Synthesis of gasoline and jet fuel range cycloalkanes and aromatics from poly(ethylene terephthalate) waste

Article abstract of DOI:10.1039/c9gc00571d

For the first time, gasoline and jet fuel range C₇-C₈ cycloalkanes and aromatics were selectively synthesized by the alcoholysis of poly(ethylene terephthalate) (PET) waste, followed by solvent-free hydrogenation and hydrodeoxygenation (HDO). It was found that methanol is highly reactive for the alcoholysis of PET waste. In the absence of any catalyst, a high yield of dimethyl terephthalate (97.3%) was achieved under mild conditions (473 K, 3.5 h). Dimethyl terephthalate exists as a solid and can be automatically separated from methanol with a decrease in temperature. Subsequently, dimethyl terephthalate was liquefied to dimethyl cyclohexane-1,4-dicarboxylate by hydrogenation over noble metal catalysts. Among the investigated catalysts, Pt/C exhibited the highest activity. Finally, the dimethyl cyclohexane-1,4-dicarboxylate as obtained was further hydrodeoxygenated to C₇-C₈ cycloalkanes and aromatics that can be used as gasoline or additives to improve the densities (or volumetric heat value) and sealabilities of current bio-jet fuels. Bimetallic Ru-Cu/SiO₂ was found to be a promising HDO catalyst. According to the characterization results, the excellent HDO performance of Ru-Cu/SiO₂ can be explained by the formation of smaller Ru-Cu alloy particles during the catalyst preparation. In real applications, dimethyl cyclohexane-1,4-dicarboxylate can also be simultaneously hydrodeoxygenated with biomass derived oxygenates to produce jet fuel with a suitable content of cycloalkanes and aromatics.

Full text of DOI:10.1039/c9gc00571d

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DOI: 10.1039/C9GC00571D
ARTICLE
Synthesis of gasoline and jet fuel range cycloalkanes and
aromatics with poly(ethyleneterephthalate) wastes
Received 00th January 20xx,
Accepted 00th January 20xx
a,b
a,c
a
a
a
a
a
Hao Tang, Ning Li, * Guangyi Li, Aiqin Wang, Yu Cong, Guoliang Xu, Xiaodong Wang and Tao
a,b
Zhang
DOI: 10.1039/x0xx00000x
7 8
For the first time, gasoline and jet fuel range C -C cycloalkanes and aromatics were selectively synthesized by the
alcoholysis of poly(ethyleneterephthalate) (PET) waste, followed by the solvent-free hydrogenation and
hydrodeoxygenation (HDO). It was found that methanol is highly reactive for the alcoholysis of PET waste. In the absence
of any catalyst, high yield of dimethyl terephthalate (97.3%) was achieved under mild conditions (473 K, 3.5 h). The
dimethyl terephthalate exists as solid and can be automatically separated from methanol with the decreasing of
temperature. Subsequently, dimethyl terephthalate was liquefied to dimethyl cyclohexane-1,4-dicarboxylate by the
hydrogenation over noble metal catalysts. Among the investigated catalysts, Pt/C exhibited the highest activity. Finally, the
dimethyl cyclohexane-1,4-dicarboxylate as obtained was further hydrodeoxygenated to C
that can be used as gasoline or additives to improve the densities (or volumetric heat value) and sealabilities of current
bio-jet fuels. Bimetallic Ru-Cu/SiO was found to be a promising HDO catalyst. According to the characterization results,
the excellent HDO performance of Ru-Cu/SiO can be explained by the formation of smaller Ru-Cu alloy particles during
7 8
-C cycloalkanes and aromatics
2
2
the catalyst preparation. In real application, dimethyl cyclohexane-1,4-dicarboxylate can also be simultaneously
hydrodeoxygenated with biomass derived oxygenates to produce the jet fuel with proper contents of cycloalkanes and
aromatics.
Poly(ethylene terephthalate) (PET) is a widely used plastic.
Due to its excellent mechanical and thermal properties, PET is
Introduction
Energy and environment are two of the most concerned issues
we are facing nowadays. With the declining of fossil energy,
the exploration of new organic carbon resource as substitute
5
produced in great scale (> 50 million tons per year). Because
PET is highly resistant to biological degradation, the recycling
of PET wastes by chemical methods has drawn tremendous
attention in recent years.7, 8 So far, most of reported processes
were concentrated on the degradation of PET to terephthalic
1
2
for the production of fuels and chemicals has become a
research hotspot. As one of the options, plastics have been
produced in industrial scale with the feedstocks mainly derived
from petroleum. The global annual production of plastics was
estimated to reach 334.83 million tons by 2020.3 These
materials have been widely used in many areas (such as
packaging, textile industry, construction, etc.). Due to the lack
of efficient technology, only a small part (~14%) of plastics is
recycled.4, 5 Most of plastics are discarded or directly burnt
after the usage, which brings a lot of environmental problems.
