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EP2356067A1 - Procédé et dispositif de production d'un gaz brut de synthèse - Google Patents

Procédé et dispositif de production d'un gaz brut de synthèse

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Publication number
EP2356067A1
EP2356067A1 EP09763885A EP09763885A EP2356067A1 EP 2356067 A1 EP2356067 A1 EP 2356067A1 EP 09763885 A EP09763885 A EP 09763885A EP 09763885 A EP09763885 A EP 09763885A EP 2356067 A1 EP2356067 A1 EP 2356067A1
Authority
EP
European Patent Office
Prior art keywords
gas
synthesis
export
export gas
steam generator
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP09763885A
Other languages
German (de)
English (en)
Inventor
Robert Millner
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SIEMENS VAI METALS Technologies GmbH
Original Assignee
Siemens VAI Metals Technologies GmbH and Co
Siemens VAI Metals Technologies GmbH Austria
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Siemens VAI Metals Technologies GmbH and Co, Siemens VAI Metals Technologies GmbH Austria filed Critical Siemens VAI Metals Technologies GmbH and Co
Publication of EP2356067A1 publication Critical patent/EP2356067A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • 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
    • C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
    • C01B3/12—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents by reaction of water vapour with carbon monoxide
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/0006—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state
    • C21B13/0013—Making spongy iron or liquid steel, by direct processes obtaining iron or steel in a molten state introduction of iron oxide into a bath of molten iron containing a carbon reductant
    • C21B13/002—Reduction of iron ores by passing through a heated column of carbon
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B13/00—Making spongy iron or liquid steel, by direct processes
    • C21B13/14—Multi-stage processes processes carried out in different vessels or furnaces
    • C21B13/143—Injection of partially reduced ore into a molten bath
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0415—Purification by absorption in liquids
    • 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
    • C01B2203/04—Integrated processes for the production of hydrogen or synthesis gas containing a purification step for the hydrogen or the synthesis gas
    • C01B2203/0455—Purification by non-catalytic desulfurisation
    • 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
    • C01B2203/04—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
    • 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
    • C01B2203/04—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
    • C01B2203/0485—Composition of the impurity the impurity being a sulfur compound
    • 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
    • C01B2203/06—Integration with other chemical processes
    • C01B2203/068—Ammonia synthesis
    • 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
    • C01B2203/0872—Methods of cooling
    • C01B2203/0883—Methods of cooling by indirect heat exchange
    • 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
    • C01B2203/146—At least two purification steps in series
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21B—MANUFACTURE OF IRON OR STEEL
    • C21B2100/00—Handling of exhaust gases produced during the manufacture of iron or steel
    • C21B2100/60—Process control or energy utilisation in the manufacture of iron or steel
    • C21B2100/66—Heat exchange
    • C—CHEMISTRY; METALLURGY
    • C21—METALLURGY OF IRON
    • C21C—PROCESSING OF PIG-IRON, e.g. REFINING, MANUFACTURE OF WROUGHT-IRON OR STEEL; TREATMENT IN MOLTEN STATE OF FERROUS ALLOYS
    • C21C2100/00—Exhaust gas
    • C21C2100/06—Energy from waste gas used in other processes
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/122—Reduction of greenhouse gas [GHG] emissions by capturing or storing CO2
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/134—Reduction of greenhouse gas [GHG] emissions by avoiding CO2, e.g. using hydrogen
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/10—Reduction of greenhouse gas [GHG] emissions
    • Y02P10/143—Reduction of greenhouse gas [GHG] emissions of methane [CH4]
    • 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
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/25—Process efficiency
    • 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
    • Y02P20/129—Energy recovery, e.g. by cogeneration, H2recovery or pressure recovery turbines
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry

Definitions

  • the invention relates to a method and a device for generating a hydrogen (H 2 ) and carbon monoxide (CO) containing gas as a starting material for chemical recovery in synthesis processes based on export gas from a metallurgical process, wherein at least a portion of the export gas in subjected to a conversion reactor with the addition of water vapor of a CO conversion and synthesis gas is formed with a defined ratio H 2 to CO.
  • H 2 hydrogen
  • CO carbon monoxide
  • export gas from metallurgical plants can be recycled, in particular thermal utilization, such as e.g. a combustion or the use of pressure can be found by an expansion turbine application.
  • thermal utilization such as e.g. a combustion or the use of pressure can be found by an expansion turbine application.
