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WO2017067648A1 - Procédé de production de gaz de synthèse - Google Patents

Procédé de production de gaz de synthèse Download PDF

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Publication number
WO2017067648A1
WO2017067648A1 PCT/EP2016/001702 EP2016001702W WO2017067648A1 WO 2017067648 A1 WO2017067648 A1 WO 2017067648A1 EP 2016001702 W EP2016001702 W EP 2016001702W WO 2017067648 A1 WO2017067648 A1 WO 2017067648A1
Authority
WO
WIPO (PCT)
Prior art keywords
reaction
regenerator
zone
heat exchange
reactor
Prior art date
Application number
PCT/EP2016/001702
Other languages
German (de)
English (en)
Inventor
Hans-Jörg ZANDER
Grigorios Kolios
Achim WECHSUNG
Original Assignee
Linde Aktiengesellschaft
Basf Se
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 Linde Aktiengesellschaft, Basf Se filed Critical Linde Aktiengesellschaft
Publication of WO2017067648A1 publication Critical patent/WO2017067648A1/fr

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10K—PURIFYING OR MODIFYING THE CHEMICAL COMPOSITION OF COMBUSTIBLE GASES CONTAINING CARBON MONOXIDE
    • C10K3/00—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide
    • C10K3/02—Modifying the chemical composition of combustible gases containing carbon monoxide to produce an improved fuel, e.g. one of different calorific value, which may be free from carbon monoxide by catalytic treatment
    • C10K3/026—Increasing the carbon monoxide content, e.g. reverse water-gas shift [RWGS]