From the point views of energy conservation and
environmental protection, it is imperative to develop new
technologies for the utilization of the waste plastics as the
feedstocks for the production of great demanded fuels and
bulk chemicals.6
9
acid or its esters (such as bis(hydroxyalkyl) terephthalate
(
BHET))10 and the further hydrogenation of these compounds
to or 1,4-
1,4-cyclohexanedicarboxylates11
cyclohexanedimethanol (1,4-CHDM).12 Cyclic hydrocarbons
including cycloalkanes and aromatics) are important
(
components of gasoline and jet fuel (two most demanded
transportation fuels). Compared with chain alkanes, cyclic
hydrocarbons have relatively higher octane-numbers, densities
(or volumetric heat values) and sealabilities. Taking into
consideration of the special chemical structure of PET (see
Scheme 1), we think that it can be used as a potential
feedstock for the production of gasoline and jet fuel range
cyclic hydrocarbons. To the best of our knowledge, there is no
report about this.
7 8
In this work, gasoline and jet fuel range C -C cycloalkanes
a.
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, No. 457
Zhongshan Road, Dalian 116023, China. E-mail: lining@dicp.ac.cn
University of Chinese Academy of Sciences, 19 A Yuquan Road, Shijingshan
District, Beijing 100049, China.
and aromatics were first synthesized by the methanolysis of
PET waste, followed by the hydrogenation of dimethyl
b.
terephthalate
dicarboxylate
(DMT)
(DMCD)
to
dimethyl
and
cyclohexane-1,4-
subsequent
Dalian National Laboratory for Clean Energy, No. 457 Zhongshan Road, Dalian
16023, China.
the
1
Electronic Supplementary Information (ESI) available: [Characterization of M/C hydrodeoxygenation (HDO) of DMCD under solvent-free
catalysts. GC chromatograms, photos, mass spectrograms of the hydrogenation
and hydrodeoxygenation products]. See DOI: 10.1039/x0xx00000x
conditions. The strategy for this process was illustrated in
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Scheme 1. As we know, most of current bio-jet fuels are
Journal Name
Hydrogen-temperature programmed reduction (H -TPR)
2
View Article Online
composed of chain alkanes. Compared with conventional jet tests of catalysts were conducted D bO yI : 10 a. 103 M9 / iCc 9r Go mC 0 e0 r5i 7t i1 cD s
fuel (a mixture of chain alkanes, cycloalkanes and aromatics), AutoChem II 2920 Automated Catalyst Characterization
these bio-jet fuels have lower densities (or volumetric heat System. Before the tests, the samples were pretreated in Ar
values) and sealabilities. To solve this problem, we also flow at 573 K for 0.5 h to remove adsorbed water and cooled
explored the simultaneous HDO of DMCD and some
representative bio-jet fuel precursors to get jet fuels which
have proper amounts of cycloalkane and aromatics.
to 323 K. At this moment, the gas was switched to 10vol% H
2
in
Ar. After the stabilization of baseline, the samples were heated
-1
from 323 K to 1073 K at a rate of 10 K min . The amount of H
2
consumption was monitored by a thermal conductivity
detector (TCD). Before the TCD, the gas passed through a cold
trap to remove the water generated during the test.
The high-resolution transmission electron microscopy
(HRTEM) images of the HDO catalysts were collected by a JEM-
2100F field emission electronic microscope. Prior to
characterization, the catalysts were pretreated in hydrogen
flow at 673 K for 2 h. The element distribution of the Ru-
7 8
Scheme 1. Strategy for the synthesis of gasoline and jet fuel range C -C
2
Cu/SiO catalyst was analyzed by a TEM (JEOL JEM-2100F)
cyclic hydrocarbons with PET wastes.
which was equipped with energy dispersive X-ray spectroscopy
(EDX) instrument. Before microscopy examination, the sample
was first suspended in ethanol by ultrasonic method then
loaded on a holey carbon film supported by a nickel TEM grid.
In-situ diffuse reflectance infrared Fourier transform
spectroscopy (In-situ DRIFTS) of the catalysts were acquired at
a spectral resolution of 4 cm-1 and an accumulation of 128
scans by a BRUKER Equinox 70 spectrometer which was
equipped with a MCT detector. Before each measurement, the
Experimental
Materials and methods
In this work, the drinking water bottle of Nongfu Spring® was
used as a representative for the waste PET. Before being used
in the alcoholysis test, the bottle was cut into 2 mm × 3 mm
species with scissors. Activated carbon loaded noble metal
(denoted as M/C, M = Pt, Ru or Pd) catalysts used in the
solvent-free hydrogenation of DMT to DMCD were purchased
from Aladdin company. Pt, Ru and Pd were chose as active
metals because their higher activity of the hydrogenation of
aromatic ring or ester group.13 According to the information
from the supplier, the metal contents in the catalysts were
2
catalyst was reduced in-situ by H at 673 K for 1 h, then purged
with He for 0.5 h. After the sample was cooled down to room
temperature, the spectrum was acquired and used as the
background. Subsequently, 5vol% CO/He was introduced into
the cell until the steady state was reached. The excess CO was
removed from the system by purging with He. Finally, the
spectra were acquired and subtracted with the background.
