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Synthesis of jet fuel additive with cyclopentanone
Accepted Manuscript
Synthesis of jet fuel additive with cyclopentanone Hao Tang , Fang Chen , Guangyi Li , Xiaofeng Yang , Yancheng Hu , Aiqin Wang , Yu Cong , Xiaodong Wang , Tao Zhang , Ning Li PII: DOI: Reference:
S2095-4956(17)31049-5 10.1016/j.jechem.2018.01.017 JECHEM 524
To appear in:
Journal of Energy Chemistry
Received date: Revised date: Accepted date:
17 November 2017 17 January 2018 24 January 2018
http://www.journals.elsevier.com/ journal-of-energy-chemistry/
Please cite this article as: Hao Tang , Fang Chen , Guangyi Li , Xiaofeng Yang , Yancheng Hu , Aiqin Wang , Yu Cong , Xiaodong Wang , Tao Zhang , Ning Li , Synthesis of jet fuel additive with cyclopentanone, Journal of Energy Chemistry (2018), doi: 10.1016/j.jechem.2018.01.017
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ACCEPTED MANUSCRIPT
Synthesis of jet fuel additive with cyclopentanone
Hao Tanga,b,§, Fang Chena,b,§, Guangyi Lia, Xiaofeng Yanga, Yancheng Hua, Aiqin
a
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese
c
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Academy of Sciences, Dalian 116023, Liaoning, China b
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Wanga,c, Yu Conga, Xiaodong Wanga, Tao Zhanga,c, Ning Lia,c,*
University of Chinese Academy of Sciences, Beijing 100049, China iChEM (Collaborative Innovation Center of Chemistry for Energy Materials),
M
Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023,
These authors contributed equally to this work.
AC
CE
PT
§
ED
Liaoning, China
*Corresponding author. E-mail: [email protected] (N. Li); Tel.: +86 411 84379738; Fax: +86 411 84685940.
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Abstract A new route was developed for the synthesis of renewable decalin with cyclopentanone which can be derived from lignocellulose. It was found that 1,2,3,4,5,6,7,8-octahydronaphthalene
could
be
selectively
produced
by
the
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hydrogenation/dehydration/rearrangement of [1,1'-bi(cyclopentylidene)]-2-one (i.e. the self-aldol condensation product of cyclopentanone) over a dual-bed catalyst system. Among the investigated catalysts, the Ru/C and Amberlyst-15 resin exhibited
[1,1'-bi(cyclopentan)]-2-ol [1,1'-bi(cyclopentan)]-2-ol
and to
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the highest activities for the hydrogenation of [1,1'-bi(cyclopentylidene)]-2-one to the
dehydration/rearrangement
of
1,2,3,4,5,6,7,8-octahydronaphthalene, respectively.
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Using Ru/C and Amberlyst-15 resin as the first bed and the second bed catalysts, 1,2,3,4,5,6,7,8-octahydronaphthalene was directly produced in high carbon yield
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(83.7%) under mild conditions (393 K, 1 MPa). After being hydrogenated, the
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1,2,3,4,5,6,7,8-octahydronaphthalene was converted to decalin which can be used as
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additive to improve the thermal stability and volumetric heat value of jet fuel.
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Keywords:
Lignocellulose;
Jet
fuel
Dehydration/rearrangement; Hydrogenation
2
additive;
Aldol
condensation;
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1. Introduction With the increase of social concern about the energy and environmental problems, the catalytic conversion of renewable, CO2 neutral and inedible biomass to high quality fuels [1–13] and value-added chemicals [14–26] has become a very hot topic.
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Jet fuel is one of the most demanded liquid transportation fuels. Globally, 12% of liquid transportation fuels are jet fuels [27]. Lignocellulose is the cheapest and the most abundant biomass. During the past years, the synthesis of jet fuel range
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hydrocarbons with the lignocellulosic platform compounds has drawn a lot of attention [28–40].
Decalin is one of the major components of JP-900, a coal-base thermally stable and
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high energy density jet fuel [41,42]. Due to its special chemical structure, decalin has been used as an additive to improve the thermally stability and volumetric heat value
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of jet fuel [43,44]. Cyclopentanone is a lignocellulosic platform compound which can
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be obtained by the aqueous phase selective hydrogenation of furfural [45–49]. To the best of our knowledge, there is no report about the production of renewable decalin
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with cyclopentanone. this
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In
work,
it
was
1,2,3,4,5,6,7,8-octahydronaphthalene
reported
for
can
selectively
be
the
first
time
produced
by
that the
hydrogenation/dehydration/rearrangement of [1,1'-bi(cyclopentylidene)]-2-one (i.e. the self-aldol condensation product of cyclopentanone) over a dual-bed (Ru/C and Amberlyst-15 resin) catalyst system. After being hydrogenated over the Pd/C catalyst, 1,2,3,4,5,6,7,8-octahydronaphthalene can be converted to decalin which can be used
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as an additive to improve the thermal stability and volumetric heat values of jet fuels. The strategy for this process is illustrated in Scheme 1. 2. Experimental 2.1. Materials
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2.1.1. Preparation of catalysts The MgAl hydrotalcite (MgAl-HT) catalyst used in the preparation of [1,1'-bi(cyclopentylidene)]-2-one was synthesized according to the literature [28] with
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some modification. The detail for the synthesis of the MgAl-HT catalyst was described in the supporting information. Activated carbon loaded noble metal (M/C, M = Ru, Pt, Rh, Pd) catalysts used in the hydrogenation reactions were prepared by
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the classical wet chemical reduction method with an activated carbon supplied by Guanghua activated carbon company. To facilitate the comparison, the theoretical
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contents of noble metals in the catalysts were controlled as 5% by weight (denoted as
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5 wt%). Taking the preparation of Ru/C catalyst for example, 3.88 g 10 wt% RuCl3•3H2O (analytical reagent grade, purity: 99.95%, supplied by HEOWNS)
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aqueous solution was added dropwise into a suspension of 3 g activated carbon and 30
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mL water. After being stirred at 318 K for 1 h, the pH of the mixture was adjusted to 9–10 by 1 mol L-1 NaOH. Subsequently, 20 g 40 wt% formaldehyde solution was added dropwise into the mixture. After being stirred at 358 K for another 70 min, the mixture was filtered, and washed with deionized water until no Cl– ion was detected in the filtrate and dried at 353 K for 3 h. Nafion resin was supplied by Jiangsu Success Resin Corporation. Amberlyst-15, Amberlyst-36 and Amberlite IRC 76CRF resins
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were purchased from the Dow Chemical Company. 2.1.2. Synthesis of [1,1'-bi(cyclopentylidene)]-2-one [1,1'-Bi(cyclopentylidene)]-2-one (i.e. 1A in Scheme 1) was synthesized by the solvent-free self-aldol condensation of cyclopentanone (analytical reagent grade,
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purity: 99.0%, supplied by Aladdin chemical reagents company) which can be produced by the aqueous phase selective hydrogenation of furfural [45-49]. The detail for the preparation of 1A was given in the supporting information. Under mild
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reaction conditions (393 K, 6 h), cyclopentanone was completely converted and a high carbon yield of 1A (87.0%) was achieved over the MgAl-HT catalyst. This result is consistent with what has been reported in the previous work of our group [37]. The
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1A as obtained was purified by vacuum distillation at 443 K and used as the feedstock for the subsequent steps.
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2.2. Activity test
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2.2.1. Hydrogenation of 1A
The activity tests of active carbon loaded noble metal catalysts for the
CE
hydrogenation of 1A were conducted in a stainless steel batch reactor. For each test,
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2.0 g 1A and 0.1 g noble metal catalyst were used. After the reaction was carried out at 393 K and 3 MPa H2 for 3 h, the mixture was quenched to room temperature. The liquid product was taken out of the reactor, filtered (to remove the catalyst) and analyzed
by
an
Agilent
7890B
gas
chromatograph
(GC).
