WO2002048027A1 - Process and apparatus for the production of ammonia - Google Patents
Process and apparatus for the production of ammonia Download PDFInfo
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- WO2002048027A1 WO2002048027A1 PCT/NL2001/000898 NL0100898W WO0248027A1 WO 2002048027 A1 WO2002048027 A1 WO 2002048027A1 NL 0100898 W NL0100898 W NL 0100898W WO 0248027 A1 WO0248027 A1 WO 0248027A1
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- stream
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- reformer
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- hydrocarbon
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- 238000000034 method Methods 0.000 title claims abstract description 108
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 230000005611 electricity Effects 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims description 86
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 69
- 229930195733 hydrocarbon Natural products 0.000 claims description 48
- 150000002430 hydrocarbons Chemical class 0.000 claims description 48
- 239000004215 Carbon black (E152) Substances 0.000 claims description 45
- 238000003786 synthesis reaction Methods 0.000 claims description 33
- 230000015572 biosynthetic process Effects 0.000 claims description 31
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 238000009434 installation Methods 0.000 claims description 26
- 238000002407 reforming Methods 0.000 claims description 26
- 239000003345 natural gas Substances 0.000 claims description 17
- 239000000567 combustion gas Substances 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 9
- 238000002485 combustion reaction Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 239000001301 oxygen Substances 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 238000009738 saturating Methods 0.000 claims description 9
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical class [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 8
- 229910002090 carbon oxide Inorganic materials 0.000 claims description 7
- 229920006395 saturated elastomer Polymers 0.000 claims description 6
- 239000000446 fuel Substances 0.000 claims description 4
- 238000002360 preparation method Methods 0.000 claims description 3
- 230000003247 decreasing effect Effects 0.000 abstract description 3
- 238000000605 extraction Methods 0.000 abstract description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 32
- 229910002092 carbon dioxide Inorganic materials 0.000 description 31
- 238000001816 cooling Methods 0.000 description 8
- 239000002918 waste heat Substances 0.000 description 8
- 239000003054 catalyst Substances 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 5
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 230000006835 compression Effects 0.000 description 4
- 238000007906 compression Methods 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 3
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 239000005864 Sulphur Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 230000002745 absorbent Effects 0.000 description 2
- 239000002250 absorbent Substances 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 description 2
- 238000011144 upstream manufacturing Methods 0.000 description 2
- WZRJTRPJURQBRM-UHFFFAOYSA-N 4-amino-n-(5-methyl-1,2-oxazol-3-yl)benzenesulfonamide;5-[(3,4,5-trimethoxyphenyl)methyl]pyrimidine-2,4-diamine Chemical compound O1C(C)=CC(NS(=O)(=O)C=2C=CC(N)=CC=2)=N1.COC1=C(OC)C(OC)=CC(CC=2C(=NC(N)=NC=2)N)=C1 WZRJTRPJURQBRM-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000498 cooling water Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003546 flue gas Substances 0.000 description 1
- 239000002737 fuel gas Substances 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 238000000629 steam reforming Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Classifications
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- 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
-
- C—CHEMISTRY; METALLURGY
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/025—Preparation or purification of gas mixtures for ammonia synthesis
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- C—CHEMISTRY; METALLURGY
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- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/38—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents using catalysts
- C01B3/382—Multi-step processes
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- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/34—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents
- C01B3/48—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air by reaction of hydrocarbons with gasifying agents followed by reaction of water vapour with carbon monoxide
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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0244—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being an autothermal reforming step, e.g. secondary reforming processes
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- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0283—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step
- C01B2203/0294—Processes for making hydrogen or synthesis gas containing a CO-shift step, i.e. a water gas shift step containing three or more CO-shift steps
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- C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
- C01B2203/0465—Composition of the impurity
- C01B2203/0475—Composition of the impurity the impurity being carbon dioxide
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- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0833—Heating by indirect heat exchange with hot fluids, other than combustion gases, product gases or non-combustive exothermic reaction product gases
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- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
- C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
- C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
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- C01B2203/08—Methods of heating or cooling
- C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
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- C01B2203/08—Methods of heating or cooling
- C01B2203/0872—Methods of cooling
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1047—Group VIII metal catalysts
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- C01B2203/12—Feeding the process for making hydrogen or synthesis gas
- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
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- C01B2203/1205—Composition of the feed
- C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
- C01B2203/1235—Hydrocarbons
- C01B2203/1241—Natural gas or methane
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- C01B2203/1264—Catalytic pre-treatment of the feed
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- C01B2203/14—Details of the flowsheet
- C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
- C01B2203/143—Three or more reforming, decomposition or partial oxidation steps in series
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- C01B2203/146—At least two purification steps in series
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- C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
- C01B2203/82—Several process steps of C01B2203/02 - C01B2203/08 integrated into a single apparatus
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- 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
- Y02P20/10—Process efficiency
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- 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
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- 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
Definitions
- the invention relates to a novel production process for ammonia that is highly integrated as far as heat balance is concerned.
- the techniques used are also suitable for improving existing plants for ammonia production.
- the invention leads to a more energy efficient process per tonne of ammonia produced that is also able to provide its own electricity requirement or is able to export electrical energy.
- ammonia synthesis gas is produced by bringing a normal hydrocarbon feed and steam into an endothermic, catalytic conversion zone operating under primary reformer conditions (primary reformer), by which means a primary reformed gas stream is produced that is brought with air into an adiabatic, catalytic conversion zone that is operating under autothermal steam reforming conditions, so that a crude, hot, ammonia synthesis gas is produced that is then fed to the endothermic catalytic conversion zone in indirect heat exchange with the hydrocarbon feed and steam in order to provide the heat for conversion in the endothermic zone.
- primary reformer primary reformer
- Air required for the operation of the adiabatic zone is supplied by a centrifugal compressor driven by a gas turbine.
- the exhaust from the gas turbine exchanges heat with the air for the secondary reformer and the heated compressed air, which is then introduced into the secondary reformer.
- WO 9748639 describes a synthesis gas production system that comprises a gas turbine and an autothermal reformer (ATR), wherein the autothermal reformer is positioned between the compressor and expander of the gas turbine and wherein the ATR produces synthesis gas and can serve as the burner for the gas turbine.
- ATR autothermal reformer
- US 4 792 441 describes ammonia synthesis in which a small proportion of the methane stream flows to the primary reformer and a major proportion of the methane stream goes to the secondary reformer. This document further describes the saturation of natural gas with steam (Figure 1). Air enriched with oxygen is used for the secondary reformer.
- the energy saving indicated above is achieved in accordance with three aspects of the invention.
- the first aspect relates to the use of a gas turbine with extraction of process air, with electricity generation coupled thereto.
- the residual heat from the gas turbine is in the first instance returned to the process.
- the second aspect relates to a reformer section, which comprises an (optional) prereformer, a primary reformer and a secondary reformer.
- An additional energy saving is achieved by heat exchange in the primary reformer between the discharge stream from the secondary reformer and the stream from the prereformer.
- the third aspect of the invention relates to carrying out the conventional CO shift conversion in three steps at successively decreasing temperature instead of the conventional two steps.
- the invention relates in particular to a combination of the abovementioned three aspects, which leads to maximum energy saving.
- the present invention now provides, according to a first aspect, a method for the preparation of ammonia, which method comprises the following steps: a) a reforming step, in which a hydrocarbon stream, a process air stream and steam are reacted to obtain a discharge stream which contains CO, CO 2 , H 2 and N 2 ; b) a CO conversion step, in which CO in the discharge stream from step a) is converted to CO 2 and H 2 ; c) a CO 2 removal step, in which CO 2 is removed from the stream obtained in step b); and d) a methanisation step, in which the residual CO and CO 2 are converted to CH 4 and H 2 O; in such a way that a synthesis gas that contains N 2 and H 2 , suitable for the production of ammonia, is obtained, after which the synthesis gas is converted to ammonia in a synthesis cycle, characterised in that at least a portion of the process air stream that is reacted in the reforming step is compressed with the aid of a compressor which is part of
- a gas turbine is installed that is partly driven by residual gases from the process.