In-situ XPS analysis was carried out by a Thermofisher
ESCALAB 250Xi spectrometer at 15 kV, 10.8 mA employing Al
5
wt%. The specific BET surface areas, average particle sizes
and metal dispersions of the investigated M/C catalysts were
illustrated in Table S1 in supporting information. The Ru/SiO
and Cu/SiO catalysts used in the solvent-free HDO of DMCD
were prepared by the incipient wetness impregnation of SiO
QingdaoOcean Chemical Ltd.) with the aqueous solutions of
RuCl 3H O and Cu(NO 3H O, respectively. For comparison,
the theoretical metal contents in the catalysts were fixed as
wt%. After impregnation, the samples were kept at room
temperature for 8 h, dried at 393 K overnight and calcined in
air at 773 K for 4 h. Analogously, the bimetallic Ru-Cu/SiO
catalyst was prepared by the incipient wetness co-
impregnation of SiO with the solution of RuCl 3H O and
Cu(NO 3H O. The theoretical total metal contents of both Ru
and Cu in the bimetallic Ru-Cu/SiO catalyst were controlled as
.5wt% (the total metal content in the catalyst was 5wt%).
Characterization
2
2
2
α
K X-ray (h = 1486.6 eV, analysis chamber base pressure > 3 ×
(
-
8
1
0 Pa). Prior to analysis, the catalysts were pretreated with
3
⋅
2
3
)
2
⋅
2
hydrogen flow at 673 K for 2 h.
Activity tests
5
The alcoholysis of PET waste was carried out in a 100 mL
stainless steel batch reactor (Parr 4848) under nitrogen
atmosphere. For each test, 1 g PET waste and 40 mL alcohol
2
(such as methanol, ethanol and butanol) were used. After
2
3
⋅
2
purging the reactor with nitrogen for three times, the mixture
was stirred at 413-473 K for 3.5 h, then quenched to room
temperature with cool water. Subsequently, an excess amount
of methanol was added to into the reaction system. According
to the saturated solutions of terephthalate products at room
temperature, the amount of methanol used in this work was
more than enough to dissolve the terephthalates from the
alcoholysis of PET waste even when they were produced at
3
)
2
⋅
2
2
2
The XRD patterns of different catalysts were obtained on a
PANalytical X’pert diffractometer operated at 40 kV and 40 mA,
α
using nickel-filtered Cu K radiation. Before the tests, the
samples were reduced by hydrogen at 673 K for 2 h (the same
pretreat conditions as we used in HDO tests).
100% yield. The residual PET is unsolvable in methanol.
Therefore, it was easily separated from the alcoholysis product
by filtration, dried at 343 K overnight and weighted to
2
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calculate the conversion of PET. The terephthalates generated
during the alcoholysis reactions were solved in methanol and
quantificationally analyzed by an Agilent 7890A GC. The PET
conversions and the terephthalate yields during alcoholysis
tests were calculated according following equations.
Results and discussion
View Article Online
DOI: 10.1039/C9GC00571D
Characterization.
The crystalline phases of HDO catalysts were characterized by
XRD. From Figure 1, we can only observe the peaks of metallic
2 2
Ru and Cu in the XRD patterns of Ru/SiO and Cu/SiO catalysts.
Conversion of PET waste (%) = (Initial weight of PET waste - the
weight of residual PET waste)/(Initial weight of PET waste) ×
No peaks of Ru (or Cu) oxides were observed. These results
mean that the Ru and Cu species can be reduced to metallic
state after being pretreated in hydrogen flow at 673 K for 2 h.
100%
Yield of terephthalate (%) = (Mole of terephthalate generated
during the alcoholysis test)/(Theoretical mole of terephthalate
which should be produced from the complete conversion of
the PET waste) × 100%
Different with those of the Ru/SiO
2
and Cu/SiO
catalyst only has one
peak at 44.1 . The intensity of this peak is evidently lower than
2
catalysts, the
XRD pattern of the bimetallic Ru-Cu/SiO
2
o
the peak of Ru (101) in the XRD patterns of Ru/SiO
2
catalyst.
The solvent-free hydrogenation of DMT was carried out in a
1
00 mL stainless steel batch reactor (Parr 4848). For each test,
0 g DMT and 1 g catalyst was used. After purging the reactor
3
and filling it with hydrogen, the mixture of DMT and catalyst
was heated to 353-433 K and vigorously stirred at that
temperature for certain time. During the reaction, hydrogen
was added from time to time to keep the system pressure at 5
MPa. After the test, the reactor was quenched to room
temperature with cool water. The unreacted hydrogen was
released. The liquid product was separated with catalyst by
filtration, diluted and analyzed by an Agilent 7890A GC. The
DMT conversions and yields of DMCD during hydrogenation
tests were calculated according following equations.
Conversion of DMT (%) = (Initial mole of DMT in the
feedstock – mole of unreacted DMT in the product)/(Initial
mole of DMT in the feedstock) × 100%
Figure 1. XRD patterns of the Ru/SiO
2
, Cu/SiO
2
and Ru-Cu/SiO
2
catalysts.
