WO2012130450A1 - Procédé de purification d'un gaz brut - Google Patents

Procédé de purification d'un gaz brut Download PDF

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Publication number
WO2012130450A1
WO2012130450A1 PCT/EP2012/001376 EP2012001376W WO2012130450A1 WO 2012130450 A1 WO2012130450 A1 WO 2012130450A1 EP 2012001376 W EP2012001376 W EP 2012001376W WO 2012130450 A1 WO2012130450 A1 WO 2012130450A1
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Prior art keywords
gas
ammonia
purified
carbon
process gas
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PCT/EP2012/001376
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English (en)
Inventor
Højlund Erik Poul NIELSEN
Roberta Cenni
Christian Wix
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Haldor Topsøe A/S
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Publication date
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Priority to CN201280015751.XA priority Critical patent/CN103501877A/zh
Publication of WO2012130450A1 publication Critical patent/WO2012130450A1/fr
Priority to ZA2013/06688A priority patent/ZA201306688B/en

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • 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
    • 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
    • C01B3/50—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification
    • C01B3/56—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids
    • C01B3/58—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction
    • C01B3/586—Separation of hydrogen or hydrogen containing gases from gaseous mixtures, e.g. purification by contacting with solids; Regeneration of used solids including a catalytic reaction the reaction being a methanation reaction
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01C—AMMONIA; CYANOGEN; COMPOUNDS THEREOF
    • C01C1/00—Ammonia; Compounds thereof
    • C01C1/02—Preparation, purification or separation of ammonia
    • C01C1/04—Preparation of ammonia by synthesis in the gas phase
    • C01C1/0405—Preparation of ammonia by synthesis in the gas phase from N2 and H2 in presence of a catalyst
    • C01C1/0488—Processes integrated with preparations of other compounds, e.g. methanol, urea or with processes for power generation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2/00—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon
    • C10G2/30—Production of liquid hydrocarbon mixtures of undefined composition from oxides of carbon from carbon monoxide with hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/002—Removal of contaminants
    • C10K1/003—Removal of contaminants of acid contaminants, e.g. acid gas removal
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K1/00—Purifying combustible gases containing carbon monoxide
    • C10K1/08—Purifying combustible gases containing carbon monoxide by washing with liquids; Reviving the used wash liquors
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/04—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment reducing the carbon monoxide content, e.g. water-gas shift [WGS]
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/06—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by mixing with gases
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/08—Production of synthetic natural gas
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L3/00—Gaseous fuels; Natural gas; Synthetic natural gas obtained by processes not covered by subclass C10G, C10K; Liquefied petroleum gas
    • C10L3/06—Natural gas; Synthetic natural gas obtained by processes not covered by C10G, C10K3/02 or C10K3/04
    • C10L3/10—Working-up natural gas or synthetic natural gas
    • C10L3/101—Removal of contaminants
    • C10L3/102—Removal of contaminants of acid contaminants
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2256/00—Main component in the product gas stream after treatment
    • B01D2256/24—Hydrocarbons
    • B01D2256/245—Methane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/10—Single element gases other than halogens
    • B01D2257/102—Nitrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D2257/00—Components to be removed
    • B01D2257/50—Carbon oxides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
    • B01D53/34—Chemical or biological purification of waste gases
    • B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
    • B01D53/75—Multi-step processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1022—Fischer-Tropsch products
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P20/00—Technologies relating to chemical industry
    • Y02P20/50—Improvements relating to the production of bulk chemicals
    • Y02P20/582—Recycling of unreacted starting or intermediate materials
    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention is directed to purification of raw gas.
  • the invention concerns removal of ni- trogen from the raw gas .
  • Industrial raw gasses arise typically from carbonaceous raw materials such as gasification of coal, oil petroleum coke, biomass and the like, as a reformed hydrocarbon feed or as coke oven gas.
  • raw gas shall comprise any gas containing hydrogen, at least one carbon oxide and nitrogen .
  • such a raw gas is obtained by the above mentioned gasification process or as off-gas from the production of coke, the so called coke oven gas.
  • These gases contain hydrogen, which inter alia is a valuable reactant for use as alternative fuel or for use in the preparation of a number of bulk chemicals and of liquid or gaseous fuels .
  • a gasification raw gas and coke oven gas may be employed in the preparation of substitute natural gas (SNG) .
  • SNG must have a high content of methane and residual amounts of impurities arising during preparation of SNG must be low if a high calorific value of SNG is required, when using SNG as replacement of natural gas.
  • a raw gas may also be converted into a liquid fuel, such as gasoline or diesel by the Fischer Tropsch or an oxygenate to gasoline process.
  • a gas stream may be recycled to recover reactants, possibly with reforming of undesired hydrocarbons such as methane into carbon monoxide.
  • a purge gas is withdrawn.
  • One such undesired component is inert nitrogen, and therefore specific removal of nitrogen is beneficial as it may reduce the purge stream, which remove raw material from the process .
  • nitrogen is still a component of coal, biomass, pet coke and other feedstocks being employed in the gasification process and will thus be released from the feedstock and transferred to the raw gas produced by gasification .
