVERSION OF

BIOMASS
Pre-treatment is the first and most important step in biomass processing. It is the key
process to modify the undesirable properties of lignocellulosic biomass in order to improve its
conversion efficiency and reduce its production cost.62 In the context of the thermochemical
conversion platform, pretreatment has been traditionally used to facilitate material handling.
However, in recent years, pre-treatment techniques commonly used in biochemical conversion
12
are beginning to be explored for the targeted amelioration of specific biomass properties.33, 63
This section narrowly focuses on the impact of these advancements on reducing the content of
inorganics in lignocellulosic biomass dedicated to thermochemical conversion. We grouped pre-
treatment techniques into four categories: (1) mechanical (e.g., comminution and mechanical
sieving); (2) thermal (e.g., torrefaction, steam explosion/liquid hot water pre-treatment, and
ultrasound/microwave irradiation); (3) chemical (e.g., treatment with acids, bases, and ionic
liquids); and (4) biological (e.g., fungal, microbial consortium, and enzymatic). Biological pre-
treatment has not yet been employed in the context of thermochemical conversion, based on our
survey. Therefore, no discussion is presented.
5.1 Mechanical pre-treatment

Mechanical pre-treatment encapsulates all of the techniques that primarily employ
mechanical energy to affect changes in biomass properties and includes comminution to reduce
particle and sieving to fractionate material based on particle size. The latter, mechanical sieving,
has been shown to significantly affect ash content of biomass by varying biomass particle sizes
and disproportionately segregating inorganic elements in different fractions.64-67 Liu et al. studied
the effect of size fractionation for switchgrass and pine bark and reported that ash content varied
greatly by different size fractions.65 Furthermore, their results showed that size fractionation
could potentially remove more than 20% of the inorganic constituents from the switchgrass and
up to 30% of inorganic constituents from raw pine bark. The fine fractions of ground switchgrass
and pine bark have larger ash content than the coarser fractions. In particular, for a sample that
varied from 0 to 0.95 mm in particle size, the fraction of biomass between 0.4−0.95 mm had the
lowest ash content, highlighting the disproportionate distribution of ash in fines. Bridgeman et al.
reported similar trends for switchgrass and reed canary grass and observed that the ash content
nearly doubled in fines (<90 μm) from 3.62 wt % to 6.0 wt % (dry basis) for reed canary grass
and 3.12 wt % to 6.88 wt % (dry basis) for switchgrass, respectively.64 Pattiya and co-workers
studied the effects of biomass size reduction on cassava stalk and rhizome.68 They found that, for
both cassava stalk and rhizome, the particle size of 0.250 mm showed much lower ash contents.
The differences among the ash contents of the biomass with a particle size of >0.250 mm were
very small. Arvelakis et al. investigated the effect of size fractionation of three different agro-
residues.69 The results showed that the total ash content in the coarse fraction samples (particle
size of >1 mm) is reduced by almost 35% from the original sample, but most of the main
13
troublesome elements (such as K, Cl, and S), which are considered to be responsible for
problematic ash thermal behavior, remained in it. For the fine fraction samples (particle sizes of
<1 mm), their ash content was significantly larger than the course samples.
While ash content increased in fines upon fractionation (see Table 5), the concentration
of individual elements in fines might vary depending on the feedstock, the definition of what
constitutes “fines” and representativeness of the samples characterization is carried on. Miranda
and colleagues reported that the concentration of elements such as nitrogen (N), phosphor (P),
sodium (Na), and potassium (K) increased in the fine fraction (<180 μm) of Norway spruce
(Picea abies (L.) Karst.) and Scots Pine (Pinus sylvestris L.) barks. However, the content of
magnesium (Mg) decreased in the fines and increased in the coarser fraction for both
feedstocks.66 However, Bridgeman and co-workers showed that all 11 elements measured in their
study (Al, Ca, K, Na, Mg, Mn, Ni, P, S, Zn, and Fe) increased in the fine fraction (<90 μm).64
5.2 Thermal pre-treatment

Thermal pre-treatment includes the techniques that primarily rely on thermal energy to
affect changes in biomass properties. While it is understood that, with increasing temperature,
several chemical reactions would occur, thermal pre-treatment techniques are primarily driven by
thermal energy delivered through a gaseous or liquid carrier. Because of the change of properties
during thermal pretreatment, the ash content of the biomass would also be changed. Pre-
treatments such as steam explosion, hot water extraction, and hydrothermal carbonization have
shown their effect on the change in ash content of several biomass materials.
Table 5 Effect of mechanical sieving on ash content for select lignocellulosic feedstocks
Ash Content (wt % dry basis)
fraction, μm < 180 180 - 250 250 - 450 450 - 850 850 – 2000 > 2000 Refs
66
birch 3.4 4.5 2.5 2.6 2.1 2.2
66
eucalyptus 23.1 14.7 15.9 7.9 6.7 4.3
67
Douglas fir 1.5 1.1 0.8 0.8 1.2 0.4
switchgrass† 10.53 8.07 7.21 5.54 4.31 -- 65
pine barka 4.93 4.04 2.79 2.40 2.38 -- 65

a
Fractions for these two feedstocks are as follow: < 150, 150 – 300, 300 – 400, 400 – 950 and >
950 μm, respectively
The typical process of commercial steam explosion involves filling a vessel with wood
chips and then pressurizing it with saturated steam at a pressure of 7000 kPa.33 The pressurized
14
steam permeates the chips, and introducing the rapid decompression defibrates the wood chips
when the vessel is suddenly opened.33 During steam explosion, lignin depolymerizes into low-
molecular-weight products (400−8000 units) and condenses with other degradation products,
which results in an increase in lignin content. Steam explosion also partially breaks down
hemicelluloses, which become predominantly soluble in water. The loss of hydroxyl groups
causes a reduction in the hygroscopicity of the biomass material, since hydroxyl groups provide
hydrogen bonding sites for water molecules in the hemicellulose and cellulose. Steam explosion
also showed effectiveness in the change of ash content for different raw biomass materials. Jeoh
and Agblevor studied the effect of steam explosion on cotton gin waste with 10.5 (±3.4) wt %
ash content.70 Results showed the effectiveness of steam explosion to reduce the ash content of
cotton gin waste to between 6.1 (±2.1) wt % and 0.0 (±0.0) wt %, depending on increasing
severities. Lam investigated the effect of steam explosion on Douglas Fir wood chips.71-72 The
study showed a slight increase (0.27% to 0.32% by weight) of the ash content for the 200 °C
treated wood pellet and a further increase (0.27% to 0.52% by weight) of the ash content of the
220 °C treated wood pellet. Tooyserkani et al. studied the steam treatment of three white
softwood species (pin, spruce, and Douglas fir) and one sample of bark at 220 °C for a residence
time of 5 min.73 Their study showed an increase in the relative ash content values for the four
samples, which, as stated in the study, cannot directly show the increase in the inorganic content
of samples; it could indicate the relative loss of other components in the samples. Wang and
Chen utilized steam explosion technology on cornstalk at 185−190 °C for a residence time of 5
min.74 The steam-exploded cornstalk showed lower ash content (1.24 wt %), compared to the
original cornstalk sample (1.59 wt %). Kemppainen et al. studied steam explosion for industrial
spruce bark at 205 °C/16.3 bar for 5 min.75 Ash content of spruce bark was reduced to 3.2 wt %
dry basis from 3.6 wt %. Biswas et al. studied the influence of steam explosion on Salix wood
chips.76 Their study resulted in the reduction of ash content in steamtreated residue (from 2.4%
to 1.8%, dry basis), especially of alkali metals (both Na and K achieved 50% of reduction).
Hot water extraction (HWE) pre-treatment is one of the leading pre-treatment methods
for improving cellulose digestibility of lignocellulosic biomass.77 The acidic liquor of HWE,
usually conducted at elevated temperatures (120−260 °C) with no added chemicals, is regarded
as an environmentally friendly pre-treatment process. Several studies have reported a noticeable
reduction of ash content upon hot water extraction with notably high removal efficiency for
15
alkali metals.78-79 The efficiency of HWE in removing alkali species can be due to the fact that
most alkali elements in biomass are present in watersoluble forms.80 Mante et al. analyzed the
hot-water treated (at 160 °C for 2 h) sugar maple samples.79 Results showed that HWE decreased
the ash contents from 0.81 wt % to 0.38 wt % dry basis. Das et al. carried out hot water treatment
on the Douglas fir and the hybrid poplar (H. pop) for 30 min at 121 °C.32 The hot-water-treated
Douglas fir sample had an ash content of 0.1 wt %, compared to the original 0.3 wt % dry basis;
the hot-water-treated hybrid poplar sample had an ash content of 5.4 wt %, compared to the
original 7.0 wt % dry basis. Their results also showed that, for both the biomass samples, hot
water extraction effectively reduced the content of Ca, Mg, Na, and K. Kemppainen et al. studied
hot water extraction as pre-treatments for industrial spruce bark at 80 °C for 120 min. The ash
content of spruce bark was reduced to 3.3 wt % dry basis, from 3.6 wt %.75
Hydrothermal carbonization (HTC) or wet torrefaction is another thermal pre-treatment
method that has been used to pretreat biomass prior to thermochemical conversion.81-82 The
objectives of hydrothermal carbonization are to produce a material with increased stability, as
well as increased carbon and energy contents.33 HTC results in three products: gases, aqueous
chemicals, and solid fuels. Temperatures for HTC are usually between 160−300 °C and pressures
below 5000 kPa.33, 81-82 The production rate of HTC is higher than that of torrefaction and,
because initial moisture content is not critical, HTC may be compatible with a broader range of
feedstocks. However, commercial-scale HTC is expected to be more expensive than dry thermal
pre-treatments such as torrefaction, because of the need for pressure vessels, which are more
expensive.33 The economics of combining HTC with fast pyrolysis have not been thoroughly
assessed in the literature. Determining whether a dry, wet, or no thermal/chemical pretreatment is
preferred prior to thermochemical conversions requires consideration of the costs and
technologies available for grinding, drying, transporting, storing, handling, and upgrading.33
HTC has the capability to reduce the ash content of pretreated biomass. According to Chen et al.,
the wet torrefaction of sugar cane bagasse was conducted at 180 °C for 5−30 min with sulfuric
acid (concentrations of 0 and 0.1 M).83 Results showed a reduction from 3.55 wt % to 1.70 wt %
of the ash content in bagasse under water torrefaction. Wet torrefaction with acid solution can
also remove ash; however, more solid was also consumed. Bach et al. investigated the effect of
wet torrefaction on Norway spruce and birch under different conditions (temperatures of 175,
200, and 225 °C; holding times of 10, 30, and 60 min; and pressures of 15.54, 70, and 160 bar).84
16
According to their results, the ash content of Norway spruce can be reduced from 0.23 wt % to
0.09 wt %, and the ash content of birch can be reduced from 0.28 wt % to 0.08 wt %. Zhang et
al. studied the effect of wet torrefaction on the ash content of duckweed samples with an ash
content of 9.7 wt %. As the wet torrefaction temperature increased from 130 °C to 250 °C, the
ash content increased from 7.6% to 19.9%.85 Table 6 summarizes studies that were focused on
thermal pretreatment and their effectiveness in ash content reduction.
5.3 Chemical pre-treatment

Chemical pre-treatment includes techniques that primarily rely on the action of chemical
agents applied at or near room temperature to affect changes in biomass properties. The
techniques reviewed here include water leaching and acid, alkali, and salt washing. Table 7
summarizes the main outcomes of studies that investigated various chemical pre-treatment
techniques for inorganic reduction.
5.3.1 Water leaching

Washing the biomass with water have been shown to be effective in removing the
majority of alkali metals (e.g., K and Na), as well as some of the chlorine contaminants.49, 86, 88
Liaw and Wu reported that an acidic leachate was produced during the batch leaching of organic
matter from biomass, resulting in the leaching of some waterinsoluble inorganic species.98 Baxter
et al. reported that 80%− 90% of the alkali metals in biomass exist in water-soluble or
ionexchangeable species form.53 Meantime, water washing is more suitable for feedstock with a
high inorganics content.53 Biomass with a low inorganics content (e.g., woody biomass) has a
higher concentration of alkali metals bound to the organic structure and thus has limits with
regard to the effectiveness of water washing, although agitation can enhance the efficiency.53
Jenkins et al. carried out experiments on inorganic removal from rice and wheat straws by water
leaching at room temperature for 24 h.86 Their results showed that 90% of K, 98% of Cl, 55% of
S, 68% of Na, 72% of P. and 68% of Mg were removed. Also, total ash concentrations were
reduced by 10% in rice straw, and by 68% for wheat straw for well-washed samples.86
Davidsson et al. studied wheat straw and wood waste (mainly pine and birch), with respect to
alkali-metal release.88 Their study found out that washing with water at room temperature for 4 h
reduced the alkali emission by 5%−30% from wood waste and wheat straw. Yu and co-workers
17
Table 6 Summary of thermal pretreatment for inorganic removal from biomass
Feedstock Experimental conditions Original ash content Final ash content Refs
(wt%, dry basis) (wt%, dry basis)
Steam Explosion
70
cotton gin At 185, 211.5, and 238 °C 10.5 6.1-0.0
waste for 20, 510, and 265 s
74
cornstalk At 185 to 190 °C for 5 1.59 1.24
min
75
spruce At 205 °C/16.3 bar for 3.6 3.2
bark 5 min
76
salix At 220 and 228 °C for 6 2.4 1.8
wood and 12 min
chips
71-72
Douglas At 200 and 220 °C for 5 0.27 0.32-0.52
fir and 10 min
73
pine At 220 °C for 5 min 0.07 0.34
73
spruce At 220 °C for 5 min 0.22 0.94
73
Douglas At 220 °C for 5 min 0.14 0.28
fir
73
fir bark
Hot Water Extraction
79
sugar At 160 °C for 2 h 0.81 0.38
maple
32
fir
32
hybrid At 121 °C for 30 min 7 5.4
poplar
75
spruce At 80 °C for 2h 3.6 3.3
bark
Hydrothermal Carbonization
83
sugarcane At 180 °C for 5 to 30 min 3.55 1.7
bagasse with sulfuric acid
84
Norway At 175, 200, 225 °C for 0.23 0.09
spruce 10, 30, 60 min, pressure at
15.54, 70, 160 bar
84
birch At 175, 200, 225 °C for 0.28 0.08
10, 30, 60 min, pressure at
15.54, 70, 160 bar
85
duckweed At 130 to 250 °C for 60 9.7 7.6 - 19.9
min
18
Table 7 Summary of chemical pretreatment for inorganic removal from biomass
Pretreatment Feedstocks Experimental conditions Outcomes Refs
Biomass particle Liquid to Time (hour) Temp Ash reduction Mass loss
size (mm) solid ratio (°C) (%) (%)
Water leaching
86
D.I. water Rice straw 70:1 24 20-25 10
86
Wheat straw 70:1 24 20-25 68
87
Miscanthus 0.25–2.00 20:1 4 (300 rpm) 25 48 5 (carbon
reduction)
88
Wheat straw 0.50–2.00 50:1 4 25 47
88
Wood waste 0.50–2.00 50:1 4 25 36
89
Miscanthus 2.00 20:1 6 22 15
89
Switchgrass 2.00 20:1 6 22 24
89
Wheatgrass 2.00 20:1 6 22 53
89
Rice straw 2.00 20:1 6 22 24
89
Wheat straw 2.00 20:1 6 22 39
89
Corn stover 2.00 20:1 6 22 47
89
Douglas fir 2.00 20:1 6 22 40
65
Switchgrass 0.40-0.95 40:1 48 20 40
32
Sugarcane 0.25 12:1 1 25 31 18-20
bagasse
90
Empty fruit 0.31 20:1 1, 3, 5, 10, 25, 40, 52
bunchs 30, 60, and 55
120 min
90
Palm kernel 0.72 20:1 1, 3, 5, 10, 25, 40, 10
shells 30, 60, and 55
120 min
56
Rice straw 0.84 40:1 24 25 14
56
Wheat straw 0.84 120:1 24 25 50
56
Switchgrass 0.84 120:1 24 25 14
56
Wood fuel 0.84 120:1 24 25 10
Acid washing
10 g/l 62.8 6.1 78
Switchgrass 0.42 20:1 0.33 85
CH3COOH
19

