CA1327271C - Autothermal production of synthesis gas - Google Patents
Autothermal production of synthesis gasInfo
- Publication number
- CA1327271C CA1327271C CA000473044A CA473044A CA1327271C CA 1327271 C CA1327271 C CA 1327271C CA 000473044 A CA000473044 A CA 000473044A CA 473044 A CA473044 A CA 473044A CA 1327271 C CA1327271 C CA 1327271C
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- reaction
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- reforming
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
- B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
- B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/384—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts the catalyst being continuously externally heated
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- C01—INORGANIC CHEMISTRY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/061—Methanol production
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- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/06—Integration with other chemical processes
- C01B2203/068—Ammonia synthesis
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
- C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/08—Methods of heating or cooling
- C01B2203/0872—Methods of cooling
- C01B2203/0883—Methods of cooling by indirect heat exchange
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- C—CHEMISTRY; METALLURGY
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1005—Arrangement or shape of catalyst
- C01B2203/1011—Packed bed of catalytic structures, e.g. particles, packing elements
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
- C01B2203/1052—Nickel or cobalt catalysts
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
- C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/16—Controlling the process
- C01B2203/1604—Starting up the process
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
Abstract
ABSTRACT
A process and apparatus are disclosed for the autothermal production of a hydrogen-rich synthesis gas. A
mixture of steam and a hydrocarbon feed gas is reacted by passing through a catalyst counter-currently to the flow of the combustion reaction effluent of the process. Reaction tubes are mounted within a heat exchange chamber of the reactor and are adapted to contain catalyst to effect the reaction of the mixture. Oxygen or oxygen-enriched air is introduced into a combustion chamber within the reactor to effect combustion, and the combustion reaction effluent is passed through a second catalyst zone to provide additional reaction and is thereafter passed about the exterior of the reaction tubes to effect heat exchange with the mixture passing through the tubes. The exothermic heat of reaction from combustion thus provides the heat for the endothermic reaction occurring within the reaction tubes and within the second catalyst zone.
A process and apparatus are disclosed for the autothermal production of a hydrogen-rich synthesis gas. A
mixture of steam and a hydrocarbon feed gas is reacted by passing through a catalyst counter-currently to the flow of the combustion reaction effluent of the process. Reaction tubes are mounted within a heat exchange chamber of the reactor and are adapted to contain catalyst to effect the reaction of the mixture. Oxygen or oxygen-enriched air is introduced into a combustion chamber within the reactor to effect combustion, and the combustion reaction effluent is passed through a second catalyst zone to provide additional reaction and is thereafter passed about the exterior of the reaction tubes to effect heat exchange with the mixture passing through the tubes. The exothermic heat of reaction from combustion thus provides the heat for the endothermic reaction occurring within the reaction tubes and within the second catalyst zone.
Description
~ ` ~32~27~ 167/104 S P E C I F I C A T I O N
AUTOTHE~MAL PRODUCTION OF SYNTHESIS GAS
BACKGROUND OF THE INVENTION
The present invention relates to a process and an apparatus for producing a hydrogen-rich e;ynthesis gas, for example, an ammonia synthesis gas.
The process for producing ammonia from a hydrocarbon feed stream, such as natural gas, is, of course, well lcnown.
Thus, a mixture of the hydrocarbon feed gas and water in the form of steam is subjected to an endothermic catalytic reaction to yield carbon monoxide and hydrogen. This reaction is commonly referred to as primary reforming. It is then necessary to introduce nitrogen, which is typically done in the form o air, to produce the requisite ammonia synthesis gas by ~ what is referred to as secondary reforming.
; In prior commercial ammonia processes, ~e primary and secondary reforming steps have typically been carried out in separate reactors, and such process is quite suitable and satisfactory in plant situations where it is necessary or desirable to produce steam for other uses within the plant.
Thus, in such processes, the hot reaction ef1uent rom the secondary xeforming operation is used to generate and/or to superheat steam, either for use otherwise within the ammonia process or for export.
In situations where the production of steam is not .
necessary, it is accordingly advantageous to utilize the heat available from the secondary reforming step for other purposes within the synthesis ga~s productlon process. One such use of the available heat rom secondary reforming is to provide ' " ~ '"'', ~ ' , . . ' ' ' 1327271 l67/ao4 the heat necessary for primary reforming. The provision of a process and apparatus to achieve such use at a high level of efficiency is accordingly a principal objective of the present invention.
The production of ammonia, as well as other products such as methanclwhich are derived from hydrocarbons, has evolved in the last several years into a sophisticated state-of-the-art technology, in which cost effective improve-ments are essential but are exceptionally difficult to accom-plish. In view of this, it is quite desirable to be able to achieve both primary reforming and secondary reforming in a single reactor, so that the overall cost of the production process can be reduced by elimination of expensive reactors and associated essential equipment.
~ There have been prior efforts to provide satisfac-torily such reactors, but certain significant shortcomings have been encountered. For example, U.S. Patent 3,751,228 describes a reactor in which the hot reformed gaseous product is removed from the botbDm of the reactor, rather than utilized to provide heat for the reforming reaction. Instead, hot gas is introduced from outside the reactor to provide the necessary heat for the reforming step. A similar reactor is described in U.S. Patent 4,127,289.
U.S. Patent 4,071,330 describes a reactor which is positioned within a fired furnace and utilizes heat transfer from the furnace across the shell of the reactor, to provide the requisite heat for the endothermic reforming reaction.
The shell is formed of a heat conducting material such as high nickel-chrome ste~l.
In V.~. Patent 3,549,335, an autothermal reactor is illustrated and described, which includes an outer shell ~7C2~
with an inner shell spaced therefrom to provide an annular passageway through which the hydrocarbon and steam mixture passes, through openings in the inner shell at the lower section of the reactor and through the primary reforming catalyst bed positioned outside of the tubes. The gas is thereafter brought into contact with the combustion reaction product and ultimately removed from the reactor. Such reaction process, utilizing atmospheric air for the combustion step, does not provide efficient utilization of the exothermic heat of reaction, as is highly desirable in today's sophisticated and competitive ~ `
state of the art.
SUMMARY OF THE INVENTION
As indicated by the foregoing, the present invention seeks to provide an improved process and apparatus for autother-mal production of a hydrogen-rich synthesis gas such as an ammonia synthesis gas in which efficient utilization is made of the exothermic heat of reaction within the synthesis gas production process.
According to the present invention there is provided in an autothermal process for producing a synthesis gas from a hydrocarbon feed stream, the improvement comprising reacting a mixture of steam and hydrocarbon feed gas by passing such mixture through catalyst in countercurrent flow to a combustion reaction effluent, out of contact with said catalyst, from a combustion reaction produced by introducing oxygen or oxygen-enriched air to an effluent from said reacting of said mixture of steam and hydrocarbon feed gas, to cool the combustion reaction effluent and to provide heat for reaction of said steam-fed gas mi~ture.
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6072~-1571 The invention also provides in an autothermal process for producing a synthesis gas from a hydrocarbon feed stream, the improvement comprising, performing primary and secondary reforming in a single vessel wherein said primary reforming is performed by reacting a mixture of steam and hydrocarbon feed gas by passing said mixture through a first catalyst in countercurrent flow to a combustion reaction effluent to cool the combustion reaction ef~luent and to provide heat for the primary reforming reaction of said mixture, and wherein sald secondary reforming is performed by passing through a second catalyst the. combustion reaction effluent wherein the combustion effluent is produced by introducing oxygen and oxygen-enriched air to effluent of said primary reforming reaction.
Preferably the mixture is passed through tubes containing catalyst and thereafter is brought into contact with oxygen or oxygen-enriched air to effect combustion, said combustion reaction effluent being then passed through a second catalyst zane to provide additional reaction, said gaseous reaction product then being passed about the exterior of said tubes, whereby the exothermic heat of ~ombustion provides the heat for the endothermic reaction occurring within the tubes.
