A Study On Catalytic Conversion of Non Food Biomass Into Chemicals Fusion of Chemical Sciences and Engineering 1st Edition Mizuho Yabushita (Auth.)
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Springer Theses
Recognizing Outstanding Ph.D. Research
Mizuho Yabushita
A Study on Catalytic
Conversion of
Non-Food Biomass
into Chemicals
Fusion of Chemical Sciences
and Engineering
Springer Theses
The series “Springer Theses” brings together a selection of the very best Ph.D.
theses from around the world and across the physical sciences. Nominated and
endorsed by two recognized specialists, each published volume has been selected
for its scientific excellence and the high impact of its contents for the pertinent field
of research. For greater accessibility to non-specialists, the published versions
include an extended introduction, as well as a foreword by the student’s supervisor
explaining the special relevance of the work for the field. As a whole, the series will
provide a valuable resource both for newcomers to the research fields described,
and for other scientists seeking detailed background information on special
questions. Finally, it provides an accredited documentation of the valuable
contributions made by today’s younger generation of scientists.
A Study on Catalytic
Conversion of Non-Food
Biomass into Chemicals
Fusion of Chemical Sciences and Engineering
Doctoral Thesis accepted by
Hokkaido University, Sapporo, Japan
123
Author Supervisor
Dr. Mizuho Yabushita Prof. Atsushi Fukuoka
Graduate School of Chemical Sciences and Institute for Catalysis
Engineering Hokkaido University
Hokkaido University Sapporo
Sapporo Japan
Japan
vii
viii Supervisor’s Foreword
ix
x Acknowledgements
1 General Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1 General Background: Why Non-Food Biomass? . . . . . . . . . . . . . 1
1.2 Cellulose . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
1.2.1 Plant-Derived Biomass: Lignocellulose. . . . . . . . . . . . . . . 2
1.2.2 Crystal Structure of Cellulose . . . . . . . . . . . . . . . . . . . . . 3
1.2.3 Glucose and Its Derivatives . . . . . . . . . . . . . . . . . . . . . . 6
1.2.4 Hydrolysis of Cellulose in Homogeneous Systems. . . . . . . 12
1.2.5 Hydrolysis of Cellulose by Heterogeneous Catalysts . . . . . 15
1.2.6 Hydrolytic Hydrogenation of Cellulose to Sorbitol. . . . . . . 20
1.3 Chitin. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.3.1 Property of Chitin . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.3.2 Transformation of Chitin . . . . . . . . . . . . . . . . . . . . . . . . 27
1.4 Objectives of This Thesis Work. . . . . . . . . . . . . . . . . . . . . . . . . 29
1.5 Outlines of This Thesis . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.5.1 Chapter 1: General Introduction . . . . . . . . . . . . . . . . . . . 30
1.5.2 Chapter 2: Hydrolysis of Cellulose to Glucose Using
Carbon Catalysts . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 30
1.5.3 Chapter 3: Mechanistic Study of Cellulose Hydrolysis
by Carbon Catalysts. . . . . . . . . . . . . . . . . . . . . . . . . ... 30
1.5.4 Chapter 4: Catalytic Depolymerization of Chitin
to N-Acetylated Monomers . . . . . . . . . . . . . . . . . . . . ... 30
1.5.5 Chapter 5: Acid-Catalyzed Dehydration of Sorbitol
to 1,4-Sorbitan . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 31
1.5.6 Chapter 6: General Conclusions . . . . . . . . . . . . . . . . ... 31
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ... 31
2 Hydrolysis of Cellulose to Glucose Using Carbon Catalysts . . . . . . . 43
2.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.2 Experimental . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.2.1 Reagents . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
2.2.2 Synthesis of Mesoporous Carbon CMK-3. . . . . . . . . . . . . 46
xi
xii Contents
3A5AF 3-Acetamido-5-acetylfuran
3-HPA 3-Hydroxypropionic acid
5-HMF 5-Hydroxymethylfurfural
AC Activated carbon
ACC Aqueous counter collision
ADP Adenosine diphosphate
AFEX Ammonia fiber explosion
AH1 Unidentified mono-anhydrohexitol 1
AH2 Unidentified mono-anhydrohexitol 2
APCI Atmospheric pressure chemical ionization
ATP Adenosine triphosphate
B3LYP Becke 3-parameter Lee-Yang-Parr
BET Brunauer-Emmett-Teller
[BMIM]Cl 1-Butyl-3-methylimidazolium chloride
CBH Cellobiohydrolase
CNF Carbon nanofiber
CNT Carbon nanotube
CP/MAS Cross polarization/magic angle spinning
