Hydrogen From Hydrocarbons Patents (Class 252/376)
  • Patent number: 6048473
    Abstract: A process for operating a system for water vapor reforming of methanol includes a mixture preparation step for preparing a water vapor/methanol mixture from water and methanol, which mixture is subsequently introduced into a reforming reactor in a quantity which depends on the load condition of the system. According to the invention, the water vapor/methanol mixture ratio of the water vapor/methanol mixture introduced into the reforming reactor is maintained at a predeterminable desired value unaffected by short-term load changing operations, to avoid undesirable short-term increases of the CO-concentration in the reformate.
    Type: Grant
    Filed: June 16, 1997
    Date of Patent: April 11, 2000
    Assignee: DaimlerChrysler AG
    Inventors: Michael Denda, Christian Duelk, Robert Gerberich, Norbert Wiesheu
  • Patent number: 5929286
    Abstract: A method of forming a hydrogen rich gas from a source of hydrocarbon fuel in which the hydrocarbon fuel contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion at a temperature not less than about 400.degree. C. for a time sufficient to generate the hydrogen rich gas while maintaining CO content less than about 5 volume percent. There is also disclosed a method of forming partially oxidized hydrocarbons from ethanes in which ethane gas contacts a two-part catalyst comprising a dehydrogenation portion and an oxide-ion conducting portion for a time and at a temperature sufficient to form an oxide.
    Type: Grant
    Filed: June 5, 1998
    Date of Patent: July 27, 1999
    Assignee: The University of Chicago
    Inventors: Michael Krumpelt, Shabbir Ahmed, Romesh Kumar, Rajiv Doshi
  • Patent number: 5925328
    Abstract: A process for the preparation of ammonia synthesis gas includes supplying a feedstock gas, optionally mixed with a flue gas, to at least one pair of reforming reactors. Each reactor has a process and fuel side and a combustion side. Each pair of reactors is arranged in parallel on the process and fuel side, and in series on the combustion side. A flame temperature in each pair of reactors is controlled by supplying an excess of combustion air to a first reactor of the pair, and oxygen-depleted combustion air to a second reactor of the pair.
    Type: Grant
    Filed: October 2, 1997
    Date of Patent: July 20, 1999
    Assignee: Haldor Topsoe A/S
    Inventors: Henrk Otto Stahl, Ib Dybkj.ae butted.r, Carsten Lau Laursen
  • Patent number: 5744067
    Abstract: This invention relates to the production of hydrogen-rich gas by the partial oxidation of a saturated gaseous hydrocarbonaceous fuel or a mixture of saturated gaseous hydrocarbonaceous fuel and a liquid hydrocabonaceous fuel in a gas generator. In the process, a saturated gaseous hydrocarbonaceous fuel from a subsequent fuel gas saturator is preheated by indirect heat exchange with a portion of shifted process gas stream from a catalytic water-gas direct shift conversion zone and reacted in said partial oxidation gas generator. The process gas stream from the noncatalytic partial oxidation gas generator is quench cooled and scrubbed with water and preheated by indirect heat exchange with a second portion of the process gas stream from the shift conversion zone prior to catalytically reacting the CO and H.sub.2 O in the process gas stream in the shift conversion zone to increase its H.sub.2 content.
    Type: Grant
    Filed: May 21, 1996
    Date of Patent: April 28, 1998
    Assignee: Texaco Inc.
    Inventor: Frederick Charles Jahnke
  • Patent number: 5211880
    Abstract: A process for the preparation of ammonia synthesis gas by steam reforming and/or partial oxidation of a hydrocarbon feedstock comprises the further steps of catalytically converting a part of the synthesis gas to methanol, liquifying and separating the prepared methanol from remaining nitrogen rich gas, then reconverting the nitrogen depleted methanol to hydrogen and carbon oxides gas and recombining the gas with the reminder of the nitrogen containing synthesis gas to obtain stoichiometric ammonia synthesis gas.
    Type: Grant
    Filed: December 20, 1991
    Date of Patent: May 18, 1993
    Assignee: Haldor Topsoe A/s
    Inventors: Ivar I. Primdahl, Giorgio P. Serra
  • Patent number: 5202057
    Abstract: Nitrogen is economically recovered from the flue gas evolved in a hydrocarbon steam reforming furnace by hydrogenation of free oxygen therein and removal of carbon dioxide and other minor impurities from the flue gas by pressure swing adsorption with recovery of high purity nitrogen is unsorbed effluent. The process is utilized to highest advantage in the production of ammonia syngas wherein natural gas or other hydrocarbon feed is subjected to steam reforming in a fuel-fired furnace. The nitrogen obtained by purification of the flue gas is combined with the purified hydrogen separated from the reformate providing the syngas for conversion to ammonia. In a preferred embodiment, the steam reforming is carried out in two stages, the first stage being performed in a conventional fuel-fired steam reforming furnace to which a major portion of the fresh hydrocarbon feed is charged.