The
[1,1'-bi(cyclopentan)]-2-ol (i.e. 1B in Scheme 1) as obtained from the hydrogenation of 1A over the Ru/C catalyst was directly used as the feedstock for the
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dehydration/rearrangement test. To integrate the hydrogenation and the subsequent dehydration/rearrangement into a one-step process. We also investigated the effects of reaction conditions on the hydrogenation of 1A over the Ru/C catalyst with a stainless steel tubular fixed-bed continuous flow reactor which has been described in our
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previous work [50]. For each test, 1.0 g Ru/C catalyst was used. 1A was pumped into the reactor (at a rate of 0.04 mL min-1) from the top of the reactor, along with hydrogen. Before reaching the catalyst, 1A was preheated to reaction temperature
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over quartz sand. After passing through the reactor and being cooled down to room temperature, the products became two phases in a gas-liquid separator. The gaseous products flowed through a back pressure regulator to maintain the system pressure at
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set value and analyzed online by an Agilent 7890B GC. The liquid products were drained from the gas-liquid separator after 4 h and analyzed by an Agilent 7890B GC.
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2.2.2. Dehydration/rearrangement of 1B
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The dehydration/rearrangement of 1B was carried out in a stainless steel tubular fixed-bed continuous flow reactor described in our previous work [50]. For each test,
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1.0 g solid acid catalyst was used. The 1B which was obtained from the
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hydrogenation of 1A over the Ru/C catalyst (without purification) was pumped into the reactor at a rate of 0.04 mL min-1 from the top of the reactor, along with nitrogen which was used as carrier gas. Before reaching the catalyst, 1B was preheated to reaction temperature over quartz sand. After passing through the reactor and being cooled down to room temperature, the products became two phases in a gas-liquid separator. The gaseous products flowed through a back pressure regulator to maintain
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the system pressure at set value and analyzed online by an Agilent 7890B GC. The liquid product was drained from the gas-liquid separator after 4 h and analyzed by another
Agilent
7890B
GC.
For
comparison,
we
studied
the
dehydration/rearrangement of 1B over the Amberlyst-15 resin using a stainless steel
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batch reactor. To do this, 7.6 g Amberlyst-15 resin and 38 g 1B were added in a stainless steel batch reactor. After being stirred at 393 K for 5.5 h, the mixture was quenched to room temperature. The liquid product was taken out from the reactor,
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filtered (to remove the catalyst), diluted and analyzed by an Agilent 7890B GC. In order to prove the negative effect of water which was generated during the reaction, we also investigated the dehydration/rearrangement of 1B over the Amberlyst-15
M
resin with a Dean-Stark apparatus. Typically, 7.6 g Amberlyst-15 resin and 38 g 1B were added into a Dean-Stark apparatus and stirred at 393 K for certain time. After
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the reaction, the product was taken out of the flask, filtered (to remove the catalyst),
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diluted and analyzed by an Agilent 7890B GC. 2.2.3. Integrated hydrogenation/dehydration/rearrangement of 1A
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To fulfill the need of real application, we explored the direct synthesis of
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1,2,3,4,5,6,7,8-octahydronaphthalene with 1A and hydrogen. The reaction was carried out in the same stainless steel tubular fixed-bed continuous flow reactor as we used in the hydrogenation of 1A (or the dehydration/rearrangement of 1B). 1.0 g Ru/C and 1.0 g Amberlyst-15 resin were used for the tests. For the single-bed catalyst system, a physical mixture of Ru/C and Amberlyst-15 resin was used as the catalyst. For the dual-bed catalyst system, the Ru/C was used as the first-bed catalyst, the
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Amberlyst-15 resin was used as the second-bed catalyst. 1A was pumped into the reactor at 0.04 mL min-1 from the top of the reactor, along with hydrogen (which was used as the carrier gas and reactant at the same time). Before reaching the catalysts, 1A was preheated to reaction temperature over quartz sand. After passing through the
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reactor and being cooled down to room temperature, the products became two phases in a gas-liquid separator. The gaseous product flowed through a back pressure regulator to maintain the system pressure at set value and analyzed online by an
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Agilent 7890B GC. The liquid product was drained from the gas-liquid separator after 4 h and analyzed by another Agilent 7890B GC.
2.2.4. Hydrogenation of the dehydration/rearrangement products
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As the final aim of this work, we synthesized decalin by the hydrogenation of the dehydration/rearrangement
products
of
1B
(i.e.
a
mixture
of
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cyclopentylidene-cyclopentanes and 1,2,3,4,5,6,7,8-octahydronaphthalene which was
reaction
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obtained from the dehydration/rearrangement of 1B without further purification). The was
carried
out
by
a
stainless
steel
batch
reactor.
2.0
g
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dehydration/rearrangement products and 0.1 g Pd/C catalyst were used in the test.
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After being stirred at 393 K and 3 MPa H2 for 3 h, the mixture was quenched to room temperature. The liquid product was taken out from the stainless steel reactor, filtered (to remove the catalyst) and analyzed by an Agilent 7890B gas chromatograph. 2.3. Characterization 2.3.1. N2-physisorption The specific Brunauer-Emmett-Teller (BET) surface areas (SBET), average pore
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volumes and average pore sizes of the investigated catalysts were measured by nitrogen physisorption which was carried out at 77 K using an ASAP 2010 apparatus. Before each measurement, the sample was evacuated at 393 K for 3 h. 2.3.2. Chemical titration
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The amounts of acid sites on the surfaces of investigated acidic resins were measure by the chemical titration method described in literature [51]. For each measurement, 0.02 g catalyst was used. The sample was dispersed into 20 mL 0.01
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mol L-1 NaOH solution, sonicated for 1 h and then centrifuged. The filtrate was titrated with 0.01 mol L-1 HCl (which has been precalibrated by a standard NaOH solution) using methyl orange as indicator. The molar amount of acid sites per gram
M
catalyst was calculated according to the consumption of HCl. 2.3.3. Microcalorimetric measurement of NH3 adsorption
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The microcalorimetric measurements of ammonia adsorption for the acidic resins
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used in the dehydration/rearrangement reaction were performed at 353 K using a BT2.15 heat-flux calorimeter (France, Seteram) connected to a gas-handling and a
CE
volumetric system employing MKS Baratron Capacitance Manometers for precision
AC
pressure measurement (±6.67×10−3 Pa). Before each measurement, ammonia (purity > 99.9%) was purified by successive freeze-pump-thaw cycles. The specific mass of sample with similar amount of acid sites was evacuated in a quartz cell at 353 K overnight under high vacuum to remove the physically adsorbed substance. The differential heat was measured as a function of acid site coverage by repeatedly introducing small dosage of ammonia onto the samples until the equilibrium pressure
9
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reached about 0.667–0.800 kPa. Then the system was evacuated overnight to remove the physically adsorbed ammonia, and a second adsorption was performed. 3. Results and discussion 3.1. Synthesis of 1A
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In the first part of this work, the [1,1'-bi(cyclopentylidene)]-2-one (i.e. 1A in Scheme 1) was synthesized by the solvent-free self-aldol condensation of cyclopentanone over the MgAl hydrotalcite (MgAl-HT) catalyst. The detail
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information for the preparation of 1A was given in the supporting information. Under mild reaction conditions (393 K, 6 h), cyclopentanone was completely converted. A high carbon yield of 1A (87.0%) was achieved over the MgAl-HT catalyst. This result
M
is consistent with what has been reported in the previous work of our group [37]. The
following steps.
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1A as obtained was purified by vacuum distillation and used as the feedstock for the
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3.2. Hydrogenation/dehydration/rearrangement of 1A
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The hydrogenation of 1A was carried over a series of activated carbon loaded noble metal catalysts. Among the tested catalysts, Ru/C had the highest carbon yield to
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[1,1'-bi(cyclopentan)]-2-ol (i.e. 1B in Scheme 1) (see Fig. 1). Over this catalyst, high carbon yield (98.1%) of 1B was obtained after the reaction was carried out under mild conditions (393 K, 3 MPa) for 3 h. To figure out the reason for the higher selectivity of Ru/C for the hydrogenation of 1A to 1B, we characterized the investigated catalysts by N2-physisorption, XRD and CO-chemisorption. From the results illustrated in Table S1, no evident correspondence was observed between the selectivity of these 10
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catalysts and their specific BET surface areas, average particle sizes or metal dispersions. According to literature [52-55], the excellent performance of the Ru/C catalyst can be comprehended by the high activity of Ru for the hydrogenation of carbonyl compounds.