Table 7 Continued
78
10 g/l C6H8O7 Switchgrass 0.42 20:1 0.33 85 52.5 6.8
10 g/l H2SO4 59.7 32.9
91
H2SO4 Douglas fir 0.42-0.85 2.5:1 3 25 47
91
Hybrid 0.42-0.85 2.5:1 3 25 46
poplar
87
1.00% HCl Miscanthus 0.25–2.00 20:1 4 (300 rpm) 25 4
92
HCl Seaweed 5.00 40:1 24 (200 25 15
rpm)
92
H2SO4 Seaweed 5.00 40:1 24 (200 25 16
rpm)
92
HNO3 Seaweed 5.00 40:1 24 (200 25 17
rpm)
93
0.1 M HCl Cotton 0.25 20:1 4 25 68
residue
93
Waste wood 0.25 20:1 4 25 24
93
1M Cotton 0.25 20:1 4 25 58
CH3COOH residue
93
Waste wood 0.25 20:1 4 25 18
88
1M Wheat straw 0.50–2.00 50:1 4 25 83
CH3COOH
88
1M Wood waste 0.50–2.00 50:1 4 25 73
CH3COOH
65
0.1 M HCl Switchgrass 0.40-0.95 20:1 48 20 72
65
5M Switchgrass 0.40-0.95 20:1 48 20 48
CH3COOH
65
0.01 M HNO3 Switchgrass 0.40-0.95 20:1 48 20 35
32
5 M HCl Sugarcane 0.25 12:1 1 25 -16 50
bagasse
94
CH3COOH Beech wood 20:1 2&4 25 & 4–15
and HNO3 50
20

Table 7 Continued
95
0.1% HNO3 Mallee 0.18-0.43 10:1 2 25 100 (Na, K, &
wood Mg removal);
96 (Ca
removal)
96
5% HCl Rice straw 0.15-0.45 25:1 24 105 95 (K
removal), 99
(Na removal)
Alkali washing
92
NaOH Seaweed 5.00 40:1 24 (200 25 51 (Cr 47
rpm) removal)
92
NH4OH Seaweed 5.00 40:1 24 (200 25 52 (Cr 35
rpm) removal)
97
NaOH Barley straw 25-30 4:1 10 min 100 86
Salt washing
91
NH4H2PO4 Douglas fir 0.42-0.85 2.5:1 3 25 -13
91
Hybrid 0.42-0.85 2.5:1 3 25 46
poplar
Chelating agent
78
EDTA Switchgrass 0.42 20:1 0.33 85 87.3 8.0
21

investigated the effect of water leaching on ash contents of wheat and rice straws, Jose tall
wheatgrass, switchgrass, miscanthus, Douglas fir, and corn stover at room temperature for 6 h.89
Their results showed that the ash contents of all feedstock samples were significantly reduced.
Leaching reduced the ash concentration in rice straw by 15% of dry matter, in wheat straw by
24%, in corn stover by 53%, in switchgrass by 24%, in miscanthus by 39%, in Jose tall
wheatgrass by 47%, and in Douglas fir by 40%. Liu and Bi reported ash removal for water
leaching of switchgrass up to 40% when leaching for 48 h at room temperature when the biomass
particle size was reduced to 0.4−0.95 mm.65 Their study showed that a combination of size
fractionation and water leaching could potentially remove more than 60% of inorganic
contaminants from the switchgrass. Lam et al. studied the effect of leaching on oil palm residues
and reported three leaching stages of empty fruit bunches achieved ash reduction from 5.47% to
2.63%, with the greatest potassium reduction being from 2.42% to 0.36%.90 Also, Das et al.
carried out water leaching for sugar cane bagasse at room temperature for 1 h.32 The results
showed that leaching reduced ash contents in sugar cane bagasse by 31% of dry matter, with a
mass loss of 18%−20%.
5.3.2 Acid washing

It has been suggested that acid washing facilitates mass transfer and higher levels of ash
removal, compared with normal water leaching.68 Scott et al. suggested that inorganics in
biomass are present in water-soluble salts and cations that are bound to reactive sites,
respectively.99 Treatment with water at room temperature is adequate for the removal of the
water-soluble part, but the cations bound to reactive sites require ion exchange. Because of the
existence of some water-insoluble inorganic elements in biomass, washing with dilute acid
(hydrochloric acid (HCl), acetic acid (CH3COOH), sulfuric acid (H2SO4), hydrofluoric acid
(HF), and nitric acid (HNO3)) has been developed for higher levels of ash removal from
biomass.65 Stylianos and co-workers94 studied the ash reduction from beech wood by acid
washing (HNO3 and CH3COOH) and found that washing with acidic solutions achieved an
inorganics removal of >90%. The los of biomass in this study varied in the range of 4%−15%.
Shi’s group96 investigated 5% HCl acid washing for rice straw at room temperature for 3 h and
reported that almost all alkali and alkaline-earth metals (AAEMs) were removed by this method.
Mourant and co-workers95 used dilute HNO3 acid (0.1 wt %) at room temperature for 2 h and
reported complete removal of all AAEM species, with the exception of calcium, for which only
22
4% of the initial content remained. Das et al. employed H2SO4 acid (0.3 wt %) on Douglas fir
(softwood) and hybrid poplar (hardwood) for 3 h at room temperature and achieved an ash
reduction of 47%.91 Banks et al. used HCl acid (1 wt %) to pretreat miscanthus at room
temperature, which resulted in 48% of ash reduction.87 However, partial hydrolysis of
hemicellulose was shown by TGA analysis in their study. Vamvuka et al. determined the extent
to which various inorganics could be removed by different acids (HCl and CH3COOH) and the
effect of acid pre-treatments on biomass ash composition.93 Their study found that ash removal
was accomplished by acid-washing of waste wood and cotton samples at room temperature,
which resulted in ash removals of 15%−24% and 57%−68%, respectively. Davidsson et al.
investigated the effect of acid washing on the release of alkali compounds.88 With 4 h of acetic
acid washing at room temperature, the study attained 73% and 83% reduction in alkali release of
wood waste and wheat straw, respectively. Liu et al. investigated several acid washing pre-
treatments (HCl, HNO3, H2SO4, and CH3COOH) to remove inorganic components from pine
bark and switchgrass.65 Their results showed that acid treatment improved inorganics removal
efficiency significantly. Acidity is the key paramount factor that affects the removal, with more
ash being removed as the pH decreased. Furthermore, the washing time and acid type were less
significant than the acidity of the liquor. In contrast with water leaching, acid washing can lead
to a large mass loss, because polysaccharides (i.e., cellulose and hemicellulose) can be partially
hydrolyzed, with 20% weight loss of coarse samples (0.4−0.95 mm) after 8 h of soaking into
0.5 M HNO3 at room temperature. Park and others also found that acid treatment of seaweed
resulted in mass losses; with HNO3, H2SO4, and HCl causing mass losses of 17%, 16%, and
15%, respectively.92
In summary, these studies clearly show that acid washing is effective in removing
inorganics from biomass and can achieve complete removal of all alkali and alkaline-earth
metals, given enough time and acidity. The main drawbacks of mineral acid washing are the
added cost associated with recovery and disposal of spent acidic liquor; the introduction of
inorganic elements that the washing process is seeking to remove in the first place; and the
resulting mass loss, in some cases, that reduces carbon availability for thermochemical
conversion. Large quantities of wastewater generated in this process are especially problematic
and lead to excessive wastewater generation. Often, mineral acid washed biomass must be
rewashed multiple times with deionized water to remove remaining mineral acid ions, such as
23
chloride (Cl−) when HCl is used or nitrate (NO3−) when nitric acid (HNO3) is used during
washing. Those drawbacks restrict the large-scale applications of acid washing in
thermochemical conversion were these residual species have undesirable consequences
downstream.
5.3.3 Base washing

Besides acid washing, base washing is investigated as another approach to avoid the
negative effects of inorganics. Park et al. explored seaweed washing with sodium hydroxide
(NaOH) and ammonium hydroxide (NH4OH) at a concentration of 1 M for 24 h and observed
51%−52% removal in Cr(VI), which is the target of their study.92 Furthermore, they reported
mass losses of 47% and 35% for NaOH and NH4OH, respectively. Kazi et al. investigated the
effectiveness of NaOH impregnation on barley straw at different levels and three temperatures
(25, 60, and 100 °C) for 10 min.97 Their results showed that a considerable amount of ash is
removed (up to 86 wt % of the initial ash), along with extractives. Few studies have explored
basic salts as a pre-treatment agent for reducing inorganic content. Das et al. investigated the
effect of salt washing on Douglas fir and hybrid poplar at room temperature for 3 h.91 They
found salt doping pre-treatment was effective in removing 46% of ash from hybrid poplar
samples. Salt pre-treatment increased the activation energies of Douglas fir, which increased the
thermal decomposition stability. Similar to that observed for acid washing, base washing of
biomass suffers from similar drawbacks related to wastewater generation due to rinsing
requirements to remove residual ions, which restricts its large-scale applications.
6. POST-TREATMENTS FOR THE THERMOCHEMICAL CONVERSION

OF BIOMASS
After thermochemical conversion, inorganics in biomass become volatile, carrying

chlorine, sulfur, alkali, and other harmful elements either in the gas or liquid products.100
Depending on the level of these inorganic species, posttreatment processes might be necessary to
reduce their potential impact on the downstream applications. In the context of gasification and
combustion, post-treatment techniques for remediating inorganic and organic gaseous
undesirable species have thus far been referenced as hot or warm gas cleanup. The application of
post-treatment application in pyrolysis is relatively new and emerged in the early 1990s, when
research suggested that biochar inorganics enhanced bio-oil polymerization during storage.28-29
24
The following section discusses only post-treatment processes applicable to pyrolysis,
gasification, and combustion products in gaseous or liquid forms.
6.1 Gas product posttreatments

Gas-phase processes, which have been evaluated to decrease inorganics and improve
product quality, employ physical methods, as well as catalysts and/or sorbents. In the context of
pyrolysis, hot gas filtration (HGF), as a physical post-treatment method, has been extensively
evaluated to explore its impact on inorganic associated with biochar, which provide nucleation
sites for polymerization or catalyze reactions.12, 29, 101-102 Hot vapor filtration was evaluated by
researchers at the U.S. National Renewable Laboratory (NREL) to assess the effect of biochar
filtration on bio-oil stability.101 They reported a significant viscosity reduction (by a factor of
≥10), as well as low alkali and alkaline-earth metals, iron, and overall total solid content
reduction when using ceramic candle filter elements. However, the same effect on viscosity was
not observed when sintered stainless steel candle filter elements were evaluated. Instead,
increasing the iron content in bio-oil filtered through the stainless steel elements upon
condensation, which suggested that elements were chemically attacked and reduced their
effectiveness by the corrosive bio-oil.29, 101 While sintered filters are the most common means of
HGF, a moving-bed granular filter was applied in HGF with noticeable ash reduction from 0.82
wt % in fresh bio-oil to 0.01 wt % after filtration in the best-case scenario.103 One adverse effect
of HGF is the resulting weight loss.101, 104 It was estimated that 10%−30% (by weight) is lost as a
result of HGF.101
In gasification and combustion, warm or hot cleanup have thus far been the primary
methods employed to remediate gas phase inorganics. Gas-phase cleanup of ammonia includes
selective catalytic oxidation or thermal catalytic decomposition.105 In both of these cases, the
catalytic reactor benefits from the high reaction temperature at the exit of the gasifier. However,
the catalyst must be tolerant to other contaminants, especially sulfur impurities (e.g., H2S, COS)
which deactivate catalysts after short operation period.106-107 Catalyst deactivation by sulfur
poisoning can be exacerbated when operating reactors at higher pressure.106 Common industrial
Ni-based reforming catalysts as well as other nickel catalyst formulations with Zn, Ce, Co, Mo,
Fe, and Ru are very effective in NH3 removal at 800−950 °C.106-109
Gas-phase sulfur species removal is achieved with the help of a sorbent, commonly a
metal oxide, through desulfurization reaction or physical adsorption. A wide range of studies
25
have explored and reported on various sorbents including CaO, CaCO3 and dolomite,110 zinc
ferrite promoted with V2O5 111 and various mixed metal oxides of La, Co, Zn, Fe, Cu.112-113 The
effective temperature varies widely, based on the sorbents, but generally ranges from 500 °C to
700 °C.112-114 Alkalimetal sorbents (e.g., Na2CO3, NaAlO2, or NaHCO3) have been shown to be
very effective in removing halides.115-116 These alkali-metal sorbents have a tendency to combine
with halides to form salts (NaCl, KCl, etc.) during thermochemical conversion. Similarly,
alkaline-earth metals (e.g., BaO, SrO, CaO, MgO) could be effective in the removal of halides,
based on thermodynamic modeling.12 In addition, inexpensive minerals (e.g., such as fly ash,
bentonite, kaoline, and bauxite) were reported to be effective for capturing trace metals during
biomass combustion.117 Besides sorbents, barriers filtration unit operations (cyclones, candle
filter, bag filters) after the gasifier have been shown to significantly reduced the concentration of
fine particules, and thus inorganics, in the gas stream.11
6.2 Liquid product posttreatments

Upon cooling, inorganics in the pyrolysis vapors are condensed into the biooil. The
multiphase nature of freshly obtained bio-oil suggested that biochar, and thus its related
inorganic elements, will predominantly reside in the aqueous phase.118-119 Liquid bio-oil filtration
has been shown to effectively reduce the alkali and alkali-earth metal content.120 Bio-oil filtration
is physical challenging to achieve and will likely require pressure filtration, because of its high
viscosity and the complex interaction between char and bio-oil to form a gelatinous substrate that
rapidly clogs the filter.121 However, the impedance to filtration can be decreased by partially or
completely dissolving the biochar−bio-oil gel, using common solvents, such as methanol or
ethanol.121
6.3 Solid product posttreatments