    Type: Grant
    Filed: April 28, 1992
    Date of Patent: April 13, 1993
    Assignee: Air Products and Chemicals, Inc.
    Inventors: David M. Nicholas, Joseph P. Bushinsky, Ravi Kumar, Wilbur C. Kratz
  • Patent number: 5122299
    Abstract: Synthesis gases are produced by reaction of steam, oxidant, and a major portion of fresh hydrocarbon feed in an exothermic catalytic reforming zone to a first reformed gas having very low methane content. The balance of the fresh feed is reacted with steam in an endothermic catalytic reforming zone to a second reformed gas having a low methane content. The first and second reformed gases are combined and passed in indirect heat exchange with reactants in the endothermic reforming zone to provide all of the heat required therein and are then recovered as product synthesis gases.
    Type: Grant
    Filed: March 14, 1991
    Date of Patent: June 16, 1992
    Assignee: The M. W. Kellogg Company
    Inventor: Joseph R. LeBlanc
  • Patent number: 5068058
    Abstract: A method is disclosed for producing ammonia synthesis gas by splitting a methane stream, combusting a portion of the methane with steam and oxygen-enriched air, converting a second portion of the methane with steam in a reformation heated by the combustion products of the first portion and combining the two portions for the water gas shift reaction followed by adsorptive separation of contained carbon dioxide.
    Type: Grant
    Filed: May 4, 1989
    Date of Patent: November 26, 1991
    Assignee: Air Products and Chemicals, Inc.
    Inventors: Joseph P. Bushinsky, David M. Nicholas, Shoou-I Wang, Nitin M. Patel
  • Patent number: 5039510
    Abstract: The endothermic reaction of a hydrocarbon feedstock with steam and/or carbon dioxide is carried out using a double-tube reactor. In one preferred form of the reactor the catalyst is present as a coating on the outside of the inner tube. In another form inner tubes are mounted in one tube-plate and the outer tubes in a second tube plate and the tube plates are disposed across a cylindrical shell so as to define a heat exchange zone (provided with a heat source) a reactants feed zone and a products offtake zone. The heat source is preferably a burner, to be fed with the product of the endothermic reaction, followed by a secondary reforming catalyst. The apparatus makes possible processes for making raw hydrogen-containing gases with advantageous internal heat recovery.
    Type: Grant
    Filed: May 23, 1988
    Date of Patent: August 13, 1991
    Assignee: Imperial Chemical Industries PLC
    Inventor: Alwyn Pinto
  • Patent number: 5011625
    Abstract: Ammonia synthesis gas is produced by reaction of steam, an oxidant, and a major portion of fresh hydrocarbon feed in an exothermic catalytic reforming zone to a first reformed gas having very low methane content. The balance of the fresh feed is reacted with steam in an endothermic catalytic reforming zone to a second reformed gas having a low methane content. The first and second reformed gases are combined and passed in indirect heat exchange with reactants in the endothermic reforming zone to provide all of the heat required therein and are then recovered as raw ammonia synthesis gas.
    Type: Grant
    Filed: December 11, 1989
    Date of Patent: April 30, 1991
    Assignee: The M. W. Kellogg Company
    Inventor: Joseph R. Le Blanc
  • Patent number: 5004592
    Abstract: The endothermic reaction of a hydrocarbon feedstock with steam and/or carbon dioxide is carried out using a double-tube reactor. In one preferred form of the reactor the catalyst is present as a coating on the outside of the inner tube. In another form inner tubes are mounted in one tube-plate and the outer tubes in a second tube plate and the tube plates are disposed across a cylindrical shell so as to define a heat exchange zone (provided with a heat source) a reactants feed zone and a products offtake zone. The heat source is preferably a burner, to be fed with the product of the endothermic reaction, followed by a secondary reforming catalyst. The apparatus makes possible processes for making raw hydrogen-containing gases with advantageous internal heat recovery.
    Type: Grant
    Filed: May 23, 1988
    Date of Patent: April 2, 1991
    Assignee: Imperial Chemical Industries PLC
    Inventor: Alwyn Pinto
  • Patent number: 4988490
    Abstract: Nitrogen is economically recovered from the flue gas evolved in a hydrocarbon steam reforming furnace by hydrogenation of free oxygen therein and removal of carbon dioxide and other minor impurities from the flue gas by pressure swing adsorption with recovery of high purity nitrogen as unsorbed effluent. The process is utilized to highest advantage in the production of ammonia syngas wherein natural gas or other hydrocarbon feed is subjected to steam reforming in a fuel-fired furnace. The nitrogen obtained by purification of the flue gas is combined with the purified hydrogen separated from the reformate providing the syngas for conversion to ammonia. In a preferred embodiment, the steam reforming is carried out in two stages, the first stage being performed in a conventional fuel-fired steam reforming furnace to which a major portion of the fresh hydrocarbon feed is charged.
    Type: Grant
    Filed: September 14, 1988
    Date of Patent: January 29, 1991
    Assignee: Air Products and Chemicals, Inc.
