Synthesis of jet fuel range high-density polycycloalkanes with polycarbonate waste

Article abstract of DOI:10.1039/c9gc01627a

Jet fuel range high-density polycycloalkanes were first synthesized with polycarbonate waste by a two-step method which was conducted under mild conditions. In the first step, polycarbonate waste was converted to bisphenol by methanolysis. Subsequently, bisphenol was further converted to polycycloalkanes by hydrodeoxygenation.

Full text of DOI:10.1039/c9gc01627a

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Synthesis of jet fuel range high-density polycycloalkanes with
polycarbonate waste
Received 00th January 20xx,
Accepted 00th January 20xx
Hao Tang,a,b Yancheng Hu,a Guangyi Li,a Aiqin Wang,a,c,d Guoliang Xu,a Yu Cong,a Xiaodong Wang,a
Tao Zhanga,d and Ning Li,*a,c
DOI: 10.1039/x0xx00000x
This paper is dedicated to the 70th anniversary of Dalian Institute of Chemical Physics, Chinese
Academy of Sciences.
www.rsc.org/
Jet fuel range high-density polycycloalkanes were first synthesized there is no report about the production of high-density
with polycarbonate wastes by a two-step method which was aviation fuel with waste plastics.
conducted under mild conditions. In the first step, polycarbonate
Polycarbonate (PC) is a leading engineering plastic which has
waste was converted to bisphenol by methanolysis. Subsequently, a high annual production capacity (~6 million tons).6 Due to its
the bisphenol was further converted to polycycloalkanes by excellent resistance to high temperature and impact, good
hydrodeoxygenation.
ductility and optical clarity, PC has been widely used in digital
storage media, electronics, construction, containers, medical,
automotive industry, protective glasses, etc..7 However, the
great demand of PCs also leads to plenty of PC waste.
Traditional waste treatments such as landfill or incineration
are not environmentally sustainable because bisphenol A, the
Due to the great social concern about the sustainable
development and environment problems, the exploration of
new organic carbon resources as the substitutes for fossil
energies has gained tremendous attention.1 Plastics are a
family of organic polymers which are widely used in our life.
Since 1950s, about 6.3 billion tons of plastics have been
produced worldwide. However, only a small part of plastic was
recycled (9%) or incinerated (12%).2 Most of them were
discarded after usage. Moreover, the chemical structure of
most plastics renders them resistant to bio-degradation, which
will lead to a lot of environmental and ecological problems.3
From the point views of environment protection and full
utilization of resources, it is imperative to develop some
efficient catalytic technologies for the catalytic conversion
valorization of waste plastics to great demanded fuels and/or
bulk chemicals.4 Polycycloalkanes are major components of
advanced jet fuels which have been widely used for aircraft
and propulsion.5 Compared with conventional jet fuels,
polycycloakanes have higher density (or volumetric heat value).
Therefore, the utilization of polycycloalkanes can significantly
increase the flight range, payload and speed of aircraft without
change the volume of oil tank. To the best of our knowledge,
major monomer of PC, has been considered as
a
xenoestrogen.8 As the result, the chemical conversion of PC
has drawn a lot of attention in recent years. So far, most of
reported work was concentrated on the pyrolysis,9
hydrolysis,10 alcoholysis,6, 11 aminolysis12 and glycolysis13 of PC
wastes. In this work, it was first reported that jet fuel range
polycycloalkanes can be selectively produced by the
alcoholysis of PC waste, followed by hydrodeoxygenation. The
polycycloalkanes as obtained have high density. As a potential
application, they can be used as high-density aviation fuels or
additives to increase the volumetric heat values of current jet
fuels. The strategy for this process is illustrated in Scheme 1.
