Halcon patents

The original Halcon patent [4] on carbonylation of MeOAc to AC2O demonstrated that Lil catalysed the reaction of Acl with MeOAc. An explanation of the activity of Lil had been put forward by workers at Eastman that involved the presence of LiOAc in the system through reaction with MeOAc, (Eq. (19)) then reaction of LiOAc with Acl (Eq. (37)) [5],... 

V, Nb, Ta, Cr, Mo, W, Sn, Mn, Re, Fe, Co, and Ni. Halcon patents [59] describe catalyst systems containing Zr, Mo/Ni, or Sn/Ni as synergistic co-catalysts. Furthermore, metals of Group VIII combined with Hf, phosphines, amines, or arsines, as promoter additives, have been reported [60]. 

Sales demand for acetophenone is largely satisfied through distikative by-product recovery from residues produced in the Hock process for phenol (qv) manufacture. Acetophenone is produced in the Hock process by decomposition of cumene hydroperoxide. A more selective synthesis of acetophenone, by cleavage of cumene hydroperoxide over a cupric catalyst, has been patented (341). Acetophenone can also be produced by oxidizing the methylphenylcarbinol intermediate which is formed in styrene (qv) production processes using ethylbenzene oxidation, such as the ARCO and Halcon process and older technologies (342,343). 

Because the epoxidation with Tl(III) is stoichiometric to produce Tl(I), reoxidation is needed. Halcon has patented processes based on such epoxidation to yield ethylene oxide (200—203). The primary benefits of such a process are claimed to be high yields of ethylene oxide, fiexibihty to produce either propylene oxide or ethylene oxide, and the potential of a useful by-product (acetaldehyde). Advances usiag organic hydroperoxides ia place of oxygen for reoxidation offer considerable promise, siace reaction rates are rapid and low pressures can be used. 

The reaction of olefin epoxidation by peracids was discovered by Prilezhaev [235]. The first observation concerning catalytic olefin epoxidation was made in 1950 by Hawkins [236]. He discovered oxide formation from cyclohexene and 1-octane during the decomposition of cumyl hydroperoxide in the medium of these hydrocarbons in the presence of vanadium pentaoxide. From 1963 to 1965, the Halcon Co. developed and patented the process of preparation of propylene oxide and styrene from propylene and ethylbenzene in which the key stage is the catalytic epoxidation of propylene by ethylbenzene hydroperoxide [237,238]. In 1965, Indictor and Brill [239] published studies on the epoxidation of several olefins by 1,1-dimethylethyl hydroperoxide catalyzed by acetylacetonates of several metals. They observed the high yield of oxide (close to 100% with respect to hydroperoxide) for catalysis by molybdenum, vanadium, and chromium acetylacetonates. The low yield of oxide (15-28%) was observed in the case of catalysis by manganese, cobalt, iron, and copper acetylacetonates. The further studies showed that molybdenum, vanadium, and... 

One molybdenum-catalyzed epoxidation, which is of indnstrial importance, needs special mention the Halcon process , which is the molybdennm-catalyzed epoxidation of propylene with TBHP or 1-phenylethyl hydroperoxide on a large scale (Scheme 74), and has been developed and patented by researchers from Halcon and Atlantic Richfield . 

Halcon International), U.S. Patent (Halcon International), U.S. Patent... 

Netherland Patent 6,515,741 (1966) assigned to Halcon International, Inc., Chem. Abstr. 65 13547a (1966). 

In early patents by Halcon, molybdenum carbonyls are claimed to be active catalysts in the presence of nickel and iodide [23]. Iridium complexes are also reported to be active in the carbonylation of olefins, in the presence of other halogen [24] or other promoting co-catalysts such as phosphines, arsines, and stibines [25]. The formation of diethyl ketone and polyketones is frequently observed. Iridium catalysts are in general less active than comparable rhodium systems. Since the water-gas shift reaction becomes dominant at higher temperatures, attempts to compensate for the lack of activity by increasing the reaction temperature have been unsuccessful. 

Epoxidation with hydroperoxides is the basis for the large-scale indirect production of propylene oxide by a process that has been called the Oxirane or Halcon processes. Early work was reported by Smith in a patent issued in 1956 [457], which described soluble heteropoly acids containing transition metals such as chromium, molybdenum, and tungsten that could be employed as homogeneous catalysts for the reaction of olefins with organic hydroperoxides and hydrogen peroxide. 

M. Pell, E. 1. Korchak, Epoxidation using ethylbenzene hydroperoxide with alkali or adsorbent treatment of recycle ehtylbenzene, U.S. Patent No. 3,439,001, 1969, Assigned to Halcon International, Inc. 

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