    Inventors: David M. Nicholas, Joseph P. Bushinsky, Ravi Kumar, Wilbur C. Kratz
  • Patent number: 4981669
    Abstract: Ammonia synthesis gas is prepared by primary and secondary reforming followed by shift and carbon oxides removal. So that the process can use naphtha and methane, e.g. natural gas, as alternative feedstocks, at least the initial part of the primary reforming catalyst is alkalized. When using a methane feedstock, the primary reformer heating and outlet temperature are reduced compared to when using naphtha, and the amount of air fed to the secondary reformer is increased, so that, after shift, the hydrogen to nitrogen molar ratio of the gas stream is lower and is such that the gas contains an excess of nitrogen. This excess of nitrogen is subsequently removed, e.g. from the ammonia synthesis loop by a cryogenic hydrogen-recovery unit treating a loop purge stream and recovering hydrogen for recycle to the loop.
    Type: Grant
    Filed: October 5, 1988
    Date of Patent: January 1, 1991
    Assignee: Imperial Chemical Industries PLC
    Inventor: Alwyn Pinto
  • Patent number: 4950309
    Abstract: Toxic refractory organic substances are decomposed by reaction with oxygen and steam at a temperature in the range of 2500.degree. F. to 3200.degree. F. Such toxic refractory organic compounds as PCB's, may be completely destroyed without contamination of the environment.
    Type: Grant
    Filed: October 14, 1988
    Date of Patent: August 21, 1990
    Assignee: Dynecology Incorporated
    Inventor: Helmut W. Schulz
  • Patent number: 4863712
    Abstract: A catalyst, or a precursor thereto, comprises, as the active material or as a support therefor, a ceramic foam having a network of irregular passages extending therethrough, said passages having an average minimum dimension in the range 20 to 300 .mu.m, said foam having a total porosity in the range 40 to 85% and an apparent density of at least 0.7 g. cm-3. The foam may be made by forming a negative replica of an open cell plastics foam by impregnation of the latter with a dispersion of the ceramic material, followed by drying and calcining the impregnated foam to remove the plastics material and to cause the ceramic material to sinter.For a steam reforming catalyst the ceramic may be alpha alumina and the active material nickel and/or cobalt.
    Type: Grant
    Filed: December 30, 1988
    Date of Patent: September 5, 1989
    Assignee: Imperial Chemical Industries PLC
    Inventors: Martyn V. Twigg, William M. Sengelow
  • Patent number: 4863707
    Abstract: A process for the production of ammonia from a hydrocarbonaceous feed, comprising preheating an inlet stream comprising a hydrocarbonaceous feed, H.sub.2 O, air and oxygen to a preheat temperature sufficiently high to initiate catalytic oxidation of the feed, introducing the preheated inlet stream into a first catalyst zone comprising a monolithic body having a plurality of gas flow passages extending therethrough and having a catalytically effective amount of palladium and platinum catalytic components dispersed therein, passing the first zone effluent to a second catalyst zone containing a platinum group metal steam reforming catalyst to form a hydrogen-containing synthesis gas, and passing the synthesis gas into an ammonia synthesis loop.
    Type: Grant
    Filed: January 6, 1989
    Date of Patent: September 5, 1989
    Assignee: Engelhard Corporation
    Inventors: William T. McShea, III, Robert M. Yarrington
  • Patent number: 4822521
    Abstract: Integrated primary-secondary reforming operations are carried out with the partly reformed product effluent from the reformer tubes of the primary reforming zone passing to a catalyst-free reaction space at the feed end of a catalyst bed in the secondary reforming zone. The exothermic heat of reaction generated in said reaction space supplies the necessary heat for the endothermic reforming reaction that occurs in the catalyst bed of the secondary reforming zone, and the still hot secondary product effluent leaving the secondary reforming zone is passed in the shell side of the primary reformer zone to supply the endothermic heat of reaction required in said primary reforming zone. Essentially autothermal operating conditions are thereby achieved so as to essentially eliminate the necessity for employing an external fuel-fired primary reformer and/or for consuming a portion of the hyrocarbon feed material for fuel purposes.
    Type: Grant
    Filed: November 17, 1986
    Date of Patent: April 18, 1989
    Assignee: UOP
    Inventor: Andrija Fuderer
  • Patent number: 4810417
    Abstract: A process for the simultaneous production of methanol synthesis gas and ammonia synthesis gas proceeds from the crude gas of a coal gasification, which initially is subjected to a H.sub.2 S-washing at low temperatures. Then follows a splitting of the desulfurized gas into two partial streams, of which one partial stream is led directly into the CO.sub.2 -washing which serves for production of the methanol-synthesis gas. Another partial stream is in contrast initially subjected to a conversion. From the converted gas then a partial stream is branched off which is provided for the production of ammonia-synthesis gas, whereas the remainder of the converted gas is led into the CO.sub.2 -washing serving for the production of the methanol-synthesis gas. The partial straem serving for the production of the ammonia-synthesis gas is treated to a separate CO.sub.2 -washing, in which simultaneously the so-called purge gas from the ammonia-synthesis is led in. The H.sub.2 S-washing and the CO.sub.
