US20060239871A1 - Low pressure drop purifier for nitrogen, methane, and argon removal from syngas - Google Patents

Low pressure drop purifier for nitrogen, methane, and argon removal from syngas Download PDF

Info

Publication number
US20060239871A1
US20060239871A1 US11/472,590 US47259006A US2006239871A1 US 20060239871 A1 US20060239871 A1 US 20060239871A1 US 47259006 A US47259006 A US 47259006A US 2006239871 A1 US2006239871 A1 US 2006239871A1
Authority
US
United States
Prior art keywords
stream
syngas
vapor
waste fluid
ammonia
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Abandoned
Application number
US11/472,590
Inventor
Avinash Malhotra
Tufail Ahmad
Bradley Welter
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to US11/472,590 priority Critical patent/US20060239871A1/en
Publication of US20060239871A1 publication Critical patent/US20060239871A1/en
Abandoned legal-status Critical Current

Links

Images

Classifications

    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0228Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream
    • F25J3/0276Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the separated product stream separation of H2/N2 mixtures, i.e. of ammonia synthesis gas
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01DSEPARATION
    • B01D3/00Distillation or related exchange processes in which liquids are contacted with gaseous media, e.g. stripping
    • B01D3/14Fractional distillation or use of a fractionation or rectification column
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/025Preparation or purification of gas mixtures for ammonia synthesis
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/50Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/506Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification at low temperatures
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01CAMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00Ammonia; Compounds thereof
    • C01C1/02Preparation, purification or separation of ammonia
    • C01C1/04Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J3/00Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification
    • F25J3/02Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream
    • F25J3/0204Processes or apparatus for separating the constituents of gaseous or liquefied gaseous mixtures involving the use of liquefaction or solidification by rectification, i.e. by continuous interchange of heat and material between a vapour stream and a liquid stream characterised by the feed stream
    • F25J3/0219Refinery gas, cracking gas, coke oven gas, gaseous mixtures containing aliphatic unsaturated CnHm or gaseous mixtures of undefined nature
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0205Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0244Processes 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02Processes for making hydrogen or synthesis gas
    • C01B2203/0283Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
    • C01B2203/0288Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing two CO-shift steps
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0435Catalytic purification
    • C01B2203/0445Selective methanation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/046Purification by cryogenic separation
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/04Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0465Composition of the impurity
    • C01B2203/0475Composition of the impurity the impurity being carbon dioxide
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06Integration with other chemical processes
    • C01B2203/068Ammonia synthesis
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0811Methods of heating the process for making hydrogen or synthesis gas by combustion of fuel
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844Methods 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
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0805Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0866Methods of heating the process for making hydrogen or synthesis gas by combination of different heating methods
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08Methods of heating or cooling
    • C01B2203/0872Methods of cooling
    • C01B2203/0883Methods of cooling by indirect heat exchange
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/142At least two reforming, decomposition or partial oxidation steps in series
    • C01B2203/143Three or more reforming, decomposition or partial oxidation steps in series
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14Details of the flowsheet
    • C01B2203/146At least two purification steps in series
    • C01B2203/147Three or more purification steps in series
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01BNON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/80Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
    • C01B2203/82Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/02Processes or apparatus using separation by rectification in a single pressure main column system
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/74Refluxing the column with at least a part of the partially condensed overhead gas
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2200/00Processes or apparatus using separation by rectification
    • F25J2200/80Processes or apparatus using separation by rectification using integrated mass and heat exchange, i.e. non-adiabatic rectification in a reflux exchanger or dephlegmator
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2210/00Processes characterised by the type or other details of the feed stream
    • F25J2210/20H2/N2 mixture, i.e. synthesis gas for or purge gas from ammonia synthesis
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00Processes or apparatus involving steps for expanding of process streams
    • F25J2240/02Expansion of a process fluid in a work-extracting turbine (i.e. isentropic expansion), e.g. of the feed stream
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2240/00Processes or apparatus involving steps for expanding of process streams
    • F25J2240/30Dynamic liquid or hydraulic expansion with extraction of work, e.g. single phase or two-phase turbine
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F25REFRIGERATION OR COOLING; COMBINED HEATING AND REFRIGERATION SYSTEMS; HEAT PUMP SYSTEMS; MANUFACTURE OR STORAGE OF ICE; LIQUEFACTION SOLIDIFICATION OF GASES
    • F25JLIQUEFACTION, SOLIDIFICATION OR SEPARATION OF GASES OR GASEOUS OR LIQUEFIED GASEOUS MIXTURES BY PRESSURE AND COLD TREATMENT OR BY BRINGING THEM INTO THE SUPERCRITICAL STATE
    • F25J2290/00Other details not covered by groups F25J2200/00 - F25J2280/00
    • F25J2290/80Retrofitting, revamping or debottlenecking of existing plant
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00Technologies relating to chemical industry
    • Y02P20/50Improvements relating to the production of bulk chemicals
    • Y02P20/52Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Physics & Mathematics (AREA)
  • Mechanical Engineering (AREA)
  • Thermal Sciences (AREA)
  • General Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Analytical Chemistry (AREA)
  • Separation By Low-Temperature Treatments (AREA)

Abstract

An apparatus for purifying a raw syngas stream containing excess nitrogen and an ammonia process plant for manufacturing ammonia from syngas with excess air for reforming and nitrogen removal with low pressure losses is disclosed. Auto-refrigeration for cooling the syngas for cryogenic hydrogen enrichment is provided by expansion of a hydrogen-lean waste fluid stream from a distillation column