- a generator that generates electricity is coupled to the gas turbine.
- the discharge gases from the gas turbine can advantageously be used to heat process streams and to generate steam.
- a suitable heat exchanger in particular a waste heat boiler, can be used for this purpose.
- the hydrocarbon stream can comprise LPG, naphtha or natural gas, but in general will be natural gas. If necessary, sulphur can be removed from the hydrocarbon stream, since sulphur, present in natural gas, would poison the catalysts used. This is carried out, for example, in two steps. In the first step organically bound sulphur is reacted with hydrogen over a CoMoX or CuMoX catalyst to give hydrogen sulphide (H 2 S). In the second step H 2 S is removed by binding to ZnO. The feed for the desulphurisation is first preheated by the discharge stream from the gas turbine to a temperature of 300 - 350 °C. The gas finally leaves the desulphurisation section at a temperature of approximately 150 °C.
- the gas stream is now, in particular, first fed through a column and saturated with water vapour.
- Process condensate is preferably used for this purpose.
- the quantity of water to be discharged or the quantity of process condensate to be stripped off is reduced by this means.
- the requirement for process steam is also reduced by the same step.
- medium-pressure steam is produced in this way, whilst this process step is in a temperature range in which normally only low-pressure steam could be generated.
- An installation is also provided for carrying out the method according to the first aspect of the invention, which installation comprises: a) a reformer section for reacting a hydrocarbon stream, a process air stream and steam; b) a CO conversion section connected via pipework to the reformer section, for converting CO present in a discharge stream from the reformer section into CO 2 and H 2 ; c) a CO 2 removal section connected via pipework to the CO conversion section, ⁇ for removal of CO 2 from a discharge stream from the CO conversion section; d) a methanisation section, connected via pipework to the CO 2 removal section, for converting the residual CO and CO 2 into CH 4 and H 2 O; characterised in that the installation is also provided with e) a gas turbine, comprising a compressor provided with a feed for air and a discharge for compressed air; a combustion chamber provided with an inlet for fuel, an inlet for compressed air connected via pipework to the discharge for compressed air from the compressor and an outlet for combustion gas; an expansion turbine provided with an inlet for combustion gas connected via pipe
- the compressor and expansion turbine in this installation are coupled via a shaft.
- the gas turbine is also coupled to a generator for generating electricity.
- a person skilled in the art can determine which type of gas turbine is suitable for the invention. Examples are standard gas turbines, where the requisite quantity of process air can be tapped off, or a "tailor-made" machine, made up of discrete elements with a compression ratio of 8 - 35 bar.
- the outlet for combustion gas from the expansion turbine is coupled via pipework to a heat exchanger suitable for heat exchange between the combustion gas and at least the process air stream and the hydrocarbon stream, in particular a waste heat boiler. Heat exchangers of this type are known to those skilled in the art.
- the present invention provides a method, in particular in combination with the first aspect of the invention, wherein the reaction of the hydrocarbon stream and process air stream in the reformer section takes place in the following successive steps: ai) a primary reforming step, in which a major proportion of the methane in the hydrocarbon stream is converted in the presence of steam to carbon oxides and hydrogen; aii) a secondary reforming step, in which the stream obtained in step ai) and the process air stream are converted to carbon oxides and hydrogen.
- the primary reforming step is preceded by aiii) a prereforming step in which higher hydrocarbons in the hydrocarbon stream are converted to methane and a portion of the methane is converted to carbon oxides and H 2 .
- aiii) higher hydrocarbons (such as ethane, propane, up to naphtha) are converted to methane and a portion of the methane is converted to carbon oxides and H 2
- higher hydrocarbons such as ethane, propane, up to naphtha
- This residual heat from the reformer section can be used to heat the incoming process gas before and/or after the prereforming step.
- Prereforming takes place in a catalyst bed at a temperature of 500 - 525 °C. As a result of the endothermic reaction, the gas temperature falls by approximately 50 °C.
- step ai which is either the first or the second step in the reformer section
- the stream obtained in step ai) is converted to carbon oxides and hydrogen at a temperature of 700 - 750 °C.
- the mixture is passed over a nickel catalyst in a tube reactor, in which the reaction takes place. Because the reaction is endothermic, the pipes are heated from the outside using natural gas combustion.
- the secondary reforming step aii) is then carried out. If the standard quantity of process air is used, the outlet temperature of 700 - 750 °C of the primary reformer is too low to achieve adequate conversion of methane in the secondary reformer, needed for the ammonia synthesis. Therefore, pre-heated, oxygen-enriched air is added in an autothermal reactor, known as a post-combustion chamber or secondary reformer, an exothermic reaction allowing the temperature to rise to approximately 1000 °C. The methane content falls to 0.3 - 0.5 % and at the same time nitrogen, which is needed for the ammonia synthesis, is added by means of the process air supplied.
- an autothermal reactor known as a post-combustion chamber or secondary reformer
- the secondary reformer and the catalyst used therein are the same as those used in the standard process.
- the reformer section comprises: ai) a primary reformer provided with a feed for hydrocarbon stream and provided with a discharge for reacted hydrocarbon stream; aii) a secondary reformer provided with a feed for reacted hydrocarbon stream coupled via pipework to the discharge from the primary reformer, a feed for process air stream and a discharge for reacted hydrocarbon stream.
- the reformer section also comprises aiii) a prereformer provided with a feed for the hydrocarbon stream and provided with a discharge for reacted hydrocarbon stream, which is coupled via pipework to the feed of the primary reformer.
- the CO content Downstream of the secondary reformer the CO content is approximately 13 %.
- the major proportion of the CO is converted to CO 2 and additional hydrogen by passing the gas mixture over two catalysts.
- the invention provides, in particular in combination with the first and/or second aspect of the invention, a method in which the CO conversion step b) is carried out in the following steps: bi) a high temperature step, in which the stream obtained in the reforming step is reacted at a temperature of 300 - 360 °C, a discharge stream being obtained; bii) a medium temperature step, in which the discharge stream from step bi) is reacted at a temperature of 200 - 250 °C, a discharge stream being obtained; biii) a low temperature step, in which the discharge stream from step bii) is reacted at a temperature of 190 - 200 °C.
- the equilibrium of the water gas shift reaction is less advantageous. This effect is reduced by carrying out the CO conversion not in two but in three steps. Residual heat is recovered after each step.
- the high temperature CO conversion takes place at a lower feed temperature (340 °C) than in the existing process (360 °C).
- the final step has an outlet temperature of 195 °C.
- the invention also provides an installation for carrying out the method according to the third aspect, which comprises a CO conversion section, comprising bi) a first conversion reactor operating at high temperature, provided with a feed coupled via pipework to the discharge for reacted hydrocarbon from the reformer section, and with a discharge; bii) a second conversion reactor operating at medium temperature, provided with a feed coupled via pipework to the discharge from the first conversion reactor, and with a discharge; biii) a third conversion reactor operating at low temperature, provided with a feed coupled via pipework to the discharge from the second conversion reactor, and with a discharge.