It is particularly preferred that the synthesis gas is for the production of ammonia and the mixture of steam and feed gas undergoes reforming when passing through the tubes and further reforming occurs as said combustion reaction effluent passes through the second catalyst zone.
3a ~ 327~7~ -The invention further provides an autothermal process for the production of a syn~hesis gas for the.use in production of at least one p.roduat selected from the group ammonia, methanol, hydrogen, oxo-alcohol and hydrocarbons by Fischer-Tropsch, aomprising subjecting a mixture of steam and hydrocarbon feed gas in a single vessel to primary reforminy by passing said mixture through one or more reaction tubes containing fixed bed catalyst counter-currently ~o the flow of a secondary re~orming reac~ion effluent of said process to produce a partially reformed gas, thereafter bringing said partially reformed gas into contact with oxygen or oxygen~
enrlched air to effect partial combustion to produce a partial combustion reaction effluent, passing the partial combustion react~ion effluent through a second ca~alyst zone to provide additlonal reforming and produce said synthesis gas, and subsequently passing said synthesis gas about the outside of said reac~ion tubes, whereby the exothermic heat of reaction from said partial combustion provides the heat for the endothermic reaction of said steam feed gas mixture and said synthesis gas is aooled by heat exchange therewith.
The invention additionally provides an autothermal process for the production of synthesis gas comprising the steps of:
supplying a mixture of combustible hydrocarbon feed gas and steam to a reaation vessel;
subjecting the mixture to endothermic primary .
reforming in a first region of the vessel by heating the mixture and passing the mixture through a first catalyst to produce a partially reformed gas;
supplying the partially reformed gas and oxygen-enriched alr ln a seaond region of the vessel ~o eflect partlal 3b .: ~
combustion of the partially reformed gas from the first region to produce a partial combustion reaction effluent containing a portion of the combustible feed gas in the second region;
subjecting the partial combustion reaction effluent to secondary reforming in a third region of the vessel by passing the partial combustion reaction effluent from the se~ond region through the third region, in ~he presence of a catalyst in the third region;
co~ducting the secondary reforming reaction effluent mixture to the first region of the vessel;
wherein exothermic heat of reaction from the partial combustlon provides sufficlent heat for the endothermic prlmary reforming.
~ The invention provides an autothermal process for the production of a synthesis gas for the use in production of at least one product selected from the group ammonia, methanol, hydrogen, oxo-alcohol and hydrocarbons by Fischer-Tropsch, comprising subjecting a mix~ure of steam and hydrocarbon feed gas in a single vessel to primary reforming by passing said mixture through one or more reaction tubes containing fixed bed catalyst counter currently to the flow of a secondary re~orming reaction effluent of said process to produce a partially reformed gas, thereafter bringing said partially reformed gas into contact with oxygen or oxygen-enriched air to effect combustion to produce a combustion reaction effluent, passing the combustion reaction effluent through a second catalyst zone to provide additional reforming and to produce said synthesis gas, and subsequently passing said synthesis yas about the outside of said reaction tuhes, whereby the exothexmic heat of reaction from said combustion provides heat for the endothermic reaction of said steam feed gas mixture and said synthesis ga,s 3c ~, .,. ~, 7 :~
6072~-1571 is cooled by heat exchange therewith.
The invention also provides an autothermal process for the production of synthesis gas comprising the steps of:
supplying a mixture of combustible hydrocarbon feed gas and steam to a reaction vessel;
subjecting the mixture to endothermic primary reforming in a first region of the vessel by heating the mixture and passing the mixture through a first catalyst to produce a reformed gas;
supplying the reformed gas and oxygen-enriched air to a second region of the vessel to effect combustion of the reformed gas from the first reglon to produce a combust:ion reaction effluent containing a portion of the combustible feed gas i'n the second reglon;
subjecting the combustion reaction effluent to secondary reforming in a third region of the veseel by passing :~
the combustion reaction effluent from the second region through the third region, in the presence of a catalys~ in the third region;
conducting the secondary reforming reaction effluent mixture to the first region of the vessel;
wherein exothermic heat of reaction from the combustion provides sufficient heat for the endothermic primary reformlng, According to another aspect of the present invention there is also provided an autothermal reactor for the production of a synthesis gas by primary xeforming and secondary reforming comprising a heat exchange chamber having a first portion and a second portion, a first inlet connected to said heat exchange chamber for the introduction of steam and feed gas to said heat exchange chamber, a plurality of reaction ;~ Bd~ 3a ., ,~, .
60724-~571 ~:.
tubes mounted within the first portion of said heat exchange chamber at a location spaced longitudinally from said first inlet in communication with said first inlet and in non-concentric relationship therewith so as to provide a flow path for the steam and feed gas from said first inle~ through said plurality of reaction tubes each of said plurality of reaction tubes containing catalyst therein to effect a first reforming reaction and being located in relation to said first inlet such that the flow of steam and feed gas introduced through said first inlet with be distributed amongst said plurality of reaction tubes, a com~ustion raactlon chamber, means communicating with said reaction tubes to pass the thus reacted gases from said tubes to said combustion reaction chamber, said means extending longitudinally from said reaction tubes and :~
extending generally into said combustion reaction chamber, a second inlet connected to said combustion reaction chamber so as to lntroduce oxy~en or oxygen-enriched air into sald combustion reaction chamber, said second inlet being in non- :
concentric relationship with said combustion reaction chamber, ~-means defining a second catalyst zone, located in the lower portion of sald heat exchange chamber, a partition separating said heat exchange chamber from said combustion reactio chamber, said partition including means to permit the passage of combustion reaction effluent therethrough to said second catalyst zone, whereln said second catalyst zone comprises a catalyst bed supported on said partition to effect a second reforming reaction, wherein said means extending longitudinally from said reaction tubes extends through said secorld catalys~
zone, whereby the combustion reaction effluent can pass through said partition and said second catalyst zone to undergo 3e 6072~-1571 addikional reforming reaction and to produce synthesis gas, an outlet for removal of said synthesis gas posi.tioned in said reactor approxlmately adjacent saicl first inlet and in non-concentric relationship with said first inlet and with said reaction tubes, so that the synthesis gas passes abou~ the outside of said reaction tubes prior to removal through said outlet which provides heat for said first reforming reaction within said reaction tubes and cools the synthesis gas.
This aspect of the invention also provides an autothermal reactor for the production of a synthesis gas in which both primary reforming and secondary reforming are achieved at a high level of efficiency, comprising a heat exchange chamber haviny a first portion and a second portion, a firs~ inlet connected to said heat exchange chamber for the introduction of steam and feed gas to said heat exchange chamber, a plurality of reaction tubes mounted within the first portion of said heat exchanger chamber at a location spaced longitudinally from said first inlet in communication with said first inlet and in non-concantric relationship therewith so as to provide a flow path for the steam and feed ga~ from said first inlet through said plurality of reaction tubes, each of said plurality of reaction tubes containing catalyst therein to effect a first reforming reaction and being located in relation to said first inlet such that the flow of steam and feed gas introduced through said first inlet will be distributed amongst said plurality of reaction tubes, a combustion reaction chamber, means communicating with said reaction tubes to pass the thus reac~ed gases from said tubes to said combustion reaction chamber, said means extending longitudinally from said reaction tubes and extenfling generally into said combustion reaction chamher, a second inlet connected to sald combustion 3f 11 3~727~
reaction chamber so as to introduce oxygen or oxygen-enrlched air into said combustion reaction chamber, said second inlet being in non-concentric relationship wlth said combustion reaction chamber, means defining a second catalyst zone located in the second portion of said heat exchange chamber, a partition separating said heat exchange chamber from said combustion reaction chamber, said partition including means to permit the passage of combustion reaction effluent therethrough to said second catalyst zone, wherein said second catalyst zone comprises a catalyst bed suppoxted on sald partition to effect a second reforming reaction.
whereby the combustion reaction effluen~ can pass ~hrough said partition and said second catalyst zone to ~undergo additional reforming reaction and to produce synthesis gas, an outlet for removal of synthesis as positioned ln said reactor approximately adjacent said first inlet and in non-concentric relationship with said first inlet and with said reaction tubes so that the synthesis gas passes about the outside of said reaction tubes prior to removal through said outlet which provides heat for said first reforming reaction within said reaction tubes and cools the synthesis gas.
