Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J8/00—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes
  • B01J8/02—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds
  • B01J8/06—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes
  • B01J8/062—Chemical or physical processes in general, conducted in the presence of fluids and solid particles; Apparatus for such processes with stationary particles, e.g. in fixed beds in tube reactors; the solid particles being arranged in tubes being installed in a furnace
• • 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
  • C01B3/22—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds
  • C01B3/24—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons
  • C01B3/26—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of gaseous or liquid organic compounds of hydrocarbons using catalysts
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/32—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by dehydrogenation with formation of free hydrogen
  • C07C5/327—Formation of non-aromatic carbon-to-carbon double bonds only
  • C07C5/333—Catalytic processes
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F22—STEAM GENERATION
  • F22B—METHODS OF STEAM GENERATION; STEAM BOILERS
  • F22B1/00—Methods of steam generation characterised by form of heating method
  • F22B1/02—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers
  • F22B1/18—Methods of steam generation characterised by form of heating method by exploitation of the heat content of hot heat carriers the heat carrier being a hot gas, e.g. waste gas such as exhaust gas of internal-combustion engines
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/00504—Controlling the temperature by means of a burner
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2208/00—Processes carried out in the presence of solid particles; Reactors therefor
  • B01J2208/00008—Controlling the process
  • B01J2208/00017—Controlling the temperature
  • B01J2208/0053—Controlling multiple zones along the direction of flow, e.g. pre-heating and after-cooling
• • 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
  • C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
  • C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition 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
  • C01B2203/14—Details of the flowsheet
  • C01B2203/142—At least two reforming, decomposition or partial oxidation steps in series
• • 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
  • C01B2203/80—Aspect of integrated processes for the production of hydrogen or synthesis gas not covered by groups C01B2203/02 - C01B2203/1695
  • C01B2203/84—Energy production
• • 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
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/584—Recycling of catalysts

Definitions

• the invention relates to one or more burners used as additional heating in the flue gas duct of a reactor for the performance of an endothermic reaction by which it is possible to produce a nearly constant amount of flue gas, the reactor being equipped with a steam generator located in the outlet of the flue gas duct of the heating chamber, and the burners being used as auxiliary burners for balancing the flue gas reduction in the flue gas duct of the heating chamber which normally occurs during the regeneration phase of the exothermic regeneration of the catalyst in use.
• the invention also refers to a device comprising one or more auxiliary burners installed in a reactor for the performance of an endothermic reaction including the necessary equipment by which it is possible to control the amount of flue gas in the outlet of the flue gas duct housing the steam generator. In this way, the steam flow obtainable from the steam generator is equalised to a substantial degree, which is of advantage in the operation of turbines or compressors.
• This device is especially suited for reactors typically used for alkane dehydrogenation processes.
• a common process for performing an alkane dehydrogenation is to pass an alkane-containing hydrocarbon mixture across a dehydrogenation catalyst which causes the alkane contained in the gas mixture to react to the corresponding alkene.
• the catalyst is provided in a typical configuration in downward reaction tubes which the reaction gas enters through an inlet duct so that the product gas which contains, as a component, the required alkene can be obtained at the outlet of the reaction tubes.
• the reaction is endothermic so that it is required to heat the reaction tubes from the outside. This is normally accomplished by means of a reactor with a heating chamber with integrated reaction tubes, which can be heated with fuel gas.
• the reaction tubes are sealed towards the heating chamber.
• the heating chamber ends in a flue gas duct where the hot flue gas is thermally utilised and finally discharged into a stack.
• the flue gas from the heating is discharged from the heating chamber via flue gas ducts. Its temperature is around 1000° C. depending on the respective constructional design.
• a steam generator is typically installed for the flue gas in or downstream of the outlet of the flue gas duct.
• An alkane dehydrogenation is typically accompanied by the formation of carbonaceous by-products which deposit on the catalyst after a certain reaction period. This will reduce the reaction yield and the production of required alkene.
• the reaction is, for this reason, interrupted after a certain period of time and the reaction gas flow across the catalyst stopped.
• an oxygen-containing gas is subsequently passed across the catalyst. It serves to remove the carbonaceous deposits and to regenerate the catalyst. After the regeneration, the alkane dehydrogenation in the respective reaction tube or reactor is resumed. According to this procedure the process is carried out in a cyclic operating mode.
• the reactor requires a significantly lower amount of heat during the regeneration period than during normal operation.
• the burners are normally operated with less fuel gas during the regeneration phase resulting in an analogously lower production of flue gas.
• WO 2007/118825 A1 describes a process for the production of olefins from hydrocarbons and a device for running the process.
• the heat supply into the catalyst bed is interrupted so that no more heat is fed to the catalyst bed when oxygen-containing gas is passed across it during regeneration and the catalyst is prevented from overheating and degradation.
• the burners are provided with a switch-off device and are re-ignited for re-start by means of pilot burners after the regeneration. Both the heating burners and the pilot burners may be equipped with a monitoring device. No indications are made with reference to the generation of steam by the use of a steam generator and a compensation of the interrupted heating.
