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(12) Patent Application Publication (10) Pub. No.: US 2005/0020856A1 Bell Et Al

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(12) Patent Application Publication (10) Pub. No.: US 2005/0020856A1 Bell Et Al US 2005.0020856A1 (19) United States (12) Patent Application Publication (10) Pub. No.: US 2005/0020856A1 Bell et al. (43) Pub. Date: Jan. 27, 2005 (54) PROCESS FOR PRODUCTION OF ACETYL (21) Appl. No.: 10/627,254 ANHYDRIDES AND OPTIONALLY ACETIC ACID FROM METHANE AND CARBON (22) Filed: Jul. 24, 2003 DOXDE Publication Classification (75) Inventors: Alexis T. Bell, Oakland, CA (US); Sudip Mukhopadhyay, Williamsville, (51) Int. Cl. ................................................. C07C 69/02 NY (US); Mark Zerella, Berkeley, CA (52) U.S. Cl. .............................................................. 562/888 (US); John Glenn Sunley, East Yorkshire (GB); Sander Gaemers, Bishop Burton (GB) (57) ABSTRACT Correspondence Address: TOWNSEND AND TOWNSEND AND CREW, Acetyl anhydrides Such as acetyl Sulfate are produced by a LLP process for comprising contacting methane and carbon diox TWO EMBARCADERO CENTER ide in an anhydrous environment in the presence of effective EIGHTH FLOOR amounts of a transition metal catalyst and a reaction pro SAN FRANCISCO, CA 94111-3834 (US) moter, and an acid anhydride compound, and optionally an acid. The acetyl anhydride can be contacted with water to (73) Assignee: THE REGENTS OF THE UNIVER- produce acetic acid or with an alcohol to produce a product SITY OF CALIFORINIA, OAKLAND, comprising an acetate ester and that may also comprise CA (US) acetic acid. Patent Application Publication Jan. 27, 2005 Sheet 1 of 3 US 2005/0020856A1 C O O O O O 4.5 4.0 35 3.0 2.5 2.0 15 ppm FIG. I. Patent Application Publication Jan. 27, 2005 Sheet 2 of 3 US 2005/0020856A1 O C O 4.5 40 3.5 3.0 2.5 2.O 15 ppm FIG 2 Patent Application Publication Jan. 27, 2005 Sheet 3 of 3 US 2005/0020856A1 T O (? G O C. O 4.5 4.O 3.5 3.0 25 20 15 ppm FIG. 3 US 2005/0020856 A1 Jan. 27, 2005 PROCESS FOR PRODUCTION OF ACETYL 0007. A number of researchers have investigated produc ANHYDRIDES AND OPTIONALLY ACETIC ACID tion of acetic acid by liquid phase carbonylation of methane FROM METHANE AND CARBON DIOXIDE with carbon monoxide, due to the favorable thermodynam ics of this reaction. See, for instance, Bagno, et al. J. Org. BACKGROUND OF THE INVENTION Chem. 1990, 55, 4284-4289; Lin, et al., Nature 1994, 368, 0001. This invention relates to the production of acetyl 613-615, Chaepaikin, et al., J. Mol. Catal. A. Chem. 2001, anhydrides, and optionally of acetic acid, and particularly to 169,89-98; Nishiguchi, et al., Chem. Lett. 1992, 1141-1142; a process for the production of Such Substances from meth Nakata, et al. J. Organomet. Chem. 1994, 473, 329-334; ane and carbon dioxide. Kurioka, et al., Chem. Lett. 1995, 244; Fujiwara, et al., Studies in Surface Science and Catalysis 1998, 119, 349 0002 The primary process route used today for produc 353; Taniguchi, et al., Org. Lett. 1999, 1(4), 557-559; tion of acetic acid is by catalytic reaction of methanol and Asadullah, et al., Tetrahedron Lett. 1999, 40, 8867-8871; carbon monoxide. Such a process, typically termed “carbo and Asadullah, et al., Chem. Int. Ed. 2000, 39(14), 2475 nylation', is described in a number of patents and publica 2478. tions. Rhodium, palladium or iridium-containing catalysts have been found especially useful for conducting this reac 0008 Kurioka et al. (1995, Supra) also reported a liquid tion. A recent example of a patent on Such a process is U.S. phase experiment in which methane was reacted with carbon Pat. No. 6,472,558 of Key et al., which describes a process dioxide in the presence of palladium acetate, cupric acetate, for reaction of methanol (and/or a reactive derivative of potassium perSulfate and trifluoroacetic acid, reportedly methanol Such as methyl acetate or dimethyl ether) and producing acetic acid. The yield was Said to have been carbon monoxide in a liquid reaction composition that 1650% (based on the palladium). This work was continued comprises methyl acetate, methyl iodide, acetic acid, water and further reported on by Taniguchi et al., Studies in and a polydentate phosphine oxide, in addition to the iridium Surface Science and Catalysis 1998, 439-442. That publi catalyst. cation described a Series of experiments in which methane and carbon dioxide were reacted in the presence of catalysts, 0003) Another process route that has been found useful primarily Vanadium-containing catalysts Such as Vanadiu for the production of acetic acid involves the catalytic m(acac) acac=acetylacetonate), Sodium metavanadate, and oxidation of ethane. Such processes are disclosed, for Vanadium pentoxide, and in the presence of liquids includ instance, in U.S. Pat. No. 6,383,977 of Karim et al. and U.S. ing pure trifluoroacetic acid (“TFA) and aqueous Solutions Pat. No. 6,399,816 of Borchert et al. In the processes of TFA, hydrochloric acid, Sulfuric acid, and sodium described in both patents, a mixed oxide catalyst containing hydroxide, as well