3 g ~7~
6572~-157 reaction chamber so as to introduce oxygen or oxygen-enriched alr into said combustion reaction chamber, said second inlet being in non-concentric relationship with said combustion reaction chamber, means defining a second catalyst zone located in the second portion of said heat exchange cha~ber, a partition separating said heat exchange cha~ber from said combustion reaction chamber, said partitlon including means to permit the passage of combustion reaction effluent therethrough to said second catalyst zone, wherein said second catalyst zone comprises a catalyst bed supported on said partition to effect a second reforming reaction, whereby the combustion reaction effluent can pass through said partition and said second catalyst zone to undergo additional reforming reaction and to produce synthesis gas, an outlet for removal of synthesis gas positioned in said reactor approximately adjacent said first inlet and in non-concentric relationship with saicl first inlet and with said reaction tubes so that the synthesis gas passes about the outside of said reaction tubes prior to removal through said outlet which 2~ provides heat for said first reforming reaction within said reaction tubes and cools the synthesis gas.
The invention further provides an autothermal reactor for production of a synthesis gas hy primary reforming and secondary reforming, said autothermal reactor comprislng a heat-exchange chamber having (a) a first inlet for introduction of steam and feed gas to said heat-exchange chamber; (b) a ~irst reforming zone having catalyst-containing reaction tubes proximal and connected to said first inlet; (c) means lor connecting said first reforming zone with; (d) a combustlon chamber having second lnlet means for introducing an oxygen containing gas lnto said combustion chamber; ~e) a ~econd 3cJ
f j~
,~ . ,, ~32727~ 60724-1571 re~orming zone containing a secondary catalyst and connected to said combustlon chamber and provided with exit means whereby the products of said second reforming zone are carried into heat-exchange relationship with said first reforming zone; and (f) outlet means for removing reaction products from the reactor. ~-In a preferred embodiment the combustion chamber and the second reformlng zone are separated by a partition porous to reaction products of the combustion chamber. The combustlon chamber may form a catalyst-free space upstream of the second reformlng zone.
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BRIE~ DESCR'IPTION_OF THE'DRA~ING
The single figure of drawing is a section view of a ' ~; . .
~:' preferred embodiment of the autothermal reactor of this invention.
t .
Description of the Preferred Embodiments ~; Referring now to the Figure of Drawing, the auto thermal reactor is designated generally by the numeral 1. The :
reactor comprises a heat exchange chamber 2 and a first inlet 3 for introduction of a mixture of steam and hydrocarbon feed - `, gas, such as natural gas. A plurality of reaction tubes 4 (only two are illustrated for purposes of clarity) are mounted ~f within the heat exchange chamber in tube plates 5 and 6. The reaction tubes are designed such that a fixed bed primary catalyst 7 may be positioned therein. The catalyst, of course, may be any suitable reforming catalyst, such as nickel, with the choice of a particular catalyst being well within the skill of the art.
Means shown as a cone shaped collector 10 with a vertically extending tube 11 are positioned in communication ~' with the reaction tubes adjacent tube plate 6 to provide for ,;'! 20 passage of the reacted partially reformed gasses from the reaction tubes to a combustion reaction chamber 12 which is provided at the bottom portion of the reactor 1. While the configuration of collector 10 is illustrated as a cone, it ... .
~, , , ., .
~ s ~ ~ - 4 -" 'I ff.~, ",~.
ri ~ 7 .~,7~ 167/104 will bç readily understood that other configurations may also be used.
A second inlet 13 is provided at the bottom of the reactor to introduce oxygen or oxygen-enriched air to effect combustion within the combustion chamberO A partition 14 is provided adjacent the end of vertically extending tube 11 to separate combustion chamber 12 from,heat exchange chamber 2. Means are provided in the form of a plurallty of openings 15 in partition 14 so that the combustion reaction effluent may pass therethrough and enter a second catalyst zone, designated generally by numeral 16, whereby the effluent may pass through the catalyst zone and undergo additional or secondary reforming to produce the desired synthesis gas.
Again, the reforming catalyst will be any of those typically ~sed, and is a matter well within the ability of those skilled in the art to select. Also, for purposes of clarity of illus-tration, only a relatively small proportion of catalyst is shown, but it will be understood that sufficient catalyst will be provided to achieve an entire zone of catalyst. -As the synthesis gas thus produced passes upwardly from the second catalyst zone, it is directed by means of flow baffles 20 about the exterior of the reaction tubes 4 to pr~ide intlmate contact between the reaction tubes and the hot effluent. This in turn permits eficient utilization of the exothermic heat of combustioD to provide the heat for the endothermic reaction occurring within the reaction tubes 4.
An outlet 21 is also provided approximately adjacent inlet 3, through which the synthesis gas is removed for purification and further processing to produce ammonia (or other product, depending upon the particular reaction process).
':; ' ' ~27~7~
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;~.
The reactor is illustrated as including manways 22, as is conventional, to provide for servicing or other maintenance.
The reactor could also be provided with additional lnlets and outlets, if desired,for flow distribution or for the intro-duction of additional fuel gas or steam to the combustion chamber.
In effecting the conversion process of this invention as applied to ammonia synthesis production, the mixture of steam and natural gas or other hydrocarbon feed gas is brought into reactor 1 through inlet 3 at a temperature of approximately 900 to 1300F. The mixture passes through the openlngs in tube sheet 5 and through reaction tubes 4, exiting from the reaction tubes through the cone-shaped collector 10 and passing through tube,ll and exiting into the lower part of reactor 1 and into the combustion chamber 12 at a temperature of approximately 1100 to 1400F. Oxygen or oxygen enriched air at a temperature , ranging from ambient to approximatelv 1000F is introduced into the combustion chamber through inlet 13 to effect combustion.
The resulting combustion reaction effluent is thus at a temper~
ature of approximately 2500 - 3500F and passes upwardly through openings 15 in partition 14, and through the second catalyst zone 16, whereby the secondary reforming operation occurs.
The synthesis gas mixture thus produced by the secondary reforming is at a temperature of approximately 1500 - 2100F and flows upwardly, as illustrated and described above, into intimate contact with the reaction tubes 4, whereby the desired heat exchange takes place to heat the steam and ~32~271 167/104 hydrocarbon feed gas mixture within tubes 4 and to cool the synthesis gas mixture. Upon exiting outlet 21, the temper-ature of the synthesis gas mixture is approximately 1000 -1300F.
The pressure within the reactor may range from essentially atmospheric up to the synthesis gas conversion pressure, which with today's technology is approximately 1200 psig, depending upon the applicable process condit ons.
A typical pressure for the production of ammonia synthesis gas is about 700 psig.
It will be appreciated from the foregoing descrip-tion that the process and reactor of this invention can be utilized for the production of synthesis gases to produce products other than ammonia, such as methanol, hydrogen, oxo-alcohol, or a hydrocarbon by Fischer-Tropsch. Inasmuch as the central process steps ze the same as those described for ammonia synthesis gas production, the process of the present inven~ion will not against be described with respect to such synthesis gases.
It is significant to the successful operation of the process of this invention that oxygen or oxygen-enriched air be introduced into the combustion chamber, instead of atmospheric air, to effect combustion. By oxygen-enriched air, it is intended to define an air mixture containing an oxygen oontent of approximately 25% or greater by volume.
