Synthesis of Renewable High-Density Fuel with Cyclopentanone

8 Jan 2017 - Advances in Nanocatalyst Design for Biofuel Production. Alessio Zuliani , Francisco Ivars , Rafael Luque. ChemCatChem 2018 10 (9), 1968- ...
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Synthesis of Renewable High-Density Fuel with Cyclopentanone Derived from Hemicellulose Wei Wang,†,‡ Ning Li,*,†,§ Guangyi Li,†,§ Shanshan Li,† Wentao Wang,† Aiqin Wang,†,§ Yu Cong,† Xiaodong Wang,† and Tao Zhang*,†,§

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†

State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, No. 457 Zhongshan Road, Dalian 116023, China ‡ Shaanxi Key Laboratory of Catalysis, School of Chemistry and Environment Science, Shaanxi Sci-Tech University, No. 1 Dongyihuan Road, Hanzhong 723001, China § iChEM (Collaborative Innovation Centre of Chemistry for Energy Materials), Dalian Institute of Chemical Physics, Chinese Academy of Sciences, No. 457 Zhongshan Road, Dalian 116023, China S Supporting Information *

ABSTRACT: 1-(3-Cyclopentyl)cyclopentyl-2-cyclopentylcyclopentane, a renewable high-density fuel, was first produced in a high overall carbon yield (∼70%) with cyclopenanone that can be derived from hemicellulose. The synthetic route used in this work contains three steps. In the first step, 2-cyclopentyl cyclopentanone was synthesized for the first time by a one-pot reaction of cyclopentanone and hydrogen under the catalysis of Raney metal and alkali hydroxides. Over the optimized catalyst (Raney cobalt + KOH), a high carbon yield (83.3%) of 2-cyclopentyl cyclopentanone was achieved at 353 K. In the second step, 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone was produced in a high carbon yield (95.4%) by the solvent-free self-aldol condensation of 2-cyclopentyl cyclopentanone under the vacuum conditions. In the third step, the 2cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone was hydrodeoxygenated over the Ni-SiO2 catalyst under solventfree conditions. High carbon yields of 1-(3-cyclopentyl)cyclopentyl-2-cyclopentylcyclopentane (88.5%) and polycycloalkanes (99.0%) were obtained. The Ni-SiO2 catalyst was stable under investigated conditions. No evident deactivation was noticed during the 50 h time on stream. The as-obtained polycycloalkane mixture has a density of 0.943 g mL−1 and a freezing point of 233.7 K. As a potential application, it can be blended into conventional high density fuels (e.g., JP-10) for rockets and missile propulsion. KEYWORDS: High density fuel, Lignocellulose, Cyclopentanone, Aldol condensation, Selective hydrogenation, Hydrodeoxygenation

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followed by isomerization and hydrogenation.9 Because the fossil energy is limited and unrenewable, it is necessary to exploit some new synthetic routes for the preparation of high density fuel with renewable biomass. In the previous work of the Harvey,10−12 Zou et al.13 and their co-workers, several synthetic routes for the renewable high density fuels have been developed using terpenes (such as pinene, limonene, camphene, crude turpentine, etc.), cineoles and linalool as the feedstocks. As we know, the terpenes, cineoles and linalool are usually obtained from some specific woods and plants. Their resources are limited. To fulfill the great demand of future application, some new synthetic routes for the production of high density fuels with cheaper and ampler biomass feedstocks should be exploited.

INTRODUCTION In recent years, the conversion of abundant and renewable biomass to high quality fuels1−3 and useful chemicals4−8 has drawn a lot of attention. Polycycloalkanes are a family of high density fuels that are widely used for special aviation and propulsion. Due to their special chemical structures, polycycloalkanes have relatively higher densities (or volumetric heat values) than traditional refined fuels.9 In real application, polycycloalkanes can be used to increase the range, payload and/or velocity of aircrafts without increasing the volume of oil tank. Alternatively, they can also be used to decrease the size of fuel tank without impairing the flight performance. This character is especially useful for some volume-constrained aircrafts (such as rocket and missile) to save more space for ordinance, electronics, and other components. The currently used high density fuels (for example JP-10, RJ4, RJ-5, etc.) are derived from fossil energy by the Diels−Alder reactions of cyclopentadiene (or methyl-cyclopentadiene) © 2017 American Chemical Society

