Beruflich Dokumente
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201100162
The production of renewable chemicals is gaining attention ity. This new chemical toolbox needs to be designed to guar-
over the past few years. The natural resources from which they antee the demands of future generations at a reasonable price.
can be derived in a sustainable way are most abundant in The surplus of functionality in sugars and glycerol consists of
sugars, cellulose and hemicellulose. These highly functionalized alcohol groups. To yield suitable renewable chemicals these
molecules need to be de-functionalized in order to be feed- natural products need to be defunctionalized by means of de-
stocks for the chemical industry. A fundamentally different ap- hydroxylation. Here we review the possible approaches and
proach to chemistry thus becomes necessary, since the tradi- evaluate them from a fundamental chemical aspect.
tionally employed oil-based chemicals normally lack functional-
1. Introduction
ChemSusChem 2011, 4, 1017 – 1034 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 1017
J. ten Dam and U. Hanefeld
1018 www.chemsuschem.org 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2011, 4, 1017 – 1034
Renewable Chemicals: Dehydroxylation of Glycerol and Polyols
2.2 Dehydration of alcohols and hydrogenation of carbon– hydrogenolysis of the ether bond offers a good opportunity to
carbon double bonds introduce selectivity into the system, as studied by Koso
et al.[8, 9] This group specifically studied the hydrogenolysis of
Isolated alcohols can be eliminated as well, which can be tetrahydrofurfuryl alcohol and tetrahydropyran methanol using
either acid- or base-catalyzed. However, lack of isomerization rhodium catalysts. They found that the addition of tungsten,
possibilities makes this process more difficult than the dehy- rhenium, and molybdenum increased both the activity and the
dration of vicinal diols (Scheme 6). The proximity of a double selectivity of the hydrogenolysis.[8] This higher selectivity is ex-
bond will offer some stabilization through a p-conjugated plained by both a smaller rhodium ensemble on a MOx-Re cat-
system, as is the case in acrolein formation. alyst and coordination of the free alcohol towards the MOx.[8]
This forms an alkoxide and the neighboring C O
bond is then cleaved by hydroxides present on the
adjacent rhodium surface. The same bimetallic
system is also highly selective in the hydrogenolysis
of tetrahydropyran methanol into 1,6-hexanediol. An
Scheme 6. Dehydration of alcohols and hydrogenation of carbon double bond. X-ray absorption near edge structure (XANES) and ex-
tended X-ray absorption fine structure (EXAFS) study
showed that the rhodium and ReOx particles have a
2.3 Condensation of alcohols and hydrogenolysis of the re-
direct interaction and it is indicated that the rhodium surface
sulting cyclic ethers
is covered by small ReOx species.[9]
This reaction sequence starts with the condensation of two al- This reaction sequence is not applicable to glycerol, since
cohols by forming a cyclic ether (Scheme 7), which can then the condensation of alcohols in order to form cyclic ethers is
be cleaved by hydrogenolysis. However, often the rehydration limited to five-membered (or larger) ring systems.
and subsequent elimination (discussed in Sections 2.1 and 2.2)
is faster than a subsequent hydrogenolysis. Nevertheless, the
3. Glycerol
Glycerol is the smallest polyol readily available from biomass. It
functions as the backbone of triglycerides, which constitute
approximately 10 % of total biomass. Glycerol is released as a
byproduct from biodiesel production. For every tonne of bio-
diesel produced, 100 kg of glycerol is generated. Consequently,
Scheme 7. Condensation of alcohols and hydrogenolysis of cyclic ether. glycerol constitutes 1 % of total biomass. Glycerol is a popular
starting material for further chemical derivatization. Although
this Review focuses on catalytic dehydration and reduction, a
Jeroen ten Dam was
range of products can be obtained through oxidation, esterifi-
born in the Nether-
cation, and etherification, stressing the versatility of this build-
lands in 1982. He ob-
ing block.[10, 11]
tained his M.Sc. in
Scheme 8 shows the dehydration and dehydroxylation
Organic Chemistry at
routes, leading to different products. Some of the intermedi-
the Radboud Univer-
ates are branching points. By choosing the appropriate cata-
sity (Nijmegen, the
lysts and conditions, selectivities can be directed towards
Netherlands). Cur-
either of these products. The processes that lead to the mole-
rently, he is pursuing
cules depicted in red will be discussed in more detail in the
his PhD at the Biocatalysis and Organic Chemistry laboratory in col-
following chapters. Scheme 9 shows that the initial dehydra-
laboration with the Catalysis Engineering laboratory at the Techni-
tion to form acetol is thermodynamically favored over the for-
sche Universiteit Delft. His main research topic is the selective pro-
mation of 3-hydroxypropanal. Moreover, whenever 3-hydroxy-
duction of chemicals from glycerol. He enjoys looking at catalysis
propanal is formed, the subsequent dehydration to form acro-
from an organic synthesis point of view.
lein is thermodynamically more likely than hydrogenation to
1,3-propanediol. This exemplifies the difficulties in achieving
Ulf Hanefeld was born in 1966 in Germany, and grew up in then
high 1,3-propanediol selectivities and it can be deduced that
(West) Berlin and London. In 1993 he received his PhD from the
the formation of 1,3-propanediol is kinetically controlled.[4]
Georg-August-Universitt zu Gçttingen, having performed the re-
search both in Gçttingen (Prof. H. Laatsch) and Seattle (Prof. H. G.
Floss). After postdoctoral years with Prof. C. W. Rees (Imperial Col- 3.1 Glycerol to 1,2-propanediol
lege London), Prof. J. Staunton (Cambridge) and Prof. J. J. Heijnen
Most of the propylene glycol, or 1,2-propanediol (12PD), is pro-
and Dr. A. J. J. Straathof (TU Delft), he took up a position in Delft.
duced by the hydration of propylene oxide. This is produced
His research at the Technische Universiteit Delft focuses on en-
via either the chlorohydrin process or the hydroperoxide pro-
zymes and heterogeneous catalysis in organic synthesis.
cess from oil-derived propylene.[12] 12PD is primarily used as a
ChemSusChem 2011, 4, 1017 – 1034 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 1019
J. ten Dam and U. Hanefeld
Scheme 9. Reaction energies for glycerol to 12PD, 13PD, acrolein, their intermediates and degradation products.[4]
1020 www.chemsuschem.org 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2011, 4, 1017 – 1034
Renewable Chemicals: Dehydroxylation of Glycerol and Polyols
ChemSusChem 2011, 4, 1017 – 1034 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 1021
J. ten Dam and U. Hanefeld
Entry Catalyst Additive Additive/metal P T TOF[c] Conversion Selectivity Selectivity Yield of Ref.
