Atmospheric hydrogenolysis of methyl formate to bio-methanol using Cu/MgO catalyst

Hendriyana, Herri Susanto, and Subagjo

Citation: AIP Conference Proceedings 1904, 020005 (2017);

View online: https://doi.org/10.1063/1.5011862
View Table of Contents: http://aip.scitation.org/toc/apc/1904/1
Published by the American Institute of Physics

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 Atmospheric Hydrogenolysis of Methyl Formate to
Bio-Methanol Using Cu/MgO Catalyst

Hendriyana1,a), Herri Susanto2 and Subagjo2

1
Chemical Engineering Department, Faculty of Engineering, Universitas Jenderal Achmad Yani, Indonesia
2
Chemical Engineering Department, Faculty of Industrial Technology, InstitutTeknologi Bandung, Indonesia

a)Corresponding author: hendriyana@lecture.unjani.ac.id

Abstract. Activity at various operating condition on the hydrogenolysis of methyl formate to bio-metanol using Cu/MgO
catalyst were tested in the range of 19.7  75.5%-wt Cu, 120±180oC, 1±2 molar feed ratio (H2/HCOOCH3) and 1.4±4.3
kg.h/kmol. Methanol was produced under the studied conditions. Copper concentration have a significant effect on the
activity of the catalyst. A maximum conversion of hydrogen was obtained at 51.7%-wt of Cu (C75M25). Higher
temperatures and space time enhanced methanol productivity, while higher molar feed ratio decreased productivity. Kinetic
experiments of hydrogenolysis of methyl formate were carried out using a C75M25 catalyst. Kinetic studies, interpreted
by applying the basis of the Langmuir–Hinshelwood model, suggested that the rate-determining step involves the reaction
of adsorbed methyl formate with adsorbed H atoms. The activation energy of this reaction was measured to be about 57
kJ.mol-1.

INTRODUCTION

The potential of biomass such as rice husk, corncob, empty fruit bunch, waste wood of forest etc. in Indonesia are
very abundant [1]. This biomass can be used as natural resources for bio-methanol synthesis via gasification process
[2]. Methanol is the simplest of all alcohols and has a wide application range. Methanol is mainly used for the
production of bulk chemicals like formaldehyde, acetic acid, and a wide variety of application products including
polymers and paints. In addition, methanol has high potential as a clean and renewable energy carrier.
Configuration process of methanol synthesis via methyl formate (MF) was developed by [2]. This process is
expected to provide better performance than the conventional methanol synthesis. Development of methanol synthesis
via methyl formate using two reactor for each reaction. The first reaction is carbonylation of methanol with CO to
methyl format using pottasium methoxide in liquid phase using batch reactor was studied by [3,4]. The second reaction
is hydrogenolisis of methyl formate with hydrogen to two molecule of methanol in gas phase using fixed bed reactor
as following equation (1).

HCOOCH3 + 2H2 ⇌ 2 CH3OH (1)

The synthesis of methanol from methyl formate in the gas phase using a fixed bed reactor has been carried out by
[5,6 and 7]. The catalyst used in the hydrogenolysis process is a Cu based with Cr2O3 as a promoter. Chromium is
relatively expensive and need to be replaced by another metal, which have cheaper prices and are expected to have
the same activity or even better. Magnesium oxide is one of the promoter that expected to be used to replace Cr2O3,
cause can dispersed Cu as well as on Cr2O3 [8]. Therefore we considered to develop the hydogenolysis process
catalyzed using Cu/MgO.

Proceedings of the 3rd International Symposium on Applied Chemistry 2017

AIP Conf. Proc. 1904, 020005-1–020005-9; https://doi.org/10.1063/1.5011862
Published by AIP Publishing. 978-0-7354-1594-2/$30.00

020005-1
 The puposes of this research is to examined of Cu/MgO catalyst performance for hydrogenolysis process of methyl
formate in the gas phase at atmospheric condition and several operating conditions such as concentration of Cu on the
catalyst, temperature, ratio of H2 to methyl formate and space time. In this paper also study kinetics of hydrogenolisis
of methyl formate using the best catalyst.

METHODOLOGY

Catalyst Preparation

Materials used for catalyst preparation were Cu(NO3)2.3H2O, Mg(NO3)2.4H2O and Na2CO3 from Merck. Catalyst
prepared by co-precipitation method. To obtain catalyst by co-precipitation method, the acid mixed solutions (0.1 M
of Cu(NO3)2 and 0.1 M of Mg(NO3)2) and base solution (1 M of Na2CO3) were added dropwise into 300 ml of
distilled water at 65oC under stirring. Then, it was filtered to obtain a solid product. The obtained product was
thoroughly washed with distilled water to remove sodium ion, and subsequently, it was dried 24 h at 120oC. After the
dried sample was calcined at 350oC for 1 h with a heating rate of 5°C/min.

