WO2016016251A1 - Procédé de production sct-cpo/sr intégré pour la production de gaz de synthèse - Google Patents

Procédé de production sct-cpo/sr intégré pour la production de gaz de synthèse Download PDF

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WO2016016251A1
WO2016016251A1 PCT/EP2015/067289 EP2015067289W WO2016016251A1 WO 2016016251 A1 WO2016016251 A1 WO 2016016251A1 EP 2015067289 W EP2015067289 W EP 2015067289W WO 2016016251 A1 WO2016016251 A1 WO 2016016251A1
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synthesis gas
gas
steam
process according
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PCT/EP2015/067289
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Luca Eugenio Basini
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Eni S.P.A.
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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—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
    • 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
    • C01B3/32—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
    • C01B3/386—Catalytic partial combustion
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/025—Processes for making hydrogen or synthesis gas containing a partial oxidation step
    • C01B2203/0261—Processes for making hydrogen or synthesis gas containing a partial oxidation step containing a catalytic partial oxidation step [CPO]
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/061—Methanol production
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/062—Hydrocarbon production, e.g. Fischer-Tropsch process
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/08—Methods of heating or cooling
    • C01B2203/0805—Methods of heating the process for making hydrogen or synthesis gas
    • C01B2203/0838—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel
    • C01B2203/0844—Methods of heating the process for making hydrogen or synthesis gas by heat exchange with exothermic reactions, other than by combustion of fuel the non-combustive exothermic reaction being another reforming reaction as defined in groups C01B2203/02 - C01B2203/0294
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—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
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1241—Natural gas or methane
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1235—Hydrocarbons
    • C01B2203/1247—Higher hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/141—At least two reforming, decomposition or partial oxidation steps in parallel
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/14—Details of the flowsheet
    • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
    • 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

