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cyclohexene in microemulsion
Geoffroy Lesage, Isariebel Quesada-Peñate, Sophie Franceschi-Messant, Emile
Pérez, Jean-Christophe Garrigues, Martine Poux, Patrick Cognet
Lesage, Geoffroy and Quesada Penate, Isariebel and Franceschi, Sophie and
Perez, Emile and Garrigues, Jean-Christophe and Poux, Martine and Cognet,
Patrick Sustainable process for adipic acid production from cyclohexene in
microemulsion. (2020) Catalysis Today, 346. 40-45. ISSN 0920-5861
a
Laboratoire de Génie Chimique, Université de Toulouse, CNRS, INPT, UPS, 4 Allée Emile Monso, F-31432 Toulouse, France
b
Laboratoire des I.M.R.C.P., UMR 5623 CNRS, Université Paul Sabatier, F-31062 Toulouse Cedex 09, France
Keywords: Adipic acid appears as an intermediate compound for the synthesis of polyamides and preferentially for the
Adipic acid production of nylon-6,6 polyamide. It can be synthesized by the oxidation of cyclohexene by hydrogen peroxide
Cyclohexene oxydation in microemulsion media which has the main advantage to lead a better contact between the two phases thus
Green process increasing the yield of the reaction. The microemulsion is generated by stearyl dimethyl benzyl ammonium
Microemulsion
chloride (C18) as a surfactant avoiding the use of harmful organic solvents and phase-transfer catalysts. The
reaction is performed under mild conditions (85 °C, 8 h) with sodium tungstate, - a no heavy metal catalyst -
leading to the production of adipic acid in high yield (> 80%). By recycling the catalyst and the surfactant, the
process becomes truly green.
⁎
Corresponding author.
E-mail address: Patrick.Cognet@ensiacet.fr (P. Cognet).
https://doi.org/10.1016/j.cattod.2019.02.065
cyclohexane in solution in acetic acid. This technique uses the cobalt Since many years, microemulsions have been used as reaction media
acetate as oxidation catalyst and operates between 90 and 100 °C. The for numerous chemical reactions [20–25]. Often considered as a simple
molar selectivity to adipic acid reaches 70–75% for conversion rates by solvent, microemulsions are employed to overcome reactant solubility
pass between 50 and 75%. Even if the yield of adipic acid is comparable problems in water. On the other hand, because of their particular in-
to that of the previous processes, the investments necessary for its im- terfacial properties which create a nanoscale contact between hydro-
plementation are very important. This is due to the cost of recovering philic and hydrophobic reactants, microemulsions could be used as
and recycling the acetic acid, the regeneration of the catalyst and the “chemical reactors”. Microemulsions allow a more homogenous solu-
cooling devices required to manage the high exothermicity of the re- bilisation of oil in water than emulsions based on micellar solutions.
action. All this explains the weak industrial development of this pro- Also, the concentration of the reactants at the interface has been
cess. exploited to induce regio-specificity or stereo-selectivity in an organic
BASF has developed a process based on the carbonylation of buta- reaction [26]. Use of microemulsions as reaction media is also com-
diene [10]. It operates in two steps: first, butadiene reacts with carbon patible with a catalytic process [27–35]. Nowadays, microemulsions
monoxide and methanol at 120 °C and 60 MP a. Dicobalt octocarbonyl are versatile reactions media for many organic syntheses but at this
(Co2(CO)8) is used as catalyst in the presence of a heterocyclic nitrogen time, no industrial reaction process based on microemulsions exits.
base. At the end, methyl pentene-3-ole is formed with a selectivity of We already described a reusable green process for the synthesis of
98 mol%. In a second step, the olefinic e ster i s t reated w ith a new adipic acid in very good yield and purity by hydrogen peroxide oxi-
quantity of carbon monoxide and methanol. The reaction is carried out dation of cyclohexene in a microemulsion [36] in a previous work. The
at 185 °C under 3 MP a. Methyl adipate is then formed with a yield of originality of the process was based on the use of microemulsions as
75 mol%. Glutarate and methyl succinate ethyl are also formed. The reaction media without cosurfactant and on the molecular economy
methyl adipate is then purified b y d istillation a nd t hen h ydrolyzed to principle, almost all the compounds acting as reagents too. Micro-
adipic acid. Despite the large investments due to the high pressures emulsions allow working in a macroscopic homogeneous media for a
implemented in the first stage, this process is economically comparable better reactivity and pure adipic acid in obtained without any difficulty
to the conventional methods. by simple filtration using a low pH.
An alternative process is based on the dimerization of acrylates. As In the present work, we propose the use of a microemulsion as re-
the previous method, the dimerization of acrylates has the advantage of action medium at 85 °C, including hydrogen peroxide as aqueous oxi-
not sourcing the adipic acid from benzene but from olefins. I n fact, dant phase, cyclohexene as reagent and oil phase and benzalkonium
methyl acrylate results from the oxidation of propylene to acrylic acid, chloride C18 as surfactant. The Krafft temperature [37] of this surfac-
which is then esterified with methanol. The dimerization of the acrylate tant allows a precipitation at 27 °C. Maintaining the pH at 1 (+ H2SO4)
then takes place in the presence of palladium chloride and benzonitrile and the temperature at 40 °C allowed us to precipitate pure adipic acid.
as catalyst. The reaction is carried out at 80 °C under a nitrogen at- The surfactant and the catalyst (Na2WO4) are then recovered by fil-
mosphere. For a contact time of 35 min per pass, a conversion of 45% tration at room temperature for a new reaction cycle.