Definitions

  • the invention relates to a process for the production of synthesis gas in which a hydrogen-containing gas stream in a reactor with a carbon dioxide-containing gas stream are reacted on a catalyst to carbon monoxide and water and a portion of the hydrogen from the hydrogen-containing gas stream with oxygen
  • Synthesis gas is to be understood as meaning a substance mixture containing hydrogen and carbon monoxide, which can be used as a basic chemical in a large number of industrial processes. For example, synthesis gas is used to produce
  • Carbon dioxide is used as a starting material to limit the emissions of carbon dioxide.
  • the reverse reaction of steam reforming occurs, producing methane and water. It is therefore necessary to choose reaction temperatures in which the equilibrium goes to the synthesis gas and away from the methane. For this purpose, high temperatures are necessary.
  • Synthesis gas can come from a
  • Reverse Wassergasshiftretress can also be generated when the hydrogen is produced via an electrolysis process, which is operated for example with excess current.
  • the reaction to a regenerative energy landscape and the recycling of sustainable resources is interesting.
  • a challenge here is the design of the reactor, which is stable under the necessary reaction conditions and in which the heat is optimally distributed.
  • Object of the present invention is therefore to provide a method in which an optimal use of heat is ensured in the reactor.
  • the object is achieved in that the reactants are preheated in a first phase of operation in a first heat exchange zone via a regenerator, further heated by the partial oxidation and then catalytically reacted in a reaction zone and the products and unreacted starting materials in a second heat exchange zone a regenerator are cooled and that the flow direction of the gas streams in the reactor is reversed in a second phase of operation.
  • reaction-resistant materials in particular oxides, such as ceramics,
  • Silicon carbide or molybdenum silicide This heat storage is warmed up by the effluent product gas. After a change of the flow direction of the regenerator is cooled by the reactant stream and thereby heats the
  • the reactant stream is composed of a hydrogen-containing and a carbon dioxide-containing gas stream.
  • the reactant stream flows into a first heat exchange zone, which contains a regenerator.
  • the reactant stream is preheated by the regenerator.
  • oxygen is introduced into the reactor, whereby the oxygen with at least a portion of the hydrogen from the
  • Reactant stream reacts. Pure oxygen or a mixture containing oxygen, in particular air, may be used. By the at least partial oxidation, the necessary heat is generated to achieve the necessary reaction temperature for the reverse Wassergasshiftretician and to suppress the reverse steam reforming.
  • the product stream contains synthesis gas consisting of hydrogen and carbon monoxide, but may also contain unreacted starting materials and by-products such as methane and water.
  • the product stream is in turn passed through a heat exchange zone containing another regenerator. This is heated by the product stream, which cools the product stream.
  • Unwanted by-products like In particular, water or methane can be removed from the synthesis gas via processes known to those skilled in the art if they are used for the later utilization of the
  • Syngas are harmful.
  • the water can be condensed out.
  • the change of the flow guide is particularly dependent on the heat capacity of the regenerators.
  • the flow guide is preferably reversed every 5 to 40 minutes, in particular every 10 to 20 minutes.
  • the oxygen can be added to the reactor in such a way that it in turn reacts with the educt stream in a partial oxidation before the reaction zone.
  • Heat transfer tubes are introduced with external heat carrier include.
  • the reactant stream is advantageously first passed through an area in which
  • Heat transfer tubes are introduced with external heat carrier, preheated and then fed into a regenerator for further heating and cooled the product stream depending on the operating phase in the first or second heat exchange zone first in a regenerator and in a region in which
  • Heat transfer tubes are introduced with external heat carrier, further cooled. These additional areas serve to preheat the reactant stream already or to further cool the product stream. This allows lower input and output
  • Outlet temperatures can be realized.
  • temperature peaks can be trapped after the flow reversal.
  • an external heat carrier can the
  • two or more reaction zones can be present, each with a catalyst region.
  • the reaction can be carried out in two or more reaction zones, each with a catalyst range.
  • an intermediate heating can also take place.
  • the reaction procedure can be chosen so that the hydrogen or the carbon monoxide are almost completely reacted.
  • Hydrogen may then be mixed with the carbon monoxide to produce synthesis gas after the reactor. Preferably, however, the hydrogen is only partially reacted.
  • reaction zone or the reaction zones and the heat transfer zones are arranged in two or more containers, through which the gas stream is passed in succession.
  • the containers may be interconnected at the top and / or bottom.
  • each container contains a heat transfer and a reaction zone and a common or separate zone in which the partial oxidation takes place.
  • one container may always be
  • the catalyst in particular the catalyst, regenerated or the regenerator preheated.
  • reaction zone or reaction zones and the heat transfer zones within a container are separated by vertical partitions into several regions.
  • the gas stream is passed through the areas one after the other. This has the advantage that within the reactor no horizontal
  • reaction zones are connected to each other at the bottom of the container.
  • the gas stream can be passed through the reaction zones in succession.
  • An alternative embodiment in each case has a separate container for the individual reaction zones, the containers being connected to one another, so that the flow guide is similar to that of a common reactor vessel.