CP-SO3H Sulfonic chloromethyl polystyrene resin
CrI Crystallinity index
CVD Chemical vapor deposition
DEPT Distortionless enhancement by polarization transfer
DF Degree of freedom
DFT Density functional theory
DMAc N,N-Dimethylacetamide
DMF 2,5-Dimethylfuran
DMSO Dimethyl sulfoxide
DOE Department of Energy
DP Degree of polymerization
DRIFT Diffuse reflectance infrared Fourier transform
DTGS Deuterated triglycine sulfate
xv
xvi Abbreviations
UV Ultraviolet
XAFS X-ray absorption fine structure
XRD X-ray diffraction
YAG Yttrium–aluminum–garnet
ZTC Zeolite-templated carbon
Chapter 1
General Introduction
1.2 Cellulose
The major components of plant-derived biomass are cellulose (30–50 %), hemi-
cellulose (10–40 %), and lignin (5–30 %) (Fig. 1.1) [11, 12]. These three polymers
are intricately intertwined with each other, forming a rigid fiber called lignocellu-
lose, and constitute cell walls in plants. Cellulose is a polymer of glucose units
(Fig. 1.2a) linked by β-1,4-glycosidic bonds. Hemicellulose is a copolymer of
several kinds of sugar molecules, and a typical building block is β-xylose
(Fig. 1.2b). Arabinose (Fig. 1.2c) is sometimes contained in hemicellulose. C6
sugars such as glucose, mannose, fructose, and galactose are also found as minor
components in hemicellulose [13, 14]. The structure of hemicellulose depends on
plants. Lignin is a 3D-network polymer and its structure depends on plants as well
as hemicellulose, making the analysis of lignin structure extremely difficult. It is
suggested that three kinds of aromatic compounds, i.e., p-coumaryl alcohol, con-
iferyl alcohol, and sinapyl alcohol (Fig. 1.3), link with each other by ether bonds to
form lignin [15].
Transformation of cellulose, hemicellulose, and lignin to useful compounds is
the mainstream of next-generation biorefinery owing to their abundance. Indeed, a
variety of reactions to produce various chemicals from lignocellulose, e.g., pyrol-
ysis, hydrolysis, hydrolytic hydrogenation, and hydrodeoxygenation, have been
reported [8, 16–18]. However, utilization of lignocellulose has still been a grand
challenge due to its recalcitrance. In this section, the author has focused on cellu-
lose, the largest component in lignocellulose, and summarized its characteristics as
well as reported catalytic transformation systems.
Fig. 1.2 Building blocks of cellulose and hemicellulose: a glucose; b xylose; and c arabinose
Fig. 1.3 Structures of proposed lignin components: a p-coumaryl alcohol; b coniferyl alcohol;
and c sinapyl alcohol
Each glucose unit in cellulose molecule has three hydroxyl groups, which form
inter- and intramolecular hydrogen bond network with those of other glucose
residues. Consequently, cellulose molecules are uniformly packed; in other words,
crystal structure of cellulose is formed. There are seven types of crystal structure,
namely Iα, Iβ, II, IIII, IIIII, IVI, and IVII, which can be identified by powder X-ray
diffraction (XRD) and solid-state 13C nuclear magnetic resonance
(NMR) spectroscopy [19, 20]. Plants produce cellulose Iβ, and bacteria have cel-
lulose Iα. In the crystal structure of cellulose I, cellulose molecules are packed in
parallel (so-called parallel chain packing, Fig. 1.4a) [19], and electron diffraction
has revealed that Iα and Iβ are composed of one-chain triclinic and two-chain
monoclinic unit cell, respectively [21]. Other types are artificially obtained by
chemical treatments of cellulose I. The mercerization using concentrated NaOH
produces type II of crystalline cellulose from type I [22], and cellulose molecules in
type II juxtapose with each other in an antiparallel manner (so-called antiparallel
chain packing, Fig. 1.4b) [19]. Cellulose IIII and IIIII are obtained from types I and
II, respectively, by a treatment with liquid ammonia [23]. The difference between
the types IIII and IIIII appears to be parallel and antiparallel chain packing,
reflecting their respective original forms [19]. Cellulose IV is prepared by treating
cellulose III in glycerol at 533 K [23]. Although both XRD and 13C NMR spec-
troscopy cannot distinguish IVI and IVII directly, acetylation of hydroxyl groups of
cellulose enables to identify them. Cellulose triacetate with parallel chain packing is
4 1 General Introduction
synthesized from cellulose IVI, and that with antiparallel chain packing is from
cellulose IVII [19].