  • export gas after a treatment e.g. used for the direct reduction of oxidic materials.
  • the combustibility of the export gas and thus the energy content expressed as calorific value is used to generate water vapor, wherein the water vapor to adjust the ratio H 2 to CO in Conversion reactor is used.
  • the steam required for the CO conversion can be at least partially generated in the process itself.
  • the export gas from a metallurgical process can be used for chemical recovery insofar as it has high contents of CO and H 2 .
  • the CO to H 2 ratio can be adjusted in a targeted manner under appropriate reaction conditions.
  • the known principle of CO conversion is used, wherein the chemical equilibrium of the water gas reaction between CO + H 2 O and CO 2 + H 2 is influenced.
  • the metallurgical process is a smelting reduction process which is operated by means of a blast furnace or by means of a melter gasifier which operates in conjunction with at least one reduction unit, in particular a reduction shaft or a fluidized bed reactor, iron raw materials containing iron oxide, in particular iron ore, Pellets or sinter, and aggregates are reduced to form a reducing gas and subsequently melted into liquid pig iron.
  • Smelting reduction processes produce a reducing gas in the process, which is used to reduce the feedstock and in particular to reduce mostly oxidic ores, such as iron ores.
  • oxidic ores such as iron ores.
  • coal or coke is gasified in the processes and a reducing gas is formed.
  • the gasification of the coal can take place in a blast furnace or in a melter gasifier, wherein the latter then the reducing gas, optionally after purification, flows into the reduction unit and runs in direct contact with the starting materials of the reduction process.
  • the reducing gas is opposite to the flow direction of the feedstock from a fluidized bed reactor to the next ⁇ etechnischt.
  • the export gas is obtained from top gas from a blast furnace or a reduction shaft or from offgas from a fluidized bed reactor or from excess gas from a melter gasifier or from mixtures of these gases.
  • Top gas is understood to mean the reducing gas after its direct contact with the starting materials and the resulting indirect reduction.
  • the person skilled in the art refers to the reducing gas as offgas, which is withdrawn from a fluidized bed reactor, in particular from the last of a series of fluidized bed reactors connected in series. Due to the usually high levels of CO and H 2 in the top gas or in the offgas, this is suitable for use in synthesis processes. Since the amount of reducing gas formed in the melter gasifier is not constant over time, so-called excess gas must be added to the export gas. The amount of excess gas results from the constant reduction gas quantity required in the reduction unit and a system pressure regulation in the melter gasifier.
  • the steam in the steam generator by the combustion of at least one further part of the export gas and / or by the use of waste heat from the metallurgical process and / or from the CO conversion and / or from the synthesis processes generated.
  • the steam required for the CO conversion can be achieved on the one hand by the combustion of export gas and on the other hand by the use of waste heat.
  • export gas By at least partially burning export gas, considerable savings in steam generation can be achieved. It is also advantageous that the combustion reduces toxic components in the export gas.
  • waste heat for example, by means of heat exchangers from the metallurgical process, from the CO conversion or from the resulting synthesis crude or from the synthesis processes are used, so that the steam generation can be very energy efficient. It can be one or -A-
  • the export gas prior to its use in the conversion reactor in a so-called saturator, preferably hot, add water and thereby increase the water vapor content in the export gas.
  • a so-called saturator preferably hot
  • condensate from the conversion reactor or the heat exchangers can be used after the conversion reactor.
  • top gas and / or offgas in particular dry, dedusted and / or purified by means of a wet dedusting, optionally cooled by means of a waste heat steam generator or a heat exchanger or a conditioning device (eg by injection of water through two-fluid nozzles) and provided as export gas.
  • the sensible heat of the export gas can be used by means of heat exchangers, so that a hot or even a largely cold export gas for the CO conversion can be provided.
  • dry dedusted and thus hot top gas and / or hot offgas its sensible heat can be used for the CO conversion, so that little or no heating can take place before the CO conversion.
  • the export gas before its supply to the conversion reactor or after its removal from the conversion reactor by means of a compressor, optionally after a separation of polyaromatic hydrocarbons from the export gas, compressed.
  • the compression causes the pressure for the CO conversion or for possible subsequent treatments of the synthesis crude gas formed in the CO conversion Gas, which is advantageous in most CO conversion process, since the already heated gas does not need to be heated so much.
  • the CO-conversion is performed, possibly after a heating of the export gas, in particular at 300-450 0 C.
