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Bioresource Technology Manuscript Draft Manuscript Number: BITE-D-11-03811 Title: A new process for converting carbohydrate biomass into

methanol based on the reduction of formic acid under hydrothermal conditions Article Type: Original research paper Keywords: biomass utilization; methanol; Cu/ZnO catalyst; hydrothermal conditions Abstract: In the present study, the reduction of formic acid into methanol using Cu as a catalyst in the presence of Zn under hydrothermal conditions was evaluated. Results showed that methanol can be produced from formic acid in a high yield of 28%, and Cu or Cu/ZnO acts as the active catalyst. Thus, combined the present results with those of previous studies that carbohydrate biomass can be easily converted into formic acid in high yield by hydrothermal oxidation, a new two-step process for the conversion of carbohydrate biomass into methanol under hydrothermal conditions can be achieved. The first step of the process is the oxidation of carbohydrates into formic acid, which is subsequently reduced into methanol in the second step, according to the following mechanism: C6H12O6 + 3 O2 6 HCOOH + 6 H2 6 CH3OH + 6 H2O. Thus, this process could be expected to emit no CO2.

Graphical Abstract

(Previous study)

This study
Proposed mechanism

*Highlights

HCOOH can easily be reduced into CH3OH under hydrothermal conditions using Zn and Cu. Cu or Cu/ZnO may act as the active catalyst. Combined with past result, the conversion of carbohydrate to CH3OH could be achieved.

*Manuscript Click here to view linked References

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A new process for converting carbohydrate biomass into methanol based on the reduction of formic acid under hydrothermal conditions
Jianke Liu,a Xu Zeng,a,* Min Cheng,a Fangming Jinb,*
a

State Key Laboratory of Pollution Control and Resources Reuse, College of Environmental Science and Engineering, Tongji University, 1239 Siping Road, Shanghai 200092, China b School of Environmental Science and Engineering, Shanghai Jiao Tong University, Shanghai 200240, China

Corresponding Author: Tel/Fax: + 86-21-54742283 (F. Jin); + 86-21-65985813 (X. Zeng). E-mail: fmjin@sjtu.edu.cn (F. Jin); zengxu2006@163.com (X. Zeng).

Abstract: In the present study, the reduction of formic acid into methanol using Cu as a catalyst in the presence of Zn under hydrothermal conditions was evaluated. Results showed that methanol can be produced from formic acid in a high yield of 28%, and Cu or Cu/ZnO acts as the active catalyst. Thus, combined the present results with those of previous studies that carbohydrate biomass can be easily converted into formic acid in high yield by hydrothermal oxidation, a new two-step process for the conversion of carbohydrate biomass into methanol under hydrothermal conditions can be achieved. The first step of the process is the oxidation of carbohydrates into formic acid, which is subsequently reduced into methanol in the second step, according to the following mechanism: C6H12O6 + 3O2 6HCOOH + 6H2 6CH3OH + 6H2O. Thus, this process could be expected to emit no CO2. Keywords: biomass utilization; methanol; Cu/ZnO catalyst; hydrothermal conditions

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1. Introduction The consumption of fossil fuels has led to the current energy crisis and serious environmental problems. To reduce the worlds dependence on fossil fuels, biomass has been paid more attention as a source of sustainable energy and a raw material for different chemical stocks (Huber et al., 2006; Jin & Enomoto, 2011; Li et al., 2001; Zhang et al., 2010; Zhang et al., 2011). Currently, many studies have been conducted on the conversion of biomass into fuels and other chemicals by biochemical/biotechnical methods (Kumar et al., 2008; Saxena et al., 2009). However, because microorganisms cannot easily degrade some types of biomass (such as cellulose), biochemical methods display several disadvantages, including a low rate of enzymatic hydrolysis and low efficiency. Thus, the development of highly effective and environmentally friendly methods for the conversion of biomass is strongly desired. Hydrothermal reactions using high temperature water (HTW) as the reaction medium have been proven to be an environmentally friendly technology for the conversion of various types of biomasses into value-added chemicals (Fang et al., 2008; Jin et al., 2010; Jing et al., 2007; Qi et al., 2008; Watchararuji et al., 2008). HTW has unique features compared to ambient liquid water. For example, the ion product (Kw) at 250 ~ 300 C is approximately three orders of magnitude greater than that of ambient liquid water, which could help to promote the reactions significantly (Akiya & Savage, 2002). The conversion of biomass into methanol, an important multipurpose base chemical, has received a significant amount of attention (Cheng et al., 2010; Hamelinck & Faaij,