Description

    CROSS REFERENCE TO RELATED APPLICATIONS
  • The present application is a divisional to co-pending U.S. patent application Ser. No. 10/604,404, filed on Jul. 17, 2003.
  • FIELD
  • The present embodiments relate generally to methods and apparatus to improve production of synthesis gas for manufacturing ammonia. The present embodiments reduces pressure losses in a nitrogen-wash purifier unit
  • BACKGROUND
  • Processes for manufacturing ammonia from a hydrocarbon and air, via a hydrogen/nitrogen synthesis gas (syngas), are well known. Extraneous syngas components typically include inert gases from the air and/or the hydrocarbon feed, such as argon and methane. When excess air is used in the syngas production, nitrogen is also present in stoichiometric excess, and must be removed from a raw makeup syngas stream or purged from an ammonia synthesis loop to maintain a desired ammonia synthesis reactor feed composition.
  • In the prior art, some syngas production methods use excess air and cryogenic syngas purification, which relies on a syngas pressure drop upstream of purification for refrigeration. The pressure drop is subsequently made up in a compressor that raises the syngas to ammonia synthesis loop pressure. This type of method also reduces the rate of recycle or purge gas flow from the ammonia reactor loop due to the upstream removal from the makeup syngas of inerts such as argon and methane in the syngas purification.
  • Other methods of ammonia synthesis use high-activity catalyst in the ammonia synthesis reactor. Purge gases are eliminated via a hydrogen enrichment process operating on a sidestream of the syngas recycled to the synthesis loop compressor. The total recycle flow is roughly three times the volumetric flowrate of the makeup syngas.
  • Other methods use air separation to provide oxygen-enriched air such that reforming produces a synthesis gas with higher hydrocarbon slip than in other ammonia manufacturing systems. A higher concentration of nonreactive gas in the ammonia synthesis is managed by purging from a residual syngas stream following recovery of ammonia product. This type of method unloads front-end gas reforming reactors, at the expense of including air separation, but ostensibly enables a smaller purge stream process after ammonia synthesis.
  • Other methods are centered on an integrated process system for synthesizing methanol and ammonia that uses a nitrogen wash by cryogenic fractionation to purify ammonia syngas, with refrigeration supplied externally and providing no recovery of expansion power in the process.
  • The present embodiments meet these needs.
  • BRIEF DESCRIPTION OF THE DRAWINGS
  • The detailed description will be better understood in conjunction with the accompanying drawings as follows:
  • FIG. 1 is a schematic process flow sheet showing prior art syngas purification using an upstream syngas feed to drive an expander and extract syngas energy as work to achieve auto-refrigeration.
  • FIG. 2 is a schematic process flow sheet of an embodiment of the present invention, using expansion of a nitrogen-rich liquid waste stream to generate auto-refrigeration in the process.
  • FIG. 3 is a schematic process flow sheet showing an alternate embodiment of the present invention wherein syngas feed or liquefied waste gas can be expanded across a liquid expander for refrigeration.
  • FIG. 4 is a block flow diagram of an embodiment of the invention showing low pressure drop nitrogen removal integrated in an ammonia synthesis process with secondary reforming with excess air and heat-exchanging reforming.
  • FIG. 5 is block flow diagram of an alternative embodiment of the invention showing low pressure drop nitrogen removal integrated in an ammonia synthesis process with conventional primary steam reforming and secondary reforming with excess air
  • The present embodiments are detailed below with reference to the listed Figures.
  • DETAILED DESCRIPTION OF THE EMBODIMENTS
  • Before explaining the present embodiments in detail, it is to be understood that the embodiments are not limited to the particular embodiments and that they can be practiced or carried out in various ways.
  • The present embodiments provide methods to purify syngas. Syngas, as an example, occurs in ammonia manufacturing processes. The methods use cryogenic distillation to purify syngas, and obtain refrigeration for the distillation from waste fluid expansion using a liquid expander to recover mechanical work from the waste fluid. These methods reduce the pressure losses in the syngas stream and concomitantly reduce compression costs and power relative to similar prior art ammonia processes utilizing nitrogen and inerts removal.
  • The methods are applicable in grassroots plant design, and can also be applied to retrofit existing synthesis gas systems to improve process performance and economics. In the retrofit, for example, the lower pressure drop of the present embodiments can allow process modification for reforming with excess air and nitrogen removal from the makeup syngas without expensive modification or replacement of the synthesis loop and/or makeup gas compressors.
  • In an embodiment, the present embodiments provide methods to purify syngas, including: (a) introducing a raw syngas stream containing excess nitrogen to a feed zone in a distillation column; (b) expanding a liquid bottoms stream from the distillation column through a liquid expander with a work output to form a cooled waste fluid stream; (c) rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content; (d) cooling the overhead vapor stream in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a relatively warm waste fluid stream; (e) separating the partially condensed overhead stream into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content; and (f) refluxing the distillation column with the condensate stream. The method can also include cooling the raw syngas stream by expansion across a Joule-Thompson (J-T) valve in advance of the introduction to the feed zone. Additionally, the method can include cooling the raw syngas stream in cross-exchange against the warm waste fluid stream and against the purified syngas vapor stream. In this embodiment, adjusting the flow to the liquid bottoms stream expansion controls liquid level in the distillation column.
  • The methods can further include producing the raw synthesis gas by reforming a hydrocarbon, wherein the reforming includes autothermal or secondary reforming with excess air. The purified syngas vapor stream can be supplied to an ammonia synthesis loop for manufacturing ammonia.
  • In an embodiment, the present embodiments provide an ammonia process. The process embodiments include reforming a hydrocarbon to form syngas. The reforming can include autothermal or secondary reforming with excess air to form a raw syngas stream containing excess nitrogen for ammonia synthesis. The process embodiments include cooling the raw syngas stream in a cross-exchanger and expanding the cooled raw syngas stream. The expanded raw syngas stream is introduced to a feed zone in a distillation column. The liquid bottoms stream from the distillation column is expanded through a liquid expander to form a cooled waste fluid stream. The process embodiments include rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content. The overhead vapor stream is cooled in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a partially warmed waste fluid stream. The partially condensed overhead stream is separated into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content. The distillation column is refluxed with the condensate stream and the purified syngas vapor stream and the partially warmed waste fluid stream are heated in one or more cross-exchangers. The purified syngas vapor stream is supplied from the cross-exchanger to an ammonia synthesis loop.
  • In an embodiment, the present embodiments can be applied to improve an ammonia process that includes the steps of reforming a hydrocarbon with excess air to form a raw syngas stream, removing nitrogen and inerts from the raw syngas stream by distillation. The cooling can be provided by process fluid expansion through an expander-generator, wherein an overhead stream is partially condensed against a waste stream cooled by expanding bottoms liquid from a distillation column, and supplying syngas with reduced nitrogen and inerts content from the distillation to an ammonia synthesis loop. The process embodiments can include optionally expanding the raw syngas stream across a Joule-Thompson valve upstream of the distillation column; and/or expanding the bottoms liquid through a liquid expander with a work output.
