Accepted Manuscript

New methyl formate synthesis method: coal to methyl formate

http://www.journals.elsevier.com/
Lingyun Rong , Zhongning Xu , Jing Sun , Guocong Guo journal-of-energy-chemistry/

PII: S2095-4956(17)30154-7
DOI: 10.1016/j.jechem.2017.07.015
Reference: JECHEM 359

To appear in: Journal of Energy Chemistry

Received date: 8 March 2017

Revised date: 26 June 2017
Accepted date: 21 July 2017

Please cite this article as: Lingyun Rong , Zhongning Xu , Jing Sun , Guocong Guo , New methyl
formate synthesis method: coal to methyl formate, Journal of Energy Chemistry (2017), doi:
10.1016/j.jechem.2017.07.015

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 ACCEPTED MANUSCRIPT

New methyl formate synthesis method: coal to methyl formate

Lingyun Ronga,b, Zhongning Xua,b,*, Jing Suna, Guocong Guoa,*

a
State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of

Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, China

b
Key Laboratory of Coal to Ethylene Glycol and Its Related Technology, Chinese Academy of

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Sciences, Fuzhou 350002, Fujian, China

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Abstract

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Methyl formate is one of the most important intermediates in C1 chemistry, which has been

employed in a wide range of industrial applications. Current synthesis methods for methyl formate
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mainly include esterification of methanol and formic acid, liquid-phase methanol carbonylation,

oxidative dehydrogenation of methanol, one-step syngas synthesis, and carbon dioxide

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hydrogenation and condensation with methanol. Liquid-phase methanol carbonylation is currently

a main commercially viable process developed by BASF Corp. for the industrial production of
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methyl formate. Recently, Fujian Institute of Research on the Structure of Matter, Chinese

Academy of Sciences has developed a new synthesis method to convert coal to methyl formate
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(denoted as CTMF). Different from the liquid-phase methanol carbonylation using homogeneous

catalysts, CTMF method features with vapor-phase methanol carbonylation using heterogeneous
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nanocatalysts, which can effectively utilize the coal-based syngas and produce value-added fine

chemicals (i.e., methyl formate). The newly developed method not only provides a new methyl
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formate synthesis technology but also contributes to the development of strategies for

synthesizing valuable chemicals from coal. In this review, we firstly provide introduction on the

development of existing methyl formate synthesis methods and then highlight the research

progress of CTMF method. Finally, a perspective on the future of CTMF is given.

Key words: Methyl formate; Coal to methyl formate; Vapor-phase methanol carbonylation;

Nanocatalyst
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* Corresponding author. Tel: +86 591 63173336; E-mail: [email protected], [email protected].

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Prof. Guocong Guo Fujian Institute of

received his BSc from Research on the Structure
Xiamen University in of Matter, CAS in 2012
1986 before joining the under the supervision of
Fujian Institute of Prof. Guocong Guo. He is
Research on the currently an associate
Structure of Matter, CAS. He subsequently professor in the Fujian Institute of Research on
completed his Ph.D. at the Chinese University the Structure of Matter, CAS. His research
of Hong Kong, under the supervision of Prof. interests focus on nanocatalysts for CO

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Thomas Mak before returning to Fujian. He is conversion to fine chemicals and engineering.

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currently a professor and the director of the He is a member of Youth Innovation Promotion
State Key Lab of Structural Chemistry. His Association, and an intellectual property

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research interests focus on inorganic-organic commissioner, CAS. He has published 19 peer-
hybrid materials, nanocatalysis materials, and reviewed papers and 40 patents, in which 25
IR non-linear optical materials. He has been
granted the Distinguished Young Scholars of
National Natural Science Foundation of China.
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patents have been granted.
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He has published about 400 peer-reviewed
papers and 90 patents.
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Dr. Zhongning Xu received his BSc from

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Northwest University in 2007, and Ph.D. from

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Dr. Jing Sun received his now a freshman at the

Ph.D. from Fujian Institute Fujian Institute of
of Research on the Research on the
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Structure of Matter, CAS in Structure of Matter, CAS.

2014 under the supervision Her current research
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of Prof. Guocong Guo and topic is the carrier effect

Kechen Wu. He is now a post-doctoral fellow. of nanocatalysts for coal to methyl formate.
His primary research interests include
heterogeneous nanocatalysis, controlled
synthesis of nanocrystals and nanostructures,
and electronic structure calculations.