ratio [bar] [K] [h 1] [%] to 12PD [%] to EG [%] 12PD [%]
Alkaline catalysts
1 Cu/SiO2[e] – – 15 528 13.2 100 87.0 4.0 87.0 [20]
2 CuO/ZnO Zn 2[a] 50 473 9.0 46.0 90.0 1.0 41.4 [21]
3 Cu/ZnO/Ga2O3 – – 50 493 18.4 96.0 82.0 2.0 78.7 [22]
4 Cu-ZnO Zn 1[a] 42 473 0.3 22.5 83.6 10.7 18.8 [23]
5 Cu-ZnO Zn 1[a] 60 473 0.9 75.0 93.9 5.5 70.4 [15]
6 Pt/hydrotalcite – – 30 493 37.2 92.1 93.0 3.9 85.7 [24]
7 Cu/MgO – – 30 453 1.0 72.0 97.6 1.3 70.3 [25]
8 Cu/MgAlO – – 30 453 2.7 80.0 98.2 1.0 78.6 [26]
9 CuO/SiO2 – – 90 473 2.6 73.4 94.3 3.6 69.2 [27]
Acidic catalysts
10 Ru/C Amberlyst 15 2[b] 80 393 16.8 12.9 55.4 12.9 7.1 [28]
11 Ru/C Amberlyst 70 19[a] 80 453 804 48.8 70.2 8.3 34.3 [29]
12 Ru/C Amberlyst 15 2[b] 80 393 38.3 21.3 76.7 – 16.3 [30]
13 Ru/C Nb2O5 2[b] 60 453 20.0 62.8 66.5 21.2 41.8 [31]
14 Ru/TiO2 – – 60 453 33.1 46.0 63.0 19.0 29.0 [32]
15 Cu/Al2O3 – – 15 473 9.2 41.9 93.3 – 39.1 [33]
16 CuAg/Al2O3 Ag 0.4[a] 15 473 6.1 27.0 96.0 – 25.9 [34]
17 Cu-STA/Al2O3[e] STA 1[b] 60 513 64.0 90.1 89.7 4.2 80.8 [35]
18 CuCr2O4 Cr 2[a] 80 493 6.3 80.0 84.0 – 67.2 [36]
19 Cu:Al Al 1[a] 70 513 4.9 76.0 89.0 – 67.6 [37]
20 Ru-Cu/TMG-bentonite Cu 0.3[a] 80 503 9.5 100 85.4 7.6 85.4 [38]
21 Ru/Al2O3 Re2(CO)10 0.5[a] 80 433 21.5 53.4 50.1 7.8 26.8 [39]
22 RuRe/SiO2 Re 1[b] 80 433 20.5 51.7 44.8 6.4 23.2 [40]
23 RuRe/ZrO2 Re 1[b] 80 433 23.7 56.9 47.2 4.0 26.9 [40]
Miscellaneous catalysts
24 Cu/Al2O3[e] – – 1 473-393 0.4 100 96.7 1.9 96.7 [41, 42]
25 Pt/NaY – – 1[d] 503 15.0 85.4 64.0 – 54.7 [43]
26 Ru/Al2O3 and – – 14[d] 493 13.7 50.1 47.2 6.3 23.6 [44]
Pt/Al2O3
27 Raney Ni – – 1[d] 453 1.0 100 25.0 32.0 25.0 [45]
1 1
[a] On a molar basis. [b] On a weight basis. [c] Turnover frequency (mmol12PD mmolmetal h ). [d] N2 pressure and in situ hydrogen formation. [e] Continuous
reaction
3.1.3 Acidic conditions sessing moderate acid sites, proved to be the most active addi-
tives, whereas the type of additive did not influence the selec-
As discussed above the elimination step can be acid- or base- tivity. The reaction conditions for Ru/C and Nb2O5 could be op-
catalyzed. In an exploratory study Tomishige et al. showed that timized to 63 % conversion and 67 % 12PD selectivity (Table 1,
the sulfonic acid resin Amberlyst 15 is a more effective additive entry 13).[31] In another paper by the same authors, ruthenium
for promoting 12PD formation than homogeneous sulfuric was immobilized on Lewis-acidic TiO2 support through a depo-
acid and hydrochloric acid. Moreover, hydrochloric acid inhibit- sition–precipitation method. In this way, the acid sites are in
ed the catalyst activity by poisoning the ruthenium surface of close proximity of the hydrogenating metallic particles. This
the Ru/C catalyst. The activity of the Ru/C and Amberlyst 15 approach resulted in a very stable catalyst that gave 46 % glyc-
system was limited to 13 % conversion (giving 55 % 12PD se- erol conversion and 63 % 12PD selectivity in only 8 h
lectivity) for a 20 wt % aqueous glycerol solution at 393 K, and (entry 14).[32]
could not be increased by applying higher temperatures be- The activity and selectivity of copper immobilized on various
cause of the low thermal stability of Amberlyst 15 (Table 1, aluminum-containing acidic supports was investigated by
entry 10).[28] This limitation could be overcome by using the Zhang et al. Pure alumina was more active than the more-
more thermostable resin Amberlyst 70. Temperatures up to acidic zeolitic supports (Hb, HY, HZSM-5, and 13X), which
453 K could be applied. This, in combination with a pre-reduc- showed minimal or no activity at all. This could be due to the
tion step of the ruthenium particles, increased conversion to preferred selectivity of the zeolites towards acrolein, or be-
49 % and 12PD selectivity to 70 %, with a remarkable TOF of cause of the strong CuO–support interaction due to the strong
804 per hour (entries 11 and 12).[29, 30] acidity of the zeolites. This interaction might prevent the pre-
Lingaiah et al. used Ru/C in combination with several ther- reduction of CuO to active metallic copper. The Cu/Al2O3 cata-
mally stable solid acids. They showed that conversion could be lyst was able to convert pure glycerol into 12PD at a conver-
linearly correlated to the number of acid sites on the solid sion of 42 %. Interestingly, no glycerol condensation products
acid. Nb2O5- and ZrO2-supported phosphotungstic acid, pos- were formed using pure glycerol and 12PD selectivity was as
1022 www.chemsuschem.org 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2011, 4, 1017 – 1034
Renewable Chemicals: Dehydroxylation of Glycerol and Polyols
high as 93 % (Table 1, entry 15).[33] By co-impregnation of Cu/ only increased the conversion of glycerol, it also improved
Al2O3 with silver, the copper could be reduced at reaction tem- 12PD and 13PD selectivity, by preventing the degradation of
perature, thereby rendering the pre-reduction step obsolete. glycerol into EG. In combination with Ru/C the rhenium im-
Although the bimetallic catalyst showed improved 12PD selec- proved both conversion and selectivity, but to a somewhat
tivity, the activity of the CuAg/Al2O3 catalyst was lower com- lesser extent. The mix of Ru/ZrO2 and Re2(CO)10 mainly im-
pared to the parent pre-reduced Cu/Al2O3 (entry 16).[34] proved the selectivity towards propanediols, while the effect
on the conversion of glycerol was less pronounced (Table 1,
entry 21). Interestingly, reasonable conversions were estab-
3.1.4 Catalyst promotion
lished at a relatively low temperature of 433 K and rhenium
A commonly used strategy to improve catalyst activity is co- showed some increase in 13PD selectivity, a more valuable
immobilization of a second metal or acid with the hydrogenat- diol.[39] This promising lead was followed up by impregnating
ing metal. Sun et al. impregnated silicotungstic acid and the rhenium and ruthenium directly on different acidic sup-
copper on alumina. The resulting catalyst was tested in a ports. Conversions between 52 and 57 % were reached using
fixed-bed reactor. The co-impregnated acid in combination bimetallic SiO2, ZrO2, H-ZSM5, and Hb catalysts, which were
with the continuous reactor resulted in good glycerol conver- higher than when using rhenium as an additive. However, the
sion (90 %) and 12PD selectivity (90 %). Moreover, the catalyst selectivity towards 12PD was only improved for RuRe/SiO2 and
was shown to be stable with regard to activity and selectivity was not improved for the other catalysts (entries 22 and 23).[40]
for 250 h (Table 1, entry 17).[35] The pretreatment of the RuRe/SiO2 catalyst was also investigat-
Yi et al. used chromium to promote the activity of copper. ed. High prereduction temperatures were not necessary and
Chromium itself showed minimal catalytic activity,[36] and im- were even decreasing the glycerol conversion, because these
pregnation of Cr2O3 with copper did not significantly improve high temperatures caused the metals to sinter. However, prere-
the catalytic properties.[46] However, by co-precipitating chro- duction at 473 K did show higher 12PD selectivity compared
mium with copper both activity and selectivity were increased to the calcined catalyst. This means that for an active and se-
tremendously. Using this method of preparation, an acidic lective catalyst, the rhenium could be in a ReOx form, while
CuCr2O4 spinel was formed. These spinels are known for stor- ruthenium should be in its metallic form.[47] An explanation for
ing hydrogen within their structure, thereby increasing their the promoting effect of rhenium is the surface acidity of ReOx.
hydrogenation activity. This resulted, in combination with the This would promote the dehydration step in the hydrogenoly-
improved acidity, in a hydrogenolysis catalyst that converted sis of glycerol. Interestingly, it also showed some enhancement
80 % of glycerol into 12PD at 84 % selectivity (Table 1, in 13PD selectivity, a more valuable diol than 12PD. This effect
entry 18).[36] Chromium however, is not an environmentally will be discussed in more detail in the chapter concerning the
friendly metal. Therefore, efforts were directed towards its re- formation of 13PD.
placement with a more benign alternative. Aluminum could be
an option. A co-precipitation Al–Cu catalyst showed higher
3.1.5 Temperature gradient
acidity compared to two commercial copper chromate cata-
lysts, which is translated in higher glycerol conversion. The Hydrogenolysis is not only optimized by developing the most
conversion could be increased up to 76 % at 513 K, while main- active and selective catalysts: reaction engineering can also
taining a high 12PD selectivity of 89 %, showing only a small contribute substantially. This is already apparent from the con-
amount of degradation of glycerol into ethylene glycol (EG) at tradicting temperature needs for dehydration and hydrogena-
this temperature (entry 19).[37] tion. Dehydration is endothermic and proceeds more rapidly at
A very active and stable bimetallic catalyst was prepared by higher temperatures, while exothermic hydrogenation can be
depositing ruthenium and subsequently copper on a bentonite performed at milder temperatures, thereby avoiding degrada-
carrier. Before the deposition of the metal, the sodium cations tion of glycerol or reaction products. Sato et al. were able to
on the carrier were exchanged by the cations of the ionic improve the hydrogenolysis of glycerol by making use of this
liquid tetramethylguanidiniumlactate. These cations (tetrame- fact. They applied Cu/Al2O3 in a fixed-bed down-flow reactor,
thylguanidinium; TMG) proved to stabilize the metal particles which had different temperatures at the top and the bottom.