Received: October 23, 2016 Revised: January 3, 2017 Published: January 8, 2017 1812

DOI: 10.1021/acssuschemeng.6b02554 ACS Sustainable Chem. Eng. 2017, 5, 1812−1817

Research Article

ACS Sustainable Chemistry & Engineering Lignocellulose is the chief constitute of forestry and agricultural residues. It is much cheaper and more abundant than other forms of biomass. In recent years, plenty of work has been carried out on the synthesis of renewable fuels with the platform compounds that can be obtained from lignocellulose.14−19 However, the reports about the production of high density fuel using lignocellulosic platform compounds are relatively few. Cyclopentanone is a lignocellulosic platform compound that can be obtained by the hydrogenation of furfural.20 On the basis of its cyclic chemical structure, this compound can be utilized for the production of renewable high density fuel. In this work, 1-(3-cyclopentyl)cyclopentyl-2cyclopentylcyclopentane, a C20 polycycloalkane with a density of 0.943 g mL−1 and a freezing point of 233.7 K, was first obtained in an overall carbon yield of ∼70% with cyclopentanone and hydrogen. To the best of our knowledge, this density is the highest among those of reported lignocellusic hydrocarbon biofuels. As a potential application, this polycycloalkane can be used as an alternative fuel for rockets and missile propulsion.

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Figure 1. Reactor for the synthesis of 2-cyclopentyl-5-(2cyclopentylcyclopentylidene)cyclopentanone. at 423 K and ∼3 kPa for 1 h. The liquid product was collected from the flask, diluted, and analyzed by the same Agilent 7890A GC instrument. According to the Supporting Information, the self-aldol condensation reactions of cyclopentanone and 2-cyclopentyl cyclopentanone under the catalysis of alkali hydroxide solution and alkali hydroxides follow heterogeneously catalyzed pathways. Hydrodeoxygenation (HDO). The HDO of the 2-cyclopentyl-5-(2cyclopentylcyclopentylidene)cyclopentanone was conducted at 533 K under solvent-free conditions. 1.8 g of Ni-SiO2 catalyst was used. Before the test, the catalyst was in situ pretreated at 733 K in a stainless steel tubular reactor by H2 flow (120 mL min−1) for 2 h. After, the reactor temperature decreased to 533 K and stabilized at that value for 0.5 h. The 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone (purified by vacuum distillation) was fed into the reactor (0.04 mL min−1) along with H2 (120 mL min−1). After passing through a gas−liquid separator and a back pressure regulator (which was used to maintain the system pressure at 6 MPa), the gas phase products were analyzed online by an Agilent 6890N GC. The CO2 in the gaseous product was separated by a RESTEK HS-DB 100/120 packed column (30 feet, 1/8 in. outer diameter, 2.0 mm inner diameter) using helium as the carrier gas (flow rate: 24 mL min−1) and analyzed by a thermal conductivity detector (TCD). The TCD and the injection port were held at 523 and 393 K, respectively. The alkanes in the gaseous product were analyzed by a FID that was connected with a RESTEK Rt-Q-BOND capillary column (30 m, 0.32 mm ID, 10 μm film) using helium as the carrier gas (flow rate of 1 mL min−1). The oven temperature was held at 323 K for 2 min, then increased to 473 K at a rate of 15 K min−1 and kept at that temperature for 10 min. The liquid phase products were collected periodically from the bottom of separator, diluted and analyzed by the Agilent 7890A GC which was used for the analysis of condensation products.

