20
M. B. Shiflett et al.
being MAGENTA, that is, magnetic nanoparticle-based liquid energy materials for
thermoelectric device application, within the framework Horizon 2020 [94].
The Austrian company
36 was started at Grambach in 2004 [50]. The founders
Roland Kalb and Michael Kotschan straightforwardly pursued the cost-efficient production of ionic liquids on an industrial scale in an entirely sustainable way while
maintaining high purity. The company introduced a product line
37 that uses a halideand waste-free synthesis route for production. This technology was developed by
Kalb in 2003 and is shown in Scheme 1. Additional details and the underlying patent
documents are given in the references [95, 96].
The proprietary method follows a modular conception. The cation of the desired
ionic liquid enters the reaction as a hydrogen carbonate or methyl carbonate, the precursor (see Scheme 1), and the anion joins as a Brønsted acid. The reaction proceeds
quantitatively with the chemical equilibrium continuously shifted by the generation
of CO 2 . Alternatively, when the corresponding Brønsted acid is not available, an
ammonium salt can be used.
The new process enabled the Austrian firm to produce multi-ton quantities of ionic
liquids (today’s annual capacity is 150 tons, by mid-2019, 500 tons). Large chemical suppliers offer selected precursors [97], and some may be the license holder
of the methods [98]. Following the customers’ requirements, the company’s bestsellers cover ionic liquids composed of the following ions: [C 2 C 1 im]
+ , [C 4 C 1 im]
+ ,
and [C 4 C 1 pyr]
+ as the cations, and [Ace]
− , [BF 4 ]
− , [CH 3 SO 3 ]
− , [OTf]
− , [NTf 2 ]
− ,
[FSI]
− , and [C 1 CO 3 ]
− as the anions. In January 2010, a group of international engineering companies
38 focusing on process plants with its headquarters in Austria took
a 70% share of the company [99].
(Cation)
+
CH 3 CO 3
‒ + H
+
(Anion)
‒ → (Cation)
+
(Anion)
‒ + CH 3 OH +
CO 2 ↑
(Cation)
+
HCO 3
‒ + H
+
(Anion)
‒ → (Cation)
+
(Anion)
‒ + H 2 O + CO 2 ↑
(Cation)
+
CH 3 CO 3
‒ + NH 4
+
(Anion)
‒ → (Cation)
+
(Anion)
‒ + CH 3 OH
+ CO 2 ↑ + NH 3 ↑
Scheme 1 Synthesis of an ionic liquid [(Cation) + (Anion) − ] by the CBILS ® method
36 Proionic GmbH.
37 Carbonate Base Ionic Liquid Synthesis, CBILS ® , Proionic GmbH.
38 VTU Group GmbH.
M. B. Shiflett et al.
being MAGENTA, that is, magnetic nanoparticle-based liquid energy materials for
thermoelectric device application, within the framework Horizon 2020 [94].
The Austrian company
36 was started at Grambach in 2004 [50]. The founders
Roland Kalb and Michael Kotschan straightforwardly pursued the cost-efficient production of ionic liquids on an industrial scale in an entirely sustainable way while
maintaining high purity. The company introduced a product line
37 that uses a halideand waste-free synthesis route for production. This technology was developed by
Kalb in 2003 and is shown in Scheme 1. Additional details and the underlying patent
documents are given in the references [95, 96].
The proprietary method follows a modular conception. The cation of the desired
ionic liquid enters the reaction as a hydrogen carbonate or methyl carbonate, the precursor (see Scheme 1), and the anion joins as a Brønsted acid. The reaction proceeds
quantitatively with the chemical equilibrium continuously shifted by the generation
of CO 2 . Alternatively, when the corresponding Brønsted acid is not available, an
ammonium salt can be used.
The new process enabled the Austrian firm to produce multi-ton quantities of ionic
liquids (today’s annual capacity is 150 tons, by mid-2019, 500 tons). Large chemical suppliers offer selected precursors [97], and some may be the license holder
of the methods [98]. Following the customers’ requirements, the company’s bestsellers cover ionic liquids composed of the following ions: [C 2 C 1 im]
+ , [C 4 C 1 im]
+ ,
and [C 4 C 1 pyr]
+ as the cations, and [Ace]
− , [BF 4 ]
− , [CH 3 SO 3 ]
− , [OTf]
− , [NTf 2 ]
− ,
[FSI]
− , and [C 1 CO 3 ]
− as the anions. In January 2010, a group of international engineering companies
38 focusing on process plants with its headquarters in Austria took
a 70% share of the company [99].
(Cation)
+
CH 3 CO 3
‒ + H
+
(Anion)
‒ → (Cation)
+
(Anion)
‒ + CH 3 OH +
CO 2 ↑
(Cation)
+
HCO 3
‒ + H
+
(Anion)
‒ → (Cation)
+
(Anion)
‒ + H 2 O + CO 2 ↑
(Cation)
+
CH 3 CO 3
‒ + NH 4
+
(Anion)
‒ → (Cation)
+
(Anion)
‒ + CH 3 OH
+ CO 2 ↑ + NH 3 ↑
Scheme 1 Synthesis of an ionic liquid [(Cation) + (Anion) − ] by the CBILS ® method
36 Proionic GmbH.
37 Carbonate Base Ionic Liquid Synthesis, CBILS ® , Proionic GmbH.
38 VTU Group GmbH.