Solvent process development

Quinacridone pigments are manufactured commercially by two distinct processes The original thermal or solvent process developed at DuPont and the more widely utiUzed polyphosphoric acid (PPA) process. Each process, with its own inherent advantages and disadvantages, differs significantly from the other but shares a common feature, the key starting material dimethyl succinoylsuccinate (DMSS) 7. Because of its crucial status in the manufacture of quinacridone pigments the synthesis of 7 also merits some discussion. 

Until World War 1 acetone was manufactured commercially by the dry distillation of calcium acetate from lime and pyroligneous acid (wood distillate) (9). During the war processes for acetic acid from acetylene and by fermentation supplanted the pyroligneous acid (10). In turn these methods were displaced by the process developed for the bacterial fermentation of carbohydrates (cornstarch and molasses) to acetone and alcohols (11). At one time Pubhcker Industries, Commercial Solvents, and National Distillers had combined biofermentation capacity of 22,700 metric tons of acetone per year. Biofermentation became noncompetitive around 1960 because of the economics of scale of the isopropyl alcohol dehydrogenation and cumene hydroperoxide processes. 

A process developed in Israel (263) uses solvent extraction using a higher alcohol or other solvating solvent. This removes phosphoric acid and some hydrochloric acid from the system driving the equiHbrium of equation 42 to the right. The same principle can be appHed in other salt—acid reactions of the form... 

Pulp-like olefin fibers are produced by a high pressure spurting process developed by Hercules Inc. and Solvay, Inc. Polypropylene or polyethylene is dissolved in volatile solvents at high temperature and pressure. After the solution is released, the solvent is volatilised, and the polymer expands into a highly fluffed, pulp-like product. Additives are included to modify the surface characteristics of the pulp. Uses include felted fabrics, substitution in whole or in part for wood pulp in papermaking, and replacement of asbestos in reinforcing appHcations (56). 

W. R. Eppedy and J. W. Taunton, "Exxon Donor Solvent Coal Liquefaction Process Development," paper presented at Coal Dilemma II ACS Meeting, Colorado Spriags, Colo., Feb. 12, 1979. 

The electrowinning process developed by Ginatta (34) has been purchased by M.A. Industries (Atlanta, Georgia), and the process is available for licensing (qv). MA Industries have also developed a process to upgrade the polypropylene chips from the battery breaking operation to pellets for use by the plastics industry. Additionally, East Penn (Lyons Station, Pennsylvania), has developed a solvent-extraction process to purify the spent acid from lead—acid batteries and use the purified acid in battery production (35). 

The early developments of solvent processing were concerned with the lubricating oil end of the cmde. Solvent extraction processes are appHed to many usefiil separations in the purification of gasoline, kerosene, diesel fuel, and other oils. In addition, solvent extraction can replace fractionation in many separation processes in the refinery. For example, propane deasphalting (Fig. 7) has replaced, to some extent, vacuum distillation as a means of removing asphalt from reduced cmde oils. 

The original hot carbonate process developed by the U.S. Bureau of Mines was found to be corrosive to carbon steel (55). Various additives have been used in order to improve the mass transfer rate as well as to inhibit corrosion. Vetrocoke, Carsol, Catacarb, Benfteld, and Lurgi processes are all activated carbonate processes. Improvements in additives and optimization of operation have made activated carbonate processes competitive with activated MDEA and nonaqueous solvent based systems. Typical energy requirements are given in Table 9. 

Several processes progressed to demonstration scales but have not been commercialized, primarily because of economic inabiHty to compete with available petroleum products. The H-Coal process developed by Hydrocarbon Research, Inc. was demonstrated at Catiettsburg, Kentucky using a 545 t/d plant and DOE support. The Exxon donor solvent Hquefaction process was not commercialized either. 

Direct-Liquefaction Kinetics All direct-liquefac tion processes consist of three basic steps (1) coal slurrying in a vehicle solvent, (2) coal dissolution under high pressure and temperature, and (3) transfer of hydrogen to the dissolved coal. However, the specific reac tion pathways and associated kinetics are not known in detail. Overall reaction schemes and semiempirical relationships have been generated by the individual process developers, but apphcations are process specific and limited to the range of the specific data bases. More extensive research into liquefaction kinetics has been conducted on the laboratory scale, and these results are discussed below. 

Most physical solvent processes are proprietary and are licensed by the company that developed the process. 

Gozdz et al. (of Bellcore) [25] recognized that poly (vinylidene difluoride) hexafluoropropylene (PVDF HFP) copolymers could form gels with organic solvents and developed an entire battery based on this concept. Typically, the gel separator is 50 pm thick and comprises 60wt. % polymer. In the Bellcore process the separator is laminated to the electrodes under pressure at elevated temperature. The use of the PVDF HFP gelling agent increases the resistivity of the electrolyte by about five times which limits the rate capability of such batteries. 

The specific application of a laboratory reactor determines its shape and size, and the degree of sophistication in design. However, no matter which application is under consideration, the final goal in process development is always the highest product yield and the lowest yields of side products, the highest activity of the reaction system (reactants + solvent + catalyst), the lowest cost, and stable and safe operation. 

In addition to the challenges cited above, there are some special issues associated with steroid chemistry that should be noted. The steroidal impurities formed in the process are generally similar in structure to the desired product and, in some cases, co-crystallization with the product is a problem. It is, therefore, critical to limit the formation of steroidal impurities in the reactions. The structural similarity between product and impurities also creates challenges in developing assays for reaction monitoring and purity determination. Furthermore, the poor solubility of these compounds in the solvents typically used in a manufacturing process makes it very difficult to achieve practical volume productivity in process development. 

The current research objective is to evaluate the surface activity of the subfractions obtained from the solvent fractionated crude oil and shale oil samples as they are passed through the separation process developed for this work. The columns used are anion exchange resin,... 

Bedford, D.A. "Solvent Process for Developing Interwell Communication Path in a Viscous Petroleum Containing Formation Such as a Tar Sand Deposit," CA Patent 1015656(1977). 

W. P. Epperly and T. W. Taunton, "Exxon Donor Solvent, Coal Liquefaction Process Development", Proceedings of the 13th Intersociety Energy Conversion Engineering Conference, Vol. 

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