  • Carbon dioxide and optionally hydrogen sulphide, if present in the raw gas may be removed by means of a conventional acid gas removal process, wherein the gas is treated with a physical carbon dioxide and hydrogen sulphide sorbent, like the known "Rectisol” or “Selexol” process or a chemical sorbent such as the known amine wash.
  • a physical carbon dioxide and hydrogen sulphide sorbent like the known "Rectisol" or "Selexol” process or a chemical sorbent such as the known amine wash.
  • cryogenic processes in which the gas is cooled below the boiling point of nitrogen. Cryogenic processes are expensive to establish and to operate.
  • the present disclosure provides a method for the reduction of undesired impurities from a raw gas, including nitrogen, by conversion of nitrogen to ammonia, which is more convenient to remove from the raw gas compared to the known methods and which at the same time may be used as feed-stock for the production of valuable chemicals, e.g. ammonium thiosulphate or urea.
  • the methanated process gas having little or no presence of carbon oxides then enters into the commonly known ammonia conversion reaction, and the produced ammonia may be separated as a liquid from the purified gas stream.
  • Ammonia in its liquid form shall herein be understood as either con- densed ammonia or ammonia dissolved in water.
  • the invention is in its broadest embodiment a process for converting a carbonaceous raw material to a liquid or gaseous carbon based fuel, comprising the steps of
  • step b) withdrawing a process gas to be purified comprising hydrogen, a carbon oxide, such as carbon monoxide or carbon dioxide and nitrogen, from a position of the process of step a)
  • step f) directing an amount of the purified gas to a position of the process of step a) ,
  • the molar flow of carbon in the carbon based fuel is greater than the molar flow of the ammonia withdrawn.
  • the molar flow of carbon in the carbon based fuel is at least two times greater than the molar flow of the ammonia withdrawn, with the associated benefit of an increased yield of fuel.
  • the process gas to be purified is a Fischer-Tropsch (FT) tail gas and the purified gas is recycled either as a feed to FT synthesis or as a feed to partial oxidation or a reforming step upstream the FT synthesis.
  • FT Fischer-Tropsch
  • the Fischer-Tropsch conversion is well known by the skilled person, and may be conducted in the presence of a catalyst such as a group VIII metal, preferably Fe, Co, Ru and Ni, or Mo as it is commonly known.
  • the process gas to be purified is withdrawn from a synthesis loop for synthesis of methanol or for synthesis of gasoline from an oxygenate and the purified gas is recycled as a feed to partial oxidation or as a feed to a reforming step upstream said synthesis loop.
  • the synthesis of methanol is well known by the skilled person, and may be conducted in the presence of a catalyst such as Cu, as it is commonly known.
  • a specific embodiment, for production of synthetic natural gas comprises the following sub-steps;
  • the synthesis of synthetic natural gas is well known by the skilled person, and may be conducted in the presence of a catalyst such as a group VIII metal, preferably Ni or Ru, as it is commonly known.
  • a catalyst such as a group VIII metal, preferably Ni or Ru, as it is commonly known.
  • Nitrogen is converted to ammonia by catalytic reaction with hydrogen further contained in the raw gas by means of the known catalytic ammonia conversion process.
  • the ammonia con- version reaction may be carried out in a once-through operation or in an ammonia synthesis loop.
  • the synthesis of ammonia is well known by the skilled person, and may be conducted in the presence of a catalyst such as a Fe or Ru, as it is commonly known.
  • this loop comprises the steps of
  • step a) separating the ammonia containing process gas into liquid phase ammonia and the purified gas iii) directing a further amount of the purified gas to the process of step a) wherein the methanated process gas to be purified is added to a position of the ammonia synthesis loop, such as immediately upstream or immediately down- stream the catalytic material. It may be beneficial to add the methanated gas, which contains water, upstream the position for withdrawal of ammonia, as the presence of even small amounts of water aids the removal.
  • Synthesizing ammonia in a synthesis loop has the benefit of increasing the yield of ammonia, and of being able to combine the methanated process gas with the ammonia containing process gas, such that water in the methanated process gas may removed with the ammonia.
  • Produced ammonia is in an embodiment removed from the raw gas by conventional condensation or conventional aqueous ammonia wash, which has the benefit of being a cost effective process for collection of ammonia.
  • the methanated process gas may subsequently be dried by e.g. cooling and separation of condensed water and/or by contact with molecular sieves being able to remove water molecules from a gas stream.
  • molecular sieves are known in the art and conventionally employed in the drying of moist gases .
  • a part of the carbon monoxide in the raw gas is converted by reaction with water, forming hydrogen and carbon dioxide according to the water gas shift reaction and thereby the concentration of hydrogen in the gas is increased and the carbon monoxide content is decreased, with the benefit of producing a raw gas with a more optimal balance between hydrogen and carbon oxides prior to
  • the carbon monoxide content will be further reduced in the subsequent methanation step, as mentioned hereinbefore.
  • a step of acid gas removal is required for removing carbon dioxide, to avoid consumption of the produced hydrogen during methanation, by reaction with carbon dioxide.
  • the treatment of the gas in an acid gas removal step whereby the amount of carbon dioxide and hydrogen sulphide, if further present in the raw gas, are reduced by chemical or physical absorption or adsorption ac- cording to known methods as already mentioned above.
  • This has the effect of providing the possibility of using catalysts which are more effective, but subject to poisoning by the presence of carbon dioxide and sulphur.
  • a methanation step prior to acid gas removal may be included, for converting carbon oxides to methane, which will not be withdrawn in the acid gas removal step. This has the associated benefit of providing a higher level of carbon in the purified gas.
