High yield lactic acid selective oxidation into acetic acid over a Mo-V-Nb mixed oxide catalyst
© Lomate et al.; licensee Springer. 2015
Received: 2 September 2014
Accepted: 8 April 2015
Published: 21 April 2015
In this paper, we report for the first time a one-pot reaction enabling total transformation of lactic acid to acetic acid over a Mo-V-Nb mixed oxide catalyst having an optimal atomic ratio 19:5:1. The mechanism of the reaction consists in two parallel ways leading to acetic acid: (i) oxi-dehydrogenation of lactic acid to pyruvic acid followed by decarboxylation and (ii) decarbonylation of lactic acid to acetaldehyde followed by oxidation. In the operating conditions we used, the catalyst is very active (total conversion of lactic acid) and selective towards acetic acid (100% selectivity). A 100% yield into acetic acid is hence obtained.
The announced depletion of oil along with the problem of global warming have shown up the urgent need for using processes based on bio-derived renewable resources for the production of fuels and starting materials of the chemical industry [1,2]. Most of these processes need a catalyst to orientate the reaction and accelerate its rate. Therefore, the development of new catalysts is of main importance to set up the processes of the tomorrow chemical industry that will make use of biomass-derived feedstocks . As examples, the synthesis of hydrogen, of liquid fuels and of precursors for plastics from renewable resources, catalysis plays a very important role [4,5]. In this context, lactic acid, which is often referred as a “sleeping giant”, has attracted much attention as an alternative resource for the production of important chemicals such as acrylic acid, 1,2-propanediol, 2,3-pentanedione, pyruvic acid,  acetaldehyde  and mainly the polylactic acid (PLA) polymer [8,9]. Lactic acid can be easily be obtained by fermentation of renewable sources such as sugars and starches or even waste streams (cheesy whey for instance) [10-12].
Acetic acid is a bulk chemical which is produced today in an amount exceeding 10 million tons per year worldwide . It is one of the most used organic acids in the chemical industry . The largest consumption of acetic acid is for the production of vinyl acetate , which is a monomer building block. About 33% of the world production of acetic acid in 2008 was used for the manufacture of vinyl acetate. The latter is mainly polymerized to polyvinyl acetate which finds application in paints and coatings or for poly vinyl alcohol and plastics. Acetic acid is furthermore employed in the synthesis of cellulose acetate, which is used to produce acetate fibres. Finally, acetic acid also finds application as food additives due to its role as acidity regulator.
As a matter of fact, nowadays more than 60% of the world acetic acid is produced by the carbonylation of petro-derived methanol . On the other hand, the carbonylation method has a significant drawback due to catalyst solubility limitations and the loss of expensive Rh metal during the separation section. As an alternative, the biological transformation of lactic acid to acetic acid is well reported. Elferink et al. reported the conversion of lactic acid to acetic acid and 1,2-propanediol using Lactobacillus buchneri whereby one mole of lactic acid yielded equimolar amount of acetic acid and 1,2-propanediol . Concerning the chemical conversion of lactic acid to acetic acid, the latter is notably reported as a side reaction in the oxidative dehydrogenation of lactic acid to pyruvic acid and dehydration of lactic acid to acrylic acid. For instance, Ai et al. obtained 9.2% yield in acetic acid form lactic acid using an iron phosphate catalyst doped with molybdenum . The formation of acetic acid (0.7%) during dehydration of lactic acid was reported by Zhang et al. over NaY zeolite modified by alkali phosphate as a catalyst . Tang et al. reported 1.3% acetic acid yield over barium phosphate catalysts in the lactic acid dehydration reaction . Peng et al. observed 3.3% yield in acetic acid as a by-product in the barium sulphate catalysed dehydration of lactic acid . Lingoes have reported the formation of 2% acetic acid in the lactic acid dehydration using barium based catalysts . Much higher yield in acetic acid by chemo-catalysis were observed by Wang et al. from glucose via lactic acid using copper oxide catalyst (32%) . Here, we report efficient and highly selective catalysts for the production of acetic acid. In this process, the catalytic oxidation of lactic acid is carried out over a multi-component Mo-V-Nb mixed oxide catalyst. To the best of our knowledge, this simple single-step catalytic process has not yet been reported and would provide a way to produce “green” acetic acid. The Mo-V-Nb is a versatile catalyst for the oxidative dehydrogenation. This catalyst mostly used in the oxidative dehydrogenation of ethane and propane [24,25]. The catalytic behaviour of this catalyst also investigated for the ammoxidation of propane to acrylonitrile [26-28]. The catalyst structure and catalytic properties of Mo-V-Nb catalyst also investigated for selective oxidation of propane to acrylic acid [29-31]. Mo-V-Nb oxide were examined in bulk and supported form for the oxidation of ethane to ethane and acetic acid .
A molybdenum-vanadium-niobium mixed oxide catalyst with the following molar ratio Mo:V:Nb = 19:5:1 was prepared as follows: 10 mmol of niobium pentachloride (Aldrich 99%) were dissolved in water (50 mL), and ammonium hydroxide (Aldrich) was added until neutral pH was reached. The white precipitate (niobium hydroxide) was then filtered, washed with water and dissolved in a hot solution of oxalic acid dihydrate (50 mmol; Aldrich 99%). Then, an aqueous solution of ammonium metavanadate (50 mmol; Aldrich 99%) was added at 90°C followed by an aqueous solution of ammonium paramolybdate (27.14 mmol; Aldrich 99%). The obtained green slurry was heated under stirring until the water was evaporated. The residue was dried for 16 h at 120°C followed by a calcination step under static air at 400°C for 4 h (heating ramp 2°C/min).