• EP 179322 B1 describes a process for the exothermic regeneration of a catalyst which has been deactivated during an endothermic catalytic conversion in the course of a discontinuous process.
• suitable application processes special reference is made to the dehydrogenation of i-butane, n-butane or mixtures thereof. If several reactors are used, it is possible to operate them alternately so that there is in total no change in the supply of heating media, combustion streams and no load change in the waste heat system. This teaching as well does not give any indications with reference to the generation of steam by the use of a steam generator or to the compensation of the interrupted heating.
• the flue gas feed to the steam generators installed in the flue gas duct is reduced.
• the dehydrogenation process works such that steam is supplied to serve as turbine steam during normal operation and also during regeneration.
• the unit itself produces less steam.
• the steam consumption level in the regeneration mode is almost as high as during normal operation. The amount of steam supplied during the regeneration phase therefore determines the amount of steam supplied to the dehydrogenation unit.
• the invention achieves this aim by a process for the constant or controlled supply of flue gas from an endothermic catalytic reaction, by which it is possible to use this flue gas to produce a steam flow which is as high as possible in quantity by means of a steam generator, in which at least one auxiliary burner is installed in the outlet of the flue gas duct, the burner being used to generate a flue gas stream which does not get into contact with the reaction tubes to be heated and by which the flue gas stream is increased in quantity on the heat exchange surfaces of the steam generator during the regeneration.
• the invention achieves this aim also by a device made up by one or more auxiliary burners at the inlet of the flue gas duct of a reactor for the performance of an endothermic catalytic reaction, the auxiliary burners being arranged in the flue gas stream behind the reaction tubes.
• the device also includes a monitoring and control device for the auxiliary burners.
• Typical endothermic catalytic processes suitable for the application of the invention are alkane dehydrogenation processes. These are, in any case, reactions which are performed in reaction tubes loadable with catalyst, the reaction tubes being arranged in a heatable reaction chamber and the reaction chamber being heated with fuel gas from burners.
• a typical process for the dehydrogenation of alkanes suited for the application of the invention is described in WO 2004/039920 A2. This document also describes a reactor in which the hydrogen generated in the alkane dehydrogenation is incinerated in a separate process step.
• the auxiliary burners are equipped with a control device by which it is possible to control the amount of combustion gas. This can be achieved by controlling the auxiliary burners by means of the flue gas temperature in the flue gas stream downstream of the auxiliary burners.
• the control device adjusts the supply of fuel gas or combustion air into the auxiliary burners.
• the auxiliary burners are used advantageously such that the temperature of the flue gas stream at the inlet of the flue gas duct is increased on the heat exchange surfaces of the steam generator.
• the temperature in the flue gas duct and on the heat exchange surfaces can be controlled via the fresh air supply into the flue gas duct if this is required.
• the auxiliary burners are advantageously equipped with a control device so as to control the fuel gas supply and thus the production of flue gas.
• the control device is governed by a temperature sensor provided near the heat exchange surfaces of the steam generator so that it is possible to control the auxiliary burners by means of the temperature in the flue gas duct. In a simpler embodiment it is also possible to provide for a manual control of the auxiliary burners.
• the control device of the auxiliary burners can also be controlled by the amount of produced steam.
• a steam flow meter for the amount of steam produced is installed in a suitable position of the steam generator so that the auxiliary burners can be controlled by the amount of steam produced.
• Processes which are qualified for the process according to the invention are in particular alkane dehydrogenation processes used to convert an alkane into an alkene by releasing hydrogen. This may be carried out in a single process. It is, however, also common practice to carry out the alkane dehydrogenation converting an alkane into an alkene by releasing hydrogen and oxidising the hydrogen in a subsequent separate process step in which a further dehydrogenation of not yet converted alkane is achieved.
• the auxiliary burners may then be installed in one or more reactors. In this way the whole endothermic process is supported by the regeneration of the catalyst.
• a device by which it is possible to run the process according to the invention Especially claimed is a device for the generation of a constant amount of steam from the waste heat of an alkane dehydrogenation process, comprising
• auxiliary burners are provided with control devices by which it is possible to control the capacity of the burners.
• Suitable control devices are, for instance, valves, gate valves, flaps or stems which serve to control the supply of fuel gas into the auxiliary burners.
• the control device may also be used to control the supply of combustion air into the auxiliary burners.
• the auxiliary burners may also be controlled by parameters measured in the outlet of the flue gas duct.
• Devices required according to the related process claims are especially sensors measuring the flow rate of the combustion gas or the temperature of the combustion gas. To serve this purpose, these are installed in the outlet of the flue gas duct. If the aim is to control the auxiliary burners by the combustion gas flow rate, the flue gas ducts are equipped with a measuring device which serves to measure the combustion gas flow rate of the flue gas in the flue gas duct, by which it is possible to control the auxiliary burner.
