High temperature reactor vessel, apparatus and method

Abstract

A reactor vessel for high-temperature catalytic reaction is provided, wherein the inlet portion has a special design. Also provided is a device comprising the reactor vessel.

Description

Technical Field

[0001] A reactor vessel for high-temperature catalytic reaction is provided, wherein the inlet portion has a special design. Also provided is a device comprising the reactor vessel. Background Art

[0002] The use of high temperatures and high pressures in chemical plants places specific demands on the materials and construction of plant components such as reactor vessels, piping, valves, etc.

[0003] Gas temperatures exceeding 750°C may be reached, at which point metals (such as stainless steel) lose their mechanical strength and begin to soften. For this reason, steel vessels and pipelines are often protected by protective coatings (such as ceramic linings, also known as brick linings).

[0004] Furthermore, gas pressures of 15-45 bar can be reached. This requires careful attention to the geometry and design of the equipment components to ensure they can withstand these pressures. Due to the large volumes of reactants being processed, these reactors often also involve rapid gas flows, which in turn place special demands on materials and structures, for example if the gases are to be mixed.

[0005] Catalytic reactor vessels require good mixing of the reactant gases before the gas stream enters the catalyst bed, as mixing of the gas stream within the bed is limited. Furthermore, at high gas flow rates, there is a risk that the gas disturbs the catalyst bed, which can lead to suboptimal catalytic conversions or even grind, abrade, or fluidize individual catalyst particles as they come into physical contact.

[0006] Typical industrial gas-phase catalytic reactors use an inlet distributor, typically a perforated plate placed at the gas inlet, below the spherical head at the top of the reactor. The high temperatures used in chemical plants limit the use of such distributors to promote gas mixing. Distributors can have complex structures that are difficult to adequately protect with coatings. Furthermore, distributors made of metal, such as stainless steel, tend to lose their mechanical strength at the high temperatures involved.

[0007] Therefore, the design and construction of chemical equipment and its components, particularly reactor vessels for high-temperature catalytic reactions, require addressing some or all of the aforementioned challenges. Reactor vessels for high-temperature applications should facilitate efficient gas mixing while avoiding additional components such as distributors. Furthermore, catalyst particle disturbance, particularly grinding, should be minimized or even avoided. Summary of the Invention

[0008] Thus, a reactor vessel for high temperature catalytic reactions is provided. The reactor comprises a body portion, an inlet end portion, and an outlet end portion, wherein the body portion extends between the inlet end portion and the outlet end portion and wherein the body portion, the inlet end portion, and the outlet end portion together define a reactor cavity, wherein

[0009] - the body portion has a substantially cylindrical form around a central axis XX of the reactor vessel;

[0010] - a catalyst bed of catalyst particles located within said reactor cavity in said body portion, said catalyst bed being defined by opposing first and second bed surfaces;

[0011] - the inlet end portion comprises one or more gas inlets;

[0012] - the outlet end portion comprises one or more gas outlets;

[0013] Its characteristics are:

[0014] - the inlet end portion (120) comprises at least one side wall (125); the side wall (125) comprises a diverging section (A), wherein the side wall (125) is connected to the main body portion (110),

[0015] - and wherein the gas inlets (121) are arranged only in the side wall (125) of the inlet end portion (120); each gas inlet (121) defines a main gas inlet flow direction vector (V) along which gas enters the reactor chamber (101), wherein the gas inlets are arranged such that the main gas inlet flow direction vector (V) does not intersect the central axis (XX),

[0016] - and wherein the interior space of the inlet end portion (120) is configured such that the cross-sectional area available for gas flow is constant or increases along the central axis XX in a direction from the gas inlet (121) to the main body portion (110).

[0017] The present invention is based on the recognition that a gas distributor, for example in the form of a perforated plate disposed at the lower end of the gas inlet portion of the reactor above the main body, can be dispensed with when all feed gas to the reactor is introduced into the gas inlet portion tangentially to the side walls of the gas inlet portion, and when the gas inlet portion has a form that expands and diverges toward the main body. In this configuration of the reactor, the gas is imparted with a spiral motion through the inlet end portion, and the inlet end portion is arranged to allow the spiral motion to continue unimpeded until the gas reaches the catalyst bed of the main body. It has also been found that the structure of the reactor can achieve sufficient mixing of the feed gas flow and thus eliminate the need for a separate gas mixer element. The expansion of the spiral flow will result in a certain degree of mixing. Finally, it has been found that the configuration of the reactor can avoid disturbance of the catalyst bed by the gas flow, because the configuration of the reactor avoids the generation of gas jets that enter the reactor and therefore the catalyst bed.