by strong coordination. Aggregation of the particles was pre- At the top, the dehydration took place at 473 K and the subse-
vented by strong electrostatic interactions of TMG with the quent hydrogenation at the bottom was performed at 393 K
negative charge in the silicate layers of the bentonite. TMG not (Scheme 12). In this way, glycerol was completely converted
only stabilized the metal particles, but also increased the and 12PD selectivity was 97 % (Table 1, entry 24).[41, 42] This is a
amount of liquid product. The ruthenium in this bimetallic cat- significant increase in 12PD formation, since using Cu/Al2O3 at
alyst provides the activity (100 % conversion), while copper a constant 463 K yielded only 80 % 12PD.[41]
suppresses the degradation of glycerol into EG, thereby ac-
commodating high 12PD selectivity (85 %; Table 1, entry 20).[38]
3.1.6 Absence of H2
The influence of rhenium on the activity of several heteroge-
neous ruthenium catalysts was investigated by He et al. The Externally added hydrogen is necessary for all previously men-
addition of heterogeneous Re2(CO)10 was most effective in tioned processes to form 12PD. Normally, this hydrogen is de-
combination with Ru/Al2O3. Together with this catalyst it not rived from fossil fuels. However, the aqueous phase reforming
ChemSusChem 2011, 4, 1017 – 1034 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 1023
J. ten Dam and U. Hanefeld
of glycerol over platinum catalysts erol, or glucose, into 13PD using a fermentation process.[48, 49] It
is known also. The hydrogen gen- is even possible to combine 13PD and hydrogen production
erated by this process can be di- from crude biomass-derived glycerol, by using a mixed culture.
rectly used for the formation of In this way, optimal use is made of glycerol biomass, without
12PD. This was shown for the first the need for prior purification.[50]
time by D’Hondt et al. They im- In this review we will concentrate on the formation of 13PD
pregnated NaY zeolite with plati- from glycerol, using heterogeneous catalytic systems. The fact
num, which was able to convert that the number of papers that report selective formation of
85 % glycerol with 64 % 12PD se- 13PD is greatly outnumbered by the number of papers report-
lectivity (Table 1, entry 25).[43] ing on selective 12PD formation is a clear sign that the forma-
Roy et al. investigated the idea tion of 13PD is more challenging. However, especially over the
of in situ generation of hydrogen last two years, the factors that are important to influence 13PD
in more detail. A combination of formation are slowly being unraveled. An overview is given in
both Ru/Al2O3 and Pt/Al2O3 was the following section. It will become clear that while for the
more active than the individual conversion of glycerol into 12PD the activity is the main chal-
Scheme 12. Temperature gra-
dient reduction of glycerol. catalysts for in situ hydrogen for- lenge, the main issue for 13PD formation is to achieve high se-
mation and subsequent 12PD for- lectivity.
mation. An optimal temperature of 493 K was found (conver-
sion 50 %, 12PD selectivity 47 %; Table 1, entry 26). Increasing
3.2.2 Reaction mechanism
the temperature would further increase glycerol conversion.
However, this would result in more gaseous products at the The formation of 13PD proceeds via 3-hydroxypropanal as an
expense of 12PD selectivity. Counter-intuitively, addition of ex- intermediate. This aldehyde is formed after an initial elimina-
ternal hydrogen was detrimental to 12PD selectivity and far tion of the secondary alcohol group of glycerol. The formed
more methane was formed, through methanation of carbon di- C C double bond undergoes a tautomerization, which yields
oxide.[44] the more stable aldehyde. Subsequent hydrogenation yields
An interesting development was reported by Yin et al. They 13PD (Scheme 13). The initial alcohol elimination is endother-
used Raney nickel for in situ hydrogen formation, thereby pre- mic and a relatively high temperature is needed for this elimi-
venting the use of precious and scarce platinum and rutheni- nation to proceed. The subsequent hydrogenation is exother-
um. Raney nickel was able to catalyze the complete conversion mic and prefers lower reaction temperatures. Lower tempera-
of glycerol in 1 h at 453 K. However, it was also very active in tures will also prevent further degradation of 13PD. Recently, it
C C bond cleavage, resulting in substantial EG selectivity has been reported that 13PD is formed at lowered tempera-
(32 %) on top of 12PD selectivity (25 %) (Table 1, entry 27).[45] tures, using rhenium oxide as an additive. This lower tempera-
To conclude, 12PD can generally be formed with good to ture indicates that the dehydration hydrogenation sequence is
very good selectivities, while in many examples the conversion no longer active and points in the direction of energetically
needs improvement. It was shown that the abundantly avail- more favorable direct hydrogenolysis (vide infra).
able copper can achieve both. By utilizing the advan-
tages of a continuous reactor, the initial dehydration
of glycerol and subsequent hydrogenation of the
formed acetal can be achieved at their respective op-
timum temperatures. This streamlines the overall re-
Scheme 13. Reaction mechanism 13PD formation via dehydration hydrogenation.
action and yields almost 100 % 12PD.
3.2.3 Solvent
3.2 Glycerol to 1,3-propanediol In 2004, Chaminand et al. were the first to report a hydroge-
nolysis reaction that produced more 13PD than 12PD (13PD/
3.2.1 Introduction
12PD ratio of 2). Using a slurry of Rh/C and tungstic acid in sul-
1,3-propanediol (13PD) is the commercially most interesting folane, they were able to convert 32 % glycerol. 13PD selectivi-
hydrogenolysis product of glycerol. It is used in resins, engine ty was 12 % and a start towards 13PD was made (Table 2,
coolants, dry-set mortars, water based inks, but most of it is entry 1).[5] This paper set the example for others to follow. The
used in the production of polypropylene teraphthalate (PPT), novelty of Chaminants report was both the use of tungstic
which is a polyester synthesized from 13PD and teraphtalic acid as an additive and sulfolane as a solvent. Kurosaka et al.
acid. It is marketed by DuPont as SORONA. Current production adopted these ideas and realized a breakthrough by impreg-
methods of 13PD are catalytic routes that use oil derivatives nating several acidic supports with tungsten oxide and plati-
such as ethylene oxide or acrolein as starting material. Ethyl- num (Table 2, entries 2–7). These catalysts were tested using
ene oxide is converted to 13PD by subsequent hydroformyla- 1,3-dimethyl-2-imidazolidinone (DMI) as solvent, which is con-
tion and hydrogenation, whereas acrolein is subsequently hy- sidered to be more stable, polar, and aprotic than sulfolane.
drated and hydrogenated.[48] It is also possible to convert glyc- These acidic supports all yielded 13PD with selectivities be-
1024 www.chemsuschem.org 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2011, 4, 1017 – 1034
Renewable Chemicals: Dehydroxylation of Glycerol and Polyols
tween 26 and 39 %. TiO2 gave the highest selectivity (but only EtOH/H2O, DMI/EtOH and DMI/H2O were tested as binary
17 % glycerol conversion), while ZrO2 stood out with a glycerol solvents (Table 2, entries 16 –18). Interestingly, the solvents
conversion of 86 %, thereby showing impressive conversion containing DMI showed a synergistic effect for 13PD selectivity.
and selectivity compared to Chaminands results.[51] It could be increased to 29 and 35 % using EtOH and H2O as
This promising lead was followed up by impregnating differ- the second solvent, respectively. On the other hand, the con-
ent hydrogenation metals on WO3/ZrO2 support. 13PD selectiv- version increased (to 46 %) whenever EtOH was present in the
ities ranged from 5 to 28 % in the order Pt > Pd > Ir > Ru > Rh, binary solvent. Another interesting finding was the decrease of
while both Pt and Rh excelled with a glycerol conversion of 12PD selectivity upon the presence of H2O in the binary sol-
86 % (Table 2, entries 7–11).[51] Gong et al. used the same Pt/ vent. This could increase the 13PD/12PD ratio up to 4.[52]
WO3/ZrO2 catalyst and examined the effect of the solvent It seems that the initial finding of Chaminand that sulfolane,
(Table 2, entries 12–15). Sulfolane and DMI were used as polar or another aprotic polar solvent, is necessary for high 13PD/
aprotic solvents and EtOH and H2O were used as polar protic 12PD ratio is not general, since high ratios are also obtained in
solvents. It was demonstrated that aprotic solvents were not the absence of these solvents. The absence of H2O can in-
necessary for high 13PD selectivity. On the contrary, the aprotic crease glycerol conversion due to beneficial equilibrium condi-
solvents produced more 12PD than 13PD, while the protic sol- tions, but high 13PD selectivities have been shown using H2O
vents produced 13PD at higher selectivities (23 and 26 %). The or EtOH. It is likely that use of sulfolane was inspired by Bullock
aprotic solvents showed comparable conversions (33–34 %) et al. They used sulfolane because their homogeneous cata-
but were outperformed by EtOH (38 %). Conversion of glycerol lysts were not stable in H2O.[53] However, this is no longer im-
in water was lagging (25 %), which can be explained by the portant when the switch to heterogeneous catalysts is made.