The crystalline structures impart good chemical and physical stability to cellu-
lose. High stability enables to use cellulose in a wide range of applications such as
fibers (e.g., rayon) [24], papers, food additives [25], and catalyst supports [26, 27].
In some cases, cellulose nanofiber is favorable for practical application due to its
high mechanical strength (equivalent to stainless steel) in addition to five times
lower density than steel [28]. The aqueous counter collision (ACC) method is
useful for preparation of cellulose nanofiber. This method drastically reduces the
length of cellulose particles from 100 μm to 100 nm and the width from 10 μm to
15 nm [29]; meanwhile, the crystal structure of cellulose is maintained.
In stark contrast to the use of cellulose itself, the robust crystalline structure of
cellulose is a drawback to its chemical transformation since the access of both
reactants and catalysts to reaction sites of cellulose, e.g., glycosidic bonds, has been
limited [30]. Crystallinity index (CrI) is a useful value to estimate the reactivity of
cellulose materials, and cellulose with low CrI is desirable for chemical transfor-
mation. CrI for a mixture of crystalline cellulose I and amorphous cellulose can be
determined by XRD (Eq. 1.1, Fig. 1.5) [31], solid-state 13C NMR spectroscopy
(Eq. 1.2, Fig. 1.6) [32], and infrared spectroscopy (IR, Eq. 1.3) [33]. XRD and 13C
NMR are commonly used and 13C NMR is the most reliable method as the peaks
derived from crystalline and amorphous parts are clearly separated [34].
I22:5 I18:5
CrIXRD ¼ 100 ð1:1Þ
I22:5
where I22.5 and I18.5 are intensities observed at 22.5° and 18.5° in XRD pattern,
respectively.
A7986
CrINMR ¼ 100 ð1:2Þ
A8692 þ A7986
1.2 Cellulose 5
where A79–86 and A86–92 are peak areas from 79 to 86 ppm and from 86 to 92 ppm in
13
C NMR spectrum, respectively.
a1372
CrIIR ¼ 100 ð1:3Þ
a2900
where α1372 and α2900 are intensities at 1372 and 2900 cm−1 in IR spectrum,
respectively.
Mechanical and chemical treatments can break the crystalline structure of cel-
lulose by dividing inter- and intramolecular hydrogen bonds, resulting in the
decrease of CrI. Mazeau et al. report that each glucose unit in crystalline cellulose Iα
and Iβ form 8 and 6.5 inter- and intramolecular hydrogen bonds, and this number
diminishes to on average 5.3 in amorphous cellulose [35]. On a laboratory scale,
milling methods such as ball-milling [36] are commonly used due to their ease of
6 1 General Introduction
handling. For example, ball-milling in a ceramic pot (900 mL) in the presence of
ZrO2 balls (1.0 cm, 1 kg) for 96 h decreased CrIXRD from 80 to 10 %, calculated
from Eq. 1.1 and the XRD patterns (Fig. 1.5) [37]. A larger scale of ball-milling
[3 L pot with Al2O3 balls (1.5 cm, 2 kg)] can reduce the treatment time to 48 h to
obtain a similar result. Besides, high-power milling methods such as planetary
ball-milling and rod-milling are more time-efficient processes and convert crys-
talline cellulose into an amorphous one within 1 h [38, 39]. In chemical methods,
the treatment of cellulose in H3PO4 decreases CrI [40], in which phosphate species
possibly form an adduct with cellulosic molecule and weaken their inter- and
intramolecular hydrogen bonds [41]. The resulting CrI values depend on the
treatment conditions: e.g., CrI changed from 85 to 79 % in 43 % H3PO4 at 298 K
for 1 h and to 33 % at 323 K for 40 min. During this acid treatment, cellulose is
partially hydrolyzed and the degree of polymerization (DP) decreases. Tsao et al.
demonstrated the treatment using supercritical CO2, reducing CrI to ca. 50 % for
1 h [42]. Other physicochemical methods such as ammonia fiber explosion (AFEX)
and SO2-steam explosion are also available [43]. The amorphous cellulose thus
prepared is expected to show higher reactivity than the crystalline one [44].