Definitions

  • the present invention relates to a process for producing synthesis gas through a process that integrates Short Contact Time - Catalytic Partial Oxidation (SCT-CPO) technology with Steam Reforming (SR) technology.
  • SCT-CPO Short Contact Time - Catalytic Partial Oxidation
  • SR Steam Reforming
  • Synthesis gas is produced with Steam Reforming (SR) technology and with Non-Catalytic Partial Oxidation (POx) and AutoThermal Reforming (ATR) technology.
  • SR Steam Reforming
  • POx Non-Catalytic Partial Oxidation
  • ATR AutoThermal Reforming
  • a relatively recent variation of the SR process is Gas Heated Reforming (GHR) which at least partially replaces the radiant heat needed for endothermic reactions with a convective source: typically the hot gas produced by combustion reactions and/or the same synthesis gas produced by ATR at a high temperature.
  • GHR Gas Heated Reforming
  • ATR and SR or GHR technologies are integrated within processes known as Combined Reforming (CR).
  • CR Combined Reforming
  • Short Contact Time - Catalytic Partial Oxidation (SCT-CPO) technology is also described in numerous documents in literature including: WO 201 1151082, WO 2009065559, WO 201 1072877, US 2009127512, WO 2007045457, WO 2006034868, US 200521 1604, WO 2005023710, DE 10232970, WO 9737929, EP 0725038, EP 0640559 e L.E. Basini e A. Guarinoni, "Short Contact Time Catalytic Partial Oxidation (SCT-CPO) for Synthesis Gas Processes and Olefins Production", Ind. Eng. Chem. Res. 2013, 52, 17023-17037.
  • Synthesis gas is used in a large number of industrial processes including Ammonia and Urea synthesis, production of H 2 for refining and obtaining fuels, synthesis of Methanol and its derivatives and synthesis of liquid hydrocarbons with the Fischer-Tropsch (F-T) process. Synthesis gas is also used in fine chemical processes and in the electronic, metal refining, glass and food industries. These numerous industrial uses require the synthesis gas to be produced with very different compositions from one another so as to minimize recycling and improve overall yields.
  • Table 1 shows the main reactions involved in the synthesis gas production processes and Table 2 the compositional characteristics of the synthesis gas required for its main uses. Table 1 ⁇ ' 298 ⁇
  • CPO Catalytic Partial Oxidation
  • EP 2142467 describes a combined process in which a gaseous hydrocarbon mixture reacts with steam in an endothermic adiabatic pre-reformer and the pre-reformed product is split into three streams fed to a Steam Methane Reformer (SMR), to a Gas Heated Reformer (GHR) and to an Autothermal Reformer (ATR) that operate in parallel.
  • SMR Steam Methane Reformer
  • GHR Gas Heated Reformer
  • ATR Autothermal Reformer
  • EP 1622827 describes a process for the production of synthesis gas starting from carbonaceous material, preferably comprising a gaseous hydrocarbon feedstock of Natural Gas, refinery gas and more generally gaseous streams containing compounds that have up to 4 carbon atoms, which envisages:
  • CSR Convective Steam Reforming Reactor
  • EP 1403216 describes a procedure for the production of synthesis gas by catalytic steam reforming in parallel in an AutoThermal Steam Reformer in series.
  • the heat required by the SR steps is, also in this case, provided by the combination of effluents from the different SR and ATR.
  • the final mixture of effluents obtained by adding the synthesis gas produced by the convectively heated SR and ATR processes has a H 2 /CO ratio comprised between 1 .8 and 2.3 v/v.
  • WO 2008017741 describes a process for the production of liquid hydrocarbons starting from biomasses, coal, lignite and crude oil residues that boil at a temperature of over 340°C, said process comprising at least:
  • FT Fischer-Tropsch
  • Endothermic adiabatic "pre-reforming" reactors are often inserted upstream of the SR and ATR reactors. These reactors are described in various documents in literature including "T.S. Christensen, Appl. Catal. A: 138(1996)285" and “I. Dybkjaer, Fuel Process. Techn. 42(1995)85".
  • the pre-reformers allow the C2+ hydrocarbons contained in the gaseous hydrocarbon streams to be converted at relatively low temperatures (about 550°C) into CO, H 2 and CH 4 reducing the possibility of parasite reactions taking place forming coal [7- 9] in the subsequent SR or ATR steps.
  • Endothermic adiabatic pre-reforming reactors are typically fed with a mixture of gaseous reagents and steam pre-heated in an oven to about 550°C.
  • a Ni based catalyst is used (in most cases) for completing reactions [10] .
  • the pre-reformed gas mixture is then sent to the reforming reactor and has a lower thermodynamic affinity to reactions forming carbonaceous residues through reactions [7- 9]. This allows the steam/carbon (Steam/C v/v) and/or Oxygen/Carbon (0 2 /C) ratios fed to the SR or ATR reactors to be reduced, improving the energy efficiency (W.D. Verduijin Ammonia Plant Saf. 33(1993)165).
  • pre-reforming units also allows the flexibility of the SR and ATR technologies to be increased with respect to the composition of the feedstock; for example, it allows feedstock to be used that range from refinery gases to naphtha.
  • endothermic adiabatic pre-reforming technology can increase the production capacity of plants without requiring significant changes to the characteristics of the reforming unit.
  • synthesis gas production technologies are used in a large number of industrial procedures to produce different products. It is therefore appropriate to be able to have a flexible synthesis gas production procedure available both with respect to production capacity and with respect to the quality of synthesis gas produced. At the same time it is very important to use high energy efficiency procedures, with low carbon dioxide emissions and that require lower capital costs with respect to traditionally exploited technologies.
  • the present patent application relates to an integrated process for producing synthesis gas which combines Short Contact Time - Catalytic Partial Oxidation (SCT-CPO) technology with Steam Reforming (SR) technology.
  • SCT-CPO Short Contact Time - Catalytic Partial Oxidation
  • SR Steam Reforming
  • a gaseous hydrocarbon stream into a first and a second stream, preferably comprising natural gas and/or refinery gas,
