Organic compounds -- part of the class 532-570 series – Organic compounds – Carbonate esters
Reexamination Certificate
2000-11-10
2001-10-30
Padmanabhan, Sreeni (Department: 1621)
Organic compounds -- part of the class 532-570 series
Organic compounds
Carbonate esters
C558S260000, C558S270000, C564S230000, C564S281000, C568S010000
Reexamination Certificate
active
06310232
ABSTRACT:
BACKGROUND OF THE INVENTION
This invention relates to catalyst recycle, and more particularly to the conversion and recycle of bromide-containing constituents of catalyst compositions used to conduct chemical reactions.
The use as catalysts of various compositions comprising transition metals is known. Among the catalyst constituents in common use are compounds of the Groups 8, 9, and 10 metals, including those having atomic numbers of at least 44 (i.e., ruthenium, rhodium, palladium, osmium, iridium and platinum), hereinafter “heavy transition metals”. Compounds of other metals, such as those of Group 8, 9, and 10 with atomic numbers less than 44, and including cobalt, lead, manganese, cerium, titanium, and copper are also useful as constituents of said catalyst compositions.
Bromide sources are also frequently present in various catalyst compositions. These include alkali metal and alkaline earth metal bromides, and onium salts, including trialkylamine hydrobromides and tetraalkylammonium, tetraalkylphosphonium, hexaalkylguanidinium, and sulphonium bromides.
The reactions in which such compounds serve a catalytic function include some which involve organic compounds as reactants, products or both. An illustration is the catalytic carbonylation of hydroxyaromatic compounds such as phenol with carbon monoxide and oxygen to yield diaryl carbonates such as diphenyl carbonate. This reaction will sometimes be designated “carbonylation” hereinafter.
In a typical carbonylation reaction, phenol is combined with a compound of a heavy transition metal, most often palladium, and other catalytic species which may include organic and inorganic co-catalysts and at least one bromide source. One or more other metal compounds, most often of lead, may be used as inorganic cocatalysts, and the use in combination therewith of bromide sources which may include alkali metal or alkaline earth metal bromides, tetraalkylammonium bromides, or hexaalkylguanidinium bromides is frequently advantageous. The resulting mixture is pressurized with carbon monoxide and oxygen to yield a product mixture containing diphenyl carbonate, unreacted phenol and by-products which include palladium in elemental and/or combined form and compounds of other metals present in the catalyst composition.
In U.S. Pat. No. 5,981,788, there is described a method of recovering and recycling carbonylation catalyst constituents which include heavy transition metals such as palladium, other metals including those of the Groups 8, 9, and 10 with atomic numbers less than 44 such as cobalt, and bromide sources such as tetraalkylammonium and hexaalkylguanidinium bromides. The recovery of the bromide source comprises simply its extraction with water, optionally following a preconcentration to lower the phenol concentration. This is practical when the other metal is cobalt, since there is essentially no chemical interaction in the presence of cobalt between hydroxyaromatic compounds such as phenol and bromide ions.
However, many of the numerous other metals employed in such catalyst compositions are not as suitable as cobalt in maintaining the presence of ionic bromide. This is particularly true of lead, which, when present, promotes conversion of the ionic bromide, typically an amount in the range of about 30-95% by weight thereof, to covalently bound bromine in the form of organic bromine compounds, predominantly bromophenols such as 2- and 4-bromophenol. Other metals can produce the similar covalently bound bromine compounds.
Conversion of ionic bromide to covalent bromine makes recovery of the cationic portion of the bromide source difficult. This may be the result of association of the cation with organic anions such as phenate. In addition to this difficulty of recovery, most ionic molecules in which the anion is a non-halogen such as phenate are not appreciably active as catalyst constituents.
It is of interest, therefore, to provide a method for recovery of bromide sources and their conversion or reconversion to compounds capable of supplying bromide ion to a catalyst composition.
SUMMARY OF THE INVENTION
The present invention is based on the discovery that a simple bromide contact step under proper conditions can reconvert the cationic portion of the bromide source to an active bromide-containing catalyst material.
In one embodiment the invention is a method for removal and recycle of ionic bromide-containing catalytic materials from a composition comprising a substantially water-insoluble organic material and comprising a bromide source, which method comprises the steps of contacting said composition with an aqueous acidic solution comprising bromide ions, thereby regenerating said bromide source, and extracting said bromide source with an aqueous liquid.
DETAILED DESCRIPTION; PREFERRED EMBODIMENTS
The method of the invention is particularly applicable to carbonylation reaction mixtures comprising at least one diaryl carbonate such as diphenyl carbonate, which is essentially water-immiscible. Unreacted hydroxyaromatic compound, such as phenol, may also be present. It is considerably more soluble in water than is diaryl carbonate. It should be understood, however, that the method of the invention may be applied equally well to any reaction affording as product an organic material having low solubility in water and employing a catalyst comprising any heavy transition metal compounds and other catalytically active metal compounds.
Also present in carbonylation reaction mixtures are catalyst constituents including a heavy transition metal compound, particularly at least one based on palladium. Typical palladium compounds which are employed as carbonylation catalysts are the salts of divalent palladium with carboxylic acids such as acetic acid and &bgr;-diketones such as 2,4-pentanedione (acetylacetone).
Co-catalysts, usually inorganic and sometimes in combination with organic, are also generally present, the inorganic co-catalyst being at least one metal compound and especially, for the purposes of this invention, a compound of a metal other than cobalt. Most often, the metal is at least one metal selected from the group consisting of lead, manganese, cerium, titanium, and copper, and mixtures thereof.
Bromide sources which may be present in the catalyst composition include alkali metal bromides, alkaline earth metal bromides, and onium salts, including trialkylamine hydrobromides and tetraalkylammonium, tetraalkylphosphonium, hexaalkylguanidinium, and sulphonium bromides; illustrative are sodium bromide, tetramethylammonium bromide, tetra-n-butylammonium bromide and hexaethylguanidinium bromide. Suitable organic cocatalysts include various terpyridine, phenanthroline, quinoline and isoquinoline compounds, with 2,2′.6′,2″-terpyridine often being preferred. These compounds and the by-products formed therefrom are generally incorporated in the organic phase during carbonylation.
The major product of the carbonylation reaction is usually a substantially homogeneous organic liquid containing diaryl carbonate (typically diphenyl carbonate), excess hydroxyaromatic compound (typically phenol) and palladium compounds, inorganic co-catalytic compounds or their by-products and bromide sources or their by-products. Also present may be organic co-catalysts such as terpyridines, or their by-products. This organic liquid may also contain covalent bromine compounds, typically bromophenols, formed by the reaction of bromide with the hydroxyaromatic compound in the presence of the other catalyst constituents.
Prior to performing the method of the invention, it is generally preferred to remove about 30-99%, preferably a major proportion, generally about 75-90% by weight, of the hydroxyaromatic compound from the organic liquid. Removal may be achieved by methods known in the art, such as simple vacuum stripping.
In an embodiment of the present invention, the organic liquid is contacted with an aqueous acidic solution containing bromide ions. Said solution is preferably of hydrogen bromide, but other acidic bromides may also be employ
Battista Richard Anthony
Moreno Phillip Oscar
Ofori John Yaw
Patel Ben Purushotam
Pressman Eric James
Brown S. Bruce
General Electric Company
Johnson Noreen C.
Padmanabhan Sreeni
Witherspoon Sikarl A.
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