  • In an embodiment, the present embodiments provide for a purification apparatus for purifying a raw syngas stream containing excess nitrogen. The embodied apparatus, can include means for introducing the raw syngas stream to a feed zone in a distillation column; means for expanding a liquid bottoms stream from the distillation column to form a cooled waste fluid stream; means for rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content; means for cooling the overhead vapor stream in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a relatively warm waste fluid stream; means for separating the partially condensed overhead stream into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content; and means for refluxing the distillation column with the condensate stream.
  • In an embodiment, the present embodiments provide for an ammonia process plant. The embodied an ammonia process plants can include means for reforming a hydrocarbon to form syngas, wherein the reforming means includes an autothermal or secondary reformer and means for supplying excess air to the autothermal or secondary reformer, to form a raw syngas stream containing excess nitrogen for ammonia synthesis; cross-exchanger means for cooling the raw syngas stream; means for expanding the cooled raw syngas stream from the cross-exchanger; means for introducing the expanded raw syngas stream to a feed zone in a distillation column; means for expanding a liquid bottoms stream from the distillation column through a liquid expander to form a cooled waste fluid stream; means for rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content; means for cooling the overhead vapor stream in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a partially warmed waste fluid stream; means for separating the partially condensed overhead stream into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content; means for refluxing the distillation column with the condensate stream; means for heating the purified syngas vapor stream in the cross-exchanger; means for heating the partially warmed waste fluid stream in the cross exchanger; and means for supplying the purified syngas vapor stream from the cross-exchanger to an ammonia synthesis loop
  • With reference to the figures, FIG. 1 depicts an example of prior art syngas purification PA. A syngas feed stream 10 drives expander 12, extracting syngas energy as work 14 to achieve auto-refrigeration. The feed stream 10 is chilled in cross-exchangers 16, 18 by indirect heat transfer with cold product streams from a distillation column 20. Between the cross-exchangers 16, 18, the raw syngas 10 is expanded in a turboexpander 12, cooling the raw syngas 10 and recovering work 14. The expander 12 can be bypassed or supplemented by using a Joule-Thompson (J-T) valve 22, for example during startup. The partially liquefied raw syngas 13 from the cross-exchanger 18 enters the distillation column 20 to be further cooled, partly condensed, and rectified, yielding a purified syngas stream 24 of lowered nitrogen and inerts content and a hydrogen-lean waste gas stream 26. The purified syngas stream 24 and waste gas stream 26 pass through the cross-exchangers 16, 18 to chill the raw syngas feed stream 10 as mentioned previously.
  • The waste gas stream 26 is discharged from the distillation column 20 as bottoms stream 28, flashed across level control valve 30, and used as a coolant in a heat exchanger 32 integral with the distillation column 20. The heat exchanger 32 cools and partially condenses overhead vapor from the column 20 to obtain syngas liquid to reflux the column 20. The makeup syngas stream 24 is compressed for conversion in ammonia synthesis reactors (not shown) that operate at higher pressures. Thus, a pressure drop incurred by the raw syngas 10 in the purification PA must be recouped downstream by consuming additional power for compression.
  • FIG. 2 depicts an embodiment of syngas purification 34 using mechanical expansion of the liquid bottoms stream 28 to generate a major fraction of the auto-refrigeration in the purification process 34. A single cross-exchanger 36 is used in place of the cross-exchangers 16, 18 of FIG. 1, although cross-exchanger 36 can include a plurality of physical stages. The raw syngas stream 10 is passed through valve station 38 upstream of the distillation column 20. The valve station 38 can include a primary, line-size valve for flow during normal operation, and a J-T secondary valve for trim and/or startup for auto-refrigeration. The raw syngas stream 10 then enters an inlet zone 40 of the column 20, preferably as a mixture of syngas vapor and liquid. In the inlet zone 40, syngas liquid separates and is collected in liquid holdup zone 42. The liquid exits the column 20 as bottoms stream 28 via a lower outlet 44. The column bottoms stream 28 is expanded through a liquid expander 46 to auto-refrigerate the bottoms 28 and recover work 48, which can be used to drive a pump, compressor, electrical generator, or the like. As used herein, a “liquid expander” is a work-output device that receives a liquid supply and produces a liquid or vapor effluent, preferably a mixed vapor-liquid effluent. Where the effluent fluid is liquid, the liquid expander 46 can be a hydraulic turbine.
  • A bypass J-T valve 50 is included for gas or two-phase flow, e.g. at startup. In operation, expansion of the bottoms stream 28 is preferably a primary source of auto-refrigeration in the syngas purification process 34 of the present embodiments, whereas the expansion across the bypass J-T valve at valve station 38 is a relatively minor source. The bypass J-T valve can be a significant refrigeration source during startup.
  • From liquid expander 46, the chilled waste fluid stream 28 enters a coolant inlet 52 of an indirect heat exchange zone 32 integral to the column 20. The flow rate to the liquid expander 46 controls the liquid level in the holdup zone 42 and also, in part, regulates conditions in the column 20, based on feedback from a syngas analyzer 56. Conditions in the column 20 determine the composition of the purified syngas stream 24. For example, more refrigeration reduces the nitrogen content; less refrigeration increases the nitrogen content. The chilled waste fluid stream 28 passes through the heat exchange zone 32, discharging from the column 20 via coolant outlet 56. During transit through the heat exchange zone 32, the bottoms stream 28 cools and partially condenses overhead vapor from the column 20.
  • From the inlet zone 40, syngas vapor flows upward through a contact zone 58 in contact with liquid flowing downward through the contact zone 58 to absorb nitrogen and enrich the hydrogen content of the vapor. At the upper end of the contact zone 58, the vapor enters a vapor riser 60 and flows to a vapor inlet zone 62 at an upper end of the heat exchange zone 32. The vapor passes tube-side through the heat exchange zone 32 for partial condensation against the waste fluid stream 28, further enriching the vapor in lower-boiling components. Vapor and condensate exit the heat exchange zone 32 and are separated in a knockout zone 64. Vapor exits the column 20 as the purified syngas stream 24, discharging via syngas outlet 66. The condensate collects in a liquid seal well 68 below the knockout zone 64 and in communication with the contact zone 58. The condensate overflows from the seal well 68 to flow downward through the contact zone 58 to the liquid holdup zone 42 as described previously.
  • FIG. 3 depicts another embodiment of a syngas purification process 70, in which the process PA of FIG. 1 can be modified or retrofitted according to the present embodiments. A bottoms liquid expander 46 is added to auto-refrigerate the bottoms stream 28 by recovering work, for example as power 48. A bypass J-T valve 50 is also installed, as in FIG. 2. The resulting retrofit purification process 70 is comparable to the inventive embodiment of FIG. 2, but can also be operated in the original configuration, if desired. For low pressure drop operation, the original syngas turboexpander 12 is bypassed and the valve 22 is set full open, or optionally bypassed (not shown).