Biochar is a solid carbon-rich residue yielded from the thermochemical decomposition of
lignocellulosic biomass in the partial or total absence of oxygen.122 The solid char has a great
variety of applications.123 It can be used as an excellent fuel for cofiring in coal-fired power
stations,124 applied as a soil amendment,123 and mixed with bio-oil to produce a bioslurry fuel for
bioenergy plants.124 However, biochar may have high inorganic contents (alkali and alkaline
earth metals, in combination with other inorganic elements) that are undesirable in power plant
fuels.125 Thus, demineralization of biochar is of great importance. Two-step water leaching has
26
been shown to leach 27%−35% of K and Na from biochar for the first 30 min, with the effect of
leaching varying for biochar from different agricultural residues.125 Water leaching could also
release nearly all chlorine within a few minutes during biochar washes.126
7. CONCLUSIONS
Biomass, with the potential to be converted to power, liquid fuels, and chemicals through
thermochemical conversion, is a promising and attractive option for global energy resources.
Biomass can be converted to energy-dense intermediates through thermochemical conversion
technologies, including combustion, gasification, and pyrolysis. However, the inorganic content
(ash) of biomass has been known for some time have significant effects on the thermochemical
conversion process and create specific downstream hazards with diversified downstream
applications:
• During pyrolysis process, the inorganic contents can have significant catalytic effects and
change the thermal degradation rate, chemical pathway, and bio-oil yield.
• During combustion process, the inorganic contents can bring various technological
problems (agglomeration, corrosion, abrasion−erosion, slagging, fouling), environmental
risks, and health concerns.
• During gasification process, the inorganic contents create diversified downstream
hazards, including minor process inefficiencies, such as corrosion and pipe blockages, as
well as catastrophic failures, such as rapid and permanent deactivation of catalysts.
Economically friendly and effective remediation technology of inorganic contaminants
challenges the commercial deployment of large-scale biomass thermochemical conversion.
Pretreatment is the first and most important step in biomass processing to improve the efficiency
of biomass handling, processing, and conversion. Effective pre-treatment technologies exist to
remove inorganic contaminants to lower concentration limits:
• Mechanical sieving changes the ash content of biomass by varying biomass particle sizes.
• Washing biomass with water, acid, alkali, or salt has been shown to be effective in
removing inorganic contents, especially the alkali and alkaline-earth metals.
• Hot water extraction has been shown to be efficient in removing the majority of alkali
metals.
27
• Some other pre-treatments, such as steam explosion and hydrothermal carbonization,
have been shown to improve lignocellulosic biomass materials. However, their effects on
inorganics removal have not been investigated.
However, the main drawbacks of these pre-treatments are that they (i) reduce the overall
efficiency due to the need of further drying process of wet biomass after pre-treatment and (ii)
increase chemicals, facilities, and drying costs. As such, activities in this area should aim to
develop pre-treatment technologies that will improve efficiency and decrease cost.
Post-treatment technologies are utilized after the thermochemical conversion to meet the
strict levels of cleanup demands for the downstream applications. A great number of
technologies exist to purify the raw synthesis gas stream that is produced by the thermochemical
conversion of biomass.
8. ACKNOWLEDGMENTS
This research was supported by Southeastern Sun Grant Center and the U.S. Department
of Transportation, Research and Innovative Technology Administration, Grant No. DTO559- 07-
G-00050. S.C.C. wishes to acknowledge the Southeastern Partnership for Integrated Biomass
Supply Systems (IBSS), which is supported by AFRI No. 2011-68005-30410 from USDA NIFA.
28
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36
CHAPTER II
HOT WATER EXTRACTION AS A PRETREATMENT FOR REDUCING
SYNGAS INORGANICS IMPURITIES – A PARAMETRIC
INVESTIGATION ON SWITCHGRASS AND LOBLOLLY PINE BARK
37
Qiaoming Liua, Nicole Labbéb, Sushil Adhikaric, Stephen C. Chmelyb and Nourredine
Abdoulmouminea,b
a
b
c
Biosystems Engineering, Auburn University, Auburn, AL
This chapter entitled “Hot water extraction as a pretreatment for reducing syngas
inorganics impurities – A parametric investigation on switchgrass and loblolly pine bark”
with the co-authors of Qiaoming Liu, Nicole Labbé, Sushil Adhikari, Stephen C. Chmely, and
Nourredine Abdoulmoumine was submitted to the journal of Fuel on September 26th, 2017.
Qiaoming Liu conducted the experiment, performed the data analysis, and drafted the
manuscript. Dr. Labbé assisted in the supply of raw materials and chemical composition analysis
of samples. Dr. Adhikari participated in the characterization of hot water extraction products. Dr.
Chmely participated in the experiment design and data interpretation. Dr. Abdoulmoumine
designed the experiments and provided help in data analysis and manuscript writing. All authors
revised this manuscript approved the final version.
1. ABSTRACT
The effects of hot water extraction on the removal of inorganic impurities (N, S, Na, K,
Mg and Ca) in biomass that are detrimental to gasification were investigated on switchgrass and
loblolly pine bark. As hot water extraction severity increased from 13 to 141 h °C, the extraction
liquor pH decreased from 6.0 to 4.5 for switchgrass and 3.6 to 3.1 for pine bark, thus resulting in
20.7 to 69.6 % of ash reduction for switchgrass and 57.0 to 73.3 % for pine bark, respectively. In
addition, the nitrogen content which results in ammonia (NH3) formation was reduced by 9.3 to
22.9 % for switchgrass and 1.0 to 6.8 % for pine bark following increment of severity.
Furthermore, sulfur which leads to hydrogen sulfide (H2S) formation was reduced from 48.3 to
62.5 % and 5.6 to 17.3 % for switchgrass and pine bark, respectively.
38
The range of potassium, sodium, magnesium and calcium reductions were 94.9 - 98.8,
47.9 - 72.4, 58.7 - 83.5 and 8.5 - 13.0 for switchgrass and 50.8 - 67.5, 29.2 - 60.1, 9.7 - 50.8 and
3.3 - 33.0 % for pine bark. Finally, statistical analysis was carried out on the statistical
significance of the extraction temperature and time as well as their interaction on the removal of
inorganic impurities. The extraction temperature, time, and the interaction differed in their effect
on liquor pH, ash reduction, mass loss, and reduction of individual inorganics.
2. INTRODUCTION
Energy and fuel produced from renewable biomass is a promising research area today
because of the reduction of greenhouse gases emission from fossil fuels and the environmental
sustainability.1 Notably, the thermochemical conversion of lignocellulosic biomass to biofuel and
energy via gasification process is attractive as it has the potential to produce gasoline through
methanol synthesis, mixed alcohols, gasoline and diesel through Fischer-Tropsch (FT) synthesis,
as well as energy through internal combustion engine, steam and gas turbines.2 Currently, the
presence of contaminants in biomass derived syngas is considered the primary hurdle for the
commercialization of syngas.3 Among the gaseous contaminants, inorganics have been
associated with catalyst poisoning, corrosion, agglomeration, and undesirable emissions during
gasification.4-5 In particular, nitrogen, sulfur, and alkali and alkaline earth metals present in
biomass result in ammonia (NH3), hydrogen sulfide (H2S), and trace metal vapors (K, Na, Ca,
and Mg), respectively at concentrations ranging from few parts per million (ppm) to few
thousands depending on the species, operating conditions, and biomass properties.6-9 Nitrogen in
biomass is mainly linking with proteins in living organic tissues.10-11 During gasification, it is
liberated as predominantly as NH3, hydrogen cyanide (HCN), molecular nitrogen (N2), heavy
tars, with a smaller part retained in solid char.12 Sulfur (S) presents in both inorganic and organic
forms in biomass. The organic forms of S are covalently bound to proteins and amino acids,
while the inorganic forms can exist as sulfate (SO42−) and sulfite (SO32−).11 During gasification,
sulfur in the biomass is primarily converted to hydrogen sulfide (H2S), which causes equipment
corrosion and catalyst deactivation in downstream applications.13-15 The alkali metals (Na and K)
in the biomass mainly remained in the form of ionic salts that were not metabolized by the
plant.16 Within the cell structure of biomass, alkali metals often exist in free ion form (Na+ and
K+) with counter ions in the fluid matter, such as chloride (Cl−) or malate (C4H4O52−).17 They can
39
also present in solid salt structures settled on the cell wall of biomass.17 A small amount of alkali
metals present in the organic matrix when attached to functional groups as carboxylates and
phenoxides.18 For in situ gasification, alkali metals can easily poison catalysts; they also pose
challenge to ex situ conditioning of syngas or downstream catalytic applications.4, 19 The
existence of alkali metals can cause corrosion and fouling in downstream processes as well.20
Alkaline-earth metals (Mg and Ca) do not usually exist in free ionic form, which is different
from the chemical status of alkali metals.11 Mg and Ca have a tendency to form complexes with
organic counterio18 These species are regarded as the major inorganic syngas contaminants and
their concentrations are strictly restricted depending of the intended syngas application.21 In fuel
synthesis applications through FT and methanol syntheses, the tolerable limit of nitrogen and
sulfur contaminants are 20 and 0.01 ppm, respectively. As for gas turbine based power
generation applications, concentrations below 50 and 0.02 ppm are desired for nitrogen and
sulfur contaminants, respectively.19 As such, contaminant removal efficiencies greater than 99 %
are typically required to ensure that inorganic contaminants in biomass derived syngas are below
these limits.
Traditionally, syngas inorganic contaminant reduction has been achieved through
downstream gas cleanup.13, 19 While effective commercial gas cleanup technologies exist, recent
technoeconomic analyses show that gas cleanup accounted for the highest share of the total
capital investment in gasification related applications.22 In recent years, pretreatment techniques
have been explored to reduce inorganic content and improve the quality of biomass prior to
pyrolysis conversion.23-30 However, the potential beneficial impact of pretreatment techniques on
reducing inorganics of concerned (N, S and metals) in gasification have drawn less attention.31
The pretreatment methods can be very different for pyrolysis and gasification due to the
downstream processes requirements for their dissimilar conversion products (bio-oil and syngas,
respectively). Consequently, this study aims to explore the impact of hot water extraction (HWE)
as an inorganic reduction pretreatment on biomass nitrogen, sulfur, and select metals (Na, K, Mg
and Ca).
40
3. MATERIALS AND METHODS
3.1 Biomass preparation and characterization

Biomass types investigated in this study were switchgrass (Panicum virgatum) obtained
through the University of Tennessee Biofuels Initiative (UTBI) and loblolly pine (Pinus taeda)
bark obtained from Auburn University. The samples were grounded and sieved to particle size
below 40 mesh (425 µm). Proximate analyses of moisture, ash, volatile matter and fixed carbon
were performed on each biomass sample according to standard methods ASTM E871-
82(2013)32, ASTM E1755-01(2015)33 and ASTM E872-82(2013)34, respectively. Ultimate
analysis of C, H, N, and O were conducted using a Perkin Elmer CHN analyzer. Fixed carbon
was determined by difference between the volatile matter and ash values. The inorganic
elemental composition of each biomass was determined by inductively coupled plasma optical
emission spectroscopy (ICP-OES) with an Optima 7300 DV spectrometer (Perkin Elmer). Prior
to ICP-OES analysis, approximately 0.5 g of each biomass sample was microwave digested
using 4 mL of concentrated nitric acid (HNO3, 70 % w/w), 3 mL of concentrated hydrochloric
acid (HCl), and 0.2 mL of hydrofluoric acidHF, 51 %) at temperatures between 160 and 210 °C
for 20 min.35 After digestion, the solution was diluted to 50 mL with Milli-Q H20 and filtered
with 0.45µm PTFE filters prior to ICP-OES analysis. All compositional and elemental analyses
were performed in triplicate.
3.2 Hot water extraction

The HWE extraction vessel consists of a 200-mL heavy-wall round bottom flask with a
screw cap fitted with ¼ in. compression fittings for a thermocouple and pressure gauge ports
(Figure 2). The extraction temperature was monitored and controlled by a PID (proportional–
summation–difference) temperature controller with continuous data logging. In this experiment,
the extraction severity (16 to 141 h °C for switchgrass and 13 to 128 h °C for pine bark,
respectively) was determined by computing the time integral of the experimentally measured
temperature recorded by a PID controller using a Matlab script. This approach enabled to capture
the contribution of the overall extraction of ramping from room to extraction set point
temperature as well as to use natural temperature fluctuations observed in experiments (Figure
9).
41
Figure 2 Schematic representation of the hot water extraction experimental setup
For each HWE experiment, approximately 5 g of each biomass sample were thoroughly
mixed with deionized (D.I.) water at 1:20 biomass to water ratio, on weight basis. This ratio was
chosen to ensure that (i) there is ample liquor for further analysis and (ii) that the thermocouple
was fully submerged even during vigorous agitation which led to the formation of a vortex in the
slurry. After reaching the appropriate extraction temperature (60, 80, 100, 120 and 140 °C), the
mixture was held there for a desired extraction time (15, 30 and 45 min). The reactor was then
allowed to cool, and the slurry was filtered to recover the undiluted filtrate for pH measurement.
The residual extracted biomass was thoroughly rinsed with 100 mL of D.I. water to remove any
deposited inorganic elements on the surface and dried at 80 °C overnight. All HWE extraction
and compositional and elemental analyses were performed in triplicate.
3.3 Characterization of hot water extraction products

The pH, total dissolved solids (TDS), inorganic elemental composition, and total organic
nitrogen (TN) were measured on the undiluted liquor collected after filtration of the HWE slurry.
ICP-OES analysis of the liquor followed the same approach used in determining biomass
inorganic elemental composition and described in 2.1. TN analysis was performed on a TOC-L
analyzer attached with TNM-L unit (Shimadzu Corp., Japan) after filtration of liquor samples
using 0.2 μm filter to remove the suspended particles. The filtrates were subsequently diluted by
a dilution factor (DF) of 3-7 depending on the extraction severity and kept in an auto-sampler for
measurement.The total mass dissolved in the liquor was determined gravimetrically by drying
42
an aliquot at 60 °C until weight loss ceased. On residual extracted solid, the compositional
changes due to HWE were monitored through proximate and ultimate analyses according to
ASTM standards previously described in 2.1. All product analyses were performed in triplicate.
3.4Statistical analyses
The effects of temperature (60, 80, 100, 120 and 140 °C) and time (15, 30 and 45 min) on the
responses (pH, mass loss, total ash and individual inorganic element - N, S, Na, K, Mg and Ca),
expressed on a dry basis, were investigated by a two-factor analysis of variance of an
unbalanced, complete factorial design with three observations per treatment at the 0.05
significance level. If necessary, Tukey-Kramer HSD (honest significant difference) was used for
multiple comparisons.36 All statistical analyses were performed using the statistical analysis
software of JMP.
4. RESULTS AND DISCUSSION
4.1 Proximate and ultimate analysis of raw switchgrass and loblolly pine bark samples
Table 8 shows proximate and ultimate results for the switchgrass and pine bark raw
samples representing herbaceous and woody biomass which differ in structure and inorganic
components. Compared to raw loblolly pine bark samples, switchgrass has more volatile matter
(VM) and ash content, as well as less fixed carbon (FC) content. Also, switchgrass has more N,
S, alkali metal (Na and K), and alkaline earth metal (Mg and Ca) content when compared to
loblolly pine bark. The proximate and ultimate analysis results of switchgrass and pine bark raw
samples are consistent with values reported by others.37-42
Besides differences in proximate and ultimate analysis components, switchgrass and pine
bark also differ in their structural components (i.e. cellulose, hemicellulose, and lignin). As an
herbaceous feedstock, switchgrass has less lignin as woody species like loblolly pine.
Switchgrass contains 38-40 % of cellulose, 28-39 % of hemicellulose, and 18-26 % of lignin,
whereas pine bark contains 17-32 % of cellulose, 17-19 % of hemicellulose, and 33-34 % of
lignin. 42-46.
43
Table 8 Proximate and ultimate analyses of raw switchgrass and loblolly pine bark
Mean (SD)
Switchgrass Pine bark
Moisture, wt. % wet basis 6.34 (0.28) 10.16 (0.42)
Proximate analysis, wt. % dry basis
Volatile matter 81.51 (0.32) 70.11 (0.19)
a
Fixed carbon 14.90 (0.33) 27.62 (0.32)
Ash 3.59 (0.23) 2.27 (0.19)
Ultimate analysis
wt. % dry basis
C 44.82 (0.4) 52.45 (1.51)
H 5.77 (0.21) 5.91 (0.04)
Oa 47.44 (0.17) 40.50 (1.55)
N 0.4 (0.03) 0.35(0.04)
ppm dry basis
Na 141 (13) 24 (1)
K 4398 (165) 1166 (19)
Mg 1644 (50) 575 (29)
Ca 2005 (17) 1835 (62)
S 563 (25) 352 (15)
Al 35 (4) 869 (25)
Fe 39 (0.3) 1169 (162)
Mn 60 (1) 78 (1)
P 1117 (44) 197 (7)
Si 5123 (313) 1268 (28)
Zn 20 (1) BDL
a
Fixed carbon and oxygen were determined by difference; SD stands for standard deviation;
BDL stands for below detection limit.
44
4.2 Effect of hot water extraction
The effects of hot water extraction on liquor pH, ash content reduction, and mass loss of
switchgrass and pine bark samples are shown as three-dimensional (3D) surface plots in
Figure 3.
The extraction liquor pH decreased from 6.0 to 4.5 for switchgrass and 3.6 to 3.1 for pine
bark following the increase of temperature as a result of extractives separated from biomass
including acetic, uronic and phenolic acids47. The rate of pH reduction increased rapidly during
switchgrass extraction when temperature increased from 100 to 140 C due to increasing
hydrolysis and extraction rate of acids with higher temperature.47-48 As pH decreased, the total
ash reduction increased from 20.7 to 69.6 % for switchgrass and from 57.0 to 73.3 % for pine
bark, respectively. Similar to the trend observed for switchgrass liquor pH, the rate of ash
reduction increased after 100 °C, indicating that the liquor pH is correlated to ash reduction of
switchgrass as previously reported by others.49-50 Furthermore, as liquor pH decreased during the
extraction of both feedstocks, the mass loss also increased from 5.1 to 15.3 % and 2.5 to 15.3 %
(dry basis) for switchgrass and pine bark, respectively.
Figure 3 Effect of temperature and time of hot water extraction on pH (a), ash reduction
(b), and mass loss (c) for switchgrass, and effect of temperature and time of hot water
extraction on pH (d), ash reduction (e), and mass loss (f) for pine bark. Red dots represent
response means for each condition and surface plot represents best fit of experimental data
45
Of the two main factors (temperature and time), the statistical analysis of variance
indicated that temperature, but not time or the interaction of temperature and time, had a
statistically significant effect on liquor pH [F(4,30) = 210.68; P < 0.0001] and ash reduction for
switchgrass [F(4,30) = 35.87; P < 0.0001]. In contrast, temperature [F(4,30) = 36.17; P <
0.0001], time [F(2,30) = 4.57; P = 0.0185], and their interaction [F(8,30) = 0.99; P = 0.0025] all
had statistically significant effects on the mass loss for switchgrass. For pine bark, temperature
[F(4,30) = 178.08; P < 0.0001], time [F(2,30) = 5.66; P = 0.0082], and their interaction [F(8,30)
= 2.42; P = 0.0377], had statistically significant effects on its liquor pH. The statistical effects of
temperature [F(4,30) = 853.63; P < 0.0001], time [F(2,30) = 25.43; P < 0.0001], and their
interaction [F(8,30) = 3.79; P = 0.0035] were also significant on the extraction mass loss.
Additionally, temperature [F(4,30) = 1.05; P < 0.0001] but not time [F(2,30) = 2.99; P = 0.0655]
or their interaction [F(8,30) = 0.28; P = 0.0486], had statistically significant effect on ash
reduction of pine bark. Compared to switchgrass, only modest reduction in ash content was
achieved for pine bark as temperature increased. Several reasons might explain this insensitivity
to temperature and time on ash reduction for pine bark. Pine bark contains more lignin (water
insoluble) than switchgrass in which most of the structural ash, the physiological-bound ash in
biomass, is located.42, 51-52 This implies that less structural carbohydrates will be hydrolyzed, thus
making physiological bound ash less accessible.52
The extraction severities varied from 16 to 141 h C for switchgrass and 13 to 128 h C
for pine bark based on the time and temperature (See Tables 9 and 10 in the supplemental
materials). The effect of hot water extraction severity is illustrated in Figure 4. Figures 4a and 4b
show the relation between extraction severity and liquor pH for switchgrass and pine bark,
respectively. As the severity is increased, liquor pH is decreased with a noticeably lower
reduction in pH for bark. The lower pH of pine bark liquor is primarily attributed to its higher
content of acidic extractives such as acetic, resin, and fatty acids.53 In parallel, ash reduction
increased with severity as the acidic liquor enhanced the solubility of ash constituents (Figures
4b and 4e). In contrast to switchgrass, only a moderate increase in ash reduction was observed as
severity increased for pine bark. However, relatively high ash reduction (57.0 %) was achieved
at lower severities due to the relatively low liquor pH that was achieved at the beginning of the
extraction. Our findings are consistent with previous reports where liquor pH decreased with
severity and induced ash reduction of sugar maple and switchgrass.49-50 The hydrolysis of acidic
46
moieties from structural and extraction of extractives as well as the removal of ash is followed by
a decrease in mass, as illustrated in figure 4c and 4f, which increased as the extraction severity
increased. The mass loss occurred due to the loss of carbon, nitrogen, sulfur, and trace metals
during hot water extraction. Based on total organic carbon (TOC) analysis of the liquor, we
observed that as severity increased from 16 to 141 h °C for switchgrass and 13 to 128 h °C for
pine bark, the total carbon loss raised from 3.7 to 10.5 wt. % for switchgrass on a dry basis and
from 1.9 to 13.3 wt % for pine bark on a dry basis, respectively. The total carbon loss during the
extraction can come from the reduction of extractives (acetic acids, phenolic acids, aldehydes,
dicarboxylic acids, resin, and fatty acids), xylose, mannose, glucose, arabinose, and galactose
from the biomass.25, 53 Studies have shown feasible approaches to utilized the listed sugars from
hot water extraction, including biochemical production of ethanol, lactic acid, and butanol
through fermentation, as well as production of health food additives.54-57
Figure 4 Effect of hot water extraction severity on pH (a and d), ash content reduction (b
and e), and mass loss (c and f) for switchgrass (above) and pine bark (below), respectively
4.2.1 Effect on nitrogen reduction and its impact on nitrogen contaminants

