Texaco Inc.

Texaco Development Corporation

Texco Inc.

Robert M Suggitt

Walter C Gates, Jr

Mitri S Najjar

Edward T Child

Ralph B Hudson, Jr

Frederick C Jahnke

Allen M Robin

Wing-Chiu F Fong

William L Lafferty, Jr

John H Estes

Thomas Frederick Leininger

Albert Brent

Edward L Cole

Matthew A McMahon

Henry C Chan

Peter L Paull

Ronald J McKeon

James K Wolfenbarger

John M Crone, Jr

Manuel E Quintana

Joseph H Coone, Jr

John F Knifton

Sheldon Herbstman

George N Richter

Roger J Corbeels

Lawrence E Estabrook

Robert J Stellaccio

Raymond F Wilson

William N Gilmer

Stanley Kravitz

A process is provided for continuously controlling the hydrocarbon heat content and flow rate of a partial oxidation unit feed-gas stream under conditions where the composition and hence the hydrocarbon heat content of the feed-gas stream is subject to variation. The hydrocarbon heat content of the incoming gases is continuously measured and compared against a design hydrocarbon heat content. An evaluating means calculates whether a moderator is required to decrease the hydrocarbon heat content to the design hydrocarbon heat content or a supplemental high hydrocarbon heat content gas is required to increase the hydrocarbon heat content to the design hydrocarbon heat content. The process utilizes recycle synthesis gas as a moderator. Once the determination is made, the process automatically adjusts flow rates of the recycle synthesis gas stream, the supplemental high hydrocarbon heat content gas stream and the incoming feed-gas stream to provide a partial oxidation unit feed-gas stream with a constant optimum hydrocarbon heat content and flow rate.

Process for continuously controlling the heat content of a partial

Part of CO-rich syngas, including volatile metal or any acid impurities, reacts with water making cleaned, heated, H.sub.2 -enriched syngas. The rest of the impure CO-rich syngas is combined with hot, H.sub.2 -enriched syngas making cleaned, H.sub.2 -rich syngas, useful for making methanol or oxo compounds.

Cleaned, H.sub.2 -enriched syngas made using water-gas shift reaction

A partial oxidation process for the production of a stream of hot clean gas substantially free from particulate matter, alkali metal compounds, hydrogen halides, hydrogen cyanide, sulfur-containing gases, and with or without ammonia for use as synthesis gas, reducing gas, or fuel gas. A pumpable hydrocarbonaceous fuel selected from the group consisting of liquid hydrocarbonaceous fuel or liquid emulsions thereof, an aqueous slurry of petroleum coke, and mixtures thereof and wherein said hydrocarbonaceous fuel contains halides, alkali metal compounds, sulfur, nitrogen and inorganic ash containing components, is reacted in a gasifier by partial oxidation to produce a hot raw gas stream comprising H.sub.2, CO, CO.sub.2, H.sub.2 O, CH.sub.4, NH.sub.3, HCN, HCl, HF, H.sub.2 S, COS, N.sub.2, Ar, particulate matter, vapor phase alkali metal compounds, and molten slag. The hot raw gas stream from the gasifier is cooled in a radiant cooler and cleaned. Optionally, ammonia is removed from the gas stream by being catalytically disproportionated into N.sub.2 and H.sub.2. The process gas stream is cooled and halides and HCN in the gas stream are reacted with a supplementary alkali metal compound to remove HCl, HF and HCN. Alkali metal halides and alkali metal cyanide, vaporized alkali metal compounds and residual fine particulate matter are removed from the gas stream by further cooling and filtering. The sulfur-containing gases in the process gas stream are then reacted at high temperature with a regenerable sulfur-reactive mixed metal oxide sulfur sorbent material to produce a sulfided sorbent material which is then separated from the hot clean purified gas stream having a temperature of at least 1000.degree. F.