[0018] A method for high temperature catalytic reaction, comprising the following steps:

[0019] - introducing a gas having a temperature of at least 750° C. into at least one gas inlet of the reactor vessel of the invention, and

[0020] - subjecting the gas to a catalytic reaction in said reactor vessel.

[0021] Also provided is an apparatus for producing synthesis gas having a predetermined H2 / CO ratio from a hydrocarbon feed. The apparatus comprises:

[0022] - a steam reforming reactor comprising a first catalyst and arranged to react the hydrocarbon feed with steam

[0023] reacting to produce a first synthesis gas stream;

[0024] - a reactor vessel as defined herein, wherein the catalyst particles are for steam reforming / methanation

[0025] and the reverse water-gas shift reaction are active;

[0026] a first feed line arranged to feed at least a portion of the first synthesis gas stream from a steam

[0027] a reforming reactor leading to at least one gas inlet of said reactor vessel;

[0028] a second feed line arranged to supply a second CO2-rich gas feed to the reactor vessel; directly via a separate gas inlet, or via a mixing section; wherein the mixing section is arranged to receive at least the first synthesis gas stream and the second gas feed from the first and second feed lines, mix the first and second gas feeds to form a gas mixture, and feed the gas mixture to the at least one gas inlet of the reactor vessel;

[0029] - the reactor vessel being arranged to react the first synthesis gas stream with the second CO 2 gas feed, thereby providing a synthesis gas having a predetermined H 2 / CO ratio through an outlet of the reactor vessel.

[0030] There is also provided a method for producing synthesis gas having a predetermined H2 / CO ratio from a hydrocarbon feed using the apparatus of the present invention.

[0031] Further details of the invention are set forth in the following description, drawings, and claims. BRIEF DESCRIPTION OF THE DRAWINGS

[0032] legend

[0033] Figure 1 Shown is a schematic diagram of a reaction vessel according to the invention viewed from a cross section along the central axis XX.

[0034] Figures 2a-2d Various embodiments of reaction vessels having various designs of inlet end portions are illustrated.

[0035] Figure 3 and Figure 4 are cross-sectional views of two possible inlet end portions along the central axis XX.

[0036] Figure 5 The high temperature reactor section is shown.

[0037] Figure 6 and Figure 7 A schematic diagram of an apparatus for producing synthesis gas is shown. Detailed Description of the Invention

[0039] definition

[0040] In the present technology, the term "high temperature" is understood to mean at least 750°C, preferably at least 800°C.

[0041] In the present art, the term "high pressure" is understood to mean at least 15 bar, preferably at least 20 bar, and up to 45 bar.

[0042] For the purposes of the present invention, the expression "resistant to thermally induced deformation and degradation" means that the lifetime of the surface in question is at least one month of operation when using gases having a reactor vessel inlet temperature of 1000°C. DETAILED DESCRIPTION

[0043] The present invention relates to a specific configuration of a high-temperature reactor vessel (e.g., an adiabatic post-reformer for converting a mixture of CO2 and syngas into CO-rich syngas). The reactor is suitable for high-temperature operation (>750°C), where mechanical solutions may be limited by temperature durability issues. The reactor vessel can be selected from an adiabatic post-reformer or a water-gas shift reactor.

[0044] Thus, a reactor vessel suitable for high-temperature catalytic reactions is provided. The reactor vessel comprises a main body portion, an inlet end portion, and an outlet end portion. The reactor vessel has a central axis XX. The main body portion has a substantially cylindrical form about the central axis XX of the reactor vessel. The main body portion extends along the central axis XX of the reactor vessel between the inlet end portion and the outlet end portion. The reactor vessel is substantially hollow, such that the main body portion, the inlet end portion, and the outlet end portion together define a reactor cavity.