Figure 5 shows the effect of hot water extraction severity on reducing nitrogen content of
switchgrass and pine bark, respectively. Biomass nitrogen content was reduced by 9.3 to 22.9 %
for switchgrass and 1.0 to 6.8 % for pine bark, respectively as severity increased from 16 to 141
h °C for switchgrass and 13 to 128 h °C for pine bark. The effect of HWE on pine bark is not as
47
effective as on switchgrass, which can be due to that pine bark has more lignin components, the
physical barriers to protect biomass from extraction, compared to switchgrass. Statistical analysis
of variance indicated that, of the two main factors (temperature and time) as well as the
interaction of temperature and time, only temperature had statistical significance on the reduction
of nitrogen content for switchgrass [F(4,30) = 9.87; P < 0.0001]; whereas for pine bark,
temperature [F(4,30) = 151.05; P < 0.0001], time [F(2,30) = 8.28; P = 0.0017], and the
interaction [F(8,30) = 2.77; P < 0.0233] all exhibited statistical significance on the reduction of
nitrogen content. The reduction in switchgrass and pine bark’s nitrogen content will
proportionally reduce ammonia concentration from 2400 to 1850 ppm and 2100 to 1957 ppm in
syngas, respectively based on 60 % N-fuel to NH3 conversion rate reported by Van der Drift and
coworkers.12
Figure 5 The effect of HWE severity on nitrogen (N) content reduction for switchgrass (a)
and pine bark (b )
4.2.2 Effect on sulfur reduction and its impact on sulfur contaminants

Figure 6 represents the effect of hot water extraction severity on reducing sulfur content
of switchgrass and pine bark, respectively. As severity increased from 16 to 141 h °C for
switchgrass and 13 to 128 h °C for pine bark, biomass sulfur content of switchgrass and pine
bark was reduced by 48.3 to 62.5 % and 5.6 to 17.3 %, respectively. The lower amount of sulfur
reduction in pine bark implied the relatively larger amount of organic sulfur existing in the
feedstock which is harder to be extracted compared to the inorganic form sulfur. Of the two main
factors (temperature and time) as well as the interaction of temperature and time, the statistical
48
analysis of variance showed that, for switchgrass, only temperature had statistical significance on
the reduction of sulfur content [F(4,30) = 21.05; P < 0.0001]. However, for pine bark,
temperature [F(4,30) = 1539.11; P < 0.0001], time [F(2,30) = 37.58; P < 0.0001], and the
interaction [F(8,30) = 5.96; P = 0.0001] all showed statistically significant effect on the reduction
of sulfur content. Based on sulfur conversion to H2S reported by Aljboura and Kawamotob58, we
predict that H2S concentration will be reduced from 552 to 213 ppm for switchgrass and 345 to
285 ppm for pine bark.
Figure 6 The effect of HWE severity on S content reduction for switchgrass (a) and pine
bark (b)
4.2.3 Effect on alkali metal reduction and its impact on syngas metal contaminants
Figure 7 shows the effect of hot water extraction severity on reducing K and Na content
for switchgrass and pine bark, respectively. The K removal ranges from 94.9 to 98.8 % for
switchgrass, which indicate K in switchgrass can be easily extracted, and from 50.8 to 67.5 % for
pine bark. The reduction of Na ranges from 47.9 to 72.4 % for switchgrass, and from 29.2 to
60.1 % for pine bark. With increasing severity, higher reduction of Na in both switchgrass and
pine bark is achieved. To achieve a higher reduction of K in pine bark, higher severity is required
for pine bark samples. The statistical analysis of variance indicated that, of the two main factors
(temperature and time) as well as the interaction of temperature and time, only temperature had
statistical significance on the reduction of K content for both switchgrass [F(4,30) = 6.05; P =
0.0011] and pine bark [F(4,30) = 4.58; P = 0.0065]. Moreover, only temperature was statistically
significant on the reduction of Na content for switchgrass [F(4,30) = 4.29; P = 0.0073].
49
However, both temperature [F(4,30) = 2.91; P = 0.0461] and time [F(2,30) = 4.29; P = 0.0274]
showed statistical significance on the reduction of Na content for pine bark.
Figure 7 The effect of HWE severity on alkali metals reduction for switchgrass (a) and pine
bark (b)
During gasification, the conversion rate of alkali metal into gas phase can be 12–34%.59 It
can be predicted that the release of gas phase K being reduced from 1495 to 18 ppm (with 34 %
K conversion rate), and gas phase Na being reduced from 48 to 13 ppm (with 34 % Na
conversion rate) for switchgrass. For pine bark, the release of gas phase K can be reduced from
396 to 129 ppm (with 34 % K conversion rate), and gas phase Na can be reduced from 8 to 3
ppm (with 34 % Na conversion rate). Due to the fairly large amount of free ionic form existing in
biomass, alkali metals are relatively easy to be extracted.
4.2.4 Effect on alkaline earth metals reduction and their impact on syngas metal contaminants
Figure 8 shows the effect of hot water extraction severity on reducing Mg and Ca content
for switchgrass and pine bark, respectively. The reduction of Mg ranges from 58.7 to 83.5 % for
switchgrass, and from 9.7 to 50.8 % for pine bark. The increase of HWE severity can further
enhance the reduction of Mg. However, the effect of HWE severity did not have significant
impact on the reduction of Ca for switchgrass, with 13.0 % of reduction, which was different
from pine bark, with 3.3 to 33.0 % reduction of Ca following increase of HWE severity. The
difficulty in extraction of Ca can due to the fact that Ca in biomass is able to effectively crosslink
lignin molecules due to its high affinity for lignin.60 It can also be a result of poor solubility of
the Ca in the complexes form. Of the two main factors (temperature and time) as well as the
50
interaction of temperature and time, the statistical analysis of variance showed that, for both
switchgrass and pine bark, temperature (switchgrass: [F(4,30) = 123.84; P < 0.0001], pine bark:
[F(4,30) = 1410.83; P < 0.0001]), time (switchgrass: [F(2,30) = 13.90; P < 0.0001], pine bark:
[F(2,30) = 43.25; P < 0.0001]), and their interaction (switchgrass: [F(8,30) = 3.55; P = 0.0053],
pine bark: [F(8,30) = 3.01; P = 0.0132]) all had statistical significance on the reduction of Mg
content. Also, temperature (switchgrass: [F(4,30) = 15.16; P < 0.0001], pine bark: [F(4,30) =
2435.50; P < 0.0001]), time (switchgrass: [F(2,30) = 5.50; P = 0.0092], pine bark: [F(2,30) =
91.01; P < 0.0001]), and the interaction (switchgrass: [F(8,30) = 4.02; P = 0.0024], pine bark:
[F(8,30) = 7.15; P < 0.0001]) all showed statistically significant effect on the reduction of Ca
content for switchgrass and pine bark, respectively.
Study reported the conversion rate of alkaline earth metal into gas phase can be 12–16 %
during gasification.59 The existence of alkaline-earth metals in syngas can cause catalyst
deactivation and are detrimental to the downstream processes. It can be predicted that the release
of gas phase Mg being reduced from 263 to 43 ppm (with 16 % Mg conversion rate), and gas
phase Ca being reduced from 321 to 279 ppm (with 16 % Ca conversion rate) for switchgrass.
For pine bark, the release of gas phase Mg can be reduced from 92 to 45 ppm (with 16 % Mg
conversion rate), and gas phase Ca can be reduced from 294 to 197 ppm (with 16 % Ca
conversion rate).
Figure 8 The effect of HWE severity on alkaline-earth metals reduction for switchgrass (a)
and pine bark (b)
51
5. CONCLUSIONS
In this study, we present the findings of a parametric investigation on the effect of hot
water extraction on the removal of switchgrass and pine bark nitrogen, sulfur and select metals
(Na, K, Mg and Ca) that lead to the formation of ammonia, hydrogen sulfide and trace metal
contaminants in syngas. Our results revealed that this pretreatment can remove up to 23 % of
nitrogen, 63 % of sulfur, 72% of sodium, 99 % of potassium, 83 % of magnesium, and 13 % of
calcium for switchgrass over the range of conditions investigated. In the case of pine bark, it
resulted in the reduction of up to 7 % of nitrogen, 17 % of sulfur, 60 % of sodium, 67 % of
potassium, 51 % of magnesium, and 34 % of calcium. These reductions correspond to the
following equivalent reduction in syngas contaminants for switchgrass and pine bark
respectively: 2400 to 1850 ppm and 2100 to 1957 ppm of NH3, 552 to 213 ppm and 345 to 285
ppm of H2S, 1495 to 18 ppm and 396 to 129 ppm of K, 48 to 13 ppm and 8 to 3 ppm of Na, 263
to 43 ppm and 92 to 45 ppm of Mg, as well as 321 to 279 ppm and 294 to 197 ppm of Ca. Within
the boundary of the experimental conditions investigated, statistical analysis of variance
(ANOVA) indicated that, for switchgrass, only temperature had a statistically significant effect
on ash reduction as well as on N, S, K, and Na removal, whereas both temperature and time had
a statistically significant effect on the removal of Mg and Ca for switchgrass. Furthermore, for
pine bark, only temperature had a statistically significant effect on ash reduction as well as on the
removal of K, while both temperature and time had a statistically significant effect on the
removal of N, S, Na, Mg, and Ca.
This work shows the benefits of hot water extraction as a pretreatment for inorganics
removal. Compared to other commonly used pretreatment reagents (sulfuric acid, nitric acid,
ethylenediaminetetraacetic acid, and sodium hydroxide), hot water extraction avoids introducing
inorganics into biomass which require additional washing (S in sulfuric acid, N in nitric acid and
ethylenediaminetetraacetic acid, as well as Na in sodium hydroxide), reduces capital cost, and is
environmental friendly. However, further post-treatment is needed to achieve syngas cleanliness
requirement for downstream conversion technologies.
52
6. ACKNOWLEDGMENTS
This research was supported by Southeastern Sun Grant Center and the US Department
of Transportation, Research and Innovative Technology Administration, Grant No. DTO559-07-
G-00050.
53
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57
8. APPENDIX
8.1 Hot water extraction experimental conditions and severities
Table 9 Summary of hot water extraction experimental conditions and severities for
switchgrass
Conditions #1 #2 #3 #4 #5
Temperature, ° C 60 80 100 120 140
Time, min 15 15 15 15 15
Severity, h ° C 16 25 37 65 86
Conditions #6 #7 #8 #9 #10
Temperature, ° C 60 80 100 120 140
Time, min 30 30 30 30 30
Severity, h ° C 22 38 55 75 100
Conditions #11 #12 #13 #14 #15
Temperature, ° C 60 80 100 120 140
Time, min 45 45 45 45 45
Severity, h ° C 33 50 78 102 141
Table 10 Summary of hot water extraction experimental conditions and severities for pine
bark
Conditions #1 #2 #3 #4 #5
Temperature, ° C 60 80 100 120 140
Time, min 15 15 15 15 15
Severity, h ° C 13 21 32 55 68
Conditions #6 #7 #8 #9 #10
Temperature, ° C 60 80 100 120 140
Time, min 30 30 30 30 30
Severity, h ° C 23 35 51 80 97
Conditions #11 #12 #13 #14 #15
Temperature, ° C 60 80 100 120 140
Time, min 45 45 45 45 45
Severity, h ° C 33 49 69 95 128
58
8.2 Summary of two-way analysis of variance results
Table 11 Summary of two-way analysis of variance results for switchgrass and pine bark
Hydrolysate pH
Temperature Time Interaction Temperature Time Interaction
DF 4 2 8 4 2 8
Error 30 30 30 30 30 30
F ratio 210.68 1.24 1.99 178.08 5.66 2.42
P < 0.0001 0.3031 0.0829 < 0.0001 0.0082 0.0377
Ash reduction
DF 4 2 8 4 2 8
Error 30 30 30 30 30 30
F ratio 35.87 1.33 2.17 1.05 2.99 0.28
P < 0.0001 0.2793 0.059 < 0.0001 0.0655 0.0486
Mass loss
DF 4 2 8 4 2 8
Error 30 30 30 30 30 30
F ratio 36.17 4.57 0.99 853.63 25.43 3.79
P < 0.0001 0.0185 0.0025 < 0.0001 < 0.0001 0.0035
N
DF 4 2 8 4 2 8
Error 30 30 30 30 30 30
F ratio 9.87 0.07 0.48 151.05 8.28 2.77
P < 0.0001 0.9329 0.8606 < 0.0001 0.0017 0.0233
S
DF 4 2 8 4 2 8
Error 30 30 30 30 30 30
F ratio 21.05 2 1.45 1539.11 37.58 5.96
P < 0.0001 0.1536 0.2181 < 0.0001 < 0.0001 0.0001
K
DF 4 2 8 4 2 8
Error 30 30 30 30 30 30
F ratio 6.05 2.19 1.5 4.58 1.03 1.03
P 0.0011 0.1299 0.1977 0.0065 0.3723 0.4434
Na
DF 4 2 8 4 2 8
Error 30 30 30 30 30 30
F ratio 4.29 3.05 0.95 2.91 4.29 1.76
P 0.0073 0.0621 0.4899 0.0461 0.0274 0.1423
59
Table 11 Continued
Mg
Temperature Time Interaction Temperature Time Interaction
DF 4 2 8 4 2 8
Error 30 30 30 30 30 30
F ratio 123.84 13.9 3.55 1410.83 43.25 3.01
P < 0.0001 < 0.0001 0.0053 < 0.0001 < 0.0001 0.0132
Ca
DF 4 2 8 4 2 8
Error 30 30 30 30 30 30
F ratio 15.16 5.5 4.02 2435.5 91.01 7.15
P < 0.0001 0.0092 0.0024 < 0.0001 < 0.0001 < 0.0001
8.3 Illustration of extraction severity
Figure 9 Illustration of the area under the curve approach used to calculate severity of
HWE
60
CHAPTER III
SYNTHESIS AND EVALUATION OF SORBENTS FOR REDUCING THE
CONCENTRATIONS OF HYDROGEN CHLORIDE IN SYNGAS
61
Qiaoming Liua, Stephen C. Chmelyb and Nourredine Abdoulmouminea,b
a
b
This chapter entitled “Synthesis and evaluation of sorbents for reducing the
concentrations of hydrogen chloride in syngas” with the co-authors of Qiaoming Liu, Stephen
C. Chmely, and Nourredine Abdoulmoumine is in preparation for submission to the journal of
Applied Catalysis A: General. Qiaoming Liu designed and performed the experiment, conducted
the data analysis, and drafted the manuscript. Dr. Chmely participated in the experiment design,
assisted with sorbents preparation, and data interpretation. Dr. Abdoulmoumine assisted in the
experiment design, provided help in sorbent analysis and manuscript writing.
1. ABSTRACT
The synthesis of NaMgAl-LDH was achieved by a spontaneous self-assembly method,