  • This configuration therefore exploits the possibilities offered by SCT-CPO technology to use, while maintaining the high energy efficiency typical of catalytic transformations, different types of feedstocks, both liquid and gaseous, which cannot be used in SR technologies and then use them for producing synthesis gas.
  • This process configuration therefore combines an SCT-CPO stage with an SR stage, so as to allow the use of compounds that SR technology cannot transform for producing synthesis gas, and in particular liquid and gaseous hydrocarbons, and compounds deriving from bio-masses also mixed together which could not be used by SR processes or by ATR processes.
  • the present invention relates to an integrated process for producing synthesis gas which comprises the following stages:
  • a gaseous hydrocarbon stream into a first and a second stream, preferably comprising natural gas and/or refinery gas,
  • the stream containing oxygen may be oxygen, air or enriched air.
  • a further pre-reforming stage is envisaged upstream either of the SCT-CPO section or the SR section, or both sections.
  • said pre-reforming stage may be exothermic adiabatic or endothermic adiabatic, and in particular the following combinations are described herein:
  • Exothermic adiabatic pre-reformer upstream of SR and upstream of SCT-CPO or Endothermic adiabatic pre-reformer upstream of SR and upstream of SCT-CPO, or Exothermic adiabatic pre-reformer upstream of SR and endothermic adiabatic pre- reformer upstream of SCT-CPO, or
  • the first and the second hydrocarbon gaseous stream can be fed to either an exothermic adiabatic pre-reformer or to an endothermic adiabatic pre-reformer. This is independent of the fact that these pre- reformers are upstream either of SR or SCT-CPO.
  • the third stream containing gaseous compounds wherein said gaseous compounds are selected from different hydrocarbons from natural gas and/or refinery gas, can be fed either to an exothermic adiabatic pre-reformer or to an endothermic adiabatic pre- reformer placed upstream of a SCT-CPO.
  • the third stream containing liquid compounds wherein said liquid compounds are selected from hydrocarbons, or compounds of various nature deriving from bio-masses, or mixtures thereof, can be fed only to an exothermic adiabatic pre-reformer placed upstream of an ST-CPO.
  • the third stream contains both liquid compounds and gaseous compounds, they can be fed only to an exothermic adiabatic pre-reformer placed upstream of an SCT- CPO.
  • the pre-reforming stage generates a reformed stream that is subsequently fed to the SCT-CPO and/or SR sections.
  • An exothermic adiabatic pre-reforming reactor exploits the same principles as the SCT- CPO process, as described for example in ITMI20120418.
  • the pre-reforming sections can be distinguished and positioned each upstream of the SR and SCT-CPO sections.
  • the exothermic adiabatic pre-reforming process also allows liquid hydrocarbon and gaseous feedstock to be pre-treated even with high olefin content and/or feedstock obtained from bio-masses that cannot be treated by endothermic adiabatic pre-reforming processes since they would cause:
  • the first and second stream of synthesis gas produced can be sent separately to a single heat exchange device for cooling to a temperature below 400°C generating co-production of steam; or can be mixed and the resulting mixture is sent to a single heat exchange device for cooling to temperature values below 400°C and for generating steam.
  • the steam generated can be used partly as a reagent in the SR section and partly fed to the SCT-CPO section.
  • the gaseous hydrocarbon stream contains sulfured compounds, it can be subjected to a hydro-desulfurization treatment before being sent to the pre-reforming sections, or before being sent to the Steam Reforming and SCT-CPO sections. If necessary, the impurities that could poison the processes downstream of the synthesis gas production reactors can also be removed after the production of synthesis gas by the SCT-CPO reactor.
  • the heat exchange device that cools the synthesis gas in the process according to the present invention is a syngas cooler which comprises:
  • said exchanger having at the lower part of the vertical tank at least one transfer line for feeding the hot gases to said tank, said transfer line being open at the two ends one of which is connected with the vertical tank and the other free and external to said tank, said transfer line being tubular shaped and projecting laterally outside said exchanger, said transfer line containing at least one central internal duct having an external jacket in which a coolant fluid circulates, said central internal duct being fluidly connected to the spiral duct and extending vertically along the tubular element inserted in the vertical tank.
  • the heat exchange device that cools the synthesis gas in the process according to the present invention is a syngas cooler which comprises:
  • said device containing in a single apparatus all the heat exchange surfaces and said surfaces being completely immersed in the fluid bath and being fluidly connected to the hot and cold sources external to said system through flows of matter.
  • the synthesis gas streams can be sent separately to Water Gas Shift (WGS) sections in which reaction [2] of Table 1 can take place, or the cooled mixture of synthesis gas can be sent to a single WGS section, hence forming in both cases a gas stream mainly containing H 2 , CO and C0 2 from which through a separation/purification process an H 2 stream with a high degree of purity can be obtained.
  • WGS Water Gas Shift
  • the stream of gas containing H 2 , CO and C0 2 can be cooled generating steam which is used in part to feed the sections of SR and SCT-CPO and partly can be exported for other uses.
  • the synthesis gas produced both by SR and by SCT-CPO can be used in a process for the synthesis of methanol, for the synthesis of ammonia and urea, or for Fischer-Tropsch synthesis, or for producing Hydrogen to be dedicated to refining processes or for other various uses such as, for example, the reduction of ferrous minerals, hydroformylations and different processes in the "fine chemistry", electronics, glass and food industries. Integration between SR and SCT-CPO sections allows operational and economic advantages in the production of synthesis gas and in the processes that use it. In particular said configuration allows both to increase the limits of the production capacity of the many existing plants and to use reagents with different compositions and to obtain synthesis gas mixtures suitable for the different production chains.