- a CO conversion section comprising bi) a first conversion reactor operating at high temperature, provided with a feed coupled via pipework to the discharge for reacted hydrocarbon from the reformer section, and with a discharge; bii) a second conversion reactor operating at medium temperature, provided with a feed coupled via pipework to the discharge from the first conversion reactor, and with a discharge; biii) a third conversion reactor operating at low temperature, provided with a feed coupled via pipe
- the installation is also provided with an installation for saturating the hydrocarbon stream with water, provided with a feed for the hydrocarbon stream, a discharge for the hydrocarbon stream saturated with water vapour, which discharge is coupled via pipework to the feed to the reformer section, and a feed and discharge for circulation water, wherein the feed and discharge for circulation water forms a cycle via pipework, wherein at least one heat exchanger is incorporated in the cycle equipped for heat exchange between the discharge lines from one or more of the conversion reactors and the water circulation cycle.
- a suitable absorbent This is, for example, an amine solution or an alkaline solvent based on K 2 CO 3 .
- the solution is regenerated by using some of the heat that is available in the gas after the CO conversion for the K 2 CO 3 process, supplemented by a quantity of low- pressure steam, available from back-pressure turbines, which are used to drive pumps and compressors, or by heat which is withdrawn from the top vapour stream from the process condensate stripper. At least 60 % of the energy costs for regeneration can be saved by selecting a suitable absorbent.
- CO 2 absorbent with which the minimum amount of regeneration energy is demanded.
- the CO 2 is preferably removed using aMDEA, but the use of Selexol is also a possibility.
- the CO and the residual CO 2 (100 to 1000 ppm) in the gas are reacted with H 2 to give CH 4 and H 2 O by passing the gas at a temperature of 300 °C over a nickel catalyst (methanisation).
- the reaction that applies here is the reverse of that in the first conversion of methane, but because of the low water content and the low temperature the CO and CO 2 are now converted to less than 1 ppm. Thus, some of the H 2 produced is lost again in this step.
- the crude synthesis gas has the correct H 2 :N 2 ratio of 3:1.
- the synthesis gas is now compressed to approximately 100 - 220 bar with the aid of a centrifugal compressor, in a number of stages with intermediate cooling.
- the final stage of the compressor is provided with a planet wheel for circulation of the gas through the synthesis cycle.
- the compressor is driven by a 100 - 220 bar steam turbine with possible 40 bar extraction and a (partial) condensation turbine.
- the residual water is removed from the synthesis gas with the aid of molecular sieves upstream of the first or upstream of the second stage of the compressor.
- the heat that is liberated during the process is used for generation of steam that can be used elsewhere in the process.
- the synthesis reaction takes place in two reactors with two beds in the first reactor.
- the conversion for each complete synthesis loop is increased, which leads to a smaller recirculation stream and less ammonia cooling.
- Figure 1 shows an installation according to the first aspect of the invention
- Figure 2 shows an installation according to the second aspect of the invention
- Figure 3 shows an installation according to the third aspect of the invention
- Figure 4 shows an example of a complete ammonia process in which the aspects of the invention have been integrated.
- Figure 1 shows the first aspect of the invention, a portion of the process air stream being compressed with the aid of the compressor 2, which forms part of the gas turbine 1.
- the air to be compressed is fed via 5 to the compressor 2 and a compressed air stream 7 leaves the compressor 2.
- a portion of this air stream is fed at ' 8 to the burner 4 of the gas turbine.
- Fuel is supplied to the burner via 18.
- the off-gases 9 from the burner are fed to the expansion turbine 3 of the gas turbine.
- the gases are fed to a heat exchanger (waste heat boiler) 11 to heat process streams and to generate steam.
- the gas turbine is furthermore provided with a shaft 6, by means of which the compressor 2 and the expander 3 are coupled. Moreover, a generator 17, by means of which electricity can be generated, is coupled to the gas turbine.
- the process air stream 7 that leaves the compressor is fed via an additional compressor 14 and line 15 via the waste heat boiler 11 to the reformer section 16. Additional oxygen is fed to the process air stream 7 at 13.
- the natural gas required in the reformer section is fed to the reformer section via 12, through the waste heat boiler 11 and the natural gas saturating unit 25 (shown diagrammatically).
- FIG. 2 shows the second aspect of the invention, that is to say the construction of the reformer section.
- a gas stream 40 which optionally has been desulphurised and saturated with water vapour and to which the requisite quantity of process steam has been added, enters the prereformer 41 and leaves this at 42. This stream then passes to the GHR 43 and leaves this at 45, in order then to be fed to the secondary reformer 46.
- a process air stream 15, which is enriched with oxygen, is fed to the secondary reformer.
- the outgoing stream from the secondary reformer 47 passes to the GHR 43, where heat exchange with the process stream 42 takes place. Finally, this stream leaves the GHR at 44 and, after heat recovery in 52, is then fed to the CO conversion section 49.
- Figure 3 shows the third aspect of the invention, that is to say the performance of the
- An air stream 15 is also fed to the reformer section 16.
- the stream issuing from the reformer section passes at 44 to a first CO conversion reactor 26 and leaves the latter at 33 and is then fed to CO conversion reactor 27 and leaves the latter at 34 and is then fed to CO conversion 28 and leaves the latter via 35 in order, after heat recovery in 53, then to be fed to the CO 2 removal section 36.
- the outgoing streams 33; 34 and 35 from the CO conversion reactors undergo heat exchange with the water stream 24 via heat exchangers 29, 30 and 31 , respectively.
- FIG. 4 An example of a complete ammonia process in which all three aspects of the invention are incorporated is shown in Figure 4.
- the gas turbine is indicated by 1.
- a process air stream 5 is fed to the compressor 2 of the gas turbine and leaves the latter via 7.
- a portion of this air stream passes via 8 to the combustion chamber 4 and leaves the latter via 9 in order then to be expanded in expander 3 in order to be fed via 10 to the waste heat boiler.
- Fuel is fed to the combustion chamber 4 of the gas turbine via 18.
- the compressed process air stream 7 passes via compressor 14 and via line 15, heat being exchanged in the waste heat boiler 11, to the secondary reformer 46.
- the hydrocarbon stream for example a natural gas stream, passes via 12 and the waste heat boiler 11 to the desulphurisation reactor 50. Following heat exchange with stream 12 in 100, the hydrocarbon stream is fed via line 20 to the saturating unit 25 and leaves the latter at 40 in order then to be fed to prereformer 41. Steam can be fed to the hydrocarbon stream 40 at 51 and heat exchange between the outgoing stream 44 from the GHR 43 takes place at 52.
- the outgoing stream 42 from the prereformer 41 is fed to the GHR at the top and, after reaction, leaves the latter via 45 in order to be fed to the secondary reformer 46. Heat is exchanged between the outgoing stream 47 from the secondary reformer 46 and the process stream 42 in the GHR. A stream 44 then issues from the GHR, which stream 44 is fed to the first CO conversion reactor 26. The outgoing stream 33 from the first CO conversion reactor 26 then passes to the second CO conversion reactor 27 and, via 34, to the third CO conversion reactor 28. Via heat exchangers 29, 30 and 31 heat is exchanged between the streams 33, 34 and 35 and the water stream 24 to the natural gas saturating unit 25.
- the stream 35 passes to the CO 2 removal installation 55, in which CO 2 is adsorbed on aMDEA (but Selexol is also a possibility).
- Gas stream 56 (free from CO 2 ) issues from the CO 2 absorption column, which stream is discharged via a liquid separator 57 as stream 58.
- the solvent stream 59 then issues from the CO 2 absorption column 55, which solvent stream 59 is fed to the stripper 60.
- the adsorbed CO 2 is removed from the solvent by means of heat.
- stream 67 is circulated over a heat exchanger 54. The requisite heat is supplied by stream 35.
- the CO 2 removed from the solvent is cooled in condenser 63. Condensate produced is separated off in liquid separator 64 and returned as stream 66 to the stripper.
- the CO 2 gas stream 65 issues from the liquid separator.