    Type: Grant
    Filed: January 10, 1983
    Date of Patent: March 7, 1989
    Assignee: Krupp-Koppers GmbH
    Inventors: Peter Diemer, Norbert Deuser
  • Patent number: 4792441
    Abstract: An ammonia synthesis gas mixture comprised of substantially pure hydrogen and nitrogen in approximately 3/1 molar ratio is obtained form two stage reforming of a methane-rich hydrocarbon charge such as natural gas. About 40% of the fresh natural gas is charged to primary steam reforming and the obtained primary reformate product, containing about 17 volume percent of unreacted methane, is mixed with the other 60% of the fresh natural gas and the mixture is subjected to oxidative reforming with enriched air containing 30 to 35 of O.sub.2, said enriched air being supplied in an amount to produce a secondary reformate containing principally hydrogen and nitrogen, accompanied by a minor amount of oxides of carbon (CO and CO.sub.2). The secondary reformate subjected to shift reaction with steam results in conversion of contained CO to CO.sub.2, thereby releasing hydrogen in an amount which together with the hydrogen previously present in said reformate obtains a H.sub.2 /N.sub.2 molar ratio of about 3/1.
    Type: Grant
    Filed: January 19, 1988
    Date of Patent: December 20, 1988
    Assignee: Air Products and Chemicals, Inc.
    Inventors: Shoou-I Wang, Nitin M. Patel, Shivaji Sircar, Rodney J. Allam
  • Patent number: 4772420
    Abstract: A raw ammonia synthesis gas, preferably containing an excess of nitrogen, is converted to synthesis ready ammonia synthesis gas by two pressure swing adsorption (PSA) stages operated in succession. If the raw gas contains carbon monoxide this is chemically removed, e.g. by methanation, between the PSA stages. In the first PSA stage, CO.sub.2 is removed and waste gas from the second PSA stage is preferably fed back to the first PSA stage for sweeping, purging or repressurizing. In a preferred system the first PSA cycle includes a sweep with CO.sub.2 -rich gas prior to depressurization and purge with second PSA waste gas. In the second PSA stage inert medium boiling gases, and any unwanted nitrogen are removed as the waste gas.
    Type: Grant
    Filed: July 13, 1987
    Date of Patent: September 20, 1988
    Assignee: Imperial Chemical Industries PLC
    Inventors: Alwyn Pinto, John B. H. Johnson
  • Patent number: 4733528
    Abstract: Energy is recovered from low calorific value gas by means of a gas turbine. Heat is recovered from the turbine exhaust by indirect heat exchange with water. The resultant hot water is used to saturate the fuel and, optionally, also the combustion air, and/or to aid regeneration of an absorbent used in a wet process to remove carbon dioxide from the gas prior to combustion.Preferably the low calorific value gas is waste gas from a PSA process used to remove impurities in the production of a hydrogen-containing gas stream from a raw gas made by primary/secondary steam reforming a hydrocarbon feedstock at superatmospheric pressure and the turbine drives the secondary reformer air compressor.
    Type: Grant
    Filed: May 30, 1986
    Date of Patent: March 29, 1988
    Assignee: Imperial Chemical Industries PLC
    Inventor: Alwyn Pinto
  • Patent number: 4725380
    Abstract: Production of ammonia synthesis gas by partial oxidation of a hydrocarbon feedstock, using air, oxygen enriched air, or oxygen depleted air, in admixture with steam, followed by shift and the removal of the excess of nitrogen, and also impurities such as carbon oxides and methane, by pressure swing adsorption (PSA). The PSA waste gas is combusted and used to heat the air and/or steam prior to the use thereof in the partial oxidation.
    Type: Grant
    Filed: August 8, 1986
    Date of Patent: February 16, 1988
    Assignee: Imperial Chemical Industries PLC
    Inventor: Alwyn Pinto
  • Patent number: 4725381
    Abstract: A carbonaceous feedstock, e.g. coal or heavy oil, having a low hydrogen to carbon atomic ratio is partially oxidized using air, or oxygen enriched or depleted air, to form a crude gas which is subjected to catalytic shift and excess steam removal. Carbon dioxide and nitrogen are then removed from the resultant raw gas, which has a hydrogen to nitrogen, plus carbon monoxide, volume ratio in the range 0.5 to 1.5 and a nitrogen content at least 10 times the carbon monoxide content, in a pressure swing adsorption process thereby producing a product gas stream containing at least 50% hydrogen and 0.5 to 40% nitrogen, by volume. The waste gas from the pressure swing adsorption may be catalytically combusted to power a turbine driving the compressor for the air or the crude gas.
