EP2170497A1

EP2170497A1 - Exchanger reactor having a bayonet tube allowing operation with pressure differences of the order of 100 bar between the tube side and the shell side.

Info

Publication number: EP2170497A1
Application number: EP08827689A
Authority: EP
Inventors: Fabrice Giroudiere; Jean Christian Tricard; Bernard Langlos
Original assignee: IFP Energies Nouvelles IFPEN
Current assignee: IFP Energies Nouvelles IFPEN
Priority date: 2007-07-20
Filing date: 2008-06-24
Publication date: 2010-04-07
Also published as: US20100254891A1; US8512645B2; RU2010106107A; JP5520823B2; FR2918904A1; WO2009024664A1; CA2692701A1; BRPI0814783B1; CA2692701C; BRPI0814783A2; FR2918904B1; JP2010534128A; CN101754803A; RU2469785C2; CN101754803B

Abstract

The present invention describes an exchanger reactor intended for implementing endothermic reactions, comprising a shell inside which the heat-transfer fluid flows, said shell enclosing a plurality of tubes inside which the reactive fluid flows, the tubes being of the bayonet type, and the reactor not having a tube plate. This reactor may operate with a pressure difference between the tube side and the shell side that may range up to 100 bar.

Description

BAYONETTE TUBE HEAT EXCHANGER REACTOR TO OPERATE WITH 100 BAR PRESSURE DIFFERENCES BETWEEN THE TUBE COAST AND THE CALANDER COAST.

FIELD OF THE INVENTION

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 exchanger reactor according to the invention makes it possible to reach reactor sizes having a diameter greater than 4 meters, or even greater than 10 meters, with a pressure difference between the inside of the tubes and the outside of the tubes of up to 30 bars. at 100 bar (1 bar = 0.1 MegaPascal), without the use of a tubular plate to ensure the distribution of the reactive fluid on all the tubes. Nevertheless, the reactor according to the invention is perfectly feasible at sizes less than 4 meters in diameter. In the remainder of the text, 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.

EXAMINATION OF THE PRIOR ART

The prior art in the field of exchanger reactors for the implementation of highly endothermic reactions such as the steam reforming reaction of a hydrocarbon fraction, corresponds to the reactor shown in FIG. 1. This type of exchanger reactor has a system of distributing the reactive fluid by means of a first tubular plate and an effluent collection system by means of a second tubular plate. 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 understanding of the invention requires exposing the limitations associated with the tubular plate. According to the prior art, 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

(respectively output). 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. In the same way, 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. In the case of a reactor exchanger according to the prior art comprising bayonet tubes, as shown in FIG. 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).

The shell side corresponds in the case of Figure 1 to the space (21) outside the reaction tubes and located below the bottom tube plate (i). 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. However, the pressure difference between the inside of the tubes (5) and the outside of the tubes (21), or calender side, which contains the coolant, may be several tens of bars. In the particular case of the steam reforming reaction, this pressure difference can reach from 25 bars to 40 bars (1 bar = 0.1 MPa). 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.

It is known to those skilled in the art that the dimensioning of a tubular plate capable of withstanding such pressure differences leads to very large thicknesses, and in practice non-achievable, as soon as the diameter of the reactor reaches a value of ten meters.

By way of example, 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). Reactor diameter

2m 5m 10m

Delta 25 bar 193 mm 483 mm 967 mm 30 bar 212 mm 530 mm 1059 mm pressure 35 bar 229 mm 572 mm 1144 mm

If 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. In fact, in a reactor according to the prior art, 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.

In the reactor according to the present invention, 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.

SUMMARY DESCRIPTION OF THE FIGURES 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.

SUMMARY DESCRIPTION OF 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 tube are located outside the reactor as shown in FIG.

According to a preferred variant of the exchanger reactor, 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).

Spacing according to a square pitch nevertheless remains perfectly within the scope of the present invention.

The inner tube (5) of 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

60 ° to the vertical. This arrangement makes it possible to clearly separate the inlet and the outlet of each bayonet tube (4), so as to facilitate the introduction of the distribution device for the reaction fluids, and the device for collecting the reaction effluents as represented in FIG. 3.

Preferably, the inner tube (5) of 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. Preferably, 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.

Preferably, 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

(5).

In general, 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.

According to the invention, 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 elongated burners are described in French patent application no.