Partial oxidation process for producing a stream of hot purified gas

A partial oxidation process for the production of a stream of hot clean gas substantially free from particulate matter, ammonia, alkali metal compounds, halides and sulfur-containing gas for use as synthesis gas, reducing gas, or fuel gas. A hydrocarbonaceous fuel comprising a solid carbonaceous fuel with or without liquid hydrocarbonaceous fuel or gaseous hydrocarbon fuel, wherein said hydrocarbonaceous fuel contains halides, alkali metal compounds, sulfur, nitrogen and inorganic ash containing components, is reacted in a gasifier by partial oxidation to produce a hot raw gas stream comprising H.sub.2, CO, CO.sub.2, H.sub.2 O, CH.sub.4, NH.sub.3, HCl, HF, H.sub.2 S, COS, N.sub.2, Ar, particulate matter, vapor phase alkali metal compounds, and molten slag. The hot raw gas stream from the gasifier is split into two streams which are separately deslagged, cleaned and recombined. Ammonia in the gas mixture is catalytically disproportionated into N.sub.2 and H.sub.2. The ammonia-free gas stream is then cooled and halides in the gas stream are reacted with a supplementary alkali metal compound to remove HCl and HF. Alkali metal halides, vaporized alkali metal compounds and residual fine particulate matter are removed from the gas stream by further cooling and filtering. The sulfur-containing gases in the process gas stream are then reacted at high temperature with a regenerable sulfur-reactive mixed metal oxide sulfur sorbent material to produce a sulfided sorbent material which is then separated from the hot clean purified gas stream having a temperature of at least 1000.degree. F.

Mechanical and electrical power are produced along with synthesis or fuel gas by the partial oxidation process with integrated combustion and steam turbines. By-product vaporized liquefied natural gas for feed to a pipeline for gas consumers is obtained by heat exchange with heat containing streams from the partial oxidation gasification and gas cleaning and purification zone; and optionally from heat containing streams from combustion and/or steam turbine zones which are integrated with the partial oxidation process. Heat from the combustion turbine exhaust gas is used as follows: (1) superheat steam for use in a steam turbine; (2) preheat water saturated clean sulfur-free synthesis or fuel gas with or without supplemental methane enrichment; (3) preheat oxygen gas for the partial oxidation zone; and (4) vaporize LNG. Pre, inter, and after stages of an air compressor are cooled by indirect heat exchange with LNG which is thereby warmed or vaporized.

Combined power cycle with liquefied natural gas (LNG) and synthesis or

Mechanical and electrical power are produced along with synthesis or fuel gas by the partial oxidation process with integrated combustion and steam turbines. By-product vaporized liquefied natural gas for feed to a pipeline for gas consumers is obtained by heat exchange with heat containing streams from the partial oxidation gasification and gas cleaning and purification zone; and optionally from heat containing streams from combustion and/or steam turbine zones which are integrated with said partial oxidation process. Heat from the combustion turbine exhaust gas is used as follows: (1) superheat steam for use in a steam turbine; (2) preheat water saturated clean sulfur-free synthesis or fuel gas with or without supplemental methane enrichment; (3) preheat oxygen gas for said partial oxidation zone; and (4) vaporize LNG. Pre, inter, and after stages of an air compressor are cooled by indirect heat exchange with LNG which is thereby warmed or vaporized.

Cryogenic liquefied natural gas (LNG) is used as a source of refrigeration and methane in the production of dry sulfur-free, methane-enriched synthesis gas or fuel gas. Raw syngas is indirectly and directly contacted with cryogenic liquefied natural gas (LNG) and cooled thereby below the dew point. Water is thereby condensed out and separated from the process gas stream. Further, the liquid LNG vaporizes and increases the methane content of the dewatered synthesis gas. Cold liquid absorbent solvent contacts the dry CH.sub.4 -enriched synthesis gas in an absorption column and absorbs the acid gases e.g. H.sub.2 S and COS and optionally H.sub.2 S+COS+CO.sub.2. In a preferred embodiment, the rich solvent absorbent is regenerated in a stripping column and the released acid gases are sent to a Claus unit for the production of elemental sulfur. In a second embodiment, the regenerated lean liquid absorbent solvent may be mixed with the dry, purified synthesis gas leaving from the top of the absorption tower. This mixture is then directly and optionally indirectly contacted with additional cryogenic liquid LNG. The CH.sub.4 content of the synthesis or fuel gas is thereby increased to a value in the range of about 10 to 80 mole %. By means of a decanter, dry, sulfur-free methane-enriched syngas product is separated from liquid absorbent solvent. The liquid absorbent solvent is then recycled to the absorption column.