  • In an embodiment, expansion of a liquid byproduct stream of purged gases (such as, the column bottoms stream 28) can generate a major portion of the auto-refrigeration required for the purification process. This generation avoids a major part of the syngas pressure loss incurred in the prior art configuration of FIG. 1. In the prior art process PA, a pressure drop of about 3.1 bars typically occurs from introduction of the syngas feed stream 10 to exit of the purified syngas stream 24. Most of this pressure drop occurs across the expander 12, which drops the raw syngas pressure by about 1.8 to 2.0 bar. In an embodiment as exampled in FIG. 2, a pressure drop from introduction of the syngas feed stream 10 to exit of the purified syngas stream 24, can be limited to a range of about 0.75 to 1.3 bar by obtaining a major portion of the required auto-refrigeration effect from expansion of the column bottoms stream 28 instead of from the raw syngas feed stream 10.
  • Referring to FIG. 4, an embodiment of an ammonia manufacturing process can include catalytic reforming of a feed including hydrocarbon 100 and steam 102 in a reactor/exchanger 104 of the type known under the trade designation KRES. Additional reforming of a feed including hydrocarbon 100 and steam 102 with excess air 106 as oxidant can be effected in secondary reformer 108. The process can include high and/or low temperature shift conversion and carbon dioxide removal 110, methanation and drying 112, syngas purification 114 as described in reference to FIG. 2 or 3, compression 116, and ammonia synthesis 118. A purge stream 120 is recycled from the ammonia synthesis 118 to upstream of the syngas purification 114 (such as, to the methanation and drying 112). The recycled stream 120 can be relatively smaller in mass flow rate than the raw syngas stream 10 (as exampled in FIG. 2), for example, in a range of from about 5 weight percent to 25 weight percent of the raw syngas stream 10, and preferably in a range of from 10 to 20 weight percent of the raw stream 10. The waste gas stream 26 can be exported for fuel gas value.
  • Referring to FIG. 5, another embodiment of an ammonia manufacturing process can include catalytic reforming of a feed including hydrocarbon 100 and steam 102 in a conventional primary reformer 122 followed by additional reforming with excess air 106 in conventional secondary catalytic reformer 124. Shift conversion and carbon dioxide removal 110, methanation and drying 112, syngas purification 114, compression 116, ammonia synthesis 118 and purge stream 120 recycle are as described in reference to FIG. 4. Waste gas stream 26 can be burned as a fuel in primary reformer 122 and/or exported for fuel gas as in FIG. 4.
  • The purification process of FIG. 2 can be used in a new plant for improved energy consumption and capital cost savings, or can be used to retrofit an existing purification process like that of FIG. 1 to reduce operating costs and/or to increase capacity. The process of FIG. 2 can be used to retrofit an existing plant that does not use purification and/or excess air. Retrofitting for reforming with excess air can increase the capacity of the existing plant and enhance the life of the tubes and/or other internals in the existing reformer(s) by shifting some of the reforming duty to the secondary reformer and lowering the operating temperature of the primary reformer. Installing nitrogen removal also allows for more flexible reforming operation (such as, higher methane slip), and less purge or recycle from the ammonia synthesis loop due to the reduction of inerts with the nitrogen removal. Nitrogen purification/excess air retrofits using the low-ΔP purification process of the present invention can improve the retrofit by reducing or eliminating the extent of modifications to the makeup syngas compressor, which can make the retrofit economically feasible for a larger number of existing ammonia plants.
  • EXAMPLE
  • The purification method of the present invention embodiment of FIG. 2 is compared to that of the prior art in FIG. 1. Both FIGS. 1 and, 2 process a raw syngas feed stream 10 to produce a purified syngas stream 24 and a waste gas stream 26, and the inlet and outlet stream compositions are the same in both cases as shown in Table 1 below.
    TABLE 1
    Purification Syngas Specifications
    Stream Composition,
    mole percent
    Raw Purified Waste
    Gas Syngas Syngas Gas
    Component (10) (24) (26)
    Hydrogen 65.8 74.7 6.6
    Nitrogen 31.4 24.9 74.2
    Methane 2.2 0.006 16.7
    Argon 0.6 0.4 2.5
    Total 100.0 100.0 100.0
  • Operation of the low-ΔP process of FIG. 2 was simulated for a 2200 metric tons per day ammonia plant to compare the operating temperatures, pressures and flow rates to those of the FIG. 1 prior art process as a base case. The results are shown in Table 2 below.
    TABLE 2
    Purification Operating Conditions
    Basis: 2200 MTPD Ammonia
    Base Case Example
    Process Stream, Location (FIG. 1) (FIG. 2)
    RAW SYNGAS (10), INLET TO
    CROSS-EXCHANGER (20)
    Temperature, ° C. 4.0 4.0
    Pressure, kPa 3,479.0 3,479.0
    Mass flow, kg/hr 142,124 142,124
    RAW SYNGAS (10), INLET
    TO COLUMN (20)
    Temperature, ° C. −172.6 −172.0
    Pressure, kPa 3,240.0 3,454.0
    Mass flow, kg/hr 142,124 142,124
    SYNGAS (24), OUTLET
    FROM COLUMN (20)
    Temperature, ° C. −178.6 −178.2
    Pressure, kPa 3,215.0 3,429.0
    Mass flow, kg/hr 99,607 99,529
    SYNGAS (24), OUTLET FROM
    CROSS-EXCHANGER (16, 20)
    Temperature, ° C. 1.3 2.1
    Pressure, kPa 3,165.0 3,404.0
    Mass flow, kg/hr 99,607 99,529
    BOTTOMS LIQUID (28), OUTLET
    FROM COLUMN (20)
    Temperature, ° C. −172.8 −172.2
    Pressure, kPa 3,240.0 3,454.0
    Mass flow, kg/hr 42,517 42,596
    WASTE FLUID (26), INLET
    TO EXCHANGER (32)
    Temperature, ° C. −186.0 −187.6
    Pressure, kPa 319.0 302.1
    Mass flow, kg/hr 42,517 42,596
    WASTE FLUID (26), OUTLET FROM
    CROSS-EXCHANGER (16, 36)
    Temperature, ° C. 1.3 2.1
    Pressure, kPa 256.4 253.3
    Mass flow, kg/hr 42,517 42,596
  • The data in Table 2 show that the flow rates and temperatures are similar, but the pressure drop for the syngas between the purification process inlet and outlet is considerably lower in the FIG. 2 example compared to the FIG. 1 base case. This will generally require less makeup gas compression to the ammonia synthesis loop pressure. The power requirements for makeup syngas compression, fluid expansion power output, and net compression and expansion were also determined for the FIG. 1 base case and the FIG. 2 example. The results are shown in Table 3 below.
    TABLE 3
    Power Balance
    Basis: 2200 MTPD Ammonia
    Base Case Example
    Compression/Expansion (FIG. 1) (FIG. 2)
    MAKEUP SYNGAS COMPRESSION, KW 8,310.66 7,453.49
    RAW SYNGAS EXPANSION, KW −203.39
    WASTE FLUID EXPANSION, KW −120.40
    NET COMPRESSION/EXPANSION 8,107.27 7,333.09
    POWER, KW
  • As seen in the data presented above, the purification process of FIG. 2 is characterized by a lower syngas pressure drop than the prior art process of FIG. 1. While less power is recovered from expansion of the waste fluid in the example of FIG. 2 than in the syngas feed expansion in the base case of FIG. 1, the reduction in makeup compression power is more significant. Thus, not only is the syngas pressure drop reduced, but the overall power requirements are also less, potentially resulting in both capital and operating cost savings in a new ammonia plant. In a retrofit of an existing non-purifier based ammonia plant, the reduced pressure drop of the FIG. 2 example can result in increased capacity and/or less significant or no modification of the makeup syngas compressor.
  • The embodiments are described above with reference to non-limiting examples provided for illustrative purposes only. Various modifications and changes will become apparent to the skilled artisan in view thereof. All such changes and modifications are intended within the scope and spirit of the appended claims and shall be embraced thereby.