  • Embodiment has the advantage that no vertical partitions are present, which are exposed to the different temperature stresses.
  • the containers in particular the reactor vessel, are usually made of metal and bricked from the inside.
  • the lining allows the container to withstand high temperatures and high temperature fluctuations without having to make the jacket from expensive materials.
  • the reaction can be carried out without pressure or with pressure, it is not pressure-dependent.
  • the choice of pressure can be selected based on the input pressure of the reactants or the desired pressure for the product stream.
  • the reaction is carried out at the pressure at which the product stream is needed. Preferably, a pressure of up to 30 or up to 50 bar is used.
  • the reaction temperature should be higher than 600 ° C.
  • a temperature of 700 to 1200 ° C and in particular from 850 to 1100 ° C is set.
  • the regenerators work at temperatures between ambient temperature and the reaction temperature, in particular at 100 to 1200 ° C. Due to the partial oxidation, the reaction temperature of 700 to 1200 ° C and in particular from 850 to 1 100 ° C is then reached.
  • the catalyst used is preferably a metal catalyst, which may be in particular copper, nickel, iron or noble metals, which are supported by alumina or zeolites.
  • the catalyst operates at temperatures of 700 to 1200 ° C and especially at 850 to 1 100 ° C.
  • the catalyst can be introduced into the reaction zone as a bed, packing or shaped body.
  • the inlet and outlet temperatures of the educt or product streams are at ambient temperature up to 200 ° C, in particular up to 100 ° C.
  • the inlet and outlet temperatures are dependent on whether in the heat exchange zone
  • Heat exchange tubes are available and with which heat transfer medium they are operated.
  • the inlet temperatures may depend on at what temperature the starting materials are present, so that temperatures above 200 ° C are possible.
  • FIG. 1 shows a schematic diagram of a reactor with a flow guide a
  • a shows a schematic diagram of a reactor with a flow guide b
  • a design variant with parallel reactor vessels shows an embodiment variant with parallel reactor vessels and two reaction zones.
  • Figure 4A shows the side view of a reactor with vertical partitions.
  • Figure 4B shows the top view of a reactor with vertical partitions.
  • FIGS. 1A and 1B each show a schematic diagram of a reactor with a reaction zone RZ and two regenerator zones R1 and R2.
  • RZ reaction zone
  • R1 and R2 regenerator zones
  • the educt stream contains at least part of hydrogen and one part of carbon dioxide.
  • the reactant stream is in the heat exchange zone, which the heat exchange tubes and the
  • Regenerator zone comprises, heated, the regenerator R1 is thereby cooled.
  • oxygen 2a is metered in and it takes place the oxygen and part of the hydrogen from the reactant stream, a partial oxidation reaction instead. This creates heat and water.
  • the remaining educt current is heated to 800 to 1100 ° C.
  • the educt stream is then passed into the reaction zone.
  • Carbon dioxide reacts in a reverse water gas shift reaction
  • Heat exchange zone ie the regenerator R2 and heat exchange tubes cooled.
  • the regenerator zone R2 is heated and the heat is stored directly in the reactor.
  • the heat exchange tubes are cooled or heated with steam.
  • the inlet or outlet temperature of the educt and product streams is between the ambient temperature and about 100 ° C.
  • Heat recovery by the partial oxidation in turn takes place before the reaction zone RZ.
  • the product stream 3b and any unreacted starting materials are cooled in the regenerator zone R1 and heated.
  • the product streams can be purified as needed by methods known to those skilled in the art.
  • FIG. 2 shows another embodiment of the device shown in FIGS. 1A and 1B
  • the regenerator zones R1 and R2 are arranged in two parallel containers in this exemplary embodiment.
  • the containers are interconnected at the top by the reaction zone RZ.
  • the oxygen is supplied instead of 2a or 2b.
  • the operation of the system is analogous to the description of Figures 1A and 1B.
  • two reaction zones RZ1 and RZ2 are provided in Figure 3, in a further embodiment, in contrast to Figure 2, two reaction zones RZ1 and RZ2 are provided.
  • only one body of oxygen dosage 2 is necessary.
  • the reaction takes place in reaction zone RZ1 or in RZ2.
  • the educt current 1 a flows through the heat exchange zone, including the regenerator zone R1, and the reaction zone RZ1. Since the temperature is still too low at this point, no reaction is full. Only after the reaction zone RZ1 oxygen 2 is supplied and there is a partial oxidation. In the reaction zone RZ2, the reaction temperature is reached, so that the reaction proceeds analogously to the description in FIGS. 1A and 1B.
  • the product stream 3a and any unreacted starting materials are over a
  • Heat exchange zone including the Regeneratorzone R2 cooled.
  • the change of the flow guide is analogous to the previously described method.
  • Reaction is then saturated, especially in reaction zone RZ1.
  • reaction zone RZ1 Depending on the type of catalyst used, it can also have a certain heat storage capacity, so that the reaction zones can also act as a kind of regenerators. Directly after changing the flow guide, if the regeneration zone is still fully heated, it may therefore already come to reactions there. The products formed there are then taken up in the educt or product stream and passed through the reactor.
  • FIG. 4A and FIG. 4B show a further exemplary embodiment.
  • Reaction and regenerator zones are arranged within a reactor vessel, but separated by vertical partitions.
  • the area for the reaction zone is smaller than the area for the regenerator zones.
  • the reaction zone is separated by a vertical partition wall, wherein the two areas are connected to each other at the lower end, so that the gas first from top to bottom and connect from bottom to top to be led.
  • the product stream 3 is passed into the regenerator zone R2 and cooled there.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Combustion & Propulsion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Hydrogen, Water And Hydrids (AREA)