[0045] In a particular embodiment of the reactor vessel of the present invention, all inner surfaces of the reactor vessel that come into contact with the gas are coated or lined with a layer of ceramic material.

[0046] The walls of the reactor vessel are typically made of metal (e.g., stainless steel) with a wall thickness of, for example, 5-10 mm, so that they can withstand the high pressures within the reactor. The inner surfaces of the reactor vessel (i.e., the reactor cavity, the gas inlet, and the gas outlet) are lined with a layer of ceramic material to insulate the metal walls from the hot gases, thereby keeping the metal components cooler. The layer of ceramic material can be in the form of Al2O3 bricks, ZrO2 bricks, or another suitable ceramic material. The layer of ceramic layer can have a thickness of 10-100 cm, for example, 50 cm. The reactor vessel is typically large, with a total length along the central axis XX of approximately 50-500 cm and a main body portion having a diameter around the central axis of approximately 50-300 cm.

[0047] The reactor vessel has an inlet end, which is the point of greatest extension along the central axis XX at the end where gas enters the vessel. An inlet end portion is defined as the portion of the vessel between the main body portion of the vessel and the inlet end. Similarly, the reactor vessel has an outlet end, which is the point of greatest extension along the central axis XX at the end where gas exits the vessel (i.e., opposite the inlet end). An outlet end portion is defined as the portion of the vessel between the main body portion of the vessel and the outlet end.

[0048] The reactor vessel has one or more sidewalls that extend primarily along the central axis XX. When the reactor vessel has a circular cross-section along its entire length (from the inlet end to the outlet end), the vessel essentially has a single sidewall that circumscribes the central axis XX. The reactor vessel may also include an end wall at the inlet end of the reactor vessel that extends primarily perpendicular to the central axis XX and encloses portions of the inlet and outlet ends. Depending on the configuration, a separate end wall may be omitted, and curved or inclined sidewalls may intersect to form the inlet and outlet ends of the reactor vessel.

[0049] The inlet end portion and the outlet end portion generally have a circular cross-section about the central axis XX of the reactor vessel. As shown in the figure, the circular cross-section is generally smaller than the cross-section of the main body portion. In addition, the circular cross-sections of the inlet end portion and the outlet end portion generally decrease from the main body portion toward the inlet end or the outlet end.

[0050] The inlet end portion includes one or more gas inlets, and the outlet end portion includes one or more gas outlets.In addition to these gas inlets and gas outlets, the wall of the reactor vessel completely surrounds the reactor cavity, as shown.

[0051] The reactor vessel is designed to stand on a substantially horizontal surface with the central axis XX aligned substantially vertically such that the inlet end portion is located at the upper end (i.e., farthest from the horizontal surface) and the outlet end portion is located at the lower end. Gas flow in the reactor vessel generally occurs in a generally downward direction, from the inlet end portion, through the main body portion, to the outlet end portion.

[0052] A catalyst bed of catalyst particles is located within the reactor cavity of the main body portion. To prevent gas bypass, the catalyst bed fills the entire cross-sectional area of ​​the main body portion of the reactor vessel. The catalyst bed is located solely within the main body portion, so that gas passes through the entire cross-sectional area of ​​the catalyst bed. The catalyst bed typically fills at least 60%, typically at least 75%, and more preferably at least 80%, of the main body portion in the direction of the central axis XX, and optionally fills the entire main body portion in the direction of the central axis XX.

[0053] The catalyst bed comprises or is composed of catalyst particles aggregated within the main body. The catalyst particles typically comprise a ceramic material, which may be catalytic in itself but is preferably coated and / or impregnated with a catalytically active metal or metal salt. The catalyst particles are typically microporous or macroporous and have dimensions in the millimeter or centimeter range. The nature, construction, and method of manufacture of the catalyst particles depend on the nature of the reaction occurring in the reactor vessel and can be selected accordingly by a skilled artisan.

[0054] The catalyst bed can comprise two or more types of different catalyst particles, which are suitably arranged in two or more separate layers. The catalyst particles can be "different" in terms of their catalytic effect (e.g., different catalyst loadings for the same catalytic reaction), their physical form (e.g., pore size, particle size), or the catalytic reaction they carry out. This allows a skilled equipment engineer to customize the reaction in the reactor vessel as needed. For example, it may be advantageous to have large catalyst particles as a top layer to avoid catalyst fluidization while having a second layer of smaller catalyst particles that will have higher catalytic activity.