The oxygen content may vary from such lower limit up to 100%, depending upon the specific reaction process. Thus, with ammonia synthesis gas production, the 2 content may vary from approximately 25% to about 40~ or more, with approximately 35% by volume being optimum for most ammonia ~32~7~ 167/~0~
synthesis gas process conditions. In methanol production, on the other hand, essentially 100~ oxygen will be used.
In any event, those skilled in the art, given the disclosure here, will be able to determine appropriate proportions and whether oxygen or oxygen-enriched air should be used.
The use of oxygen-enriched air instead of atmospheric air provides a number of important advantages. Thus, better control of the nitrogen content of the combustion effluent is achieved due to the ability to control the ratio of oxygen to nitrogen in the mixture. Control of the nitrogen content is extremely important to the process of this invention, because nitrogen tends to carry out heat rom the reactor, thereby decreasing the high level heat that is otherwise available from the combustion reaction for process use.
By controlling the nitrogen content, therefore, the present process avoias unnecessary loss of available hea~ and enables the highest level of available ~eat to be matched with the highest level of use, within the process.
As those skilled in the art will appreciate, steam could also be introduced into the combustion chamber with the oxygen-enriched air. This would enable the introduction of additional steam reactant to compensate for the depletion resulting irom the primary reforming reaction. It would also ~acilitate control of the combustion temperature and enhance operation of upstream oxygen-enriched air preheating equip-ment.
It will also be apparent to those skilled in:the art that the process and apparatus of the present invention have .significant additional advantages over prior processes ~ 3~7271 167/104 and reactoxs. Thus, the capital cost necessary ~or the present reactor is significantly lower than for standard fired reformers. Additionally, the present invention is readily susceptible to use with high pressure reforming, and is vexy suitable for modularization, which is of paramount importance in developing countries or in the utilization of off-shore associated gas. Furthermore, start-up time can be reduced, which results in turn in a savings in gas usage, and the reformer time on stand-by, with inefficient gas use when the synthesis unit is down, can also be reduced. The present invention is also more amenable to automatic start-up and control than multiple pass, multiple burner fired primary reformers currently in use.
It should also be mentioned that although the auto-thermal reactor illustrated and described herein is a vertically disposed reactor with the heat exchange chamber positioned above the secondary reformer catalyst ~d and combustion chamber, other physical arrangement for such reactor will become apparent to those skilled in the art, given a reading of the present disclosure. Similarly, although a preferred form of the invention utili7es reaction tubes with catalyst therein as illustrated and described, it would be within the skill of the art, given the disclosure herein, to modify the flow path within the reactor so that the gaseous product exiting the second or secondary reforming catalyst zone would pass through the tubes and the incoming steam-feed gas mixture would pass through A catalyst bed outside of the tubes. Such embodiments, of course, are intended to be included within the scope of the present invention, as long as the essential features and principles described above are present.
_ g _ ` ~ 3 ~ 7 ~ ~ 167/104 It should also be mentioned that the shell or wall of reactor 1 is insulated internally, as shown at 8, with a material such as reinforcing ceramic to minimize heat transfer across the shell. This results in conservation of heat, the protection of personnel in the vicinity of the reactor, and also in a lower capital cost since a material such as carbon steel can be used for the shell. Additionally, the reaction tubes 4, within tubes plates 5 and 6, are hung or suspended within the reactor from the wall thereof as illustrated in 25. This allows the use of thin wall tubes, which are less expensive and have better heat transfer characteristics than thicker tubes; since thin wall tubes have more strength in tension than compression, they are mounted within the reactor vessel by suspension, as otherwise the tube- cou d deform or ven collapse.
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AUTOTHE~MAL PRODUCTION OF SYNTHESIS GAS
BACKGROUND OF THE INVENTION
The present invention relates to a process and an apparatus for producing a hydrogen-rich e;ynthesis gas, for example, an ammonia synthesis gas.
The process for producing ammonia from a hydrocarbon feed stream, such as natural gas, is, of course, well lcnown.
Thus, a mixture of the hydrocarbon feed gas and water in the form of steam is subjected to an endothermic catalytic reaction to yield carbon monoxide and hydrogen. This reaction is commonly referred to as primary reforming. It is then necessary to introduce nitrogen, which is typically done in the form o air, to produce the requisite ammonia synthesis gas by ~ what is referred to as secondary reforming.
; In prior commercial ammonia processes, ~e primary and secondary reforming steps have typically been carried out in separate reactors, and such process is quite suitable and satisfactory in plant situations where it is necessary or desirable to produce steam for other uses within the plant.
Thus, in such processes, the hot reaction ef1uent rom the secondary xeforming operation is used to generate and/or to superheat steam, either for use otherwise within the ammonia process or for export.
In situations where the production of steam is not .
necessary, it is accordingly advantageous to utilize the heat available from the secondary reforming step for other purposes within the synthesis ga~s productlon process. One such use of the available heat rom secondary reforming is to provide ' " ~ '"'', ~ ' , . . ' ' ' 1327271 l67/ao4 the heat necessary for primary reforming. The provision of a process and apparatus to achieve such use at a high level of efficiency is accordingly a principal objective of the present invention.
The production of ammonia, as well as other products such as methanclwhich are derived from hydrocarbons, has evolved in the last several years into a sophisticated state-of-the-art technology, in which cost effective improve-ments are essential but are exceptionally difficult to accom-plish. In view of this, it is quite desirable to be able to achieve both primary reforming and secondary reforming in a single reactor, so that the overall cost of the production process can be reduced by elimination of expensive reactors and associated essential equipment.
~ There have been prior efforts to provide satisfac-torily such reactors, but certain significant shortcomings have been encountered. For example, U.S. Patent 3,751,228 describes a reactor in which the hot reformed gaseous product is removed from the botbDm of the reactor, rather than utilized to provide heat for the reforming reaction. Instead, hot gas is introduced from outside the reactor to provide the necessary heat for the reforming step. A similar reactor is described in U.S. Patent 4,127,289.
U.S. Patent 4,071,330 describes a reactor which is positioned within a fired furnace and utilizes heat transfer from the furnace across the shell of the reactor, to provide the requisite heat for the endothermic reforming reaction.
The shell is formed of a heat conducting material such as high nickel-chrome ste~l.
In V.~. Patent 3,549,335, an autothermal reactor is illustrated and described, which includes an outer shell ~7C2~
with an inner shell spaced therefrom to provide an annular passageway through which the hydrocarbon and steam mixture passes, through openings in the inner shell at the lower section of the reactor and through the primary reforming catalyst bed positioned outside of the tubes. The gas is thereafter brought into contact with the combustion reaction product and ultimately removed from the reactor. Such reaction process, utilizing atmospheric air for the combustion step, does not provide efficient utilization of the exothermic heat of reaction, as is highly desirable in today's sophisticated and competitive ~ `
state of the art.
SUMMARY OF THE INVENTION
As indicated by the foregoing, the present invention seeks to provide an improved process and apparatus for autother-mal production of a hydrogen-rich synthesis gas such as an ammonia synthesis gas in which efficient utilization is made of the exothermic heat of reaction within the synthesis gas production process.
According to the present invention there is provided in an autothermal process for producing a synthesis gas from a hydrocarbon feed stream, the improvement comprising reacting a mixture of steam and hydrocarbon feed gas by passing such mixture through catalyst in countercurrent flow to a combustion reaction effluent, out of contact with said catalyst, from a combustion reaction produced by introducing oxygen or oxygen-enriched air to an effluent from said reacting of said mixture of steam and hydrocarbon feed gas, to cool the combustion reaction effluent and to provide heat for reaction of said steam-fed gas mi~ture.
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~3~7~7~
6072~-1571 The invention also provides in an autothermal process for producing a synthesis gas from a hydrocarbon feed stream, the improvement comprising, performing primary and secondary reforming in a single vessel wherein said primary reforming is performed by reacting a mixture of steam and hydrocarbon feed gas by passing said mixture through a first catalyst in countercurrent flow to a combustion reaction effluent to cool the combustion reaction ef~luent and to provide heat for the primary reforming reaction of said mixture, and wherein sald secondary reforming is performed by passing through a second catalyst the. combustion reaction effluent wherein the combustion effluent is produced by introducing oxygen and oxygen-enriched air to effluent of said primary reforming reaction.