The Mo-V-Nb oxide catalyst was characterised by different physico-chemical techniques, as described in the followings. Powder in-situ temperature X-ray diffraction measurement was performed (RT to 500°C) on a Bruker D8 advance diffractometer, using the CuKα radiation (λ = 1.5506 Å) as an X-ray source, in the 2θ range of 10-80° with steps of 0.02° per second. The composition and oxidation state of the elements present on the catalyst surface was determined by X-ray photoelectron spectroscopy (XPS). The XPS experiments were performed on a KRATOS Ultra instrument using a hemispherical energy analyzer. Monochromatic AlKα X-rays (hν = 1486 eV) were used as the excitation source. The source was operated at 150 W. All the spectra were acquired at normal incidence, takeoff angle set at 90°, with the charge neutralizer switched on. The base pressure of the instrument was maintained at less than 6.66 × 10−13 bar. All the survey scans were collected with a pass energy of 160 eV and a step size of 1 eV/step while thigh-resolution spectra were collected with a pass energy of 40 eV and a step size of 0.1 eV/step. All the binding energies were referenced to the carbon 1 s CHx component set to 285 eV.
Ammonia temperature-programed desorption (NH3-TPD) was carried out to measure the surface acidity of the catalyst. First, 50 mg of catalyst were treated under helium flow (30 mL/min) at 250°C for 2 h. After the pre-treatment, the catalyst was saturated with ammonia at 130°C using pulse-wise injection. Finally, NH3-TPD desorption was carried out in helium at a heating rate of 10°C/min within the temperature range of 130 to 700°C. The signal was recorded by a thermo-conductive detector (TCD).
For the elemental analysis by energy dispersive X-Ray Fluorescence (XRF) a M4 Tornado from Bruker was employed. This tool is used for element characterization using small-spot Micro X-ray Fluorescence (Micro-XRF) analysis. For each sample 30 points were measured for in order to cover whole sample surface, with spot sizes of 200 μm for each point.
The atomic composition of the catalyst was further evaluated by EDX analysis. Elemental analysis was performed by energy dispersive X-ray spectroscopy on a Hitachi S3600N electron microscope equipped with a Thermo Ultradry EDX detector using an acceleration voltage of 30 kV.
The specific surface area and pore volume of the catalyst were measured through nitrogen adsorption at the liquid nitrogen temperature (77 K) using a Micrometrics ASAP 2010 instrument. The specific surface area (S BET ) was evaluated by using the multi-point BET method, while the pore size distribution was calculated according to the Barrett–Joyner–Halenda (BJH) formula applied to the desorption branch. The total pore volume (Vp) was calculated using the isotherms at the relative pressure (P/P 0 ) of 0.98.
The reducibility of the catalysts was evaluated by temperature-programmed reduction (TPR) using gaseous hydrogen as reducing agent. A typical experiment was performed with 100 mg of catalyst loaded into a quartz reactor and pre-treated in a He flow (30 mL/min) at 100°C for 2 h. Afterwards, the catalyst was heated from 100°C to 700°C (heating rate of 5°C/min) under the reductive gas H2/He (5 mol.% H2 in He; 30 mL/min). The effluent gas was analysed by a thermal conductivity detector (TCD).
Raman measurements were performed on a HORIBA HT Raman with a confocal microscope Raman system using an excitation wavelength of 532 nm supplied by a Renishaw HPNIR laser (10 mW). The Raman spectra were collected at room temperature in air in the region of 100–1100 cm−1.
Results and discussion
The textural properties were determined by nitrogen physisorption. The specific surface of the catalyst was 10 m2/g with a pore volume of 0.022 cm3/g and an average pore diameter of 3 nm, which is characteristic for a classical bulk catalyst.
Textural, redox and acid properties of the Mo-V-Nb catalyst
BET surface area (m 2 /g)
Pore volume (cm 3 /g)
Pore size (Å)
Total acidity (mmol/g)
H 2 consumption mmol/g
The reducibility was also studied using temperature-programmed reduction (TPR). The results are reported in Table 1. The reduction peak of the Mo-V-Nb catalyst occurred at high temperature (650°C) and showed a hydrogen consumption of 6.47 mmol/g.
Atomic composition of the catalyst measured by XPS and XRF
Catalytic performance of Mo-V-Nb catalyst
LA conversion (%)
In the present work, a Mo-V-Nb mixed oxide catalyst having an atomic ratio of 19:5:1 was synthesized and used for the direct oxidation of lactic acid to acetic acid. The catalyst was extensively characterized by nitrogen adsorption-desorption, XRD, EDX, XRF, XPS, TPR and ammonia TPD. The results show that the Mo-V-Nb mixed oxide catalyst presents both redox and acid properties enabling the parallel formation of acetaldehyde and pyruvic acid as intermediates, which give acetic acid at higher lactic acid conversion. Thus at 250°C, a remarkable yield into acetic acid is obtained (100%).
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