calcined at 700 °C, and evaluated along with three commercial sorbents (Na2CO3, NaAlO2, and
commercial LDH) as hot gas cleanup sorbents for HCl sorption in a fixed bed reactor at 400 °C
to 600 °C. It has been shown that all sorbents were thermally stable during the hot gas cleanup
temperature range between 300 °C to 700 °C. During fixed bed experiment, calcined LDH
exhibited great effectiveness in capture of HCl at 400 °C to 600 °C with more than 14 h of
breakthrough time. The better performance of calcined LDH compared to calcined commercial
LDH supported the enhancement of incorporation of Na in the LDH framework for HCl
sorption. The Na-based sorbents showed various effectiveness on HCl removal with comparison
of breakthrough time: calcined LDH > calcined NaAlO2 > calcined Na2CO3 at 400 °C; calcined
LDH = calcined NaAlO2 > calcined Na2CO3 at 500 °C; and calcined Na2CO3 = calcined NaAlO2
= calcined LDH at 600 °C.
62
2. INTRODUCTION
During gasification, biomass is converted into raw syngas and deleterious organic (tars)
and inorganic impurities. While treatment techniques enable removal of most inorganic
contaminants in biomass, they are not unable to achieve removal levels necessary to avoid
downstream challenges.1-14 Syngas cleanup strategies are therefore of great importance to get rid
of residual inorganic contaminants after the gasification stage. The removal of gas phase
inorganics is crucial because they create specific downstream hazards such as equipment
corrosion and rapid and permanent deactivation of catalysts in downstream processes.15-17 Over
the years, much research effort has been devoted to cleaning biomass derived syngas.15 The three
types of gas cleaning processes commonly used are cold, intermediate, and hot temperature gas
cleanup methods and can be classified according to their operational temperature of the cleanup
reactors.15, 17 The cold gas cleanup approach, which is most commonly used, requires scrubbing
syngas at room temperature (~25 °C) through a solvent (commonly water) to absorb inorganic
impurities such as ammonia (NH3), hydrogen chloride (HCl) and hydrogen sulfide (H2S). The
main drawback of cold gas cleanup is the loss in efficiency during the process due to syngas
cooling. Warm gas cleanuprequires moderate syngas cooling to induce inorganic condensation.
It can also involve the usage of sorbents such as activated carbon and silica for adsorbing
inorganic constituents.17 Nevertheless, warm gas cleanup leads to loss of efficiency due to
cooling and uncontrolled deposition of inorganic elements on surfaces which lead to corrosion.
In contrast to the previous approaches, hot gas cleanup occurs at high temperature to adsorb or
decompose impurities in gas phase. The advantages of hot gas cleanup include the increased
efficiency and reduced waste streams.17 However, thermal instability and low removal
efficiencies remain significant challenges to enable wide adoption of this approach.15, 17-18
In recent years, research efforts have been focused on tars, NH3 and H2S abatement
through hot gas cleanup.15, 18 Chlorine contaminants have received much less attention partially
due to their small concentration relative to other contaminants (i.e. tars, NH3 and H2S) in
biomass derived syngas. However, the concentration of chlorine contaminants can be as high as
500 ppm in biomass derived syngas.18
Layered double hydroxide (LDH) materials have gained considerable interest and have
been used as catalysts, ion-exchange materials, sorbents, supports, and absorbers lately.19 These
63
CC
materials have a general formula of [7=V VCCC (OH)2]x+[P= x− II
]#\ · yH2O] , where M and M
III
represent divalent and trivalent metal cations, respectively, and An− is an n-valent anion.20 LDH
materials could be engineered for specific purposes since the cations and anions can be chosen
based on their effectiveness for specific applications. MII could be Ni2+, Zn2+, Mg2+, Mn2+, or
Cu2+; MIII could be Fe3+, Al3+, or Cr3+, and P= could be 8= 8= = = =
9 , : , 9 , , or . Few
studies confirmed the potential of HCl adsorption using calcined LDH mixed metal oxides albeit
at lower temperatures.21-22
In this study, a Na-Mg-Al LDH based sorbent was synthesized and benchmarked against
a commercially available Mg–Al LDH, as well as other sorbents (sodium aluminate (NaAlO2)
and sodium carbonate (Na2CO3)), for hot gas cleanup (400 to 600 °C) of HCl at concentrations
observed in biomass derived syngas. We hypothesize that incorporating sodium (Na) into the
magnesium (Mg) and aluminum (Al) LDH framework will improve the HCl removal efficiency
relative to the commercial LDH.
3.1 Sorbent synthesis and preparation

Na-Mg-Al LDH was synthesized by a spontaneous self-assembly method which enables
the insertion of guest molecules into a layered host to generate composite materials of layered
structure.19, 23. Na-Mg-Al LDH was synthesized by co-precipitation technique in which the guest
specie is included in the reaction solution, followed by aging (40 h) to form the final
composite.24 The pH value of a 100 ml aqueous solution containing Mg{ 9 |2 (0.03 mol), and
Al{ 9 |3 (0.01 mol) was adjusted to about 10 pH with Na2CO3. The obtained slurry was then
filtered and washed with D.I water. By drying the filtrate in the oven at 80 °C, Na-Mg-Al LDH
sample was then obtained. The calcination was carried out in an electric furnace at 700 °C for 4 h
under oxygen atmosphere. The commercial sorbents (Na2CO3, NaAlO2, and commercial LDH)
were acquired from Strem Chemicals Inc. and Sigma-Aldrich Chemistry and calcined in the
electric furnace at 700 °C for 4 h under air prior to testing the sorption reactor. All sorbents were
pelletized and/or size reduced to particle size between 250 and 850 μm.
64
3.2 Sorbent characterization
Inductively Coupled Plasma - Optical Emission Spectroscopy (ICP-OES) was conducted
for the elemental composition analysis of synthesized LDH. 0.01 g sample of LDH and calcined
LDH were analyzed by ICP-OES for metal components. The sample was digested using
Multiwave 3000 (Anton Paar, VA, USA) digester with 4 ml concentrated HNO3 (trace metal
grade, 67-70% w/w), 3 ml H2O2, and 0.2 ml HF at 160 - 210 °C for 20 min at 1150 W. After
digestion, the reaction solution was diluted to 50 ml with Milli-Q H20. The samples were then
filtered and analyzed for their elemental composition. Additionally, all sorbents were subjected
thermogravimetric analysis (TGA) to evaluate their thermal stability at hot gas cleanup
temperatures. Sorbents were analyzed under nitrogen (N2) atmosphere from room temperature
30 °C to 105 °C at 15 °C/min. The temperature was held at that set point for 30.0 min to outgas
moisture and other gases adsorbed on the surface and pores. The furnace was then raised to
700 °C at 5 °C /min. The overall mass loss was quantified, and all samples were analyzed in
triplicate.
Furthermore, the specific surface area and pore volume of the fresh, uncalcined sorbents
were measured by N2 adsorption using a Beckman Coulter surface area analyzer. Prior to the
analysis, all samples were outgassed at 120 °C for 60 min. All samples were analyzed in
triplicate.
In addition, Powder X-ray Diffraction (PXRD) was performed using a Panalytical
Empyrean diffractometer with a CuK alpha1 (high resolution) source (λ = 0.15406 nm) using a
voltage of 45 kV and a current of 40 mA. Surface morphology was examined by scanning
electron microscopy (SEM) using a ZEISS EVO MA15 Scanning Microscope. Energy dispersive
X-ray spectroscopy (Bruker xFlash 6130) was used to determine surface elemental composition
of LDH, CLDH, and CLDH after sorption tests. PXRD and SEM-EDS were collected at the Joint
Institute for Advanced Materials (JIAM) at the University of Tennessee, Knoxville.
3.3Sorption study, sampling and analysis procedure

In order to evaluate the performance of the synthesized LDH and commercial sorbents
for HCl removal from a gas stream, adsorption experiments were carried out with a gas mixture
containing 200 ppm of HCl and a balance of nitrogen (N2). Figure 10 depicts the schematics of
the experimental setup which consists of (1) an HCl specialty mixed gas (200 ppm HCl/balance
N2) cylinder; (2) mass flow controller; (3) an electric furnace; (4) a PID temperature controller;
65
(5) a sorbent bed; (6) coarse wool plugs; (7) a ½ ‘’ outside diameter and 15.5 ‘’ length tubular
fixed bed reactor; (8) sodium hydroxide (NaOH, 1 M) filled impinger with a coarse porosity
fritted tip for gas sparging and; (9) NaOH filled Erlenmeyer flask for trapping unremoved HCl.
Figure 10 Schematic representation of the fixed bed experimental setup
The fixed bed reactor was loaded with 0.814 g of calcined Na-Mg-Al-LDH (0.003 mol
Na and 0.003 mol Mg, with weight hourly space velocity (WHSV) of approximately 9 h-1), 0.353
g of calcined commercial LDH (0.003 mol Mg with WHSV of approximately 20 h-1) , 0.637g of
calcined Na2CO3 (0.006 mol Na with WHSV of approximately 11 h-1), and 0.984 g of calcined
NaAlO2 (0.006 mol Na with WHSV of approximately 7 h-1) sandwiched in between two coarse
wool plugs during different experiments. The reactor was then preheated for 20 min under N2
flow before the hydrogen HCl gas was introduced at a flow rate of 100 ml min−1. Sorption
experiments were carried out for 14 hours at 400, 500, and 600 °C (Figure 17) and atmospheric
pressure in duplicate runs. The impinger scrubbing solution was sampled every 120 min for the
first 4 samples and every 69 min for the rest 6 samples, and the aliquots were analyzed using ion
chromatography (IC). The gas phase hydrogen chloride reacts with NaOH in solution according
to the reaction below.
x 0 x 8 (1)
66
Thus, we analyzed the chlorine ion concentration to determine the gas phase hydrogen
chloride concentration. This is achieved using a Dionex Model ICS-2100 ion chromatograph
(Sunnyvale, CA, USA) fitted with a Dionex ASRS Suppressor detector was employed. The
separation was achieved by a Dionex IonPac AS11-HC-4μm column. The flow-rate of eluent
was 1 ml/min. All separations were conducted at 30 °C. The chromatographic separation was
affected by a gradient program which consisted of KOH gradient eluent from 5 mM to 23 mM.
The outlet concentration of HCl after the reactor was calculated by determining the chlorine
content in solution at each sampling time interval.
.@No z .@No y.K"7 (2)
In equation (2), .@No (μmol 23 = ) is the number of moles of chlorine dissolved in NaOH
scrubbing solution for a sampling interval time . K , .@No (μmol " /ml) is the change in chlorine
concentration during . K , and .K"7 is volume of NaOH initial scrubbing solution (200 ml)
discounted for the volume of the previous aliquot which is typically 4 ml. Thus, we obtain the
outlet molar flow rate of HCl at each sampling time step, . K , through the following relationship:
.Po
@No z (3)
.Uo
Finally, we obtain the outlet gas phase concentration of HCl through a mass balance by
dividing the outlet molar flow rate of HCl by the total flow rate, Ftotal, determined through
equation 4
Beq
@No z o
(4)
Bvtvkq
where the total molar flow rate is computed from the mass flow rate, which is controlled
during the experiment.
3.4Model of HCl Sorption

The modeling of the fixed bed experiment is carried out based on the conservative
equation derived from the sorbent and HCl mass balance:25
67
[@ [@ [R
$ x 6 x '? z ( (5)
[U [U [U
where $ is the bed porosity, C is the HCl gas concentration in the bed, V0 is the bed
velocity in the empty bed, '? is the sorbent mass per unit volume of bed, and q is the HCl
adsorbed based on unit mass of CLDH sorbent.
The correlation of the HCl and the sorbent during sorption test can be obtained when
assuming a constant breakthrough pattern through the bed: 25
@ R
z z ? (6)
@^ R^
where C0 is the inlet HCl concentration, q0 is the HCl saturated absorbing condition of the
CLDH sorbent, and XB is the conversion extent of the CLDH sorbent.
Take the sorbent particles into consideration, the shrinking core model is used for the
evaluation of the sorption data. The rate controlling steps of the sorption should be the chemical
reaction on the sorbent surface or the product layer diffusion, or both. The first order surface
chemical reaction rate is defined as: 25
IDc
" z ,& 8 T T (7)
IU
And the diffusion rate of HCl per sorbent particle is: 25
IDc :YAm {@"@u |

" z (8)
IU S"_ "E"_
The amount of HCl absorbed by CLDH during sorption test per unit time is: 25
IDc : Zd IR
" z &9 (9)
IU 9 7"W IU
T can be eliminated by solving equations (7) for T and (8) for {"T |. Thus, the
combination of the new equation having only C and equation (9) gives:
Ea Zd IR @
z (10)
9 7"W IU S"` Mu <{S"_ "E"_ | Am
68
The shrinking radius r can be replaced by the sorbent conversion XB by r = R(1 - XB) 1/3
and yields:
IR @
z {_"j "` a {_"j |"_ a "_ (11)
IU d| d
<
gi gf
where
H{7"W| 9{7"W|
F z T A z J (12)
Zd E Zd E`
By inserting equation (6) into equation (11), the final expression of the sorption kinetics
is obtained:
I{@ @^ | {@ @^ |
z {_"e e^ ||"` a {_"e e^ ||"_ a "_
(13)
IU <
g_ g`
9{7"W|X 9{7"W|X
7 z T 8 z J (14)
EU_ ` E ` U_ `
where % z
6 is the residence time of gas in the empty bed. The value of C/C0 is
given from breakthrough curves. MATLAB R2016a was applied to fit the experimental data
using equation (13).
Also, the root mean square error (RMSE), mean absolute error (MAE), and quality of fit
(FIT) statistical tests were carried out in MATLAB R2016a to evaluate the kinetic modeling
based on equations (15-17).
` 7 D
z L>K{! L " L |8 (15)
D
7 D
z L>K ! L " L (16)
D
69
h `
pb_{{JVQJSKOJPUGNp "QSJIKHUJIp | D` |
z )(( (17)
JVQJSKOJPUGNrkw
where N is the observation number; ! L are the experimental values for
observation j; L are the predicted values for observation j; and ! OGV is the
maximum value amidst all observations.
4.1 Characterization of sorbents
4.1.1 Elemental analysis of synthesized sorbent by ICP-OES

Estimates of the Mg2+/Na+/Al3+ ratio of the synthesized LDH and calcined synthesized-
LDH were calculated by dividing the Mg2+ and Na+ concentrations by the Al3+ concentration as
determined by ICP-OES. Mg/Na/Al in synthesized LDH uncalcined and calcined showed cation
ratios 3.1:3.5:1 and 3.1:2.9:1, respectively. The Mg/Al ratios (3.1:1) in synthesized LDH before
and after calcination both agree with the Mg/Al ratio in commercial LDH which is 3:1.
4.1.2 Thermogravimetric analysis (TGA)

The thermogravimetric (TG) analysis results are shown in Figure 11 and depict the
thermal stability of the sorbents. We observe that calcined Na2CO3 exhibited the highest stability
with a maximum of 0.11 wt. % mass loss followed by calcined NaAlO2 and calcined Na-Mg-Al-
LDH with less than 1.84 and 3.33 wt. % mass loss, respectively. The calcined commercial LDH
(cComLDH) had the lowest thermal stability with less than 9.85 wt. % mass loss. Our findings
on the thermal degradation of cComLDH is consistent with reports by others for an LDH
material with similar Mg/Al molar ratio calcined at 550 C for 4h.26
Table 12 presents the weight loss of the four sorbents based on their original weight
during thermogravimetric analysis at 30, 105, 300, 500 and 700 C. From 30 to 105 C, all
sorbents encountered weight losses due to their moisture evaporation (physically adsorbed
water), with 0.11 % for calcined Na2CO3 (cNa2CO3), 1.53 % for calcined NaAlO2 (cNaAlO2),
0.86 % for calcined Na-Mg-Al LDH (cLDH), and 2.98 % for calcined commercial LDH
(cComLDH). From 105 to 300 C, the further weight loss of cLDH and cComLDH occurred
70
mainly due to the dehydroxylation, consistent with other studies27-28, while the weight of
cNa2CO3 and cNaAlO2 stayed stable.
Figure 11 TGA curves of calcined sorbents
Table 12 Weight loss (%) of the sorbents during TGA