Preferably the mixture is passed through tubes containing catalyst and thereafter is brought into contact with oxygen or oxygen-enriched air to effect combustion, said combustion reaction effluent being then passed through a second catalyst zane to provide additional reaction, said gaseous reaction product then being passed about the exterior of said tubes, whereby the exothermic heat of ~ombustion provides the heat for the endothermic reaction occurring within the tubes.
It is particularly preferred that the synthesis gas is for the production of ammonia and the mixture of steam and feed gas undergoes reforming when passing through the tubes and further reforming occurs as said combustion reaction effluent passes through the second catalyst zone.
3a ~ 327~7~ -The invention further provides an autothermal process for the production of a syn~hesis gas for the.use in production of at least one p.roduat selected from the group ammonia, methanol, hydrogen, oxo-alcohol and hydrocarbons by Fischer-Tropsch, aomprising subjecting a mixture of steam and hydrocarbon feed gas in a single vessel to primary reforminy by passing said mixture through one or more reaction tubes containing fixed bed catalyst counter-currently ~o the flow of a secondary re~orming reac~ion effluent of said process to produce a partially reformed gas, thereafter bringing said partially reformed gas into contact with oxygen or oxygen~
enrlched air to effect partial combustion to produce a partial combustion reaction effluent, passing the partial combustion react~ion effluent through a second ca~alyst zone to provide additlonal reforming and produce said synthesis gas, and subsequently passing said synthesis gas about the outside of said reac~ion tubes, whereby the exothermic heat of reaction from said partial combustion provides the heat for the endothermic reaction of said steam feed gas mixture and said synthesis gas is aooled by heat exchange therewith.
The invention additionally provides an autothermal process for the production of synthesis gas comprising the steps of:
supplying a mixture of combustible hydrocarbon feed gas and steam to a reaation vessel;
subjecting the mixture to endothermic primary .
reforming in a first region of the vessel by heating the mixture and passing the mixture through a first catalyst to produce a partially reformed gas;
supplying the partially reformed gas and oxygen-enriched alr ln a seaond region of the vessel ~o eflect partlal 3b .: ~
combustion of the partially reformed gas from the first region to produce a partial combustion reaction effluent containing a portion of the combustible feed gas in the second region;
subjecting the partial combustion reaction effluent to secondary reforming in a third region of the vessel by passing the partial combustion reaction effluent from the se~ond region through the third region, in ~he presence of a catalyst in the third region;
co~ducting the secondary reforming reaction effluent mixture to the first region of the vessel;
wherein exothermic heat of reaction from the partial combustlon provides sufficlent heat for the endothermic prlmary reforming.
~ The invention provides an autothermal process for the production of a synthesis gas for the use in production of at least one product selected from the group ammonia, methanol, hydrogen, oxo-alcohol and hydrocarbons by Fischer-Tropsch, comprising subjecting a mix~ure of steam and hydrocarbon feed gas in a single vessel to primary reforming by passing said mixture through one or more reaction tubes containing fixed bed catalyst counter currently to the flow of a secondary re~orming reaction effluent of said process to produce a partially reformed gas, thereafter bringing said partially reformed gas into contact with oxygen or oxygen-enriched air to effect combustion to produce a combustion reaction effluent, passing the combustion reaction effluent through a second catalyst zone to provide additional reforming and to produce said synthesis gas, and subsequently passing said synthesis yas about the outside of said reaction tuhes, whereby the exothexmic heat of reaction from said combustion provides heat for the endothermic reaction of said steam feed gas mixture and said synthesis ga,s 3c ~, .,. ~, 7 :~
6072~-1571 is cooled by heat exchange therewith.
The invention also provides an autothermal process for the production of synthesis gas comprising the steps of:
supplying a mixture of combustible hydrocarbon feed gas and steam to a reaction vessel;
subjecting the mixture to endothermic primary reforming in a first region of the vessel by heating the mixture and passing the mixture through a first catalyst to produce a reformed gas;
supplying the reformed gas and oxygen-enriched air to a second region of the vessel to effect combustion of the reformed gas from the first reglon to produce a combust:ion reaction effluent containing a portion of the combustible feed gas i'n the second reglon;
subjecting the combustion reaction effluent to secondary reforming in a third region of the veseel by passing :~
the combustion reaction effluent from the second region through the third region, in the presence of a catalys~ in the third region;
conducting the secondary reforming reaction effluent mixture to the first region of the vessel;
wherein exothermic heat of reaction from the combustion provides sufficient heat for the endothermic primary reformlng, According to another aspect of the present invention there is also provided an autothermal reactor for the production of a synthesis gas by primary xeforming and secondary reforming comprising a heat exchange chamber having a first portion and a second portion, a first inlet connected to said heat exchange chamber for the introduction of steam and feed gas to said heat exchange chamber, a plurality of reaction ;~ Bd~ 3a ., ,~, .
60724-~571 ~:.
tubes mounted within the first portion of said heat exchange chamber at a location spaced longitudinally from said first inlet in communication with said first inlet and in non-concentric relationship therewith so as to provide a flow path for the steam and feed gas from said first inle~ through said plurality of reaction tubes each of said plurality of reaction tubes containing catalyst therein to effect a first reforming reaction and being located in relation to said first inlet such that the flow of steam and feed gas introduced through said first inlet with be distributed amongst said plurality of reaction tubes, a com~ustion raactlon chamber, means communicating with said reaction tubes to pass the thus reacted gases from said tubes to said combustion reaction chamber, said means extending longitudinally from said reaction tubes and :~
extending generally into said combustion reaction chamber, a second inlet connected to said combustion reaction chamber so as to lntroduce oxy~en or oxygen-enriched air into sald combustion reaction chamber, said second inlet being in non- :
concentric relationship with said combustion reaction chamber, ~-means defining a second catalyst zone, located in the lower portion of sald heat exchange chamber, a partition separating said heat exchange chamber from said combustion reactio chamber, said partition including means to permit the passage of combustion reaction effluent therethrough to said second catalyst zone, whereln said second catalyst zone comprises a catalyst bed supported on said partition to effect a second reforming reaction, wherein said means extending longitudinally from said reaction tubes extends through said secorld catalys~
zone, whereby the combustion reaction effluent can pass through said partition and said second catalyst zone to undergo 3e 6072~-1571 addikional reforming reaction and to produce synthesis gas, an outlet for removal of said synthesis gas posi.tioned in said reactor approxlmately adjacent saicl first inlet and in non-concentric relationship with said first inlet and with said reaction tubes, so that the synthesis gas passes abou~ the outside of said reaction tubes prior to removal through said outlet which provides heat for said first reforming reaction within said reaction tubes and cools the synthesis gas.