Yield of DMCD (%) = (Mole of DMCD in the product/Mole of
DMT in the feedstock) × 100%
The solvent-free HDO of DMCD was carried out in a 316 L
stainless steel fixed-bed tubular reactor which has been
described in our previous work 14
catalysts (1.8 g) were in-situ reduced by H
.
Prior to reaction, the
flow at 673 K for 2
2
h. After cooling down the reactor to reaction temperature and
increasing the system pressure to set values, DMCD was
−
1
pumped into the reactor (at a rate of 0.04 mL min ) with
−
1
hydrogen (at a flow rate of 120 mL min ). The products from
the outlet of the reactor become two phases in a gas-liquid
separator. The gaseous products passed through the back-
pressure regulator and were analyzed online by an Agilent
2 2 2 2
Figure 2. H -TPR profiles of the Ru/SiO , Cu/SiO and Ru-Cu/SiO catalysts.
The redox properties of the Ru/SiO
2
, Cu/SiO
2
and Ru-Cu/SiO
2
7890A GC. The liquid phase products were withdrawn
catalysts were investigated as well. From Figure 2, we can see
that the H -TPR profile of Ru/SiO has a peak at 413 K.
According to literature,15 this peak can be assigned to the
reduction of RuO to metallic Ru. The H -TPR profile of Cu/SiO
2
periodically from the gas-liquid separator and analyzed by
another Agilent 7890A GC. The conversion of DMCD and the
2
2
7 8
yields of C -C aromatics and cycloalkanes during HDO tests
2
2
were calculated according to following equations.
Conversion of DMCD (%) = (Mole of DMCD fed into the
reactor – mol of unreacted DMCD in the HDO product)/(Mole
of DMCD fed into the reactor)×100%
catalyst demonstrated an unresolved peak range between 450
K and 580 K. According to previous report,16 the peak centred
at 502 K can be attributed to the reduction of CuO to Cu
while the peak centred at 533 K can be explained by the
further reduction of Cu O to metallic Cu. Different with the
catalysts, the H -TPR profile of the Ru-
catalyst exhibited a main peak at 448 K and a small
catalyst,
-TPR profile of Ru-Cu/SiO
2
O,
Yield of C
HDO product/Mole of DMCD fed into the reactor) ×100%
Yield of C -C cycloalkanes (%) = (Mole of C -C cycloalkanes in
7 8 7 8
-C aromatics (%) = (Mole of C -C aromatics in the
2
Ru/SiO
2
2
and Cu/SiO
2
2
7
8
7
8
Cu/SiO
the HDO product/Mole of DMCD fed into the reactor) ×100%
shoulder peak at 555 K. Compared with the Ru/SiO
the main reduction peak in the H
2
2
2
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catalyst shifted to a higher temperature. From this result, we
can see that there is some strong interaction between the Ru
View Article Online
DOI: 10.1039/C9GC00571D
(a)
(b)
2
and Cu species in the Ru-Cu/SiO catalyst. Moreover, it was
also noticed that the reduction peak of Cu species at 555 K is
very weak and evidently lower than what it should be (as
compared to that for the Cu/SiO
could be rationalized because the hydrogen spillover effect of
Ru species promoted the reduction of CuO
species.17 As the
result, some reduction peak CuO species was shifted to lower
temperature and involved in the main reduction peak in the
2
catalyst). This phenomenon
x
x
2 2
H -TPR profile of Ru-Cu/SiO catalyst.
Ru/SiO
Cu/SiO
Figure 4. HRTEM image (a) and X-EDS spectra (b, c) of the Ru-Cu/SiO
2
catalyst.
Ru-Cu/SiO
2
2 2 2
Figure 3. TEM images of the Ru/SiO , Cu/SiO and Ru-Cu/SiO catalysts.
Figure 3 shows the TEM images of the Ru/SiO
Ru-Cu/SiO catalysts. According to the statistical results, the
average diameter of metal particles on the surface of the Ru-
Cu/SiO catalyst is evidently lower than those over the Ru/SiO
and Cu/SiO catalysts, which is in line with the XRD results.
According to Figure 4a, the lattice spacing of the metallic
particles on the Ru-Cu/SiO catalyst was estimated as 0.20 nm.
2 2
, Cu/SiO and
2
2
2
2 2 2
Figure 5. CO DRIFTS of the Ru/SiO , Cu/SiO and Ru-Cu/SiO catalysts.
2
From Figure 5, we can see that the CO DRIFTS of Ru/SiO
-
2
1
-1
-1
catalyst has three peaks at 2125 cm , 2073 cm and 2021 cm .
According to literature,20 the peak at 2021cm can be assigned
2
-1
This lattice spacing is larger than that of Cu(200) (0.18 nm)18
but smaller than the lattice spacing of the Ru(101) (0.21 nm).19
0
to the CO which is linearly adsorbed on Ru , while the two
-
1
-1
bands at 2073 cm and 2125 cm can be attributed to the CO
which is linearly adsorbed on Ruδ+ sites. The CO DRIFTS of
Based on this result, we think that Ru-Cu alloy was formed on
catalyst. To further verify this
catalyst by X-
the surface of Ru-Cu/SiO
2
-
1
Cu/SiO
be assigned to the CO which is linearly adsorbed on Cu0.
