BASF BASIL process

In the BASF BASIL process that utilizes A-methylimidazole to scavenge HCl byproduct, the acidic ionic liquid A-methylimidazolium chloride [HMIMJCl was formed, with a melting point of 75°C (13,102). Recently, the group of Bronsted acidic ionic liquids with the same cation was extended to include other anions, such as BFF, TfO , and TsO . The melting point of the salt is between 30 and 109°C. Strong hydrogen bonding in the tosylate salt was characterized by IR spectroscopy. 

BASF—BASIL process, 2007 http //www2.basf.de/en/intermed/nbd/ products/ionio liquids. 

BASF s BASIL process [15] and the Dimersol process [16] have both been commercialized. The former uses the ionic liquid as a phase transfer catalyst to produce alkoxyphenylphosphines which are precursors for the synthesis of photoinitiators used in printing inks and wood coatings. The imidazole acts as a proton scavenger in the reaction of phenyl-chlorophosphines with alcohols to produce phosphines. The Dimersol process uses a Lewis acid catalyst for the dimerization of butenes to produce Cs olefins which are usually further hydroformylated giving C9 alcohols used in the manufacture of plasticizers. Several other processes are also at the pilot plant scale and some ionic liquids are used commercially as additive e.g. binders in paints. 

In 2002 BASF established the first dedicated industrial-scale ionic liquid-based process [7]. The so-called BASIL process (BASIL = Biphasic Acid Scavenging utilizing Ionic Liquids) is used for the synthesis of alkoxyphenylphosphines, which are important raw materials in the production of BASF s Lucirines (Scheme 9-3), substances that are used as photoinitiators to cure coatings and printing inks by exposure to UV light. 

Fig. 9-4 Today the BASIL process is run in a small jet reactor that has a capacity of 690 000 kg h". BASF Aktiengesellschaft 2002.

Figure 3 The BASIL process. After the reaction two clear liquid phases are obtained the upper one is the pure product and the lower is the ionic liquid HMIMCI ( BASF Aktiengesellschaft 2002).

During 2003 we saw the first published process based on ILs [6], In its BASIL process (see Section 5.3.2), BASF has disclosed the involvement of an imidazolium-based ionic-liquid in the production of alkoxyphenylphosphines. This constitutes an impressive demonstration that IL technology can result in significant financial savings. Another process said to be poised for licensing is the French Petroleum Institute s butene dimerization process, the Difasol process (see Section 5.3.1). Besides these, some more promising applications are currently under investigation, and are hoped to be disclosed in the near future. Notable examples of research areas are in electrochemistry (batteries), biocatalysis, and the application of ILs in extraction processes, e.g., the deep desulfurization of diesel oil. 

BASF s Basil process uses ILs as functional materials and not as a solvent The IL (e.g., methylimidazolium chlorhydrate) is formed during the chemical reaction while scavenging acid byproducts (e.g., HCl). The generation of IL leads to the formation of two clear phases in the reactor, thus solving the problem of separation of byproduct and the elimination of solid formation. This leads to an increase in reaction rate and productivity and a decrease in reactor volume. 

Using the BASIL process (the acronym stands for Biphasic Add Scavenging utilizing Ionic Liquids), BASF was the first company to transfer ionic liquids from laboratory to commercial dimensions, and the BASIL process became the first large-scale industrial process worldwide that uses ionic hquids. 

The use of BASF s BASIL process for scavenging hydrochloric adds in the chemical synthesis of phosphorus compounds like 02POR or 0P (OR)2 by reaction of 02PC1 (or 0PCI2) and ROH offers significant advantages over the conventional system (Figure 3.8). 

Fig. 20.15 BASIL process with a much smaller jet reactor. Image copyright from BASF—The Chemical Company...

A significant commercial application of Bronsted acidic ILs has been by BASF with their range of BASIL processes, which involve ILs in industrial processes. These include the PIL [HMImjCl, where the PIL is produced from using 1-methylimidazolium as an acid scavenger of HCl, and the Bronsted acidic AIL [EMIm]HS04, used in liquid-liquid extraction. In 2003, Rogers and Seddon reported that, for one particular BASIL process, the productivity had been increased by a factor of 80 000 compared to the conventional process ... 

ILs are known [35,36]. Two prominent examples are the BASIL process from BASF [37] and the dissolution of cellulose to make high-value fibers out of it [38]. 

Maase M, Massonne K, Uerdingen E, Vagt U (2006) BASIL - BASF s processes based on ionic liquids. Aldrich Chem Files 6(9) 3... 

BASIL [Biphasic Acid Scavenging utilizing Ionic Liquids] A range of catalytic processes for synthetic organic chemistry. These processes use ionic liquids as solvents, from which it is easy to recover the catalysts. Developed by BASF from 2002 and first commercialized in 2004 for the synthesis of alkoxyphenyl phosphines. Awarded the Entec Medal for safety and environmental innovation in 2005. 

The processes are ordered within the Tables according to their industrial relevance, starting with the two commercial processes — Ruhrchemie/Rhone-Poulenc s oxo process and the SHOP process of Shell [5]. As has been described in the preceding chapters, all other developments are more or less proposals rather than processes they are on the way from laboratory scale to first pilot plant apphcations and finally to industrial scale — some are in an advanced stage of realization, such as the Difasol process of IFP, BASIL of BASF, or Swan s TMCH process. For both tables, the degree of reahzatiorf depends on a few criteria, but decisive ones, which will be discussed below. 

Fig. 20.14 (a) Large reactors for conventional method, (b) Small reactor for BASIL S process. Image copyright from BASF— The Chemical Company... 

The first industrial process to involve ionic liquids was introduced by BASF in 2002. Called BASIL", this technology addresses the problem of HCl formed as a byproduct in the synthesis of alkoxyphenylphosphanes (eq. 9.86). Before the advent of ionic liquids, HCl was scavenged by a tertiary amine, forming a solid [RsNHJCl salt which was separated by filtration. On a commercial scale, this operation is expensive. BASF now uses 1-methylimidazole to scavenge HCl (eq. 9.87). 1-Methylimidazolium chloride is an ionic liquid (mp 348 K) which is immiscible with the reaction solvent. Separation of the two liquid phases is achieved at a lower cost than the filtration previously needed. Deprotonation of the 1-methylimidazolium cation regenerates imidazole which is recycled. 

Basil A trademark used by BASF for their range of processes using ionic liquids, which includes BASIL. Basset See DR. 

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