R
R'
R
R'
O
CH3OH
O
+
H3CO
OCH3
Methanolysis
O
O
HO
OH
n
Hydrodeoxygenation
(HDO)
H2
R or R' = CH3 or H
R
R'
R
R'
+
+ isomers
Scheme 1. Strategy for the synthesis of jet fuel range C13-C15
a. CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian
Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
E-mail: lining@dicp.ac.cn.
polycycloalkanes with PC wastes.
First of all, we investigated the alcoholysis and glycolysis of
PC waste. It was noticed that these reactions can even take
place in the absence of catalyst. Based on our analysis (see
Figure S1 in supporting information, both bisphenol A (i.e. 1A
in Scheme 2) and corresponding carbonates were identified as
the products. The reaction pathways were proposed in
b. University of Chinese Academy of Sciences, Beijing 100049, China.
c. Dalian National Laboratory for Clean Energy, Dalian 116023, China.
d. State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian 116023, China.
Electronic Supplementary Information (ESI) available: [details of the preparation,
activity tests and characterization of catalysts. GC chromatograms, mass
spectrograms and NMR spectra of the products]. See DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
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Scheme 2. From it, we can see that the 1A as obtained has increment of initial substrate dosage will lead to VtiheweAdrteicclerOenalisnee
DOI: 10.1039/C9GC01627A
bicyclic carbon chain structure and proper carbon chain length of PC conversion and 1A yield.
for jet fuel. Therefore, it can be potentially used as a precursor
for high-density jet fuel. The carbonates which were generated
100
accompanying with 1A can be used as feedstocks for the
production of many chemicals, solvents and the fuel additives
to increase the octane number or oxygen content of
gasoline.14 Among the investigated alcohols and polyols,
methanol exhibited the highest reactivity for the degradation
of PC waste (see Figure 1). Under the investigated conditions
(453 K, 3 h), the PC waste was completely converted, high yield
(~90%) of 1A was achieved in the absence of any catalyst.
Taking into the consideration of lower price of methanol, we
believe it is a promising reactant to produce 1A from PC
wastes.
Conversion of PC waste
Yield of 1A
80
60
40
20
0
413
433
Reaction temperature (K)
473
453
O
CH3OH
+
H3CO
OCH3
453 K, 3 h
HO
OH
1A
Figure 2. Conversion of PC waste and the yield of 1A in methanol as the
function of reaction temperature. Reaction conditions: 3 h; 1 g PC waste
and 40 mL methanol were used for each test.
O
OH
+
453 K, 3 h
O
O
HO
OH
1A
O
HO
O
O
n
100
80
OH
O
O
O
+
+
PC waste
453 K, 3 h
HO
OH
1A
1A
OH
HO
O
O
O
Conversion of PC waste
60
453 K, 3 h
HO
OH
Yield of 1A
Scheme 2. Reaction pathways for the alcoholysis or glycolysis of PC waste.
40
Conversion of PC waste
Yield of 1A
20
0
100
80
60
40
20
0
9
2
4
1
5
6
3
8
7
Mass of substrate (g)
Figure 3. Conversion of PC waste and the yield of 1A in methanol as the
function of initial substrate dosage. Reaction conditions: 453 K, 3 h; 40 mL
methanol were used for each test.
Subsequently, we explored the synthesis of polycycloalkane
by the HDO of 1A. First, we compared the performances of
activated carbon loaded noble metal catalysts for this reaction.
From Figure 4, it was noticed that Pt/C has significantly higher
activity than those of Pd/C and Ru/C for the hydrogenation of
Ethanol
1,2-Propylene
glycol
Ethylene
glycol
Methanol
Figure 1. Conversions of substrate and the yields of 1A from the alcoholysis 1A. According to the characterization results illustrated in
or glycolysis of PC waste. Reaction conditions: 453 K, 3 h; 1 g PC waste and Table S1 in supporting information, no clear relationship was
40 mL alcohol (or polyol) were used for each test.
observed between the activities of catalysts and their specific
surface areas, average metal particle sizes or metal dispersions.