formation of H2O during the reaction.[52] Instead, results suggest that a protic solvent improves the re-
action towards 13PD. This might be caused by facilitating a
Entry Catalyst Additive Additive/ Solvent Reactor P T TOF[a] Conversion Selectivity Selectivity Yield of 13PD/ Ref.
metal type [bar] [K] [h 1] [%] to 13PD [%] to 12PD [%] 13PD [%] 12PD
ratio ratio
1 Rh/C H2WO4 10 Sulfolane batch 80 453 0.1 32.0 12.0 6.0 3.8 2.0 [5]
2 Pt/WO3/TiO2 WO3 2.9 DMI batch 80 443 1.1 16.9 38.5 42.0 6.5 0.9 [51]
3 Pt/WO3/HY WO3 8.6 DMI batch 80 443 1.2 25.9 27.8 34.4 7.2 0.8 [51]
4 Pt/WO3/Al- WO3 8.6 DMI batch 80 443 1.3 27.8 27.0 25.2 7.5 1.1 [51]
MCM-41
5 Pt/WO3/SiO2- WO3 8.6 DMI batch 80 443 1.8 42.2 26.1 27.5 11.0 0.9 [51]
Al2O3
6 Pt/WO3/Al2O3 WO3 8.6 DMI batch 80 443 2.2 43.9 30.1 25.1 13.2 1.2 [51]
7 Pt/WO3/ZrO2 WO3 8.6 DMI batch 80 443 4.0 85.8 28.2 14.6 24.2 1.9 [51]
8 Pd/WO3/ZrO2 WO3 8.6 DMI batch 80 443 0.8 24.0 19.6 27.5 4.7 0.7 [51]
9 Ir/WO3/ZrO2 WO3 8.6 DMI batch 80 443 0.5 21.8 14.2 30.7 3.1 0.5 [51]
10 Ru/WO3/ZrO2 WO3 8.6 DMI batch 80 443 0.6 46.7 7.3 19.5 3.4 0.4 [51]
11 Rh/WO3/ZrO2 WO3 8.6 DMI batch 80 443 0.7 86.4 4.7 32.6 4.1 0.1 [51]
12 Pt/WO3/ZrO2 WO3 8.6 DMI batch 55 443 1.9 32.5 15.2 18.2 4.9 0.8 [52]
13 Pt/WO3/ZrO2 WO3 8.6 Sulfolane batch 55 443 0.8 33.8 5.3 14.6 1.8 0.4 [52]
14 Pt/WO3/ZrO2 WO3 8.6 EtOH batch 55 443 2.6 38.2 23.0 13.6 8.8 1.7 [52]
15 Pt/WO3/ZrO2 WO3 8.6 H2O batch 55 443 2.3 24.7 25.7 15.0 6.3 1.7 [52]
16 Pt/WO3/ZrO2 WO3 8.6 DMI-H2O batch 55 443 4.2 31.6 34.9 8.7 11.0 4.0 [52]
17 Pt/WO3/ZrO2 WO3 8.6 DMI- batch 55 443 4.6 45.6 29.3 18.9 13.4 1.6 [52]
EtOH
18 Pt/WO3/ZrO2 WO3 8.6 EtOH- batch 55 443 3.3 45.7 21.2 8.0 9.7 2.7 [52]
H2O
19 Pt/WO3/ZrO2 WO3 8.6 H2O continuous 40 403 4.0 70.2 45.6 2.6 32.0 17.8 [54]
20 Pt/WO3/TiO2/ WO3/TiO2 2.1[b] H2O batch 55 453 2.8 15.3 50.5 9.2 7.7 5.5 [55]
SiO2
21 Cu-STA/SiO2 STA 0.033 – continuous 5.4 483 0.2 83.4 32.1 22.2 26.8 1.4 [56]
22 Rh/SiO2 Amberlyst – H2O batch 80 393 1.1 14.3 9.8 26.0 1.4 0.4 [57]
15
23 Rh-ReOx/SiO2 ReOx 0.5 H2O batch 80 393 17.3 79.0 14.0 41.5 11.9 0.3 [58, 59]
24 Rh-MoOx/SiO2 MoOx 0.0625 H2O batch 80 393 4.3 46.0 6.0 32.1 2.8 0.2 [58]
25 Rh-WOx/SiO2 WOx 0.125 H2O batch 80 393 6.0 34.0 11.3 43.2 3.8 0.3 [58]
26 Ir-ReOx/SiO2 ReOx and 1 H2O batch 80 393 12.0 50.0 49.0 10.0 24.5 4.9 [60]
H2SO4
27 Pt-Re/C Re 1 H2O batch 40 443 11.9 20.0 34.0 33.0 6.8 1.0 [61]
28 Pt-Re/C Re 1 H2O batch 40 443 5.7 45.0 29.0 27.0 13.1 1.1 [61]
ChemSusChem 2011, 4, 1017 – 1034 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 1025
J. ten Dam and U. Hanefeld
proton transfer from the (solid) acid to the secondary alcohol, rosity was increased by subsequently impregnating TiO2, WO3,
which can then be eliminated. The polar character of the sol- and Pt on SiO2. This increased the 13PD selectivity (51 %) and
vents is useful in stabilizing a charged intermediate. Using doubled catalyst activity (conversion 15 %) (Table 2,
aqueous glycerol needs the initial elimination to work against entry 20).[55] It was found that TiO2 was responsible for a good
equilibrium. However, this can be overcome by swift reduction dispersity of the platinum particles while the WO3 provided
of the formed double bond. This can be achieved by active the Brønsted acidic sites, necessary for 13PD selectivity.
catalysts and using favorable hydrogenation conditions. That is Huang et al. used the heteropoly acid silicotungstic acid
moderate temperatures, since hydrogenation is an exothermic (STA) as the tungsten source for their hydrogenolysis catalyst.
reaction. This superacid was impregnated onto SiO2 to give STA/SiO2. In
a subsequent step, copper was impregnated, to introduce the
hydrogenation metal. A vapor phase reaction is necessary
3.2.4 Additives since STA is soluble in H2O and would wash out of the catalyst
in case aqueous glycerol was used. This Cu-STA/SiO2 catalyst
Tungsten was tested in a vapor phase fixed bed reactor and gave high
Qin et al. also used Pt/WO3/ZrO2 as a catalyst. Using a fixed- conversion (83 %) and good 13PD selectivity (32 %).[56] Howev-
bed reactor they were able to obtain both high conversion er, the 13PD/12PD ratio was much lower (1.4) compared to the
(70 %) and good 13PD selectivity (46 %) using aqueous glycerol previous catalyst, but is still very impressive for the abundantly
at only 403 K (Table 2, entry 19).[54] The authors ascribe the low available copper catalyst (Table 2, entry 21).
reaction temperature to the ability of the catalyst to activate
hydrogen as proton and hydride. First, hydrogen is homolyti- Rhenium
cally split into hydrogen atoms (1, Figure 2), which can spill-
over onto the WO3/ZrO2 surface (2, Figure 2). Here the hydro- In an initial screening by Furikado et al., Rh/SiO2 was found to
gen atom can donate an electron to a Lewis acidic site, gener- give most hydrogenolysis products from 12 catalysts tested
ating a proton (3, Figure 2). This proton can be transferred to (Rh, Ru, Pt, and Pd on SiO2, Al2O3, and C) at a relatively low
the substrate alcohol and a second hydrogen atom, acting as temperature (393 K). Al2O3 was not effective under the condi-
an acid, combines with the electron to form a hydride (4, tions used. This was due to more demanding pre-reducing
Figure 2), stabilized on the Lewis acid site. This hydride is then conditions of Al2O3 supported catalysts.[57] The addition of Am-
finally used as a reductant.[62, 63] This hypothesis is supported berlyst 15 improved the catalytic activity of Rh/SiO2. Earlier, the
by NH3 chemisorption measurements using supports that were same group established this enhancing effect of the sulfonic
calcined at different temperatures. Increasing the calcination acid resin for Ru/C.[28] However, so far both the Ru/C and Rh/
temperature leads to higher acidity, resulting in higher conver- SiO2 catalyst are more selective for 12PD, even though Rh/SiO2
sion.[54] showed 10 % 13PD selectivity (Table 2, entry 22).[57] Interesting-
The high 13PD selectivity can also be explained by this ly, a degradation study showed that 13PD is dehydrated over
proton and hydride transfer mechanism over Pt/WO3/ZrO2, Ru/C, while this is limited over Rh/SiO2, which opens up new
since protonation of secondary alcohols is preferred over pri- opportunities for a selective 13PD catalyst.[57]
mary ones. This results in an excellent 13PD/12PD ratio To study the effect of tungsten, molybdenum, and rhenium
(Table 2, entry 19).[54] Another reason for the high 13PD selec- as additives, these metals were impregnated onto Rh/SiO2. All
tivity could be the use of a continuous flow reactor. This will three additives increase activity, but this is most pronounced
limit the degradation of 13PD formed, thereby increasing the for rhenium. Both rhenium and tungsten increase 13PD selec-
yield. tivity, while this effect is not observed for molybdenum con-
Gong et al. found that a Pt/WO3/TiO2 catalyst showed good taining catalysts (Table 2, entries 23 to 25).[58, 59]
selectivity towards 13PD (44 %). However, activity was lagging Due to both activity and selectivity enhancement of the cat-
due to the non-porous character of the TiO2 support. The po- alyst by ReOx, the Rh-ReOx/SiO2 catalyst was characterized in
more detail. EXAFS analysis revealed that Re is present as Re7+
on the calcined catalyst, while the reductive pre-treatment re-
duced rhenium to an oxidation state of Re2+ to Re2.5+. This pre-
treatment also resulted in a direct contact between Re and Rh
and it is suggested that ReOx clusters are in close contact to
Rh particles.[58]
The authors were able to increase the 13PD selectivity tre-
mendously by impregnating rhenium on Ir/SiO2. However,
some additional sulfuric acid was needed, possibly because of
the lower hydrogenation activity of iridium. This is unexpected,
since the relatively low operating temperature suggests a
direct hydrogenolysis involving the ReOx species, while the sul-
Figure 2. Homolytic cleavage of hydrogen on platinum and subsequent furic acid induces an elimination mechanism, which does not
spillover. show 13PD selectivity.[64] Upon addition of sulfuric acid the
1026 www.chemsuschem.org 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2011, 4, 1017 – 1034
Renewable Chemicals: Dehydroxylation of Glycerol and Polyols
conversion of glycerol was increased to 80 % at a 13PD selec- served. Another interesting additive with respect to 13PD se-
tivity of 48 %. Initial 13PD selectivity was as high as 68 % and a lectivity is ReOx. Using this oxide, the reaction temperature
satisfying 13PD/12PD ratio of 5 was reached (Table 2, could be lowered to 393 K, suggesting a direct hydrogenolysis
entry 26).[60] mechanism.