Dissolution of cellulose is another method to improve its reactivity [45], as
dissolved cellulose is expected to completely lose the crystalline structure.
Cellulose is almost insoluble in water [46] except for at high temperatures with
extremely high pressures (e.g., 603 K, 345 MPa) [47]. In contrast to water, lithium
chloride/N,N-dimethylacetamide (LiCl/DMAc) dissolves cellulose well, where Cl‾
species cleaves inter- and intramolecular hydrogen bonds of cellulose [48, 49].
Schweizer’s reagent [Cu(NH3)4(H2O)2](OH)2 also dissolves cellulose since the Cu2
+
species forms a complex with cellulose and divides hydrogen bonds [50]. These
two solvents are well known and are widely used in the field of cellulose research
and industry [48, 51]. In 2002, Rogers et al. found new solvents for cellulose, ionic
liquids (ILs) such as 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) [52]. This
report fascinated many researchers to use a variety of ILs as cellulose solvents due
to their chemical and thermal stability as well as tunability of physicochemical
properties [53]. Besides, it is known that vapor pressure of ILs is almost zero, which
enables to conduct reactions easily even in common vessels; in other words, high
pressure reactors are not necessary. The dissolution mechanism of cellulose into ILs
is almost the same as that into LiCl/DMAc [53].
Fig. 1.7 Derivatization of glucose. Further transformations of sorbitol and 5-HMF are depicted in
Figs. 1.10 and 1.11, respectively
a good precursor to valuable chemicals as well as glucose (Fig. 1.10) [65]. For
example, n-hexane and (E)-hexatriene are obtained by complete removal of
hydroxyl groups [66, 67]. Sorbitol undergoes dehydration in the presence of acid
catalysts to give two cyclized products, 1,4-anhydrosorbitol (1,4-sorbitan) and
1,4:3,6-dianhydrosorbitol (isosorbide). 1,4-Sorbitan is a raw material for various
environmentally benign surfactants, e.g., fatty acid esters (Span) and polysorbates
(Tween), which are useful as emulsifiers, insecticides, and soft templates for material
synthesis [68]. The emulsifiers are applied to food, cosmetic, and pharmaceutical
industries owing to their low-toxicity to humans [69]. Isosorbide itself and isosor-
bide dinitrate are medicines for Meniere’s disease and angina pectoris, respectively
[70]. Isosorbide-based polymers are outstanding engineering plastics showing good
transparencies and high glass transition temperatures; Mitsubishi Chemical, Teijin,
and Sabic provide isosorbide-based polycarbonates [71–73]. Other polymers such as
polyethylene isosorbide terephthalate (PEIT) are also under consideration as an
alternative to PET [74]. To date, the dehydration of sorbitol has been conducted by
using H2SO4 in industrial processes [75]. H2SO4 can control the ratio of 1,4-sorbitan
and isosorbide by changing reaction conditions. For example, 58 % yield of
1,4-sorbitan and 18 % yield of isosorbide are formed for 18 min (Table 1.1, entry 1),
1.2 Cellulose 9
Fig. 1.9 Top 12 building block chemicals produced from biomass resources, suggested by DOE
in the United States [64]
whereas isosorbide (66 %) becomes the major product for 48 min (entry 2). It is
noteworthy that the details of the catalysis for sorbitol dehydration by H2SO4 have
not yet been revealed. Recently, a variety of heterogeneous catalysts have been
developed to produce isosorbide from sorbitol on a laboratory scale (Table 1.1,
entries 3–13), e.g., immobilized H3PW12O40 [76], metal phosphate [77], CuSO4
[78], Ru modified Raney Cu [79], sulfonated polystyrene resin (Amberlyst 35) [80],
sulfonated oxides [81, 82], and zeolites [83–86]. Heterogeneous catalysts are ben-
eficial to industrial processes because they are easily separated from reaction
products and recycled. Although the selective production of isosorbide by hetero-
geneous catalysts has been reported as shown above, that of 1,4-sorbitan still
remains a grand challenge since 1,4-sorbitan readily undergoes subsequent dehy-
dration to form isosorbide in the presence of acids. Takagaki et al. reported that
10 1 General Introduction
i.e., sorbitol and 1,4-sorbitan. In other words, selective interaction between catalysts
and sorbitol would enable to produce 1,4-sorbitan in good yield and selectivity.