  • exothermic pre-reformers allow to reduce the energy consumptions of the subsequent reaction stages and they increase further the flexibility of the synthesis gas production processes. Furthermore, exothermic pre-reformers also allow to treat complex gaseous hydrocarbon feedstock rich in olefins such as some refinery gases and in general gaseous, liquid feedstocks and oxygenated compounds that an endothermic pre- reformer or an SR would otherwise not be able to process, since they would cause the deactivation of catalytic systems and the formation of carbonaceous deposits.
  • the integrated process described and claimed also requires less pre-heating of reagents hence preventing using large pre-heating ovens with high associated C0 2 emissions that are difficult to recover; it also offers the possibility to integrate the use of gaseous and/or liquid hydrocarbon feedstocks also mixed together, with compounds deriving from bio- masses increasing the "bio” share in products of different industrial processes such as refining and hydrocarbon fuel production processes.
  • FIG. 1 - 9 describe some preferred embodiments according to the present invention.
  • a liquid stream containing liquid hydrocarbons or compounds deriving from bio-masses, or mixtures thereof (3) is mixed with oxygen, or air, or enriched air (4) and steam (5).
  • a stream containing refinery gas or natural gas, or mixtures thereof (2) is desulfurized in a hydro-desulfurization treatment (6) and subsequently mixed with steam (1 ).
  • Said mixture is separated into two parts and sent partly to an SR, partly mixed with the mixture containing the liquid reagents to be fed to an SCT-CPO reactor.
  • the SR and CPO reactors each produce a synthesis gas that is cooled in two heat exchangers (8,9) generating steam which is sent for feeding (1 , 12) or exported for other uses (13).
  • Figure 2 reproduces the diagram of Figure 1 in part, with the difference that the synthesis gas streams produced are mixed and cooled in a single heat exchanger (8) generating steam that is sent for feeding the reactors (1 , 12) or exported for other uses (13).
  • FIG. 3 reproduces in part the same diagram as Figure 1.
  • the synthesis gas produced by the SR and by SCT-CPO is cooled (7, 8) generating steam.
  • the two streams of synthesis gas are then mixed and made to react in a water gas shift section (WGS 14).
  • the "shifted" synthesis gas is cooled (15) generating steam.
  • Figure 4 reproduces in part the diagram of Figure 3 but the streams of synthesis gas produced in S and SCT-CPO are cooled in (7, 8) and sent to two WGS reactors (14, 16). Then the products from WGS are mixed and further cooled in a single exchanger (15) generating steam which in part can be exported (13), and bringing the synthesis gas (9) to the suitable temperature for the subsequent stages in the processes that use it.
  • a liquid stream containing liquid hydrocarbons or compounds deriving from bio-masses, or mixtures thereof (3), is mixed with oxygen, or air, or enriched air (4) and steam (5).
  • a stream containing refinery gas or natural gas, or mixtures thereof (2), is desulfurized in a hydro-desulfurization treatment (6) and subsequently separated into two parts.
  • One part is mixed with the mixture containing the liquid reagents to be fed to an exothermic pre-reformer reactor (9) positioned upstream of SCT-CPO.
  • the other part is mixed with steam (1 ) and is sent to an endothermic pre-reformer (8), positioned upstream of SR.
  • the SR and SCT-CPO units each produce a synthesis gas that is cooled in two separate waste heat boiler heat exchangers (7,8) generating steam.
  • the steam is in part recirculated for feeding (12,1 ) and in part is steam for external uses (13).
  • the cooled synthesis gas is then joined into a single stream (11 ).
  • a stream of refinery gas or natural gas, or mixtures thereof (2) is hydro- desulfurized (6).
  • the stream thus treated is separated into two parts and sent in part to an SR after being mixed with steam (1 ); in part it is mixed with a stream containing oxygen, air or enriched air (4) and to a liquid stream containing liquid hydrocarbons or compounds deriving from bio-masses, or mixtures thereof (3); such a mixture is then fed to an SCT-CPO reactor.
  • SR and SCT-CPO each produce a synthesis gas that is cooled in two heat exchangers (8,7) which may be waste heat boiler (WHB) type, or a syngas cooler (SGC) as described in this text. Both generate steam which is exported (19) for other purposes.
  • the two streams of synthesis gas appropriately cooled, are sent to a WGS reactor (14) which produces a shifted gas rich in H 2 (20) which is further cooled in the heat exchange device (8).
  • the synthesis gas (9) thus obtained is made available for different uses.
  • Figure 7 reproduces the diagram of Figure 1 and in addition the synthesis gas (11 ) is compressed (24) and sent to a Methanol synthesis reactor (23). The product obtained is purified in a distillation step (22).
  • Figure 8 starts from the diagram of Figure 1 and is integrated with a section for producing ammonia.
  • the cooled synthesis gas (1 1 ) is made to react in a WGS section (14).
  • the stream thus obtained is sent to a carbon dioxide removal unit (26) and then to a
  • Ammonia (31 ) the process provides CO 2 (30) and the ratios between the flows of both streams can be optimized to be used in a Urea synthesis stage which is not indicated in the process diagram of Figure 8.
  • Figure 9 starts from the diagram of Figure 1 and is integrated with a Fischer Tropsch section.
  • the synthesis gas obtained (1 1 ) has a compositional ratio in which H 2 /CO is about 2 v/v, and is sent to a Fischer - Tropsch synthesis reactor (32) obtaining a product that is subject to a hydro-treatment (33) in the presence of H 2 (34) for maximizing the yield of "middle distillates”.
  • a part (24) of the recycling gas (36) of the Fischer - Tropsch process is sent to the SCT-CPO reactor.