EXPERIMENTAL SECTION

Catalyst Preparation. The KOH, NaOH, and LiOH were supplied by Aladdin Chemical Reagent Co., Ltd. Raney Co, Raney nickel, Raney copper, and Raney iron were purchased from Dalian Tongyong Chemical Co., Ltd. The Ni-SiO2 catalyst utilized in the solvent-free hydrodeoxygenation (HDO) step was prepared in accordance with the literature21 by the deposition−precipitation (DP) method. Typically, 250 mLof Ni(NO3)2·6H2O (10.2 g) aqueous solution was divided into two parts. 6.3 g of urea was added to one part (50 mL), then the urea solution was added dropwise to the rest of the Ni(NO3)2·6H2O solution (200 mL) together with 1.9 g of SiO2 and 0.3 mL of HNO3 (65 wt %) under vigorous stirring at 353 K. After the precipitation process, the resulting suspension was rapidly heated to 363 K and stirred at that temperature for 10 h. Then the solid was filtered, washed to neutral, desiccated at 383 K for 10 h, and heated in air flow at 773 K for 4 h. Activity Test. Synthesis of 2-Cyclopentyl Cyclopentanone. The direct synthesis of 2-cyclopentyl cyclopentanone by the one-pot reaction of cyclopentanone and hydrogen was conducted with a stainless steel batch reactor. For each test, 2.0 g of cyclopentanone, 2.0 mL of alkali hydroxide solution (1.25 mol L−1), and 0.1 g of Raney metal were utilized. Before the test, the stainless steel batch reactor was purged by argon for three times. The mixture of catalyst and reactant was stirred at 353 K for 6 h. (According to the blank experiment result that is illustrated in Figure S1, the carbon yield of cyclopentylidene cyclopentanone over KOH at 353 K increased with reaction time, reached the maximum after 6 h and stabilized. Therefore, we chose 6 h as the reaction time for the first stage of the one-pot reaction.) At this moment, hydrogen was introduced into the reactor until the system pressure reached 2.0 MPa. The reaction was conducted at 353 K for additional 2 h. Subsequently, the stainless steel batch reactor was quenched with ice. The liquid products were collected from the stainless steel batch reactor, extracted using ethyl acetate, and analyzed by an Agilent 7890A gas chromatograph (GC) equipped with a HPINNOWAX capillary column (30 m, 0.25 mm ID, 0.5 mm film) and a flame ionization detector (FID). The oven temperature was held at 313 K for 2 min, increased to 553 K at a rate of 15 K min−1, and stayed at that temperature for 5 min. Helium was used as the carrier gas at a flow rate of 1.5 mL min−1. Synthesis of 2-Cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone. The self-aldol condensation of 2-cyclopentyl cyclopentanone to 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone was conducted in a flask that was connected with a condenser and a water pump to remove the water generated during the reaction (see Figure 1). Typically, 5.0 g of 2-cyclopentyl cyclopentanone and 0.25 g of alkali hydroxide were vigorously stirred

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RESULTS AND DISSCUSSION Synthesis of 2-Cyclopentyl cyclopentanone. 2-Cyclopentyl cylopentanone has a jasmine like smell and can be used as perfume, flavouring or wood preservative.22 In the first part of this work, we explored the direct synthesis of 2-cyclopentyl cylopentanone by the one-pot reaction of cylopentanone and hydrogen under the catalysis of different Raney metals and alkali hydroxides. On the basis of GC analysis and NMR spectra (see Figures S2−S4), 2-cyclopentyl cylopentanone, 2-cyclopentylidene cyclopentanone and small amount of cyclopentanol were identified in the liquid products. According to Scheme 1, the 2-cyclopentylidene cyclopentanone was generated from the self-aldol condensation of cylopentanone. Cyclopentyl cylopentanone was produced by the selective hydrogenation of C C bond in 2-cyclopentylidene cyclopentanone. The cyclopentanol was generated by the hydrogenation of unreacted 1813

DOI: 10.1021/acssuschemeng.6b02554 ACS Sustainable Chem. Eng. 2017, 5, 1812−1817

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ACS Sustainable Chemistry & Engineering Scheme 1. Reaction Pathways for the Generation of 2Cyclopentyl Cylopentanone, 2-Cyclopentylidene Cyclopentanone, and Cyclopentanonol