Daniel et al. prepared a co-impregnated Pt Re/C catalyst.
High temperature catalyst treatment led to higher rhenium in-
3.3 Glycerol to acrolein
corporation into the platinum particle with minimal metal sin-
tering, which resulted in high 13PD selectivity (34 % selectivity Current industrial acrolein production is based on the oxida-
at 20 % conversion) (Table 2, entry 27 and 28).[61] tion of propene over BiMoOx-based catalysts.[66] Acrolein itself
Tomishige et al. proposed a mechanism how rhenium oxide is mainly used as a precursor for DL-methionine synthesis. This
can promote activity and 13PD selectivity (Scheme 14).[58–60, 65] essential amino acid cannot be synthesized by mammals and
Initially, glycerol is adsorbed as an alkoxide species. Subse- is therefore added to animal feed to accelerate growth. Acrole-
quently, an acidic proton transforms a hydroxyl group in a in production from glycerol is a promising alternative route
leaving group and a hydride, originating from adsorbed hydro- and involves total dehydration of glycerol. Acrolein can be
gen, expels a water molecule. Finally, propanediol is desorbed formed either in the liquid phase or in the gas phase. General-
and the initial catalyst is recovered. At this point it is not clear ly, the gas phase gives higher acrolein yields. The process is
which factor determines either 12PD or 13PD selectivity, but it normally performed in a continuous reactor, which can prevent
is suggested that the size of the ReOx particle plays a role in further reactions of the reactive acrolein. An excellent recent
steric selection.[60] It must be noted that in most examples review on acrolein from glycerol shows that high conversions
where Re was used as an additive, 12PD selectivity is still and selectivities are already obtained using various catalysts,
higher than 13PD selectivity, while switching to iridium the for- reactor types and reaction phases (Table 3, entries 1–8).[67]
mation of 13PD was favored over 12PD formation, reflected in However, a general challenge for efficient catalysts is to de-
the 13PD to 12PD ratio. crease coke formation or circumvent catalyst deactivation in
The formation of 13PD is not as straightforward as it seems. another way. By tuning the pore sizes of the catalyst, the cata-
It is only formed under acidic conditions and in all cases 12PD lyst lifetime can be extended.[68]
formation is observed as a byproduct. In fact, in most exam-
ples where 13PD is formed, 12PD is the major product. There
3.3.1 Reaction mechanism
are a few examples where 13PD is formed as the major prod-
uct and most of these processes use platinum as the hydroge- The acrolein formation pathway closely resembles the dehy-
nation metal and tungsten as additive. When this combination dration-hydrogenation pathway of 13PD formation. Instead of
was used in a continuous reactor a 13PD yield of 32 % could hydrogenating the 3-hydroxypropanal, another hydroxyl group
be reached, while only a minimal 12PD formation was ob- is eliminated, resulting in the stable p-system of acrolein
Scheme 14. Proposed mechanism for ReOx enhanced glycerol conversion and 13PD selectivity.
ChemSusChem 2011, 4, 1017 – 1034 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 1027
J. ten Dam and U. Hanefeld
Entry Catalyst Additive Time on WHSV[a] P T Reactor type Phase Conversion Acrolein sel- Acrolein Ref.
stream [h] [h 1] [bar] [K] [%] ectivity [%] yield [%]
1 STA/SiO2 – 5 n.a. 1 548 continuous gas 100 87.0 87.0 [67]
2 Nd4(P2O7)3 – 8 227[b] 1 593 continuous gas 87.2 79.9 69.7 [67]
3 Gd4(P2O7)3 – 8 227[b] 1 593 continuous gas 88.2 78.9 69.6 [67]
4 Sm4(P2O7)3 – 8 227[b] 1 593 continuous gas 89.7 77.8 69.8 [67]
5 ZSM-5 – n.a. n.a. 1 588 continuous gas 98.3 74.9 73.6 [67]
6 H2SO4 – n.a. n.a. 345 673 continuous supercritical 92.0 80.4 74.0 [67]
7 H2SO4 – n.a. n.a. 345 623 batch liquid 55.0 86.0 47.3 [67]
8 ZnSO4 – n.a n.a. 250 633 continuous liquid 50.0 75.0 37.5 [67]
9 WO3/ZrO2 – 10 80[b] 1 588 continuous gas 100 65.0 65.0 [69]
10 Nb2O5 – 10 80[b] 1 588 continuous gas 88.0 51.0 44.9 [70]
11 Nb2O5-SiO2 – 2 80 1 593 continuous gas 100 65.0 65.0 [71]
12 ZSM-5 – 2 7.2 1 588 continuous gas 93.7 57.4 53.8 [72]
13 TiAl – 10 400[b] 1 588 continuous gas 67.0 52.0 34.8 [73]
14 TiZr – 10 400[b] 1 588 continuous gas 60.0 45.0 27.0 [73]
15 STA/SiO2 – 5 0.6 1 548 continuous gas 98.3 86.2 84.7 [74]
16 PTA/ZrO2 – 10 400[b] 1 588 continuous gas 76.0 71.0 54.0 [75, 76]
17 CsPTA – 1 2.8 1 548 continuous gas 100 98.0 98.0 [7]
18 CsPTA – 5 2.8 1 548 continuous gas 41.0 94.0 38.5 [7]
19 Pd/CsPTA H2 5 2.8 1 548 continuous gas 79.0 96.0 75.8 [7]
20 ZrNbO – 48 0.5 1 573 continuous gas 99.0 72.0 71.3 [77]
21 VOHPO4 O2 10 0.5 1 573 continuous gas 100 66.0 66.0 [78]
22 VPO O2 10 0.5 1 573 continuous gas 100 64.0 64.0 [79]
23 ZSM-5 – n.a. 335 1 623 continuous gas 100 62.1 62.1 [80]
[a] Weight hourly space volume (massglycerol masscatalyst 1 h 1). [b] Gas hourly space volume (Vfeed Vcatalyst 1 h 1).
1028 www.chemsuschem.org 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2011, 4, 1017 – 1034
Renewable Chemicals: Dehydroxylation of Glycerol and Polyols
This effect was also noticed by Tsukuda et al. A series of SiO2 moving bed reactor. In this reactor catalyst and substrate are
supported silicotungstic acids (STA) showed improved perfor- fed simultaneously, however the catalyst regeneration unit and
mance, both in activity and selectivity, when the pore sizes re-feeding unit is absent. This resulted in 62 % selectivity at
where increased from 3 to 10 nm. Their STA/SiO2 with an aver- 100 % conversion, using H-ZSM-5 as a catalyst (Table 3,
age pore size of 10 nm showed an excellent conversion (98 %) entry 23). The advantage of this type of operation is that while
and very high acrolein selectivity (86 %) during the first 5 h of the catalyst is regenerated by burning off the coke, the pro-
reaction (Table 3, entry 15).[74] duced heat is used to maintain the process temperate.[80]
In another paper by Chai et al., the performance of phos- Acidity and porosity are the main parameters that influence
photungstic acid (PTA) on SiO2 and ZrO2 was compared. PTA activity and selectivity of the catalyst. These can be effectively
on ZrO2 showed superior activity and selectivity and was able controlled and high acrolein yields can be obtained. However,
to produce a 54 % yield, even after 10 h on stream. This is ex- the catalysts have only a limited lifetime due to coke formation
plained by the higher stability and dispersion of the PTA on during the reaction. Interestingly, highly selective acrolein cata-
the ZrO2 surface, compared to the SiO2 carrier (Table 3, lysts often consist of a tungsten containing heteropolyacid.
entry 16).[75, 76] These materials show 13PD selectivity in combination with a
PTA can be used as a heterogeneous catalyst by preparing hydrogenation catalyst. This can be explained by the identical
its insoluble cesium salt. Its initial performance is outstanding: initial steps in both acrolein as well as 13PD formation.
