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
• • 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
  • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J19/24—Stationary reactors without moving elements inside
  • B01J19/2415—Tubular reactors
  • B01J19/2425—Tubular reactors in parallel
• • 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
• • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
  • F28—HEAT EXCHANGE IN GENERAL
  • F28D—HEAT-EXCHANGE APPARATUS, NOT PROVIDED FOR IN ANOTHER SUBCLASS, IN WHICH THE HEAT-EXCHANGE MEDIA DO NOT COME INTO DIRECT CONTACT
  • F28D7/00—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall
  • F28D7/10—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically
  • F28D7/12—Heat-exchange apparatus having stationary tubular conduit assemblies for both heat-exchange media, the media being in contact with different sides of a conduit wall the conduits being arranged one within the other, e.g. concentrically the surrounding tube being closed at one end, e.g. return type
• • 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
  • B01J2208/00176—Controlling the temperature by indirect heat exchange with heat exchange elements outside the bed of solid particles outside the reactor
• • 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
• • 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
  • B01J2208/00743—Feeding or discharging of solids
  • B01J2208/00769—Details of feeding or discharging
• • 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
  • B01J2208/00796—Details of the reactor or of the particulate material
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—Controlling the temperature
  • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
  • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
  • B01J2219/00099—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor the reactor being immersed in the heat exchange medium
• • 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
  • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
  • B01J2219/00049—Controlling or regulating processes
  • B01J2219/00051—Controlling the temperature
  • B01J2219/00157—Controlling the temperature by means of a burner

Definitions

• the present invention relates to an exchanger reactor consisting of a shell enclosing a plurality of tubes, a structure that the skilled person qualifies as tubes / calender, said exchanger reactor allowing the implementation of highly endothermic reactions such as the steam reforming reaction of the gas natural, the reactive fluid circulating inside the tubes, and the coolant circulating outside the tubes (also called calender side by the skilled person).
• the reactor according to the invention is perfectly feasible at sizes less than 4 meters in diameter.
• the term "tube side” will be used to refer to the chemical reaction and the circulation of the reaction fluids inside said tubes, and to the "shell side” to designate what relates to heat transfer. from the heat transfer fluid to the reaction fluid and the circulation of said heat transfer fluid.
• a bayonet tube (4) can be defined as consisting of an inner tube (5) contained in an outer tube (6), the inner tube (5) and the outer tube (6) being substantially coaxial.
• the heat transfer fluid is generally generated by combustion carried out outside the exchanger reactor by any combustion system such as furnaces or boilers using burners.
• the heat transfer fluid may also consist of recovery fumes, or a hot fluid available on the site such as steam.
• the circulation of the heat transfer fluid can be channeled inside chimneys (10) surrounding, at least over a certain length, the bayonet tubes (4) and defining an annular space (10) suitable for the circulation of the heat transfer fluid to the inside said annular space.
• the tube plate in the exchanger reactor can be defined as a perforated plate extending substantially along a section of the reactor, each perforation receiving a reaction tube.
• the set of reaction tubes thus has its inlet (or outlet) end located on the inlet tubular plate
• the inlet tubular plate (i) thus separates the volume of the reactor into a first space (20) located above said tube plate, this first space containing the reaction fluid and allowing its distribution in each of the reaction tubes, and a second space (21) below said tubular plate, the second space surrounding the tubes and containing only the coolant.
• the outlet tubular plate (s) separates the volume of the reactor into a third space (22) located above said tube plate, this third space containing only the reaction effluents from each reaction tube.
• the first space (20) is in fact between the inlet tubular plate (i) and the outlet tubular plate (s) and contains only the reaction fluid introduced into said space (20) through the tubing labeled A on the figure 1.
• the reactor has two tubular plates, one upper receiving the outlet end of the central tubes (5). ), the lower one (i) receiving the inlet end of the annular zone between the central tube (5) and the outer tube (6).
• the distribution of the reaction fluid is done by the space (20) between the lower tubular plate (i) and the upper tubular plate (s), by means of the inlet pipe (A).