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Abstract
The invention relates to a novel production process for ammonia that is highly integrated as far as heat balance is concerned. According to a first aspect a gas turbine with extraction of process air, with electricity production coupled thereto, is used. The residual heat from the gas turbine is in the first instance returned to the process. The second aspect relates to a reformer section which comprises an (optional) prereformer, a primary reformer and a secondary reformer. An additional saving in energy is achieved by heat exchange in the primary reformer between the discharge stream from the secondary reformer and the stream from the prereformer. The third aspect of the invention relates to carrying out the conventional CO shift conversion in three steps at successively decreasing temperature instead of in the customary two steps.
Description
PROCESS AND APPARATUS FOR THE PRODUCTION OF AMMONIA
The invention relates to a novel production process for ammonia that is highly integrated as far as heat balance is concerned. The techniques used are also suitable for improving existing plants for ammonia production. The invention leads to a more energy efficient process per tonne of ammonia produced that is also able to provide its own electricity requirement or is able to export electrical energy.
In view of the continuing global demand for ammonia and the high energy costs that are associated with the production of NH3 in existing processes, there is a continuous need to increase the existing production capacity or even to replace existing plants completely. Various processes and measures for appreciably reducing the energy consumption of the ammonia process have been proposed over the years. These mainly related to the manner in which steam was generated and the location thereof in the process.
Prior art
In US 4 479 925 it is described that ammonia synthesis gas is produced by bringing a normal hydrocarbon feed and steam into an endothermic, catalytic conversion zone operating under primary reformer conditions (primary reformer), by which means a primary reformed gas stream is produced that is brought with air into an adiabatic, catalytic conversion zone that is operating under autothermal steam reforming conditions, so that a crude, hot, ammonia synthesis gas is produced that is then fed to the endothermic catalytic conversion zone in indirect heat exchange with the hydrocarbon feed and steam in order to provide the heat for conversion in the endothermic zone.
Air required for the operation of the adiabatic zone (secondary reformer) is supplied by a centrifugal compressor driven by a gas turbine. The exhaust from the gas turbine exchanges heat with the air for the secondary reformer and the heated compressed air, which is then introduced into the secondary reformer.
WO 9748639 describes a synthesis gas production system that comprises a gas turbine and an autothermal reformer (ATR), wherein the autothermal reformer is positioned between the compressor and expander of the gas turbine and wherein the ATR produces synthesis gas and can serve as the burner for the gas turbine.
US 4 792 441 describes ammonia synthesis in which a small proportion of the methane stream flows to the primary reformer and a major proportion of the methane
stream goes to the secondary reformer. This document further describes the saturation of natural gas with steam (Figure 1). Air enriched with oxygen is used for the secondary reformer.
Although the prior art offers various solutions for improving the heat balance of the process for the preparation of ammonia, it has now been found that an appreciable saving in energy can be obtained by using the first, second and third aspects of the invention, in particular by combination of these aspects. Whereas a conventional process requires approximately 8 - 10 Gcal/tonne energy, according to the invention this can be reduced to approximately 6.4 Gcal/tonne.
Summary of the invention
The energy saving indicated above is achieved in accordance with three aspects of the invention. The first aspect relates to the use of a gas turbine with extraction of process air, with electricity generation coupled thereto. The residual heat from the gas turbine is in the first instance returned to the process.
The second aspect relates to a reformer section, which comprises an (optional) prereformer, a primary reformer and a secondary reformer. An additional energy saving is achieved by heat exchange in the primary reformer between the discharge stream from the secondary reformer and the stream from the prereformer. The third aspect of the invention relates to carrying out the conventional CO shift conversion in three steps at successively decreasing temperature instead of the conventional two steps.
Finally, the invention relates in particular to a combination of the abovementioned three aspects, which leads to maximum energy saving.
Detailed description of the invention
The present invention now provides, according to a first aspect, a method for the preparation of ammonia, which method comprises the following steps: a) a reforming step, in which a hydrocarbon stream, a process air stream and steam are reacted to obtain a discharge stream which contains CO, CO2, H2 and N2; b) a CO conversion step, in which CO in the discharge stream from step a) is converted to CO2 and H2;
c) a CO2 removal step, in which CO2 is removed from the stream obtained in step b); and d) a methanisation step, in which the residual CO and CO2 are converted to CH4 and H2O; in such a way that a synthesis gas that contains N2 and H2, suitable for the production of ammonia, is obtained, after which the synthesis gas is converted to ammonia in a synthesis cycle, characterised in that at least a portion of the process air stream that is reacted in the reforming step is compressed with the aid of a compressor which is part of a gas turbine.
According to this aspect a gas turbine is installed that is partly driven by residual gases from the process. A generator that generates electricity is coupled to the gas turbine.
In addition to the advantage that the gas turbine simultaneously provides for compression of the process air stream and generation of electricity, the discharge gases from the gas turbine can advantageously be used to heat process streams and to generate steam. A suitable heat exchanger, in particular a waste heat boiler, can be used for this purpose.
In particular, the hydrocarbon stream and the process air stream are heated and process steam is generated in this way. Additional heating can be provided if necessary, in order thus to create an adequate heat content in the discharge gases.
If a conventional gas turbine is used, it will be possible to feed a maximum of approximately 15 % compressed air to the process. The remainder of the air goes to the combustion chamber of the gas turbine. The gas turbine provides for compression of the air to a pressure of 8 to 20 bar. Before the process air stream is fed to the reforming step it can be further compressed if necessary, for example to a pressure of 35 to 50 bar.
The hydrocarbon stream can comprise LPG, naphtha or natural gas, but in general will be natural gas. If necessary, sulphur can be removed from the hydrocarbon stream, since sulphur, present in natural gas, would poison the catalysts used. This is carried out, for example, in two steps. In the first step organically bound sulphur is reacted with hydrogen over a CoMoX or CuMoX catalyst to give hydrogen sulphide (H2S). In the second step H2S is removed by binding to ZnO.
The feed for the desulphurisation is first preheated by the discharge stream from the gas turbine to a temperature of 300 - 350 °C. The gas finally leaves the desulphurisation section at a temperature of approximately 150 °C.
The gas stream is now, in particular, first fed through a column and saturated with water vapour. Process condensate is preferably used for this purpose. The quantity of water to be discharged or the quantity of process condensate to be stripped off is reduced by this means. The requirement for process steam is also reduced by the same step. Moreover, medium-pressure steam is produced in this way, whilst this process step is in a temperature range in which normally only low-pressure steam could be generated. An installation is also provided for carrying out the method according to the first aspect of the invention, which installation comprises: a) a reformer section for reacting a hydrocarbon stream, a process air stream and steam; b) a CO conversion section connected via pipework to the reformer section, for converting CO present in a discharge stream from the reformer section into CO2 and H2; c) a CO2 removal section connected via pipework to the CO conversion section, ■ for removal of CO2 from a discharge stream from the CO conversion section; d) a methanisation section, connected via pipework to the CO2 removal section, for converting the residual CO and CO2 into CH4 and H2O; characterised in that the installation is also provided with e) a gas turbine, comprising a compressor provided with a feed for air and a discharge for compressed air; a combustion chamber provided with an inlet for fuel, an inlet for compressed air connected via pipework to the discharge for compressed air from the compressor and an outlet for combustion gas; an expansion turbine provided with an inlet for combustion gas connected via pipework to the outlet for combustion gas from the combustion chamber, and an outlet for combustion gas after expansion in the expansion turbine; wherein the discharge for compressed air from the compressor is also connected via pipework to the reformer section in order to provide at least a portion of the process air stream.
Preferably, the compressor and expansion turbine in this installation are coupled via a shaft. The gas turbine is also coupled to a generator for generating electricity.