Catalyst Characterization

Surface area of the catalysts was analyzed by N2 physio adsorption a Quantochrome Instruments Nova 3200e
instrument. Concentrations of Cu and Mg in the catalyst was analyzed using Atomic Absorption Spectroscopy (AAS)
with the type of Varian Spectra AA 200. The X-ray diffraction patterns of the samples were recorded on a BRUKER
D-8 Advance X-ray diffractometer by employing CuKα radiation (40 kV, 30 mA). The morphology was observed on
a scanning electron microscopy (SEM) instrument with Energy Dispersive X-Ray System and JSM-6360LA type.

Activation and Synthesis Procedure

The activation and hydrogenolysis reaction was conducted in a packed bed reactor system operated at atmospheric
pressure and diagrams can be seen in FIGURE 1. Catalyst was activated (reduced) insitu with a mixed stream of
hydrogen and nitrogen. The reducing gas was introduced into the reactor at a flowrate of 55 NmL/min.g. In order to
get a one step CuO reduction, it is necessary to keep the reducing gas flowrate of more than 15 mL/min [9-10].
Temperature and time on streaming of reduction are 200oC and 5 h.

01= gas cylinder of H2 04= gas regulator 07= thermometer 10= fixed bed reactor 13= buble soap meter
02= gas cylinder of 5%-H2 05= ice bath 08= input sampling port 11= output sampling port
03=gas cylinder of H2 06= saturator 09= electrical furnace 12= liquid trap

FIGURE 1. Schematic representation of the apparatus used for hydrogenolysis experiments

Synthesis of bio-methanol from methyl fromate carried out at 120-180oC and feed molar ratio (H2/MF) 1 - 2.
Methyl formate was introduced to the reactor by passing of mixed gas (95% H2 and N2 balance) through saturators.

020005-2
The gas flow rates were controlled by needle valve. The products were analyzed gas chromatographs equipped with
thermal conductivity detectors and a Porapak Q column. A liquid trap on ice-bath after reactor was used to condense
liquid products from the gas. Conversion of hydrogen calculations were as follows:

 AH 2 / AN 2 input   AH 2 / AN 2 ouput (2)

XH2 
 AH 2 / AN 2 input

RESULTS AND DISCUSSION

Catalyst Characterization
The XRD patterns of the calcined catalysts are shown in FIGURE 2. The diffraction peaks corresponding to
copper-containing phases are not observed for C25M75, C50M50 catalysts, in agreement with the high copper
dispersion, while the most intense reflections corresponding to CuO (at 2θ values of 35,55º and 38,78º) are clearly
visible for the catalysts C75M25, C90M10 and C100M0. The crystalline phase of MgO was confirmed from 2θ values
(42o, 62o and 78o).

FIGURE 2. XRD patterns of Cu/MgO catalyst

The crystallite size of CuO, specific surface area and pore volume of catalysts calculated by BET method are listed
in TABLE 1. Site active of Cu determined by hydrogen consumption method are also presented in TABLE 1.
TABLE 1. Chemical composition and physical properties of oxide catalysts
Mass frac. of Cu Crystallite size of CuO BET Active site of Cu0
Catalyst
(%wt) (nm) (m2/g) (mg/g)
C100M0 75.5 15 12 683
C90M10 75.0 19 27 489
C75M25 51.7 7 52 289
C50M50 38.9 6 52 205
C25M75 19.7 8 73 144

020005-3
 Effect of Cu Concentration On The Catalyst

FIGURE 3 shows plots of the hydrogenolysis activities and stabilities versus time on stream for catalysts
containing various amounts of copper. The unpromoted catalyst (C100M0) exhibited high activity at the beginning,
but the rate dropped sharply and approaching a relatively steady state after 2 h. This high activity can be attributed to
the number of active site of Cu0 683 mg-Cu0/g-cat (FIGURE 4). The surface area of the catalyst C100M0 very small
(12.25 m2/g), causing activity declined sharply due to the most of the surface area of the catalyst blocked by deposition
of foulant in the form of polymerized formaldehyde [5,11], so that the reactants can not enter into the pores of the
catalyst. It was found that formaldehyde adsorbed on clean Cu forms poly(oxymethylene) [7].