Figure 3. Cyclopentanone conversion (black bars) and the carbon yields of 2-cyclopentyl cylopentanone (dark gray bars), 2-cyclopentylidene cyclopentanone (light gray bars), and cyclopentanonol (white bars) under the catalysis of Raney Co and alkali hydroxides. Reaction conditions: 353 K, 8 h; 2.0 g cyclopentanone, 0.1 g Raney Co, 2.0 mL alkali hydroxide solution (1.25 mol L−1).

cyclopentanone (or the cyclopentanone from the retro-aldol condensation of 2-cyclopentylidene cyclopentanone). From the results shown in Figure 2, the mixture of Raney Co and KOH solution (denoted as Raney Co + KOH) exhibited

S6), 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone was detected as the predominate product from this reaction. This compound exists as a liquid at room temperature (see Figure S7). Therefore, it can be directly converted to 1-(3-cyclopentyl)cyclopentyl-2-cyclopentylcyclopentane by the solvent-free hydrodeoxygenation (see Scheme 2). From the results shown in Figure 4, it is noticed that the removal of water from the reaction system by vacuum distillation can significantly increase the carbon yield of 2cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone over KOH catalyst. This phenomenon can be explained by two reasons: (1) The aldol condensation reactions are reversible. Therefore, the removal of water is favorable for the formation of 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone from the pointview of reaction equilibrium. (2) The removal of water can also promote the generation of 2cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone by suppressing the retro-aldol condensation. Subsequently, we compared the catalytic performances of various alkali hydroxides (see Figure 5 and Figure S8). Among them, KOH exhibited the highest activity. Over it, high carbon y i eld ( 95 .4 % ) a n d T O N o f 2- cyc lope nt yl-5 -(2 cyclopentylcyclopentylidene)cyclopentanone were gained after the reaction was conducted at 423 K for 1 h. Similar as what we observed in the one-pot reaction of cyclopentanone and hydrogen, the high activity of KOH can be comprehended by its higher base strength. The impacts of reaction temperature and reaction time on the performance of KOH catalyst were also explored. Based on Figure 6 and 7, the 2-cyclopentyl cyclopentanone conversion and carbon yield of 2-cyclopentyl-5-(2cyclopentylcyclopentylidene)cyclopentanone over KOH increased with reaction temperature (or reaction time), reached the maximum after reacting at 423 K for 1 h, then leveled off. Hydrodeoxygenation (HDO). Finally, we also studied the solvent-free HDO of 2-cyclopentyl-5-(2cyclopentylcyclopentylidene)cyclopentanone over the Ni-SiO2 catalyst. According to the result of GC−MS analysis (see Figures S9−S12), the 2-cyclopentyl-5-(2cyclopentylcyclopentylidene)cyclopentanone was completely converted after being hydrodeoxygenated over the Ni-SiO2 catalyst under investigated conditions (533 K and 6 MPa). 1-

Figure 2. Cyclopentanone conversions (black bars) and the carbon yields of 2-cyclopentyl cylopentanone (dark gray bars), 2-cyclopentylidene cyclopentanone (light gray bars), and cyclopentanonol (white bars) under the catalysis of KOH and Raney metals. Reaction conditions: 353 K, 8 h; 2.0 g cyclopentanone, 0.1 g Raney metal, 2.0 mL KOH solution (1.25 mol L−1).

the best performance among the investigated catalyst systems. Over it, 94.8% cyclopentanone conversion and 83.3% carbon yield of 2-cyclopentyl cylopentanone were obtained after reacted at 353 K for 6 h. For comparison, we also studied the catalytic performances of Raney Co and other alkali hydroxides. According to Figure 3, the carbon yields of 2cyclopentyl cylopentanone over the Raney Co + NaOH and Raney Co + LiOH catalysts are obviously lower than that over the Raney Co + KOH catalyst. On the contrary, the carbon yields of cyclopentanol over the Raney Co + NaOH and Raney Co + LiOH catalysts are obviously higher than that over the Raney Co + KOH catalyst. This result can be rationalized because the base strength of KOH is higher than those of LiOH and NaOH. As we know, the higher base strength of the catalyst is favorable for the deprotonation (or the generation of carbanion) which is considered as the first step for the basecatalyzed aldol condensation reactions. Synthesis of 2-Cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone. In the second step, we explored the self-aldol condensation of the 2cyclopentyl cyclopentanone under the catalysis of KOH. Based on the result of GC−MS analysis (see Figures S5 and 1814