• FIG. 1 clearly shows that in an exchanger reactor according to the prior art and comprising bayonet tubes, the inlet and outlet of each bayonet tube (4) is at the level of the inlet and outlet tubular plates, therefore inside the reactor.
• the lower tube plate (i) can therefore have its upper surface adjacent to the fluid introduction zone (20), and its lower face adjacent to the circulation zone of the coolant (21) which undergo a pressure difference of 25. at 50 bars.
• the table below gives the tube plate thickness in mm (10 "3 meters) for reactor diameters ranging from 2 to 10 meters, and for a pressure difference on either side of the tubular plate of 25, 30 and 35 bar (in the ordinate).
• a maximum thickness of the tube plate is assumed to be of the order of 400 mm, this results in a limit in the size of the reactor which is established at about 5 meters in diameter for a pressure difference of both sides. other of the 25-bar tubular plate. This size limit is even smaller if the pressure difference on both sides of the tube plate is greater. Thus, if the pressure difference on either side of the tube plate reaches 35 bars, the maximum diameter of the reactor is only about 3 meters. From the point of view of mechanical strength, there is also a limit in the permissible tube density on the tube plate, which depends on the diameter of the tubes and is about 10 tubes / m 2 for a tube diameter of 170 mm.
• the reactor according to the present invention makes it possible to exceed the size limit of the reactors according to the prior art, that is to say comprising a tubular plate, by eliminating said tubular plate, the distribution of the reactive fluids and the collection of the effluents being entirely effected. outside the reactor.
• the exchanger reactor according to the present invention makes it possible to solve a second problem related to the catalyst filling of the bayonet tubes.
• the catalyst filling of the bayonet tubes is done by the space (20) between the two tubular plates. But this space is limited and made very inconvenient by the presence of the many tubes attached to the upper tube plate.
• the filling of the bayonet tubes is done by their end located outside the reactor which is in a much less restrictive environment.
• Another advantage of the reactor according to the invention is that it operates with a coolant whose generation is carried out in situ, that is to say by means of a combustion carried out even within the exchanger reactor, shell side.
• Such "in situ" combustion can be achieved by means of burners such as those described in the French application 06 / 10,999, the said burners, generally of elongated shape, interposed between the bayonet tubes.
• FIG. 1 represents a prior art bayonet tube exchanger reactor having a lower tubular plate for the distribution of reactive fluids, and an upper tubular plate for the collection of effluents.
• FIG. 2 represents an exchanger reactor according to the invention, that is to say without a tube plate, with the end of the bayonet tubes located outside the reactor, the heat transfer fluid being derived from a combustion carried out inside of the reactor by means of elongated burners interposed between the bayonet tubes.
• FIG. 3 represents an example of a device for distributing and collecting reaction fluids in the reactor according to the invention.
• FIG. 4 represents an example of burners that can be used to ensure the generation of the heat transfer fluid inside the exchanger reactor according to the invention.
• the exchanger reactor according to the present invention consists of a cylindrical shell closed by an upper cap and a lower bottom, inside which circulates the coolant, said shell enclosing a plurality of parallel tubes of substantially vertical axis, inside which the reaction fluid circulates, the reaction tubes being of bayonet type and having a density of between 2 and 12 tubes per m 2 of section of the reactor, the spacing between each bayonet tube, or center-to-center distance, being between 2 and 5 times the inner diameter of the outer tube (6), the inlet and the outlet of each bayonet tube being located outside the reactor, and the coolant being obtained by a combustion carried out in situ by means of long burners (8) interposed between said bayonet tubes (4) forming a triangular pitch, the distance between the burners being between e 2 and 5 times the diameter of the outer tube (6) of a bayonet tube.
• the reactor according to the invention does not comprise a tube plate. In the exchanger reactor according to the present invention, the inlet and the outlet of each bayonet
• each bayonet tube (4) is surrounded by a cylindrical chimney (10) substantially coaxial with the bayonet tube, the coolant circulating inside the annular space (11) between the wall external of the bayonet tube (4) and said chimney (10) with a speed of between 20 m / s and 50 m / s.
• the bayonet tubes are preferably assembled in a triangular pitch.
