WO2013156480A1 - Réacteur à faisceau tubulaire à récupération de chaleur à partir de gaz de réaction - Google Patents

Réacteur à faisceau tubulaire à récupération de chaleur à partir de gaz de réaction Download PDF

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Publication number
WO2013156480A1
WO2013156480A1 PCT/EP2013/057906 EP2013057906W WO2013156480A1 WO 2013156480 A1 WO2013156480 A1 WO 2013156480A1 EP 2013057906 W EP2013057906 W EP 2013057906W WO 2013156480 A1 WO2013156480 A1 WO 2013156480A1
Authority
WO
WIPO (PCT)
Prior art keywords
tube bundle
bundle reactor
heat transfer
transfer medium
reactor
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.)
Ceased
Application number
PCT/EP2013/057906
Other languages
German (de)
English (en)
Inventor
Manfred Baldauf
Agnes BAUMGÄRTNER
Martin Ise
Alexander Tremel
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 AG
Siemens Corp
Original Assignee
Siemens AG
Siemens Corp
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 AG, Siemens Corp filed Critical Siemens AG
Priority to EP13717263.1A priority Critical patent/EP2825301A1/fr
Publication of WO2013156480A1 publication Critical patent/WO2013156480A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • B01J8/067—Heating or cooling the reactor
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C1/00—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon
    • C07C1/02—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon
    • C07C1/04—Preparation of hydrocarbons from one or more compounds, none of them being a hydrocarbon from oxides of a carbon from carbon monoxide with hydrogen
    • C07C1/0405—Apparatus
    • C07C1/041—Reactors
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
    • C25B15/00—Operating or servicing cells
    • C25B15/08—Supplying or removing reactants or electrolytes; Regeneration of electrolytes
    • C25B15/087—Recycling of electrolyte to electrochemical cell
    • 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
    • B01J2208/00106—Controlling the temperature by indirect heat exchange
    • B01J2208/00168—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles
    • B01J2208/00212—Plates; Jackets; Cylinders
    • B01J2208/00221—Plates; Jackets; Cylinders comprising baffles for guiding the flow of the heat exchange medium
    • 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
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Definitions