  • SNG is produced by catalytic methanation of carbon oxides with hydrogen.
  • carbon oxides are converted to methane during purification of the process gas to be purified.
  • the ratio (H 2 - C0 2 ) / (CO+C0 2 ) in the feed may optionally be around 3, where H 2 , CO, and C0 2 represents the molar flow of the given components .
  • hydrogen sulphide which also may be present in the raw gas is also adsorbed in the chemical or physical wash.
  • Spent washing solution may be regenerated by desorbing carbon dioxide and hydrogen sulphide.
  • a part of the desorbed carbon dioxide can be recycled to the purified raw gas for use in the synthesis of carbon based fuel, with the benefit of increasing the fuel yield.
  • a part of the desorbed carbon dioxide can also be used in the synthesis of urea from ammonia, with the benefit of urea being a more valuable product than ammonia.
  • Desorbed hydrogen sulphide may be utilized for the preparation of ammonium thiosulphate by reaction with ammonia being obtained in the purification of the raw gas as e.g. de- scribed in European patent no.1 375 422.
  • the method of the invention is also useful to reduce the nitrogen concentration in recycle streams, thus affording a reduction of the recycle and, possibly, of the volume to purge, particularly for processes in which the additional amount of methane being formed in the methanation step is beneficial or can be converted downstream e.g. in a reform- ing process, such as autothermal reforming or steam reforming.
  • a reform- ing process such as autothermal reforming or steam reforming.
  • Fig.l represents an embodiment in which a carbonaceous raw material is converted to a liquid fuel, employing the disclosed purification process.
  • Fig.2 represents an embodiment in which a carbonaceous raw material is converted to synthethic natural gas, employing the disclosed purification process.
  • Figure 1 shows a specific embodiment of the invention, in which a carbonaceous raw material is provided to a process for synthesis of a liquid fuel 104 as a raw gas 100.
  • the raw gas containing nitrogen 100 is converted into a fuel 104 such as methanol, gasoline, diesel and naphtha by a catalytical reaction in a reactor 102.
  • Hydrogen and carbon monoxide are consumed during the production of fuels creating a stream of process gas to be purified which is rich in nitrogen.
  • the process gas to be purified 106 may be directed to a water-gas shift stage 108, if it is required to convert CO into hydrogen to ensure a surplus of hydrogen after CO and C0 2 are converted into methane in the methanation step 116 according to the following reactions:
  • a reasonable surplus of hydrogen shall also ensure a partial conversion of nitrogen into ammonia in a downstream ammonia synthesis 118.
  • the optimum molar flow of molecular hydrogen into the downstream methanation reactor 116 may be calculated as follow: H 2 > 3*CO + 4*C0 2 + 3*N 2 , where H 2 , CO, C0 2 , N 2 represents the molar flow of the given components.
  • Water may be removed from the shifted gas by conventional methods, including cooling down shifted gas to about 40°C in a condenser 110 and then separating the condensed water.
  • the C0 2 content is adjusted according to the equation above to ensure a surplus of hydrogen into the methanation reactor, by removal of excess C0 2 114 in an acid gas wash 112.
  • the partly purified process gas is sent to the methanation step 116 to convert CO and C0 2 into methane, as these two components are poisons to ammonia catalyst.
  • a methanated process gas comprising hydrogen, nitrogen and methane is sent to an ammonia synthesis loop 118 to at least partly convert nitrogen into ammonia which may be separated from the stream of ammonia containing gas, in a condenser operating around -5°C, forming a purified gas stream with a reduced concentration of nitrogen, and a liq- uid stream of ammonia 119.
  • An additional aqueous ammonia wash 120 may be used to remove remaining ammonia 122.
  • the purified gas stream is then reformed in 124 to convert methane into synthesis gas, i.e. CO and H 2 , creating a reformed purified gas for the fuel synthesis in 102.
  • a build up of other impurities such as Ar in the synthesis gas is avoided by a purge stream.
  • the C0 2 concentration is too high in the reformed purified gas then it can be removed by means of a acid gas removal unit 126.
  • Figure 2 shows an alternative embodiment of the invention, in which a carbonaceous raw material is provided to a process for production of synthethic natural gas 204 as a raw gas 200, containing nitrogen.
  • a first part of the raw synthesis gas is sent to a water- gas shift stage 202, in order to convert CO and water into hydrogen and C0 2 to ensure a surplus of hydrogen when CO and C0 2 are converted into methane at a later stage accord- ing to the following reactions:
  • Water is removed from the shifted gas in a condenser 210 by cooling down shifted gas to about 40°C and followed by separation the condensed water.
  • the C0 2 content is adjusted according to the equation above to ensure a surplus hydrogen into the methanation reactor, by removal of excess C0 2 214 in an acid gas wash 212.
  • the partly purified process gas to be purified is sent to the methanation step 216 to convert CO and C0 2 into methane, as these two components are poisons to ammonia cata- lyst.
  • a methanated process gas comprising hydrogen, nitrogen and methane is sent to an ammonia synthesis loop 218 to partly convert nitrogen into ammonia which may be separated in ara- monia wash 220 on from the gas stream forming a purified gas stream having a reduced concentration of nitrogen, and a stream of ammonia 222.
  • the part of the synthesis gas which was not directed to wa- ter-gas shift is treated in an Acid Gas Removal stage 226 to remove sour gasses, such as H 2 S and C0 2 forming a treated synthesis gas.
  • This treated synthesis gas stream is then combined with the purified gas stream to form a feed gas for a SNG synthesis unit 230, wherein (H 2 -C0 2 ) / (C0 2 +CO) ⁇ 3.
  • Fischer Tropsch process a process gas to be purified with a content of 24% N 2 was purified according to an embodiment of the present disclosure, according to Figure 1.
  • the gas compositions in the process will be as shown in table 1.
  • the composition of the gas to be purified from was similar, but the requirements to CO content in the purified gas was higher. Therefore a further example