[0055] Catalyst bed is limited by first and second bed surfaces.The first bed surface is the surface located closest to the reactor vessel inlet end portion (that is, when the reactor vessel is vertically erected as described above, the upper surface of the catalyst bed).The first bed surface can be arranged to be substantially perpendicular to the central axis XX.Airflow enters the catalyst bed on the first bed surface, flows through the catalyst bed, and leaves the catalyst bed on the second bed surface (that is, when the reactor vessel is vertically erected as described above, the lower surface of the catalyst bed).Once airflow enters the catalyst bed, the physical presence of catalyst particles reduces gas mixing and reduces the gas flow in the direction perpendicular to the central axis XX.Therefore, it is important to maximize gas mixing before gas enters the catalyst bed.

[0056] The catalyst bed is supported by and in contact with the sidewalls of the main body of the reactor vessel. The main body may also contain catalytically inert particles. These may be mixed with the catalyst particles or present in one or more separate layers. In one aspect, the layer of catalytically inert particles is arranged on the surface of the first bed. This arrangement provides a "buffer" layer that further protects the catalyst particles of the catalyst bed from physical disturbance and / or abrasion.

[0057] In the outlet end section, the catalyst bed is supported on catalytically inert particles and / or a ceramic support structure.

[0058] The inlet end portion and the gas inlet of the reactor vessel have a specific design. The inlet end portion comprises at least one side wall; the side wall (125) comprises a diverging section (A), wherein the side wall is connected to the main body portion.

[0059] The "diverging section (A)" is a section of the inlet end portion located at the intersection of the inlet end portion and the main body portion. In this diverging section, the sidewalls of the inlet end portion diverge from the main body portion in the direction of the central axis XX. In other words, the cross-sectional area of ​​the inlet end portion decreases in the diverging section A from the main body portion in the direction of the central axis XX. This means that the sidewalls in the diverging section A are closer to each other (and closer to the central axis XX) than the sidewalls in the main body portion. To facilitate construction of the inlet end portion, the divergence of the diverging section A is gradual; that is, the sidewalls in this diverging section A are inclined or curved toward each other.

[0060] Gas inlets are disposed in a sidewall of the inlet end portion. Each gas inlet defines a primary gas inlet flow direction vector (V) along which gas enters the reactor chamber. The gas inlets are arranged such that the primary gas inlet flow direction vector (V) does not intersect the central axis (XX).

[0061] The specific design of the gas inlet and inlet end section means that gas entering the inlet end section via the inlet initially follows a spiral or circular path about the central axis XX. Because the main gas inlet flow direction vector (V) does not intersect the central axis (XX), the linear motion of the gas is converted into rotational motion about the central axis XX. As the gas passes through the reactor vessel, the diverging section (A) increases the radius of the spiral or circular path in the direction of the central axis XX, thereby slowing the gas flow. At all stages, the changes in gas flow direction and / or flow rate promote mixing.

[0062] The specific design of the gas inlet and the inlet end section is designed so that the cross-section of the inlet and the inlet section (as measured perpendicular to the central axis of the relevant cross-section) increases monotonically along the main flow direction vector in the gas inlet and the inlet end section. This embodiment allows the gas velocity to be gradually decelerated, thereby eliminating or significantly reducing the tendency of the gas flow to form jets; no special mechanical installation is required, such as a configured inlet distributor, such as a perforated plate.

[0063] Monotonically increasing can be understood as a function, such as f(z), where all combinations of x and y such that x ≤ y result in f(x) ≤ f(y).

[0064] This technology demonstrates how the combination of a conical head and a vortex inlet enables a reactor configuration that eliminates the need for dedicated flow distributors or mixers. As mentioned above, when reaction temperatures exceed 800°C, it is difficult to provide an inlet distributor for the reactor due to the mechanical weakness of typical steels used in these applications. By using a conical head and providing a vortex mechanism, the reactor inlet of the given configuration allows for uniform distribution and mixing of the feed across the downstream catalyst bed without any mechanical distributors.