    Type: Grant
    Filed: August 7, 1986
    Date of Patent: February 16, 1988
    Assignee: Imperial Chemical Industries PLC
    Inventor: Alwyn Pinto
  • Patent number: 4699772
    Abstract: In a process for preparing ammonia from hydrogen and nitrogen the synthesis gas mixture is produced by partial oxidation, in the presence of a suitable catalyst, at a pressure of from 35 to 150 bar and temperatures of from 850.degree.-1200.degree. C. at the exit of the partial oxidation zone, followed by removal of the carbon oxides and water from the gaseous effluent of the partial oxidation zone. The air used for the catalytic partial oxidation is supplied in such a quantity that the molar ratio of hydrogen to nitrogen in the synthesis gas is between 2.5 and 3 to 1 and is enriched with such a quantity of oxygen that the total quantity of oxygen is sufficient to effect the required degree of hydrocarbon conversion.
    Type: Grant
    Filed: January 31, 1986
    Date of Patent: October 13, 1987
    Assignee: Stamicarbon B.V.
    Inventor: Hans C. de Lathouder
  • Patent number: 4695442
    Abstract: Ammonia synthesis gas is made from a raw gas comprising hydrogen, carbon dioxide and medium boiling point gases including nitrogen in excess of the proportion required in ammonia synthesis gas, by a pressure swing adsorption process characterized by feeding to the adsorbent a raw gas in which hydrogen and total medium boiling point gases are present in a volume ratio in the range 1.25 to 2.5, and the medium boiling point gases comprise nitrogen to the extent of at least 90% v/v on the total such gases. Preferred ways of making the raw gas, of ensuring purity of the product gas and of recovering useful heat are described.
    Type: Grant
    Filed: February 20, 1985
    Date of Patent: September 22, 1987
    Assignee: Imperial Chemical Industries PLC
    Inventors: Alwyn Pinto, John B. H. Johnson
  • Patent number: 4671893
    Abstract: Carbon dioxide is removed from a raw gas containing hydrogen, carbon dioxide, and intermediate boiling gas, e.g. nitrogen, to give a gas suitable for use as a synthesis gas by a wet carbon dioxide removal process, and the resultant carbon dioxide depleted gas is subjected to pressure swing adsorption (PSA) to remove some, or all, of the intermediate boiling gas and the bulk of any residual carbon dioxide. The PSA waste gas is used to strip the absorbent liquid in the regeneration of the latter in the wet carbon dioxide removal process.The process is of particular utility in the manufacture of ammonia synthesis gas from a raw gas containing an excess of nitrogen, particularly as prepared by primary/secondary reforming/shift of a carbonaceous feedstock with partial bypass of the primary reforming stage.
    Type: Grant
    Filed: February 24, 1986
    Date of Patent: June 9, 1987
    Assignee: Imperial Chemical Industries Plc
    Inventor: Alwyn Pinto
  • Patent number: 4668494
    Abstract: A method of using solar energy in a chemical synthesis process comprising steam reforming hydrocarbons or gasifying carbonaceous fuel, converting the product of the steam reforming of hydrocarbons or the gasifying of carbonaceous fuels to an ammonia synthesis gas, converting the ammonia synthesis gas to ammonia, supplying the heat required for the steam reforming of hydrocarbons or the gasifying of carbonaceous fuels by a heat transfer fluid, heating the heat transfer fluid in a solar receiver when solar energy is available, heating the heat transfer fluid by combusting a portion of the ammonia when sufficient solar energy is not available to supply the necessary heat to the heat transfer fluid.
    Type: Grant
    Filed: December 24, 1984
    Date of Patent: May 26, 1987
    Assignee: Foster Wheeler Energy Corporation
    Inventor: James P. Van Hook
  • Patent number: 4613492
    Abstract: A process for the production of ammonia wherein excess nitrogen is fed to the secondary reformer and a cryogenic unit is employed to obtain a nitrogen-rich stream which is recycled at least in part to the cryogenic unit.
    Type: Grant
    Filed: October 1, 1985
    Date of Patent: September 23, 1986
    Assignee: Humphreys & Glasgow, Ltd.
    Inventor: Christopher L. Winter
  • Patent number: 4592860
    Abstract: A fluid hydrocarbon feed stream is converted with excess air to a mixture of hydrogen and carbon monoxide, also containing the nitrogen content of said air. Following high temperature shift conversion to convert said carbon monoxide to hydrogen and carbon dioxide, the gas mixture is passed to a pressure saving adsorption system used to produce an impure ammonia synthesis gas mixture of hydrogen and nitrogen, with excess nitrogen being separated and removed therefrom with the impurities discharged from the system at high operating pressures, the purge gas effluent from the pressure swing adsorption system can be passed to an expansion turbine for desirable power energy. The ammonia synthesis gas, which can be passed to a methanator for final purification, is thus produced without the need for employing an air separation plant or a nitrogen plant.