Claims (17)

1) An apparatus for purifying a raw syngas stream containing excess nitrogen comprising:
means for introducing the raw syngas stream to a feed zone in a distillation column;
means for expanding a liquid bottoms stream from the distillation column through a liquid expander with a work output to form a cooled waste fluid stream;
means for rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content;
means for cooling the overhead vapor stream in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a relatively warm waste fluid stream;
means for separating the partially condensed overhead stream into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content; and
means for refluxing the distillation column with the condensate stream.
2) The apparatus of claim 1, further comprising means for cooling and expanding the raw syngas stream across a Joule-Thompson valve in advance of the introduction to the feed zone.
3) The apparatus of claim 2, wherein the means for expanding the liquid bottoms stream comprises a hydraulic turbine.
4) The apparatus of claim 1, wherein the relatively warm waste fluid stream from the overhead vapor cooling consists of a vapor phase.
5) The apparatus of claim 1, wherein the relatively warm waste fluid stream from the liquid expander comprises mixed vapor and liquid.
6) The apparatus of claim 1, wherein a liquid level in the distillation column is controlled by adjusting flow the expansion to the liquid bottoms stream.
7) The apparatus of claim 1, further comprising means for producing the raw synthesis gas by reforming a hydrocarbon, wherein the means for producing the raw synthesis gas comprises autothermal or secondary reforming with excess air.
8) The apparatus of claim 1, further comprising means for supplying the purified syngas vapor stream to an ammonia synthesis loop to form ammonia.
9) An ammonia process plant comprising:
means for reforming a hydrocarbon to form syngas, wherein the reforming means include an autothermal or secondary reformer and means for supplying excess air to the autothermal or secondary reformer to form a raw syngas stream containing excess nitrogen for ammonia synthesis;
cross-exchanger means for cooling the raw syngas stream;
means for expanding the cooled raw syngas stream from the cross-exchanger;
means for introducing the expanded raw syngas stream to a feed zone in a distillation column;
means for expanding a liquid bottoms stream from the distillation column through a liquid expander with a work output to form a cooled waste fluid stream;
means for rectifying vapor from the feed zone in the distillation column to form an overhead vapor stream of reduced nitrogen and inerts content;
means for cooling the overhead vapor stream in indirect heat exchange with the cooled waste fluid stream to form a partially condensed overhead stream and a partially warmed waste fluid stream;
means for separating the partially condensed overhead stream into a condensate stream and a purified syngas vapor stream of reduced nitrogen and inerts content;
means for refluxing the distillation column with the condensate stream;
means for heating the purified syngas vapor stream in the cross-exchanger;
means for heating the partially warmed waste fluid stream in the cross exchanger;
means for supplying the purified syngas vapor stream from the cross-exchanger to an ammonia synthesis loop.
10) The ammonia process plant of claim 9, further comprising means for cooling and expanding the raw syngas stream across a Joule-Thompson valve in advance of the introduction to the feed zone.
11) The ammonia process plant of claim 10, wherein the means for cooling of the raw syngas stream includes cross-exchange against the partially warmed waste fluid stream and against the purified syngas vapor stream.
12) The ammonia process plant of claim 9, wherein the means for expanding the liquid bottoms stream comprises a hydraulic turbine.
13) The ammonia process plant of claim 9, wherein the partially warmed waste fluid stream from cooling of the overhead vapor stream consists of a vapor phase.
14) The ammonia process plant of claim 9, wherein waste fluid from the liquid expander comprises mixed vapor and liquid.
15) The ammonia process plant of claim 9, wherein a liquid level in the distillation column is controlled by adjusting flow the expansion to the liquid bottoms stream.
16) The ammonia process plant of claim 9, further comprising means for producing the raw synthesis gas by reforming a hydrocarbon, wherein the means for producing the raw synthesis gas comprises autothermal or secondary reforming with excess air.
17) The ammonia process plant of claim 9, further comprising means for supplying the purified syngas vapor stream to an ammonia synthesis loop to form ammonia.
US11/472,590 2003-07-17 2006-06-22 Low pressure drop purifier for nitrogen, methane, and argon removal from syngas Abandoned US20060239871A1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US11/472,590 US20060239871A1 (en) 2003-07-17 2006-06-22 Low pressure drop purifier for nitrogen, methane, and argon removal from syngas