  • CO-heat conversion (for example, with the use of catalysts based on iron / chromium or cobalt basis) offer the advantage that they have no high sensitivity to sulfur or sulfur compounds such as H 2 S, so that up to 100 ppmv sulfur can be used and further therefore also suitable for the sulfur compounds commonly present in export gases.
  • export gas from smelting reduction processes has the advantage that these have only very low sulfur contents.
  • the sulfur introduced via the raw materials and additives is largely desulfurized by means of the additives and removed from the iron production process via the slag of the smelting reduction plant.
  • the content of sulfur in the export gas usually bound as H 2 S and COS significantly lower than in known coal gasification processes. Therefore, no separate desulfurization must take place before the CO conversion, since the export gas already contains sufficiently low amounts of sulfur, sometimes less than 10 ppm.
  • the synthesis crude gas is operated by means of one or more preheating unit Waste heat generator cooled to adjust the temperature.
  • Waste heat generator cooled to adjust the temperature.
  • the waste heat of the synthesis crude gas which is already present with the desired amount ratio H 2 to CO, can be used in conventional heat exchangers or else for the production of water vapor.
  • the synthesis gas is first cooled and then subjected to a deposition process, in particular an absorption process, preferably a physical absorption or a chemical absorption or a physical / chemical absorption, in which sulfur and CO 2 from the synthesis gas at least partially, in particular substantially completely, be deposited.
  • a deposition process in particular an absorption process, preferably a physical absorption or a chemical absorption or a physical / chemical absorption, in which sulfur and CO 2 from the synthesis gas at least partially, in particular substantially completely, be deposited.
  • Known physical absorption processes are the Rectisol® ® - or Selexolpro- process
  • known chemical absorption process are amine scrubbing or the Benfield process and as physical / chemical absorption of Sulfinol mixes is known.
  • the synthesis gas is compressed to about 10-35 barg.
  • the synthesis gas treated in the deposition process in particular to a temperature of 200 to 400 0 C, heated and optionally desulfurized in a further Feinentschwefelungs-, in particular by means of zinc oxide or activated carbon.
  • the additional fine desulfurization stage enables a further reduction of the sulfur content in the synthesis gas to very low residual contents of less than 0.02 ppmv H 2 S, as required, for example, for methanol production with ⁇ 0.1 ppmv.
  • By heating the optimum for the desulfurization process temperature of about 200 - 400 0 C is set.
  • a fine desulfurization for example, zinc oxide adsorption or activated carbon, etc. may be used.
  • the waste heat produced during cooling of the synthesis gas in the heat exchanger is utilized to heat the synthesis gas treated in the deposition process.
  • efficient heating of the treated synthesis raw gas can take place.
  • a particularly advantageous variant of the method according to the invention provides that the steam arising during cooling in the waste heat steam generator is fed to the conversion reactor for use in the CO conversion. Thus, the energy demand for steam generation can be reduced.
  • a special embodiment of the method according to the invention provides that the, in particular in the deposition process treated, synthesis gas is heated by means of a heat exchanger to a temperature of 200 to 450 0 C.
  • the heat can be used, which is incurred during cooling of the synthesis gas in the heat exchanger prior to its treatment in the deposition process.
  • the synthesis crude gas is thereby necessary for a subsequent synthesis process
  • the crude synthesis gas optionally before the further fine desulfurization stage and / or prior to the synthesis process, is compressed by means of a compressor.
  • the compression takes place at a pressure level necessary for the respective synthesis process.
  • the heating occurring during the compression of the synthesis raw gas reduces the necessary energy supply in order to bring the synthesis raw gas to the process temperatures necessary in the fine desulfurization stage and / or a subsequent synthesis process.
  • the separated sulfur is separated from the separated CO 2 in a sulfur regeneration device, wherein the remaining CO 2 in the metallurgical process instead of nitrogen, in particular for gas barriers to the atmosphere, can be used.
  • a sulfur regeneration device wherein the remaining CO 2 in the metallurgical process instead of nitrogen, in particular for gas barriers to the atmosphere, can be used.
  • the hydrogen sulfide oxidation process LO-CAT II
  • the desulfurized CO 2 can now be used in technical applications, such as for gas barriers for sealing process units to the atmosphere or released into the atmosphere.
  • the further part of the export gas is cached before its combustion in the steam generator to compensate for volume and / or calorific value fluctuations in the export gas in a gas tank.