together with a 92% selectivity into linear dimer are obtained. The ester
formed is then purified by fractionation, hydrogenation and hydrolysis 2. Materials and methods
to adipic acid. This process is advantageous compared to conventional
routes due to the low cost of raw materials. 2.1. Materials
All these processes are not sustainable and green and the develop-
ment of a new process less damaging for the environment is of crucial Benzalkonium chloride C18 (90%, Sigma-Aldrich), cyclohexene
importance [11–15]. (99%, Sigma-Aldrich), sulfuric acid (95–97%, Sigma-Aldrich), dihy-
Adipic acid can be also obtained by oxidation of cyclohexene by drated sodium tungstate (99%, Sigma-Aldrich), hydrogen peroxide
hydrogen peroxide in the presence of a catalyst [16] (Scheme 1). Recent (30 wt%, Sigma-Aldrich), were used for the reaction experiments as
works show the last advances on the development specially either on received without purification. Methanol (99.9%, Fluka) and toluene
the choice of the catalyst or the type of process (batch and continuous) (99.9%, Sigma-Aldrich) were used for cyclohexene GC analysis.
[17,18]. Potassium permanganate (98.5%, Sigma-Aldrich) was used for hy-
In a previous work, we have shown the interest to introduce mi- drogen peroxide titration. Sodium hydroxide solution (30%, Analar
croemulsions as a new green solvent for the production of adipic acid Normapur) was used for adipic acid titration.
[19] using hydrogen peroxide and benzalkonium chlorides as surfac-
tant.
2.2. Synthesis of adipic acid in microemulsion
A microemulsion is a system formed of water, oil, amphiphilic
agents, which is transparent and thermodynamically stable. Physical
Reactions were carried out in a 1.4 L cylindrical water-jacketed
and chemical properties of the microemulsion are interesting, in par-
glass reactor equipped with a magnetic stirring bar and a reflux con-
ticular from the point of view of thermodynamic stability, low forma-
denser. BenzCl C18 (82.5 g), hydrogen peroxide (30% solution,
tion barrier kinetics, low viscosity and excessively low interfacial ten-
1321.5 g), sodium tungstate (20.5 g) and sulfuric acid (46 g) were in-
sion. Given these particular properties, microemulsions become more
troduced at one time. The mixture was strongly stirred at 70 °C until
significant i n b oth r esearch a nd i ndustry. A m icroemulsion distin-
total dissolution and then 150 g of cyclohexene were added. The solu-
guishes by the size of its dispersed droplets in the range between 50 and
tion was maintained at 85 °C during 8 h [36].
1000 Å. The dispersed molecules merge with the water molecules and
Oxidation of cyclohexene by H2O2 typically involves epoxidation of
are defined a s t ransparent l iquid / l iquid d ispersions o f w ater a nd oil.
the double bond, its opening and transformation to a diol, and then a
They are not very viscous and their formation is spontaneous and re-
Baeyer-Villiger oxidation and multiple hydrolysis steps resulting in
quires very little energy.
adipic acid (Scheme 2) [38,39].
After cooling at 40 °C for 1 h, adipic acid precipitated and was re- 2.4.1. Cyclohexene titration
covered by Büchner filtration (fritted glass funnels with pore size of Gas chromatography (Varian CP-3800) with a flame-ionization de-
2–4 μm). The crude product was washed with cold water (10 mL) and tector was used to determine the quantity of remaining cyclohexene.
the white powder was then dried at 40 °C (cycle 1). For recyclability Separation was accomplished using a MachereyeNagel Optima-1-
studies, the filtrate was cooled at 20 °C and the solid (BenzCl C18, so- Accent-0.25 mm column (30 m, 0.25 mm). 1 μL of a solution prepared
dium tungstate and remained adipic acid) was recovered by Büchner with 500 mg of crude reaction mixture, 50 mg of toluene (internal
filtration. This mixture was reintroduced into the reactor with hydrogen standard) and 500 mg of methanol was injected. The GC settings were
peroxide and cyclohexene (with the same quantities as for the first programmed as follows: injector temperature 150 °C (1 mL/min, split
cycle) for a new cycle (8 h at 85 °C (Fig. 1)). ratio: 10); detector temperature 350 °C; column temperature 50 °C for
In order to improve the solid/liquid separation step, some pre- 5 min. The detection limit was 1 mg L−1. The accuracy for measure-
liminary ultrafiltration experiments were carried out. The study was ments of samples containing a concentration of 30.4 mg L−1 was +/-
performed with a dead-end filtration unit (Berghof) with a hydrophilic 1.3 mg L−1.
coated polyvinylidenefluoride membrane (ETNA 10 P P). The effective
membrane area was 3.52 × 10−3 m2 and the total effective volume 2.4.2. Adipic acid titration
was about 300 mL. Stirring speed (200 rpm) and temperature (20 °C) Adipic acid concentration was determined by acid-base titration. A
were maintained constant in all tests. The cell was filled with 100 mL of 0.025 N NaOH solution was prepared and was standardized with a
the liquid waste containing adipic acid, surfactant and catalyst. The H2SO4 solution (0.025 N) in an automatic titrator Mettler Toledo DL50.
filtration was conducted until a volume reduction factor (VRF) of 3 Adipic acid formation was followed by NaOH titration. Measurements
(33 mL of permeate had been collected). Then, the resulting concentrate were performed at least three times.
(the volume remaining in the storage) was added at the beginning of
the reaction cycle with the reactants.
2.4.3. Adipic acid purity
The adipic acid purity was determined by HPLC in a Waters Alliance