Miss Lingyun Rong received her BSc from

Nanyang Normal University in 2016. She is
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1. Introduction

Methyl formate (MF) is one of the most important intermediates in C1 chemistry [1]. It has been
widely used for the production of more than 50 chemicals, including formic acid, N, N-
dimethylformamide, methanamide, dimethyl carbonate, acetic acid, methyl glycolate, ethylene glycol,
methyl methacrylate, and high-purity CO etc. Similar to methanol, MF is also a universal intermediate

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[2]. In addition, MF can also be directly used as smoke fumigant and bactericide for treating tobacco,

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dried fruit, and grains; or as a solvent for nitrocellulose and cellulose acetate. In medical field, it has also

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been used as a raw material to synthesize sulfonic acid methyl pyrimidine, sulfamonomethoxine,
antitussive dextromethorphan, and other drugs.

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The global output in MF industry is more than 6 million tons in 2016. However, the production in
China is less than 0.5 million tons. To meet the market demand, a significant amount of the MF has to be
imported. In the period of 2012–2016, the average annual growth rate of China’s import and export
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trade deficit reaches up to 20%, which severely affects the development of MF industry.

To date, MF synthesis methods mainly include esterification of methanol and formic acid [3],
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liquid-phase methanol carbonylation [4], methanol dehydrogenation [5], oxidative dehydrogenation of

methanol [6], one-step syngas method [7], as well as carbon dioxide hydrogenation-condensation with
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methanol [8]. Among those, esterification of methanol and formic acid, liquid-phase methanol
carbonylation, and methanol dehydrogenation have been commercialized for industrial MF production.
This review firstly provides introduction on the research status and development of the existing MF
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synthesis methods and then focuses on a newly developed synthesis method for converting coal to
methyl formate, which was developed by Fujian Institute of Research on the Structure of Matter,
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Chinese Academy of Sciences.

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2. Development of existing MF synthesis methods

2.1. Esterification of methanol and formic acid

CH3OH + HCOOH → HCOOCH3 + H2O ∆H = -5.1 kcal/mol (1)

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Methanol and formic acid can be esterified (Eq. 1) to produce MF with a strong acid catalyst [3].
Although its process conditions are simple, this technology has the disadvantages of high consumption
of formic acid and severe equipment corrosion. It has been abandoned in developed countries albeit
being used by some small factories in China.

2.2. Liquid-phase methanol carbonylation

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CO + CH3OH → HCOOCH3 ∆H = -11.5 kcal/mol (2)

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Liquid-phase methanol carbonylation (Eq. 2) was first successfully industrialized by BASF Corp. in
1982 [9]. Currently, sodium methoxide is used as the homogeneous catalyst to synthesize MF at 80 °C

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and 4.0 MPa. Liquid-phase methanol carbonylation has been the mainstream technology of synthesizing
MF in chemical industry, which is also called BASF technology. The advantage of BASF technology is its

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high selectivity to MF. However, the disadvantages include: (1) sodium methoxide is moisture sensitive,
thus requiring high purity raw materials. For example, the H2O content in methanol and H2O, CO2, O2,
and sulfide contents in CO gas must be less than 10−6. Consequently, the costs of its raw materials and
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the purification are high; (2) sodium methoxide is a strong base that can cause severe equipment
corrosion. The reaction pressure is high at approximately 4.0 MPa. A high-pressure agitated reactor is
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thus required, leading to a high investment on the equipment; (3) the methanol conversion is low at
only about 30%; (4) the reaction is homogeneous, and separating catalyst from product is difficult and
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costly. Large-scale continuous production cannot be achieved; and (5) the solubility of sodium
methoxide in MF is low. In this case, when the consumption of methanol is higher than a certain value,
sodium methoxide will form solid precipitation and block pipes and valves. Hence, the actual operation
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is difficult, and the production is affected [4].