as Simply in water. The best results were multiple metals is used. Karim et al. discloses catalysts obtained in a system that contained only TFA, the worst containing molybdenum, Vanadium, niobium and palladium, results were with water alone. while Borchert et al. discloses containing molybdenum and palladium, plus preferably Vanadium, niobium, antimony, 0009 Taniguchi et al. (1998) hypothesized that the acetic nickel and calcium. acid was produced by reaction of methane and carbon 0004 Methane is the lowest molecular weight, and sim dioxide, but subsequent work by others (and by us) showed plest in Structure, of the hydrocarbons. Because of the that this was not correct; in the Taniguchi et al. Work the existence of large reserves of methane Worldwide it has been acetic acid would have been produced primarily if not considered desirable for Some time to develop processes to entirely by reaction of methane and TFA, with concomitant convert methane to more valuable chemicals. Processes for production of one mole of fluoroform for each mole of acetic production of acetic acid from methanol represent an ulti acid produced by this reaction. TFA, however, is an expen mate use of methane, but in current commercial practice, the Sive feedstock for the production of acetic acid. In addition, methane first must be converted to methanol. A process that it is difficult to reconvert the fluoroform byproduct to TFA produces acetic acid directly from methane would be more for recycle or reuse. desirable. 0010 Nizova et al., Chem. Commun. 1998, 1885 reported 0005. A small amount of work has been conducted so far results of reactions of methane with carbon monoxide in on the direct conversion of methane to acetic acid, for aqueous Systems to produce acetic acid. The authors men instance by reaction of methane with carbon dioxide. A tion that they had also produced acetic acid by reaction of proceSS for production of acetic acid by Such a reaction was methane and carbon dioxide in an aqueous System, in the disclosed in the 1924 British patent 226,248 of Dreyfus. The presence of a Sodium metavanadate/pyrazine-2-carboxylic patent describes a proceSS involving gas phase reaction of acid catalyst. However, the yield (based on methane) methane with carbon monoxide and/or carbon dioxide in the appears to have been quite low and pressures rather high (50 presence of a catalyst that preferably contains nickel car bar). Piao et al., J. Organomet. Chem. 1999, 574, 116-120 bonate. Apparently a mixture of acetic acid, acetaldehyde and Yin et al., Appl. Organomet. Chem. 2000, 14, 438-442 and possibly acetone is obtained. No data on yields or reported on catalytic partial oxidation of methane to methyl trifluoroacetate, in the presence of trifluoroacetic acid and a conversions is contained in this patent. Small amount of trifluoroacetic acid anhydride, but with no 0006 PCT application WO 96/05163 of Hoechst A. G. CO or CO present. More recently, Reis et al., Angew. Chem. describes a gas phase reaction of methane and carbon Int. Ed. 2003, 42,821 described production of acetic acid dioxide to produce acetic acid, using a catalyst containing from methane in a Single-pot reaction, with trifluoroacetic one or more Group VIA, VIIA and/or VIIIA metals. Selec acid and various Vanadium-containing catalysts, notably tivities of 70-95% based on methane are asserted; however amavadine, CaVION(CH(CH)COO))), but in the the application contains no exemplary data. absence of carbon dioxide. US 2005/0020856 A1 Jan. 27, 2005 0011. It would be desirable to provide a process for 0021 FIG. 3 depicts H NMR analysis of a product production of acetic acid more directly from methane, and obtained by contacting methane, carbon dioxide and fuming particularly from a process that involves methane and car Sulfuric acid, before addition of water. bon dioxide rather than carbon monoxide Since carbon dioxide is relatively cheap, and additional oxygen is not DETAILED DESCRIPTION OF THE needed. A process conducted under relatively mild condi INVENTION tions, adaptable to industrial use rather than a laboratory 0022. This invention comprises a process for producing curiosity, and with good conversions and/or yields, would be an acetyl anhydride comprising contacting methane and highly desirable. carbon dioxide in an anhydrous environment in the presence 0012. An improved process for the production of acetyl of effective amounts of a transition metal catalyst and a anhydrides also would be desirable. An acetyl anhydride reaction promoter, and an acid anhydride compound, and compound can be defined as a compound, which upon optionally an acid, to produce a product comprising the reaction with water liberates acetic acid and another non acetyl anhydride. hydrohalogenoic acid. Alternatively an acetyl anhydride 0023 The invention further comprises a process for pro compound may be described as a compound in which the ducing a product comprising acetic acid in two steps, hydroxy group of acetic acid has been replaced with the comprising: anion of a non-hydrohalogenoic acid.
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