Similar to that of Cu/SiO , the CO DRIFTS of Ru-Cu/SiO catalyst
2
catalyst only has one peak at 2125 cm which should
hypothesis, we also characterized the Ru-Cu/SiO
2
ray energy dispersive spectroscopy (X-EDS). From the X-EDS
spectra (see Figure 4c) of some points which were randomly
chosen in the area shown in Figure 4b, both Ru and Cu species
were observed simultaneously. This result further confirms the
2
2
-
1
also has a unique peak at 2125 cm . As what has been
suggested in literature,21 this phenomenon may be explained
by the enrichment of Cu on the surface of Ru-Cu alloy particles
2
formation of Ru-Cu alloy on the surface of Ru-Cu/SiO catalyst.
2
formed on the Ru-Cu/SiO catalyst.
4
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Figure 6 shows the XPS spectra of the Ru/SiO
2
, Cu/SiO
2
and
Besides methanol, ethanol was also found to beVieewffAertcictlievOenlfinoer
Ru-Cu/SiO
2
catalysts. From the binding energies of Ru 3d and the alcoholysis of PET waste. How eD v Oe Ir: ,10 .i 1t 0s 39 r/ eC a9 Gc tCi v0 i0t 5y 71 Di s
Cu 2p in these catalysts, we can see that the Ru and Cu species evidently lower than that of methanol. In contrast, the butanol
in the catalysts exist as metallic states. This is consistent with is inactive for the alcoholysis of PET waste under the
the XRD results. Compared with the monometallic Ru/SiO
Cu/SiO catalysts, the binding energies of both Ru 3d and Cu information). The reaction pathways for the generation of
p in the bimetallic Ru-Cu/SiO catalyst shift to a lower values. DMT and diethyl terephthalate (DET) from the alcoholysis of
2
and investigated conditions (see Figure S1 in supporting
2
2
2
This result can be considered as another evidence for the PET were proposed in Scheme 2. Taking into consideration the
strong interaction (or electrons transfer) between the Ru and lower price and higher reactivity of methanol than ethanol and
Cu species in the bimetallic Ru-Cu/SiO
2
catalyst.22
butanol, we think that it is a good choice for the alcoholysis of
PET waste in real application.
Scheme 2. Reaction pathways for the alcoholysis of PET waste with
different alcohols at 453 K.
Figure 6. Ru 3d and Cu 2p XPS spectra of the Ru/SiO
Cu/SiO catalysts.
2 2
, Cu/SiO and Ru-
2
Activity test
Alcoholysis of PET waste
. First of all, we studied the
depolymerisation of PET waste by alcoholysis with a series of
alcohols (see Figure 7). Among them, methanol exhibited the
highest reactivity for the alcoholysis of PET waste. This is
8
consistent with what has been reported by literature. After
the alcoholysis reaction was carried out in methanol at 453 K
for 3.5 h, PET waste was completely converted in the absence
of any catalyst. High yield (90.1%) of DMT was achieved.
Figure 8. Conversion of PET waste and the DMT yield from the
methanolysis of PET waste as the function of reaction temperature.
Reaction conditions: 3.5 h; 1 g PET waste and 40 mL methanol were used in
each test.
The effects of reaction conditions (such as reaction
temperature, mass of substrate and reaction time) on the
methanolysis of PET waste were investigated as well. From
Figure 8, we can see that methanol is very reactive for the
alcoholysis of PET waste. High PET conversion (100%) and DMT
yield (86.5%) were achieved even at 433 K. After we raised
reaction temperature to 473 K, the PET waste was almost
totally converted to DMT (in a yield of 97.3%) after 3.5 h. With
the increase of substrate concentration in the reaction system,
the PET conversion and DMT yield decreased (see Figure 9).
However, this problem can be solved by further increase
reaction time (see Figure 10).
Figure 7. Conversions of PET waste and the yields of terephthalates from
the alcoholysis of PET waste in the absence of catalyst. Reaction conditions:
4
53 K, 3.5 h; 1 g PET waste and 40 mL alcohol were used in each test.
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and DMT by settling (or filtration) instead of disVtieilwlaAtrtiioclne.OnTlihnee
DOI: 10.1039/C9GC00571D
methanol phase which contains small amount DMT can be
recycled and reused for the alcoholysis of PET waste (see
Figure 11).
Solvent-free hydrogenation of DMT. As we mentioned earlier,
the DMT obtained from the alcoholysis of PET waste exists as a
solid at room temperature. To increase its fluidity, we
hydrogenated it before the HDO test. The hydrogenation of
DMT was carried over a series of activated carbon loaded
noble metal catalysts under solvent-free conditions. Based on
the analysis of hydrogenation product by GC-MS, DMCD was
identified as the major product from the solvent-free
hydrogenation of DMT (see Figure S3 in supporting
information). Among the investigated catalysts, Pt/C exhibited
the highest activity for the hydrogenation of DMT to DMCD
Figure 9. Conversion of PET waste and the DMT yield from the
methanolysis of PET waste as the function of substrate mass. Reaction
conditions: 473 K, 3.5 h; 40 mL methanol were used in each test.