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Over the Rh/C, Pt/C and Pd/C catalysts, [1,1'-bi(cyclopentan)]-2-one (i.e. 1C in Scheme 2) was identfied as the major hydrogenation product (see Fig. S1 in supporting information), no [1,1'-bi(cyclopentylidene)]-2-ol (i.e. 1D in Scheme 2) was
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detected in the hydrogenation products. This result can be rationalized because the hydrogenation of C=C bond is faster and dynamically more favorable than the hydrogenation of C=O bond [56]. It is very interesting that di(cyclopentane) (i.e. 1E
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in Scheme 2) was also identified in the hydrogenation product over the Pt/C catalyst. This product may generated from the hydrogenolysis of 1A over the Pt/C catalyst.
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Taking into considersation of the higher selectivity and the relatively lower cost of
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Ru/C than those of Rh/C, Pt/C and Pd/C, we think it is a promising catalyst in the future application.
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The reusability of the Ru/C catalyst in the hydrogenation of 1A was checked as
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well. As we can see from the Fig. S2 in supporting information, the Ru/C catalyst is stable under the investiaged conditions. No evident deactivation was noticed during four repeated usages. Subsequently, we investigated the dehydration of 1B over a series of acidic resins. From Fig. 2, we can see that the strong solid acids which have –SO3H group as the active sites (such as Nafion, Amerlyst-15 and Amberlyst-36 resins [57–59]) are very
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active for the dehydration of 1B. Over them, high 1B conversions (> 90%) were achieved at 393 K. In contrast, the conversion of 1B (0.1%) over the Amberlite IRC 76CRF resin (a weak acid resin which has –COOH group as the active sites [60]) is very low under the same conditions.
supporting
information),
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From the analysis of GC-MS and NMR spectra (see Fig. S3 and Fig. S4 in cyclopentylidene-cyclopentanes
and
1,2,3,4,5,6,7,8-octahydronaphthalene (i.e. 1F and 1G in Scheme 3) were identified as
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the two major products from the reaction of 1B over the Nafion, Amerlyst-15 and Amberlyst-36 resins. According to the reaction pathways which were proposed in Scheme 3, 1G is generated by the rearrangement of 1F from the dehydration of 1B.
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From the DFT calculation results listed in the Table S2 in supporting information, we can see that the lowest energy of 1,2,3,4,5,6,7,8-octahydronaphthalene is lower than
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those of cyclopentylidene-cyclopentanes and other octahydronaphthalenes. This may
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be one reason for the further rearrangement of cyclopentylidene-cyclopentanes to 1,2,3,4,5,6,7,8-octahydronaphthalene over strong acid resins. As another possibility,
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the rearrangement of 1F to 1G can also be explained by the principles of carbocation
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chemistry. It is well known that tertiary carbocation is more stable than secondary carbocation. From Scheme 3, we can see that 1F has only one carbon atom which can form tertiary carbocation, while 1G has two carbon atoms which can form tertiary carbocation. As the result, 1G is more stable than 1F. Among the investigated catalysts,
Amberlyst-15
resin
exhibited
the
best
performance
for
the
dehydration/rearrangement of 1B to 1G. Over it, high carbon yield (85.1%) of 1G can
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be
achieved
at
393
K.
The
stability
of
Amberlyst-15
resin
in
the
dehydration/rearrangement of 1B was also investigated. As we can see from Fig. S5 in supporting information, the Amberlyst-15 resin is stable under the investigated conditions. No evident deactivation was noticed during the 8 h continuous test.
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To figure out the reason for the excellent performance of Amberlyst-15 resin, we characterized the Nafion, Amerlyst-15 and Amberlyst-36 resins by a series of technologies. According to the microcalorimetric measurements of ammonia
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adsorption illustrated in Fig. 3, the acid strengths of these strong acidic resins (which were indicated by the NH3 adsorption heats) decrease in the order of Nafion (219 kJ mol-1) > Amberlyst-15 (156 kJ mol-1), Amberlyst-36 (157 kJ mol-1). This sequence is with
the
activity
sequence
of
these
acidic
resins
in
the
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different
dehydration/rearrangement of 1B to 1G. Analogously, there is no clear relationship
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between the carbon yields of 1G and the specific surface areas or the amounts of acid
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sites on the surfaces of these acidic resins (see Table 1). Based on these results, we can’t simply attribute the higher activity of Amberlyst-15 resin to the acidity or BET
CE
surface area of this catalyst. However, it is noticed from Table 1 that the average pore
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sizes (or pore volumes) of these acidic resins decrease in the order of Amberlyst-15 > Nafion > Amberlyst-36. This sequence is consistent with the activity sequence of these resins in the dehydration/rearrangement of 1B to 1G. As we know, the internal diffusion is very important for low-temperature liquid phase reactions. Therefore, larger pore resin is favourable for the rearrangement of 1F to 1G (or desorption of 1G from the catalyst). This may be the reason for the higher carbon yield of 1G over the
13
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Amberlyst-15 resin. The influence of reactor type on the catalytic performance of Amberlyst-15 resin for the dehydration/rearrangement of 1B was studied. From Fig. 4, we can see that the fix-bed
continuous
flow
reactor
is
better
than
batch
reactor
for
the
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dehydration/rearrangement of 1B. Such an advantage is also significant even when the later was carried out at longer contacting time. Moreover, it was noticed that the catalytic performance of Amberlyst-15 resin can also be significantly improved when
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we used the Dean-Stark apparatus to replace the batch reactor. However, the advantage of Dean-Stark apparatus is less evident than that of the fix-bed continuous flow reactor under the investigated conditions. These results can be rationalized
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because the H2O molecules generated from the dehydration of 1B have lone pair electrons. In reaction, they can act as a Lewis base to occupy the proton sites on
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Amberlyst-15 resin and thus inhibit the acid-catalyzed rearrangement of 1F to 1G.
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Therefore, the removing of water is favourable for the dehydration/rearrangement of 1B. That is the reason why higher carbon yields of 1G were achieved in the
CE
Dean-Stark apparatus and the fix-bed continuous flow reactor (in which the water was
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removed from the catalyst during the reaction). Compared with the Dean-Stark apparatus, the fix-bed continuous flow reactor is more efficient for the removal of water under the investigated reaction conditions. Due to this reason, higher carbon yield of 1G was achieved when we used the fix-bed continuous flow reactor. To verify this speculation, we did some additional experiments. From the Fig. S6, it was noticed that the conversion of 1B to 1G is a two-step reaction. In the first step, 1B is
14
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converted to 1F by dehydration. In the second step, 1F was rearranged to 1G over acid sites. Based on the results illustrated in Fig. S7 and Fig. S8, we can see that the presence of water has evident negative effect on the acid-catalyzed rearrangement of 1F to 1G.
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The effect of system pressure on the performance of the Amberlyst-15 resin was investigated. It is noticed from Fig. 5 that the increase of system pressure is unfavourable for the dehydration/rearrangement of 1B to 1G. Such a negative effect is
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more evident when system pressure is higher than 1.0 MPa. This can be explained because high system pressure restrains the evaporation (or removal) of water from the surface
of
Amberlyst-15
resin,
is
unfavorable
for
the
M
dehydration/rearrangement of 1B.
which
To fulfil the need of real application, we also tried the direct production of 1G with
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1A and hydrogen which acts as reactant and carrier gas at the same time. Based on
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their excellent performances for the hydrogenation of 1A to 1B and the subsequent dehydration/rearrangement of 1B to 1G, Ru/C and Amberlyst-15 resin were selected
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as the catalysts. Before doing this, we studied the effects of hydrogen pressure and
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flow rate on the hydrogenation of 1A over the Ru/C catalyst using the fixed-bed continuous flow reactor which was used for the dehydration/rearrangement of 1B. From the results illustrated in Fig. S9 and Fig. S10 in supporting information, high hydrogen pressure and flow rate are favourable for the hydrogenation of 1A to 1B over the Ru/C catalyst. Taking into the consideration of the fact that too high carrier gas flow rate and system pressure will increase the energy consumption and restrain
15
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the dehydration/rearrangement reaction, we conducted the tests under 393 K, 1 MPa, at a hydrogen flow rate of 150 mL min-1. First, we tried to synthesize 1G with 1A and hydrogen by a single-bed catalyst system (see Fig. 6a) using the physical mixture of Ru/C and Amberlyst-15 resin. From the analysis of GC-MS (see Fig. S11a in
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supporting information), bi(cyclopentane) was identified as the major product from this method. This phenomenon can be explained because the hydrogenation of 1F is faster than its rearrangement to 1G. Therefore, the 1F generated from the
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hydrogenation and dehydration of 1A was directly hydrogenated to bi(cyclopentane) before it being converted to 1G by rearrangement. As a solution to this problem, we designed a dual-bed system for the direct production of 1G with 1A and hydrogen
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(see Fig. 6b). In the first bed, the 1A was hydrogenated to 1B over the Ru/C catalyst. The 1B from the first bed was further converted to 1G in the second bed by the
ED
dehydration/rearrangement over Amberlyst-15 resin. As we expected, high carbon
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yield of 1G (78.2%) was achieved over the dual-bed catalyst system (see Fig. S11b in supporting information). This value is very close to the one (83.7%) which was
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obtained over the Amberlyst-15 resin using 1B as the feedstock.