In principle a person skilled in the art can determine which type of gas turbine is suitable for the invention. Examples are standard gas turbines, where the requisite quantity of process air can be tapped off, or a "tailor-made" machine, made up of discrete elements with a compression ratio of 8 - 35 bar. The outlet for combustion gas from the expansion turbine is coupled via pipework to a heat exchanger suitable for heat exchange between the combustion gas and at least the process air stream and the hydrocarbon stream, in particular a waste heat boiler. Heat exchangers of this type are known to those skilled in the art.
A compressor, provided with a feed for process air coupled via pipework to the discharge for compressed air (optionally enriched with oxygen) from the gas turbine and provided with a discharge for compressed process air coupled via pipework to the reformer section is optionally provided for further compression of the process air stream.
According to a second aspect, the present invention provides a method, in particular in combination with the first aspect of the invention, wherein the reaction of the hydrocarbon stream and process air stream in the reformer section takes place in the following successive steps: ai) a primary reforming step, in which a major proportion of the methane in the hydrocarbon stream is converted in the presence of steam to carbon oxides and hydrogen; aii) a secondary reforming step, in which the stream obtained in step ai) and the process air stream are converted to carbon oxides and hydrogen.
Preferably, and if necessary, the primary reforming step is preceded by aiii) a prereforming step in which higher hydrocarbons in the hydrocarbon stream are converted to methane and a portion of the methane is converted to carbon oxides and H2. In this prereforming step aiii) higher hydrocarbons (such as ethane, propane, up to naphtha) are converted to methane and a portion of the methane is converted to carbon oxides and H2 As a result more residual heat can be recovered from the reformer section.
This residual heat from the reformer section can be used to heat the incoming process gas before and/or after the prereforming step. Prereforming takes place in a catalyst bed at a temperature of 500 - 525 °C. As a result of the endothermic reaction, the gas temperature falls by approximately 50 °C.
In the primary reforming step ai), which is either the first or the second step in the reformer section, the stream obtained in step ai) is converted to carbon oxides and
hydrogen at a temperature of 700 - 750 °C. The mixture is passed over a nickel catalyst in a tube reactor, in which the reaction takes place. Because the reaction is endothermic, the pipes are heated from the outside using natural gas combustion.
Preferably, in this step heat is exchanged between the discharge stream from the secondary reformer and the process stream that flows through the primary reformer. Preferably, a gas heated reformer (GHR) is used for this purpose. The heat integration of the reforming step is substantially improved by this means. The essential feature of the GHR is that the primary reformer is a tube reactor, the heating medium (jacket side) being the hot gas from the secondary reformer (approximately 1000 °C). The outlet temperature from the primary reformer is lower than in the conventional process.
In order to generate the required amount of heat it is necessary to inject air enriched with oxygen into the secondary reformer, by which means the amount of heat needed for primary reforming is generated.
The secondary reforming step aii) is then carried out. If the standard quantity of process air is used, the outlet temperature of 700 - 750 °C of the primary reformer is too low to achieve adequate conversion of methane in the secondary reformer, needed for the ammonia synthesis. Therefore, pre-heated, oxygen-enriched air is added in an autothermal reactor, known as a post-combustion chamber or secondary reformer, an exothermic reaction allowing the temperature to rise to approximately 1000 °C. The methane content falls to 0.3 - 0.5 % and at the same time nitrogen, which is needed for the ammonia synthesis, is added by means of the process air supplied.
The secondary reformer and the catalyst used therein are the same as those used in the standard process.
According to the second aspect, an installation is also provided in which the reformer section comprises: ai) a primary reformer provided with a feed for hydrocarbon stream and provided with a discharge for reacted hydrocarbon stream; aii) a secondary reformer provided with a feed for reacted hydrocarbon stream coupled via pipework to the discharge from the primary reformer, a feed for process air stream and a discharge for reacted hydrocarbon stream. Preferably, the reformer section also comprises
aiii) a prereformer provided with a feed for the hydrocarbon stream and provided with a discharge for reacted hydrocarbon stream, which is coupled via pipework to the feed of the primary reformer.
Downstream of the secondary reformer the CO content is approximately 13 %. The major proportion of the CO is converted to CO2 and additional hydrogen by passing the gas mixture over two catalysts.
According to a third aspect, the invention provides, in particular in combination with the first and/or second aspect of the invention, a method in which the CO conversion step b) is carried out in the following steps: bi) a high temperature step, in which the stream obtained in the reforming step is reacted at a temperature of 300 - 360 °C, a discharge stream being obtained; bii) a medium temperature step, in which the discharge stream from step bi) is reacted at a temperature of 200 - 250 °C, a discharge stream being obtained; biii) a low temperature step, in which the discharge stream from step bii) is reacted at a temperature of 190 - 200 °C.
Preferably heat exchange takes place between water used for the saturation of the hydrocarbon stream and one or more, preferably all, of the discharge streams from steps bi), bii) and biii). As a result of the low steam/carbon ratio in the reformer, the equilibrium of the water gas shift reaction is less advantageous. This effect is reduced by carrying out the CO conversion not in two but in three steps. Residual heat is recovered after each step. The high temperature CO conversion takes place at a lower feed temperature (340 °C) than in the existing process (360 °C). The final step has an outlet temperature of 195 °C. The invention also provides an installation for carrying out the method according to the third aspect, which comprises a CO conversion section, comprising bi) a first conversion reactor operating at high temperature, provided with a feed coupled via pipework to the discharge for reacted hydrocarbon from the reformer section, and with a discharge; bii) a second conversion reactor operating at medium temperature, provided with a feed coupled via pipework to the discharge from the first conversion reactor, and with a discharge;
biii) a third conversion reactor operating at low temperature, provided with a feed coupled via pipework to the discharge from the second conversion reactor, and with a discharge.
Preferably, the installation is also provided with an installation for saturating the hydrocarbon stream with water, provided with a feed for the hydrocarbon stream, a discharge for the hydrocarbon stream saturated with water vapour, which discharge is coupled via pipework to the feed to the reformer section, and a feed and discharge for circulation water, wherein the feed and discharge for circulation water forms a cycle via pipework, wherein at least one heat exchanger is incorporated in the cycle equipped for heat exchange between the discharge lines from one or more of the conversion reactors and the water circulation cycle.
The other steps in the ammonia process, CO2 removal, methanisation and the actual ammonia synthesis, take place largely in accordance with conventional processes, which are explained briefly below.
All oxygen compounds poison the synthesis catalysts and therefore CO2, CO and H2O have to be removed. First of all the carbon dioxide is removed by washing the gas with a suitable absorbent. This is, for example, an amine solution or an alkaline solvent based on K2CO3. The solution is regenerated by using some of the heat that is available in the gas after the CO conversion for the K2CO3 process, supplemented by a quantity of low- pressure steam, available from back-pressure turbines, which are used to drive pumps and compressors, or by heat which is withdrawn from the top vapour stream from the process condensate stripper. At least 60 % of the energy costs for regeneration can be saved by selecting a suitable
CO2 absorbent with which the minimum amount of regeneration energy is demanded. According to the invention, the CO2 is preferably removed using aMDEA, but the use of Selexol is also a possibility.
In the following step in the ammonia process the CO and the residual CO2 (100 to 1000 ppm) in the gas are reacted with H2 to give CH4 and H2O by passing the gas at a temperature of 300 °C over a nickel catalyst (methanisation). The reaction that applies here is the reverse of that in the first conversion of methane, but because of the low water
content and the low temperature the CO and CO2 are now converted to less than 1 ppm. Thus, some of the H2 produced is lost again in this step.
Following these process steps the crude synthesis gas has the correct H2:N2 ratio of 3:1. The synthesis gas is now compressed to approximately 100 - 220 bar with the aid of a centrifugal compressor, in a number of stages with intermediate cooling. The final stage of the compressor is provided with a planet wheel for circulation of the gas through the synthesis cycle. The compressor is driven by a 100 - 220 bar steam turbine with possible 40 bar extraction and a (partial) condensation turbine. The residual water is removed from the synthesis gas with the aid of molecular sieves upstream of the first or upstream of the second stage of the compressor.