(see Figure 12). Over the Pt/C catalyst, high DMT conversion
73.1%) and good DMCD yield (71.1%) were achieved after the
(
reaction was carried out at 373 K for 7 h. The activities of
investigated catalysts decrease in the order of Pt/C > Ru/C >
Pd/C. This sequence is consistent with the activity sequence of
these catalysts for hydrogenation of other aromatic
compounds such as p-xylene (see Figure S4 in supporting
information). Based on these results, we can attribute the
higher DMT conversion and DMCD yield over the Pt/C to the
high activity of this catalyst for the hydrogenation of benzene
ring.
Figure 10. Conversion of PET waste and the DMT yield from the
methanolysis of PET waste as the function of reaction temperature.
Reaction conditions: 473 K; 4 g PET waste and 40 mL methanol were used
in each test.
Figure 12. Conversions of DMT and the yields of DMCD over different noble
metal catalysts. Reaction conditions: 373 K, 5 MPa H
g catalyst were used in each test.
2
, 7 h; 30 g DMT and 1
The effects of reaction conditions (such as reaction
temperature, catalyst dosage and reaction time) over the
catalytic performance of Pt/C were investigated (see Figures
Figure 11. Block flow diagram for the production of DMT with PET waste 13-15). Under the optimized conditions (413 K, 1.0 g catalyst
and methanol.
and 10 h), DMT was completely converted and high yield
99.2 %) of DMCD was achieved over the Pt/C catalyst (see
(
Due to its low solubility in methanol, most of the DMT
generated during the alcoholysis test automatically separated
from methanol when the reaction system was cooled down to
room temperature (see Figure S2 in supporting information).
In real application, this is advantageous because the energy
consumption can be decreased if we can separate methanol
Figure 15). The DMCD obtained from the hydrogenation of
DMT exists as a liquid at room temperature (see Figure S5 in
supporting information). Therefore, it can be directly used for
the subsequent HDO process in the absence of solvent.
6
| J. Name., 2012, 00, 1-3
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Green Chemistry
Journal Name
ARTICLE
Cu/SiO
2
and bimetallic Ru-Cu/SiO
2
catalysts. The activity tests
View Article Online
DOI: 10.1039/C9GC00571D
2
were carried out at 643 K and 6 MPa H . From the analysis of
gas phase and liquid phase products, it was found that DMCD
was completely converted over the Ru/SiO catalyst. Methane
2
was identified as the major product (see Table S2 in supporting
information). This result can be explained by the high
methanation activity of Ru catalyst. In contrast, DMCD was
only partially hydrodeoxygenated over the Cu/SiO
see Figure 16 and the Figure S6 in supporting information).
Low total yield (32.1%) of C -C hydrocarbons was obtained
under the investigated conditions. Compared with the Ru/SiO
and Cu/SiO , the bimetallic Ru-Cu/SiO catalyst exhibited
2
catalyst
(
7
8
2
2
2
evident advantage in the HDO of DMCD. Over it, DMCD was
completely converted under the investigated conditions. High
7 8
total yield of C -C cycloalkanes and aromatics (93.9%) was
Figure 13. Conversion of DMT and the yield of DMCD over the Pt/C catalyst achieved. Based on the characterization results, the excellent
as the function of reaction temperature. Reaction conditions: 5 MPa H , 7 h; performance of Ru-Cu/SiO
0 g DMT and 1 g Pt/C catalyst were used in each test.
2
2
catalyst can be explained by the
3
formation of smaller Ru-Cu alloy which has higher efficiency
for hydrodeoxygenation than Cu and lower methanation
activity than Ru. As potential applications, the
hydrocarbons as obtained can be either used as gasoline (the
octane numbers of the C -C hydrocarbons were listed in Table
7 8
C -C
7
8
S3 in supporting information) to reduce the dependence of our
society on fossil energy or blended into bio-jet fuels to
improve their densities (or heat values) and sealabilities. The
methane which was obtained as by-product from the HDO of
DMCD can be oxidized to methanol which is used in the
alcoholysis step.23
Figure 14. Conversion of DMT and the yield of DMCD over the Pt/C as the
function of catalyst dosage. Reaction conditions: 413 K, 5 MPa H
DMT was used in each test.
2
, 7 h; 30 g
Figure 16. Conversions of DMCD and the yields of different hydrocarbons over
the Ru/SiO
2 2 2
, Cu/SiO and Ru-Cu/SiO catalysts. Reaction conditions: 643 K, 6 MPa
-1
flow rate: 120 mL min-1.
H
2
; 1.8 g catalyst, DMCD feedspeed: 0.04 mL min , H
2
According to the literature about the HDO of esters24 and
the intermediates which were identified in the GC-MS
chromatogram of HDO product at a space velocity which was
four times of the one used in the HDO tests (see Figure S7-S12
in supporting information), the reaction pathways for the
Figure 15. Conversion of DMT and the yield of DMCD over the Pt/C catalyst
production of C
of DMCD was proposed (see Scheme 3). From Scheme 3, we
can see that the C cycloalkanes in the HDO product were
generated by the hydrogenation of ester groups of DMCD
7 8
-C cycloalkanes and aromatics from the HDO
as the function of reaction time. Reaction conditions: 413 K, 5 MPa H
DMT and 1 g Pt/C catalyst were used in each test.