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3.3 Hydrogenation of the hydrogenation/dehydration/rearrangement products Finally, we also investigated the hydrogenation of the dehydration/rearrangement
products (i.e. a mixture of 1F and 1G) under the catalysis of Pd/C. Under mild reaction conditions (393 K and 3.0 MPa H2), high carbon yield (96.0%) of decalin was obtained (see Figs. S12-S14 in supporting information). At the same time, we also identified small amount of bi(cyclopentane) (carbon yield: 4.0%) in the
16
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hydrogenation product. According to our measurement, the hydrogenation product as obtained has a high density (~0.87 g mL-1) and a low freezing point (228.7 K). As a potential application, it can be used as an additive to improve the thermal stability and volumetric heat values of jet fuels [43,44]. The reusability of Pd/C catalyst for the
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hydrogenation of the dehydration/rearrangement products (i.e. a mixture of 1F and 1G) was investigated. As we can see from Fig. S15, the Pd/C catalyst is stable under the investigated conditions. No evident deactivation was noticed during the three
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repeated usages.
In the previous work of our group [39], decalin has been synthesized by the intramolecular dehydration of cyclopentanol to cyclopentene, followed by
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oligomerization/rearrangement of cyclopentene and hydrogenation (see Scheme 4). Compared with this route, higher carbon yield (65.3% vs. 47.1%) of decalin can be
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achieved by the current route, which is advantageous in real application.
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4. Conclusions
In this work, a new route was developed for the production of renewable declain
CE
with cyclopentanone which can be derived from hemicellulose. It was found that
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1,2,3,4,5,6,7,8-octahydronaphthalene can be directly produced at high carbon yield (83.7%)
by
the
hydrogenation/dehydration/rearrangement
reaction
of
[1,1'-bi(cyclopentylidene)]-2-one (i.e. the self-aldol condensation product of cyclpentanone) over a dual-bed Ru/C and Amberlyst-15 catalyst system. The 1,2,3,4,5,6,7,8-octahydronaphthalene as obtained can be further hydrogenated to decalin over a Pd/C catalyst. This work offered a new route for the synthesis of
17
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renewable decalin which can be used as an additive to improve the thermal stability and volumetric heat values of jet fuels. Acknowledgments This work was funded by the National Natural Science Foundation of China (no.
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21776273; 21721004; 21690080; 21690082), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100), the National Key Projects for Fundamental Research and Development of China (2016YFA0202801), Dalian
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Science Foundation for Distinguished Young Scholars (no. 2015R005), Department of Science and Technology of Liaoning Province (under contract of 2015020086-101)
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and 100-talent project of Dalian Institute of Chemical Physics (DICP).
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ACCEPTED MANUSCRIPT 4535-4586. [58] B.G. Harvey, M.E. Wright, R.L. Quintana, Energy Fuels, 24 (2010) 267-273. [59] R. Weingarten, G.A. Tompsett, W.C. Conner, G.W. Huber, J. Catal., 279 (2011) 174-182.
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Scheme 1. Reaction pathway for the synthesis of decalin with cyclopentanone
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and hydrogen.
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Scheme 2. Reaction pathways for the generation of different products from the
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hydrogenation (or hydrogenolysis) of 1A.
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(i.e.
1F)
or
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Scheme 3. Reaction pathways for the generation of cyclopentylidene-cyclopentanes 1,2,3,4,5,6,7,8-octahydronaphthalene
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dehydration/rearrangement of 1B.
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(i.e.
1G)
from
the
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Scheme 4. Comparison of our previous and current routes for the synthesis of renewable decalin.
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80
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60
40
20
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Conversion or carbon yield (%)
100
0 Ru/C
Rh/C
Pt/C
Pd/C
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Figure 1. Conversion of 1A (black bars), the carbon yields of 1B (red bars), 1C (blue bars) and 1E (yellow bars) over different noble metal catalysts. Reaction conditions:
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393 K, 3 MPa H2, 3 h; 0.1 g catalyst, 2.0 g 1A.
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80
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60 40 20 0 n fio a N
5
t-3
t-1
ys erl
b Am
6
IRC e t i F rl be CR 6 m 7 A
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Conversion or carbon yield (%)
100
b Am
ys erl
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Figure 2. Conversion of 1B (black bars), the carbon yields of 1F (blue bars) and 1G (red bars) over different acidic resins. Reaction condition: 393 K, 0.1 MPa; 1.0 g
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catalyst; 1B flow rate: 0.04 mL min-1; N2 flow rate: 100 mL min-1.
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Nafion Amberlyst-15 Amberlyst-36
200
150
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-1
Heat of adsorption (kJ mol )
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100
50
0
1
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0
2 3 -1 NH3 coverage (mmol g )
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5
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Figure 3. Adsorption heat versus NH3 coverage at 353 K on the Nafion (■),
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Amberlyst-15 (▲), and Amberlyst-36 (●) resins.
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80
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60
40
20
0 Fixed bed continuous flow reactor
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Conversion or carbon yield (%)
100
Dean-Stark apparatus
Batch reactor
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Figure 4. Conversion of 1B (black bars), the carbon yields of 1F (blue bars) and 1G (red bars) over the Amberlyst-15 resin as the function of reactor. Reaction conditions:
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For fix-bed continuous flow reactor: 393 K, 0.1 MPa, 1.0 g catalyst; 1B flow rate:
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0.04 mL min-1; N2 flow rate: 150 mL min-1. For Dean-Stark apparatus and batch
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reactor: 393 K, 5.5 h; 7.6 g catalyst, 38 g 1B.
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80 Conversion of 1B Carbon yield of 1F Carbon yield of 1G
60 40 20
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0
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Conversion or carbon yield (%)
100
0.1
0.3 1.0 System pressure (MPa)
3.0
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Figure 5. Conversion of 1B (■), the carbon yields of 1F (▼) and 1G (▲) over the Amberlyst-15 resin as the function of system pressure. Reaction conditions: 393 K,
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1.0 g catalyst; 1B flow rate: 0.04 mL min-1; N2 flow rate: 150 mL min-1.
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(a)
(b)
Quartz sand
Quartz sand
Ru/C (1st bed)
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Physical mixture of Ru/C and Amberlyst-15
Amberlyst-15 (2nd bed)
Quartz wool
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Quartz wool
Dual-bed catalyst system
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Single-bed catalyst system
Figure 6. Single-bed (a) and dual-bed catalyst systems (b) used for the direct
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synthesis of 1G with 1A and hydrogen.
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Table 1. Specific surface areas (SBET), average pore volumes, average pore sizes and the amounts of acid sites of different acid resins. SBET
Average pore
Average pore
Acid amount
(m g )
volume (cm3 g-1)a
size (nm)a
(mmol g-1)b
Nafion
7.1
0.04
19.6
4.01
Amberlyst-36
7.0
0.01
8.2
Amberlyst-15
42.8
0.29
25.0
2
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Measured by N2-physisorption. b Measured by chemical titration.
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a
-1 a
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Catalyst
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4.05 4.68
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Graphical abstract
Renewable decalin was first synthesized in high carbon yield (~75%) with cyclopentanone by solid base catalysed solvent-free aldol condensation followed by hydrogenation/dehydration/rearrangement over a dual-bed catalyst system (Ru/C +
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Amberlyst-15) and hydrogenation over Pd/C catalyst.