  • export gas which has a largely constant calorific value and is present in a constant amount.
  • the export gas is cached in a gas container, whereby calorific value and volume fluctuations can be compensated.
  • a part of the export gas is discharged for use as fuel gas in other heating devices.
  • remaining amounts of export gas, which are not used for steam generation or for CO conversion, be recycled, in addition to a thermal utilization and a use of the pressure energy is possible.
  • Synthesis processes work at very different pressures, temperatures and with different ratios H 2 to CO.
  • the production of methanol requires a ratio H 2 to CO of 2.0 to 2.3 or in other words a ratio (H 2 -CO 2 ) / (CO + CO 2 ) equal to 2.03, while, for example, the oxo-alcohol synthesis requires a ratio of 1, 0 to 1, 2. Due to the flexibility of the process, it is therefore possible to tailor the synthesis gas exactly to the respective synthesis process.
  • At least part of the water vapor formed in the steam generator is supplied as an energy carrier to the deposition process, wherein a thermal expulsion of the absorbed CO 2 from the absorption liquid used in the deposition process.
  • tail gas of a CO 2 removal device of the metallurgical process is mixed with the other part of the export gas and burned in the steam generator.
  • other process gases such as those occurring in devices for CO 2 removal, can also be used to generate steam.
  • purge gas is mixed from the synthesis process with the other part of the export gas and burned in the steam generator.
  • Purge gas is produced during the recycling of gases in synthesis processes.
  • the synthesis process usually only a part of the syngas can be converted, since then the thermodynamic equilibrium is reached. To increase the turnover, therefore, a circulation procedure is required, whereby process water and e.g. Methanol condensed out and separated.
  • the unreacted synthesis gas is recycled to the synthesis reactor.
  • a part must be discharged as purge gas from the cycle, which can be thermally utilized together with export gas.
  • waste heat from the metallurgical process is used to produce steam and the water vapor thus generated is fed to the conversion reactor and / or the separation process.
  • This waste heat from the metallurgical process itself and the water vapor thus obtained for the CO conversion or for a Absorption liquid can be used, so that a further increase in efficiency can be achieved.
  • the waste heat can be obtained, for example, from hot top gas, offgas or excess gas.
  • Metallurgical processes usually require further auxiliary processes, e.g. Provide process materials for the metallurgical process.
  • An example is an oxygen production, which is usually coupled with metallurgical processes. Waste heat can therefore also from such auxiliary processes or plants, such. an oxygen production or a synthesis gas treatment can be used for steam generation.
  • a special embodiment of the method according to the invention provides that, in addition to or instead of the export gas, partially oxidized hydrocarbons, in particular natural gas, asphalt, coal or naphtha, are used.
  • the additional gases instead of or in addition to the export gas, a redundant process can be achieved, so that even with a planned shutdown of the metallurgical process or in case of disturbances, the operation of the synthesis process can be maintained.
  • the device according to the invention provides that the export gas source is conductively connected to the conversion reactor, so that at least part of the export gas in the conversion reactor can be subjected to CO conversion with the addition of water vapor.
  • a synthesis gas is formed with a defined ratio H 2 to CO.
  • the export gas source is connected in line with the steam generator, so that a further part of the export gas in the steam generator can be at least partially burned to form steam and the water vapor formed can be fed to the conversion reactor via a steam line.
  • the conversion reactor can be supplied by means of steam from a waste heat recovery system.
  • a possible variant of the device according to the invention provides that a separation device is provided for separating sulfur and CO 2 from the synthesis gas, which is connected to the conversion reactor via a crude gas line.
  • a separation device known devices are used, which are constructed for example of an absorption and a stripping column. Such devices can be found in the prior art.
  • a steam line which leads from the steam generator or waste heat recovery system to the separation device is provided so that water vapor or alternatively also energy in the form of a hot gas stream can be supplied to the separation device.
  • the energy required for the mostly thermal expulsion of the CO 2 can be applied by the supply of water vapor or waste heat, so that no additional energy source is needed.
  • a heat exchanger and / or a preheater and / or a water cooler and / or a waste heat steam generator is or are provided for cooling the synthesis raw gas derived from the conversion reactor in the crude gas line.
  • cooling is necessary, whereby the dissipated heat can be dissipated in a heat exchanger or used for steam generation.
  • gas-gas heat exchangers or liquid-gas heat exchangers can be used, the latter enabling a greater cooling of the synthesis gas.