  • the invention relates to a tube bundle reactor for chemical synthesis and a method for operating the tube bundle reactor.
  • Known tube bundle reactors comprise a shell in which there is a heat transfer medium and reaction tubes for performing a chemical synthesis in the shell. They are used in particular in strongly exothermic reactions, since they are characterized by the very good cooling based on the heat transfer to the reaction tubes. The cooling takes place by means of a heat transfer medium, which is in contact with the reactor tubes. The temperature of the heat transfer medium after the reactor results from the released heat of reaction.
  • a heat transfer medium which is in contact with the reactor tubes.
  • the temperature of the heat transfer medium after the reactor results from the released heat of reaction.
  • the highest possible temperature of the heat transfer medium is desired.
  • the effectiveness of heat transfer of the heat of reaction to the heat transfer medium to achieve a sufficiently high temperature of the heat transfer medium is disadvantageously too low in existing shell and tube reactors.
  • the object of the present invention is to specify a tube bundle reactor and a method for operating a tube bundle reactor with which the heat transfer of the heat of reaction to a heat transfer medium is improved.
  • the object is achieved with respect to the reactor by a tube bundle reactor having the features of claim 1.
  • the object is achieved by the method specified in claim 9.
  • the dependent claims relate to advantageous developments of the invention.
  • the tube bundle reactor for chemical synthesis comprises reactor tubes, an outer shell, an inner shell and a space bounded by both casings.
  • the intermediate space has at least one gas line for guiding the reaction products of the chemical synthesis.
  • the outer shell has at least one opening for guiding heat transfer medium into the intermediate space.
  • the inner shell has at least one opening for guiding heat transfer medium into the inner shell.
  • a heat transfer medium is conducted into the intermediate space. Furthermore, a first gas stream of chemical synthesis products is passed through the gas line in the space so that the heat transfer medium is heated. The heat transfer medium is then fed into the inner shell of the tube bundle reactor. The heat transfer medium is further heated in the inner shell by means of the heat of the chemical synthesis. Finally, the heated heat transfer medium is led out of the tube bundle reactor.
  • the heat transfer medium is heated by means of the heat of the reaction tubes in the inner shell of the tube bundle reactor.
  • the heat of the product gases in the intermediate space for heating the heat transfer medium is advantageously used.
  • heat is advantageously transferred from the inner shell directly to the heat transfer medium in the intermediate space via the inner shell. As a result, an overall improved heat yield in the tube bundle reactor is achieved.
  • the reactor tubes comprise a catalyst bed and / or the reactor tubes are coated on the inside with catalyst.
  • the reactor tubes and / or the gas line on the outside on ribs, knobs or fins are advantageously improved by the surface enlargement. Furthermore, it is possible to increase the surface area of the inner shell in order to improve the heat transfer between the space and the space enclosed by the inner shell.
  • the tube bundle reactor comprises means for uniformly distributing the heat transfer medium in the inner shell and / or the intermediate space.
  • these means include in particular fillers, distributor bases or internals.
  • the tube bundle reactor comprises means for adjusting a mass flow of the heat transfer medium for temperature control.
  • the temperature in the tube bundle reactor can be adjusted such that in particular the yield of the chemical synthesis is maximum.
  • the composition of the product gas in particular with regard to upper limit values of residual gases.
  • the temperature of the heat transfer medium when leaving the tube bundle reactor is adjustable, so that a further process, in particular a distillation or an electrolysis, is heated with this heat transfer medium.
  • the tube bundle reactor comprises a device for setting an operating pressure of the tube bundle. reactor for temperature control.
  • the temperature in the tube bundle reactor can be adjusted such that in particular the yield of the chemical synthesis is maximum.
  • the composition of the product gas in particular with regard to upper limit values of residual gases.
  • the temperature of the heat transfer medium when leaving the tube bundle reactor is advantageously adjustable.
  • the tube bundle reactor comprises at least one means for returning heat transfer medium from a first point of the intermediate space to a second point of the intermediate space for temperature control.
  • the temperature in the tube bundle reactor can be adjusted such that in particular the yield of the chemical synthesis is maximum.
  • the composition of the product gas in particular with regard to upper limit values of residual gases.
  • the temperature of the heat transfer medium when leaving the tube bundle reactor is adjustable.
  • the reactor tubes are fastened with means for compensating thermal expansion effects in the tube bundle reactor.
  • These means are in particular hoses or flexible metal compensators.
  • a methanization or a methanol synthesis is carried out as the chemical synthesis.
  • the resulting in the methanation of synthetic natural gas is advantageously stored in the existing natural gas network.
  • a first part of the product gas is recycled to the educt gas of the chemical synthesis.
  • the yield, the degree of conversion and / or the selectivity of chemical synthesis are thereby advantageously increased.
  • the temperature of the tube bundle reactor can advantageously be regulated by this recycling.
  • the heat transfer medium changes in the intermediate space and / or in the inner shell at least once the state of matter, in particular from liquid to vapor.
  • the products of the chemical synthesis at least once change the state of matter, in particular from vapor to liquid.
  • an arrangement comprises a high-temperature electrolyzer and a tube bundle reactor, wherein the heat transfer medium is water and / or water vapor and the water vapor serves as a starting material for the high-temperature electrolyzer.
  • high-temperature electrolyzer and tube bundle reactor are materially coupled, whereby the overall efficiency of the reaction and the electrolysis increases.
  • At least one reactant of the chemical synthesis is produced in the arrangement in the high-temperature electrolyzer.
  • Hydrogen produced in particular in the electrolysis or, in the case of co-electrolysis, synthesis gas is fed to the Ruhrbündel reactor as educt gas.