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Numerous investigations have also been performed in academia aiming at fundamental

understanding of the liquid-phase methanol carbonylation reaction. For example, Zhang et al. [10] and
Wang et al. [11] studied the kinetics of liquid-phase methanol carbonylation, and analyzed the optimal
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process conditions. Liu et al. reported a new catalytic system, sodium methoxide-propylene oxide
catalyst [12]. In other works, liquid-phase synthesis of MF was achieved by He et al. [13], through a
green carbonylation of methanol with CO on a soluble copper nanocluster catalyst, with high activity
(e.g. 2.7–6.1 molMFmolCu-1h-1) and 100% MF selectivity under mild reaction conditions (353–443 K, 0.3–
3.0 MPa CO). Meanwhile, heterogeneous strongly basic resins [14–16] have been investigated and found
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to be promising for the industrial application, but the thermal stability of those basic resins still need to
be further improved.

2.3. Methanol dehydrogenation

2CH3OH → HCOOCH3 + 2H2 ∆H = +9.0 kcal/mol (3)

Methanol dehydrogenation is an endothermic reaction with hydrogen being a useful byproduct (Eq.

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3). Since methanol is the only raw material, the technique is simple and the equipment investment is

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low. Therefore, methanol dehydrogenation has attracted considerable attention.

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Japan Mitsubishi Gas Chemical Co. Ltd. first achieved the industrialization of methanol
dehydrogenation using Cu-Zn-Zr/Al2O3 catalyst [5]. Under 250 °C and ambient pressure, the conversion
of methanol is 58.5%, and the selectivity to MF is 90% [9]. Copper-based catalysts were found to show

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good performance in methanol dehydrogenation [17]. Currently, the reported catalysts are Cu/SiO2 [18],
Cu/Cr2O3 [19], Cu/ZrO2 [20], Cu/ZnO [21], Cu/MgO [22], CuAl2O4 [23] etc. Especially, over the Cu/Cr2O3
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catalyst [20], 99% selectivity to MF at 48% conversion of methanol was obtained at 480 K and
atmospheric pressure.
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170–210 °C. The selectivity to MF is higher than 98%, but the yield of MF is only 13% per pass [9].
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Research institutes in China started the study in this field in the 1990s. Cu-Zr-K catalyst, which was
developed by Li et al. [24], provided a methanol conversion of 32% and selectivity to MF of 90% at the
conditions of 0.1–2.0 MPa and 200–500 °C. Li et al. [25] also reported that the Cu-B2O3/SiO2 catalyst
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exhibited an excellent selectivity to MF (85%–91%) at methanol conversion of 22%–25% under 270 °C

and ambient pressure. Moreover, Cu-ZnO-ZrO2/SiO2 catalyst was prepared via the sol-gel method by
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Wang et al. [26]. Using the catalyst of n(Cu)/n(Zn)/n(Zr) = 10/2/1, a methanol conversion of 46.2% with a
selectivity of 84.7% to MF was obtained at 260 °C.
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It should be mentioned that, despite of the abovementioned progress achieved, the methanol
conversion for methanol dehydrogenation is low due to the thermodynamic equilibrium limitation.

2.4. Oxidative dehydrogenation of methanol

2CH3OH + O2 → HCOOCH3 + 2H2O ∆H = -102.5 kcal/mol (4)

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Oxidative dehydrogenation of methanol is a strong exothermic reaction (Eq. 4). Metal oxides and
noble metals are the two most commonly used catalysts, which mainly include: 1) SnO2-MoO3 [27], V-Ti-
O [28], ReOx/CeO2 [29], Fe2O3/SiO2 [30], RuOx/ZrO2 [31], and other composite oxides; 2) Au [32], Ag [33],
Pd [34], Pt [35], Au-Ag [36], and Au-Pd [37]. To our knowledge, in terms of the mildness of the reaction
conditions and single-pass conversion, the noble metal catalysts, especially the double noble metal
catalysts, are superior to the non-noble metal ones. For example, Wang et al. [37] reported that

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graphene supported Au-Pd bimetallic nanoparticles exhibited high catalytic activity, with a methanol
conversion of 90.2% and TOF of 0.377 s-1 at 70 °C. In addition, methanol oxidative dehydrogenation to

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MF on metal oxides catalysts involves rate-determining C-H activation steps to form formaldehyde and

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subsequent formaldehyde reacting with intermediates derived from methanol or formaldehyde [6, 38].
Especially, MF can be produced by formaldehyde dimerization (Tishchenko reaction), which is an
important route. Recently, Liu et al. [39] reported that the yield of MF could reach to 97% through the