  • a fine desulfurization stage in particular based on zinc oxide or activated carbon, is provided for the separation of residual sulfur from the synthesis gas already treated in the separation apparatus.
  • Such Feinentschwefelungs syndromen can as zinc oxide adsorption or activated carbon processes which take place in adsorption columns.
  • An advantageous embodiment of the device according to the invention provides that at least one compressor, in particular a single-stage or multistage compressor, for compression of the export gas prior to introduction into the conversion reactor and / or a compressor for compression of the synthesis raw gas prior to introduction into the separator or are provided in the desulfurization or is.
  • Multi-stage compressors are used primarily when higher densities are needed. During compression, the compressed gas heats up.
  • An advantage of the split on two compressors is given by the fact that after the deposition of CO 2 and sulfur only a part of the syngas (eg about 55% for a methanol production) must be compressed to the pressure required for the synthesis process, as a large Part of the synthesis gas in the form of CO 2 in the separator (eg about 45% for a methanol production) is already deposited.
  • the separation device is connected in terms of line with the fine desulfurization, this compound optionally by preheating leads, so that the synthesis gas can be heated prior to its introduction into the desulfurization.
  • the synthesis gas can be adjusted to a temperature which is optimal for the desulfurization stage and / or the synthesis process, energy-efficient heating of the gas taking place through the use of the waste heat.
  • a sulfur regeneration device for the regeneration of sulfur from the separated in the deposition device mixture of sulfur and CO 2 .
  • Sulfur is deposited as a filter cake
  • the deposition device can
  • the export gas source is a smelting reduction plant and comprises in particular a blast furnace or a melter gasifier with at least one reduction unit.
  • Such metallurgical aggregates produce export gas in an amount and quality sufficient for chemical utilization, whereby the method according to the invention is used. Due to the possibility of adjusting the export gas in terms of its composition such systems are particularly well suited as an export gas source.
  • the reduction unit is designed as a blast furnace or as a reduction shaft or as a fluidized bed reactor or as at least two series-connected fluidized bed reactors.
  • the reducing gases generated in the reduction units are withdrawn after the reaction with the feedstocks to be reduced from the aggregates.
  • a CO and H 2 -rich gas is produced which can be used as export gas after dedusting and / or scrubbing.
  • a possible variant of the device according to the invention provides that a gas container is provided for temporarily storing the further part of the export gas before its combustion in the steam generator, so that volume and / or calorific value variations in the export gas can be compensated.
  • the volume of the gas container is chosen such that, despite plant-induced fluctuations in the export gas quantity or its composition, a largely constant supply of the steam generator can be ensured.
  • a tar removal device for removing polyaromatic hydrocarbons from the export gas is provided, which is arranged in the connecting line between the export gas source and the conversion reactor. This allows unwanted inventory parts which may adversely affect gas processing (eg compaction) and chemical recovery.
  • the waste heat recovery and / or the heat exchanger and / or the preheater for generating water vapor are provided and connected in line with the conversion reactor, so that water vapor formed can be fed to the conversion reactor.
  • the waste heat can be used to generate steam.
  • the synthesis plants can be provided with waste heat steam generators (for example, in the case of isothermal process control of the synthesis process), so that waste heat from the synthesis processes for steam generation can also be used.
  • Fig. 1 scheme of the method according to the invention on the basis of a smelting reduction plant according to the type "COREX ®"
  • Fig. 2 Schematic of the method according to the invention on the basis of a smelting reduction plant according to the type "FINEX ®"
  • Fig. 3 Scheme of the inventive method based on a blast furnace
  • the part A comprises the melt reduction plant
  • plant part B comprises the plant for the production of Syntheserrohgases and the synthesis products
  • part of the plant C relates to the steam generation.
  • a smelting unit such as a melter gasifier 1 pig iron RE is reduced from the reduced in the reduction unit 2 feedstocks and to produce a introduced, where in direct contact of the reducing gas with the feedstock at least partial reduction to sponge iron occurs. Further details on the treatment of the reducing gas prior to its entry into the reduction unit 2 will not be discussed in more detail, since this belongs to the prior art and is well known to the person skilled in the art.
  • the reduction gas is withdrawn after reduction in the reduction unit 2 as a top gas TG from the reduction unit 2 and at least one dry dedusting 3 or a wet dedusting 4 supplied and cleaned. It is also possible to combine a pre-cleaning in the dry dedusting 3 with a subsequent wet dedusting 4.