98 % yield during the first hour of reaction (Table 3, entry 17).
However, the catalyst is prone to severe deactivation due to
coking. Selectivity, on the other hand, could be maintained 3.4 Glycerol to other products
(Table 3, entry 18). Coking could be delayed by impregnation
3.4.1 Lactic acid
of the CsPTA with a small amount of palladium and co-feeding
with hydrogen. In this way a conversion of 79 % accompanied Most papers on deoxygenation of glycerol concern the forma-
by a selectivity of 96 % could be reached (Table 3, entry 19).[7] tion of either 1,2-propanediol, 1,3-propanediol or acrolein.
However, there are some other interesting possibilities. For in-
stance, in case 1,2-propanediol is produced under alkaline con-
3.3.3 Catalyst deactivation
ditions, lactic acid is often found as a side product.[81, 82]
All catalysts mentioned before suffer from deactivation due to Lactic acid is a widely used chemical in the food, pharma-
coke formation. This is unavoidable due to the acidic nature of ceutical and chemical industries. The demand for lactic acid in-
the catalysts and the elevated temperature. Interestingly, the creases, mainly due to the use of polylactic acid as a biode-
deactivation of a ZrNbO catalyst was very limited compared to gradable polymer. Currently, lactic acid is produced through
impregnated NbOx/ZrO2 catalyst. A high glycerol conversion the fermentation of carbohydrates. However, this process can
and acrolein selectivity could be maintained for over 48 h be more efficient and other, alternative routes should be inves-
(Table 3, entry 20), which was explained by the formation of a tigated.
solid solution of Nb into the ZrO2 due to the ZrNbO synthesis The fact that lactic acid, having an oxidized carbon, is
method.[77] formed under reductive conditions seems somewhat strange
Loading CsPTA with a platinum group metal and co-feeding at first, but the observation that this only occurs under alkaline
hydrogen, as demonstrated in a previous example, is one pos- conditions is a clue to its formation process. This resembles
sibility to readily remove the formed coke from the catalyst. the 1,2-propanediol formation (Scheme 10), but instead of
However, adding precious metal and the introduction of a re- being reduced after dehydration, the intermediate is subjected
ductive atmosphere is not ideal. to a disproportionation via an intramolecular Cannizzaro reac-
Another possibility is to oxidize the formed coke, by adding tion.[83] The metallic catalyst is necessary for the initial dehydro-
oxygen. This was done by Wang et al. over a vanadium phos- genation, which allows lower reaction temperatures compared
phate oxide (VPO) and a vanadium oxide hydrophosphate to the hydrothermal formation of lactic acid (Scheme 16).[84]
(VOHPO4) catalyst. In this case, the oxygen present in the feed However, lactic acid is normally formed under oxidative con-
can also re-oxidize vanadium to its active form. By adding ditions, which do not need high temperatures for dehydrogen-
oxygen, the conversion was increased from 43 % to 100 % and ation.[85] Under oxidative conditions, glycerol is readily oxidized
selectivity from 35 % to 66 % (Table 3, entry 21 and 22). In to glyceraldehyde. The art lies in facilitating the subsequent
theory, acrolein could also be oxidized to acrylic acid, an im- dehydration, which will yield lactic acid, instead of oxidation,
portant monomer in polymer chemistry. However, in this case to yield glyceric acid (Scheme 17).[85]
only small amounts of acrylic acid were formed.[78, 79]
A technological solution for the coking problem would be
3.4.2 Aromatics
an FCC type reactor. In these reactors both catalyst and sub-
strate are continuously fed to the reactor and separated after- In case aromatics are mentioned in combination with biomass,
wards. This allows for catalyst regeneration outside catalysis one immediately thinks of lignin. Lignin is abundant in wood
conditions. This opens up the opportunity to burn off the coke and its amount is only surpassed by cellulose. However, lignin
and then feed the regenerated catalyst to the reactor. This consists of a mix of methoxylated monolignols and needs to
type of operation was simulated by Corma et al. using a be degraded into a multitude of chemicals, before it can be
ChemSusChem 2011, 4, 1017 – 1034 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 1029
J. ten Dam and U. Hanefeld
1030 www.chemsuschem.org 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2011, 4, 1017 – 1034
Renewable Chemicals: Dehydroxylation of Glycerol and Polyols
is a result of a C C bond cleavage, which is an inefficient use separate from water, which facilitates the subsequent upgrad-
of glycerol feedstock and its formation has to be suppressed ing to fuel and chemicals.[102, 103]
to allow for higher propanediol selectivities. For instance, a duel-bed catalytic system was used to con-
The formation of ethylene glycol proceeds via a retro-aldol vert the mono-functional chemical stream from the PtRe/C cat-
condensation, followed by a hydrogenation (Scheme 20).[13] alyst into C7 to C12+ molecules. A CeZrOx catalyst was used for
The formation of ethylene glycol is influenced by the type of ketonization of the carboxylic acid feed, while Pd/ZrO2 was
metal that is used. For instance, higher amounts of ethylene used as an aldol condensation and hydrogenation catalyst. The
glycol are formed upon addition of platinum to a Ni/Al2O3 cat- resulting C C coupled products were finally dehydrated and
hydrogenated over Pt/SiO2-Al2O3 to give diesel-like al-
kanes.[104]
C O bond cleavage and hydrogenation are the re-
Scheme 20. Ethylene glycol formation via retro aldol.
actions that form the basis of aqueous phase hydro-
deoxygenation. Often, sometimes unwanted, C C
alyst.[95] Ethylene glycol formation is also more pronounced on bond scission is also observed. Li and Huber sought to clarify
ruthenium catalysts, while copper catalysts are normally very the reaction pathways in aqueous phase hydrodeoxygenation
selective towards 12PD. These are indications that ethylene over a Pt/SiO2 Al2O3 catalyst by studying these three reaction
glycol can also be formed by a deformylation pathway. types. They found that C O bond cleavage mainly occurs via
dehydration over Brønsted acidic sites while C C bond scis-
sions involve a retro-aldol condensation or decarbonylation
4. Longer Chain Polyols
over Pt metallic surface. By using these three reactions they
A considerable research effort has been directed to the conver- were able to construct a degradation pathway for sorbitol and
sion of glycerol. It is the smallest polyol readily available from they foresee that the product selectivity can be altered by
biomass. Despite its limited size it already offers a plethora of tuning the activity of individual reactions.[105]
possible products. Compared to cellulose, constituting 35–50 % In case sorbitol is treated under alkaline hydrogenating con-
of total biomass, glycerol is only a minor component. Before ditions it is subjected to C C bond scission through a retro-
cellulose can be used as a starting material for chemicals, it aldol reaction and subsequent hydrogenation (Scheme 21) sim-
has to be broken down into its glucose monomers. Current re- ilar to the formation of ethylene glycol.[13] In 1958 Clark report-
search focuses on heterogeneous acidic catalysts for the hy- ed the formation of 12PD, ethylene glycol and glycerol using a
drolysis of cellulose.[96–98] One of the encountered problems is Ni/kieselguhr catalyst and Ca(OH)2 as an additive.[106] Back then,
the crystallinity of cellulose. This order in the cellulose fiber the formation of glycerol was the main objective, while nowa-
hinders the accessibility of the 1,4-glucosidic bond for hydroly- days the formation of both 12PD and ethylene glycol is pre-
sis. ferred.