Therefore, we think that the excellent performance of Pt/C
should be attributed to its higher activity for the
hydrogenation of bezene ring in aromatic compounds.15 Based
on our analysis (see Figures S2-S4 in supporting information),
The effects of reaction conditions on the conversion of PC
waste and 1A yield were studied. From Figure 2, it was noticed
that the PC waste conversion and 1A yield increased with the
increment of reaction temperature then stabilized when the
reaction temperature was higher than 453 K. This result means
that high reaction temperature is favorable for the
methanolysis of PC waste. With the increase of initial substrate
dosage from 1 g to 7 g, no evident decrease of PC waste
conversion or 1A yield was observed (see Figure 3). This is
advantageous in real application. However, the further
4,4'-(propane-2,2-diyl)dicyclohexanol
and
4-(2-
cyclohexylpropan-2-yl)cyclohexanol (i.e. 1B and 1C in Scheme
3) from the total hydrogenation and partial HDO of 1A were
identified as the major products. No propane-2,2-
diyldicyclohexane (i.e. 1D in Scheme 3) from the complete
2 | J. Name., 2012, 00, 1-3
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HDO of 1A was detected in the product even after we previous work of Huber et al.,16 the dehydration followed by
View Article Online
DOI: 10.1039/C9GC01627A
increased the reaction temperature from 373 K to 453 K (see hydrogenation has been found to be the major pathway for
Figure 5).
the HDO of biomass derived oxygenates. Among the
investigated zeolites (see Figure 6), the H-β exhibited the best
promotion effect. This can be rationalized by two reasons: 1)
Pore size. As we can see from the structures of different
zeolite supports illustrated in Figure S10 in supporting
information, H-ZSM-5 zeolite only has 10-membered pore. In
contrast, the H-β zeolite has 12 members pores in three
dimensions whereas H-MOR has 12 member pores only in one
dimension (8 members in another dimension).17 The bigger
pore size of H-β is beneficial for mass transfer that is very
important for the liquid-phase reactions at low temperature. 2)
Acidity. Based on the NH3-TPD and NH3 chemisorption results
shown in Figure 7 and Table 1, the H-β zeolite has higher acid
strength and acid amount than those of H-MOR. This may be
another reason why the H-β zeolite is better than the H-MOR
for the HDO of 1A. Besides 1D, some C7-C8 cycloalkanes were
also obtained from the HDO of 1A. According to literature,18
the C7-C8 cycloalkanes may generated from the hydrocracking
of 1D which is easier to occur at the highly branched carbon
(this is because the alkyl group has electron donation effect
which can increase the stability of carbonium ion). As a
potential application, these cycloalkanes can be blended into
the current gasoline or jet fuel.
H2
H2
Hydrodeoxygenation
OH
Hydrogenation
OH
HO
1C
HO
OH
1A
1B
H2
Hydrodeoxygenation
H2, Pt/C + H-zeolite
Hydrodeoxygenation
+ isomers
1D
Scheme 3. Reaction pathways for the hydrodeoxygenation (HDO) of 1A.
Reaction conditions: 373-453 K, 3 MPa H2, 1 h; 5 mmol 1A, 40 mL
cyclohexane, 0.04 g Pt/C catalyst and 0.5 g (or 0 g) zeolite were used for
each test.
Conversion of 1A
Yield of 1C
Yield of 1B
Yield of 1D
100
80
60
40
20
0
1A conversion
Yield of 1D
Yield of 1B
Yield of C7-C8 cycloalkanes
Yield of 1C
Pt/C
Pd/C
Ru/C
100
80
60
40
20
0
Figure 4. Conversions of 1A and the yields of products over the M/C (M = Pt,
Pd, Ru) catalysts. Reaction conditions: 373 K, 3 MPa H2, 1 h; 5 mmol 1A, 40
mL cyclohexane, 0.04 g catalyst were used for each test.