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2002; Kumabe et al., 2008). For the storage, transportation, and use of energy, methanol is a promising alternative to oil and natural gas. Moreover, methanol is a convenient and clean liquid fuel that is often used as a carrier of energy for fuel cell applications, especially mobile and transportation devices. However, methanol is predominantly produced from syngas. In this process, avoidance of high methane conversion and coke deposition are desired (Lee & Sardesai, 2005; Meshkini et al., 2010). More importantly, though syngas could be produced from CO2 and CH4 (Li et al., 2001), the conventional generation of syngas is dependent on fossil fuels and releases large amounts of CO2 and other by-products. Therefore, the development of new processes for the production of methanol from biomass via environmentally friendly hydrothermal reactions is important. In previous studies, carbohydrate biomass was efficiently converted into formic acid under mild hydrothermal conditions at 250 C (Jin et al., 2008). Although formic acid is an important organic chemical, methanol has wider applications as a fuel, and the demand for methanol is high. Additionally, the utilization of formic acid is restricted due to its difficult separation from aqueous solution. If formic acid could be readily and efficiently reduced into methanol under mild conditions, then carbohydrate biomass could be converted into methanol via the following two step process: C6H12O6 + 3O2 6HCOOH HCOOH + 2H2 CH3OH + H2O (1) (2)

The process described in Eqs. 1 and 2 has a benefit of without greenhouse gas CO2

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emitting. The source of hydrogen is important for the reduction of formic acid, and water may be the best potential hydrogen source, if the technology is sufficient. Metals with a high reductive potential can be used to produce hydrogen from water. In our previous studies, Zn easily reacted with water to produce large amounts of hydrogen under hydrothermal conditions. The use of Zn as a reductant under hydrothermal conditions has the following benefits: (i) hydrogen produced by the oxidation of Zn could be active, unlike stable gaseous hydrogen, which may easily reduce formic acid into methanol; (ii) the oxidative product ZnO may catalyze the reduction of formic acid since ZnO is traditionally utilized as a hydrogenation catalyst due to the production of lattice oxygen vacancies by retreatment (Chen et al., 1999; Fujitani & Nakamura, 2000); (iii) problems related to hydrogen storage can be avoided because hydrogen can be stored as Zn. Cu is often used as a catalyst in many reactions and industrial applications, such as the synthesis of methanol from mixtures of CO2/CO/H2 (Liu et al., 2003; Wainwright & Trimm, 1995). In addition, Cu is relatively cheap and easily available. The purpose of the present investigation was to study the catalytic reduction of formic acid to methanol under hydrothermal conditions using Cu as a catalyst in the presence of Zn. The reaction conditions leading to the highest yield of methanol were determined, and the mechanism for the reduction of carbohydrate biomass (glucose) to methanol was investigated.

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2. Material and methods 2.1 Materials Analytical grade Cu and Zn powder (mesh size less than 200) and formic acid (98%) were used in the present study and were obtained from Sino-pharm Chemical Reagent Co., Ltd. Methanol (99.9%, Sigma) was used for the qualitative analysis of products in liquid samples. Deionized water was used throughout the study.

2.2 Experimental procedure All of the experiments were conducted in a batch SUS 316 tubing reactor. Schematic depictions of the experimental set-up have been provided elsewhere (Jin et al., 2003; Jin et al., 2001). The experimental procedure was conducted as follows. First, 2 mL of an aqueous solution of formic acid and the desired amount of Cu and Zn were loaded into the reactor. The concentration of formic acid was set to 60 gL-1, and the batch reactor was filled to 35% of the total reactor volume with the reaction solution. Next, the reactor was sealed and immerged into a salt bath, which was preheated to the desired temperature. After a given amount of time, the reactor was removed and placed into a cold water bath to quench the reaction. Upon cooling, a sample of the reaction mixture was collected and filtered with a 0.22-m syringe filter for GC-FID and HPLC analysis. Gaseous and solid samples were analyzed by GC-TCD and XRD, respectively, as necessary.

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2.3 Product analysis Quantitative estimates of methanol production were based on the average values obtained from the GC-FID analysis of three samples. An Agilent 6890 gas chromatograph equipped with a flame ionization detector was used for the quantification of methanol. The oven temperature of the gas chromatograph was initially set to 40 C for 1 min and was increased at a rate of 7 C /min to 110 C. This temperature was maintained for 1 min and was increased at a rate of 35 C/min to 220 C. The samples were separated on a DB-WAX capillary column using nitrogen as a carrier gas. The yield of methanol was defined as the ratio of the amount of carbon in methanol to that of formic acid added to the reactor. HPLC analyses were performed on a chromatograph equipped with an RSpak KC-811 (SHODEX) column and a UV detector (210 nm). Gas samples were analyzed with a GC (HP-5890 Series II) equipped with a HP-1 packing column (30 m 0.25 mm ID) and a TCD detector. Solid samples were analyzed by X-ray diffraction (XRD, Bruker D8 Advance).