• the spacing between each bayonet tube, or center-to-center distance, is generally between 2 and 5 times the inner diameter of the outer tube (6).
• each bayonet tube (4) passes through the outer tube (6) at a point outside the reactor, at a distance of at least 1 meter from the upper cap of the exchanger reactor, and at an angle between 30 ° and
• each bayonet tube (4) is fed from a main supply duct branching into N branches, each branch supplying an inner tube, N being between 5 and 100, and being preferentially between 10 and 50.
• the outer tube (6) of each bayonet tube (4) is connected to a primary collector, itself connected to a secondary collector and so on until the final collector which corresponds to a number M of collectors between 2 and 10.
• the reactive fluid is introduced through the inlet end of the annular zone (7) between the outer tube (6) and the inner tube (5), said annular zone (7) being at least partially filled with catalyst.
• the reaction effluents are recovered by the outlet end of the central tube
• the coolant consists of combustion fumes, said combustion taking place in situ, that is to say by means of burners located inside the reactor itself and interposed between the bayonet tubes in a separate equipment. of the present exchanger reactor.
• the flue gases leave the reactor through the outlet pipe (G) located in the upper part of the reactor.
• the heat transfer fluid providing the heat required for the reaction is obtained by combustion carried out in situ by means of long burners (8) interposed between the bayonet tubes (4).
• These burners have a central fuel distributor (27) having an orifice distribution (30) possibly non-uniform, and having a porous element (28) of annular shape surrounding the central distributor (27) at least over its entire length Lb, the thickness of said porous element (28) being between 0.5 and 5 cm, and the inner surface of said porous material (28) being located at a distance from the central distributor (27) of between 0.5 cm and 10 cm.
• the elongated burners form a triangular pitch, the distance between the burners being between 2 and 5 times the outer diameter of the bayonet tubes .
• the invention also consists of a process for steam reforming a hydrocarbon fraction using the present exchanger reactor.
• the fuel used to carry out the combustion in situ is a gas containing more than 90% hydrogen.
• the temperature inside the reaction tubes is generally between 700 ° C. and 950 ° C.
• the exchanger reactor according to the present invention is intended for the implementation of highly endothermic reactions and at temperature levels of up to 950 ° C. Typically, it may be used for steam reforming hydrocarbon cuts, in particular naphtha or natural gas for the production of hydrogen.
• the exchanger reactor according to the invention consists of a generally cylindrical calender (1) closed in its upper part by a cap (2) of substantially ellipsoidal shape and in its lower part by a bottom (3) of substantially ellipsoidal shape said calender (1) enclosing a plurality of vertical tubes (4) of length (L) extending along the cylindrical portion of the calender (1).
• the tubes (4) are bayonet type, that is to say they consist of an inner tube (5) contained in an outer tube (6), the inner tube and the outer tube being substantially coaxial. Coaxiality is obtained for example by means of centering fins welded at regular intervals on the inner tube (5) and which make it possible to maintain a fixed spacing with the outer tube (6).
• the annular space (7) between the inner tube (5) and the outer tube (6) is generally filled with catalyst, this catalyst having the form of cylindrical particles, which in the case of the steam reforming reaction, have a length typical of a few millimeters and a diameter of a few millimeters.
• the shape of the catalyst particles is not a characteristic element of the invention which is compatible with any form of catalyst particles whose size allows the introduction into the annular portion (7) of the vertical tubes (4).
• the reaction fluid is preferably introduced into the bayonet tube (4) by the catalytic annular zone (7), the inlet end of which is outside the reactor, the steam reforming reactions developing in the catalytic annular zone, and the effluents being recovered at the outlet of the central tube (5), said outlet being also located outside the reactor.
• reaction fluid is introduced through the central tube (5) and the effluents recovered at the outlet of the annular zone (7) is also possible.
• the reactive fluids thus circulate inside the bayonet tubes (4), first down the annular zone (7) of the tube, then up along the central tube (5), said tubes (4). ) having their inlet / outlet end located outside the exchanger reactor, and said tubes (4) being heated by a coolant flowing from the calender side (8).
