Catalytic gasification process with recovery of alkali metal from char

This application claims priority under 35 U.S.C. §119 from U.S. Provisional Application Ser. No. 61/017,293 (filed Dec. 28, 2007), the disclosure of which is incorporated by reference herein for all purposes as if fully set forth.

This application is related to commonly owned U.S. application Ser. No. 11/421,511, filed Jun. 1, 2006, entitled “CATALYTIC STEAM GASIFICATION PROCESS WITH RECOVERY AND RECYCLE OF ALKALI METAL COMPOUNDS”; U.S. application Ser. No. ______, (filed concurrently herewith), entitled “CATALYTIC GASIFICATION PROCESS WITH RECOVERY OF ALKALI METAL FROM CHAR” (attorney docket no. FN-0014 US NP1); U.S. application Ser. No. ______, (filed concurrently herewith), entitled “CATALYTIC GASIFICATION PROCESS WITH RECOVERY OF ALKALI METAL FROM CHAR” (attorney docket no. FN-0015 US NP1); and U.S. application Ser. No. ______, (filed concurrently herewith), entitled “CATALYTIC GASIFICATION PROCESS WITH RECOVERY OF ALKALI METAL FROM CHAR” (attorney docket no. FN-0016 US NP1).

The present invention relates to a catalytic gasification process that involves the extraction and recovery of alkali metal from char that remains following catalytic gasification of a carbonaceous composition. Further, the invention relates to processes for extracting and recovering alkali metal from char by reacting a char particulate with an alkali hydroxide, calcium oxide and/or calcium hydroxide, and carbon dioxide under suitable temperature and pressure so as to convert insoluble alkali metal compounds contained in the insoluble char particulate to soluble alkali metal compounds.

In view of numerous factors such as higher energy prices and environmental concerns, the production of value-added gaseous products from lower-fuel-value carbonaceous feedstocks, such as petroleum coke and coal, is receiving renewed attention. The catalytic gasification of such materials to produce methane and other value-added gases is disclosed, for example, in U.S. Pat. No. 3,828,474, U.S. Pat. No. 3,998,607, U.S. Pat. No. 4,057,512, U.S. Pat. No. 4,092,125, U.S. Pat. No. 4,094,650, U.S. Pat. No. 4,204,843, U.S. Pat. No. 4,468,231, U.S. Pat. No. 4,500,323, U.S. Pat. No. 4,541,841, U.S. Pat. No. 4,551,155, U.S. Pat. No. 4,558,027, U.S. Pat. No. 4,606,105, U.S. Pat. No. 4,617,027, U.S. Pat. No. 4,609,456, U.S. Pat. No. 5,017,282, U.S. Pat. No. 5,055,181, U.S. Pat. No. 6,187,465, U.S. Pat. No. 6,790,430, U.S. Pat. No. 6,894,183, U.S. Pat. No. 6,955,695, US2003/0167961A1, US2006/0265953A1, US2007/000177A1, US2007/083072A1, US2007/0277437A1 and GB 1599932.

Gasification of a carbonaceous material, such as coal or petroleum coke, can be catalyzed by loading the carbonaceous material with a catalyst comprising an alkali metal source. U.S. Patent Application Publication Nos. US2007/0000177A1 and US2007/0083072A1, both incorporated herein by reference, disclose the alkali-metal-catalyzed gasification of carbonaceous materials. Lower-fuel-value carbon sources, such as coal, typically contain quantities of inorganic matter, including compounds of silicon, aluminum, calcium, iron, vanadium, sulfur, and the like. This inorganic content is referred to as ash. Silica and alumina are especially common ash components. At temperatures above 500-600° C., alkali metal compounds can react with the alumina and silica to form alkali metal aluminosilicates. As an aluminosilicate, the alkali metal compound is substantially insoluble in water and has little effectiveness as a gasification catalyst.