    Type: Grant
    Filed: February 7, 1984
    Date of Patent: June 3, 1986
    Assignee: Union Carbide Corporation
    Inventor: Andrija Fuderer
  • Patent number: 4592903
    Abstract: In a process for producing ammonia which comprises: (a) primary catalytically reforming at super atmospheric pressure in a direct-fired primary reforming zone, a hydrocarbon feedstock with steam to produce a gas containing carbon oxides, hydrogen and methane; (b) secondary catalytically reforming the gas from step (a) by introducing air and bringing the mixture towards equilibrium thereby producing a secondary reformer effluent gas containing nitrogen, carbon oxides, hydrogen and a decreased quantity of methane; (c) converting carbon monoxide catalytically with steam to carbon dioxide and hydrogen; (d) removing carbon oxides to give an ammonia synthesis gas comprising nitrogen and hydrogen and compressing the gas to ammonia synthesis pressure; (e) reacting the synthesis gas in an ammonia synthesis zone to produce ammonia and recovering ammonia from the reacted gas to produce an ammonia-depleted gas stream; (f) recycling at least a portion of the ammonia-depleted gas stream to the ammonia synthesis zone; and (
    Type: Grant
    Filed: February 13, 1985
    Date of Patent: June 3, 1986
    Assignee: Exxon Research & Engineering Co.
    Inventors: Robert M. Osman, Robert G. Byington
  • Patent number: 4578214
    Abstract: A process for producing ammonia synthesis gas in which a pressure swing adsorption unit is utilized to replace former CO.sub.2 removal, methanation, drying and purification steps. To increase the efficiency of the process, a hydrogen fuel cell is utilized to generate electricity and a high purity nitrogen purge stream for a pressure swing absorption unit. Accordingly, after reforming and high temperature catalytic shift conversion, the feed stream is divided into a first stream to feed the fuel cell and a second stream which is directly introduced to the pressure swing adsorption unit. After the first stream is reacted in the fuel cell, a nitrogen rich stream is passed to a de-oxygenation unit and then utilized as the pressure swing adsorption purge stream.
    Type: Grant
    Filed: February 6, 1984
    Date of Patent: March 25, 1986
    Assignee: C F Braun & Co.
    Inventor: Robert R. J. Jungerhans
  • Patent number: 4553981
    Abstract: Effluent gas streams for steam reforming, partial oxidation or coal gasification operations are advantageously treated in shift conversion, scrubbing and pressure swing adsorption units for recovery of a purified, hydrogen-containing product gas stream. By recycling a portion of the waste gas removed from the pressure swing adsorption system to the shift conversion unit and/or to the effluent gas generation operation, enhanced product recovery is achieved without the necessity for employing low temperature shift or for achieving essentially complete removal of the carbon dioxide content of the gas being treated prior to its passage to said pressure swing adsorption system.
    Type: Grant
    Filed: February 7, 1984
    Date of Patent: November 19, 1985
    Assignee: Union Carbide Corporation
    Inventor: Andrija Fuderer
  • Patent number: 4479925
    Abstract: Ammonia synthesis gas having excess nitrogen is produced in a reactor-exchanger primary reformer followed by an autothermal secondary reformer wherein process air for the latter is preheated by heat exchange with gas turbine exhaust and the primary reformer is heated by synthesis gas from the secondary reformer.
    Type: Grant
    Filed: September 13, 1982
    Date of Patent: October 30, 1984
    Assignee: The M. W. Kellogg Company
    Inventors: Philip J. Shires, John R. Cassata, Bernard G. Mandelik, Christiaan P. van Dijk
  • Patent number: 4436696
    Abstract: A process for high temperature sintering of ferrous powder metallurgy compacts having a substantially uniform carbon distribution which comprises:(a) heating the ferrous powder metallurgy compact in the heating zone of a sintering furnace to a temperature of about 2,300.degree. to 2,550.degree. F. (1,260.degree. to 1,399.degree. C.),(b) introducing to the heating zone an atmosphere comprising about 2 to less than 10 volume percent hydrogen, about 0.5 to 2.0 volume percent carbon monoxide, about 0.5 to 1.0 volume percent methane and the balance nitrogen, and(c) removing the sintered product from the furnace.
    Type: Grant
    Filed: May 20, 1981
    Date of Patent: March 13, 1984
    Assignee: Air Products and Chemicals, Inc.
    Inventors: Daniel M. Buck, Alan T. Sibley, John J. Kaiser
  • Patent number: 4409196
    Abstract: A process for producing a gas stream for ammonia synthesis in which a gas stream containing hydrogen and nitrogen in excess of ammonia synthesis requirements, e.g. obtained by partial oxidation of natural gas, coal or oil, is treated to remove other component gases and thereafter subjected to a separation stage, e.g. in a cryogenic separator, to separate a hydrogen-nitrogen stream having the desired hydrogen:nitrogen ratio which is injected into the reactor for ammonia synthesis, and a waste nitrogen stream which may be utilized in power generation or washing stages.