This aspect of the invention also provides an autothermal reactor for the production of a synthesis gas in which both primary reforming and secondary reforming are achieved at a high level of efficiency, comprising a heat exchange chamber haviny a first portion and a second portion, a firs~ inlet connected to said heat exchange chamber for the introduction of steam and feed gas to said heat exchange chamber, a plurality of reaction tubes mounted within the first portion of said heat exchanger chamber at a location spaced longitudinally from said first inlet in communication with said first inlet and in non-concantric relationship therewith so as to provide a flow path for the steam and feed ga~ from said first inlet through said plurality of reaction tubes, each of said plurality of reaction tubes containing catalyst therein to effect a first reforming reaction and being located in relation to said first inlet such that the flow of steam and feed gas introduced through said first inlet will be distributed amongst said plurality of reaction tubes, a combustion reaction chamber, means communicating with said reaction tubes to pass the thus reac~ed gases from said tubes to said combustion reaction chamber, said means extending longitudinally from said reaction tubes and extenfling generally into said combustion reaction chamher, a second inlet connected to sald combustion 3f 11 3~727~
reaction chamber so as to introduce oxygen or oxygen-enrlched air into said combustion reaction chamber, said second inlet being in non-concentric relationship wlth said combustion reaction chamber, means defining a second catalyst zone located in the second portion of said heat exchange chamber, a partition separating said heat exchange chamber from said combustion reaction chamber, said partition including means to permit the passage of combustion reaction effluent therethrough to said second catalyst zone, wherein said second catalyst zone comprises a catalyst bed suppoxted on sald partition to effect a second reforming reaction.
whereby the combustion reaction effluen~ can pass ~hrough said partition and said second catalyst zone to ~undergo additional reforming reaction and to produce synthesis gas, an outlet for removal of synthesis as positioned ln said reactor approximately adjacent said first inlet and in non-concentric relationship with said first inlet and with said reaction tubes so that the synthesis gas passes about the outside of said reaction tubes prior to removal through said outlet which provides heat for said first reforming reaction within said reaction tubes and cools the synthesis gas.
3 g ~7~
6572~-157 reaction chamber so as to introduce oxygen or oxygen-enriched alr into said combustion reaction chamber, said second inlet being in non-concentric relationship with said combustion reaction chamber, means defining a second catalyst zone located in the second portion of said heat exchange cha~ber, a partition separating said heat exchange cha~ber from said combustion reaction chamber, said partitlon including means to permit the passage of combustion reaction effluent therethrough to said second catalyst zone, wherein said second catalyst zone comprises a catalyst bed supported on said partition to effect a second reforming reaction, whereby the combustion reaction effluent can pass through said partition and said second catalyst zone to undergo additional reforming reaction and to produce synthesis gas, an outlet for removal of synthesis gas positioned in said reactor approximately adjacent said first inlet and in non-concentric relationship with saicl first inlet and with said reaction tubes so that the synthesis gas passes about the outside of said reaction tubes prior to removal through said outlet which 2~ provides heat for said first reforming reaction within said reaction tubes and cools the synthesis gas.
The invention further provides an autothermal reactor for production of a synthesis gas hy primary reforming and secondary reforming, said autothermal reactor comprislng a heat-exchange chamber having (a) a first inlet for introduction of steam and feed gas to said heat-exchange chamber; (b) a ~irst reforming zone having catalyst-containing reaction tubes proximal and connected to said first inlet; (c) means lor connecting said first reforming zone with; (d) a combustlon chamber having second lnlet means for introducing an oxygen containing gas lnto said combustion chamber; ~e) a ~econd 3cJ
f j~
,~ . ,, ~32727~ 60724-1571 re~orming zone containing a secondary catalyst and connected to said combustlon chamber and provided with exit means whereby the products of said second reforming zone are carried into heat-exchange relationship with said first reforming zone; and (f) outlet means for removing reaction products from the reactor. ~-In a preferred embodiment the combustion chamber and the second reformlng zone are separated by a partition porous to reaction products of the combustion chamber. The combustlon chamber may form a catalyst-free space upstream of the second reformlng zone.
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BRIE~ DESCR'IPTION_OF THE'DRA~ING
The single figure of drawing is a section view of a ' ~; . .
~:' preferred embodiment of the autothermal reactor of this invention.
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Description of the Preferred Embodiments ~; Referring now to the Figure of Drawing, the auto thermal reactor is designated generally by the numeral 1. The :
reactor comprises a heat exchange chamber 2 and a first inlet 3 for introduction of a mixture of steam and hydrocarbon feed - `, gas, such as natural gas. A plurality of reaction tubes 4 (only two are illustrated for purposes of clarity) are mounted ~f within the heat exchange chamber in tube plates 5 and 6. The reaction tubes are designed such that a fixed bed primary catalyst 7 may be positioned therein. The catalyst, of course, may be any suitable reforming catalyst, such as nickel, with the choice of a particular catalyst being well within the skill of the art.
Means shown as a cone shaped collector 10 with a vertically extending tube 11 are positioned in communication ~' with the reaction tubes adjacent tube plate 6 to provide for ,;'! 20 passage of the reacted partially reformed gasses from the reaction tubes to a combustion reaction chamber 12 which is provided at the bottom portion of the reactor 1. While the configuration of collector 10 is illustrated as a cone, it ... .
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~ s ~ ~ - 4 -" 'I ff.~, ",~.
ri ~ 7 .~,7~ 167/104 will bç readily understood that other configurations may also be used.
A second inlet 13 is provided at the bottom of the reactor to introduce oxygen or oxygen-enriched air to effect combustion within the combustion chamberO A partition 14 is provided adjacent the end of vertically extending tube 11 to separate combustion chamber 12 from,heat exchange chamber 2. Means are provided in the form of a plurallty of openings 15 in partition 14 so that the combustion reaction effluent may pass therethrough and enter a second catalyst zone, designated generally by numeral 16, whereby the effluent may pass through the catalyst zone and undergo additional or secondary reforming to produce the desired synthesis gas.
Again, the reforming catalyst will be any of those typically ~sed, and is a matter well within the ability of those skilled in the art to select. Also, for purposes of clarity of illus-tration, only a relatively small proportion of catalyst is shown, but it will be understood that sufficient catalyst will be provided to achieve an entire zone of catalyst. -As the synthesis gas thus produced passes upwardly from the second catalyst zone, it is directed by means of flow baffles 20 about the exterior of the reaction tubes 4 to pr~ide intlmate contact between the reaction tubes and the hot effluent. This in turn permits eficient utilization of the exothermic heat of combustioD to provide the heat for the endothermic reaction occurring within the reaction tubes 4.
An outlet 21 is also provided approximately adjacent inlet 3, through which the synthesis gas is removed for purification and further processing to produce ammonia (or other product, depending upon the particular reaction process).
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The reactor is illustrated as including manways 22, as is conventional, to provide for servicing or other maintenance.
The reactor could also be provided with additional lnlets and outlets, if desired,for flow distribution or for the intro-duction of additional fuel gas or steam to the combustion chamber.
In effecting the conversion process of this invention as applied to ammonia synthesis production, the mixture of steam and natural gas or other hydrocarbon feed gas is brought into reactor 1 through inlet 3 at a temperature of approximately 900 to 1300F. The mixture passes through the openlngs in tube sheet 5 and through reaction tubes 4, exiting from the reaction tubes through the cone-shaped collector 10 and passing through tube,ll and exiting into the lower part of reactor 1 and into the combustion chamber 12 at a temperature of approximately 1100 to 1400F. Oxygen or oxygen enriched air at a temperature , ranging from ambient to approximatelv 1000F is introduced into the combustion chamber through inlet 13 to effect combustion.
The resulting combustion reaction effluent is thus at a temper~
ature of approximately 2500 - 3500F and passes upwardly through openings 15 in partition 14, and through the second catalyst zone 16, whereby the secondary reforming operation occurs.
The synthesis gas mixture thus produced by the secondary reforming is at a temperature of approximately 1500 - 2100F and flows upwardly, as illustrated and described above, into intimate contact with the reaction tubes 4, whereby the desired heat exchange takes place to heat the steam and ~32~271 167/104 hydrocarbon feed gas mixture within tubes 4 and to cool the synthesis gas mixture. Upon exiting outlet 21, the temper-ature of the synthesis gas mixture is approximately 1000 -1300F.
The pressure within the reactor may range from essentially atmospheric up to the synthesis gas conversion pressure, which with today's technology is approximately 1200 psig, depending upon the applicable process condit ons.
A typical pressure for the production of ammonia synthesis gas is about 700 psig.