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Synthesis of jet fuel additive with cyclopentanone Hao Tang , Fang Chen , Guangyi Li , Xiaofeng Yang , Yancheng Hu , Aiqin Wang , Yu Cong , Xiaodong Wang , Tao Zhang , Ning Li PII: DOI: Reference:
S2095-4956(17)31049-5 10.1016/j.jechem.2018.01.017 JECHEM 524
To appear in:
Journal of Energy Chemistry
Received date: Revised date: Accepted date:
17 November 2017 17 January 2018 24 January 2018
http://www.journals.elsevier.com/ journal-of-energy-chemistry/
Please cite this article as: Hao Tang , Fang Chen , Guangyi Li , Xiaofeng Yang , Yancheng Hu , Aiqin Wang , Yu Cong , Xiaodong Wang , Tao Zhang , Ning Li , Synthesis of jet fuel additive with cyclopentanone, Journal of Energy Chemistry (2018), doi: 10.1016/j.jechem.2018.01.017
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Synthesis of jet fuel additive with cyclopentanone
Hao Tanga,b,§, Fang Chena,b,§, Guangyi Lia, Xiaofeng Yanga, Yancheng Hua, Aiqin
a
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese
c
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Academy of Sciences, Dalian 116023, Liaoning, China b
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Wanga,c, Yu Conga, Xiaodong Wanga, Tao Zhanga,c, Ning Lia,c,*
University of Chinese Academy of Sciences, Beijing 100049, China iChEM (Collaborative Innovation Center of Chemistry for Energy Materials),
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Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023,
These authors contributed equally to this work.
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§
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Liaoning, China
*Corresponding author. E-mail: [email protected] (N. Li); Tel.: +86 411 84379738; Fax: +86 411 84685940.
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Abstract A new route was developed for the synthesis of renewable decalin with cyclopentanone which can be derived from lignocellulose. It was found that 1,2,3,4,5,6,7,8-octahydronaphthalene
could
be
selectively
produced
by
the
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hydrogenation/dehydration/rearrangement of [1,1'-bi(cyclopentylidene)]-2-one (i.e. the self-aldol condensation product of cyclopentanone) over a dual-bed catalyst system. Among the investigated catalysts, the Ru/C and Amberlyst-15 resin exhibited
[1,1'-bi(cyclopentan)]-2-ol [1,1'-bi(cyclopentan)]-2-ol
and to
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the highest activities for the hydrogenation of [1,1'-bi(cyclopentylidene)]-2-one to the
dehydration/rearrangement
of
1,2,3,4,5,6,7,8-octahydronaphthalene, respectively.
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Using Ru/C and Amberlyst-15 resin as the first bed and the second bed catalysts, 1,2,3,4,5,6,7,8-octahydronaphthalene was directly produced in high carbon yield
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(83.7%) under mild conditions (393 K, 1 MPa). After being hydrogenated, the
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1,2,3,4,5,6,7,8-octahydronaphthalene was converted to decalin which can be used as
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additive to improve the thermal stability and volumetric heat value of jet fuel.
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Keywords:
Lignocellulose;
Jet
fuel
Dehydration/rearrangement; Hydrogenation
2
additive;
Aldol
condensation;
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1. Introduction With the increase of social concern about the energy and environmental problems, the catalytic conversion of renewable, CO2 neutral and inedible biomass to high quality fuels [1–13] and value-added chemicals [14–26] has become a very hot topic.
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Jet fuel is one of the most demanded liquid transportation fuels. Globally, 12% of liquid transportation fuels are jet fuels [27]. Lignocellulose is the cheapest and the most abundant biomass. During the past years, the synthesis of jet fuel range
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hydrocarbons with the lignocellulosic platform compounds has drawn a lot of attention [28–40].
Decalin is one of the major components of JP-900, a coal-base thermally stable and
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high energy density jet fuel [41,42]. Due to its special chemical structure, decalin has been used as an additive to improve the thermally stability and volumetric heat value
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of jet fuel [43,44]. Cyclopentanone is a lignocellulosic platform compound which can
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be obtained by the aqueous phase selective hydrogenation of furfural [45–49]. To the best of our knowledge, there is no report about the production of renewable decalin
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with cyclopentanone. this
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In
work,
it
was
1,2,3,4,5,6,7,8-octahydronaphthalene
reported
for
can
selectively
be
the
first
time
produced
by
that the
hydrogenation/dehydration/rearrangement of [1,1'-bi(cyclopentylidene)]-2-one (i.e. the self-aldol condensation product of cyclopentanone) over a dual-bed (Ru/C and Amberlyst-15 resin) catalyst system. After being hydrogenated over the Pd/C catalyst, 1,2,3,4,5,6,7,8-octahydronaphthalene can be converted to decalin which can be used
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as an additive to improve the thermal stability and volumetric heat values of jet fuels. The strategy for this process is illustrated in Scheme 1. 2. Experimental 2.1. Materials
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2.1.1. Preparation of catalysts The MgAl hydrotalcite (MgAl-HT) catalyst used in the preparation of [1,1'-bi(cyclopentylidene)]-2-one was synthesized according to the literature [28] with
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some modification. The detail for the synthesis of the MgAl-HT catalyst was described in the supporting information. Activated carbon loaded noble metal (M/C, M = Ru, Pt, Rh, Pd) catalysts used in the hydrogenation reactions were prepared by
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the classical wet chemical reduction method with an activated carbon supplied by Guanghua activated carbon company. To facilitate the comparison, the theoretical
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contents of noble metals in the catalysts were controlled as 5% by weight (denoted as
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5 wt%). Taking the preparation of Ru/C catalyst for example, 3.88 g 10 wt% RuCl3•3H2O (analytical reagent grade, purity: 99.95%, supplied by HEOWNS)
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aqueous solution was added dropwise into a suspension of 3 g activated carbon and 30
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mL water. After being stirred at 318 K for 1 h, the pH of the mixture was adjusted to 9–10 by 1 mol L-1 NaOH. Subsequently, 20 g 40 wt% formaldehyde solution was added dropwise into the mixture. After being stirred at 358 K for another 70 min, the mixture was filtered, and washed with deionized water until no Cl– ion was detected in the filtrate and dried at 353 K for 3 h. Nafion resin was supplied by Jiangsu Success Resin Corporation. Amberlyst-15, Amberlyst-36 and Amberlite IRC 76CRF resins
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were purchased from the Dow Chemical Company. 2.1.2. Synthesis of [1,1'-bi(cyclopentylidene)]-2-one [1,1'-Bi(cyclopentylidene)]-2-one (i.e. 1A in Scheme 1) was synthesized by the solvent-free self-aldol condensation of cyclopentanone (analytical reagent grade,
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purity: 99.0%, supplied by Aladdin chemical reagents company) which can be produced by the aqueous phase selective hydrogenation of furfural [45-49]. The detail for the preparation of 1A was given in the supporting information. Under mild
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reaction conditions (393 K, 6 h), cyclopentanone was completely converted and a high carbon yield of 1A (87.0%) was achieved over the MgAl-HT catalyst. This result is consistent with what has been reported in the previous work of our group [37]. The
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1A as obtained was purified by vacuum distillation at 443 K and used as the feedstock for the subsequent steps.
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2.2. Activity test
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2.2.1. Hydrogenation of 1A
The activity tests of active carbon loaded noble metal catalysts for the
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hydrogenation of 1A were conducted in a stainless steel batch reactor. For each test,
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2.0 g 1A and 0.1 g noble metal catalyst were used. After the reaction was carried out at 393 K and 3 MPa H2 for 3 h, the mixture was quenched to room temperature. The liquid product was taken out of the reactor, filtered (to remove the catalyst) and analyzed
by
an
Agilent
7890B
gas
chromatograph
(GC).
The
[1,1'-bi(cyclopentan)]-2-ol (i.e. 1B in Scheme 1) as obtained from the hydrogenation of 1A over the Ru/C catalyst was directly used as the feedstock for the
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dehydration/rearrangement test. To integrate the hydrogenation and the subsequent dehydration/rearrangement into a one-step process. We also investigated the effects of reaction conditions on the hydrogenation of 1A over the Ru/C catalyst with a stainless steel tubular fixed-bed continuous flow reactor which has been described in our
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previous work [50]. For each test, 1.0 g Ru/C catalyst was used. 1A was pumped into the reactor (at a rate of 0.04 mL min-1) from the top of the reactor, along with hydrogen. Before reaching the catalyst, 1A was preheated to reaction temperature
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over quartz sand. After passing through the reactor and being cooled down to room temperature, the products became two phases in a gas-liquid separator. The gaseous products flowed through a back pressure regulator to maintain the system pressure at
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set value and analyzed online by an Agilent 7890B GC. The liquid products were drained from the gas-liquid separator after 4 h and analyzed by an Agilent 7890B GC.