Process for producing dry, sulfur-free, CH.sub.4 -enriched synthesis or

A process for producing high purity hyrogen is disclosed. Specifically, the process includes (1) partially oxidizing a gaseous hydrocarbonaceous feedstock to produce a synthesis gas mixture of carbon monoxide and hydrogen, (2) reacting the synthesis gas mixture with steam to convert the carbon monoxide into a raw gas mixture which primarily includes carbon dioxide and hydrogen, and (3) subjecting the raw gas mixture to pressure swing adsorption to purify the raw gas mixture, thereby producing high purity hydrogen and a reject gas mixture of impurities. The gaseous hydrocarbonaceous feed is specific, inasmuch as it is characterized by containing a major component which includes at least one C.sub.1 -C.sub.3 hydrocarbon and which has an average molecular weight of up to about 30.

Process for producing high purity hydrogen

A process for producing high purity hydrogen is disclosed. Specifically, the process includes (1) partially oxidizing a refinery offgas feedstock to produce a synthesis gas mixture of carbon monoxide and hydrogen, (2) reacting the synthesis gas mixture with steam to convert the carbon monoxide into a raw gas mixture which primarily includes carbon dioxide and hydrogen, and (3) purifying the raw gas mixture to produce high purity hydrogen and a reject gas mixture of impurities. In a preferred embodiment, the purification step occurs in a pressure swing adsorption unit. Alternative embodiments are also described, each of which essentially involve the optional treatment and/or use of the reject gas mixture of impurities.

Municipal sanitary sewage sludge is disposed of by an improved partial oxidation process without polluting the environment. Aqueous slurries of sewage sludge are upgraded by hydrothermal treatment, preferably while being sheared, concentrated, and then mixed with a supplemental fuel, preferably coal. A pumpable aqueous slurry of sewage sludge-coal and/or petroleum coke is thereby produced having a greater total solids and heat content (HHV) as well as containing an increased amount of sewage sludge for reacting with free-oxygen containing gas in a free-flow partial oxidation gas generator. Hot quench water or steam produced by cooling the hot raw effluent stream of synthesis gas, reducing gas or fuel gas from the gasifier may provide heat for the hydrothermal step.

Partial oxidation of sewage sludge

Municipal sanitary sewage sludge is disposed of by an improved partial oxidation process without polluting the environment. Aqueous slurries of sewage sludge are upgraded by being sheared without heating, concentrated if necessary, and then mixed with a supplemental fuel, preferably coal. In one embodiment, the aqueous slurry of sewage sludge and the supplemental coal and/or petroleum coke are introduced into a shearing mixer for simultaneous shearing and mixing together. A pumpable aqueous slurry of sewage sludge-coal and/or petroleum coke is thereby produced having an increased amount of total solids and an increased heat content (HHV) as well as containing an increased amount of sewage sludge for reacting with free-oxygen containing gas in a free-flow partial oxidation gas generator. Hot quench water or steam produced by cooling the hot raw effluent stream of synthesis gas, reducing gas or fuel gas from the gasifier may provide heat for indirect heat exchange with other streams in the process.

Gasifier for combusting a particulated carbonaceous fuel by injecting a stream of the fuel into the gasifier combustion chamber together with a combustion supporting gas. The fuel mixture is burned to produce a usable gas and a particulated residual, both of which are directed into a liquid holding quench chamber. A constricted, frusto-conical throat which conducts the usable gas and particulated residual includes one or more nozzles that open into the throat and serve to direct pressurized jets of a scouring fluid into contact with residual particles which have become deposited on the throat wall, to displace the latter and thereby keep the throat void of such deposits.