However, its abundance in biomass is not proportional to Sorbitol can be converted into mainly 12PD using Ni/NaY as
the amount of research focusing on the conversion of cellu- a catalyst (66 % conversion, 62 % 12PD selectivity), while Pt/
lose-derived glucose to chemicals. This is a result of the com- NaY yields primarily glycerol (43 % conversion, 62 % glycerol se-
plexity of glucose compared to glycerol. Besides its additional lectivity). The addition of Ca(OH)2 increases the conversion of
hydroxyl groups, it also has an aldehyde functionality, which sorbitol in both cases (to 75 % and 60 % conversion, respective-
significantly increases the challenge of selective glucose con- ly). It is postulated that the difference in product selectivity is a
version. This challenge is often met by hydrogenating glucose result from other modes of adsorption of sorbitol over the two
to sorbitol, thereby greatly reducing the reaction possibilities. metals.[107]
Employing an acidic catalyst, sorbitol can be converted into Employing a Ru/CNF catalyst (CNF = carbon nanofiber) with
isosorbide via a stepwise dehydration via 1,4-anhydrosorbi- Ca(OH)2 as a promoter, Zhou et al. were able to form ethylene
tol.[99] However, the protons needed for acid catalyzed dehy- glycol, 12PD, and glycerol. The benefits of using CNF instead
dration can also be directly provided by high temperature of normal carbonaceous support are the higher dispersity of
water, thereby avoiding the addition of a separate acidic cata- metal on the carbon surface and the limited amount of micro-
lyst.[100] By combining a reduction catalyst with an acidic cata- pores in CNF, which cause mass transfer limitations.[108, 109] Simi-
lyst, cellulose can also directly be converted into isosorbide, lar conditions can be applied using xylitol as a starting materi-
merging the cellulose hydrolysis, glycose reduction and sorbi- al. This will also yield mainly 12PD, ethylene glycol and glycer-
tol dehydration into one process.[101] ol. However, lactic acid is observed as a major product as well.
A strategy employed by the group of Dumesic is to reduce Sun et al. found that the activity increased using the following
the functionality of sorbitol and glucose through hydrodeoxy- metals: Rh > Pd > Ru > Pt. The support of ruthenium catalysts
genation over a PtRe/C catalyst. PtRe/C is both a deoxygenat- influenced activity as well (TiO2 > ZrO2 > Mg2Al2Ox > Al2O3 > C)
ing and reforming catalyst, providing the hydrogen for hydro- and lactic acid selectivity increased upon increased basicity of
genation reactions. This combination of reactivity yields alka- the support.[110]
nes and a scale of mono-functional chemicals, like mono-alco- Another interesting process is the formation of 5-hydroxy-
hols, heterocycles, ketones and acids. Due to their extensive methylfurfural (HMF) by dehydration of fructose.[111] Riisager
deoxygenation (80 % of initial oxygen removed) they phase demonstrated the conversion of aqueous solutions of fructose
ChemSusChem 2011, 4, 1017 – 1034 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 1031
J. ten Dam and U. Hanefeld
and hydrochloric acid by microwave irradiation. The advantage anion facilitates the conversion of glucose into fructose which
of microwave irradiation lies in swift and precise heating and is then dehydrated to HMF.[115, 116]
could thereby increase the formation rate of HMF, compared Yong et al. showed that the addition of sterically hindered
to thermal heating. The product distribution was comparable carbene ligands, similar to the imidazolium anion of the ionic
for the two heating methods, which proved microwave irradia- liquid, could improve the reaction yield even more. These li-
tion to be an efficient alternative heating method.[112] gands prevent over-coordination, thereby leaving the chromi-
In another paper by the same group, fructose was converted um center in its most active state, yielding 81 % HMF from glu-
into HMF using boric acid as an additive. Boric acid is not suffi- cose.[117]
ciently acidic by itself for fructose dehydration. However, by In a communication Binder et al. described the formation of
forming borate esters with fructose, the reaction mixture is HMF from glucose using dimethyl acetamide together with a
acidified through a shift in equilibrium and HMF is readily halide salt as a solvent, thereby circumventing the use of an
formed. The addition of sodium chloride further improved ionic liquid. They found that the halide played an important
HMF yield. This was ascribed to a salting-out effect in the two- role in the reaction mechanism as a nucleophile, by quenching
phase system. By increasing the extraction of the formed HMF an intermediate oxonium ion in HMF formation (Scheme 22).
it is no longer prone to rehydration due to a shift of the equi- Bromide proved to be most efficient and chromium tribromide
librium.[113] gave a HMF yield of 80 %.118
Obviously, formation of HMF from glucose instead of fruc- Interestingly, they were also able to convert cellulose directly
tose would be preferred from an availability point of view, into HMF. Here, they used additional ionic liquid, to dissolve
since glucose can be generated from cellulose. However, this cellulose. Hydrochloride was added for the hydrolysis of the
calls for the isomerization of glucose into fructose, prior to de- glucoside bonds. Overall, an impressive yield of 54 % HMF
hydration. This isomerization is catalyzed by alkaline sites, from cellulose was obtained.[118]
while the formed fructose is dehydrated to HMF on acidic Another group reported the direct conversion of cellulose
sites. Yan et al. synthesized a SO42 /ZrO2 Al2O3 catalyst that into HMF through the addition of RuCl3. The RuCl3 is able to ef-
bears both alkaline and acidic sites, and were thereby able to ficiently hydrolyse cellulose to glucose, while CrCl2 is essential
directly convert glucose into HMF in a 48 % yield, using DMSO for a smooth conversion of glucose into fructose, which is
as a solvent.[114] then dehydrated to form HMF.[119]
Zhao et al. were able to gener-
ate a remarkable HMF yield of
68 % from glucose, by using
chromium dichloride as a cata-
lyst and an imidazolium-based
ionic liquid as a solvent. The
benefit of using an ionic liquid
as a solvent is twofold. Firstly,
HMF degradation is minimized
by minimizing water interac-
tions. Secondly, and more impor-
tantly, the imidazolium ionic
liquid takes part in the reaction
mechanism (Scheme 22).[115]
Despite extensive catalyst test-
ing, only chromium showed
high HMF yields. This metal is
thought to form a trichloride
anion, with the ionic liquid
cation as a counterion. This Scheme 22. HMF formation from glucose.
1032 www.chemsuschem.org 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2011, 4, 1017 – 1034
Renewable Chemicals: Dehydroxylation of Glycerol and Polyols
ChemSusChem 2011, 4, 1017 – 1034 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim www.chemsuschem.org 1033
J. ten Dam and U. Hanefeld
[38] T. Jiang, Y. X. Zhou, S. G. Liang, H. Z. Liu, B. X. Han, Green Chem. 2009, [81] E. P. Maris, R. J. Davis, J. Catal. 2007, 249, 328.
11, 1000. [82] E. P. Maris, W. C. Ketchie, M. Murayama, R. J. Davis, J. Catal. 2007, 251,
[39] L. Ma, D. H. He, Z. P. Li, Catal. Commun. 2008, 9, 2489. 281.
[40] L. Ma, D. H. He, Top. Catal. 2009, 52, 834. [83] P. P. Pescarmona, K. P. F. Janssen, C. Delaet, C. Stroobants, K. Hou-
[41] M. Akiyama, S. Sato, R. Takahashi, K. Inui, M. Yokota, Appl. Catal. A: thoofd, A. Philippaerts, C. D. Jonghe, J. S. Paul, P. A. Jacobs, B. F. Sels,
Gen. 2009, 371, 60. Green Chem. 2010, 12, 1083.
[42] S. Sato, M. Akiyama, K. Inui, M. Yokota, Chem. Lett. 2009, 38, 560. [84] Z. Shen, F. M. Jin, Y. L. Zhang, B. Wu, A. Kishita, K. Tohji, H. Kishida, Ind.
[43] E. D’Hondt, S. Van de Vyver, B. F. Sels, P. A. Jacobs, Chem. Commun. Eng. Chem. Res. 2009, 48, 8920.
2008, 6011. [85] Y. H. Shen, S. H. Zhang, H. J. Li, Y. Ren, H. C. Liu, Chem. Eur. J. 2010, 16,
[44] D. Roy, B. Subramaniam, R. V. Chaudhari, Catal. Today 2010, 156, 31. 7368.
[45] A. Y. Yin, X. Y. Guo, W. L. Dai, K. N. Fan, Green Chem. 2009, 11, 1514. [86] T. Q. Hoang, X. L. Zhu, L. L. Lobban, D. E. Resasco, R. G. Mallinson,
[46] N. D. Kim, S. Oh, J. B. Joo, K. S. Jung, J. Yi, Korean J. Chem. Eng. 2010, Catal. Commun. 2010, 11, 977.
27, 431. [87] T. Q. Hoang, X. L. Zhu, T. Sooknoi, D. E. Resasco, R. G. Mallinson, J.
[47] L. Ma, D. H. He, Catal. Today 2010, 149, 148. Catal. 2010, 271, 201.
[48] G. A. Kraus, Clean 2008, 36, 648. [88] X. L. Zhu, L. L. Lobban, R. G. Mallinson, D. E. Resasco, J. Catal. 2010,
[49] R. K. Saxena, P. Anand, S. Saran, J. Isar, Biotechnol. Adv. 2009, 27, 895. 271, 88.
[50] P. A. Selembo, J. M. Perez, W. A. Lloyd, B. E. Logan, Biotechnol. Bioeng. [89] T. Q. Hoang, X. L. Zhu, T. Danuthai, L. L. Lobban, D. E. Resasco, R. G.
2009, 104, 1098. Mallinson, Energy Fuels 2010, 24, 3804.