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Scheme 2. Reaction Pathways for the Generation of 2-Cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone, and 1-(3Cyclopentyl)cyclopentyl-2-cyclopentylcyclopentane

Figure 6. 2-Cyclopentyl cyclopentanone conversion (■) and the carbon yield of 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone (▲) over KOH as the function of reaction temperature. Reaction conditions: 1 h, ∼3 kPa; 5.0 g 2-cyclopentyl cyclopentanone, 0.25 g KOH.

Figure 4. 2-Cyclopentyl cyclopentanone conversion (black bars) and the carbon yield of 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone (light gray bars) over KOH. Reaction conditions: 423 K, 1 h at the system pressure of 0.1 MPa or ∼3 kPa; 5.0 g cyclopentanone, 0.25 g KOH.

Figure 7. 2-Cyclopentyl cyclopentanone conversion (■) and the carbon yield of 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone (▲) over KOH as the function of reaction time. Reaction conditions: 423 K, ∼3 kPa; 5.0 g 2-cyclopentyl cyclopentanone, 0.25 g KOH.

Figure 5. 2-Cyclopentyl cyclopentanone conversions (black bars) and the carbon yields of 2-cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone (light gray bars) over alkali hydroxides. Reaction conditions: 423 K, 1 h at the system pressure of ∼3 kPa; 5.0 g 2cyclopentyl cyclopentanone, 0.25 g alkali hydroxide.

cyclopentylcyclopentylidene)cyclopentanone. From Figure S13, we can see that the Ni-SiO2 catalyst is stable when 2cyclopentyl-5-(2-cyclopentylcyclopentylidene)cyclopentanone conversion is around 80%. No distinct deactivation was observed during the 50 h time on stream either. According our measurement, the density and the freezing point of the polycycloalkanes mixture obtained in this work were 0.943 g mL−1 and 233.7 K, respectively. These properties are comparable with those of JP-10 and the hydrogenated pinene dimers which have been reported in the previous work of Harvey,10,24,25 Zou,13,26 and their co-workers (see Table 1). To the best of our knowledge, this density (0.943 g mL−1) is the highest among the reported lignocellulosic liquid hydrocarbon fuels.

(3-Cyclopentyl)cyclopentyl-2-cyclopentylcyclopentane was detected as the predominate product. Meanwhile, small amounts of 1,3-dicyclopentyl cyclopentane and 2-cyclopentyl cyclopentane were also detected in the HDO product. The carbon yields of 1-(3-cyclopentyl)cyclopentyl-2-cyclopentylcyclopentane and polycycloalkanes were measured as 88.5% and 99.0%, respectively (see Figure 8). As what has been reported in our previous work about other reaction system,23 the Ni-SiO2 catalyst is stable for the solvent-free HDO of 2-cyclopentyl-5(2-cyclopentylcyclopentylidene)cyclopentanone. No distinct deactivation was observed during the 50 h time on stream. To verify further the good stability of the Ni-SiO2 catalyst, we increased the space velocity of 2-cyclopentyl-5-(21815

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application, it can be blended into conventional high density fuels (such as JP-10) for rockets and missile propulsion.

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ASSOCIATED CONTENT

S Supporting Information *

The Supporting Information is available free of charge on the ACS Publications website at DOI: 10.1021/acssuschemeng.6b02554. Blank experiment result for the aldol condensation of cyclopentanone under the catalysis of KOH solution; GC−MS chromatograms, 1H and 13C NMR spectra and photo of the different products; activity test results for the solvent-free self-aldol condensation of 2-cyclopentyl cylopentanone under the catalysis of equal moles of alkali hydroxide; the stability test of the Ni-SiO2 catalyst at high space velocity (PDF)

Figure 8. Carbon yields of different cycloalkanes over the Ni-SiO2 catalyst as the function of reaction time. Reaction conditions: 533 K, 6.0 MPa, 1.80 g catalyst; 2-cyclopentyl-5-(2cyclopentylcyclopentylidene)cyclopentanone flow rate 0.04 mL min−1; hydrogen flow rate 120 mL min−1.