The actual synthesis reaction takes place in accordance with the reaction equation given below in a reactor containing a number of beds, under a pressure of 100 to 220 bar and a temperature of 400 to 500 °C. The outlet ammonia content is approximately 12 to 20 %.
The heat that is liberated during the process is used for generation of steam that can be used elsewhere in the process.
Preferably, the synthesis reaction takes place in two reactors with two beds in the first reactor. By cooling downstream of the second bed and placing a third bed in a second reactor the conversion for each complete synthesis loop is increased, which leads to a smaller recirculation stream and less ammonia cooling.
Following heat exchange and water cooling the reactor effluent is further cooled by vaporising ammonia, the major proportion of the ammonia formed being condensed. Liquid ammonia is then separated off as product in a flash vessel. The residual gas still contains approximately 2 to 5 % ammonia, depending on the temperature, and is recirculated in the final step of the synthesis gas compressor. Argon and methane dissolve inadequately in the ammonia produced and have to be discharged to prevent accumulation. Hydrogen is then recovered from discharge gas. The remaining discharge gas is used as fuel gas.
The invention will now be explained with reference to the figures, in which
Figure 1 shows an installation according to the first aspect of the invention,
Figure 2 shows an installation according to the second aspect of the invention,
Figure 3 shows an installation according to the third aspect of the invention and Figure 4 shows an example of a complete ammonia process in which the aspects of the invention have been integrated.
Figure 1 shows the first aspect of the invention, a portion of the process air stream being compressed with the aid of the compressor 2, which forms part of the gas turbine 1. The air to be compressed is fed via 5 to the compressor 2 and a compressed air stream 7 leaves the compressor 2. A portion of this air stream is fed at '8 to the burner 4 of the gas turbine. Fuel is supplied to the burner via 18. The off-gases 9 from the burner are fed to the expansion turbine 3 of the gas turbine. Via the outlet 10 of the expansion turbine, the gases are fed to a heat exchanger (waste heat boiler) 11 to heat process streams and to generate steam.
The gas turbine is furthermore provided with a shaft 6, by means of which the compressor 2 and the expander 3 are coupled. Moreover, a generator 17, by means of which electricity can be generated, is coupled to the gas turbine.
The process air stream 7 that leaves the compressor is fed via an additional compressor 14 and line 15 via the waste heat boiler 11 to the reformer section 16. Additional oxygen is fed to the process air stream 7 at 13. The natural gas required in the reformer section is fed to the reformer section via 12, through the waste heat boiler 11 and the natural gas saturating unit 25 (shown diagrammatically).
Figure 2 shows the second aspect of the invention, that is to say the construction of the reformer section. A gas stream 40, which optionally has been desulphurised and saturated with water vapour and to which the requisite quantity of process steam has been added, enters the prereformer 41 and leaves this at 42. This stream then passes to the GHR 43 and leaves this at 45, in order then to be fed to the secondary reformer 46. A process air stream 15, which is enriched with oxygen, is fed to the secondary reformer. The outgoing stream from the secondary reformer 47 passes to the GHR 43, where heat exchange with the process stream 42 takes place. Finally, this stream leaves the GHR at 44 and, after heat recovery in 52, is then fed to the CO conversion section 49. Figure 3 shows the third aspect of the invention, that is to say the performance of the
CO conversion step in three steps at different, decreasing temperatures. In Figure 3 gas is fed at 20 to a natural gas saturating unit 25. The process condensate required for natural gas saturation is supplied at 37. The gas leaves the natural gas saturating unit at 40 and, after
admixing with steam 51, is fed to the reformer section 16. Water vapour is also fed to the natural gas saturating unit by circulation of hot water via line 24. This water is heated via heat exchangers 29, 30 and 31.
An air stream 15 is also fed to the reformer section 16. The stream issuing from the reformer section passes at 44 to a first CO conversion reactor 26 and leaves the latter at 33 and is then fed to CO conversion reactor 27 and leaves the latter at 34 and is then fed to CO conversion 28 and leaves the latter via 35 in order, after heat recovery in 53, then to be fed to the CO2 removal section 36. The outgoing streams 33; 34 and 35 from the CO conversion reactors undergo heat exchange with the water stream 24 via heat exchangers 29, 30 and 31 , respectively.
An example of a complete ammonia process in which all three aspects of the invention are incorporated is shown in Figure 4. Corresponding components are numbered correspondingly to Figures 1 to 3. For instance, the gas turbine is indicated by 1. A process air stream 5 is fed to the compressor 2 of the gas turbine and leaves the latter via 7. A portion of this air stream passes via 8 to the combustion chamber 4 and leaves the latter via 9 in order then to be expanded in expander 3 in order to be fed via 10 to the waste heat boiler. Fuel is fed to the combustion chamber 4 of the gas turbine via 18. After feeding in additional O2 at 13, the compressed process air stream 7 passes via compressor 14 and via line 15, heat being exchanged in the waste heat boiler 11, to the secondary reformer 46. The hydrocarbon stream, for example a natural gas stream, passes via 12 and the waste heat boiler 11 to the desulphurisation reactor 50. Following heat exchange with stream 12 in 100, the hydrocarbon stream is fed via line 20 to the saturating unit 25 and leaves the latter at 40 in order then to be fed to prereformer 41. Steam can be fed to the hydrocarbon stream 40 at 51 and heat exchange between the outgoing stream 44 from the GHR 43 takes place at 52.
The outgoing stream 42 from the prereformer 41 is fed to the GHR at the top and, after reaction, leaves the latter via 45 in order to be fed to the secondary reformer 46. Heat is exchanged between the outgoing stream 47 from the secondary reformer 46 and the process stream 42 in the GHR. A stream 44 then issues from the GHR, which stream 44 is fed to the first CO conversion reactor 26. The outgoing stream 33 from the first CO conversion reactor 26 then passes to the second CO conversion reactor 27 and, via 34, to the third CO conversion
reactor 28. Via heat exchangers 29, 30 and 31 heat is exchanged between the streams 33, 34 and 35 and the water stream 24 to the natural gas saturating unit 25.
After heat recovery in 53, the stream 35 passes to the CO2 removal installation 55, in which CO2 is adsorbed on aMDEA (but Selexol is also a possibility). Gas stream 56 (free from CO2) issues from the CO2 absorption column, which stream is discharged via a liquid separator 57 as stream 58. The solvent stream 59 then issues from the CO2 absorption column 55, which solvent stream 59 is fed to the stripper 60. The adsorbed CO2 is removed from the solvent by means of heat. For this purpose stream 67 is circulated over a heat exchanger 54. The requisite heat is supplied by stream 35. The CO2 removed from the solvent is cooled in condenser 63. Condensate produced is separated off in liquid separator 64 and returned as stream 66 to the stripper. The CO2 gas stream 65 issues from the liquid separator.
A stream 58 issues from the CO2 removal section, which stream 58 is fed to methanator 69. Heat is exchanged between stream 58 and the outgoing stream 70 from the methanator 69 via heat exchanger 68. Stream 70 is fed to condensate separator 71 and passes via 73 to a first compressor 74. A stream of condensed water vapour 72 issues from condensate separator 71. The stream from compressor 74 passes via 75 to a molecular sieve 76. A stream 77 issues from the molecular sieve, which stream 77 contains all water vapour adsorbed on the molecular sieve after regeneration. Downstream of the molecular sieve the synthesis gas 78 flows to the second synthesis gas compressor 79. A recirculation stream 101 from the synthesis circuit is fed to the synthesis feed 78 in this synthesis gas compressor.