Gasifier with gas scroured throat

A process for the production of demercurized synthesis gas, reducing gas or fuel gas. Mercury-containing fossil fuels e.g. coal were reacted by partial oxidation to produce gaseous mixtures comprising H.sub.2, CO, H.sub.2 O, CO.sub.2, H.sub.2 S, COS, entrained slag and/or ash, mercury vapor, and optionally CH.sub.4, NH.sub.3, N.sub.2 and Ar. Unexpectedly, the mercury vapor was produced in the reaction zone; and it was found to be thermodynamically stable even in the presence of H.sub.2 S under the strong reducing conditions that prevailed in the gas generator. No new sulfides of mercury were formed. The mercury vapors were removed from the main body of the process gas stream in a pressurized solvent scrubber at a relatively low temperature. By this means, the mercury vapor was condensed and simultaneously the mercury and sulfur contents of the clean process gas stream were reduced to low levels. In one embodiment, the last vestiges of mercury were removed from the demercurized product gas stream by carbon sorption.

Production of demercurized synthesis gas, reducing gas, or fuel gas

Synthesis gas, fuel gas, or reducing gas is produced by the noncatalytic partial oxidation of a sulfur-containing liquid hydrocarbonaceous fuel or a slurry of sulfur-containing solid carbonaceous fuel with a free-oxygen containing gas in the free-flow reaction zone of a refractory lined gas generator at an autogenous temperature in the range of about 1900.degree. F. to 2900.degree. F. and above the ash-fusion temperature of the slag formed in the reaction zone, so that about 75 to 95 weight percent of the carbon in the fuel feed to the reaction zone is converted into carbon oxides. At least a portion of the hot effluent gas stream from the reaction zone is passed through a free-flow radiant cooler in admixture with an iron-containing additive. In the radiant cooler at least a portion of the sulfur-containing gases e.g. H.sub.2 S and COS react with the iron-containing additive to produce particulate matter comprising iron oxysulfide. Further, a portion of this newly formed particulate matter and/or the iron-containing additive combine with molten slag and/or ash in the hot raw gas stream passing through the radiant gas cooler. The slag produced thereby has a reduced ash fusion temperature and a reduced viscosity. The remainder of the newly formed particulate matter comprising iron oxysulfide and particulate carbon are entrained in the effluent gas stream leaving the radiant syngas cooler and are separated from the effluent gas stream and optionally recycled to the partial oxidation reaction zone in admixture with fresh fuel feed.

POX process with high temperature desulfurization of syngas

Synthesis gas, fuel gas, or reducing gas is produced by the noncatalytic partial oxidation of a sulfur-containing liquid hydrocarbonaceous fuel or a slurry of sulfur-containing solid carbonaceous fuel with a free-oxygen containing gas in the first free-flow reaction zone located in a refractory lined gas generator at an autogenous temperature in the range of about 1900.degree. F. to 2900.degree. F. and above the ash-fusion temperature of the slag formed in the reaction zone. About 85 to 99 weight percent of the carbon in the fuel feed to the reaction zone is converted into carbon oxides. At least a portion of the hot effluent gas stream from the reaction zone is passed through a free-flow second reaction zone R.sub.2 in admixture with a second portion of sulfur-containing fuel and an iron-containing additive. In the second reaction zone the carbon in the second portion of fuel, unconverted fuel and particulate matter from R.sub.1 react with H.sub.2 O and/or CO.sub.2 to produce supplemental H.sub.2 and/or carbon oxides. Further, at least a portion of the sulfur-containing gases e.g. H.sub.2 S and COS react with the iron-containing additive to produce particulate matter comprising iron oxysulfide. Further, a portion of this newly formed particulate matter and/or the iron-containing additive combine with molten slag and/or ash in the hot raw gas stream passing through the second gas cooler. The slag produced thereby has a reduced ash fusion temperature and a reduced viscosity. The remainder of the newly formed particulate matter comprising iron oxysulfide and particulate carbon are entrained in the effluent gas stream leaving the second reaction zone and are separated from the effluent gas stream and optionally recycled to the partial oxidation reaction zone in admixture with fresh fuel feed.

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Wappingers Falls, NY, United States of America

Robert M Suggitt