• the H / D ratio between the height H of the reactor and its diameter D is generally between 2 and 8, and preferably between 2.5 and 6.
• the bayonet tubes (4) are generally equipped with a chimney (10) which surrounds them in a substantially coaxial manner, making it possible to obtain a circulation velocity of the combustion fumes along the tube to be heated between 5 m / s and 50 m / s, and preferably between 20 m / s and 40 m / s.
• the number of tubes to be heated per m 2 of section of the reactor is generally between 2 and 12, and preferably between 3 and 8.
• reactor section is meant the geometric section supposed to be empty of any internal.
• the bayonet tubes (4) most often form a triangular pitch with a center-to-center distance of between 2 and 5 times the inside diameter of the outer tube (6).
• the example below provides the dimensioning of a reactor exchanger according to the invention intended to produce 90000 Nm3 / hour of H2 by steam reforming of natural gas.
• the fuel used to provide the calories necessary for the steam reforming reaction has the following composition in mol%: H 2: 92.10%
• the flue gas temperature circulating on the shell side is on average: 1200 ° C.
• the pressure inside the bayonet tubes is: 35 bar
• the flue gas pressure circulating on the shell side is: 5 bar
• the pressure difference between tube and calender is therefore 30 bars.
• the main dimensions of the reactor according to the invention are as follows:
• the tubes are of the bayonet type Length of the tubes: 12m External diameter of the tubes to be heated: 200mm Diameter of the central tube: 50mm Distance center to center of the tubes to be heated: 300mm Number of tubes: 235 tubes distributed in triangular pitch
• each catalyst particle having the following dimensions:
• the reaction fluid is fed into each reaction tube through the inlet end of the outer tube (6).
• the inlet manifold of the reaction fluids has a branch shape such as that shown in FIG.
• reaction effluent is recovered by the outlet end of the central tube (5).
• the outlet collector of the reaction effluents has a 4-branch shape such as that represented in FIG. 3.
• the central tube (5) separates from the outer tube (6) at a distance of 2 meters above the upper dome of the reactor according to an angle of 30 ° to the vertical.
• the catalyst is filled by the inlet end of the outer tubes (6). Access to the annular zone of the outer tube (6) is facilitated by the disassembly of the sleeves in the upper part.
• the central tube (5) having its end deviated outside the outer tube (6) of the bayonet, there is no risk of putting catalyst in the central tube (5) when loading the space annular.
• the bayonet tubes can be vibrated, for example by their lower end accessible via a manhole in the calender and by means of a vibrator attached the time of loading to the tube concerned.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Engineering & Computer Science (AREA)
• Physics & Mathematics (AREA)
• Thermal Sciences (AREA)
• Mechanical Engineering (AREA)
• General Engineering & Computer Science (AREA)
• Devices And Processes Conducted In The Presence Of Fluids And Solid Particles (AREA)
• Heat-Exchange Devices With Radiators And Conduit Assemblies (AREA)
• Hydrogen, Water And Hydrids (AREA)
• Physical Or Chemical Processes And Apparatus (AREA)

Applications Claiming Priority (2)

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• 2007
  • 2007-07-20 FR FR0705316A patent/FR2918904B1/fr not_active Expired - Fee Related
• 2008
  • 2008-06-24 WO PCT/FR2008/000888 patent/WO2009024664A1/fr active Application Filing
  • 2008-06-24 US US12/669,212 patent/US8512645B2/en not_active Expired - Fee Related
  • 2008-06-24 BR BRPI0814783A patent/BRPI0814783B1/pt not_active IP Right Cessation
  • 2008-06-24 JP JP2010517432A patent/JP5520823B2/ja active Active
  • 2008-06-24 RU RU2010106107/02A patent/RU2469785C2/ru not_active IP Right Cessation
  • 2008-06-24 EP EP08827689A patent/EP2170497A1/fr not_active Withdrawn
  • 2008-06-24 CA CA2692701A patent/CA2692701C/fr not_active Expired - Fee Related
  • 2008-06-24 CN CN2008800254053A patent/CN101754803B/zh not_active Expired - Fee Related

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