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Table 1. Densities and Freezing Points of JP-10 Fuel, Hydrogenated Pinene Dimers and the Polycycloalkanes Mixture Obtained in This Work

Density (g mL−1) Freezing point (K)

JP10a

Hydrogenated pinene dimersa

Polycycloalkanes mixture obtained in this workb

0.94

0.938

0.943

194

243

233.7

AUTHOR INFORMATION

Corresponding Authors

*Prof. Tao Zhang. Tel: +86-411-84379015. Fax: +86-41184691570. E-mail: [email protected]. *Prof. Ning Li. Tel.: +86-411-84379738. Fax: +86-41184685940. E-mail: [email protected]. ORCID

Ning Li: 0000-0002-8235-8801 Tao Zhang: 0000-0001-9470-7215 Notes

The authors declare no competing financial interest.

a

According to the values reported in the literature.10 bMeasured in this work.

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ACKNOWLEDGMENTS This work was funded by the National Natural Science Foundation of China (no. 21277140, 21476229, 21506213, 21690082, 21690084, and 21672210), Dalian Science Foundation for Distinguished Young Scholars (no. 2015R005), the Strategic Priority Research Program of the Chinese Academy of Sciences (XDB17020100), Department of Science and Technology of Liaoning Province (under contract of 2015020086-101) and 100-talent project of Dalian Institute of Chemical Physics (DICP). Dr. Wei Wang appreciates the Education Department of Shaanxi Provincial Government Research Project (no. 16JK1146), the Funds of Research Programs of Shaanxi University of Technology (no. SLGQD13(2)-1) for financial support.

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CONCLUSIONS Herein, we reported a new route for the production of a high density fuel, 1-(3-cyclopentyl)cyclopentyl-2-cyclopentylcyclopentane, with cyclopenanone that can be derived from lignocellulose. This route is composed of three steps: In the first step, 2-cyclopentyl cyclopentanone was obtained by the one-pot reaction of cyclopentanone and hydrogen under the catalysis of different Raney metals and alkali hydroxides. Among the investigated catalysts, the Raney Co + KOH exhibited the best performance. Over this catalyst, 83.3% carbon yield of 2cyclopentyl cyclopentanone was obtained under mild conditions (353 K, 2 MPa). In the second step, 2-cyclopentyl-5-(2cyclopentylcyclopentylidene)cyclopentanone was synthesized by the self-aldol condensation of 2-cyclopentyl cyclopentanone under the catalysis of alkali hydroxides. Lower system pressure is favorable for this reaction, which can be explained by reaction equilibrium and restraining the retro-aldol condensation. Among the investigated catalysts, KOH exhibited the highest activity which can be comprehended by its higher base strength. In the third step, the 2-cyclopentyl-5-(2cyclopentylcyclopentylidene)cyclopentanone which can be obtained at 95.4% carbon yield from the second step was further hydrodeoxygenated under solvent-free conditions. The Ni-SiO2 catalyst exhibited high activity and good stability for the HDO reaction. Over it, high carbon yields of 1-(3cyclopentyl)cyclopentyl-2-cyclopentyl cyclopentane (88.5%) and polycycloalkanes (99.0%) were achieved. No evident deactivation was observed during the 50 h time on-stream. The as-obtained polycycloalkanes mixture has a density of 0.943 g mL−1 and a freezing point of 233.7 K. As a potential

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DOI: 10.1021/acssuschemeng.6b02554 ACS Sustainable Chem. Eng. 2017, 5, 1812−1817

Research Article

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DOI: 10.1021/acssuschemeng.6b02554 ACS Sustainable Chem. Eng. 2017, 5, 1812−1817