Percent mass loss, %
Temperature, °C 30 105 300 500 700
cNa2CO3 0.00 0.11 0.11 0.05 0.04
cNaAlO2 0.00 1.53 1.84 1.79 1.78
cLDH 0.00 0.86 2.27 2.85 3.33
cComLDH 0.00 2.98 7.44 9.14 9.85
4.1.3 BET analysis

The BET surface area and pore volume of calcined sorbents were listed in Table 13.
Table 13 Summary of BET analysis results of sorbents calcined at 700 °C

cLDH cComLDH cNaAlO2 cNa2CO3
Total Pore Volume (ml/g) 0.027 (0.005) 0.116 (0.015) 0.002 (0.000) 0.001 (0.000)
BET Surface Area (m2/g) 4.292 (0.196) 55.019 (0.981) 0.545 (0.021) 0.057 (0.012)
†
Values in parentheses represent the standard deviation.
The surface area of the samples can be affected by their chemical composition as well as
calcination temperature and time. The surface area of cComLDH created by the calcination
process comes from the formation of pores and channels due to the evaporation of water and the
removal of carbon dioxide.29 Table 14 summarizes the BET analysis results of MgAlO from
71
literature. It is stated that MgAlO mixed oxides calcined at 350 to 450 C have a relatively high
surface area (>200 m2/g) and 0.5-0.8 ml/g of total pore volume.26, 30-33 The MgAlO oxides
calcined at 500 C has a lower surface area of 82.2 m2/g with a pore volume of 0.85 ml/g.34 As
reported, samples calcined at temperatures within the decomposition temperature range exhibit a
maximum value of the surface area, which decreases following the temperature increase
following further calcination35-36, which can explain the lower surface area for cComLDH which
was calcined at a relatively high temperature 700 C for 4 h. The surface area and pore volume of
cLDH are significantly smaller than the cComLDH, which may be explained by the
accumulation of Na in the compounds. The average pore volume and BET surface area of the
calcined sorbents increased in the following order: cComLDH > cLDH > cNaAlO2 > cNa2CO3.
Table 14 Comparison of BET analysis results of MgAlO from literature

Sorbents Total Pore BET Surface Calcined Calcined
Volume (ml/g) Area (m2/g) Temperature (/) Duration (h) Refs
37
MgAlO - 39.9 800 2
34
MgAlO 0.85 82.2 500 8
36
MgAlO - 115 800 6
36
MgAlO - 194 400 6
30
MgAlO 0.8 210 450 15
4.2 HCl sorption study

Figure 12 shows the concentration of 23 = in NaOH solution for sorbents at 400, 500, and
600 °C, respectively. Following increasing of time, the 23 = concentration increased for all four
sorbents. At 400 °C to 600 °C, cComLDH had the highest 23 = concentration in NaOH solution,
indicating the least effectiveness of cComLDH in the removal of HCl gas. Compared to
cComLDH, the sodium-based sorbents were more effective in capturing HCl. Relatively low
concentration for cNa2CO3 and lower concentrations for cLDH as well as cNaAlO2 occurred at
400 °C. From 400 °C to 600 °C, cLDH, cNa2CO3 and cNaAlO2 had low concentration of 23 = in
NaOH solution.
Figure 13 depicts the outlet HCl breakthrough curves of various sorbents. As the least
competent sorbent, cComLDH reached the 1 ppm HCl breakthrough in less than 2 h (Table 15)
at 400 to 600 °C. For cNa2CO3, it is less effective (2.9 h) at 400 °C than 500 °C (13.2 h) and
72
600 °C (> 14 h). The breakthrough time for 0.006 mol cNa2CO3 in this study is consistent with
around 4 h breakthrough time for 0.012 mol Na2CO3 in the literature.38 For cNaAlO2, it less
effective that cLDH at 400 °C (10.3 h for 0.006 mol), which is in consistence with approximately
18 h breakthrough time for 0.012 mol NaAlO2 at same temperature from literature38. At 500 to
600 °C, cNaAlO2 exhibited its effectiveness (> 14 h) in capturing HCl. As the most effective
sorbent, cLDH reached more than 14 h of breakthrough time from 400 °C to 600 °C. The
breakthrough time of cComLDH and cLDH suggests that the Na in the cLDH could sufficiently
participate in the removal of HCl. It is clear that, the incorporation of Na in the LDH framework
enhanced the effectiveness of HCl sorption. Additionally, Na-based sorbents exhibited different
effects following temperature change: with cLDH > cNaAlO2 > cNa2CO3 at 400 °C; cLDH =
cNaAlO2 > cNa2CO3 at 500 °C; and cNa2CO3 = cNaAlO2 = cLDH at 600 °C.
Figure 12 The concentration of 45= in NaOH solution for sorbents at 400, 500, and 600 °C
Figure 13 The concentration of outlet HCl gas for sorbents at 400, 500, and 600 °C with
grey line representing 1 ppm breakthrough
Table 15 Summary of 1 ppm HCl breakthrough time of sorbents

Breakthrough time, h
Temperature, °C cComLDH cLDH cNaAlO2 cNa2CO3
400 <2 > 14 10.3 2.9
500 <2 > 14 > 14 13.2
600 <2 > 14 > 14 > 14
73
The surface morphology and surface elemental composition of LDH, CLDH, and CLDH
samples after sorption tests were reported in Figure 14.
The SEM micrographs (Figure 14) and elemental compositions (Table 16) at 500 and
2000 magnification of cLDH exhibited the amorphous surface morphology of the original
calcined LDH sample (Figure 14 a) with 0% Cl on the surface. Moreover, the EDS atom % of
the elements demonstrates that Na and Cl on the cLDH surface have a positive correlation.
Additionally, the SEM micrographs of cLDH after 14 h sorption reveal the formation of NaCl
crystals which result in a cuboidal morphology39 (Figure 14 d).
PXRD patterns of the original LDH sample, calcined LDH sample, calcined LDH sample
after 28 h of HCl sorption, and references are shown in Figure 15.
The PXRD pattern of the original LDH sample (Figure 15 a blue) contains peaks
corresponding to ((Mg6Al2)(OH)18(H2O)4)0.375, NaNO3, Na2CO3, and Mg36Al61.7 resulted from
the co-precipitation synthesis. After calcination at 700 C, peaks corresponding to Na3.893(CO3)2,
NaNO3, Mg2O(OH)2, and Al2O3 are observed in the PXRD pattern of the calcined LDH sample
(Figure 15 b blue). Peaks corresponding to (Mg6Al2)(OH)18(H2O)4)0.375 and Mg36Al61.7 are absent
in the calcined sample. Figure 15 c reveals the generation of NaCl and Na6MgCl8 in the calcined
LDH sample after 28 h of HCl sorption. Peak corresponding to NaNO3 is not observed.
Observations from SEM-EDS and PXRD analysis implied that Na in CLDH existed in
Table 16 Summary surface elemental composition of cLDH and cLDH samples after
sorption tests shown in Figure 15
Surface elemental composition, atom % (SD)
C N O Na Mg Al Si Cl
500 X Magnification
cLDH 7.8 5.0 57.5 17.2 8.0 4.2 0.2 0.0
(2.8) (3.0) (2.0) (4.4) (4.1) (3.7) (0.2) (0.0)
cLDH after 14 h 6.5 1.4 39.2 13.9 20.4 6.3 0.4 11.9
sorption at 400 °C (2.5) (0.5) (11.1) (11.3) (8.3) (2.8) (0.1) (8.1)
cLDH after 14 h 9.3 1.5 45.0 19.4 9.4 3.8 0.5 11.1
sorption at 500 °C (3.1) (0.5) (17.2) (10.7) (5.9) (2.7) (0.5) (11.9)
cLDH after 14 h 7.3 2.0 30.5 28.7 6.1 1.5 0.2 23.8
sorption at 600 °C (0.4) (0.1) (7.3) (3.7) (2.1) (0.4) (0.0) (5.5)
2000 X Magnification
cLDH 4.8 5.3 55.5 19.2 10.3 4.7 0.3 0.0
(1.8) (2.5) (2.0) (3.1) (3.6) (1.7) (0.1) (0.0)
cLDH after 14 h 6.5 1.3 38.1 16.2 18.4 5.9 0.3 13.2
sorption at 400 °C (1.5) (0.6) (10.2) (10.8) (7.5) (2.6) (0.2) (8.5)
cLDH after 14 h 13.7 2.0 24.2 30.6 7.3 1.7 0.2 20.2
sorption at 500 °C (2.5) (1.0) (23.3) (15.7) (11.4) (1.8) (0.2) (17.3)
cLDH after 14 h 10.2 2.3 5.8 44.8 1.0 0.4 0.1 35.4
sorption at 600 °C (3.4) (0.1) (2.9) (2.3) (0.2) (0.1) (0.0) (3.3)
74
Figure 14 SEM micrographs of: (a) cLDH; (b) cLDH after 14 h sorption at 400 °C; (c)
cLDH after 14 h sorption at 500 °C; (d) cLDH after 14 h sorption at 600 °C with 2000 X
magnification, and (e) cLDH; (f) cLDH after 14 h sorption at 400 °C; (g) cLDH after 14 h
sorption at 500 °C; (h) cLDH after 14 h sorption at 600 °C with 500 X magnification
Figure 15 PXRD diffractograms of: (a) original LDH sample and references
(((Mg6Al2)(OH)18(H2O)4)0.375, NaNO3, Na2CO3, and Mg36Al61.7), (b) calcined LDH sample
and references (Na3.893(CO3)2, NaNO3, Mg2O(OH)2, and Al2O3), and (c) calcined LDH
sample after 28 h of HCl sorption and references (NaCl, Na2CO3, Al2O3·3H2O, MgO, and
Na6MgCl8)
NaNO3 and Na2CO3. During sorption, HCl gas reacted with NaNO3 and Na2CO3, resulting in
NaCl.
4.3 Kinetics model fitting of HCl removal reaction

A kinetic model was applied to investigate the HCl removal reaction in the fixed bed
reactor (Figure 16) with modeling results shown in Table 17.
5. CONCLUSIONS
In this study, we present the findings of the synthesis and evaluation of Mg and Na
layered double hydroxide based high temperature sorbents for hydrogen chloride removal.
Sodium-based LDH was successfully synthesized with Mg/Na/Al cation ratios of 3.1:3.5:1 and
same Mg/Al ration with commercial LDH. The results of this experimental study exhibited the
effectiveness, thermal stability, and efficiency of cLDH in capturing HCl gas contaminant at hot
75
gas cleanup temperatures (400 to 600 °C). Sorption of HCl for commercial sorbents (cComLDH,
cNaAlO2, and cNa2CO3) were also conducted for comparison. The better performance of cLDH
compared to cComLDH supported the enhancement of incorporation of Na in the LDH
framework for HCl sorption. At different temperature, Na-based sorbents showed various
effectiveness on HCl removal with the comparison of their breakthrough time: cLDH > cNaAlO2
> cNa2CO3 at 400 °C; cLDH = cNaAlO2 > cNa2CO3 at 500 °C; and cNa2CO3 = cNaAlO2 =
cLDH at 600 °C.
Figure 16 Kinetics model fitting of HCl removal reaction
Table 17 Summary of kinetic model results

K1 K2 RMSE MAE FIT
Prediction 0.176 0.031 0.012 0.005 0.001
Upper 95% CI 0.174 0.028 - - -
Lower 95% CI 0.178 0.035 - - -
6. ACKNOWLEDGMENTS
This research was supported by Southeastern Sun Grant Center and the US Department
of Transportation, Research and Innovative Technology Administration, Grant No. DTO559-07-
G-00050.
76
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79
8. APPENDIX
8.1 Reaction temperature
Figure 17 The reactor temperature of 14 h HCl sorption test at 400 °C, 500 °C, and 600 °C,
respectively
8.2 Actual experimental setup
Figure 18 Actual experimental setup
80
8.3 MATLAB code for kinetics model fitting of HCl removal reaction at 600 °C
function kineticmodelfit
% NOTES:
% 1. The ‘thetas’represent unknown parameters
% 2. c represents c/co
function C=kinetics(theta,t)
c0=0.000001;
[T,Cv]=ode45(@DifEq,t,c0);
%
function dC=DifEq(t,c)
dcdt=zeros(1,1);
dcdt(1)=c(1)/(((1-c(1))^(-2/3)/theta(1))+(((1-c(1))^(-1/3)-1)/theta(2)));
dC=dcdt;
end
C=Cv;
end
t=[0
2
4
6
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
48
81
62
74
76
78
80
90
92
94];
c=[0
0.00455
0.000617731
0.00441703
0.002012437
0.000878427
0.000338951
0
0
0
0.000506478
0.004128482
0.003874334
0
0.00016041
0.001960343
0.002738948
0
0.004897379
0
0.00087644
0.003785403
0.003525883
0.001053385
0.001153267
0.015925802
0.102857634
0.23240775
0.297805814
0.330752707
0.362009257
0.671808318
0.72731774
0.777737679];
theta0=[0.17572;0.03136];
82
[theta,Rsdnrm,Rsd,ExFlg,OptmInfo,Lmda,Jmat]=lsqcurvefit(@kinetics,theta0,t,c);
fprintf(1,'\tRate Constants:\n')
for k1 = 1:length(theta)
fprintf(1, '\t\tTheta(%d) = %8.5f\n', k1, theta(k1))
end
% Find the specific cv at certain t time
index = find(t == 0);[cv_point]= Cv (index);fprintf(1, '\t\t %8.5f\n', [cv_point]);

index = find(t == 2);cv_point1= Cv (index);fprintf(1, '\t\t %8.5f\n',
cv_point1);[cv_point]=[cv_point cv_point1];
83
cv_point=cv_point';
% Use the built in MAE Mean Absolute Error function and pass in
% the "error" part.
builtInMAE = mae(c-cv_point)
% Built FIT equation

builtFIT = 100*(sum((c - cv_point).^2)/(34^2))/0.777737679;
% Built Confidence interval 95% of theta

CI = nlparci(theta,Rsd,'jacobian',Jmat)
theta1=[0.1738;0.0278];
theta2=[0.1776;0.0350];
tv = linspace(min(t), max(t));
84
Cfit = kinetics(theta, tv);
Cfit1 = kinetics(theta1, tv);
Cfit2 = kinetics(theta2, tv);
figure(1)
plot(t, c, 'p')
hold on
hlp = plot(tv, Cfit);
hlp = plot(tv, Cfit1);
hlp = plot(tv, Cfit2);
hold off
grid
xlabel('Time')
ylabel('C/Co')
legend(hlp, 'C_1(t)','Location','N')
% Plot Confidence interval 95%

hold on
% Data output
fprintf(1,'\tCv:\n')
fprintf(1, '\t\t %8.5f\n', Cv)
fprintf(1,'\tSize of t:\n')
size(t)
fprintf(1,'\tSize of c:\n')
size(c)
fprintf(1,'\tSize of Cv:\n')
size(Cv)
fprintf(1,'\tSize of cv_point:\n')
fprintf(1, '\t\t %8.5f\n', cv_point)
size(cv_point)
RMSE = sqrt(mean((c - cv_point).^2));

fprintf(1,'\tRMSE:\n')
fprintf(1, '\t\t %8.5f\n',RMSE)
fprintf(1,'\tMAE:\n')
fprintf(1, '\t\t %8.5f\n',builtInMAE)
fprintf(1,'\tFIT:\n')
fprintf(1, '\t\t %8.5f\n',builtFIT)
Int = trapz(t,c)
fprintf(1,'\tArea under the curve:\n')
85
fprintf(1, '\t\t %8.5f\n',Int)
end
86
CHAPTER IV
TECHNO-ECONOMIC ANALYSIS OF A CONCEPTUAL BIOREFINERY
– HOT WATER EXTRACTION INTEGRATED TO A HYBRID
BIOCHEMICAL AND THERMOCHEMICAL CONVERSION PROCESS
FOR HIGH ASH LIGNOCELLULOSIC BIOMASS TO HYDROCARBON
FUELS AND SUCCINIC ACID
87
Qiaoming Liua, Nicole Labbéb and Nourredine Abdoulmouminea,b
a
b
The manuscript of this chapter entitled “Techno-economic analysis of a conceptual