Abstract

Le procédé ci-décrit qui permet de convertir une matière première carbonée en combustible liquide ou gazeux à base de carbone comprend les étapes consistant à : a) convertir ladite matière première carbonée en combustible à base de carbone; b) soutirer un gaz de procédé à purifier comprenant de l'hydrogène, de l'oxyde de carbone, tel que du monoxyde de carbone ou du dioxyde de carbone et de l'azote, d'une position du procédé de l'étape a; c) soumettre le gaz de procédé à purifier à une réaction de méthanisation pour convertir l'oxyde de carbone contenu dans le gaz de procédé à purifier en méthane et obtenir un gaz de procédé méthanisé; d) diriger le gaz de procédé méthanisé soit vers un procédé de synthèse d'ammoniac unique, soit vers une boucle de synthèse d'ammoniac pour convertir l'azote contenu dans le gaz en ammoniac et obtenir un gaz de procédé contenant de l'ammoniac; e) soutirer l'ammoniac en phase liquide du gaz de procédé contenant de l'ammoniac à purifier de l'étape d) pour obtenir un gaz purifié ayant une teneur réduite en azote; et f) diriger une certaine quantité du gaz purifié vers une position du procédé de l'étape a), le flux molaire de carbone dans le combustible à base de carbone étant supérieur au flux molaire de l'ammoniac soutiré.
PCT/EP2012/001376 2011-03-29 2012-03-29 Procédé de purification d'un gaz brut WO2012130450A1 (fr)

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ZA2013/06688A ZA201306688B (en) 2011-03-29 2013-09-05 Method for the purification of raw gas

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CN113891858A (zh) * 2019-03-22 2022-01-04 顺冠投资有限公司 产生氨和尿素的催化气化

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CN113249147A (zh) * 2021-06-30 2021-08-13 杨皓 一种焦炉煤气联产lng与合成氨的改进工艺

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