3. Results and discussion 3.1 Effect of Cu and Zn on the reduction of formic acid into methanol Experiments with and without Cu were firstly conducted in the presence of Zn to investigate the effect of Cu on the reduction of formic acid to methanol. As shown in Fig. 1(A), the yield of methanol was only 0.1% in the absence of Cu; however, the methanol yield greatly increased in the presence of Cu and showed a growing trend with

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the amount of Cu increased from 0 to 12 mmol. When the amount of Cu was increased to 12 mmol, the methanol yield reached 25.3%. These results indicated that Cu has great effect on improving the formation of methanol from formic acid under hydrothermal conditions in the presence of Zn. Fig. 1(B) shows the effect of the amount of Zn on the yield of methanol. The experiments were conducted for 5 h at 300 C with 12 mmol of Cu, and the amount of Zn was varied from 2.6 to 9.1 mmol. The yield of methanol significantly increased with the increase in the amount of Zn, and a yield of 16.6% was achieved with 9.1 mmol of Zn. The reduction of formic acid into methanol in the presence of Zn can be explained as follows: Zn + H2O ZnO + H2 HCOOH + 2H2 CH3OH + H2O HCOOH + 2Zn + H2O CH3OH + 2ZnO (3) (4) (5)

According to Eq. (5), the theoretical ratio of formic acid to Zn is 1: 2. Thus, when the amount of Zn is greater than 5.2 mmol, the theoretical amount of hydrogen required for the complete reduction of 2.6 mmol of formic acid has been exceeded. The observed increase in the yield of methanol at Zn contents greater than 5.2 mmol may be attributed to an increase in the partial pressure of hydrogen, which shifts the reaction equilibrium toward the generation of methanol. Many studies on the synthesis of methanol from syngas have demonstrated that the partial pressure of hydrogen can promote the synthesis of methanol (Lee & Sardesai, 2005). As shown in Fig. 1(B), the yield of

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methanol obtained with 6.5 mmol of Zn was slightly lower than that of 9.1 mmol of Zn. Taking into account security, the amount of Zn was set at 6.5 mmol in the following experiments. As shown in Fig. 2, which displays the XRD pattern of the solid residue obtained from the hydrothermal reaction conducted at 300 C for 7 h with 6.5 mmol of Zn and 12 mmol of Cu, Cu remained in its elementary state, while Zn was oxidized into ZnO. This result indicated that Cu and Zn acted as a catalyst and reductant, respectively.

3.2 Effect of the reaction temperature and time on the methanol yield To investigate the effect of the reaction temperature on the methanol yield, a series of experiments were conducted at temperatures ranging from 250 to 325 C and a fixed reaction time of 7 h. As illustrated in Fig. 3(A), the methanol yield increased with an increase in temperature and reached a maximum at 300 C. However, the yield of methanol decreased sharply when the temperature exceeded 300 C. Thus, reaction temperatures greater than 300 C should be avoided to obtain high yields of methanol. The observed decrease in the methanol yield at temperatures greater than 300 C may be due to the decomposition of methanol at higher temperatures. As shown in Fig. 3(B), the reaction time also had a significant effect on the yield of methanol. The methanol yield increased dramatically as the reaction time increased to 7 h and increased slightly as the reaction time increased from 7 to 9 h. However, the yield of methanol decreased rapidly when the reaction time was greater than 9 h. The

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observed increase in the methanol yield during the rst 9 h may be due to the fact that methanol formation was faster than methanol decomposition. On the other hand, the decomposition of methanol may be in the ascendant after 9 h, consequently, the yield of methanol decreased with a further increase in reaction time.

3.3 Mechanism and discussion Possible pathways for the formation of methanol from formic acid under hydrothermal conditions were investigated. Two reaction pathways are possible. For instance, due to the presence of a reductant (Zn) in HTW, formic acid may be directly reduced to methanol by hydrogen released from water. Alternatively, methanol may be synthesized by CO2, H2 and CO generated from the decomposition of formic acid. A series of experiments were conducted at shorter reaction times ranging from 5 to 120 min with 12 mmol of Cu and 6.5 mmol of Zn at 300 C to identify intermediates. As shown in Fig. 4(A), the amount of residual formic acid was low (ca. 0.3%) even at a reaction time of 5 min; however, the yield of methanol was also low. Thus, the direct reduction of formic acid to methanol may not be a predominant reaction. To examine the second pathway, gas samples were analyzed by GC-TCD. As shown in Fig. 4(B), a large amount of H2 and CO2 and trace amounts of CO were detected. These gases may be produced from the decomposition of formic acid. Generally accepted pathways for the decomposition of formic acid include decarboxylation (Eq. (6)) and dehydration (Eq. (7)).