Via line 80 the combined synthesis gas stream passes from compressor 79 via the heat exchanger 81 to the first synthesis reactor 82, which has two beds. A stream 83 issues from the first synthesis reactor, superheated steam being recovered from this stream via heat exchangers 84 and 85 before this stream is fed to second synthesis reactor 86. The outgoing stream 87 passes via heat exchangers 88 for steam production and 81 for heating the feed to the ammonia chilling section, which comprises heat exchangers 89, 90, 91, 92 and 94, after which ammonia 96 is separated off in separator 95. The recirculation stream 97 is returned to compressor 79. A discharge stream 98 is returned to the process.
In addition to the abovementioned advantages, the present invention offers the following advantages compared with the state of the art:
• The residual heat from the process is used to heat the process streams. In particular the use of residual heat from the secondary reformer is used as part of the heat source for the primary reformer.
• The shortage of heat in the reforming section is made up by enriching the process air with additional oxygen. By this means heating in an inefficient primary reformer is avoided and the heat is fed directly to the primary reformer. Maximum conversion of methane to carbon monoxide and hydrogen is obtained by the use of oxygen-enriched air in the secondary reformer. v Surplus process heat at too low a temperature to be able to generate steam at sufficiently high pressure is fed to a circulating stream of hot water, that serves for saturating natural gas (feed), as a result of which the requirement for process steam decreases.
• The heat requirement for the CO2 wash liquid regeneration is reduced to a level for which adequate residual heat is still available. • Part of the off-gas heat from the gas turbine is used for preheating the feed for the primary reformer and process air. The remaining heat is used to produce steam.
• By carrying out the CO shift conversion in three instead of two steps, with intermediate cooling, maximum conversion of CO to CO2 is obtained, whilst, moreover, additional heat recovery takes place. The residual heat from the shift conversion effluent is taken up by a circulating water stream by means of which natural gas is saturated. v CO2 removal takes place by an energy-efficient process, such as by using Selexol or aMDEA.
• By increasing the synthesis gas conversion to ammonia to the highest possible concentration, approximately 20 %, depending on the pressure, a greater proportion of cooling and condensation of ammonia can be carried out by cooling water, as a result of which the burden on the ammonia cooling installation is reduced.
• The evaporation pressure in the ammonia cooling installation is adjusted so that the ammonia vapour can be used directly in processing processes. • Compressors and pumps are driven only by steam turbines, to the extent that steam is available. Other driving is by means of electric motors.
Electricity for own use is generated by a generator coupled to a gas turbine. The flue gases from this gas turbine are used for the generation of steam.
Claims
1. Method for the preparation of ammonia, which method comprises the following steps: a) a reforming step, in which a hydrocarbon stream, a process air stream and steam are reacted to obtain a discharge stream which contains CO, CO2, H2 and N2; b) a CO conversion step, in which CO in the discharge stream from step a) is converted to CO2 and H2; c) a CO2 removal step, in which CO2 is removed from the stream obtained in step b); and d) a methanisation step, in which the residual CO and CO2 are converted to CH4 and H2O; in such a way that a synthesis gas that contains N2 and H2, suitable for the production of ammonia, is obtained, after which the synthesis gas is converted to ammonia in a synthesis cycle, characterised in that at least a portion of the process air stream that is reacted in the reforming step is compressed with the aid of a compressor which is part of a gas turbine.
2. Method according to Claim 1, wherein the entire process air stream that is reacted in the reforming step is compressed with the aid of the compressor which forms part of the gas turbine.
3. Method according to Claim 1, wherein the process air stream is further compressed before this stream is fed to the reforming step.
4. Method according to one of Claims 1 to 3, wherein the hydrocarbon stream is heated by heat exchange with discharge gases from the gas turbine before it is fed to the reforming step.
5. Method according to one of Claims 1 to 4, wherein the process air stream is heated by heat exchange with discharge gases from the gas turbine before it is fed to the reforming step.
6. Method according to one of the preceding claims, wherein the process air sfream is enriched with oxygen before it is fed to the reforming step.
7. Method according to one of the preceding claims, wherein the hydrocarbon stream comprises natural gas, LPG or naphtha, preferably natural gas.
8. Method according to one of the preceding claims, wherein the hydrocarbon stream is saturated with water vapour before it is fed to the reformer step.
9. Method, preferably according to one of the preceding claims, wherein the reforming step a) takes place in the following successive steps: ai) a primary reforming step, in which a major proportion of the methane in the hydrocarbon stream is converted in the presence of steam to carbon oxides and hydrogen; aii) a secondary reforming step, in which the sfream obtained in step ai) and the process air sfream are converted to carbon oxides and hydrogen.
10. Method according to Claim 9, wherein the primary reforming step is preceded by: aiii) a prereforming step in which higher hydrocarbons in the hydrocarbon stream are converted to methane and a portion of the methane is converted to CO and H2.
11. Method according to Claim 9 or 10, wherein heat exchange takes place between the stream obtained in the secondary reforming step and the stream which is subjected to the primary reforming step.
12. Method, preferably according to one of the preceding claims, wherein the CO conversion step b) is carried out in the following successive steps: bi) a high temperature step, in which the stream obtained in the reforming step is reacted at a temperature of 300 - 360 °C, a discharge stream being obtained; bii) a medium temperature step, in which the discharge stream from step bi) is reacted at a temperature of 200 - 250 °C, a discharge stream being obtained; biii) a low temperature step, in which the discharge stream from step bii) is reacted at a temperature of 190 - 200 °C.
13. Method according to Claims 8 and 12, wherein heat exchange takes place between circulation water used for the saturation of the hydrocarbon stream and one or more, preferably all, of the discharge streams from steps bi), bii) and biii).
14. Installation for carrying out the method according to one of the preceding claims, which comprises: a) a reformer section for reacting a hydrocarbon stream, a process air stream and steam; b) a CO conversion section connected via pipework to the reformer section, for converting CO present in a discharge sfream from the reformer section into CO2 and H2; c) a CO2 removal section connected via pipework to the CO conversion section, for removal of CO2 from a discharge stream from the CO conversion section; d) a methanisation section, connected via pipework to the CO2 removal section, for converting the residual CO and CO2 into CH4 and H2O; characterised in that the installation is also provided with e) a gas turbine, comprising a compressor provided with a feed for air and a discharge for compressed air; a combustion chamber provided with an inlet for fuel, an inlet for compressed air connected via pipework to the discharge for compressed air from the compressor and an outlet for combustion gas; an expansion turbine provided with an inlet for combustion gas connected via pipework to the outlet for combustion gas from the combustion chamber, and an outlet for combustion gas after expansion in the expansion turbine; wherein the discharge for compressed air from the compressor is also connected via pipework to the reformer section in order to provide at least a portion of the process air stream.
15. Installation according to Claim 14, wherein the compressor and expansion turbine are coupled via a shaft.
16. Installation according to Claim 14 or 15, wherein the gas turbine is coupled to a generator for the generation of electricity.
17. Installation according to one of Claims 14 to 16, wherein the outlet for combustion gases from the expansion turbine is coupled via pipework to a heat exchanger suitable for heat exchange between the combustion gas and at least the process air sfream and the hydrocarbon stream.
18. Installation according to one of Claims 14 to 17, which also comprises a compressor provided with a feed for process air coupled via pipework to the discharge for compressed air from the gas turbine and provided with a discharge for compressed process air coupled via pipework to the reformer section.
19. Installation, preferably according to one of Claims 12 to 18, wherein the reformer section a) comprises: ai) a primary reformer provided with a feed for hydrocarbon stream and provided with a discharge for reacted hydrocarbon stream; aii) a secondary reformer provided with a feed for hydrocarbon stream coupled via pipework to the discharge from the primary reformer, a feed for process air stream and a discharge for reacted hydrocarbon sfream.
