11 Toward Industrialization of Ionic Liquids
271
agricultural by-products are used as feedstocks for the replacement of petroleum.
Low-cost protic ionic liquids feed the proprietary BioFlex process, which fractionates cellulose, hemicellulose, and lignin. By-products as well as heavy metals present
in feedstock (e.g., construction wood waste) can be recovered.
Versum Materials, a spin-off of Air Products, applies ionic liquids for the storage
of hazardous gases used in the electronic industry in their GASGUARD
® technology. For example, BF 3 , PH 3 , or AsH 3 are complexed with ionic liquids, such as
[C n mim][BF 4 ], [C n mim][Cu 2 Cl 3 ], and [C n mim][Cu 2 Br 3 ], by Lewis acid–base interactions using sub-atmospheric pressure. The technology circumvents the need for
conventional steel cylinders and high-pressure storage conditions. The desired gases
are released by applying mild temperatures or vacuum in a safe and controllable
manner.
IoLiTec is currently piloting bromide-based ionic liquids as solvents and additives in a redox flow electrolyte for zinc–bromine batteries. Here, the bromide anion
complexes bromine to form tribromide and reduces self-discharge and vapor pressure
within the system [23]. IoLiTec is also testing ionic liquids as solvents and reagents
for the purification of biogas in a pilot-scale project.
Supelco commercialized the use of ionic liquids as a stationary phase in gas chromatography columns showing high to extremely high polarity, unmatched thermal
and chemical stability, low bleed, and unique selectivity (see Chap. 6). PETRONAS
operates the first commercial application of the SILP technology [36] to remove
mercury from natural gas. The chlorocuprate(II) ionic liquid reagent is immobilized
on a solid silica support and effectively removes elemental, organic, and inorganic
mercury with an expected service life up to three times greater than conventional
sorbents. The technology was developed in cooperation with Clariant and QUILL
and commercialized in 2014 [45] (see also Chap. 3). Hitachi High-Tech uses ionic
liquids as visualization reagents for scanning electron microscopy (SEM). By coating samples—including biological specimens—with a thin layer of a hydrophilic
ionic liquid, observation in the SEM proceeds efficiently without the need for prior
preparation or fixation. Sample visualization is facilitated by the negligible vapor
pressure, electrical conductivity, and polarity of the ionic liquids. The product was
commercialized under the label HILEM
® IL 1000.
Finally, proionic, one of the leading manufacturers of ionic liquids worldwide,
commercialized its proprietary Carbonate Based Ionic Liquid Synthesis (CBILS
® ) in
2003. CBILS
® is one of the most advanced commercialized processes for a “green”
industrial production of high-purity ionic liquids, and proionic has reached an annual
production capacity in the 100 metric ton range. This entirely halide-free, and virtually waste-free, production route [46, 47] uses carbonic acid esters as quaternization
reagents forming ionic liquid key-intermediates with ammonium-, phosphonium-,
imidazolium-, pyrrolidinium-, or morpholinium-type cations and methylcarbonate
anions. The ionic liquid methylcarbonates are true platform chemicals, which can
easily be converted into final products upon a facile hydrolytic reaction with Brønsted
acids or ammonium salts. The conjugate base of the Brønsted acid or the ammonium
salt anion becomes the anion of the ionic liquid final product. CBILS
® chemistry
271
agricultural by-products are used as feedstocks for the replacement of petroleum.
Low-cost protic ionic liquids feed the proprietary BioFlex process, which fractionates cellulose, hemicellulose, and lignin. By-products as well as heavy metals present
in feedstock (e.g., construction wood waste) can be recovered.
Versum Materials, a spin-off of Air Products, applies ionic liquids for the storage
of hazardous gases used in the electronic industry in their GASGUARD
® technology. For example, BF 3 , PH 3 , or AsH 3 are complexed with ionic liquids, such as
[C n mim][BF 4 ], [C n mim][Cu 2 Cl 3 ], and [C n mim][Cu 2 Br 3 ], by Lewis acid–base interactions using sub-atmospheric pressure. The technology circumvents the need for
conventional steel cylinders and high-pressure storage conditions. The desired gases
are released by applying mild temperatures or vacuum in a safe and controllable
manner.
IoLiTec is currently piloting bromide-based ionic liquids as solvents and additives in a redox flow electrolyte for zinc–bromine batteries. Here, the bromide anion
complexes bromine to form tribromide and reduces self-discharge and vapor pressure
within the system [23]. IoLiTec is also testing ionic liquids as solvents and reagents
for the purification of biogas in a pilot-scale project.
Supelco commercialized the use of ionic liquids as a stationary phase in gas chromatography columns showing high to extremely high polarity, unmatched thermal
and chemical stability, low bleed, and unique selectivity (see Chap. 6). PETRONAS
operates the first commercial application of the SILP technology [36] to remove
mercury from natural gas. The chlorocuprate(II) ionic liquid reagent is immobilized
on a solid silica support and effectively removes elemental, organic, and inorganic
mercury with an expected service life up to three times greater than conventional
sorbents. The technology was developed in cooperation with Clariant and QUILL
and commercialized in 2014 [45] (see also Chap. 3). Hitachi High-Tech uses ionic
liquids as visualization reagents for scanning electron microscopy (SEM). By coating samples—including biological specimens—with a thin layer of a hydrophilic
ionic liquid, observation in the SEM proceeds efficiently without the need for prior
preparation or fixation. Sample visualization is facilitated by the negligible vapor
pressure, electrical conductivity, and polarity of the ionic liquids. The product was
commercialized under the label HILEM
® IL 1000.
Finally, proionic, one of the leading manufacturers of ionic liquids worldwide,
commercialized its proprietary Carbonate Based Ionic Liquid Synthesis (CBILS
® ) in
2003. CBILS
® is one of the most advanced commercialized processes for a “green”
industrial production of high-purity ionic liquids, and proionic has reached an annual
production capacity in the 100 metric ton range. This entirely halide-free, and virtually waste-free, production route [46, 47] uses carbonic acid esters as quaternization
reagents forming ionic liquid key-intermediates with ammonium-, phosphonium-,
imidazolium-, pyrrolidinium-, or morpholinium-type cations and methylcarbonate
anions. The ionic liquid methylcarbonates are true platform chemicals, which can
easily be converted into final products upon a facile hydrolytic reaction with Brønsted
acids or ammonium salts. The conjugate base of the Brønsted acid or the ammonium
salt anion becomes the anion of the ionic liquid final product. CBILS
® chemistry