  • the top gas can also be used for waste heat recovery 5, e.g. a heat exchanger or a waste heat steam generator, fed and thereby cooled.
  • the purified and possibly cooled top gas is provided as an export gas to the plant part B.
  • Plant part A serves as export gas source.
  • this export gas source may also serve another same or other metallurgical plant or combustors for the partial oxidation of natural gas, steam reformer based on natural gas or Flugstromvergaser for gasification of coal as a gas source.
  • the export gas is first compressed in a compressor 6, such as a compressor, whereby a pressure necessary for the conversion reactor 7 or the CO conversion is set.
  • a compressor 6 such as a compressor
  • polyaromatic hydrocarbons can be separated from the export gas by means of a tar removal device.
  • the CO conversion takes place with the addition of steam, which is supplied via the steam line 9 from the steam generator 10 to the conversion reactor 7, wherein there is a shift of the proportions CO and H 2 comes.
  • the reaction can be controlled selectively, wherein the synthesis gas is generated.
  • the synthesis gas is first cooled by means of the heat exchanger 1 1, 12, and the preheater 13, which may also be designed as a heat exchanger, and optionally by means of another water cooler 14, these units are arranged in the crude gas line 19.
  • the hot synthesis gas can be cooled by means of a waste heat steam generator 15 and thereby used to generate water vapor.
  • the cooled synthesis gas is then fed to a separator 16 for separating sulfur and CO 2 from the synthesis gas, wherein the separated sulfur and CO 2 are fed to a desulfurization stage 17.
  • the sulfur is separated from the CO 2 to form a sulfur cake SK.
  • the now almost sulfur-free CO 2 can be used as a process gas in metallurgical processes, such as in gas barriers, or be released into the atmosphere.
  • the purified synthesis gas we are now supplied after compression in a compressor 18 of the preheater 13, wherein the purified synthesis gas is heated using the waste heat from the synthesis gas after leaving the conversion reactor 7.
  • the now heated synthesis crude gas is optionally fed to a fine desulfurization stage 20, wherein in adsorption columns based on a zinc oxide adsorption or an activated carbon method, sulfur or hydrogen sulfide (H 2 S) is separated.
  • this adsorption treatment is carried out at temperatures of about 200 to 400 0 C.
  • the desulfurized and hot synthesis gas can be further heated by means of the heat exchanger 12 as needed, with an advantageous for the subsequent chemical recovery temperature of about 200 to 450 0 C is set.
  • the compressed export gas can via a Bypass line 21 are passed to the conversion reactor or the heat exchanger 11.
  • Both the conversion reactor 7 and the separator 16 require large amounts of water vapor for operation.
  • the export gas source is connected to a steam generator 10 via a line.
  • water vapor is generated by means of the heat of combustion of the export gas and fed to the conversion reactor 7 and the deposition device 16 via steam lines 9a and 9b.
  • the steam ducts 9a and 9b can also be supplied via an additional steam duct 9c, this being steam that originates from the waste heat from the metallurgical process, the gas treatment or the synthesis process, and e.g. was generated by means of waste heat steam generator using hot process media.
  • the plant part C includes not only the steam generator 10 but also a gas container 22 for temporarily storing the part of the export gas which is provided for combustion in the steam generator 10, wherein quantity and / or calorific value variations in the export gas can be compensated. In the event that excess export gas should be present, this can also be provided via a derivative 23 for other purposes, e.g. used in coal drying plants, fine coal drying plants or ore drying plants. Condensates formed in the separation device 16 can be returned to the steam generator 10 via a condensate line 24.
  • the purified and heated raw synthesis gas can be used, for example, as a starting material for the production of methane, methanol, oxo alcohols or also Fischer-Tropsch fuels in chemical synthesis processes SPrSP 4 , whereby the raw synthesis gas is in each case tuned to the synthesis process.
  • Purge gas from the synthesis process can be mixed with the further part of the export gas via a purge gas line 30 and fed to the gas container 22 and subsequently burned in the steam generator 10.
  • Figure 2 shows a view similar to Figure 1 system, wherein the part A is formed by a FINEX ® -Schmelzreduktionsstrom.
  • the reducing gas formed in the melter gasifier is passed through the fluidized bed reactors R1, R2, R3 and R4 and flows in the opposite direction to the flow direction of the fine ore, which is reduced in the fluidized bed reactors R1, R2, R3 and R4 and then melted in the melter gasifier 1.