5-Hydroxymethylfurfural (5-HMF) has attracted much attention as 5-HMF
derivatives are applicable in many fields (Fig. 1.11). The production of 5-HMF
from glucose is as yet under consideration in laboratories, but high-yielding syn-
thesis of 5-HMF has been achieved. ILs and biphasic solvent systems (water and
organic solvents) are typical reaction media for this transformation since the pro-
duced 5-HMF is effectively extracted to organic solvents and its further degradation
in water could be inhibited [88]. Zhang et al. demonstrated the first direct synthesis
of 5-HMF from glucose using CrCl2 in ILs [89]. CrCl2 associates with glucose and
then accelerates the reaction. Later, mechanistic studies have revealed that the
transformation of glucose to 5-HMF requires both Lewis and Brønsted acids, as
Lewis acids are necessary for epimerization of glucose to fructose [90] and
Brønsted ones are for successive dehydration of fructose to 5-HMF [91]. This
insight leads to the development of bifunctional heterogeneous catalysts such as
Sn-modified BEA zeolite [92], sulfonated oxides [93], and BEA zeolite [94].
Although these catalytic systems require biphasic systems, Hara et al. synthesized
5-HMF from glucose in 81 % yield in water by using phosphate/TiO2 as a catalyst
[95]. Surprisingly, this phosphate/TiO2 catalyst works even in water, as typical
Lewis acids are quenched in the presence of water molecules. 5-HMF is derivatized
to a variety of chemicals as shown in Fig. 1.11. The hydrodeoxygenated product of
5-HMF is 2,5-dimethylfuran (DMF) [2], high-octane number fuel with high energy
density (30,000 kJ L−1). DMF is further transformed into p-xylene, a precursor to
PET, through Diels-Alder reaction with acrolein or ethylene [96, 97]. The oxidation
of 5-HMF over metal catalysts provides 2,5-furandicarboxylic acid (FDCA) [98,
99], which could be a polymer-substrate alternative to terephthalic acid. 5-HMF
also undergoes hydrolysis to form levulinic acid and formic acid [100]. Levulinic
acid is a good building block of polymers, lubricants, and medicines [101].
Furthermore, Dumesic et al. demonstrated the production of C8–C15 alkanes for jet
12 1 General Introduction
Production of glucose from cellulose is one of the target reactions in biorefinery due
to the wide applications of glucose as mentioned in Sect. 1.2.3. Hydrolysis of
cellulose to glucose (Fig. 1.12) is a grand challenge due to recalcitrance of cellu-
lose, and researchers have made efforts to depolymerize cellulose using various
kinds of catalytic systems. In this section, the author summarizes the reported
homogeneous catalytic systems to hydrolyze cellulose.
The conventional catalysts for cellulose hydrolysis to glucose are H2SO4 and
cellulase enzymes [103, 104]. Industrial processes employing an H2SO4 aqueous
solution are known as the Scholler process using diluted H2SO4 (0.5 %) developed
in Germany [105] and Hokkaido process employing concentrated H2SO4
(30–70 %) operated in Japan [106], and the processes produced glucose in up to
90 % yield. However, these processes are unprofitable due to equipment corrosion
by H2SO4, complicated separation system of glucose from reaction cocktail, and
acidic waste disposal; to date, they have been suspended.
Recently, mechanocatalytic depolymerization of cellulose using acid catalysts,
e.g., kaolinite (Al2Si2O7 · 2H2O) and H2SO4, without solvents or heat has been
reported. In a work by Blair et al., cellulose and kaolinite were planetary ball-milled
together at 350 rpm for 3 h, and 84 % of cellulose was depolymerized into
water-soluble products [107]. Rinaldi et al. conducted planetary ball-milling of
H2SO4-impregnated cellulose at 350 rpm for 2 h, and cellulose was almost com-
pletely hydrolyzed into water-soluble oligosaccharides [108]. In these systems, the
glycosidic bonds activated by acids receive mechanical force to be activated and
cleaved. Beltramini et al. characterized the produced oligomers in detail using 2D
NMR and found the formation of branched polymers linked by α-1,6-glycosidic
bonds, which improved the solubility of the oligomers [109]. This insight indicates
that both hydrolysis and condensation of glucans occur during the milling process.