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US10/604,404 US7090816B2 (en) 2003-07-17 2003-07-17 Low-delta P purifier for nitrogen, methane, and argon removal from syngas
US11/472,590 US20060239871A1 (en) 2003-07-17 2006-06-22 Low pressure drop purifier for nitrogen, methane, and argon removal from syngas

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US10/604,404 Division US7090816B2 (en) 2003-07-17 2003-07-17 Low-delta P purifier for nitrogen, methane, and argon removal from syngas

Publications (1)

Publication Number Publication Date
US20060239871A1 true US20060239871A1 (en) 2006-10-26

Family

ID=33539949

Family Applications (2)

Application Number Title Priority Date Filing Date
US10/604,404 Active 2024-08-12 US7090816B2 (en) 2003-07-17 2003-07-17 Low-delta P purifier for nitrogen, methane, and argon removal from syngas
US11/472,590 Abandoned US20060239871A1 (en) 2003-07-17 2006-06-22 Low pressure drop purifier for nitrogen, methane, and argon removal from syngas

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US10/604,404 Active 2024-08-12 US7090816B2 (en) 2003-07-17 2003-07-17 Low-delta P purifier for nitrogen, methane, and argon removal from syngas

Country Status (7)

Country Link
US (2) US7090816B2 (en)
EP (1) EP1503160B1 (en)
CN (1) CN100519406C (en)
CA (1) CA2473045C (en)
DE (1) DE602004016796D1 (en)
MX (1) MXPA04006957A (en)
RU (1) RU2331575C2 (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20100051876A1 (en) * 2008-08-28 2010-03-04 Ammonia Casale S.A. Process for the production of ammonia synthesis gas with improved cryogenic purification
US20100300144A1 (en) * 2009-04-24 2010-12-02 Madison Joel V Liquefied Gas Expander And Integrated Joule-Thomson Valve
US20120308466A1 (en) * 2007-08-08 2012-12-06 Ammonia Casale S.A. Process for Producing Ammonia Synthesis Gas
WO2014207011A1 (en) * 2013-06-26 2014-12-31 Casale Sa A process for purification of a synthesis gas containing hydrogen and impurities
CN109612203A (en) * 2018-11-22 2019-04-12 山东润银生物化工股份有限公司 A kind of processing method of discharge gas in ammonia synthesis