[51] T. Kurosaka, H. Maruyama, I. Naribayashi, Y. Sasaki, Catal. Commun. [90] M. O. Guerrero-Prez, M. A. BaÇares, ChemSusChem 2008, 1, 511.
2008, 9, 1360. [91] V. Calvino-Casilda, M. O. Guerrero-Prez, M. A. BaÇares, Green Chem.
[52] L. F. Gong, Y. L, Y. J. Ding, R. H. Lin, J. W. Li, W. D. Dong, T. Wang, W. M. 2009, 11, 939.
Chen, Chin. J. Catal. 2009, 30, 1189. [92] B. M. Bell, J. R. Briggs, R. M. Campbell, S. M. Chambers, P. D. Gaarenst-
[53] M. Schlaf, P. Ghosh, P. J. Fagan, E. Hauptman, R. M. Bullock, Angew. room, J. G. Hippler, B. D. Hook, K. Kearns, J. M. Kenney, W. J. Kruper,
Chem. 2001, 113, 4005; Angew. Chem. Int. Ed. 2001, 40, 3887. D. J. Schreck, C. N. Theriault, C. P. Wolfe, Clean 2008, 36, 657.
[54] L. Z. Qin, M. J. Song, C. L. Chen, Green Chem. 2010, 12, 1466. [93] E. Santacesaria, R. Tesser, M. Di Serio, L. Casale, D. Verde, Ind. Eng.
[55] L. F. Gong, Y. A. Lu, Y. J. Ding, R. H. Lin, J. W. Li, W. D. Dong, T. Wang, Chem. Res. 2010, 49, 964.
W. M. Chen, Appl. Catal. A: Gen. 2010, 390, 119. [94] R. Tesser, E. Santacesaria, M. Di Serio, G. Di Nuzzi, V. Fiandra, Ind. Eng.
[56] L. Huang, Y. L. Zhu, H. Y. Zheng, G. Q. Ding, Y. W. Li, Catal. Lett. 2009, Chem. Res. 2007, 46, 6456.
131, 312. [95] N. Ueda, Y. Nakagawa, K. Tomishige, Chem. Lett. 2010, 39, 506.
[57] I. Furikado, T. Miyazawa, S. Koso, A. Shimao, K. Kunimori, K. Tomishige, [96] P. L. Dhepe, A. Fukuoka, ChemSusChem 2008, 1, 969.
Green Chem. 2007, 9, 582. [97] R. Rinaldi, F. Schth, Energy Environ. Sci. 2009, 2, 610.
[58] Y. Shinmi, S. Koso, T. Kubota, Y. Nakagawa, K. Tomishige, Appl. Catal. B: [98] R. Rinaldi, F. Schth, ChemSusChem 2009, 2, 1096.
Environm. 2010, 94, 318. [99] P. Sun, D. H. Yu, Y. Hu, Z. C. Tang, J. J. Xia, H. Li, H. Huang, Korean J.
[59] A. Shimao, S. Koso, N. Ueda, Y. Shinmi, I. Furikado, K. Tomishige, Chem. Chem. Eng. 2011, 28, 99.
Lett. 2009, 38, 540. [100] A. Yamaguchi, N. Hiyoshi, O. Sato, M. Shirai, Green Chem. 2011, 13,
[60] Y. Nakagawa, Y. Shinmi, S. Koso, K. Tomishige, J. Catal. 2010, 272, 191. 873.
[61] O. M. Daniel, A. DeLaRiva, E. L. Kunkes, A. K. Datye, J. A. Dumesic, R. J. [101] G. F. Liang, C. Y. Wu, L. M. He, J. Ming, H. Y. Cheng, L. H. Zhuo, F. Y.
Davis, ChemCatChem 2010, 2, 1107. Zhao, Green Chem. 2011, 13, 839.
[62] S. Triwahyono, A. A. Jalil, H. Hattori, J. Nat. Gas Chem. 2007, 16, 252. [102] E. L. Kunkes, D. A. Simonetti, R. M. West, J. C. Serrano-Ruiz, C. A. Grt-
[63] S. Triwahyono, T. Yamada, H. Hattori, Appl. Catal. A: Gen. 2003, 242, ner, J. A. Dumesic, Science 2008, 322, 417.
101. [103] R. M. West, E. L. Kunkes, D. A. Simonetti, J. A. Dumesic, Catal. Today
[64] S. Koso, I. Furikado, A. Shimao, T. Miyazawa, K. Kunimori, K. Tomishige, 2009, 147, 115.
Chem. Commun. 2009, 2035. [104] E. I. Grbz, E. L. Kunkes, J. A. Dumesic, Green Chem. 2010, 12, 223.
[65] Y. Amada, S. Koso, Y. Nakagawa, K. Tomishige, ChemSusChem 2010, 3, [105] N. Li, G. W. Huber, J. Catal. 2010, 270, 48.
728. [106] I. T. Clark, Ind. Eng. Chem. 1958, 50, 1125.
[66] G. W. Keulks, L. D. Krenzke, T. M. Notermann, in Advances in Catalysis [107] M. Banu, S. Sivasanker, T. M. Sankaranarayanan, P. Venuvanalingam,
(Eds.: D. D. Eley, H. Pines, P. B. Weisz), Vol. 27, Academic Press, New Catal. Commun. 2011, 12, 673.
York 1979, pp. 183 – 225. [108] L. Zhao, J. H. Zhou, Z. J. Sui, X. G. Zhou, Chem. Eng. Sci. 2009, 65, 30.
[67] B. Katryniok, S. Paul, M. Capron, F. Dumeignil, ChemSusChem 2009, 2, [109] J. H. Zhou, M. G. Zhang, L. Zhao, P. Li, X. G. Zhou, W. K. Yuan, Catal.
719. Today 2009, 147, S225.
[68] W. Suprun, M. Lutecki, T. Haber, H. Papp, J. Mol. Catal. A: Chem. 2009, [110] J. Y. Sun, H. C. Liu, Green Chem. 2011, 13, 135.
309, 71. [111] A. A. Rosatella, S. P. Simeonov, R. F. M. Frade, C. A. M. Afonso, Green
[69] S. H. Chai, H. P. Wang, Y. Liang, B. Q. Xu, Green Chem. 2007, 9, 1130. Chem. 2011, 13, 754.
[70] S. H. Chai, H. P. Wang, Y. Liang, B. Q. Xu, J. Catal. 2007, 250, 342. [112] T. S. Hansen, J. M. Woodley, A. Riisager, Carbohydr. Res. 2009, 344,
[71] N. R. Shiju, D. R. Brown, K. Wilson, G. Rothenberg, Top. Catal. 2010, 53, 2568.
1217. [113] T. S. Hansen, J. Mielby, A. Riisager, Green Chem. 2011, 13, 109.
[72] Y. T. Kim, K. D. Jung, E. D. Park, Microporous Mesoporous Mater. 2010, [114] H. P. Yan, Y. Yang, D. M. Tong, X. Xiang, C. W. Hu, Catal. Commun. 2009,
131, 28. 10, 1558.
[73] L. Z. Tao, S. H. Chai, Y. Zuo, W. T. Zheng, Y. Liang, B. Q. Xu, Catal. Today [115] H. B. Zhao, J. E. Holladay, H. Brown, Z. C. Zhang, Science 2007, 316,
2010, 158, 310. 1597.
[74] E. Tsukuda, S. Sato, R. Takahashi, T. Sodesawa, Catal. Commun. 2007, 8, [116] T. Sthlberg, M. G. Sørensen, A. Riisager, Green Chem. 2010, 12, 321.
1349. [117] G. Yong, Y. G. Zhang, J. Y. Ying, Angew. Chem. 2008, 120, 9485; Angew.
[75] S. H. Chai, H. P. Wang, Y. Liang, B. Q. Xu, Green Chem. 2008, 10, 1087. Chem. Int. Ed. 2008, 47, 9345.
[76] S. H. Chai, H. P. Wang, Y. Liang, B. Q. Xu, Appl. Catal. A: Gen. 2009, 353, [118] J. B. Binder, R. T. Raines, J. Am. Chem. Soc. 2009, 131, 1979.
213. [119] B. Kim, J. Jeong, D. Lee, S. Kim, H. J. Yoon, Y. S. Lee, J. K. Cho, Green
[77] P. Lauriol-Garbay, J. M. M. Millet, S. Loridant, V. Bellire-Baca, P. Rey, J. Chem. 2011, 13, 1503.
Catal. 2011, 280, 68.
[78] F. Wang, J. L. Dubois, W. Ueda, J. Catal. 2009, 268, 260.
[79] F. Wang, J. L. Dubois, W. Ueda, Appl. Catal. A: Gen. 2010, 376, 25.
[80] A. Corma, G. W. Huber, L. Sauvanaud, P. O’Connor, J. Catal. 2008, 257,
163. Received: March 25, 2011
1034 www.chemsuschem.org 2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim ChemSusChem 2011, 4, 1017 – 1034