100
80
Conversion of 1A
60
Yield of 1B
Yield of 1C
Pt/C
Pt/C+H-MOR Pt/C+H-ZSM-5 Pt/C+H-
40
20
0
Yield of 1D
Figure 6. Conversion of 1A and the yields of products under the co-catalysis
of Pt/C and acidic zeolites. Reaction conditions: 453 K, 3 MPa H2, 1 h; 5
mmol 1A, 40 mL cyclohexane, 0.04 g Pt/C and 0.5 g zeolite were used for
each test.
Table 1. Specific surface areas (SBET), acid mounts and pore sizes of the
360
380
400
420
440
460
zeolites used in this work.
Reaction temperature (K)
Zeolite
H-MOR
H-ZSM-5
H-β
SBET
(m2 g-1)a
Acid amount
(mmol g-1)b
0.79
Pore size
(nm)c
Reference
Figure 5. Conversion of 1A and the yield of products over the Pt/C as the
function of reaction temperature. Reaction conditions: 3 MPa H2, 1 h; 5
mmol 1A, 40 mL cyclohexane, 0.04 g Pt/C catalyst were used for each test.
17
413
0.65×0.7
0.26×0.57
0.51×0.55
0.53×0.56
0.66×0.67
0.56×0.56
17, 19
19
To overcome this problem, some acidic zeolites (such as H-
MOR, H-ZSM-5 and H-β) were introduced as the co-catalysts
for the HDO of 1A. As we expected, the presence of acidic
zeolites significantly increased the carbon yield of 1D from the
complete HDO of 1A (see Figures S5-S9 in supporting
information). This can be explained because the presence of
acid sites promotes the dehydration of 1B and 1C. In the
311
482
0.99
0.68
a Measured by N2-physisorption. b Measured by chemisorption. c The values
reported in literature.
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View Article Online
DOI: 10.1039/C9GC01627A
(a)
H-MOR
100
80
60
Conversion of 1A
Yield of 1B
Yield of 1C
Yield of 1D
400
500
600
700
700
700
800
Temperature (K)
40
(b)
H-ZSM-5
Yield of C7-C8 cycloalkanes
20
0
1
2
3
4
400
500
600
800
Reaction time (h)
Temperature (K)
Figure 9. Conversion of 1A and the yields of products over the Pt/C + H-β
catalyst as the function of reaction time. Reaction conditions: 413 K, 3 MPa
H2; 5 mmol 1A, 40 mL cyclohexane, 0.04 g Pt/C and 0.5 g H-β zeolite were
used for each test.
(c)
H-
As we know, 1A is produced by the condensation of acetone
and phenol. Acetone can be obtained by the acetone-butanol-
ethanol fermentation of lignocellulose.21 Phenol can be
derived from lignin.22 Therefore, this work provides a new
400
500
600
800
Temperature (K)
Figure 7. NH3-TPD profiles of the H-MOR (a), H-ZSM-5 (b) and H-β (c) method for the production of renewable high-density aviation
zeolites.
fuel with lignocellulose. As the analogues of 1A, 4,4'-(ethane-
1,1-diyl)diphenol and 4,4'-methylenediphenol (i.e. 2A and 3A
in Figure 10) are two bisphenols which be produced by the
The influences of reaction temperature and reaction time on
the catalytic performance of Pt/C + H-β catalyst were
investigated as well (see Figures 8 and 9). Under the optimized
conditions, high yield (87%) of 1D was achieved. According to
literature,20 this compound has high density (0.92 g mL-1) at
room temperature. Therefore, it can be potentially used as
high-density aviation fuel or additive to improve the
volumetric heat values of current jet fuels.
condensation
of
phenol
with
acetaldehyde
and
formaldehyde23 from the partial oxidation of ethanol and
methane from fermentation of lignocellulose. In real
application, 3A has been widely used as a substitute for 1A.8
As an extension of this work, we also explored the HDO of 2A
and 3A over the Pt/C + H-β catalyst (see Figure 10). To
facilitate the comparison, the experiments were carried out
under the optimized conditions for the HDO of 1A. As we
expected, 2A and 3A were totally converted under the
investigated conditions. High yields of jet fuel range
polycycloalkanes were achieved (see Figure 10). It is very
interesting that tricycloalkanes were also obtained
accompanying with dicycloalkanes when we used 2A and 3A as
the feedstocks (see Figures S11-S16 in supporting information).