Families Citing this family (36)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040219088A1 (en) * 2003-04-29 2004-11-04 Harvey Wen Mini ammonia plant
US8083793B2 (en) 2005-02-28 2011-12-27 Medtronic, Inc. Two piece heart valves including multiple lobe valves and methods for implanting them
US7720343B2 (en) 2006-02-13 2010-05-18 Adc Telecommunications, Inc. Fiber distribution hub with swing frame and modular termination panels
US7816602B2 (en) 2006-02-13 2010-10-19 Adc Telecommunications, Inc. Fiber distribution hub with outside accessible grounding terminals
US7481074B2 (en) * 2006-03-01 2009-01-27 Air Products And Chemicals, Inc. Self-contained distillation purifier/superheater for liquid-fill product container and delivery systems
US20080016768A1 (en) 2006-07-18 2008-01-24 Togna Keith A Chemically-modified mixed fuels, methods of production and used thereof
BRPI0717540A2 (en) * 2006-09-28 2013-10-22 Heart Leaflet Technologies Inc SUPPLY INSTRUMENT FOR THE PERCUTANEOUS SUPPLY OF A PROSTHESIS
DE102006055973A1 (en) * 2006-11-24 2008-05-29 Borsig Gmbh Heat exchanger for cooling cracked gas
WO2009016625A2 (en) * 2007-07-29 2009-02-05 Baruchi Barry Baruch Kimchi Method and system for the separation of a mixture containing carbon dioxide, hydrocarbon, and hydrogen
US8229265B2 (en) 2007-11-21 2012-07-24 Adc Telecommunications, Inc. Fiber distribution hub with multiple configurations
EP2135841A1 (en) * 2008-06-20 2009-12-23 Ammonia Casale S.A. Process for the production of syngas for ammonia synthesis
US20090320520A1 (en) * 2008-06-30 2009-12-31 David Ross Parsnick Nitrogen liquefier retrofit for an air separation plant
US8617270B2 (en) 2008-12-03 2013-12-31 Kellogg Brown & Root Llc Systems and methods for improving ammonia synthesis efficiency
EP2292554A1 (en) * 2009-09-02 2011-03-09 Ammonia Casale S.A. Production of ammonia make-up syngas with cryogenic purification
EP2301886A1 (en) * 2009-09-03 2011-03-30 Ammonia Casale S.A. Waste heat recovery in a chemical process and plant, particularly for the synthesis of ammonia
US8377154B2 (en) * 2010-05-18 2013-02-19 Kellogg Brown & Root Llc Gasification system and process for maximizing production of syngas and syngas-derived products
RU2438975C1 (en) * 2010-07-21 2012-01-10 ООО "Проектный офис" Method of producing stoichiometric hydronitric mixture, method of producing ammonia using said mixture and apparatus for realising said methods
US8889093B2 (en) * 2010-09-16 2014-11-18 Kellogg Brown & Root Llc High pressure cyrogenic process and system for producing ammonia products
EP2665678A4 (en) * 2011-01-17 2018-04-04 L'Air Liquide Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude Process and apparatus for production of ammonia synthesis gas and pure methane by cryogenic separation
US8889037B2 (en) * 2011-02-01 2014-11-18 Kellogg Brown & Root Llc Systems and methods for producing syngas and products therefrom
CN103557675B (en) * 2013-10-30 2015-05-27 河南开元空分集团有限公司 Cryogenic distillation liquidation system and method for synthesis ammonia chemical tail gas
US20160067040A1 (en) * 2014-09-09 2016-03-10 Boston Scientific Scimed, Inc. Valve locking mechanism
US10426617B2 (en) * 2015-03-06 2019-10-01 Boston Scientific Scimed, Inc. Low profile valve locking mechanism and commissure assembly
US20180086634A1 (en) * 2015-05-14 2018-03-29 Shell Oil Company Process for preparing a syngas and syngas cooling device
DE102015210801A1 (en) 2015-06-12 2016-12-15 Thyssenkrupp Ag Multi-pressure process for the production of ammonia without enrichment of inert gas
US10082332B2 (en) 2015-10-29 2018-09-25 Praxair Technology, Inc. System and method for argon recovery from the tail gas of an ammonia production plant
WO2017123434A1 (en) 2016-01-11 2017-07-20 Praxair Technology, Inc. System and method for rare gas recovery
DE102016105127A1 (en) 2016-03-18 2017-09-21 Thyssenkrupp Ag Method and apparatus for treating a gas mixture
US10309720B2 (en) 2016-03-21 2019-06-04 Praxair Technology, Inc. System and method for argon recovery from a feed stream comprising hydrogen, methane, nitrogen and argon
US10072890B2 (en) 2016-03-21 2018-09-11 Praxair Technology, Inc. System and method for enhanced argon recovery from a feed stream comprising hydrogen, methane, nitrogen and argon
US10088229B2 (en) 2016-09-21 2018-10-02 Praxair Technology, Inc. System and method for cryogenic purification of a feed stream comprising hydrogen, methane, nitrogen and argon
US10024595B2 (en) 2016-09-21 2018-07-17 Praxair Technology, Inc. System and method for cryogenic purification of a feed stream comprising hydrogen, methane, nitrogen and argon
US10295251B2 (en) 2016-09-21 2019-05-21 Praxair Technology, Inc. System and method for cryogenic purification of a feed stream comprising hydrogen, methane, nitrogen and argon
US10870810B2 (en) 2017-07-20 2020-12-22 Proteum Energy, Llc Method and system for converting associated gas
DE102018210921A1 (en) 2018-07-03 2019-08-14 Thyssenkrupp Ag Prevention of VOC and HAP emissions from the degasser of synthesis gas processing plants
CN112179046B (en) * 2020-10-13 2022-09-06 丁玉龙 Liquid air energy storage and ammonia synthesis integrated device and method

Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3442613A (en) * 1965-10-22 1969-05-06 Braun & Co C F Hydrocarbon reforming for production of a synthesis gas from which ammonia can be prepared
US3549335A (en) * 1965-10-22 1970-12-22 Braun & Co C F Autothermal reactor
US3572046A (en) * 1965-10-22 1971-03-23 Braun & Co C F Apparatus for purification of raw ammonia synthesis gas
US4296085A (en) * 1980-01-07 1981-10-20 Banquy David L Process for the production of ammonia and the corresponding synthesis gas
US4334902A (en) * 1979-12-12 1982-06-15 Compagnie Francaise D'etudes Et De Construction "Technip" Method of and system for refrigerating a fluid to be cooled down to a low temperature
US4549890A (en) * 1982-12-23 1985-10-29 Air Products And Chemicals, Inc. Process and plant for removing methane and argon from crude ammonia synthesis gas
US4568530A (en) * 1984-10-16 1986-02-04 The M. W. Kellogg Company Ammonia synthesis
US4613492A (en) * 1982-09-01 1986-09-23 Humphreys & Glasgow, Ltd. Production of synthesis gas
US4681745A (en) * 1982-04-14 1987-07-21 Imperial Chemical Industries Plc Ammonia production process
US5180570A (en) * 1992-01-23 1993-01-19 Lee Jing M Integrated process for making methanol and ammonia
US5935544A (en) * 1996-06-06 1999-08-10 Brown & Root, Inc. Moderate excess nitrogen Braun Purifier™ process and method for retrofitting non-Braun Purifier™ ammonia plants
US6178774B1 (en) * 1998-02-20 2001-01-30 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and plant for the combined production of an ammonia synthesis mixture and carbon monoxide
US20020102200A1 (en) * 2000-04-10 2002-08-01 Jungerhans Robert Rudolf Josef Purification of gases, in synthesis gas production process

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB1156003A (en) * 1965-10-22 1969-06-25 Braun & Co C F Ammonia Synthesis Gas Purification Process and Apparatus.
US3422613A (en) * 1967-05-08 1969-01-21 Turbo Machine Co Yarn assembly apparatus for false twisting yarn
US4970867A (en) * 1989-08-21 1990-11-20 Air Products And Chemicals, Inc. Liquefaction of natural gas using process-loaded expanders
JPH06159931A (en) * 1992-11-27 1994-06-07 Kobe Steel Ltd Synthesis gas refining apparatus