It will be appreciated from the foregoing descrip-tion that the process and reactor of this invention can be utilized for the production of synthesis gases to produce products other than ammonia, such as methanol, hydrogen, oxo-alcohol, or a hydrocarbon by Fischer-Tropsch. Inasmuch as the central process steps ze the same as those described for ammonia synthesis gas production, the process of the present inven~ion will not against be described with respect to such synthesis gases.
It is significant to the successful operation of the process of this invention that oxygen or oxygen-enriched air be introduced into the combustion chamber, instead of atmospheric air, to effect combustion. By oxygen-enriched air, it is intended to define an air mixture containing an oxygen oontent of approximately 25% or greater by volume.
The oxygen content may vary from such lower limit up to 100%, depending upon the specific reaction process. Thus, with ammonia synthesis gas production, the 2 content may vary from approximately 25% to about 40~ or more, with approximately 35% by volume being optimum for most ammonia ~32~7~ 167/~0~
synthesis gas process conditions. In methanol production, on the other hand, essentially 100~ oxygen will be used.
In any event, those skilled in the art, given the disclosure here, will be able to determine appropriate proportions and whether oxygen or oxygen-enriched air should be used.
The use of oxygen-enriched air instead of atmospheric air provides a number of important advantages. Thus, better control of the nitrogen content of the combustion effluent is achieved due to the ability to control the ratio of oxygen to nitrogen in the mixture. Control of the nitrogen content is extremely important to the process of this invention, because nitrogen tends to carry out heat rom the reactor, thereby decreasing the high level heat that is otherwise available from the combustion reaction for process use.
By controlling the nitrogen content, therefore, the present process avoias unnecessary loss of available hea~ and enables the highest level of available ~eat to be matched with the highest level of use, within the process.
As those skilled in the art will appreciate, steam could also be introduced into the combustion chamber with the oxygen-enriched air. This would enable the introduction of additional steam reactant to compensate for the depletion resulting irom the primary reforming reaction. It would also ~acilitate control of the combustion temperature and enhance operation of upstream oxygen-enriched air preheating equip-ment.
It will also be apparent to those skilled in:the art that the process and apparatus of the present invention have .significant additional advantages over prior processes ~ 3~7271 167/104 and reactoxs. Thus, the capital cost necessary ~or the present reactor is significantly lower than for standard fired reformers. Additionally, the present invention is readily susceptible to use with high pressure reforming, and is vexy suitable for modularization, which is of paramount importance in developing countries or in the utilization of off-shore associated gas. Furthermore, start-up time can be reduced, which results in turn in a savings in gas usage, and the reformer time on stand-by, with inefficient gas use when the synthesis unit is down, can also be reduced. The present invention is also more amenable to automatic start-up and control than multiple pass, multiple burner fired primary reformers currently in use.
It should also be mentioned that although the auto-thermal reactor illustrated and described herein is a vertically disposed reactor with the heat exchange chamber positioned above the secondary reformer catalyst ~d and combustion chamber, other physical arrangement for such reactor will become apparent to those skilled in the art, given a reading of the present disclosure. Similarly, although a preferred form of the invention utili7es reaction tubes with catalyst therein as illustrated and described, it would be within the skill of the art, given the disclosure herein, to modify the flow path within the reactor so that the gaseous product exiting the second or secondary reforming catalyst zone would pass through the tubes and the incoming steam-feed gas mixture would pass through A catalyst bed outside of the tubes. Such embodiments, of course, are intended to be included within the scope of the present invention, as long as the essential features and principles described above are present.
_ g _ ` ~ 3 ~ 7 ~ ~ 167/104 It should also be mentioned that the shell or wall of reactor 1 is insulated internally, as shown at 8, with a material such as reinforcing ceramic to minimize heat transfer across the shell. This results in conservation of heat, the protection of personnel in the vicinity of the reactor, and also in a lower capital cost since a material such as carbon steel can be used for the shell. Additionally, the reaction tubes 4, within tubes plates 5 and 6, are hung or suspended within the reactor from the wall thereof as illustrated in 25. This allows the use of thin wall tubes, which are less expensive and have better heat transfer characteristics than thicker tubes; since thin wall tubes have more strength in tension than compression, they are mounted within the reactor vessel by suspension, as otherwise the tube- cou d deform or ven collapse.
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Claims (8)
1. An autothermal reactor for the production of a synthesis gas by primary reforming and secondary reforming comprising a heat exchange chamber having a first portion and a second portion, a first inlet connected to said heat exchange chamber for the introduction of steam and feed gas to said heat exchange chamber, a plurality of reaction tubes mounted within the first portion of said heat exchange chamber at a location spaced longitudinally from said first inlet in communication with said first inlet and in non-concentric relationship therewith so as to provide a flow path for the steam and feed gas from said first inlet through said plurality of reaction tubes, each of said plurality of reaction tubes containing catalyst therein to effect a first reforming reaction and being located in relation to said first inlet such that the flow of steam and feed gas introduced through said first inlet will be distributed amongst said plurality of reaction tubes, a combustion reaction chamber, means communicating with said reaction tubes to pass the thus reacted gases from said tubes to said combustion reaction chamber, said means extending longitudinally from said reaction tubes and extending generally into said combustion reaction chamber, a second inlet connected to said combustion reaction chamber means defining a second catalyst zone, located in the lower portion of said heat exchange chamber, a partition separating said heat exchange chamber from said combustion reaction chamber, said partition including means to permit the passage of combustion reaction effluent therethrough to said second catalyst zone, wherein said second catalyst zone comprises a catalyst bed supported on said partition to effect a second reforming reaction, wherein said means extending longitudinally from said reaction rubes extends through said second catalyst zone, whereby the combustion reaction effluent can pass through said partition and said second catalyst zone to undergo additional reforming reaction and to produce synthesis gas, an outlet for removal of said synthesis gas positioned in said reactor approximately adjacent said first inlet and in non-concentric relationship with said first inlet and with said reaction tubes, so that the synthesis gas passes about the outside of said reaction tubes prior to removal through said outlet, which provides heat for said first reforming reaction within said reaction tobes and cools the synthesis gas.
2. An autothermal reactor for the production of a synthesis gas in which both primary reforming and secondary reforming are achieved at a high level of efficiency, comprising a heat excgange chamber having a first portion and a second portion, a first inlet connected to said heat exchange chamber for the introduction of steam and feed gas to said heat exchange chamber, a plurality of reaction tubes mounted within the first portion of said heat exchanger chamber at a location spaced longitudinally from said first inlet in communication with said first inlet and in non-concentric relationship therewith so as to provide a flow path for the steam and feed gas from said first inlet through said plurality of reaction tubes, each of said plurality of reaction tubes containing catalyst therein to effect a first reforming reaction and being located in relation to said first inlet such that the flow of steam and feed gas introduced through said first inlet will be distributed amongst said plurality of reaction tubes, a combustion reaction chamber, means communicating with said reaction tubes to pass the thus reacted gasess from said tubes to said combustion reaction chamber, said means extending longitudinally from said reaction tubes and extnding generally into said combustion reaction chamber, a second inlet connected to said combustion reaction chamber so as to introduce oxygen or oxygen-enriched air into said combustion reaction chamber, said second inlet being in non-concentric relationship with said combustion reaction chamber, means defining a second catalyst zone located in the second portion of said heat exchange chamber, a partition separating said heat exchange chamber from said combustion reaction chamber, said partition including mean to permit the passage of combustion reaction effluent therethrough to said second catalyst zone, wherein said second catalyst zone comprises a catalyst bed supported on said partition to effect a second reforming reaction.
whereby the combustion reaction effluent can pass through said partition and said second catalyst zone to undergo additional reforming reaction and to produce synthesis gas, an outlet for removal of synthesis gas positioned in said reactor approximately adjacnet said first inlet and in non-concentric relationship with said first inlet and with said reaction tubes to that the synthesis gas passes about the outside of said reaction tubes prior to removal through said outlet which provides heat for said first reforming reaction within said reaction tubes and cools the synthesis gas.
whereby the combustion reaction effluent can pass through said partition and said second catalyst zone to undergo additional reforming reaction and to produce synthesis gas, an outlet for removal of synthesis gas positioned in said reactor approximately adjacnet said first inlet and in non-concentric relationship with said first inlet and with said reaction tubes to that the synthesis gas passes about the outside of said reaction tubes prior to removal through said outlet which provides heat for said first reforming reaction within said reaction tubes and cools the synthesis gas.