At typical gasification temperatures, most components of ash are not gasified, and thus build up with other compounds in the gasification reactor as a solid residue referred to as char. For catalytic gasification, char generally includes ash, unconverted carbonaceous material, and alkali metal compounds (from the catalyst). The char must be periodically withdrawn from the reactor through a solid purge. The char may contain substantial quantities of alkali metal compounds. The alkali metal compounds may exist in the char as soluble species, such as potassium carbonate, but may also exist as insoluble species, such as potassium aluminosilicate (e.g., kaliophilite). It is desirable to recover the soluble and the insoluble alkali metal compounds from the solid purge for subsequent reuse as a gasification catalyst. A need remains for efficient processes for recovering soluble and insoluble alkali metal compounds from char. Such processes should effect substantial recovery of alkali metal compounds from the char, minimize the complexity of the processing steps, reduce the use of consumable raw materials, and generate few waste products that require disposal.

The present invention provides processes for converting a carbonaceous composition into a plurality of gaseous products with recovery of soluble alkali metal compounds that can be reused as a gasification catalyst. The invention further provides processes for extracting and recovering catalytically useful alkali metal compounds from soluble and insoluble alkali metal compounds contained in char, where the processes involve thermal quenching of the char in an aqueous medium followed by treatment of the char particulate with an alkali metal hydroxide, calcium oxide and/or calcium hydroxide, and carbon dioxide gas under hydrothermal conditions.

In a first aspect, the invention provides a process for extracting and recovering alkali metal from a char, the char comprising (i) one or more soluble alkali metal compounds and (ii) insoluble matter comprising one or more insoluble alkali metal compounds, the process comprising the steps of: (a) providing char at an elevated temperature ranging from 50° C. to 600° C.; (b) quenching the char in an aqueous medium to fracture the char and form a quenched char slurry; (c) separating the quenched char slurry into a first liquid stream and an insoluble matter stream, the first liquid stream comprising at least a portion of the soluble alkali metal compounds from the char, and the insoluble matter stream comprising residual soluble alkali metal compounds and a first insoluble matter comprising insoluble alkali metal compounds; (d) recovering the first liquid stream; (e) contacting the first insoluble matter with an alkali metal hydroxide and calcium oxide, calcium hydroxide, or both, under suitable pressure and temperature so as to convert at least a portion of the insoluble alkali metal compounds in the first insoluble matter to one or more soluble alkali metal compounds and produce a first leached slurry comprising soluble alkali metal compounds and partially extracted insoluble matter, wherein the partially extracted insoluble matter comprises insoluble alkali metal compounds; (f) contacting the first leached slurry with carbon dioxide under suitable pressure and temperature so to convert at least a portion of the insoluble alkali metal compounds in the partially extracted insoluble matter to one or more soluble alkali metal compounds and produce a second leached slurry comprising soluble alkali metal compounds and a residual insoluble matter; (g) separating the second leached slurry into a second liquid stream and a residual insoluble matter stream, the second liquid stream comprising a predominant portion of the soluble alkali metal compounds from the second leached slurry, and the residual insoluble matter stream comprising residual soluble alkali metal compounds and residual insoluble alkali metal compounds; (h) recovering the second liquid stream; and (i) washing the residual insoluble matter stream to recover substantially all of the residual soluble alkali metal compounds in the residual insoluble matter stream as a first wash stream, wherein the quenching and contacting are performed in the substantial absence of gaseous oxygen.

In a second aspect, the invention provides a process for catalytically converting a carbonaceous composition, in the presence of an alkali metal gasification catalyst, into a plurality of gaseous products and recovering a gasification catalyst, the process comprising the steps of: (a) supplying a carbonaceous composition to a gasification reactor, the carbonaceous composition comprising an ash; (b) reacting the carbonaceous composition in the gasifying gasification reactor in the presence of steam and an alkali metal gasification catalyst under suitable temperature and pressure to form (i) a char comprising the alkali metal from the alkali metal gasification catalyst in the form of one or more soluble alkali metal compounds and one or more insoluble alkali metal compounds, and (ii) a plurality of gaseous products comprising methane and at least one or more of hydrogen, carbon monoxide, carbon dioxide, hydrogen sulfide, ammonia, and other higher hydrocarbons, the gasification catalyst comprising an alkali metal; (c) removing a portion of the char and from the gasification reactor; (d) extracting and recovering a substantial portion of the alkali metal from the char according to any process of the first aspect; and (e) at least partially separating the plurality of gaseous products to produce a stream comprising a predominant amount of one of the gaseous products.

The process can be run continuously, and the recovered alkali metal can be recycled back into the process to minimize the amount of makeup catalyst required.