    Type: Grant
    Filed: February 5, 1981
    Date of Patent: October 11, 1983
    Assignee: Foster Wheeler Energy Corporation
    Inventors: Geoffrey F. Skinner, Wieslaw M. Kowal
  • Patent number: 4376758
    Abstract: A process for synthesizing ammonia is disclosed comprising the steps of generating the synthesis gas from hydrocarbons by the primary reforming of said hydrocarbon with steam and by the secondary reforming of the resulting gaseous mixture with oxygen; subjecting a portion of the starting hydrocarbon mixed with the steam to a tertiary reforming in which the necessary heat is provided by the gaseous reaction mixture leaving the secondary reforming; causing the ammonia synthesis to occur at low pressure with drying of the gas sent to the synthesis reactor by employing a molecular sieve; causing the ammonia contained in the reacted gas to be absorbed by water; and subjecting the ammonia solution so obtained to a distillation which may be a conventional distillation step or one effected by means of two distillation columns operating at different pressures.
    Type: Grant
    Filed: January 6, 1981
    Date of Patent: March 15, 1983
    Assignee: Montedison S.p.A.
    Inventors: Giorgio Pagani, Dino Bosco, Lorenzo Brambilla
  • Patent number: 4376717
    Abstract: An improved process is disclosed for preparing gases containing hydrogen and nitrogen and which is especially suitable for the synthesis of ammonia. Using natural gas or virgin naphtha as the starting materials, the reforming reaction with steam takes place in two serially arranged stages, the first of which occurs at an inlet temperature of from 400.degree. C. to 650.degree. C. and an exit temperature of from 650.degree. C. to 750.degree. C., a conversion of from 20% to 50% being effected, the second stage working at an exit temperature of from 750.degree. C. to 850.degree. C. and the conversion being increased up to 70%. Air reforming is carried out under conditions at which the exit temperature of the gas is between 920.degree. C. and 1050.degree. C. and the sensible heat of the effluent gases from the air reforming at such temperature condition is employed to activate the second steam reforming stage. Tube bundle heat-exchangers, the tubes of which are filled with an appropriate catalyst, are used.
    Type: Grant
    Filed: December 11, 1980
    Date of Patent: March 15, 1983
    Assignee: Snamprogetti, S.p.A.
    Inventors: Vincenzo Lagana', Francesco Saviano, Piero Bisi
  • Patent number: 4296085
    Abstract: A process to produce ammonia from a hydrocarbon feedstock, involving basically the following steps:Dividing the feedstock into two fractions,Subjecting the first fraction to a primary steam reforming reaction, at high pressure and moderate temperature,Combining the effluent from the primary reforming with the second fraction of the feedstock, and subjecting the mixture thereof to a secondary adiabatic reforming reaction with an amount of air in excess to that needed for ammonia synthesis,Subjecting the synthesis gas produced to a CO shift conversion reaction, and then to CO.sub.
    Type: Grant
    Filed: March 19, 1980
    Date of Patent: October 20, 1981
    Inventor: David L. Banquy
  • Patent number: 4261856
    Abstract: Ammonia synthesis gas is prepared by contacting coal with air and steam in a fluidized bed. Heat for the reaction is provided by downward flowing hot char through the fluidized bed. The char is heated externally of the fluidized bed by combustion of fuel and/or a portion of the char. Control of the ratio of steam and air to the coal provides a gasification product of approximately 3 moles carbon monoxide plus hydrogen per mole of nitrogen.
    Type: Grant
    Filed: August 24, 1979
    Date of Patent: April 14, 1981
    Assignee: Monsanto Company
    Inventor: Talmage D. McMinn, Jr.
  • Patent number: 4253986
    Abstract: Ammonia synthesis gas is prepared by contacting coal with air and steam in a fluidized bed. Heat for the reaction is provided by downward flowing hot thermal refractory material through the fluidized bed. The refractory material is heated externally of the fluidized bed by combustion of fuel. Control of the ratio of steam and air to the coal provides a gasification product of approximately 3 moles carbon monoxide plus hydrogen per mole of nitrogen.
    Type: Grant
    Filed: August 24, 1979
    Date of Patent: March 3, 1981
    Assignee: Monsanto Company
    Inventor: Talmage D. McMinn, Jr.
  • Patent number: 4193776
    Abstract: The object of the invention is a method for the purification of the process condensate from synthesis gases or hydrogen plant.The process condensate is purified from contaminations dissolved in it by stripping it with process steam before it is used in the chemical process of the raw material conversion into hydrogen or synthesis gas at the pressure that is equal or higher than the pressure of this conversion process. The total steam containing volatile products of the process condensate degassing is recycled to the gas generation process and the process condensate is eventual transported to the water treatment station before using it as boiler feed water.
    Type: Grant
    Filed: February 28, 1979
    Date of Patent: March 18, 1980
    Assignee: Instytut Nawozow Sztucznych
    Inventors: Tadeusz Wasala, Marek Dmoch, Henryk Jozwiak
  • Patent number: 4171343
    Abstract: An improved startup procedure for the synthesis of ammonia in which preheated feed streams of desulfurized hydrocarbon gas, steam and air are routed through an ammonia train having a primary and secondary reformer, a high and low temperature CO shifter, a CO.sub.2 removal system, a methanator and a synthesis converter system. The improvement comprises simultaneously heating the primary and secondary reformers with steam while heating the low temperature CO shifter with preheated desulfurized hydrocarbon gas. After these systems have been heated sufficiently, feed streams of preheated desulfurized hydrocarbon gas and steam are injected into the reformers along with the addition of air into the secondary reformer to produce reformed gas which is then used to preheat the high temperature CO shifter. Simultaneously, exhaust gas from the low temperature CO shifter along with a portion of the gas converted in the high temperature CO shifter is used to preheat the CO.sub.2 removal system.