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2.2.2. Dehydration/rearrangement of 1B
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The dehydration/rearrangement of 1B was carried out in a stainless steel tubular fixed-bed continuous flow reactor described in our previous work [50]. For each test,
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1.0 g solid acid catalyst was used. The 1B which was obtained from the
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hydrogenation of 1A over the Ru/C catalyst (without purification) was pumped into the reactor at a rate of 0.04 mL min-1 from the top of the reactor, along with nitrogen which was used as carrier gas. Before reaching the catalyst, 1B was preheated to reaction temperature over quartz sand. After passing through the reactor and being cooled down to room temperature, the products became two phases in a gas-liquid separator. The gaseous products flowed through a back pressure regulator to maintain
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the system pressure at set value and analyzed online by an Agilent 7890B GC. The liquid product was drained from the gas-liquid separator after 4 h and analyzed by another
Agilent
7890B
GC.
For
comparison,
we
studied
the
dehydration/rearrangement of 1B over the Amberlyst-15 resin using a stainless steel
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batch reactor. To do this, 7.6 g Amberlyst-15 resin and 38 g 1B were added in a stainless steel batch reactor. After being stirred at 393 K for 5.5 h, the mixture was quenched to room temperature. The liquid product was taken out from the reactor,
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filtered (to remove the catalyst), diluted and analyzed by an Agilent 7890B GC. In order to prove the negative effect of water which was generated during the reaction, we also investigated the dehydration/rearrangement of 1B over the Amberlyst-15
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resin with a Dean-Stark apparatus. Typically, 7.6 g Amberlyst-15 resin and 38 g 1B were added into a Dean-Stark apparatus and stirred at 393 K for certain time. After
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the reaction, the product was taken out of the flask, filtered (to remove the catalyst),
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diluted and analyzed by an Agilent 7890B GC. 2.2.3. Integrated hydrogenation/dehydration/rearrangement of 1A
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To fulfill the need of real application, we explored the direct synthesis of
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1,2,3,4,5,6,7,8-octahydronaphthalene with 1A and hydrogen. The reaction was carried out in the same stainless steel tubular fixed-bed continuous flow reactor as we used in the hydrogenation of 1A (or the dehydration/rearrangement of 1B). 1.0 g Ru/C and 1.0 g Amberlyst-15 resin were used for the tests. For the single-bed catalyst system, a physical mixture of Ru/C and Amberlyst-15 resin was used as the catalyst. For the dual-bed catalyst system, the Ru/C was used as the first-bed catalyst, the
7
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Amberlyst-15 resin was used as the second-bed catalyst. 1A was pumped into the reactor at 0.04 mL min-1 from the top of the reactor, along with hydrogen (which was used as the carrier gas and reactant at the same time). Before reaching the catalysts, 1A was preheated to reaction temperature over quartz sand. After passing through the
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reactor and being cooled down to room temperature, the products became two phases in a gas-liquid separator. The gaseous product flowed through a back pressure regulator to maintain the system pressure at set value and analyzed online by an
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Agilent 7890B GC. The liquid product was drained from the gas-liquid separator after 4 h and analyzed by another Agilent 7890B GC.
2.2.4. Hydrogenation of the dehydration/rearrangement products
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As the final aim of this work, we synthesized decalin by the hydrogenation of the dehydration/rearrangement
products
of
1B
(i.e.
a
mixture
of
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cyclopentylidene-cyclopentanes and 1,2,3,4,5,6,7,8-octahydronaphthalene which was
reaction
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obtained from the dehydration/rearrangement of 1B without further purification). The was
carried
out
by
a
stainless
steel
batch
reactor.
2.0
g
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dehydration/rearrangement products and 0.1 g Pd/C catalyst were used in the test.
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After being stirred at 393 K and 3 MPa H2 for 3 h, the mixture was quenched to room temperature. The liquid product was taken out from the stainless steel reactor, filtered (to remove the catalyst) and analyzed by an Agilent 7890B gas chromatograph. 2.3. Characterization 2.3.1. N2-physisorption The specific Brunauer-Emmett-Teller (BET) surface areas (SBET), average pore
8
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volumes and average pore sizes of the investigated catalysts were measured by nitrogen physisorption which was carried out at 77 K using an ASAP 2010 apparatus. Before each measurement, the sample was evacuated at 393 K for 3 h. 2.3.2. Chemical titration
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The amounts of acid sites on the surfaces of investigated acidic resins were measure by the chemical titration method described in literature [51]. For each measurement, 0.02 g catalyst was used. The sample was dispersed into 20 mL 0.01
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mol L-1 NaOH solution, sonicated for 1 h and then centrifuged. The filtrate was titrated with 0.01 mol L-1 HCl (which has been precalibrated by a standard NaOH solution) using methyl orange as indicator. The molar amount of acid sites per gram
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catalyst was calculated according to the consumption of HCl. 2.3.3. Microcalorimetric measurement of NH3 adsorption
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The microcalorimetric measurements of ammonia adsorption for the acidic resins
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used in the dehydration/rearrangement reaction were performed at 353 K using a BT2.15 heat-flux calorimeter (France, Seteram) connected to a gas-handling and a
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volumetric system employing MKS Baratron Capacitance Manometers for precision
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pressure measurement (±6.67×10−3 Pa). Before each measurement, ammonia (purity > 99.9%) was purified by successive freeze-pump-thaw cycles. The specific mass of sample with similar amount of acid sites was evacuated in a quartz cell at 353 K overnight under high vacuum to remove the physically adsorbed substance. The differential heat was measured as a function of acid site coverage by repeatedly introducing small dosage of ammonia onto the samples until the equilibrium pressure
9
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reached about 0.667–0.800 kPa. Then the system was evacuated overnight to remove the physically adsorbed ammonia, and a second adsorption was performed. 3. Results and discussion 3.1. Synthesis of 1A
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In the first part of this work, the [1,1'-bi(cyclopentylidene)]-2-one (i.e. 1A in Scheme 1) was synthesized by the solvent-free self-aldol condensation of cyclopentanone over the MgAl hydrotalcite (MgAl-HT) catalyst. The detail
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information for the preparation of 1A was given in the supporting information. Under mild reaction conditions (393 K, 6 h), cyclopentanone was completely converted. A high carbon yield of 1A (87.0%) was achieved over the MgAl-HT catalyst. This result
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is consistent with what has been reported in the previous work of our group [37]. The
following steps.
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1A as obtained was purified by vacuum distillation and used as the feedstock for the
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3.2. Hydrogenation/dehydration/rearrangement of 1A
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The hydrogenation of 1A was carried over a series of activated carbon loaded noble metal catalysts. Among the tested catalysts, Ru/C had the highest carbon yield to
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[1,1'-bi(cyclopentan)]-2-ol (i.e. 1B in Scheme 1) (see Fig. 1). Over this catalyst, high carbon yield (98.1%) of 1B was obtained after the reaction was carried out under mild conditions (393 K, 3 MPa) for 3 h. To figure out the reason for the higher selectivity of Ru/C for the hydrogenation of 1A to 1B, we characterized the investigated catalysts by N2-physisorption, XRD and CO-chemisorption. From the results illustrated in Table S1, no evident correspondence was observed between the selectivity of these 10
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catalysts and their specific BET surface areas, average particle sizes or metal dispersions. According to literature [52-55], the excellent performance of the Ru/C catalyst can be comprehended by the high activity of Ru for the hydrogenation of carbonyl compounds.
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Over the Rh/C, Pt/C and Pd/C catalysts, [1,1'-bi(cyclopentan)]-2-one (i.e. 1C in Scheme 2) was identfied as the major hydrogenation product (see Fig. S1 in supporting information), no [1,1'-bi(cyclopentylidene)]-2-ol (i.e. 1D in Scheme 2) was
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detected in the hydrogenation products. This result can be rationalized because the hydrogenation of C=C bond is faster and dynamically more favorable than the hydrogenation of C=O bond [56]. It is very interesting that di(cyclopentane) (i.e. 1E
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in Scheme 2) was also identified in the hydrogenation product over the Pt/C catalyst. This product may generated from the hydrogenolysis of 1A over the Pt/C catalyst.