biorefinery – Hot water extraction integrated to a hybrid biochemical and thermochemical
conversion process for high ash lignocellulosic biomass to hydrocarbon fuels and succinic
acid” with the co-authors of Qiaoming Liu, Nicole Labbé, and Nourredine Abdoulmoumine is in
preparation for submission to the journal of Biofuels, Bioproducts & Biorefining. Qiaoming Liu
performed the techno-economic analysis and drafted the manuscript. Dr. Labbé contributed to
the revision of the manuscript. Dr. Abdoulmoumine assisted in the experiment design, techno-
economic analysis, and manuscript writing.
1. ABSTRACT
This work investigates in detail of the techno-economic impact of hot water extraction
(HWE) and subsequent succinic acid (SA) production on the thermochemical conversion of high
ash content biomass. This study models two scenarios for procuring high octane hydrocarbons: i)
without HWE and the biorefinery process of the extracts to succinic acid and ii) with the
pretreatment and biorefinery process. As a result of the HWE and SA production scenario, 3753
kg/h of succinic acid crystal can be produced for a production of 34,916 US gal/h of gasoline.
Total installed equipment cost is estimated to be $231.91 million for the base case scenario. For
the HWE and SA production scenario, the total installed equipment cost is estimated to be
$280.54 million. The 2017 base case scenario calculates a minimum fuel selling price (MFSP) of
$4.26 per gallon of gasoline. Moreover, the present analysis calculates am MFSP of $4.73 for a
gallon of gasoline blendstock for the HWE scenario. The analysis shows that HWE of high ash
content biomass for high-octane gasoline production has the potential to be a supplement of
gasoline with environmental sustainability. The fermentative succinic acid production from
HWE biomass is feasible. Also, this pathway can be important for attracting industrialization
88
interest on the thermochemical conversion of high ash content biomass. The results of TEA in
this study can be a base case for future exploration and a basis for with other similar scenarios.
2. INTRODUCTION
With the increasing demand for energy, the depletion of crude oil reservation, and the
growing concern of greenhouse gas emission, the biofuel derived from renewable biomass
resources has substantial economic, environmental, and social effects. Under such circumstances,
the development of biomass-derived energy, especially of liquid fuels such as gasoline used in
transportation, is particularly attractive and draws much attention. Efforts have been made to
enable the production of infrastructure-compatible and cost-competitive liquid fuels from
biomass. Among the various possibilities of fuel synthesis, the production of gasification-derived
synthesis gas or syngas (a mixture of CO and H2) followed by high-octane hydrocarbons
synthesis is promising for comprehensive future implementation.
The conversion process is based on a conceptual technology from NREL for obtaining
methanol from syngas, the conversion of methanol to dimethyl ether (DME), and DME
conversion into high-octane, gasoline-range hydrocarbons.1 At lower temperature synthesis
process condition compared to conventional methanol-to-gasoline (MTG) process, the proposed
conversion method produced a low-aromatic, branched-paraffin product with an expected
average octane number of more than 93, greater than the expected average octane number of
hydrocarbon compounds derived from the conventional MTG process.1
Currently, one of the primary obstacles for the commercialization of biomass-derived
syngas is the existence of contaminants during biomass gasification.2 Among the contaminants,
inorganic vapor has been associated with catalyst deactivation, corrosion, agglomeration, and
undesirable emissions during the conversion process.3, 4 Hot water extraction (HWE), as an
environmentally friendly and promising inorganic reduction pretreatment proven in our former
study, results in the removal of alkali and alkaline earth metals, as well as a certain portion of
sulfur and nitrogen from biomass, thus from biomass-derived syngas. Besides inorganic
contaminants, the switchgrass extracts derived from the HWE process consist of approximately
24% of free sugars, 9% of oligomeric sugars, 3% of alditols, and acetic acid.5, 6 This offers an
opportunity for the biorefinery scheme considering the use of crude sugars from the HWE
process for the production of succinic acid through fermentation, which can then be used as ion
89
chelator, surfactant, additive in the pharmaceutical and food industries7, as well as raw material
for biodegradable polymers8.
This study models two scenarios for procuring high octane hydrocarbons using NREL1
model as a base case: i) without HWE and the biorefinery process of the extracts to succinic acid
and ii) with the pretreatment and biorefinery process. Each of the scenarios is modeled in detail,
and economic analysis is performed assuming a “Nth” plant design (Table 18), which assumes a
successfully established industry with mature technology and several operating plants. It
eliminated any first-of-a-kind costs when building the pioneer facilities and provided a standard
basis for comparison between different conversion technologies. Consequently, the aim of this
study is to evaluate the economic potential the HWE pretreatment used by extracting inorganic
contaminants from biomass prior to gasification process. In particular, this study will seek to
address the impact of HWE as well as the biorefinery process of the extracts to succinic acid on
the indirect liquefaction (IDL) platform overall plant economic performance.
The design capacity of biomass gasification plants assumed here process 2000 dry
tonnes/day of switchgrass for gasification with an anticipated 7,884 h/year operating time. Major
processing steps include feed handling, HWE pretreatment, succinic acid production, feedstock
gasification, syngas cleanup, syngas conversion to methanol, the dehydration conversion of
methanol to dimethyl ether (DME), and DME to high-octane hydrocarbons conversion. A
schematic of the biomass indirect liquefaction process to produce high-octane, gasoline-range
hydrocarbons is shown in Figure 19.
3.1 Feed handling, hot water extraction, and succinic acid production
The modeled switchgrass has a moisture content of 6.3%, with an ash content of 3.6%
and field chopped size of 20 to 40 mm. After hot water extraction, the field chopped switchgrass
with 80% moisture content is dried to 10% moisture. The delivered cost (including grower
payment/access cost, harvest and collection, landing preprocessing, transportation,
preprocessing, storage, and handling) of switchgrass, as determined from the Idaho National
Laboratory (INL), is $66.68/dry U.S. ton (in 2011 dollars).9 The ultimate analysis results of
woody biomass and switchgrass after HWE are shown in Table 19. Upon delivery, the
switchgrass is then blended in heated water in a batch reactor at 140 °C for 45 min under
90
Table 18 Summary of Nth Plant Assumptions
Assumption Value of assumption
Internal rate of return 10%
Plant financing by equity 40% of total capital investment
Plant financing by debt 60% of total capital investment
Plant life 30 years
Income tax rate 35%
Interest rate for debt financing 8.0% annually
Term for debt financing 10 years
Working capital cost 5.0% of fixed capital investment
(excluding the cost of land purchase)
Depreciation schedulea 7-year MACRS schedule
Construction period (spending 3 years (8% Y1, 60% Y2, 32% Y3)
schedule)
Plant salvage value No value
Start-up time 6 months
Revenue = 50% of normal
Revenue and costs during startup Variable costs = 75% of normal
Fixed costs = 100% of normal
On-stream percentage after startup 90% (7,884 operating hours per year)
a
Capital depreciation is computed based on the IRS Modified Accelerated Cost Recovery
System (MACRS).
Figure 19 Biomass gasification and the production of high-octane hydrocarbons diagram
Table 19 Ultimate analysis of woody biomass and switchgrass after HWE

Component Weight % (Dry Basis)
Woody biomass After HWE
Carbon 44.82 46.50
Hydrogen 5.77 6.14
Nitrogen 0.4 0.24
Sulfur 0.06 0.02
Oxygen 47.44 46.86
Ash 3.59 1.02
91
autogenous pressure. After the HWE process, the product is then filtered into solid switchgrass
extract for gasification and liquid extract which is then transferred to a fermenter for succinic
acid production.10 The modeled production plant of succinic acid crystals is composed of two
main sections: upstream section of succinic acid fermentation and downstream section of
concentration as well as purification, as depicted in Figure 20. The fermentation section starts
with the sterilization of feed(E-102-104) where Anaerobiospirillum succiniciproducens (AS)
with nutrient mixture and recycled Na2Succinate is heated to 121 °C and cooled to 37 °C for the
fermenter. The fermentation product is then centrifuged (F-102) to cell mass removal. The
centrifuged cells are recycled to the fermenter (V-102) while the cell-free product is sent to the
adsorption columns and desorption columns (C-106). The adsorption is carried out through
zeolite columns while succinic acid desorption being conducted by hot water at 150 °C. The
desorption columns are exposed to hot air to remove fouling components every three cycles.
After desorption, the effluent is fed to a flash drum (V-103) for excess heat removal and to an
evaporator for further concentration (E-105). The product is then transferred to a crystallizer (V-
105) where the crystals are produced and filtered by rotary vacuum filter (F-103). The wet
crystals are fed to a rotary dryer for final dying (E-106).
Figure 20 Succinic acid production plant flow diagram
On the other side, the extracted switchgrass is dried by a cross-flow dryer to 10%
moisture and pre-heated prior to feeding into the gasifier, using process waste heat.
92
3.2 Gasification
During gasification, the extracted switchgrass is indirectly gasified at 870°C using the
heat supplied by a char combustor heated circulating synthetic olivine sand. The gasifier is
operated at low-pressure (0.124 MPa) with injected steam for the stabilization of the biomass and
olivine flow. Syngas is thus produced with tars and solid char. The char and olivine are separated
from the syngas through the cyclones. The former is fed to the combustor for char combustion,
leading to the temperature increase of olivine to greater than 982 °C. After then, the olivine and
residual ash flow to a pair of cyclones where olivine is captured, separated with the fines of ash
and olivine, and fed back to the gasifier. The left fines of ash and olivine are cooled, moistened,
and removed to waste.
3.3Syngas cleanup and compression

During syngas cleanup process, the reformation of tars, methane, and other hydrocarbons
to additional CO and H2 happens, while the particulates being removed through scrubbing. The
compression is conducted for the cleaned syngas. Specifically, the syngas after gasification is fed
into the catalytic tar reformer at 910 °C (temperature at the reactor outlet) where the conversion
of methane, tars, other hydrocarbons, and NH3 happened. The catalyst regenerator burns coke
deposits from the catalyst (Ni/Mg/K supported on alumina) particles and gains supplemental
combustion gases to provided heat for the tar reforming process. After exiting the tar reformer,
syngas is cooled to 60 °C via heat exchangers and scrubbed for removal of particulates,
ammonia, halides, and residual tars. The syngas after scrubbing is then compressed by a three-
stage centrifugal compressor to 2.96 MPa.
3.4Methanol synthesis
The compressed syngas after cleanup and compression process is sent to an amine-based
acid gas removal (AGR) unit to remove the CO2 and H2S before entering the reactor for
methanol synthesis. The recovered H2S-rich acid gas stream is converted to elemental sulfur for
disposal through the Merichem LO-CAT sulfur recovery unit while CO2 is sent to the feed
sterilization.
After AGR, the cleaned syngas is separated into two parts: i) one part (about 6% of the
syngas) for H2 separation in a pressure swing adsorption (PSA) system, and ii) the rest for
exothermic methanol synthesis within a fixed-bed reactor which has a copper/zinc oxide/alumina
catalyst with associated reactions shown below:
93
x *8 1 9 (18)
+8 x 8 1 9 x 8 (19)
x 8 1 8 x 8 (20)
The heat removal and temperature control of the reactor depend on the steam production.
The methanol product and unconverted syngas are cooled by heat-exchange and followed by
methanol condensation and the recycling of unconverted syngas.
3.5Methanol conditioning
The crude liquid methanol from the synthesis reactor is fed to a distillation column that
removes dissolved gases (mainly CO2) to the tar reformer. The methanol stream is then cooled to
43 °C and fed to a distillation column for methanol de-gassing. The de-gassed methanol is
subsequently transferred to a storage tank for high-octane gasoline synthesis.
3.6High-octane gasoline synthesis

Methanol from storage is converted into DME on commercial catalyst gamma alumina
(γ-Al2O3) at 250°C and 0.965 MPa in an adiabatic packed bed reactor with the reaction shown
below:
*9 1 9 9 x 8 (21)
DME is then fed to the bed reactors which have metal modified beta-zeolite (H-BEA)
catalyst for the production of high-octane gasoline. The conversion of DME is at a maximum
temperature of 232°C with the overall conversion of 92.5%. The C4 products as well as
unconverted DME are recycled for additional reactions in the reactors. Heat removal and
temperature control of the synthesis is conducted with the use of the adiabatic reactors.
Moreover, water is supplied by process water as well as the reformer steam. The regeneration of
the catalyst is achieved by the catalyst regenerator that burns off the coke deposits of the catalyst
particles. The simplified methanol to hydrocarbons flow diagram is shown in Figure 21.
94
4. ECONOMIC ANALYSIS
4.1 Capital cost estimation

The capital costs were estimated for each area. The equipment cost was determined using
literature sources which were adjusted to match our design scale and corrected to the design year
according to equations (15) and (16), respectively.
Figure 21 Simplified methanol to hydrocarbons flow diagram
FHGNJlmuons P
867; z (22)
FHGNJdkum
!
*()- z y !*()- (23)

Where n varied for individual equipment in each area and cost indexes (i.e., Index2017) were
taken from Chemical Engineering’s (CE) Plant Cost Index.1 The total purchased equipment cost
(TPEC) and the total installed cost (TIC) of the area were then calculated using the individual
equipment and installed equipment cost for each area. The total direct cost (TDC) was
determined using the total cost of the total installed and site development costs. The site
development cost was calculated as 4% of the inside battery limits (ISBL: A100-500, A1400,
and A1500) total installed cost. The indirect cost was determined from the total direct cost and
95
included the prorated expenses, home office and construction fees, field expenses, project
contingency, and other costs (start-up and permits) estimated at 10, 20, 10, 10 and 10% of the
total direct cost. Finally, the working capital was determined as 5% of the total fixed capital
investment (FCI), the summation of the total direct and indirect costs, excluding the land cost.
4.2 Production cost estimation

The annual operating cost was determined based a plant processing capacity, the mass
and energy balance of the process analysis and 7884 h/year operation with delivered switchgrass
at $66.68/dry U.S. ton (in 2011 dollars). The fixed capital includes the labor, direct overhead,
maintenance, overhead expenses and interest financing. The labor requirement for this integrated
plant is shown in Table 20.
Table 20 Plant workforce and salary per position

Position Title Salary (2017) Number of Positions $MM/yr
Plant manager $161,362 1 $0.161
Plant engineer $76,839 1 $0.077
Maintenance supervisor $62,569 1 $0.063
Laboratory manager $61,471 1 $0.061
Shift supervisor $52,690 5 $0.263
Lab technician $43,908 2 $0.088
Maintenance technician $43,908 16 $0.703
Shift operators $43,908 20 $0.878
Yard employees $30,736 12 $0.369
Clerks and secretaries $39,517 3 $0.119
Business manager $56,000 1 $0.056
Procurement manager $80,523 1 $0.081
Total Salaries (2017) $2.92
The maintenance cost is taken as 3 % of FCI cost. Finally, the overhead expenses are
estimated as the combined costs of plant overhead, taken as 65% of labor and maintenance costs,
and tax and insurance costs, taken as 1% of the total FCI cost.
4.3 Economic analysis

The minimum fuel selling price (MFSP) of our product, high-octane hydrocarbons is
determined based on a net zero present value at the end of the project lifetime (30 years). Also,
the sensitivity analysis is conducted for the determination of the impact of the uncertainties in
our assumptions on the minimum selling price (MSFP) of the high-octane hydrocarbons.
96
5.1 Process performance of HWE and succinic acid production

The flow rates of simulated feed and products are modeled and shown in Table 21. For a
production of 34,916 US gal/h of gasoline, 3753 kg/h of succinic acid crystal can be produced.
The process also generate sulfur as by-product, and the amount of its production is reduced in
scenario II due to the HWE process. The annual production of succinic acid crystal is 29,592
metric tons, which could be utilized as a precursor of many essential chemicals in chemical,
pharmaceutical, and food industries.8 It also stands out with its sustainability impacts when
compare with petrochemical counterpart due to the consumption of greenhouse gas CO2 by the
bacteria during succinic acid fermentation.11
Table 21 Feed and product flow rates for high-octane hydrocarbons and succinic acid
production process
Scenario I Flow rates (lb/h)
Without HWE & SA production
Raw materials
Woody biomass (dry) 138,718
Product and wastewater stream
Gasoline 34,916 (US gal/h)
Sulfur 119
Wastewater 11,337
Scenario II
With HWE & SA production
Raw materials
Switchgrass (dry) 216,904
Product and wastewater stream
Gasoline 34,916 (US gal/h)
Succinic acid crystal 3753 (kg/h)
Sulfur 45
Wastewater 951,873
5.2 Total capital investment