No researchers have so far explained the origin of water molecules that react with
the substrate to hydrolyze glycosidic bonds and form hydroxyl groups. The author
speculates that cellulose undergoes hydrolysis by physisorbed water on the
1.2 Cellulose 13
O N leaving the hill we took a road that led us towards the north.
We first rounded the western end of the scarp of the detached
plateau parallel to which we had marched on coming from Bu
Gerara, and, about two hours after our start, ascended a steepish
bank on to the top of the plateau, which here was only about fifty feet
high.
From the summit of a small hill close by, a huge cliff stretching to
the north and south, as far as it was possible to see, was visible, far
off in the east; this was evidently the eastern boundary of the Farafra
depression, and, as I afterwards discovered, the continuation of the
cliff to the north of Bu Gerara.
The scarp was too far for me to be able to see any details of its
surface, with the light behind it, and as the top of it showed as only a
straight line, there were no points on it to which I could take a
bearing.
In these circumstances it was impossible either to fix its position
or to estimate the direction in which it ran. I several times met with
this difficulty, but found that, when a cliff faced towards the south, it
was only necessary for me to wait till the sun came round far enough
to begin to light up its surface, and then a rough estimate of the
direction in which it ran could be obtained by taking a bearing on to
the sun itself. This dodge was especially useful when it was
necessary to map the continuation of a cliff, part of which had
already been surveyed and the remainder of it could only be seen
from one point, such as the top of a high hill.
The part of the Farafra depression in which we found ourselves
was an absolutely featureless plain, of hard level sand, that sloped
slightly towards the foot of the scarp on our east. Here and there we
came across patches of greenish clay, with white lines running
through it, showing above the surface of the sand.
The Persian King, Cambyses, during his occupation of Egypt,
sent a great army across the desert to destroy the oracle of Jupiter
Ammon in Siwa Oasis. The army never reached Siwa; but was lost
in the desert. Its last resting-place is unknown, but, according to
native reports, the whole host perished of thirst in this huge
depression in which the oasis of Farafra lies.
I happened to mention to Qwaytin the subject of singing sands,
and asked him if he had ever heard any. He told me that somewhere
in the north of the Farafra depression there was a rock that was
supposed to be the “church” of the spirits of the lost Persian army. It
was called the “infidel rock,” because it “sang on Sunday.” It
appeared to be some form of musical sands.
It was not until the third day after our start from the treasure hill
that we sighted in the west the field of dunes that occupies the
centre of the Farafra wady. They appeared to be almost white in
colour, and lay a long way off.
Qwaytin told me that we should reach the Kairowin hattia on our
third day after leaving his hill. It will give some idea of his utter
incompetence as a guide when I say that we did not actually get
there until two days later.
He came into my tent on the first evening and began yarning in an
aimless sort of way, as he generally did as a preliminary to serious
business, and I endeavoured to extract some information from him
as to the topography of the Bedayat country, with which he was well
acquainted.
But he at once got impatient and changed the subject to that of
his confounded hill. He ended by asking—almost demanding—that
we should go back there to have another look at it, and to make
certain that there was not another hill in the neighbourhood which
might be the one indicated in his book. On my refusing to do so, he
flounced out of the tent—he was certainly a queer customer to deal
with.
Whenever I spoke to him the next day he began gassing about his
wretched hill, and saying that he wanted to go back to it; but towards
evening he rather recovered himself, and when he came to my tent I
again threw out feelers about the country of the Bedayat, though he
declined to tell me anything about the district, he started giving me a
lot of information about the Bedayat themselves, which, as they are
an almost unknown race, proved extremely interesting.
They claim to be descended from an afrit, whom, for some crime,
either David or Solomon shut up in a box, till he grew to such an
enormous size that he burst it open. There still exists apparently a
mongrel Bedayat—Tibbu tribe, known as the M’Khiat er Rih, that
possess the miraculous power of being able to walk over sand
without leaving any tracks behind them—a most useful
accomplishment in the desert for a race of born freebooters. This
peculiarity they owe to the fact that wherever they go they are
followed by a wind that immediately obliterates their footprints!