06 / 10.999

They are in the remainder of the text understood by means of FIG. 4 as burners without precombination of cylindrical geometry, length Lb and diameter Db, with a ratio Lb / Db of between 10 and 500, and preferably between 30 and

300.

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. This is precisely the distance corresponding to the zone noted (29) in FIG. 4. Preferably, 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. According to a variant of the process according to the invention, the fuel used to carry out the combustion in situ is a gas containing more than 90% hydrogen. In general, the process for steam reforming a hydrocarbon fraction using the exchanger reactor according to the invention is carried out at a calender side pressure of between 1 and 10 bars absolute, (1 bar = 10 ⁵ pascal), and at a pressure at inside the bayonet tubes between 25 and 50 bar absolute. The temperature inside the reaction tubes is generally between 700 ^° C. and 950 ^° C.

DETAILED DESCRIPTION OF THE INVENTION

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 description which follows relates to FIG.

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.

Another configuration in which the 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 nature of the coolant does not matter in the context of the present invention. These are fumes resulting from a combustion carried out inside the exchanger reactor itself by means of specific burners such as those described in French Patent Application No. 06 / 10,999.

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. By 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).

When the in situ combustion generating heat transfer fluid is carried out by means of elongated burners, these ci are inserted between the bayonet tubes and thus form a triangular pitch with a center to center distance between burner between 2 and 5 times the outer diameter of said bayonet tubes.

EXAMPLE ACCORDING TO THE INVENTION

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%

CH4: 5.35% CO2: 0.78% CO: 1.5% N2: 0.25%. The temperature inside the bayonet tubes is: 900 ^° C.

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:

Total reactor height (with upper and lower bottoms): 16m Reactor diameter: 7m H / D ratio: 2.3

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

Outer diameter of porous burners: 100mm Length of porous burners: 5m Number of porous burners: 470

Center to center distance between porous burner: 600mm

The annular portion of the bayonet tubes is filled by means of a nickel-based steam reforming catalyst in the form of cylindrical pellets, each catalyst particle having the following dimensions:

- diameter of the pellets: 10mm,

- length of the pellets: 13 mm.

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.

The 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. To promote loading, 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.

Claims

1-Reactor exchanger consisting of a cylindrical calender 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 within which circulates the reaction fluid, the tubes being of bayonet type and having a density of between 2 and 12 tubes per m 2 of reactor section, 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 heat transfer fluid being obtained by a combustion produced in situ by means of long burners (8); interposing between said bayonet tubes (4) forming a triangular pitch, the distance between the burners being between 2 and 5 times the diameter of the outer tube ( 6) a bayonet tube.

2- exchanger reactor according to claim 1, wherein each bayonet tube is surrounded by a cylindrical chimney (10) substantially coaxial with the outer tube (6).

3-exchanger reactor according to any one of claims 1 to 2, wherein the inner tube (5) of each bayonet tube passes through the outer tube (6) at a point outside the reactor, at a distance of at least 1 meter with respect to the upper cap of the exchanger reactor and at an angle between 30 ° and 60 ° relative to the vertical.

4. Exchanger reactor according to any one of claims 1 to 3, wherein the inner tube (5) of each bayonet tube is fed from a main supply tube branching N branches, each branch feeding an inner tube (5). ), N being between 5 and 100, and preferably being between 10 and 50.

5. Reactor exchanger according to any one of claims 1 to 5, wherein the outer tube (6) of each bayonet tube is connected to a primary collector, itself connected to a secondary collector, and so on until the final collector corresponding to a number M of collectors between 2 and 10.

6. Process for steam reforming a hydrocarbon fraction using the exchanger reactor according to any one of claims 1 to 5, wherein the calender side pressure is between 1 and 10 bar absolute, and the pressure inside the bayonet tubes. is between 25 and 50 bar absolute.

7. A method of steam reforming a hydrocarbon fraction using the exchanger reactor according to any one of claims 1 to 5, wherein the fuel used to carry out the combustion in situ is a part of the steam reforming effluent.

8- A method of steam reforming a hydrocarbon fraction using the exchanger reactor according to any one of claims 1 to 5, wherein the heat transfer fluid circulates inside the annular space (11) between the outer wall (6). ) of the bayonet tube and the chimney (10) surrounding said tube with a speed of between 20 m / s and 50 m / s.

9-process for steam reforming a hydrocarbon fraction using the reactor according to any one of claims 1 to 5, wherein the reactive fluid is introduced through the inlet end of the annular zone (7), and the effluents are recovered by the outlet end of the central tube (5).