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Taking into considersation of the higher selectivity and the relatively lower cost of
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Ru/C than those of Rh/C, Pt/C and Pd/C, we think it is a promising catalyst in the future application.
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The reusability of the Ru/C catalyst in the hydrogenation of 1A was checked as
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well. As we can see from the Fig. S2 in supporting information, the Ru/C catalyst is stable under the investiaged conditions. No evident deactivation was noticed during four repeated usages. Subsequently, we investigated the dehydration of 1B over a series of acidic resins. From Fig. 2, we can see that the strong solid acids which have –SO3H group as the active sites (such as Nafion, Amerlyst-15 and Amberlyst-36 resins [57–59]) are very
11
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active for the dehydration of 1B. Over them, high 1B conversions (> 90%) were achieved at 393 K. In contrast, the conversion of 1B (0.1%) over the Amberlite IRC 76CRF resin (a weak acid resin which has –COOH group as the active sites [60]) is very low under the same conditions.
supporting
information),
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From the analysis of GC-MS and NMR spectra (see Fig. S3 and Fig. S4 in cyclopentylidene-cyclopentanes
and
1,2,3,4,5,6,7,8-octahydronaphthalene (i.e. 1F and 1G in Scheme 3) were identified as
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the two major products from the reaction of 1B over the Nafion, Amerlyst-15 and Amberlyst-36 resins. According to the reaction pathways which were proposed in Scheme 3, 1G is generated by the rearrangement of 1F from the dehydration of 1B.
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From the DFT calculation results listed in the Table S2 in supporting information, we can see that the lowest energy of 1,2,3,4,5,6,7,8-octahydronaphthalene is lower than
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those of cyclopentylidene-cyclopentanes and other octahydronaphthalenes. This may
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be one reason for the further rearrangement of cyclopentylidene-cyclopentanes to 1,2,3,4,5,6,7,8-octahydronaphthalene over strong acid resins. As another possibility,
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the rearrangement of 1F to 1G can also be explained by the principles of carbocation
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chemistry. It is well known that tertiary carbocation is more stable than secondary carbocation. From Scheme 3, we can see that 1F has only one carbon atom which can form tertiary carbocation, while 1G has two carbon atoms which can form tertiary carbocation. As the result, 1G is more stable than 1F. Among the investigated catalysts,
Amberlyst-15
resin
exhibited
the
best
performance
for
the
dehydration/rearrangement of 1B to 1G. Over it, high carbon yield (85.1%) of 1G can
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be
achieved
at
393
K.
The
stability
of
Amberlyst-15
resin
in
the
dehydration/rearrangement of 1B was also investigated. As we can see from Fig. S5 in supporting information, the Amberlyst-15 resin is stable under the investigated conditions. No evident deactivation was noticed during the 8 h continuous test.
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To figure out the reason for the excellent performance of Amberlyst-15 resin, we characterized the Nafion, Amerlyst-15 and Amberlyst-36 resins by a series of technologies. According to the microcalorimetric measurements of ammonia
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adsorption illustrated in Fig. 3, the acid strengths of these strong acidic resins (which were indicated by the NH3 adsorption heats) decrease in the order of Nafion (219 kJ mol-1) > Amberlyst-15 (156 kJ mol-1), Amberlyst-36 (157 kJ mol-1). This sequence is with
the
activity
sequence
of
these
acidic
resins
in
the
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different
dehydration/rearrangement of 1B to 1G. Analogously, there is no clear relationship
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between the carbon yields of 1G and the specific surface areas or the amounts of acid
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sites on the surfaces of these acidic resins (see Table 1). Based on these results, we can’t simply attribute the higher activity of Amberlyst-15 resin to the acidity or BET
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surface area of this catalyst. However, it is noticed from Table 1 that the average pore
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sizes (or pore volumes) of these acidic resins decrease in the order of Amberlyst-15 > Nafion > Amberlyst-36. This sequence is consistent with the activity sequence of these resins in the dehydration/rearrangement of 1B to 1G. As we know, the internal diffusion is very important for low-temperature liquid phase reactions. Therefore, larger pore resin is favourable for the rearrangement of 1F to 1G (or desorption of 1G from the catalyst). This may be the reason for the higher carbon yield of 1G over the
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Amberlyst-15 resin. The influence of reactor type on the catalytic performance of Amberlyst-15 resin for the dehydration/rearrangement of 1B was studied. From Fig. 4, we can see that the fix-bed
continuous
flow
reactor
is
better
than
batch
reactor
for
the
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dehydration/rearrangement of 1B. Such an advantage is also significant even when the later was carried out at longer contacting time. Moreover, it was noticed that the catalytic performance of Amberlyst-15 resin can also be significantly improved when
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we used the Dean-Stark apparatus to replace the batch reactor. However, the advantage of Dean-Stark apparatus is less evident than that of the fix-bed continuous flow reactor under the investigated conditions. These results can be rationalized
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because the H2O molecules generated from the dehydration of 1B have lone pair electrons. In reaction, they can act as a Lewis base to occupy the proton sites on
ED
Amberlyst-15 resin and thus inhibit the acid-catalyzed rearrangement of 1F to 1G.
PT
Therefore, the removing of water is favourable for the dehydration/rearrangement of 1B. That is the reason why higher carbon yields of 1G were achieved in the
CE
Dean-Stark apparatus and the fix-bed continuous flow reactor (in which the water was
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removed from the catalyst during the reaction). Compared with the Dean-Stark apparatus, the fix-bed continuous flow reactor is more efficient for the removal of water under the investigated reaction conditions. Due to this reason, higher carbon yield of 1G was achieved when we used the fix-bed continuous flow reactor. To verify this speculation, we did some additional experiments. From the Fig. S6, it was noticed that the conversion of 1B to 1G is a two-step reaction. In the first step, 1B is
14
ACCEPTED MANUSCRIPT
converted to 1F by dehydration. In the second step, 1F was rearranged to 1G over acid sites. Based on the results illustrated in Fig. S7 and Fig. S8, we can see that the presence of water has evident negative effect on the acid-catalyzed rearrangement of 1F to 1G.
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The effect of system pressure on the performance of the Amberlyst-15 resin was investigated. It is noticed from Fig. 5 that the increase of system pressure is unfavourable for the dehydration/rearrangement of 1B to 1G. Such a negative effect is
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more evident when system pressure is higher than 1.0 MPa. This can be explained because high system pressure restrains the evaporation (or removal) of water from the surface
of
Amberlyst-15
resin,
is
unfavorable
for
the
M
dehydration/rearrangement of 1B.
which
To fulfil the need of real application, we also tried the direct production of 1G with
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1A and hydrogen which acts as reactant and carrier gas at the same time. Based on
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their excellent performances for the hydrogenation of 1A to 1B and the subsequent dehydration/rearrangement of 1B to 1G, Ru/C and Amberlyst-15 resin were selected
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as the catalysts. Before doing this, we studied the effects of hydrogen pressure and
AC
flow rate on the hydrogenation of 1A over the Ru/C catalyst using the fixed-bed continuous flow reactor which was used for the dehydration/rearrangement of 1B. From the results illustrated in Fig. S9 and Fig. S10 in supporting information, high hydrogen pressure and flow rate are favourable for the hydrogenation of 1A to 1B over the Ru/C catalyst. Taking into the consideration of the fact that too high carrier gas flow rate and system pressure will increase the energy consumption and restrain
15
ACCEPTED MANUSCRIPT
the dehydration/rearrangement reaction, we conducted the tests under 393 K, 1 MPa, at a hydrogen flow rate of 150 mL min-1. First, we tried to synthesize 1G with 1A and hydrogen by a single-bed catalyst system (see Fig. 6a) using the physical mixture of Ru/C and Amberlyst-15 resin. From the analysis of GC-MS (see Fig. S11a in
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supporting information), bi(cyclopentane) was identified as the major product from this method. This phenomenon can be explained because the hydrogenation of 1F is faster than its rearrangement to 1G. Therefore, the 1F generated from the
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hydrogenation and dehydration of 1A was directly hydrogenated to bi(cyclopentane) before it being converted to 1G by rearrangement. As a solution to this problem, we designed a dual-bed system for the direct production of 1G with 1A and hydrogen
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(see Fig. 6b). In the first bed, the 1A was hydrogenated to 1B over the Ru/C catalyst. The 1B from the first bed was further converted to 1G in the second bed by the
ED
dehydration/rearrangement over Amberlyst-15 resin. As we expected, high carbon
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yield of 1G (78.2%) was achieved over the dual-bed catalyst system (see Fig. S11b in supporting information). This value is very close to the one (83.7%) which was
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obtained over the Amberlyst-15 resin using 1B as the feedstock.