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formaldehyde dimerization using ZrO2 catalyst at 120 °C in a series reactor.
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However, the most metal oxides catalysts are not active and/or selective enough from the
industrial standpoint, and the high cost of noble metals hampers their practical applications. Thus, it is
still highly demanding to develop efficient catalysts for the oxidative dehydrogenation of methanol.
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2.5. One-step syngas method

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2CO + 2H2 → HCOOCH3 ∆H = -31.9 kcal/mol (5)

One-step syngas method (Eq. 5) is an atom-economic reaction that maximizes the usage of
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resources and minimizes the generation of industrial “three wastes”, which is the most promising route
for MF production. Catalysts are mainly divided into two categories: 1) the complexes of Group VIII
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elements (including Co, Ru, Ir etc.) as homogeneous catalysts [40]; and 2) Cu-based heterogeneous
catalysts [41].
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1) The homogeneous complex catalysts require high temperature and pressure. Both the
conversion of syngas and selectivity to MF are very low. Thus, the complex homogeneous catalysts need
to be further improved.

2) Inexpensive Cu-based catalysts are found to show high activity [42], which has become the main
research direction [43]. Recently, Zhao et al. [7] developed a CuO/CaO-ZrO2 bifunctional catalyst, on
which the space-time yield of MF reach up to 89.4 g·L−1·h−1 at 170 °C and 5.0 MPa. Compared with the
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liquid-phase methanol carbonylation, the production cost for one-step syngas method is expected to be
reduced by 30%–50%. The key of future research for one-step syngas method is to significantly increase
the product selectivity and space-time yield.

2.6. Carbon dioxide hydrogenation and condensation with methanol

CH3OH + CO2 + H2 → HCOOCH3 + H2O ∆H = -1.9 kcal/mol (6)

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In 1972, Kolomnikov et al. reported that organometallic catalyst, such as [RuHCl(PPh3)3]/BF3 could

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catalyze the hydrogenation of CO2 to MF (Eq. 6) [44]. In 1978, Evans and Newell found that the anionic
iron carbonyl hydrides [HFe3(CO)11]- could also catalyze this reaction in the presence of the

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corresponding alcohol [8]. However, there have been few reports on heterogeneous catalysts. Notably,
Yu et al. [45] demonstrated that a high selectivity (>96%) to MF and TOF of 38 h-1 were obtained by using

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the Pd/Cu/ZnO catalyst at 150 °C, 1 MPa CO2 and 5 MPa H2 in 2007.

Due to the concern of climate change caused by the increased level of carbon dioxide, the
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utilization of CO2 as raw materials is of great significance to produce value-added chemicals. To this end,
it is pivotal to develop the carbon dioxide hydrogenation-condensation reaction for MF production.
However, carbon dioxide is a thermodynamically stable molecule with standard Gibbs free energy of -
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394.38 kJ/mol, meaning that its activation is extremely hard and requires intense energy input. It is thus
essential to develop highly efficient catalysts and catalytic processes to effectively convert CO2 into MF.
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In summary, the esterification of methanol and formic acid has been gradually eliminated. Liquid-
phase methanol carbonylation is currently the main approach for large-scale MF production, however,
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adopting sodium methoxide homogeneous catalyst has several disadvantages. Methanol

dehydrogenation has also achieved small-scale industrial production, but this reaction is limited by
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thermodynamic equilibrium, resulting in a very low conversion of methanol. While the oxidative
dehydrogenation of methanol is not thermodynamically limited, the selectivity to MF is too low to
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commercialize. The one-step syngas method and carbon dioxide hydrogenation and condensation with
methanol are both at the inception stage with low activity and selectivity.

3. The new synthesis method of coal to methyl formate

As abovementioned, the existing synthesis methods for industrial production of MF still have
various disadvantages. It is desirable to innovate catalytic process, specifically by replacing
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homogeneous catalyst with heterogeneous catalyst for liquid-phase methanol carbonylation and
developing a more easy-to-operate vapor-phase reaction.