On our fourth day after leaving the treasure hill, our road
converged towards the dunes lying on our west, and, as Qwaytin
seemed to be hopelessly lost, I climbed one of the biggest of them
with him to try and make out our position.
From the top, the east and west scarp, with a break in it leading
up to Baharia Oasis, that lies on the north of Farafra, could be seen
in the far distance, but no sign of the hattia Kairowin was visible. In
front of us, however, was a high three-headed sif, or longitudinal
sand dune, that Qwaytin declared to be the landmark for the hattia
from the south.
As we were getting very short of water, the news that the hattia
was not in sight caused something like consternation among my
men. They all started grumbling at Qwaytin’s ignorance of the road,
and Ibrahim went so far as to ask him point-blank why he called
himself a guide, if he knew so little about the desert.
This coming from a young Sudani, hardly out of his ’teens, to an
elderly Arab guide, who, moreover, was a sheykh of his tribe, was a
great ayb, and Qwaytin was intensely put out. Qway, under the
circumstances, would have retaliated with some stinging remarks on
the inferiority of “slaves” and the respect that was due from a boy to
his elders and superiors in rank; but Qwaytin lacked his ready
powers of vituperation. He was a slow-witted old curmudgeon, and
failed entirely to put Ibrahim in his place. His own men stood up for
him in a feeble sort of way. But they were no match for Ibrahim, and
eventually gave up any attempt to defend their sheykh, probably
feeling themselves that there was not much to be said in his
defence. As I rather wanted to encourage a certain amount of friction
between my men and Qwaytin’s, I left them to settle their differences
as best they could, with the result that Qwaytin and his men got
much the worst of the wrangle.
Kairowin hattia measures some eighteen miles from north to
south, by seven from east to west. It consists of a level scrub-
covered area, in which, here and there, are to be seen a few
neglected-looking palms. A number of wells have been sunk here at
various times; one on the extreme eastern edge of the hattia, where
the road coming from Assiut first enters the scrub, is known as Bir
Murr. This well, which I did not visit, is said to be sanded up. Another
well somewhere to the north, I believe, is known as Bir Abd el Qadr.
There are also several others, all of which seem to be impartially
named Bir Kairowin. Probably water can be found under all the lower
lying parts of the hattia by digging for a few feet into the ground,
which throughout this district consists of chalk.
The wells in every case apparently give water so thick with chalk
particles that when first drawn from them it is almost as milky as
whitewash. Attempts to clear the water by passing it through a
Berkefeld filter failed, as the chalk clogged the filter after a few
strokes. But when it had been allowed to stand for a few hours, most
of the chalk settled down to the bottom, and the water that was
poured off passed quite easily through the filter, after which it proved
to be of quite good quality.
I, unfortunately, forgot to wind my watches the first night in the
hattia, and so allowed the half chronometer I had been using in
taking my observations to run down. As I was depending on it for my
longitudes, this necessitated a stay of two or three days in the camp
in order to ascertain its new rate after it had been rewound.
These watches are for some reason only made so as to run for
one day. As oversights of this kind must be of common occurrence
with travellers, it would seem to be preferable that they should be
made so as to run for two days, and be furnished with an up and
down indicator to show how long an interval has elapsed since they
were last wound.
I spent a considerable part of the time while in the hattia in trying,
without success, to get a shot at gazelle. There appeared to be very
few in the district, though a considerable number of old tracks were
to be seen where they had been feeding on the scrub.
This scarcity of game may perhaps have been due to the fact that
a few bedawin were at that time living there in charge of some
camels belonging to the Senussi zawia at Qasr Farafra. These men
kept away from the camp, but I saw them and their camels several
times wandering about in the scrub, and twice found small hovels
constructed of brushwood, in which they had been living—they had,
so far as I could see, no tents.
My men spent most of their time in grubbing about in some large
mounds. On the top of one of these, about thirty feet high, Ibrahim
found some burnt bricks. The whole mound was covered by a thick
growth of terfa bushes, among which the sand had collected,
completely hiding any building there might have been beneath it.
It must have been originally a building of some size and of
considerable height, and was perhaps a tower. The men unearthed
part of a small room at the base of the mound. It had been well built,
of the same burnt bricks, and the interior was covered with plaster. A
few pieces of broken pottery were found, one of them covered with a
green glaze. There were four or five other mounds of a similar nature
in the neighbourhood; but we had neither time nor implements
thoroughly to examine them.