  • high-temperature electrolyzer and tube bundle reactor are materially coupled, whereby the overall efficiency of the reaction and the electrolysis increases. The invention will be explained below with reference to an embodiment with reference to the drawings.
  • FIG. 1 shows a flow chart for a high-temperature electrolysis
  • FIG. 2 shows schematically the construction of the tube bundle reactor.
  • the arrangement shown in Figure 1 comprises a tube bundle reactor 1, a high temperature electrolyzer 2, a first heat exchanger 3 and a second heat exchanger 11.
  • the tube bundle reactor 1 is carried out as a chemical synthesis methanation.
  • methanation synthesis gas is converted to methane and water.
  • the product gas 18 thus comprises methane (synthetic natural gas) and water.
  • the waste heat from the exothermic synthesis is used to heat a water stream 4 to a water vapor stream 5.
  • the water vapor stream 5 thus produced is mixed with a first carbon dioxide stream 8 and fed to the first heat exchanger 3. There, the water vapor and carbon dioxide stream is further heated and supplied to the high-temperature electrolyser 2 as superheated steam and carbon dioxide stream 7.
  • synthesis gas 6 and oxygen are produced.
  • the synthesis gas 6 comprises predominantly hydrogen and carbon monoxide, but also small residual amounts of water vapor and carbon dioxide.
  • the synthesis gas 6 is supplied to the first heat exchanger 3. There it serves to heat the steam stream 5 and first
  • Carbon dioxide stream 8 The synthesis gas 6 is then fed to the tube bundle reactor 1 as Eduktstrom. Furthermore, a second carbon dioxide stream 9 is fed directly to the tube bundle reactor 1. The two carbon dioxide streams 8, 9 are fed from the same carbon dioxide tank 21.
  • the high-temperature electrolyzer 2 is additionally rinsed with an air stream 13.
  • the acid produced in the electrolysis The ceramic electrolysis membrane 12 can pass in ionic form and leaves the high-temperature electrolyzer 2 as an oxygen-rich gas stream 14.
  • the air stream 13 is preheated in the second heat exchanger 11 with the oxygen-rich gas stream 14.
  • a part of the synthesis gas 6 produced in the electrolysis is fed to the first heat exchanger 3 via a return line 10. This prevents oxidation of the nickel-containing hydrogen electrode.
  • the thermal integration of the production of water vapor from water by the methanation in the tube bundle reactor 1 significantly increases the efficiency. This thermal integration is achieved by adjusting the ratio of the first
  • Carbon dioxide stream 8 to the second carbon dioxide stream 9 further optimized.
  • the quality of the product gas 18 produced in the methanation can also be influenced by adjusting this ratio.
  • the sole supply of carbon dioxide via the first carbon dioxide stream 8 to the high-temperature electrolyzer 2 represents a first limiting case of this ratio.
  • carbon dioxide is fed exclusively to the tube bundle reactor 1 via the second carbon dioxide stream 9.
  • the composition of the product gas 18 is also determined by the ratio of the carbon dioxide streams 8, 9 in the manner improves that the methane content increases.
  • the methanation of carbon monoxide from the synthesis gas results in a different gas composition of the synthetic natural gas than the feeding of carbon dioxide directly to the methanation.
  • a defined ratio carbon dioxide high temperature electrolyzer to carbon dioxide shell and tube reactor
  • FIG. 2 shows a tube bundle reactor 1 which comprises an inner shell 19, an outer shell 15 and a gap 16.
  • reactor tubes 20 are filled with catalyst in the form of a fixed bed.
  • the reactor tubes 20 may alternatively be coated on the inside with catalyst or filled with a catalyst suspension.
  • the outside of the reactor tubes 20 and the gas line 17 is provided with ribs. This improves the heat transfer.
  • the outside of the reactor tubes 20 and / or the gas line 17 comprises knobs or fins.
  • the reactor tubes 20 are heat-compensated complained, so that the thermal expansion of the reactor tubes 20 is compensated by suitable intermediate elements, such as hoses and flexible metal compensators.
  • the produced natural gas is collected from the reactor tubes 20 in a product gas collector.
  • the water and / or the water vapor flow in countercurrent to the water and / or water vapor in the intermediate space 16.
  • the synthesis gas 6 produced in the high-temperature electrolyzer 2 is mixed with the second carbon dioxide stream 9 and fed to the tube bundle reactor 1. There, the gas stream is distributed to the reactor tubes 20.
  • the conversion of synthesis gas 6 to product gas 18, which comprises methane and water, takes place by means of the methanation.
  • the waste heat, produced during methanation is used directly to heat water to water vapor.
  • the water is first supplied to the intermediate space 16 as a water stream 4. Here it is preheated by means of the generated product gas 18 in the interspace gas line 17. If the water from the product gas 18 condenses in the interspace gas line 17, then the preheating is rendered particularly effective by the heat of condensation released.
  • the water now flows as water and as water vapor into the inner shell 19 of the tube bundle reactor 1. There, the water is heated further. Internals in the inner shell 19 distribute the water and water vapor evenly. Alternatively, the distribution takes place by means of a filling body fill in the inner shell 19.
  • the water vapor which arises in the process leaves the tube bundle reactor 1 as a water vapor stream 5.
  • the temperature of the tube bundle reactor 1 can be adjusted via the water flow 4. If the water flow 4 chosen so high that it comes to a damming of liquid water in the intermediate space 16, this water cools the inner shell 19 and the reactor tubes 20. If the water flow 4 is chosen so high that liquid water enters the inner shell 19, evaporates Water in the inner shell 19, which additionally increases the cooling of the reactor tubes 20.
  • Another way to influence the temperature in the tube bundle reactor 1 is the choice of operating pressure. As the pressure increases, the boiling point of the water rises. As a result, the temperature level in the entire tube bundle reactor 1 increases.
  • the temperature of the tube bundle reactor 1 can alternatively be influenced via a return of the cold product gas 18 to the reactor inlet.
  • the temperature in the tube bundle reactor 1 can be influenced by liquid water the space 16 above the addition of the water stream 4 to the tube bundle reactor 1 is removed. This liquid water is mixed with the water stream 4 and fed to the tube bundle reactor 1 again.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Sustainable Development (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)