3. The reactor of claim 1 or 2 further comprising flow baffles which are positioned within the first portion of said heat-exchange chamber to direct the flow of combustion reaction effluent about said reaction tubes.
4. The reactor of claim 1 or 2 in which said means communicating with said reaction tubes is a collector positioned adjacent the outlet end of said reaction tubes with a pipe extending vertically downward therefrom through said partition and into said combustion chamber.
5. The reactor of claim 1 or 2 further comprising suspension means for attaching said plurality of reaction tubes to said reactor.
6. The reactor of claim 1 or 2 in which the wall of said reactor is internally insulated to maximize heat utilization.
7. An autothermal reactor for production of a synthesis gas by primary reforming and secondary reforming, said autothermal reactor comprising a heat-exchange chamber having (a) a first inlet for introduction of steam and feed gas to said heat-exchange chamber; (b) a first reforming zone having catalyst-containing reaction tubes proximal and connected to said first inlet; (c) means for connecting said first reforming zone with; (d) a catalyst-free combustion chamber having second inlet means for introducing an oxygen containing gas into said combustion chamber; (e) a second reforming zone containing a secondary catalyst and connected to said combustion chamber and provided with exit means whereby the products of said second reforming zone are carried into heat-exchange relationship with said first reforming zone; and (f) outlet means for removing reaction products from the reactor.
8. An autothermal reactor according to claim 7 wherein said combustion chamber and said second reforming zone are separated by a partition porous to reaction products of the combustion chamber.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US574,921 | 1984-01-30 | ||
| US06/574,921 US4666680A (en) | 1984-01-30 | 1984-01-30 | Autothermal production of synthesis gas |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1327271C true CA1327271C (en) | 1994-03-01 |
Family
ID=24298191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000473044A Expired - Fee Related CA1327271C (en) | 1984-01-30 | 1985-01-29 | Autothermal production of synthesis gas |
Country Status (15)
| Country | Link |
|---|---|
| US (1) | US4666680A (en) |
| JP (1) | JPS60186401A (en) |
| AT (1) | AT392628B (en) |
| AU (1) | AU576214B2 (en) |
| BR (1) | BR8500393A (en) |
| CA (1) | CA1327271C (en) |
| DK (1) | DK166770B1 (en) |
| GB (1) | GB2153382B (en) |
| IN (1) | IN163324B (en) |
| MY (1) | MY101681A (en) |
| NL (1) | NL192572C (en) |
| NO (1) | NO170921C (en) |
| NZ (1) | NZ210933A (en) |
| SU (1) | SU1713420A3 (en) |
| ZA (1) | ZA85527B (en) |
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| GB8629497D0 (en) * | 1986-12-10 | 1987-01-21 | British Petroleum Co Plc | Apparatus |
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| DE3803082A1 (en) * | 1988-02-03 | 1989-08-17 | Uhde Gmbh | MULTI-STAGE PROCESS FOR GENERATING H (DOWN ARROW) 2 (DOWN ARROW) AND CO-CONTAINING SYNTHESIS GAS |
| DE3803081A1 (en) * | 1988-02-03 | 1989-08-10 | Uhde Gmbh | Apparatus for carrying out a multistage generation of synthesis gas |
| JPH01261201A (en) * | 1988-04-12 | 1989-10-18 | Mitsubishi Gas Chem Co Inc | Hydrocarbon reforming reactor |
| GB2222533A (en) * | 1988-04-20 | 1990-03-14 | Humphreys & Glasgow Ltd | Combined tubular primary and secondary reformer |
| DE3813863A1 (en) * | 1988-04-23 | 1989-11-02 | Uhde Gmbh | DEVICE FOR RECEIVING CATALYSTS, ESPECIALLY IN THE PRODUCTION OF SYNTHESIS GAS |
| GB2217728B (en) * | 1988-04-28 | 1992-02-26 | Humphreys & Glasgow Ltd | Combined reformer |
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| US5122299A (en) * | 1989-12-11 | 1992-06-16 | The M. W. Kellogg Company | Autothermal steam reforming process |
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| JPH07126201A (en) * | 1993-10-27 | 1995-05-16 | Mitsubishi Gas Chem Co Inc | Methanol production process |
| US5980840A (en) * | 1997-04-25 | 1999-11-09 | Bp Amoco Corporation | Autothermic reactor and process using oxygen ion--conducting dense ceramic membrane |
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| DE10119083C1 (en) * | 2001-04-19 | 2002-11-28 | Joachim Alfred Wuenning | Compact steam reformer |
| US20050063899A1 (en) * | 2003-08-21 | 2005-03-24 | Syntroleum Corporation | Two-stage auto thermal reforming process and system |
| US7435401B2 (en) * | 2004-07-02 | 2008-10-14 | Kellogg Brown & Root Llc | Pseudoisothermal ammonia process |
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-
1984
- 1984-01-30 US US06/574,921 patent/US4666680A/en not_active Expired - Lifetime
-
1985
- 1985-01-23 ZA ZA85527A patent/ZA85527B/en unknown
- 1985-01-24 GB GB08501758A patent/GB2153382B/en not_active Expired
- 1985-01-24 NZ NZ210933A patent/NZ210933A/en unknown
- 1985-01-28 DK DK038385A patent/DK166770B1/en not_active IP Right Cessation
- 1985-01-28 NO NO850329A patent/NO170921C/en unknown
- 1985-01-29 JP JP60015259A patent/JPS60186401A/en active Granted
- 1985-01-29 SU SU853856865A patent/SU1713420A3/en active
- 1985-01-29 BR BR8500393A patent/BR8500393A/en not_active IP Right Cessation
- 1985-01-29 NL NL8500238A patent/NL192572C/en not_active IP Right Cessation
- 1985-01-29 AU AU38135/85A patent/AU576214B2/en not_active Ceased
- 1985-01-29 CA CA000473044A patent/CA1327271C/en not_active Expired - Fee Related
- 1985-01-29 AT AT241/85A patent/AT392628B/en not_active IP Right Cessation
- 1985-01-31 IN IN67/CAL/85A patent/IN163324B/en unknown
-
1987
- 1987-10-01 MY MYPI87002711A patent/MY101681A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| NO170921B (en) | 1992-09-21 |
| BR8500393A (en) | 1985-09-10 |
| US4666680A (en) | 1987-05-19 |
| AU576214B2 (en) | 1988-08-18 |
| NZ210933A (en) | 1987-07-31 |
| GB8501758D0 (en) | 1985-02-27 |
| NO170921C (en) | 1992-12-30 |
| GB2153382A (en) | 1985-08-21 |
| ATA24185A (en) | 1990-10-15 |
| IN163324B (en) | 1988-09-10 |
| NL192572B (en) | 1997-06-02 |
| GB2153382B (en) | 1987-06-24 |
| MY101681A (en) | 1991-12-31 |
| JPS60186401A (en) | 1985-09-21 |
| NL192572C (en) | 1997-10-03 |
| ZA85527B (en) | 1995-04-06 |
| NO850329L (en) | 1985-07-31 |
| DK38385D0 (en) | 1985-01-28 |
| SU1713420A3 (en) | 1992-02-15 |
| AT392628B (en) | 1991-05-10 |
| DK38385A (en) | 1985-07-31 |
| AU3813585A (en) | 1985-08-08 |
| JPH0522641B2 (en) | 1993-03-30 |
| NL8500238A (en) | 1985-08-16 |
| DK166770B1 (en) | 1993-07-12 |
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