    Type: Grant
    Filed: August 7, 1978
    Date of Patent: October 16, 1979
    Assignee: Standard Oil Company (Indiana)
    Inventors: Paul J. Faust, Otto C. Pless, Jr.
  • Patent number: 4057510
    Abstract: A nitrogen-rich inert gas mixture is produced by the partial oxidation of a hydrocarbonaceous feed containing substantially no metals nor noncombustible materials with air in a free-flow, unpacked, refractory-lined gas generator at a temperature in the range of about 1300.degree. to 3000.degree. F. and a pressure in the range of about 1 to 250 atmospheres. The product gas will comprise a mixture of nitrogen, argon and carbon dioxide and may contain small amounts of hydrogen and carbon monoxide, depending on the O/C atomic ratio selected. The atomic ratio of free oxygen in said air to carbon in said hydrocarbonaceous fuel is in the range of about 1.7 to stoichiometric, or slightly less than stoichiometric. By operating at this level of O/C atomic ratio, the H.sub.2 + CO content of the product gas may be minimized or deleted, substantially all of the particulate carbon may be oxidized, substantially no NO.sub.x is produced, and the product gas contains substantially no free oxygen.
    Type: Grant
    Filed: September 29, 1975
    Date of Patent: November 8, 1977
    Assignee: Texaco Inc.
    Inventors: William B. Crouch, Carolina P. Fabiero, Allen M. Robin
  • Patent number: 4051231
    Abstract: A gas mixer and reactor is provided which includes an elongated gas flow chamber with a nozzle arrangement at its inlet end for passing a first gaseous reactant into the interior of the chamber, toward the outlet of the chamber from points uniformly about the inner periphery of the chamber, and an annular nozzle arrangement near the outlet of the gas flow chamber for directing another gaseous reactant, or reactants, through the outlet of the gas flow chamber and into a thermal reaction chamber which communicates with the outlet of the gas flow chamber. In this manner controlled amounts of gaseous reactants may be thoroughly admixed and reacted to produce an atmosphere of desired composition. Atmospheres for kilns having controlled amounts of free hydrogen, carbon monoxide, oxygen, or carbon for example, are produced by burning controlled ratios of fuel, air and in some cases an inert gas, mixed by the reactor.
    Type: Grant
    Filed: March 31, 1976
    Date of Patent: September 27, 1977
    Assignee: Ford, Bacon & Davis Texas, Inc.
    Inventors: Desmond H. Bond, George W. Taggart, Kurt S. Jaeger
  • Patent number: 4008163
    Abstract: Methods of preparing fluid mixtures in a chamber under close temperature and pressure controls in which liquid water is introduced into the chamber along with gases selected from the group consisting of oxidizing and reducing gases for providing in the liquid water a mixture of carbon dioxide, hydrogen and carbon monoxide, and of oxidizing and carburizing gases for providing in the liquid water a mixture of carbon dioxide, methane, hydrogen and carbon monoxide under reaction conditions. The liquid water in the chamber is maintained under close temperature control of from about 32.degree. F. to about 160.degree. F. and gases in the chamber are maintained under control pressures from ambient atmospheric up to 218.5 atmospheres so that a saturated fluid mixture is generated having predetermined properties as determined by the controlled temperatures and pressures.
    Type: Grant
    Filed: March 13, 1972
    Date of Patent: February 15, 1977
    Inventor: Glenn R. Ingels
  • Patent number: 3945942
    Abstract: A partial oxidation burner and process for the manufacture of synthesis gas, reducing gas and other gas mixtures substantially comprising H.sub.2 and CO. A hydrocarbon, oxygen-rich gas and, optionally, H.sub.2 O or some other temperature moderator are introduced into the reaction zone of a synthesis gas generator in which, by partial oxidation at an autogenous temperature in the range of about 1700.degree. to 3500.degree.F. and a pressure in the range of about 1 to 250 atmospheres, said synthesis, fuel, or reducing gas is produced. For example, a hydrocarbon is introduced into the reaction zone by way of the inner assembly of a novel multitube burner, and a mixture of oxygen-rich gas and steam is passed through a coaxial conduit disposed about the outside of said inner assembly. Said inner assembly comprises a central conduit of circular cross-section, having a plurality of parallel open-ended tubes extending downstream from the exit end of said central conduit and in communication therewith.
    Type: Grant
    Filed: October 30, 1972
    Date of Patent: March 23, 1976
    Assignee: Texaco Development Corporation
    Inventors: Charles P. Marion, Blake Reynolds