[0065] In one aspect, as Figure 2b As shown, the diverging section (A) has a substantially frustoconical form, wherein the sidewalls of the inlet end portion diverge from the main body portion in the direction of the central axis XX, and the inlet end portion further comprises an end wall, wherein the sidewalls of the inlet end portion extend between the main body portion and the end wall. This simple design reduces the amount of wall area, thereby reducing the amount of material used in the vessel structure. This design can also be used in locations where the maximum available height of the reaction vessel is limited.

[0066] On the other hand, Figure 2c and 2d As shown, the side wall of the inlet end portion includes a divergent section (A) and a non-divergent section (B) adjacent to the divergent section (A). In the non-divergent section (B), the side wall of the inlet end portion extends in a direction substantially parallel to the central axis XX. In essence, the non-divergent section B has a substantially cylindrical shape, preferably around the same central axis XX. In other words, the design takes the form of a larger diameter cylinder (main body portion) connected to a smaller diameter cylinder (non-divergent section B) by the side wall of the divergent section A. Similarly, in this regard, as shown in the figure, the inlet end portion can also include an end wall, wherein the side wall of the inlet end portion extends between the main body portion and the end wall. The end wall is present at the inlet end of the reactor vessel, which closes the non-divergent section B.

[0067] In this regard, the gas inlet can be arranged in the side wall of the non-diverging section (B) of the inlet end portion. This arrangement is advantageous because it allows connecting the horizontal gas inlets to the vertical side wall (of the non-diverging section B) more easily than connecting them to the inclined side wall of the diverging section A.

[0068] On the other hand ( Figure 2a ), the side walls consisting of the diverging section (A). Thus, the inlet end portion has a substantially conical form that narrows from the main body along the central axis XX. The inlet end of the reactor vessel is thus pointed and does not itself have an end wall.

[0069] In a preferred aspect, the gas inlets are arranged such that each gas flow direction vector (V) lies in a plane substantially perpendicular to the central axis XX. Figures 2a-2c In the display, Figure 2d Compared to the gas inlet on the right side of the reactor vessel, it is not arranged perpendicular to the central axis XX. Likewise, when the components of the reactor vessel are arranged at right angles, construction is easier and the gas flows can be more easily predicted and adjusted.

[0070] The gas inlet suitably has the form of a circular hollow cylinder, wherein the main gas inlet flow direction vector (V) constitutes the central axis of said hollow cylinder. The gas inlet typically comprises an inlet pipe (which has the form of a circular hollow cylinder), wherein the main gas inlet flow direction vector (V) constitutes the central axis of said hollow cylinder. The inlet pipe has an inlet side wall, defining the circular hollow cylinder, and the inlet side wall is arranged in extension of a tangent (T) to the side wall of the inlet end portion. Figure 4 In comparison, this Figure 3 This arrangement means that the airflow enters the inlet end portion at a point close to one of the side walls of the inlet end portion and acquires maximum rotational energy (vortex).

[0071] Optionally, the inlet end portion includes two or more gas inlets and is arranged so that each inlet provides a different gas stream to the reactor vessel. The gas streams are "different" in terms of their chemical composition. For example, where the reactor vessel is an adiabatic post-converter, one gas inlet can be arranged to provide synthesis gas while another can be arranged to provide a CO2-rich gas feed. Where the reactor vessel is an adiabatic post-converter, one gas inlet can be arranged to provide synthesis gas while another can be arranged to provide a CO2-rich gas feed.

[0072] Alternatively, the inlet end portion may comprise one gas inlet arranged to provide a mixture of different gases to the reactor vessel via said one gas inlet (see Figures 2a-2c This would require mixing the gases upstream of the gas inlet. This design with a single inlet is simple to construct and reduces the number of joints in the vessel, thereby reducing the chance of failure at the joints. Gas flow and mixing within the vessel is also easier to design and adjust when there is only one gas inlet.

[0073] If the gas feeds are mixed before being fed to the reactor vessel, the reactor vessel may be included in a "reactor section". Thus there is provided a high temperature reactor section comprising

[0074] - a reactor vessel as defined herein;

[0075] - a first feed line arranged to supply a first gas feed;

[0076] - a second feed line arranged to supply a second gas feed;

[0077] - Mixing section;

[0078] wherein the mixing section is arranged to receive at least first and second gas feeds from the first and second feed lines, mix the first and second gas feeds to form a gas mixture, and feed the gas mixture to at least one gas inlet of the reactor vessel.