AC
3.3 Hydrogenation of the hydrogenation/dehydration/rearrangement products Finally, we also investigated the hydrogenation of the dehydration/rearrangement
products (i.e. a mixture of 1F and 1G) under the catalysis of Pd/C. Under mild reaction conditions (393 K and 3.0 MPa H2), high carbon yield (96.0%) of decalin was obtained (see Figs. S12-S14 in supporting information). At the same time, we also identified small amount of bi(cyclopentane) (carbon yield: 4.0%) in the
16
ACCEPTED MANUSCRIPT
hydrogenation product. According to our measurement, the hydrogenation product as obtained has a high density (~0.87 g mL-1) and a low freezing point (228.7 K). As a potential application, it can be used as an additive to improve the thermal stability and volumetric heat values of jet fuels [43,44]. The reusability of Pd/C catalyst for the
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hydrogenation of the dehydration/rearrangement products (i.e. a mixture of 1F and 1G) was investigated. As we can see from Fig. S15, the Pd/C catalyst is stable under the investigated conditions. No evident deactivation was noticed during the three
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repeated usages.
In the previous work of our group [39], decalin has been synthesized by the intramolecular dehydration of cyclopentanol to cyclopentene, followed by
M
oligomerization/rearrangement of cyclopentene and hydrogenation (see Scheme 4). Compared with this route, higher carbon yield (65.3% vs. 47.1%) of decalin can be
ED
achieved by the current route, which is advantageous in real application.
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4. Conclusions
In this work, a new route was developed for the production of renewable declain
CE
with cyclopentanone which can be derived from hemicellulose. It was found that
AC
1,2,3,4,5,6,7,8-octahydronaphthalene can be directly produced at high carbon yield (83.7%)
by
the
hydrogenation/dehydration/rearrangement
reaction
of
[1,1'-bi(cyclopentylidene)]-2-one (i.e. the self-aldol condensation product of cyclpentanone) over a dual-bed Ru/C and Amberlyst-15 catalyst system. The 1,2,3,4,5,6,7,8-octahydronaphthalene as obtained can be further hydrogenated to decalin over a Pd/C catalyst. This work offered a new route for the synthesis of
17
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renewable decalin which can be used as an additive to improve the thermal stability and volumetric heat values of jet fuels. Acknowledgments This work was funded by the National Natural Science Foundation of China (no.
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21776273; 21721004; 21690080; 21690082), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100), the National Key Projects for Fundamental Research and Development of China (2016YFA0202801), Dalian
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Science Foundation for Distinguished Young Scholars (no. 2015R005), Department of Science and Technology of Liaoning Province (under contract of 2015020086-101)
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CE
PT
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and 100-talent project of Dalian Institute of Chemical Physics (DICP).
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[54] L. Corbel-Demailly, B.-K. Ly, D.-P. Minh, B. Tapin, C. Especel, F. Epron, A. Cabiac, E. Guillon, M. Besson, C. Pinel, ChemSusChem, 6 (2013) 2388-2395.
[55] C. Michel, J. Zaffran, A.M. Ruppert, J. Matras-Michalska, M. Jedrzejczyk, J. Grams, P. Sautet, Chem. Commun. (Cambridge, U. K.), 50 (2014) 12450-12453. [56] P. Gallezot, D. Richard, Catal. Rev.-Sci. Eng., 40 (1998) 81-126. [57] K.A. Mauritz, R.B. Moore, Chem. Rev. (Washington, DC, U. S.), 104 (2004)
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ACCEPTED MANUSCRIPT 4535-4586. [58] B.G. Harvey, M.E. Wright, R.L. Quintana, Energy Fuels, 24 (2010) 267-273. [59] R. Weingarten, G.A. Tompsett, W.C. Conner, G.W. Huber, J. Catal., 279 (2011) 174-182.
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[60] P.A. Riveros, Hydrometallurgy, 72 (2004) 279-290.
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Scheme 1. Reaction pathway for the synthesis of decalin with cyclopentanone
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and hydrogen.
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Scheme 2. Reaction pathways for the generation of different products from the
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hydrogenation (or hydrogenolysis) of 1A.
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(i.e.
1F)
or
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Scheme 3. Reaction pathways for the generation of cyclopentylidene-cyclopentanes 1,2,3,4,5,6,7,8-octahydronaphthalene
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dehydration/rearrangement of 1B.
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(i.e.
1G)
from
the
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Scheme 4. Comparison of our previous and current routes for the synthesis of renewable decalin.
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60
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Conversion or carbon yield (%)
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0 Ru/C
Rh/C
Pt/C
Pd/C
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Figure 1. Conversion of 1A (black bars), the carbon yields of 1B (red bars), 1C (blue bars) and 1E (yellow bars) over different noble metal catalysts. Reaction conditions:
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393 K, 3 MPa H2, 3 h; 0.1 g catalyst, 2.0 g 1A.
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60 40 20 0 n fio a N
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t-3
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ys erl
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IRC e t i F rl be CR 6 m 7 A
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b Am
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Figure 2. Conversion of 1B (black bars), the carbon yields of 1F (blue bars) and 1G (red bars) over different acidic resins. Reaction condition: 393 K, 0.1 MPa; 1.0 g
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catalyst; 1B flow rate: 0.04 mL min-1; N2 flow rate: 100 mL min-1.
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Nafion Amberlyst-15 Amberlyst-36
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Heat of adsorption (kJ mol )
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2 3 -1 NH3 coverage (mmol g )
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Figure 3. Adsorption heat versus NH3 coverage at 353 K on the Nafion (■),
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Amberlyst-15 (▲), and Amberlyst-36 (●) resins.
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80
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0 Fixed bed continuous flow reactor
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Dean-Stark apparatus
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Figure 4. Conversion of 1B (black bars), the carbon yields of 1F (blue bars) and 1G (red bars) over the Amberlyst-15 resin as the function of reactor. Reaction conditions:
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For fix-bed continuous flow reactor: 393 K, 0.1 MPa, 1.0 g catalyst; 1B flow rate:
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0.04 mL min-1; N2 flow rate: 150 mL min-1. For Dean-Stark apparatus and batch
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reactor: 393 K, 5.5 h; 7.6 g catalyst, 38 g 1B.
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80 Conversion of 1B Carbon yield of 1F Carbon yield of 1G
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0.1
0.3 1.0 System pressure (MPa)
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Figure 5. Conversion of 1B (■), the carbon yields of 1F (▼) and 1G (▲) over the Amberlyst-15 resin as the function of system pressure. Reaction conditions: 393 K,
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(a)
(b)
Quartz sand
Quartz sand
Ru/C (1st bed)
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Single-bed catalyst system
Figure 6. Single-bed (a) and dual-bed catalyst systems (b) used for the direct
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synthesis of 1G with 1A and hydrogen.
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Table 1. Specific surface areas (SBET), average pore volumes, average pore sizes and the amounts of acid sites of different acid resins. SBET
Average pore
Average pore
Acid amount
(m g )
volume (cm3 g-1)a
size (nm)a
(mmol g-1)b
Nafion
7.1
0.04
19.6
4.01
Amberlyst-36
7.0
0.01
8.2
Amberlyst-15
42.8
0.29
25.0
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a
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Catalyst
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4.05 4.68
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Graphical abstract
Renewable decalin was first synthesized in high carbon yield (~75%) with cyclopentanone by solid base catalysed solvent-free aldol condensation followed by hydrogenation/dehydration/rearrangement over a dual-bed catalyst system (Ru/C +
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Amberlyst-15) and hydrogenation over Pd/C catalyst.
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