FIGURE 3. Variation in the activity of catalysts with time-on-stream at 150oC and H2/HCOOCH3=2

The addition around 7.0 %-wt of magnesium in the catalyst (C90M10) increased the activity and stability of
catalysts. It can be seen from the level of rate production of methanol is greater than C100M0. This is due to catalyst
surface area of C90M0 greater than C100M0, polymer may only cover part of the surface area of C90M10 catalyst.
Increases in the amount of magnesium oxide until 13.4%-wt had a significant effect on activity and stability. However,
further increases of magnesium oxide in C50M50 and C25M75 cause a decrease in rate production of methanol. This
may due to the copper sites active is become decreased (FIGURE 4).

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 FIGURE 4. Effect of the number of site active and the surface area of the catalyst towards the conversion of H2 mass of
catalyst= 1 g; H2/HCOOCH3= 2; Temp.= 150oC

FIGURE 5. Yield of methanol for various catalysts mass of catalyst= 1 g; H2/HCOOCH3= 2; Temp.= 150oC

Yield of the liquid product are collected in the condenser column for 5 h presented in FIGURE 5. These figure
shows the optimum catalyst composition is C75M25. In addition, the yield of liquid product can also support and
strengthen the hypothesis related to the effect of the number of copper active sites and surface area.

Effect of Temperature

Reaction of methyl formate hydrogenolisis is highly exothermic and is unfavorable at high temperatures. The
dependence of the conversion of H2 and rate production of methanol on the temperature is shown in FIGURE 6.
Under the conditions studied, methanol was formed with 13-72% of H2 conversion. Increasing temperatures enhanced
methanol productivity. A maximum of rate production of methanol was obtained at 180oC.

020005-5
 FIGURE 6. Effect temperature to H2 conversion and rate production of methanol mass of catalyst= 1 g; H2/HCOOCH3= 2

Effect of Feed Molar Ratio

Effect of the feed composition (ratio of H2/HCOOCH3) on the productivity has been investigated and shown in
FIGURE 7. Methanol production rate decrease with the increasing ratio of H2/HCOOCH3. This suggests that the
effect of the partial pressure of H2 to the reaction rate is much smaller than the partial pressure of methyl formate.

FIGURE 7. Effect feed molar ratio to rate production of methanol mass of catalyst= 1 g; Temp.= 150oC

Effect of Space Time

The influence of the space-time at various temperatures to the H2 conversion is presented in FIGURE 8. With
increasing space-time at a constant temperature can increase the conversion of H2.

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 FIGURE 8. Effect space time to conversion of H2 at feed molar ratio H2/HCOOCH3=2

Kinetics

We developed a mechanistic consideration based on the Langmuir-Hinshelwood mechanism, to explain

phenomena of reaction and also to achieve a proper kinetic model with the experimental data of hydrogenolysis of
methyl formate over C75M25 catalyst. According to the rationale explained from [7 and 11], five elementary reaction
steps were set up as follows:
Step 1: H2 + 2 ⇌ 2H 
Step 2: HCOOCH3 +  ⇌HCOOCH3
Step 3: HCOOCH3 + H  CHO + CH3OH + 
Step 4: CHO + H ⇌CH2O* + *
Step 5: CH2O + H ⇌CH3O* + *
Step 6: CH3O + H ⇌CH3OH + 2*
Rate expressions were derived by assuming step 3 as the rate-determining step (RDS), while the assumption of the
rapid equilibrium is made to the other steps. The equation of rate kinetic expressed as follows:

k hid K MF CMF K H0,52CH0,52

 rMF 
1  K MF CMF  K H 2C H 2  
1/ 2 2 (3)

where −rMF is the rate of methyl formate consumption (mol/s.L); CMF and CH2 is concentration of methyl formate and
hydrogen, respectively; k is the specific rate constant and has units of L0.5.mol0.5.s-1 ; KMF and KH2 are the equilibrium
adsorption constants for methyl formate (with units of mol0.5.L-0.5) and hydrogen (units mol-1.L1). The equilibrium
constant is defined as the ratio of the rate constant of the forward reaction to that of the backward reaction. Constraints
of equilibrium adsorption constants as function of the adosrption enthalpy and entropy derived by Boudart et al. (1967)
[12]. Equation of equilibrium adsorption constants is expressed as follows.