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HCOOH CO2 + H2 HCOOH CO + H2O

(6) (7)

Decomposition via Eq. (6) is the predominant pathway in the presence of water (Wakai et al., 2004; Yasaka et al., 2006; Yu & Savage, 1998). Thus, the formation of methanol may be attributed to the formation of CO2 and H2 by the decomposition of formic acid. Based on the aforementioned facts and the mechanism of conventional methanol synthesis from mixtures of CO2/CO/H2, a possible reaction mechanism was proposed and is shown in Fig. 5. First, formic acid rapidly decomposed to CO2 and H2, and a large amount of H2 and ZnO was formed by the oxidization of Zn. ZnO may act as a catalyst in the production of methanol via the following mechanism: due to the formation of oxygen vacancies in its lattice, ZnO is activated by the absorption of active hydrogen. In this step, H2 molecules are split into H(a) on the surface of Cu/ZnO. Next, H(a) reacts with oxygen atoms in ZnO crystals to produce H2O, which desorbs from the surface of Cu/ZnO, resulting in the formation of an oxygen vacancy and the reduction of ZnO to ZnO1-x. Subsequently, CO2 adsorbs onto the oxygen vacancies of the ZnO1-x lattice, and residual H(a) attacks the C-O bond nearest Zn in ZnO-C-O. Thus, the catalytic cycle is completed by the regeneration of Cu/ZnO, and the formation of CH3OH is achieved. Furthermore, to determine if ZnO acts as a catalyst, an experiment with Fe as a reductant at 300 C for 3 h with 12 mmol of Cu was conducted. As a result, Methanol was not detected in the liquid sample, thus, it could be concluded that ZnO may play a

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synergistic role with Cu as the catalyst in the synthesis of methanol.

3.4 Cycle of ZnO and prospects of the two-step process The present study demonstrated that formic acid can be reduced into methanol using Zn as a reductant. However, cycle of Zn is needed for large-scale production. The Steinfeld group reported that ZnO can be converted into Zn by solar energy (Haueter et al., 1999; Steinfeld et al., 1995), and a novel solar chemical reactor has been designed (Steinfeld et al., 1998). Thus, by combining technologies that use solar energy to reduce ZnO to Zn with hydrothermal reactions that employ Zn as the reductant, the recycling of Zn or ZnO can be achieved. Moreover, a process for the conversion of ZnO to Zn using biomass such as carbohydrates as the reductant under mild hydrothermal conditions is currently being investigated in our laboratory. Based on the present results and those of previous studies that carbohydrate biomass can be easily converted into formic acid in high yield by hydrothermal oxidation, a new two-step process for the conversion of carbohydrate biomass into methanol under hydrothermal conditions. The proposed process has the following advantages: (i) CO2, a common greenhouse gas, was not emitted; (ii) noble metal catalysts were not required, which reduces the cost of the process and limits heavy metal pollution; (iii) rather than pure hydrogen gas, Zn can be used to provide hydrogen, which prevents problems associated with hydrogen storage; (iv) the reductant (Zn) is cheap and can be recycled.

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4. Conclusions Formic acid can be converted into methanol under mild hydrothermal conditions using Cu as a catalyst in the presence of Zn. After 9 h, the maximum methanol yield was 28% at 300 C. Methanol may be formed from CO2 and H2, which is produced through the decomposition of formic acid. Moreover, Cu or Cu/ZnO may act as a catalyst in the conversion of formic acid into methanol. Thus, a new two-step process for the production of methanol from carbohydrate biomass based on the reduction of formic acid can be achieved.

Acknowledgements The authors gratefully acknowledge financial support from the National Natural Science Foundation of China (No. 21077078), National High Technology Research and Development Program of China (No. 2009AA063903), and Projects of International Cooperation by Shanghai Committee of Science and Technology, China (No. 09160708100).

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FIGURE CAPTION Fig. 1. Effect of the amount of Cu (A) and Zn (B) on the methanol yield (A. Temp: 300 C; Time: 7 h; Zn: 6.5 mmol; B. Temp: 300 C; Time: 5 h; Cu: 12 mmol). Fig. 2. XRD pattern of the solid residue obtained after the reaction (Temp: 300 C; Time: 7 h; Zn: 6.5 mmol; Cu: 12 mmol). Fig. 3. Effect of the reaction temperature (A) and reaction time (B) on the methanol yield (A. Time: 7 h; Zn: 6.5 mmol; Cu: 12 mmol; B. Temp: 300 C; Zn: 6.5 mmol; Cu: 12 mmol). Fig. 4. Effect of shorter reaction times on formic acid decomposition and the yield of methanol (A) and gaseous products (B) (Temp: 300 C; Zn: 6.5 mmol; Cu: 12 mmol). Fig. 5. Proposed mechanism of the synthesis of methanol from formic acid.

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: ZnO : Cu

Intensity (cps)

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Fig. 2.

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Fig. 4.

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Fig. 5.

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