Patent Citations (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3549335A (en) * 1965-10-22 1970-12-22 Braun & Co C F Autothermal reactor
US3572046A (en) * 1965-10-22 1971-03-23 Braun & Co C F Apparatus for purification of raw ammonia synthesis gas
US3442613A (en) * 1965-10-22 1969-05-06 Braun & Co C F Hydrocarbon reforming for production of a synthesis gas from which ammonia can be prepared
US4334902A (en) * 1979-12-12 1982-06-15 Compagnie Francaise D'etudes Et De Construction "Technip" Method of and system for refrigerating a fluid to be cooled down to a low temperature
US4296085A (en) * 1980-01-07 1981-10-20 Banquy David L Process for the production of ammonia and the corresponding synthesis gas
US4681745A (en) * 1982-04-14 1987-07-21 Imperial Chemical Industries Plc Ammonia production process
US4613492A (en) * 1982-09-01 1986-09-23 Humphreys & Glasgow, Ltd. Production of synthesis gas
US4549890A (en) * 1982-12-23 1985-10-29 Air Products And Chemicals, Inc. Process and plant for removing methane and argon from crude ammonia synthesis gas
US4568530A (en) * 1984-10-16 1986-02-04 The M. W. Kellogg Company Ammonia synthesis
US5180570A (en) * 1992-01-23 1993-01-19 Lee Jing M Integrated process for making methanol and ammonia
US5935544A (en) * 1996-06-06 1999-08-10 Brown & Root, Inc. Moderate excess nitrogen Braun Purifier™ process and method for retrofitting non-Braun Purifier™ ammonia plants
US6178774B1 (en) * 1998-02-20 2001-01-30 L'air Liquide, Societe Anonyme Pour L'etude Et L'exploitation Des Procedes Georges Claude Process and plant for the combined production of an ammonia synthesis mixture and carbon monoxide
US20020102200A1 (en) * 2000-04-10 2002-08-01 Jungerhans Robert Rudolf Josef Purification of gases, in synthesis gas production process

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20120308466A1 (en) * 2007-08-08 2012-12-06 Ammonia Casale S.A. Process for Producing Ammonia Synthesis Gas
US20150086465A1 (en) * 2007-08-08 2015-03-26 Casale Sa Process for Producing Ammonia Synthesis Gas
US10464818B2 (en) 2007-08-08 2019-11-05 Casale Sa Process for producing ammonia synthesis gas
US20100051876A1 (en) * 2008-08-28 2010-03-04 Ammonia Casale S.A. Process for the production of ammonia synthesis gas with improved cryogenic purification
US20100300144A1 (en) * 2009-04-24 2010-12-02 Madison Joel V Liquefied Gas Expander And Integrated Joule-Thomson Valve
US8683824B2 (en) * 2009-04-24 2014-04-01 Ebara International Corporation Liquefied gas expander and integrated Joule-Thomson valve
US9335092B2 (en) 2009-04-24 2016-05-10 Ebara International Corporation Method of gas expansion using liquefied gas expander and integrated Joule-Thomson valve
US9593882B2 (en) 2009-04-24 2017-03-14 Ebara International Corporation Three-way integrated Joule-Thomson valve and liquefied gas expander
WO2014207011A1 (en) * 2013-06-26 2014-12-31 Casale Sa A process for purification of a synthesis gas containing hydrogen and impurities
EP2818447A1 (en) * 2013-06-26 2014-12-31 Ammonia Casale S.A. A process for purification of a synthesis gas containing hydrogen and impurities
US10816264B2 (en) 2013-06-26 2020-10-27 Casale Sa Process for purification of a synthesis gas containing hydrogen and impurities
CN109612203A (en) * 2018-11-22 2019-04-12 山东润银生物化工股份有限公司 A kind of processing method of discharge gas in ammonia synthesis

Also Published As

Publication number Publication date
EP1503160A1 (en) 2005-02-02
RU2004121999A (en) 2006-01-20
CN100519406C (en) 2009-07-29
RU2331575C2 (en) 2008-08-20
CA2473045A1 (en) 2005-01-17
CA2473045C (en) 2011-09-27
DE602004016796D1 (en) 2008-11-13
CN1597496A (en) 2005-03-23
EP1503160B1 (en) 2008-10-01
MXPA04006957A (en) 2005-06-17
US7090816B2 (en) 2006-08-15
US20050013768A1 (en) 2005-01-20

Similar Documents

Publication Publication Date Title
US7090816B2 (en) Low-delta P purifier for nitrogen, methane, and argon removal from syngas
US5736116A (en) Ammonia production with enriched air reforming and nitrogen injection into the synthesis loop
US10040691B2 (en) Hydrogen and nitrogen recovery from ammonia purge gas
US8247463B2 (en) Method of coproducing methanol and ammonia
US8591770B2 (en) Process for the production of syngas for ammonia synthesis
KR102217256B1 (en) Method and apparatus for producing carbon monoxide
US20120213676A1 (en) Process for the Production of Ammonia Synthesis Gas With Improved Cryogenic Purification
RU2519940C2 (en) Methanol synthesis method
EP2473440B1 (en) Production of ammonia make-up syngas with cryogenic purification
US5935544A (en) Moderate excess nitrogen Braun Purifier™ process and method for retrofitting non-Braun Purifier™ ammonia plants
US20220274050A1 (en) Method for treating gas by adsorption using thermally optimised hot flash solvent regeneration
MXPA02008603A (en) Ammonia synthesis process and apparatus for use therein.
AU2016338144B2 (en) Process for making a synthesis gas by reforming of a hydrocarbon and including recovery of carbon dioxide at high temperature
US3407146A (en) Process for the recovery of hydrogennitrogen mixtures with reduced carbon-monoxide content
JP4841591B2 (en) Nitrogen production method and apparatus
JP2006132854A (en) Nitrogen manufacturing method and device

Legal Events

Date Code Title Description
STCB Information on status: application discontinuation

Free format text: ABANDONED -- FAILURE TO RESPOND TO AN OFFICE ACTION