Abstract

La présente invention concerne un procédé intégré de production de gaz de synthèse qui comprend les étapes suivantes : a) division d'un flux d'hydrocarbures gazeux en un premier et un deuxième flux, comprenant de préférence du gaz naturel et/ou du gaz de raffinerie, b) envoi du premier flux, après mélange avec de la vapeur d'eau, à une section de reformage à la vapeur pour produire ainsi un premier flux de gaz de synthèse, c) envoi du deuxième flux à une section d'oxydation partielle catalytique à temps de contact court, après mélange avec un flux contenant de l'oxygène, de la vapeur d'eau et éventuellement du CO2, et un troisième flux contenant des composés liquides et/ou gazeux, dans lequel lesdits composés gazeux sont choisis parmi des hydrocarbures autres que du gaz naturel et/ou du gaz de raffinerie, ou parmi des composés gazeux issus de biomasses, et dans lequel lesdits composés liquides sont choisis parmi des hydrocarbures, ou des composés de natures diverses issus de biomasses, ou des mélanges de ceux-ci, et, de ce fait, production d'un second flux de gaz de synthèse.
PCT/EP2015/067289 2014-07-29 2015-07-28 Procédé de production sct-cpo/sr intégré pour la production de gaz de synthèse WO2016016251A1 (fr)

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ITMI20141373 2014-07-29

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WO2016070988A1 (fr) * 2014-11-05 2016-05-12 Linde Aktiengesellschaft Procédé d'utilisation du co2 dans la production de syngaz
WO2020058859A1 (fr) * 2018-09-19 2020-03-26 Eni S.P.A. Procédé de production de méthanol à partir d'hydrocarbures gazeux
DE102019005934A1 (de) * 2019-08-22 2021-02-25 Giesecke+Devrient Mobile Security Gmbh Chipkarte
IT202100011189A1 (it) 2021-05-03 2022-11-03 Nextchem S P A Processo a basso impatto ambientale per la riduzione di minerali ferrosi in altoforno impiegante gas di sintesi
IT202100012551A1 (it) 2021-05-14 2022-11-14 Rosetti Marino S P A Processo per la conversione della co2
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WO2016070988A1 (fr) * 2014-11-05 2016-05-12 Linde Aktiengesellschaft Procédé d'utilisation du co2 dans la production de syngaz
WO2020058859A1 (fr) * 2018-09-19 2020-03-26 Eni S.P.A. Procédé de production de méthanol à partir d'hydrocarbures gazeux
US11492315B2 (en) 2018-09-19 2022-11-08 Eni S.P.A. Process for the production of methanol from gaseous hydrocarbons
DE102019005934A1 (de) * 2019-08-22 2021-02-25 Giesecke+Devrient Mobile Security Gmbh Chipkarte
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US11880731B2 (en) 2019-08-22 2024-01-23 Giesecke+Devrient Mobile Security Gmbh Chip card
IT202100011189A1 (it) 2021-05-03 2022-11-03 Nextchem S P A Processo a basso impatto ambientale per la riduzione di minerali ferrosi in altoforno impiegante gas di sintesi
WO2022233769A1 (fr) 2021-05-03 2022-11-10 NextChem S.p.A. Procédé d'utilisation de gaz de synthèse pour améliorer l'impact environnemental de la réduction de minerai de fer dans des hauts fourneaux
IT202100012551A1 (it) 2021-05-14 2022-11-14 Rosetti Marino S P A Processo per la conversione della co2
IT202100015473A1 (it) 2021-06-14 2022-12-14 Nextchem S P A Metodo di produzione di catalizzatori per processi chimici ad alta temperatura e catalizzatori cosi' ottenuti
WO2022263409A1 (fr) 2021-06-14 2022-12-22 NextChem S.p.A. Procédé de production de catalyseurs pour procédés chimiques à haute température et catalyseurs ainsi obtenus

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