Table 22 is total purchased equipment costs, installation factors, and total installed costs
by process area. The capital costs for each process area are based on data NREL design reports,
industry equipment suppliers, and published literature. Total installed equipment cost is
estimated to be $231.91 million for the base case scenario. The most expensive process area of
the base case scenario is Area 300 of syngas cleanup and compression which takes up 28.15% of
total installed equipment cost. For the HWE and SA production scenario, the total installed
equipment cost is estimated to be $280.54 million. Area 300 is still the most expensive process
97
Table 22 Capital cost estimates per process area for both scenarios (2017 U.S. dollars)
Process areas Total purchased Installation Total installed cost
equipment cost factor (TIC)
Scenario I (TPEC) f installation MM$ %
A100: Raw material handling 0.09 2.00 0.18 0.08
A200: Gasification 20.08 2.32 46.50 20.05
A300: Syngas cleanup 33.59 1.94 65.27 28.15
A400: Methanol synthesis & acid gas removal 15.12 2.28 34.41 14.84
A500: Methanol conditioning 1.19 2.65 3.15 1.36
A600: Power generation & steam system 16.61 2.15 35.76 15.42
A700: Cooling water & other utilities 2.24 2.23 5.00 2.16
A1400: High octane hydrocarbons Synthesis 21.01 1.68 35.20 15.18
A1500: Product recovery 2.86 2.25 6.44 2.78
Total 112.78 2.06 231.91 100.00
Scenario II
A100: Raw material handling, HWE, SA 28.40 1.72 48.82 17.40
production
A200: Gasification 20.08 2.32 46.50 16.58
A300: Syngas cleanup 33.59 1.94 65.27 23.27
A400: Methanol synthesis & acid gas removal 15.12 2.28 34.41 12.26
A500: Methanol conditioning 1.19 2.65 3.15 1.12
A600: Power generation & steam system 16.61 2.15 35.76 12.75
A700: Cooling water & other utilities 2.24 2.23 5.00 1.78
A1400: High octane hydrocarbons Synthesis 21.01 1.68 35.20 12.55
A1500: Product recovery 2.86 2.25 6.44 2.30
Total 141.09 1.99 280.54 100.00
98

area, with 23.27% share of total installed equipment cost. The indirect costs of the plant
including prorated expenses, the fees for home office and construction, field expenses, project
contingency, and other costs (start-up and permits) are estimated by applying factors rest on the
total direct cost (TDC). The chosen factors are the same with both scenarios and are summarized
in Table 23. The summary of the project costs for the base case scenario and the HWE scenario
is presented in Table 24.
Table 23 Indirect cost factors for both scenarios

Indirect Costs % of TPEC % of TDC* % of FCI*
Prorated expenses 21.2 10 6.3
Home office and construction fees 42.5 20 12.5
Field expenses 21.2 10 6.3
Project contingency 21.2 10 6.3
Other costs (start-up and permits) 21.2 10 6.3
Total indirect costs 127.4 60 37.5
Working capital 5
*Land purchase cost is excluded here.
Table 24 Summary of the project costs

Scenario I Scenario II
Total purchased equipment cost (TPEC) $112,776,248 $141,086,415
Installation factor 2.056 1.988
Total installed cost (TIC) $231,905,233 $280,543,265
Other direct costs
Site development 4.0% of ISBL $7,610,727 $9,556,249
Total direct costs (TDC) $239,515,961 $290,099,514
Indirect costs % of TDC (ex Land)
Prorated expenses 10.00% $23,951,596 $29,009,951
Home office &construction fees 20.00% $47,903,192 $58,019,903
Field expenses 10.00% $23,951,596 $29,009,951
Project contingency 10.00% $23,951,596 $29,009,951
Other costs (start-up and permits) 10.00% $23,951,596 $29,009,951
Total indirect costs 60.00% $143,709,576 $174,059,708
Fixed capital investment (FCI) $383,225,537 $464,159,222
Land (not depreciated) $1,610,000 $1,610,000
Working capital 5.0% of FCI (ex $19,161,277 $23,207,961
Land)
Total capital investment (TCI) $403,996,814 $488,977,183
5.3Operating costs
The operating costs of both scenarios are evaluated based on 7,884 operating hours per
year. The operating costs are determined based on variable and fixed operating costs. By-

99
products, raw materials, consumables, and utilities together contribute to the total variable
operating cost which is $74.99 million per year for the base case scenario and $72.33 million per
year for the HWE scenario, respectively. The total fixed operating cost, including labor,
maintenance, overhead expense, and interest on debt financing, is $57.13 million per year for the
base case scenario and $68.17 million per year for the HWE scenario, respectively.
5.4Minimum fuel selling price

The NREL study 1 quantified the economic feasibility of its 2011 model by fixing the 30-year
plant life, 40% equity set with 10% internal rate of return, the remaining 60% debt set at 8%
interest, and calculating the high-octane gasoline MFSP. The present analysis evaluates
economic feasibility in the same manner, in order for a straightforward comparison between two
scenarios. The 2017 base case scenario calculates an MFSP of $4.26 per gallon of gasoline. The
present analysis calculates an MFSP of $4.73 for a 2000 gallon of gasoline blendstock. The cost
contribution details of two scenarios for high-octane hydrocarbons from each process area are
shown in Figure 22 and Figure 23. The economic viability is one of the most crucial factors to
the success of the biofuels industry; the sustainability is another very crucial factor. The analysis
shows that HWE of high ash content biomass for high-octane gasoline production has the
potential to be supplement of gasoline with environmental sustainability. The fermentative
succinic acid production from HWE biomass is feasible. Moreover, this pathway can be
important for attracting industrialization interest on the thermochemical conversion of high ash
content biomass. TEA results in this study can be a base case for future exploration and a basis
for with other similar scenarios.

100
Figure 22 Cost contribution details of the base case scenario
Figure 23 Cost contribution details of the HWE and SA production scenario
101
6. REFERENCES
1. E. C. D. Tan, M. Talmadge, A. Dutta, J. Hensley, L. J. Snowden-Swan, D. Humbird, J.

Schaidle and M. Biddy, Biofuels, Bioproducts and Biorefining, 2016, 10, 17-35.
2. M. M. Yung, W. S. Jablonski and K. A. Magrini-Bair, Energy & Fuels, 2009, 23, 1874-
1887.
3. S. Q. Turn, C. M. Kinoshita, D. M. Ishimura and J. Zhou, Fuel, 1998, 77, 135-146.
4. Å. Kling, C. Andersson, Å. Myringer, D. Eskilsson and S. G. Järås, Applied Catalysis B:
Environmental, 2007, 69, 240-251.
5. S.-F. Chen, R. A. Mowery, R. S. Sevcik, C. J. Scarlata and C. K. Chambliss, Journal of
Agricultural and Food Chemistry, 2010, 58, 3251-3258.
6. S. Liu, Biotechnology advances, 2010, 28, 563-582.
7. J. G. Zeikus, M. K. Jain and P. Elankovan, Applied Microbiology and Biotechnology,
1999, 51, 545-552.
8. H. Song and S. Y. Lee, Enzyme and Microbial Technology, 2006, 39, 352-361.
9. J. Jacobson, K. Cafferty, M. Roni, P. Lamers and K. Kenney, Idaho National Laboratory,
Idaho Falls, ID, 2014.
10. Ç. Efe, L. A. M. van der Wielen and A. J. J. Straathof, Biomass and Bioenergy, 2013, 56,
479-492.
11. B. C. Klein, J. F. L. Silva, T. L. Junqueira, S. C. Rabelo, P. V. Arruda, J. L. Ienczak, P. E.
Mantelatto, J. G. C. Pradella, S. V. Junior and A. Bonomi, Biofuels, Bioproducts and
Biorefining, DOI: 10.1002/bbb.1813, n/a-n/a.

102
CONCLUSIONS AND FUTURE PERSPECTIVES

103
1. CONCLUSIONS
Biomass, one of the most promising renewable resources, can be used to produce power,
liquid fuels, and chemicals through thermochemical and biochemical conversions. However, the
presence of biomass inorganics is detrimental to processes in both routes, making high ash
lignocellulosic biomass less valuable for further usage. This research explored the treatment
approaches for reducing biomass inorganic impurities during gasification. The effects of hot
water extraction on the removal of inorganic impurities (N, S, Na, K, Mg and Ca) in biomass as a
pretreatment were revealed. A NaMgAl-LDH sorbent was evaluated to be efficient and stable for
hot gas clean-up of HCl gas, with better performances than three commercial sorbents (Na2CO3,
NaAlO2, and commercial LDH). The techno-economic analysis of a conceptual biorefinery with
HWE integrated to a hybrid biochemical and thermochemical conversion process for high ash
lignocellulosic biomass to hydrocarbon fuels and succinic acid resulted in a minimum fuel
selling price of $4.73 per gallon of gasoline with 3753 kg/h of succinic acid crystal production.
In the first section, HWE was applied to the high ash content switchgrass and loblolly
pine bark samples with 13 to 141 h °C extraction severity as pretreatment. The extraction liquor
pH decreased from 6.0 to 4.5 for switchgrass and 3.6 to 3.1 for pine bark following the increase
of HWE severity as a result of extractives including acetic, uronic, and phenolic acids separated
from biomass. As a result of the decreasing pH, the total ash reduction of switchgrass and pine
bark increased from 20.7 to 69.6 % and from 57.0 to 73.3 %, respectively. The mass loss also
increased from 5.1 to 15.3 % and 2.5 to 15.3 % (dry basis) following the decrease of the pH for
switchgrass and pine bark, respectively. This mass loss included the loss of carbon, nitrogen,
sulfur, and trace metals during HWE. The two-way analysis of variance revealed that, of the two
main factors (temperature and time), only temperature, but not time or the interaction of
temperature and time, had a statistically significant effect on the total ash reduction for both
switchgrass and pine bark. The study on HWE also revealed the removal of individual inorganics
achieved including up to 23 % of nitrogen, 63 % of sulfur, 72% of sodium, 99 % of potassium,
83 % of magnesium, and 13 % of calcium for switchgrass, as well as 7 % of nitrogen, 17 % of
sulfur, 60 % of sodium, 67 % of potassium, 51 % of magnesium, and 34 % of calcium for pine
bark. These reductions correspond to the equivalent reduction in syngas contaminants for both
switchgrass and pine bark.

104
In the next section, the effectiveness for HCl gas sorption of NaMgAl-LDH along with
three commercial sorbents (Na2CO3, NaAlO2, and commercial LDH) were evaluated for post-
gasification treatment. The NaMgAl-LDH sorbent was synthesized by a spontaneous self-
assembly method and characterized with Na2CO3, NaAlO2, and commercial LDH. The Sodium-
based LDH was successfully synthesized with the same Mg/Al ration (3 : 1) of commercial
LDH. The result revealed that all sorbents were thermally stable during the hot gas cleanup
temperature range between 300 °C to 700 °C. For HCl sorption study, cLDH exhibited better
performance compared to cComLDH, which supported the enhancement of incorporation of Na
in the LDH framework for HCl sorption. Moreover, calcined LDH exhibited great effectiveness
in the capture of HCl at 400 °C to 600 °C with more than 14 h of breakthrough time during fixed
bed experiment, the most effective among all chosen sorbent. The results indicated a promising
application of cLDH in HCl sorption for post-gasification treatment.
In the third section, two scenarios for procuring high octane hydrocarbons using NREL
model as a base case was studied to evaluate the feasibility of a conceptual biorefinery – Hot
water extraction integrated to a hybrid biochemical and thermochemical conversion process for
high ash lignocellulosic biomass to high-octane hydrocarbons and succinic acid. A design
capacity of 2000 (dry) tonnes/day of switchgrass for gasification with an anticipated 7,884 h/year
operating time was assumed. As a result of modeling, 3753 kg/h of the succinic acid crystal can
be produced for a production of 34,916 US gal/h of gasoline. The annual production of succinic
acid crystal thus is 29,592 metric tons. The techno-economic analyses of two scenarios of
thermochemical conversion process: i) with and ii) without HWE and biochemical conversion
were conducted in 2017 U.S. dollars. The present analysis calculates an MFSP of $4.73 for a
gallon of gasoline blendstock under the conversion without HWE and biochemical conversion
scenario. The MFSP for the conversion without HWE and biochemical conversion was
calculated as $4.26 per gallon of gasoline. The environmental sustainability offered by the hybrid
biochemical and thermochemical conversion process suggested the potential of its product to be
a supplement of gasoline derived from petroleum industry.

105
2. RECOMMENDATIONS FOR FUTURE WORK
Future work recommended based on this study includes:

(1) Investigate the effect of HWE on more a diversified group of high ash lignocellulosic
biomass since the result of chapter 2 showed the impact of HWE on total ash reduction and
individual inorganics differed between switchgrass and pine bark.
(2) A broaden time length of HWE can be evaluated on biomass.
(3) The regeneration ability and economic feasibility of NaMgAl-LDH can be investigated and
compared with other commercial sorbents.
(4) More data points can be added to investigate the HCl removal reaction in the fixed bed
reactor at 600 °C. And the sorption experiment of cLDH can be conducted at 400 and 500 °C for
kinetics study and modeling.
(5) The performance of cLDH to remove HCl as well as other gas phase contaminants from
syngas can be evaluated.
(6) The environmental sustainability of HWE on high ash content biomass for high-octane
gasoline production with SA production can be investigated and compared with the base case
scenario in detail.
(7) Sensitivity analysis can be performed to examine the impact of changes in different process
parameters, material costs, by-product selling price, and financial assumptions on the MFSP of
high-octane hydrocarbons.

106
VITA
Qiaoming Liu was born in Meishan, China and got a bachelor of science in Agricultural
Engineering from the China Agricultural University, in Beijing, China. She continued to study
Biosystems Engineering at the University of Tennessee, Knoxville.

107

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University of Tennessee, Knoxville

TRACE: Tennessee Research and Creative

Masters Theses Graduate School

Pretreatment and Posttreatment Approaches for Reducing

Follow this and additional works at: https://trace.tennessee.edu/utk_gradthes

I am submitting herewith a thesis written by Qiaoming Liu entitled "Pretreatment and

Nourredine H. Abdoulmoumine, Stephen C. Chmely, Major Professor

We have read this thesis and recommend its acceptance:

Accepted for the Council:

Vice Provost and Dean of the Graduate School

(Original signatures are on file with official student records.)

Inorganic Impurities during Gasification

A Thesis Presented for the

The University of Tennessee, Knoxville

All rights reserved.

During gasification, biomass can be thermally decomposed into a mixture of combustible

CHAPTER I Biomass Treatment Strategies for Thermochemical Conversion .............................. 2

CHAPTER IV Techno-Economic Analysis of a Conceptual Biorefinery – Hot Water Extraction

CONCLUSIONS AND FUTURE PERSPECTIVES ................................................................. 103

VITA ........................................................................................................................................... 107

Table 1 Origin of inorganic matter in lignocellulosic biomassa ..................................................... 6

Copyright © 2017 by authors and American Chemical Society

Biomass is among the most promising renewable resources to provide a sustainable

The excessive consumption, finite reserves, and established contribution to the

3. THE ORIGIN, NATURE, AND VARIABILITY OF INORGANICS IN

Table 2 Common nature of inorganic in lignocellulosic biomass

4. THE EFFECT OF INORGANICS ON BIOMASS THERMOCHEMICAL

Thermochemical conversion technologies (combustion, gasification, and pyrolysis) are

Figure 1 Pathways to aerosols: ejection of biomass inorganics during primary aerosol

Table 3 Typical syngas applications and associated cleaning requirements11

alkali index      fouling < 0.17 0.17 - 0.34 > 0.34

5. PRE-TREATMENTS FOR THERMOCHEMICAL CONVERSION OF

5.1 Mechanical pre-treatment

5.2 Thermal pre-treatment

pine barka 4.93 4.04 2.79 2.40 2.38 -- 65

5.3 Chemical pre-treatment

5.3.1 Water leaching

5.3.2 Acid washing

5.3.3 Base washing

6. POST-TREATMENTS FOR THE THERMOCHEMICAL CONVERSION

After thermochemical conversion, inorganics in biomass become volatile, carrying

6.1 Gas product posttreatments

6.2 Liquid product posttreatments

6.3 Solid product posttreatments

3.1 Biomass preparation and characterization

3.2 Hot water extraction

3.3 Characterization of hot water extraction products

4. RESULTS AND DISCUSSION

4.2.1 Effect on nitrogen reduction and its impact on nitrogen contaminants

4.2.2 Effect on sulfur reduction and its impact on sulfur contaminants

8.1 Hot water extraction experimental conditions and severities

8.3 Illustration of extraction severity

The synthesis of NaMgAl-LDH was achieved by a spontaneous self-assembly method,

3. MATERIALS AND METHODS

3.1 Sorbent synthesis and preparation

3.3Sorption study, sampling and analysis procedure

Figure 10 Schematic representation of the fixed bed experimental setup

 x   0  x 8 (1)

.@No z .@No y.K"7 (2)

3.4Model of HCl Sorption

And the diffusion rate of HCl per sorbent particle is: 25

IDc :YAm {@"@u |

4. RESULTS AND DISCUSSION

alkali index fouling < 0.17 0.17 - 0.34 > 0.34

x 0 x 8 (1)

.@No z .@No y.K"7 (2)

+8 x 8 1 9 x 8 (19)

*9 1 9 9 x 8 (21)