The tricycloalkane yield increases with the decrease of methyl
group number in the substrates. This result means that the
presence of alkyl group is unfavorable for the generation of
tricycloalkanes. When 3A was used as substrate, the
tricycloalkane 3F was obtained as major product. This is
advantageous in real application because tricycloalkanes have
higher densities than those of dicycloalkanes (see Table 2).
100
Conversion of 1A
Yield of 1C
Yield of C7-C8 cycloalkanes
Yield of 1B
Yield of 1D
80
60
40
20
0
393
413
Reaction temperature (K)
433
453
Figure 8. Conversion of 1A and the yields of products over the Pt/C + H-β
catalyst as the function of reaction temperature. Reaction conditions: 3
MPa H2, 1 h; 5 mmol 1A, 40 mL cyclohexane, 0.04 g Pt/C and 0.5 g H-β were
used for each test.
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View Article Online
DOI: 10.1039/C9GC01627A
H2
100
+
Pt/C, H-
Conversion of 3A
Yield of 3D
Yield of 3E
HO
OH
1A
+ isomers
1D
+ isomers
1E Yield: 0%
Yield: 87%
80
Yield of 3F
H2
60
+
+
Pt/C, H-
HO
HO
OH
OH
2A
3A
+ isomers
2E Yield: 45%
+ isomers
2D Yield: 52%
40
H2
Pt/C, H-
20
+ isomers
+ isomers
3E Yield: 65%
3D Yield: 25%
0
Figure 10. Results for the HDO of bisphenols over the Pt/C + H-β catalyst.
Reaction conditions: 413 K, 3 MPa H2, 4 h; 5 mmol bisphenol, 40 mL
cyclohexane, 0.04 g Pt/C and 0.5 g H-β zeolite were used for each test.
0
0.1
0.6
0.25
0.4
0.5
Mass of H- (g)
Figure 11. Conversion of 3A and the yield of products over Pt/C + H-β as the
function of H-β dosage. Reaction conditions: 413 K, 3 MPa H2, 4 h; 5 mmol
3A, 40 mL cyclohexane, 0.04 g Pt/C and H-β zeolite were used for each test.
Table 2. Densities and the freezing points of polycycloalkane products.
Polycycloalkane
Density (g mL-1)
Freezing point (K)
Reference
20
0.92
288.6
The effect of reaction time on the catalytic performance of
Pt/C + Hβ was studied as well. Based on the results illustrated
in previous literature25, 26 and Figure 12, the reaction pathways
for the generation of different products from the HDO of 3A
over Pt/C + H-β catalyst was proposed as Scheme 4. As the first
step, one benzene ring of 3A is hydrogenated, which leads to
the generation of 3G. 3G is converted to 3H over the acid sites
which may be generated by the hydrogen spillover of Pt/C.
Subsequently, 3H is hydrogenated to 3F. These three steps are
very fast because neither 3G nor 3H is identified in the HDO
product. Then, the 3F is further hydrodeoxygenated to 3E
under the co-catalysis of Pt/C and H-β. With the extension of
reaction time, 3E may be hydrocraked to 3D and/or its isomers.
As another possibility, 3D may also be directly produced by the
HDO of 3A.
20
24
20
25
0.89
0.96
0.88
0.96
252.1
270.0
254.3
258.0
To get deeper insight into the cyclization during the HDO of
1A, we investigated the influence of H-β dosage on the
catalytic performance of Pt/C + H-β (see Figures 11). In the
absence of H-β zeolite, dodecahydro-1H-fluoren-3-ol (i.e. 3F in
Scheme 4) was obtained as the main product from the
hydrogenation of 3A over the Pt/C catalyst (see Figure 11 and
Figures S17-S18 in supporting information). This result means
that the cyclization can take place even in the absence of H-β.