20. Installation according to Claim 19, also provided with aiii) a prereformer provided with a feed for the hydrocarbon stream and provided with a discharge for reacted hydrocarbon sfream coupled via pipework to the feed for the primary reformer.
21. Installation according to Claim 19 or 20, wherein the primary reformer is equipped for heat exchange between the discharge sfream from the secondary reformer and the hydrocarbon sfream.
22. Installation, preferably according to one of Claims 14 to 21, wherein the CO conversion section comprises: bi) a first conversion reactor operating at high temperature, provided with a feed coupled via pipework to the discharge for reacted hydrocarbon from the reformer section, and with a discharge; bii) a second conversion reactor operating at medium temperature, provided with a feed coupled via pipework to the discharge from the first conversion reactor, and with a discharge; biii) a third conversion reactor operating at low temperature, provided with a feed coupled via pipework to the discharge from the second conversion reactor, and with a discharge.
23. Installation according to Claim 22, also provided with an installation for saturating the hydrocarbon sfream with water, provided with a feed for the hydrocarbon stream, a discharge for the hydrocarbon stream saturated with water vapour, which discharge is coupled via pipework to the feed to the reformer section, and a feed and discharge for circulation water, wherein the feed and discharge for circulation water forms a cycle via pipework, wherein at least one heat exchanger is incorporated in the cycle equipped for heat exchange between the discharge lines from one or more of the conversion reactors and the water circulation cycle.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| AU2002219713A AU2002219713A1 (en) | 2000-12-11 | 2001-12-11 | Process and apparatus for the production of ammonia |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| NL1016848A NL1016848C2 (en) | 2000-12-11 | 2000-12-11 | Method and device for the preparation of ammonia. |
| NL1016848 | 2000-12-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| WO2002048027A1 true WO2002048027A1 (en) | 2002-06-20 |
Family
ID=19772563
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/NL2001/000898 WO2002048027A1 (en) | 2000-12-11 | 2001-12-11 | Process and apparatus for the production of ammonia |
Country Status (3)
| Country | Link |
|---|---|
| AU (1) | AU2002219713A1 (en) |
| NL (1) | NL1016848C2 (en) |
| WO (1) | WO2002048027A1 (en) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005080257A1 (en) * | 2004-02-20 | 2005-09-01 | Herbert Gehmair | Method for the production of synthesis gas for ammonia synthesis by steam reforming of natural gas |
| EP1698588A1 (en) * | 2005-03-04 | 2006-09-06 | Ammonia Casale S.A. | Ammonia synthesis process |
| EP2321386A1 (en) * | 2008-07-18 | 2011-05-18 | Kellogg Brown & Root LLC | Catalytic partial oxidation reforming |
| WO2011077107A1 (en) * | 2009-12-22 | 2011-06-30 | Johnson Matthey Plc | Conversion of hydrocarbons to carbon dioxide and electrical power |
| EP2404869A1 (en) * | 2010-07-06 | 2012-01-11 | Ammonia Casale S.A. | Process for producing ammonia synthesis gas |
| US9102534B2 (en) | 2009-12-22 | 2015-08-11 | Johnson Matthey Plc | Conversion of hydrocarbons to carbon dioxide and electrical power |
| EP2910523A1 (en) * | 2014-02-21 | 2015-08-26 | Haldor Topsoe A/S | Methanation process with a passive heat exchange medium |
| EP3623343A1 (en) * | 2018-09-11 | 2020-03-18 | Casale Sa | Process for the synthesis of ammonia |
| WO2022060355A1 (en) * | 2020-09-16 | 2022-03-24 | Exxonmobil Research And Engineering Company | Ammonia and urea production in reverse flow reactors |
| CN115199367A (en) * | 2022-07-08 | 2022-10-18 | 集美大学 | Power generation system and method based on coupling zero-energy-consumption carbon dioxide capture of chemical reinjection natural gas reforming gas turbine |
| CN115298416A (en) * | 2020-03-19 | 2022-11-04 | 凯洛格·布朗及鲁特有限公司 | Power augmentation for gas turbines |
| RU2788872C2 (en) * | 2018-09-11 | 2023-01-25 | Касале Са | Ammonia synthesis method |
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Cited By (22)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005080257A1 (en) * | 2004-02-20 | 2005-09-01 | Herbert Gehmair | Method for the production of synthesis gas for ammonia synthesis by steam reforming of natural gas |
| EP1698588A1 (en) * | 2005-03-04 | 2006-09-06 | Ammonia Casale S.A. | Ammonia synthesis process |
| WO2006094619A1 (en) * | 2005-03-04 | 2006-09-14 | Ammonia Casale S.A. | Ammonia synthesis process |
| EP2321386A4 (en) * | 2008-07-18 | 2011-11-30 | Kellogg Brown & Root Llc | Catalytic partial oxidation reforming |
| EP2321386A1 (en) * | 2008-07-18 | 2011-05-18 | Kellogg Brown & Root LLC | Catalytic partial oxidation reforming |
| US9102534B2 (en) | 2009-12-22 | 2015-08-11 | Johnson Matthey Plc | Conversion of hydrocarbons to carbon dioxide and electrical power |
| AU2010334600B2 (en) * | 2009-12-22 | 2015-02-05 | Johnson Matthey Plc | Conversion of hydrocarbons to carbon dioxide and electrical power |
| US9216903B2 (en) | 2009-12-22 | 2015-12-22 | Johnson Matthey Plc | Conversion of hydrocarbons to carbon dioxide and electrical power |
| WO2011077107A1 (en) * | 2009-12-22 | 2011-06-30 | Johnson Matthey Plc | Conversion of hydrocarbons to carbon dioxide and electrical power |
| US10087074B2 (en) | 2010-07-06 | 2018-10-02 | Casale Sa | Process for producing ammonia synthesis gas |
| CN102971251A (en) * | 2010-07-06 | 2013-03-13 | 阿梅尼亚·卡萨莱股份有限公司 | Process for producing ammonia synthesis gas |
| RU2565321C2 (en) * | 2010-07-06 | 2015-10-20 | Касале Са | Method of obtaining synthesis-gas for ammonia production |
| WO2012004032A1 (en) * | 2010-07-06 | 2012-01-12 | Ammonia Casale Sa | Process for producing ammonia synthesis gas |
| EP2404869A1 (en) * | 2010-07-06 | 2012-01-11 | Ammonia Casale S.A. | Process for producing ammonia synthesis gas |
| EP2910523A1 (en) * | 2014-02-21 | 2015-08-26 | Haldor Topsoe A/S | Methanation process with a passive heat exchange medium |
| EP3623343A1 (en) * | 2018-09-11 | 2020-03-18 | Casale Sa | Process for the synthesis of ammonia |
| WO2020052832A1 (en) * | 2018-09-11 | 2020-03-19 | Casale Sa | Process for the synthesis of ammonia |
| RU2788872C2 (en) * | 2018-09-11 | 2023-01-25 | Касале Са | Ammonia synthesis method |
| US12122681B2 (en) | 2018-09-11 | 2024-10-22 | Casale Sa | Process for the synthesis of ammonia |
| CN115298416A (en) * | 2020-03-19 | 2022-11-04 | 凯洛格·布朗及鲁特有限公司 | Power augmentation for gas turbines |
| WO2022060355A1 (en) * | 2020-09-16 | 2022-03-24 | Exxonmobil Research And Engineering Company | Ammonia and urea production in reverse flow reactors |
| CN115199367A (en) * | 2022-07-08 | 2022-10-18 | 集美大学 | Power generation system and method based on coupling zero-energy-consumption carbon dioxide capture of chemical reinjection natural gas reforming gas turbine |
Also Published As
| Publication number | Publication date |
|---|---|
| NL1016848C2 (en) | 2002-06-13 |
| AU2002219713A1 (en) | 2002-06-24 |
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