 S H H 2 
K H 2  exp  H 2   (4)
 R RT 

 S H MF 
K MF  exp MF   (5)
 R RT 

020005-7
 After deriving the rate expressions, we determined the kinetic parameters (k, KMF and KH2) to fit the data obtained
at the temperatures of 120, 150, and 180oC, using the nonlinear regression analysis. Since experiments at each
temperature produced 6 data points. The aim of the data-fitting procedure is to minimize the mean-square differences
between calculated values of the concentration and the concentration values obtained directly from the experimental
data using the differential method. Mathematically this can be expressed by the following equation:

SSE   C
all data
calc  C data 
2
(6)
The calculated concentration obtained were compared with the experimental data, as shown in Fig. 9 and 10. All
kinetic parameters in RDS model are summarized in TABLE 2.
TABLE 2. Langmuir-Hinshelwood model kinetic parameters for hydrogenolysis of methyl formate to bio-methanol over
C75M25 catalyst
Temp. khid KH2 KMF Ea
(oC) (L0,5/mol0,5.s) (mol/L)0,5 (mol/L)-1 (kJ/mol)
120 1.30 0.039 8.31
150 5.50 0.019 4.04 57.48
180 13.27 0.011 2.95

FIGURE 9. Comparison of H2 concentration of ata and calculated as space time funtion over C75M25 catalyst

FIGURE 10. Comparison of H2 concentration of ata and calculated as space time funtion over C75M25 catalyst

020005-8
 Adsorption entropy of H2 and methyl formate is smaller than the entropy of the gas. Additionally, adsorption
enthalpy of H2 and methyl formate is also greater than zero as shown in the following equation.

H2:
entropy: 0 < -(-106,40) < 130,7 J.mol-1.K-1
enthalpy: -(-31217) > 0 J.mol-1
Methyl formate:
entropy: 0 < -(-47,47) < 285,3 J.mol-1.K-1
enthalpy: -(-255745) > 0 J/mol

CONCLUSIONS

The results of the analysis of X-Ray Diffraction (XRD), all catalyst calcination results form the CuO and MgO.
The surface area of the catalyst is affected by the concentration of Cu in the catalyst and CuO crystal size is formed.
The number of catalytically active centers Cu0 influenced by the content of Cu in the catalyst.
Site active area of Cu and the surface area of the catalyst particles is a very important parameter and the effect on
performance of the hydrogenolysis reaction process. Cu0 active surface area is too large to be easily deactivated when
the surface area of the particles are too small. In contrast, the active surface area is too small Cu0 while the surface
area of the particles are too big too do not give a good performance. So that these two parameters to be optimized.
The catalysts have high activity and most stable is C75M25.
Langmuir-Hinshelwood kinetic model explains that the reaction rate is controlled by the reaction of adsorbed
methyl formate with adsorbed H atoms. The activation energy for the model Langmuir-Hinshelwood is equal to 57.48
kJ mol-1 and the frequency factor of the collision of 6.05 107 L0,5 mol-0,5s-1.

ACKNOWLEDGEMENTS

This research supported with Hibah Terapan 2017 from the Directorate of Higher Education. We also thanked for
the University of Jenderal Achmad Yani for support through Hibah Disertasi program of the Directorate of Higher
Education (Higher Education) in 2015.

REFERENCES

1. P. Bambang (Presented in Indonesia-German Workshop and Seminar, September 26th - 27th) (2012).
2. Hendriyana, H. Susanto and Subagjo, AIP Conference Proceedings, 1699, 050010 (2015)
3. Hendriyana, Subagjo and H. Susanto, Procedia Chemistry, 16, 716 – 722 (2015)
4. S. J. Choi, J. S. Lee and Y. G. Kim, Journal of the Korean Institute of Chemical Engineers, 32 no 3, 317-324,
(1994)
5. D. M. Monti, M. S. Walnwrlght and D. L. Trimm, Ind. Eng. Chem. Prod. Res. Dev., 24, 397-401 (1985)
6. K. M. Kim, H. C. Woo, M. Cheong, J. C. Kim, H. J. Kyung, S. Lee and Y. G. Kim, Applied Catalysis A:
General, 83, 15-30 (1992)
7. X. Huang, N.W. Cant, J.W. Evans and M.S. Wainwright, Catalysis Today, 93–95, 113–119 (2004)
8. S. Zander, (PhD Dissertation, Von der Fakultät II-Mathematik und Naturwissenschaften der Technischen
Universität Berlin) (2013)
9. J.Y. Kim, J.A. Rodriguez, J.C. Hanson, A.I. Frenkel and P.L. Lee, JACS article, Published on web 08/06/2003
10. J.A. Rodriguez, J.Y. Kim, J.C. Hanson, M. Perez and A.I. Frenkel, Catalysis Letters, 85: No. 3-4 (2003)
11. L. Ma and M. S. Wainwright, Catalyst of Organic Reactions, 225-243 (2003)
12. G.F. Froment, K.B. Bischoff and J. De Wilde (Chemical reactor analysis and design”, 3rd edition, Jhon Willey
& Sons, Inc)

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