Acetic Acid Purification Column

The purification unit consists of three valve-tray columns. The production medium for AA in the purification stage at 130-200 °C contains up to 16% water, 26% methyl iodide, and other components, such as methyl acetate (MA), methanol (MeOH), hydrogen iodide (HI), formic acid (FA), and propionic acid (PA) (PEP Report, 1994). The fractionation column removes the light components and portions of water in the mixture, and the dehydration column treats both water and FA. The last column, which is an SSC, produces the final AA product from the side draw by cutting off the remaining light and heavy components from 

Fractionation column Dehydration column Refining column 

To predict the vapor-liquid equilibrium (VLE) of these simulations, the NRTL-HOC property model, which uses the Hayden-O Connell equation of state as the vapor-phase model and the NRTL for the liquid phase, was employed (Aspen Technology, 2009). 

Master Comp Mole Frao (Formic Acid) 0.0039  

Master Comp Moie Frao (Aoetio Acid) 0.9908  

---

The bottoms from the solvent recovery (or a2eotropic dehydration column) are fed to the foremns column where acetic acid, some acryflc acid, and final traces of water are removed overhead. The overhead mixture is sent to an acetic acid purification column where a technical grade of acetic acid suitable for ester manufacture is recovered as a by-product. The bottoms from the acetic acid recovery column are recycled to the reflux to the foremns column. The bottoms from the foremns column are fed to the product column where the glacial acryflc acid of commerce is taken overhead. Bottoms from the product column are stripped to recover acryflc acid values and the high boilers are burned. The principal losses of acryflc acid in this process are to the aqueous raffinate and to the aqueous layer from the dehydration column and to dimeri2ation of acryflc acid to 3-acryloxypropionic acid. If necessary, the product column bottoms stripper may include provision for a short-contact-time cracker to crack this dimer back to acryflc acid (60). 

The bottoms from the solvent recovery (or azeotropic dehydration column) are fed to the foreruns column where acetic acid, some acrylic acid, and final traces of water are removed overhead The overhead mixture is sent to an acetic acid purification column where a technical grade of acetic acid suitable for ester manufacture is recovered as a by-product. The bottoms from the acetic acid recovery column are recycled to the reflux to the foreruns column. 

Figure 9.10 Acetic acid purification unit of three conventional columns (Long and Lee, 2011). Source Reproduced from Long and Lee, 2011, with permission from John Wiley Sons.

Long, N.V.D., Lee, S.H. and Lee, M. (2010) Design and optimization of a dividing wall column for debottlenecking of the acetic acid purification. Chemical Engineering and Processing, 49, 825-835. 

Purification of the activation products (PMs). The methylamine activation product dissolved in methanol is purified by chromatography, first on a column of silica gel using a mixed solvent of chloroform/ethanol, followed by reversed-phase HPLC on a column of divinylbenzene resin (such as Jordi Reversed-Phase and Hamilton PRP-1) using various solvent systems suitable for the target substance (for example, acetonitrile/water containing 0.15% acetic acid). 

A clean-up process-scale RP-HPLC step has been introduced into production of human insulin prb. The C8 or C18 RP-HPLC column used displays an internal volume of 80 1 or more, and up to 1200 g of insulin may be loaded during a single purification run (Figure 11.4). Separation is achieved using an acidic (often acetic-acid-based) mobile phase (i.e. set at a pH value sufficiently below the insulin pi value of 5.3 in order to keep it fully in solution). The insulin is usually loaded in the water-rich acidic mobile phase, followed by gradient elution using acetonitrile (insulin typically elutes at 15-30 per cent acetonitrile). 

The first problem encountered once the peptide has been successfully synthesized is that standard purification protocols fail. Although very hydrophobic peptides are soluble in acids such as TFA, these harsh conditions are not suitable for purification, because they can reduce column life times and denature native protein structures. Hence residual acid has to be removed, and many peptides can then be redissolved in mixtures of water and tert-butanol. Peptides with a strong tendency to aggregate may be dissolved either in trifluoroethanol (TFE), hexafluoroisopropanol (HFIP), mixtures of 1-propanol and 1-butanol, 20% acetic acid or 70-90% formic acid. 

Protein A columns can be used many times. It is not recommended to use the same column for purification of different antibodies because of possible crosscontamination. Should this, however, become necessary, the column has to be washed with several column volumes of alternating pH (PBS followed by 100 mM glycine, pH 3.0, or 100 mM acetic acid). This step should also include a denaturant wash with 2 M urea. 

Figure 13 Purification of pravastatin sodium by preparative liquid chromatography. Reprinted from [12], copyright 2001, with permission from Elsevier. (Column 125 X 4.6 mm i.d. 3 pm Hypersil ODS mobile-phase gradient methanol water triethylamine acetic acid 45 54.8 0.1 0.1 for 13 min, to 99.8 0 0.1 0.1 over 9 min flow rate 1.2 ml/min detector UV 235 nm.)...

In our laboratory crude preparations of aphantoxins and anatoxin-a(s) are extracted similarly except at the final stages of purification (Fig. 2). A Bio-gel P-2 column (2.2 x 80 cm) is used for aphantoxins gel filtration and a Sephadex G-15 (2.6 x 42 cm) column for ana-toxin-(s). Both toxins are eluted with 0.1 M acetic acid at 1.5 ml/ min. Fractions of aphantoxins from Bio-gel P-2 run are spotted on thin-layer chromatography plates (Silica gel-60, EM reagents) and developed according to Buckley et al. (1976) (31). The Rf values for the aphantoxins, saxitoxin and neosaxitoxin standards (Table 1) indicates that two of the aphantoxins (i.e. I and II) are similar to saxitoxin and neosaxitoxin. 

Procedures. Chromatographic Purification of Ozonization Products. Ozonization products from ethyl 10-undecenoate and 1-octene were chromatographed on silica gel columns (Baker) and eluted with 15 or 25% ether in petroleum ether (b.p., 30°-60°). Fractions were examined by thin-layer chromatography (TLC) on silica gel G Chroma-gram sheet eluted with 40% ether in petroleum ether. For development of ozonide and peroxide spots, 3% KI in 1% aqueous acetic acid spray was better than iodine. The spots (of iodine) faded, but a permanent record was made by Xerox copying. Color of die spots varied from light brown (ozonide) to purple-brown (hydroperoxide), and the rate of development of this color was related to structure (diperoxide > hydroperoxide > ozonide). 2,4-Dinitrophenylhydrazine spray revealed aldehyde spots and also reacted with ozonides and hydroperoxides. Fractions were evaporated at room temperature or below in a rotary evaporator. 

In this preparation the nitroso compound may be added in solution form to a solution to the amine at low temperature. The solvent may be a suitable mixture of acetic acid and ethanol as well as acetic acid alone. The product may also be extracted from a reaction mixture diluted with water by use of ether [32]. Purification of the final product may be carried out by chromatography on an alumina column. 

---