Abstract

L'invention concerne un réacteur à faisceau tubulaire pour la synthèse chimique, un procédé pour faire fonctionner un réacteur à faisceau tubulaire et un dispositif composé d'un réacteur à faisceau tubulaire et d'une électrolyse haute température. Le réacteur à faisceau tubulaire comporte une enveloppe extérieure, une enveloppe intérieure et un espace intermédiaire délimité par les deux enveloppes, contenant au moins une conduite de gaz. L'espace intermédiaire et l'enveloppe intérieure sont remplis de milieu caloporteur. L'échange de chaleur entre la chaleur de réaction et le milieu caloporteur est amélioré du fait que la chaleur du gaz de réaction est également transférée vers l'espace intermédiaire. En outre, la température peut être régulée dans le réacteur à faisceau tubulaire.
PCT/EP2013/057906 2012-04-20 2013-04-16 Réacteur à faisceau tubulaire à récupération de chaleur à partir de gaz de réaction Ceased WO2013156480A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP13717263.1A EP2825301A1 (fr) 2012-04-20 2013-04-16 Réacteur à faisceau tubulaire à récupération de chaleur à partir de gaz de réaction

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102012206540.7 2012-04-20
DE102012206540A DE102012206540A1 (de) 2012-04-20 2012-04-20 Rohrbündelreaktor mit Wärmerückgewinnung aus Produktgas

Publications (1)

Publication Number Publication Date
WO2013156480A1 true WO2013156480A1 (fr) 2013-10-24

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PCT/EP2013/057906 Ceased WO2013156480A1 (fr) 2012-04-20 2013-04-16 Réacteur à faisceau tubulaire à récupération de chaleur à partir de gaz de réaction

Country Status (3)

Country Link
EP (1) EP2825301A1 (fr)
DE (1) DE102012206540A1 (fr)
WO (1) WO2013156480A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3511442A1 (fr) * 2018-01-12 2019-07-17 Linde Aktiengesellschaft Production d'un produit gazeux contenant du monoxyde de carbone
CN121631245A (zh) * 2026-02-03 2026-03-10 上海中弗新能源科技股份有限公司 一种soec电解制氢高效稳流蒸汽发生器结构

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3441917A1 (de) * 1983-09-06 1986-05-28 MAN Gutehoffnungshütte GmbH, 4200 Oberhausen Stehender reaktor zur erzeugung von methanol
WO2001055027A1 (fr) * 2000-01-25 2001-08-02 Imperial Chemical Industries Plc Dispositif de reformage a la vapeur
WO2003031050A1 (fr) * 2001-10-09 2003-04-17 Jonhson Matthey Plc Reacteur echangeur de chaleur
US20070000173A1 (en) * 2005-06-28 2007-01-04 Michael Boe Compact reforming reactor

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005001952A1 (de) * 2005-01-14 2006-07-27 Man Dwe Gmbh Rohrbündelreaktor zur Durchführung exothermer oder endothermer Gasphasenreaktionen
DE102005004604A1 (de) * 2005-02-01 2006-08-10 Basf Ag Verfahren zur Steuerung einer Hydrierung
DE102010040757A1 (de) * 2010-09-14 2012-03-15 Man Diesel & Turbo Se Rohrbündelreaktor

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE3441917A1 (de) * 1983-09-06 1986-05-28 MAN Gutehoffnungshütte GmbH, 4200 Oberhausen Stehender reaktor zur erzeugung von methanol
WO2001055027A1 (fr) * 2000-01-25 2001-08-02 Imperial Chemical Industries Plc Dispositif de reformage a la vapeur
WO2003031050A1 (fr) * 2001-10-09 2003-04-17 Jonhson Matthey Plc Reacteur echangeur de chaleur
US20070000173A1 (en) * 2005-06-28 2007-01-04 Michael Boe Compact reforming reactor

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3511442A1 (fr) * 2018-01-12 2019-07-17 Linde Aktiengesellschaft Production d'un produit gazeux contenant du monoxyde de carbone
WO2019137827A1 (fr) * 2018-01-12 2019-07-18 Linde Aktiengesellschaft Fabrication d'un produit gazeux contenant du monoxyde de carbone
CN121631245A (zh) * 2026-02-03 2026-03-10 上海中弗新能源科技股份有限公司 一种soec电解制氢高效稳流蒸汽发生器结构

Also Published As

Publication number Publication date
EP2825301A1 (fr) 2015-01-21
DE102012206540A1 (de) 2013-10-24

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