• the flue gas ducts are provided with a device for measuring the temperature of the flue gas in the flue gas duct by which it is possible to control the auxiliary burner. If a comparison measurement in comparison to the overall flow rate or temperature of the flue gas is required, appropriate sensors can be installed in the flue gas duct itself or on the heat exchange surfaces of the steam generator. In another embodiment it is also possible to use Lambda probes for measuring the oxygen content in the flue gas duct, should the auxiliary burners be controlled by the oxygen content in the flue gas duct.
• the reactor for integrating the device according to the invention is typically configured as is common practice according to the state of the art.
• this includes a reactor for carrying out an endothermic reaction with integrated reaction tubes which can be loaded with a catalyst, burners which do not get into contact with the catalyst or the reaction gas and heat the reaction tubes from the outside, an inlet for the reaction gas and an outlet for the product gas in the reaction tubes, an inlet for the fuel gas and a flue gas duct, and a steam generator with heat exchange surfaces in or downstream of the outlet of the flue g as duct.
• the main burners and the auxiliary burners according to the invention may be installed in any position in the heating chamber or in the flue gas duct. This applies analogously to the heat exchange surfaces to be heated.
• the burners, reaction tubes or steam generators can be provided as single or as multiple units.
• the auxiliary burners are, in any case, arranged such that the escaping flue gases do not get into contact with the reaction tubes and the enclosed catalyst.
• auxiliary burners To control the auxiliary burners especially such devices may be used that serve the purpose of burner control according to the state of the art. These are typically valves, gate valves, flaps or stems which serve to control the supply of fuel gas or combustion air into the auxiliary burners.
• valves To measure control data, especially thermocouples, pressure gauges, gas flow meters and oxygen probes may be used.
• auxiliary burners used as auxiliary burners may be gas burners, liquid-fuel burners, rocket burners or solid-fuel blower burners. The type is determined by the size of the flue gas duct and of the heat exchange surfaces.
• the auxiliary burner device according to the invention also includes suitable ignition devices as there are, for example, electric or electronic igniters, pilot burner or flint stones.
• the auxiliary burners are preferably equipped with a control device by which the capacity of the auxiliary burner/s can be controlled. This can be implemented such that the flue gas duct, for example, is equipped with a device for measuring the flue gas temperature in the flue gas duct and by which the capacity of the auxiliary burner/s can be controlled.
• steam generators are used which may be arranged as desired and provided in any number desired. Typically these are steam generators which are arranged as indirect heat exchangers with heat exchange surfaces. These may be of optional design. These may also include measuring devices for measuring the amount of steam produced.
• the steam generators which are heated by means of the auxiliary burner/s may be equipped with a steam flow meter by which it is possible to control the capacity of the auxiliary burner/s.
• ancillary equipment such as pipelines, for example. These may be of optional design and number.
• the device according to the invention involves the advantage that an amount of steam which is as constant as possible throughout the duration of the process can be generated from the waste heat of an alkane dehydrogenation.
• the generation of steam from the waste heat of the before-mentioned processes can be optimised and used to recover mechanical energy.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Combustion & Propulsion (AREA)
• Mechanical Engineering (AREA)
• Health & Medical Sciences (AREA)
• Sustainable Energy (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• General Engineering & Computer Science (AREA)
• Sustainable Development (AREA)
• General Health & Medical Sciences (AREA)
• Inorganic Chemistry (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
• Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Hydrogen, Water And Hydrids (AREA)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

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• 2009
  • 2009-03-13 DE DE102009012663A patent/DE102009012663B3/de not_active Revoked
• 2010
  • 2010-03-01 BR BRPI1006356A patent/BRPI1006356A2/pt not_active Application Discontinuation
  • 2010-03-01 CN CN2010800112308A patent/CN102348500B/zh not_active Expired - Fee Related
  • 2010-03-01 WO PCT/EP2010/001238 patent/WO2010102734A1/de active Application Filing
  • 2010-03-01 CA CA2754378A patent/CA2754378C/en not_active Expired - Fee Related
  • 2010-03-01 MX MX2011009544A patent/MX2011009544A/es active IP Right Grant
  • 2010-03-01 MY MYPI2011004196A patent/MY160486A/en unknown
  • 2010-03-01 US US13/256,081 patent/US20120060824A1/en not_active Abandoned
  • 2010-03-01 DK DK10714568.2T patent/DK2406000T3/da active
  • 2010-03-01 EP EP10714568A patent/EP2406000B1/de not_active Revoked
  • 2010-03-01 ES ES10714568T patent/ES2392152T3/es active Active
  • 2010-03-01 KR KR1020117023904A patent/KR101583854B1/ko not_active IP Right Cessation
  • 2010-03-01 RU RU2011140430/05A patent/RU2518971C2/ru not_active IP Right Cessation
  • 2010-03-01 JP JP2011553321A patent/JP5619785B2/ja not_active Expired - Fee Related
  • 2010-03-10 AR ARP100100717A patent/AR076102A1/es not_active Application Discontinuation
• 2011
  • 2011-09-12 EG EG2011091516A patent/EG27042A/xx active
  • 2011-09-28 ZA ZA2011/07076A patent/ZA201107076B/en unknown
  • 2011-10-07 CO CO11132668A patent/CO6440574A2/es active IP Right Grant

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