2
; 30 g
8
Solvent-free HDO of DMCD. As the final aim of this work, we
followed by dehydration and hydrogenation, while the C
aromatics were generated by the hydrogenation of ester
8
2
studied the solvent-free HDO of DMCD over the Ru/SiO ,
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
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Page 8 of 10
ARTICLE
Journal Name
groups of DMCD followed by dehydrogenation, dehydration aromatics from the HDO of DMCD. This can be coVmiewpArretihclee nOdnliende
DOI: 10.1039/C9GC00571D
and dehydrogenation. Different with C
reaction pathways for the generation of C
aromatics also involves an
8
hydrocarbons, the from the pointviews of thermodynamics (because
7
cycloalkanes and dehydrogenation is an endothermic reaction) and reaction
additional equilibrium. Subsequently, we also explored the catalyst
hydrogenation/decarbonylation step (this has been proved by dosage on the performance of Ru-Cu/SiO
the presence of CO in the gas phase product (see Table S2 in was noticed that the DMCD conversion, the total yield of cyclic
supporting information)). As the result, one carbon atom will hydrocarbons and the yield of C -C aromatics over Ru-Cu/SiO
2
. From Figure 19, it
7
8
2
be lost from the carbon chain of DMCD.
increased with the catalyst dosage and reached the maximum
when 1.8 g catalyst was used for the test. In contrast, a
volcanic shape relationship was observed between the catalyst
dosage and the yield of C
catalyst. These results further confirm that the C
are generated from the dehydrogenation of C -C
7
-C
8
cycloalkanes over Ru-Cu/SiO
-C aromatics
cycloalkanes.
2
7
8
7
8
7 8
Scheme 3. Reaction pathways for the generation of C -C cycloalkanes and
aromatics from the solvent-free HDO of DMCD.
Figure 18. Conversion of DMCD and the yields of different hydrocarbons
over the Ru-Cu/SiO catalyst as the function of system pressure. Reaction
conditions: 673 K; 1.8 g Ru-Cu/SiO catalyst, DMCD feedspeed: 0.04 mL
2
2
min , H
2
flow rate: 120 mL min-1.
-1
Figure 17. Conversion of DMCD and the yields of different hydrocarbons
over the Ru-Cu/SiO catalyst as the function of reaction temperature.
Reaction conditions: 6 MPa; 1.8 g Ru-Cu/SiO catalyst, DMCD feedspeed:
2
2
.04 mL min , H
2
flow rate: 120 mL min-1.
-
1
0
The effects of reaction temperature and system pressure on
cycloalkanes and aromatics over the
catalyst were investigated. From the
the yields of C
7
-C
8
bimetallic Ru-Cu/SiO
2
results illustrated in Figure 17, we can see that the conversion
of DMCD and the total yield of C -C hydrocarbons over the
Ru-Cu/SiO catalyst increased with reaction temperature,
7
8
Figure 19. Conversion of DMCD and the yields of different hydrocarbons
over the Ru-Cu/SiO as the function of catalyst dosage. Reaction conditions:
2
2
reached the maximum at 643 K and stabilized with the further
increase of reaction temperature to 673 K. Analogous
relationship was found between the system pressure and the
-1
4
2
MPa, 673 K; 1.8 g Ru-Cu/SiO catalyst, DMCD feedspeed: 0.04 mL min ,
-1
H
2
flow rate: 120 mL min .
conversion of DMCD or the total yield of C
over the Ru-Cu/SiO catalyst (see Figure 18). Meanwhile, it was HDO of DMCD is advantageous due to following two reasons. 1)
also noticed that higher reaction temperature and lower As we can see from Table S3 in supporting information, the C
system pressure are favourable for the production of C -C aromatics as obtained have higher octane numbers and
-C
7 8
hydrocarbons
In real application, the production of aromatics from the
2
7
-
7
8
C
8
8
| J. Name., 2012, 00, 1-3
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Page 9 of 10
Green Chemistry
Journal Name
densities than those of the C
ARTICLE
8
-C cycloalkanes. Moreover, the cycloalkanes and aromatics were obtained at thVeiewsaArmticele Otnimlinee
7
presence of aromatic hydrocarbons in the jet fuel is also (see Table 1). In the future application D, Oi It : 1i 0s .1 p0 o3 9s /s Ci b9 lGe C 0t o0 5 7u 1 sDe
necessary to ensure the shrinkage of aged elastomer seals and biomass and PET waste simultaneously to produce jet fuel with
prevent the leakage of fuel. For safety reason, there must be proper contents of cycloalkanes and aromatics.
8
-25% aromatic hydrocarbons in the current jet fuels.25 2)
Table 1. Conversions of feedstocks, the yields of different hydrocarbons
From the point view of stoichiometry, the production of C -C
7
8
from the solvent-free simultaneous HDO of DMCD and biomass derived jet
aromatics from the HDO of DMCD needs less hydrogen than fuel precursors. Reaction conditions: 673 K, 4 MPa H
2 2
; 1.8 g Ru-Cu/SiO
-
1
the one which is need for the production of C
-C
7 8
cycloalkanes. catalyst, feedspeed of liquid reactants: 0.04 mL min , H
2
flow rate: 120 mL
-1
min .