  • the reducing gas is withdrawn from the fluidized-bed reactor R4 as offgas OG, cooled in a heat exchanger 29 and made available as export gas after dedusting.
  • the tail gas of a CO 2 removal plant 28, such as a pressure swing adsorption plant (PSA or VPSA plant) can be supplied together with export gas to the gas tank 22 and used for steam generation in the steam generator 10.
  • PSA or VPSA plant pressure swing adsorption plant
  • FIG. 3 shows a plant which is in principle the same, the plant part A being formed by a blast furnace with connected supply units.
  • the top gas from the blast furnace 25 is first dedusted in a dry dedusting 26, optionally subsequently further purified in a wet dedusting 27 and made available as export gas for the plant part B or C.
  • the tail gas of a CO 2 removal plant 28 can also be supplied together with export gas to the gas container 22 and used for steam generation in the steam generator 10.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Health & Medical Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Combustion & Propulsion (AREA)
  • Inorganic Chemistry (AREA)
  • Waste-Gas Treatment And Other Accessory Devices For Furnaces (AREA)
  • Industrial Gases (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Hydrogen, Water And Hydrids (AREA)
  • Manufacture Of Iron (AREA)

Abstract

L'invention concerne un procédé et un dispositif de production d'un gaz contenant un hydrogène (H2) et du monoxyde de carbone (CO), comme matière première d'une valorisation chimique p.ex. dans les procédés de synthèse à base de gaz de dégagement issus d'un procédé métallurgique. Une partie du gaz de dégagement est soumise, par adjonction de vapeur d'eau, à une conversion en CO, ce qui permet d'obtenir un gaz brut de synthèse ayant un rapport H2 / CO défini. Le procédé selon l'invention permet de générer dans au moins un générateur de vapeur au moins partiellement la vapeur d'eau nécessaire à la conversion en CO.
EP09763885A 2008-11-21 2009-11-03 Procédé et dispositif de production d'un gaz brut de synthèse Withdrawn EP2356067A1 (fr)

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AT0182208A AT507632A1 (de) 2008-11-21 2008-11-21 Verfahren und vorrichtung zur erzeugung eines syntheserohgases
PCT/EP2009/064494 WO2010057767A1 (fr) 2008-11-21 2009-11-03 Procédé et dispositif de production d'un gaz brut de synthèse

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EP (1) EP2356067A1 (fr)
JP (1) JP2012509456A (fr)
KR (1) KR20110097875A (fr)
CN (1) CN102256894B (fr)
AR (1) AR074367A1 (fr)
AT (1) AT507632A1 (fr)
AU (1) AU2009317452B2 (fr)
BR (1) BRPI0921381A2 (fr)
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RU (1) RU2515325C2 (fr)
TW (1) TW201026601A (fr)
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CN109181784B (zh) * 2018-09-27 2020-06-12 中国成达工程有限公司 一种将粗合成气中多组分复杂有机硫转化为硫化氢的装置及工艺
CN111253973A (zh) * 2018-11-30 2020-06-09 浙江天禄环境科技有限公司 一种气化还原制备合成气的方法和系统
CN111268645B (zh) * 2020-01-21 2022-04-08 华烁科技股份有限公司 一种含有co的原料气变换及热回收方法
CN111471489A (zh) * 2020-04-01 2020-07-31 华东理工大学 一种含碳固体废弃物制备合成气的方法及装置
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US20110284800A1 (en) 2011-11-24
AR074367A1 (es) 2011-01-12
TW201026601A (en) 2010-07-16
KR20110097875A (ko) 2011-08-31
WO2010057767A9 (fr) 2010-12-29
WO2010057767A1 (fr) 2010-05-27
AT507632A1 (de) 2010-06-15
AU2009317452B2 (en) 2014-02-20
UA106053C2 (uk) 2014-07-25
US8821760B2 (en) 2014-09-02
RU2515325C2 (ru) 2014-05-10
CA2744280A1 (fr) 2010-05-27
BRPI0921381A2 (pt) 2015-12-29
AU2009317452A1 (en) 2010-05-27
CN102256894A (zh) 2011-11-23
JP2012509456A (ja) 2012-04-19
RU2011125340A (ru) 2012-12-27
CA2744280C (fr) 2016-10-25
CN102256894B (zh) 2013-11-27

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