Coal to ethylene glycol (CTEG) was first industrialized by Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Sciences after 30 years of basic and applied research.
1,200,000 tons of production plants for the first-generation CTEG technology have been built. To
improve the first-generation CTEG catalysts, the effect of facet, particle size, support have been

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systematically investigated [46, 47], and new preparation methods have been developed to synthesize

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highly efficient catalysts in terms of utilization and even substitution of the costly noble metals [48–50].
The new-generation CTEG technology with intellectual property rights is also developed. 1000 and

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600,000 tons of production plants are being built in Guizhou province, China. The new-generation CTEG
catalysts can significantly reduce the loading of noble metals while reinforcing the catalytic

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performance. Compared with the first-generation CTEG technology, the capital expenditure and
operating cost of the new-generation one reduce by 25% and 20%, respectively. The previous research
progress has laid a solid theoretical and experimental foundation for coal to methyl formate (CTMF)
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method.

3.1. Introduction to CTMF method

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In China, coal is rich, but its utilization is relatively low efficient. In addition, the fine chemical ratio
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of China is lower than that of the developed countries. Therefore, achieving the catalytic conversion of
coal-based syngas to value-added fine chemicals is of great significance in China.
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Inspired by the new-generation CTEG technology, a novel vapor-phase synthesis method of CTMF
has been successfully developed by Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences.
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The CTMF method includes two major processes (Fig. 1): 1) Syngas is obtained by coal gasification
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(Eq. 7); and 2) Syngas and methanol are efficiently converted on noble metal nanocatalysts to produce
MF (Eq. 8).

Coal to syngas:

C + H2O → CO + H2 (7)

Syngas and methanol to MF:

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2CO + H2 + 2CH3OH + 0.5O2 → 2HCOOCH3 + H2O (8)

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Fig. 1. Schematic diagram of CTMF method.
Noble metal nanocatalysts have been developed for CTMF, which is less sensitive to the impurity

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(i.e., H2O) in the raw materials. The catalytic system is also not corrosive to equipment. In addition,
tubular fixed bed reactor is used, so that the separation of product and catalyst is facile. Especially, the
production process is continuous, and the productivity can be easily scaled up to an annual output of
100,000 to 200,000 tons.

3.2. Research progress of CTMF method

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CTMF is a multi-component catalytic process involving several reactive intermediates. Competitive

coupling reaction between these active intermediates will produce MF and many by-products.
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Therefore, catalyst plays the key role in obtaining high selectivity to MF.
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The research experience on CTEG catalysts facilitates the development of CTMF catalysts. Through
the research on controllable synthesis and structure–activity relationship, a high-performance noble
metal nanocatalyst has been developed with the space–time yield of MF 1270 g·L−1·h−1 and the
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selectivity to MF 96% under the conditions of 140 °C, 0.1 MPa, 3000 h-1 of gas hourly space velocity [51,
52].
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3.3. Advances in industrialization

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To date, four Chinese patents [51–54] about the synthesis method and catalysts for CTMF have
been applied and granted. Meanwhile, two patents [55, 56] have been applied in the United States and
European Union through the Patent Cooperation Treaty (PCT) [57], respectively. Currently, the scale-up
tests for catalysts’ synthesis is in process.

4. Conclusions and perspectives

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As one of the most important intermediates in C1 chemistry, MF has attracted increasing attention. The
mainstream BASF technology using sodium methoxide homogeneous catalyst possesses many disadvantages.
Other methods, such as oxidative dehydrogenation of methanol, one-step syngas method, and carbon dioxide
hydrogenation and condensation with methanol have not yet been industrialized. The main reason is that the
performance and stability of catalysts cannot meet the requirements for industrial production. Developing new
synthesis methods for MF production is thus highly demanding. Inspired by the new-generation CTEG
technology, a novel vapor-phase CTMF has been successfully developed by Fujian Institute of Research on the

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Structure of Matter, Chinese Academy of Sciences through innovating the catalytic process. Noble metal

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nanocatalysts with high activity and stability have been successfully synthesized to convert coal-based syngas
to a value-added fine chemical, MF. The new CTMF technology not only provides an alternative synthesis

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route for MF production and thus promotes the upgrade of MF industry, but provides opportunities for the
development of coal to other fine chemicals.

Acknowledgements
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This work was supported by the National Key R&D Program of China (2017YFA0206802), the National
Natural Science Foundation of China (91545201, 91645116, 21403237), and the Programs of the Chinese
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Academy of Sciences (XDB20010100, ZDRW-CN-2016-1, QYZDJ-SSW-SLH028).
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Graphic abstract

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Fujian Institute of Research on the Structure of Matter has successfully developed a novel

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synthesis method of coal to methyl formate (CTMF) through innovating the catalytic process.
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