As the total result of their treasure hunt in Kairowin the men only
unearthed one corpse and a few bits of broken pottery, without
finding even a single copper coin to gratify their cupidity. They were
consequently considerably disillusioned with their occupation, and I
experienced no difficulty in getting them to start for Qasr Farafra.
I made first for the main well, that is known as the Bir Kairowin, in
order to close my traverse. The water lay about eight feet below the
surface; access being gained to it by the usual sloping path, cut out
of one of its sides. By the top of the well was a mud-built trough for
watering camels, with an empty paraffin tin lying beside it for use as
a bucket.
Immediately on leaving the hattia we got into the dunes, which
cover a large area in the centre of the Farafra depression. The first
two or three dunes gave a little difficulty, but we found the rest of
them quite easy to cross. They were all, so far as I could see, of a
very elongated whalebacked type, which ran roughly from north to
south, in the direction of the prevailing wind.
Qasr Farafra lay almost due west from our camp. Soon after we
got into the sand it became clear that Qwaytin was again hopelessly
lost, as I found we were marching almost due south. I was obliged to
put it to my guide, as inoffensively as I could, that if he would change
the direction in which he was leading us by a mere right angle, we
might perhaps reach our destination, instead of going on to Dakhla
Oasis as we seemed to be doing. Qwaytin was so hopelessly lost
that he accepted my suggestion without the slightest argument.
Soon after this we got out of the sand on to level desert, where a
large number of black nodules of iron pyrites were to be seen lying
on the surface. Further on some fine specimens of sand erosion
were met with in the shape of chalk “mushrooms” and table rocks.
Otherwise this part of the desert was quite featureless. The road lay
entirely over white chalk, which caused a rather trying glare in the
blazing sunlight.
We sighted Qasr Farafra on the evening of the second day after
leaving Kairowin hattia; but as night fell before we could reach it, we
camped a few miles away from the village. Two hours’ march on the
following morning brought us into the oasis. On the outskirts we
passed a patch of ground on which the sand was encroaching, some
palms lying on the north of it being almost entirely submerged.
We camped on the northern side of the village. A large crowd of
natives came out and stood watching us while the tent was being
pitched. Among them was a sulky-looking fellow whom I was told
was the ’omda; so, as soon as the tent was pitched, I invited him and
some of the other men standing by to come in.
We had foolishly camped too close to the village, with the result
that throughout the greater part of the day the camp was surrounded
by a crowd of men and children watching all our actions, peering into
the tent, thronging round the theodolite, when I began to take
observations, and generally showing an ill-mannerly curiosity that
was in great contrast to the conduct of the natives of the other oases
in which we stayed. Farafra being the least known of the Egyptian
oases, the advent of a European was an event of such rare
occurrence that the natives had evidently decided to make the most
of it.
The natives of Farafra Oasis, who are known as the Farfaroni, or
sometimes as the Farafaroni, are a far more vigorous lot than those
of Kharga and Dakhla. They were a surly unpleasant-looking crowd.
The day after our arrival, I went out with the ’omda and Qwaytin to
see the village and plantations. With the exception of an ezba at ’Ain
Sheykh Murzuk, where there are a few houses, a Senussi zawia and
a family or two continuously resident to tend the cultivation near the
well, Qasr Farafra is the only permanently inhabited spot in the
whole Farafra depression. It is a poor little place with a total
population of about five hundred and fifty inhabitants. The houses
are of the usual mud-built type, and in most cases little better than
huts; almost the only exception being that of a square tower,
showing in places the remains of battlements, attributed, perhaps
rightly, by the natives to the Romans, who are said to have erected it
as a keep to protect the village.
This proved to be rather an interesting place. It is not inhabited,
but the door is kept locked with a watchman perpetually on guard
over it. The building is used solely as a storehouse, each family in
the village having the right to the use of one of the rooms that it
contains—there were said to be no less than one hundred and
twenty-five chambers in the building.
The ’omda showed us over the tower. The entrance lay through a
strong wooden door, at the top of a flight of steps, in a passage
entered in the middle of one of the outer walls, the walls on either
side of which were pierced with apertures, apparently intended for
use as loop-holes. The passage extended the whole height of the
building and was unroofed, in order that stones might be dropped
from above on to any assailant attempting to attack the door.
BOY WITH CROSS-BOW, FARAFRA.