Abstract

La présente invention concerne un procédé de production de gaz de synthèse au cours duquel un flux gazeux renfermant de l'hydrogène avec un flux gazeux renfermant du dioxyde de carbone sur un catalyseur est transformé dans un réacteur en monoxyde de carbone et en eau et une partie de l'hydrogène issu du flux gazeux renfermant de l'hydrogène est utilisée avec de l'oxygène pour produire de l'énergie, les réactifs étant préalablement chauffés dans une première zone d'échange de chaleur au moyen d'un régénérateur, puis réchauffés par oxydation partielle et ensuite soumis à une réaction catalytique dans une zone de réaction. Les produits et les réactifs n'ayant pas réagi sont refroidis dans une seconde zone d'échange de chaleur au moyen d'un régénérateur. Le sens d'écoulement des flux gazeux dans le réacteur peut être inversé.
PCT/EP2016/001702 2015-10-22 2016-10-13 Procédé de production de gaz de synthèse WO2017067648A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102015014158 2015-10-22
DE102015014158.9 2015-10-22

Publications (1)

Publication Number Publication Date
WO2017067648A1 true WO2017067648A1 (fr) 2017-04-27

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019048236A1 (fr) * 2017-09-08 2019-03-14 Karlsruher Institut für Technologie Réacteur de conversion et mise en oeuvre du procédé associé
US11964872B2 (en) 2018-12-03 2024-04-23 Shell Usa, Inc. Process and reactor for converting carbon dioxide into carbon monoxide

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0291857A2 (fr) * 1987-05-18 1988-11-23 Air Products And Chemicals, Inc. Méthode de production d'oxyde de carbone
FR2963932A1 (fr) * 2010-12-23 2012-02-24 Commissariat Energie Atomique Procede de recyclage ameliore du co2 par reaction inverse du gaz a l'eau (rwgs)
WO2013135664A1 (fr) * 2012-03-13 2013-09-19 Bayer Intellectual Property Gmbh Procédé pour réduire du dioxyde de carbone à haute température sur des catalyseurs à base d'oxyde métallique mixte comprenant des métaux précieux sur des supports à base d'oxydes et dopés avec de l'aluminium, du cer et/ou du zirconium

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0291857A2 (fr) * 1987-05-18 1988-11-23 Air Products And Chemicals, Inc. Méthode de production d'oxyde de carbone
FR2963932A1 (fr) * 2010-12-23 2012-02-24 Commissariat Energie Atomique Procede de recyclage ameliore du co2 par reaction inverse du gaz a l'eau (rwgs)
WO2013135664A1 (fr) * 2012-03-13 2013-09-19 Bayer Intellectual Property Gmbh Procédé pour réduire du dioxyde de carbone à haute température sur des catalyseurs à base d'oxyde métallique mixte comprenant des métaux précieux sur des supports à base d'oxydes et dopés avec de l'aluminium, du cer et/ou du zirconium

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2019048236A1 (fr) * 2017-09-08 2019-03-14 Karlsruher Institut für Technologie Réacteur de conversion et mise en oeuvre du procédé associé
AU2018330243B2 (en) * 2017-09-08 2023-12-14 Ineratec Gmbh Conversion reactor and management of method
US11964872B2 (en) 2018-12-03 2024-04-23 Shell Usa, Inc. Process and reactor for converting carbon dioxide into carbon monoxide

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