Taking into consideration of the total yield of C
7
-C
8
a
Feedstock 1b
Feedstock 2c
hydrocarbons, octane numbers and densities of specific Conversion or yield
hydrocarbon products and the influence system pressure or
Conversion of DMCD (%)
Conversion of methyl laurate (%)
100
100
—
100
—
100
reaction temperature on facility cost and energy consumption, Conversion of 5,5’-(butane-1,1-diyl)bis(2-
methylfuran) (%)
we think that 673 K, 4 MPa and 1.8 g catalyst are the
optimized reaction conditions for the HDO of DMCD over the
Ru-Cu/SiO catalyst.
Yield of C
Yield of C
7
-C
-C
8
aromatics (%)
cycloalkanes (%)
33.4
64.9
32.1
65.7
97.8
7
8
2
7 8
Total yield of C -C cyclic hydrocarbons 98.3
(
%)
Yield of C
8
-C16 jet fuel chain alkanes (%)
99.8
81.8
a
The conversions of feedstocks and yields of different products were
calculated according to the method described in supporting information.
b
Mixture of DMCD and methyl laurate at the mass ratio of 1:1. c Mixture of
DMCD and 5,5’-(butane-1,1-diyl)bis(2-methylfuran) at the mass ratio of 1:1.
Conclusions
7 8
Gasoline and jet fuel range C -C cycloalkanes and aromatics
were produced at high overall yield (95%) by the alcoholysis of
PET waste, followed by the solvent-free hydrogenation and
HDO. Methanol was found to be highly reactive for the
alcoholysis of PET waste. In the absence of catalyst, 97.3%
yield of DMT was achieved from the methanolysis of PET waste
after the reaction was carried out at 473 K for 3.5 h. The DMT
as obtained can be automatically separated from methanol at
room temperature and liquefied to DMCD by the solvent-free
hydrogenation over Pt/C catalyst. Finally, the DMCD was
Figure 20. Conversion of DMCD and the yields of different hydrocarbons
over the Ru-Cu/SiO catalyst as the function of time on stream. Reaction
conditions: 673 K, 4 MPa H ; 1.8 g Ru-Cu/SiO catalyst, DMCD flow rate:
flow rate: 120 mL min-1.
2
2
2
-1
0
.04 mL min , H
2
further hydrodeoxygenated to gasoline and jet fuel range C
cycloalkanes and aromatics over bimetallic Ru-Cu/SiO catalyst.
Under the optimized conditions, 98.4% total yield of C -C
cycloalkanes and aromatics was achieved. The C -C cyclic
7 8
-C
To fulfil the need of real application, we also checked the
stability of the Ru-Cu/SiO catalyst for the solvent-free HDO of
DMCD under the optimized conditions (673 K and 4 MPa H ).
From Figure 20 and Figure S13 in supporting information, no
evident deactivation of the Ru-Cu/SiO catalyst was observed
during the 22 h continuous tests. This result indicates that the
Ru-Cu/SiO catalyst is stable under the investigated conditions.
2
7
8
2
7
8
2
hydrocarbons as obtained can be blended with conventional
bio-jet fuel to improve their densities (or volumetric heat
values) and sealabilities. In future application, it is also possible
to combine the hydrodeoxygenation of DMCD with those of
biomass derived jet fuel precursors to produce jet fuel with
proper contents of cycloalkanes and aromatics. This work
offered a feasible method for the utilization of PET wastes to
make the most demanded transportation liquid fuels.
2
2
As we know, HDO is an important step in many reported
routes for bio-jet fuel production. To decrease the investment
of facility, we also explored the solvent-free simultaneous HDO
of DMCD and some representative bio-jet fuel precursors.
Methyl laurate and 5,5’-(butane-1,1-diyl)bis(2-methylfuran)
are two representative bio-jet fuel precursors which can be
produced by the transesterification of lauric oils26 or the
Conflicts of interest
hydroxylalkylation/alkylation of lignocellulose derived 2- There are no conflicts to declare.
methylfuran and butanal.27 In this work, we investigated the
solvent-free HDO of the mixtures which were prepared with
the same mass of DMCD and methyl laurate (or 5,5’-(butane- Acknowledgements
1
,1-diyl)bis(2-methylfuran)). Under the optimized reaction
conditions (673 K and 4 MPa H ), all of the oxygenates in the
feedstocks were completely hydrodeoxygenated over the Ru-
Cu/SiO catalyst. High yield of jet fuel range chain alkanes,
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
2
2
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ARTICLE
Journal Name
1
3 M. Jacquin, D. J. Jones, J. Rozière, S. Albertazzi, VAie.wVAartcicclearOi,nliMne.
(
XDB17020100, XDA 21060200), the National Key Projects for
Fundamental Research and Development of China
2016YFA0202801), Dalian Science Foundation for
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