With the increase of H-β dosage, the 3E yield increased which
can be explained by the HDO of 3E under the co-catalysis of
Pt/C + H-β. The 3E yield reached the maximum when 0.5 g H-β
was used together with Pt/C. With the further increment of H-
β dosage, the 3E yield decreased, while the 3D yield increased.
This can be explained by the further hydrocracking of 3E to 3D
under the co-catalysis of Pt/C + H-β.
100
Conversion of 3A
Yield of 3E
Yield of 3D
Yield of 3F
80
60
40
20
0
2
1
6
0.5
3
4
5
Reaction time (h)
H2
Figure 12. Conversion of 3A and the yields of products over the Pt/C + H-β
catalyst as the function of reaction time. Reaction conditions: 413 K, 3 MPa
H2; 5 mmol 3A, 40 mL cyclohexane, 0.04 g Pt/C and 0.5 g H-β zeolite were
used for each test.
Hydrogenation
Alkylation
HO
OH
OH
HO
OH
3A
3G
3H
H2
Hydrodeoxygenation
H2
Hydrogenation
H2
H2
Hydeodeoxygenation
Hydrocracking
OH
3F
+ isomers
+ isomers
3D
3E
Scheme 4. Reaction pathways for the generation of different products from
the HDO of 3A over the Pt/C + H-β catalyst.
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Conclusions
Jet fuel range polycycloalkanes were selectively synthesized at
high overall yield (~80%) by the methanolysis of PC waste,
followed by the HDO. Methanol was found to be highly
reactive for the alcoholysis of PC waste. In the absence of
catalyst, high yield (~90%) of bisphenol A was achieved from
the methanolysis of PC waste after the reaction was carried
out at 453 K for 3 h. Subsequently, the bisphenol A was further
hydrodeoxygenated to jet fuel range C15 bicycloalkanes under
the co-catalysis of activated carbon loaded noble metal and
acidic zeolites. Among the investigated catalyst systems, the
combination of Pt/C and H-β (denotes as Pt/C + H-β) exhibited
the best performance, which can be rationalized by the high
activity of Pt/C for hydrogenation of benzene ring, the high
pore size and acidity of H-β zeolite. The Pt/C + H-β catalyst is
also applicable for the synthesis of C13-C15 polycycloalkanes
with the bisphenols which can be derived from lignocellulose.
The C13-C15 polycycloalkanes as obtained have higher densities.
As a potential application, they can be used as advanced
aviation fuels or fuel additives to improve the volumetric heat
value of current jet fuels.
2
R. Geyer, J. R. Jambeck and K. L. Law, Science Advances, 2017, 3,
e1700782.
3
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Conflicts of interest
There are no conflicts to declare.
5
6
7
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (no. 21690082; 21776273; 21721004),
DNL Cooperation Fund, CAS (DNL180301), the Strategic
Priority Research Program of the Chinese Academy of Sciences
(XDB17020100, XDA 21060200), the National Key Projects for
Fundamental Research and Development of China
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Table of contents entry
R
R'
R
R'
O
CH3OH
O
+
H3CO
OCH3
Methanolysis
O
O
HO
OH
n
Hydrodeoxygenation
(HDO)
H2
R or R' = CH3 or H
R
R'
R
R'
+
+ isomers
Synthesis of jet fuel range high-density polycycloalkanes with
polycarbonate waste
Hao Tang, Yancheng Hu, Guangyi Li, Aiqin Wang, Guoliang Xu, Yu Cong, Xiaodong Wang, Tao Zhang
and Ning Li*
Jet fuel range high-density C13-C15 cycloalkanes were first synthesized at high overall yield (~80%) with
polycarbonate wastes.