[0079] The high temperature reactor section may comprise a gas inlet line connecting the mixing section and the at least one gas inlet, arranged to feed the gas mixture from the mixing section to the at least one gas inlet through one or more, preferably two or more, 90° angles. In this arrangement, the first gas feed is suitably a syngas feed and the second gas feed is suitably a CO2-rich feed.

[0080] A second aspect of the present invention relates to a reactor vessel (100) for high-temperature catalytic reactions, the reactor (100) comprising a main body portion (110), an inlet end portion (120) and an outlet end portion (130), wherein the main body portion (110) extends between the inlet end portion (120) and the outlet end portion (130) along a central axis XX of the reactor vessel (100), and wherein the main body portion (110), the inlet end portion (120) and the outlet end portion (130) together define a reactor chamber (101);

[0081] - the body portion (110) has a substantially cylindrical form around a central axis XX of the reactor vessel (100);

[0082] - a catalyst bed (200) of catalyst particles (201) located within the reactor chamber (101) in the body portion (110);

[0083] - the inlet end portion (120) comprises one or more gas inlets (121);

[0084] - the outlet end portion (130) comprises one or more gas outlets (131);

[0085] Its characteristics are:

[0086] The inlet end portion (120) includes at least one side wall (125); the side wall (125) includes a diverging section (A), wherein the side wall (125) is connected to the main body portion (110),

[0087] wherein the gas inlets (121) are arranged in a side wall (125) of the inlet end portion (120); each gas inlet (121) defines a main gas inlet flow direction vector (V) along which gas enters the reactor chamber (101), wherein the gas inlets are arranged such that the main gas inlet flow direction vector (V) does not intersect the central axis (XX), and

[0088] Wherein all gas-contacting interior surfaces of the reactor vessel resist thermally induced deformation and degradation by contact with gas having a temperature of at least 750°C.

[0089] A third aspect of the present invention relates to a reactor vessel (100) for high-temperature catalytic reactions, the reactor (100) comprising a main body portion (110), an inlet end portion (120) and an outlet end portion (130), wherein the main body portion (110) extends between the inlet end portion (120) and the outlet end portion (130) along a central axis XX of the reactor vessel (100), and wherein the main body portion (110), the inlet end portion (120) and the outlet end portion (130) together define a reactor chamber (101);

[0090] - the body portion (110) has a substantially cylindrical form around a central axis XX of the reactor vessel (100);

[0091] - a catalyst bed (200) of catalyst particles (201) located within the reactor chamber (101) in the body portion (110);

[0092] - the inlet end portion (120) comprises one or more gas inlets (121);

[0093] - the outlet end portion (130) comprises one or more gas outlets (131);

[0094] Its characteristics are:

[0095] The inlet end portion (120) includes at least one side wall (125); the side wall (125) includes a diverging section (A), wherein the side wall (125) is connected to the main body portion (110),

[0096] wherein the gas inlets (121) are arranged in a side wall (125) of the inlet end portion (120); each gas inlet (121) defines a main gas inlet flow direction vector (V) along which gas enters the reactor chamber (101), wherein the gas inlets are arranged such that the main gas inlet flow direction vector (V) does not intersect the central axis (XX), and

[0097] All inner surfaces of the reactor vessel that come into contact with the gas are lined or coated with a layer of ceramic material.

[0098] An apparatus for producing synthesis gas having a predetermined H2 / CO ratio from a hydrocarbon feed is provided. The apparatus comprises:

[0099] a steam reforming reactor comprising a first catalyst and arranged to at least partially react the hydrocarbon feed with steam to produce a first synthesis gas stream

[0100] - A reactor vessel as defined herein, wherein the catalyst particles comprise a catalyst active for steam reforming / methanation and reverse water gas shift reactions;

[0101] - a first feed line arranged to direct at least a portion of the first synthesis gas stream from a steam reforming reactor to at least one gas inlet of the reactor vessel;

[0102] a second feed line arranged to supply a second CO2-rich gas feed to the reactor vessel; directly via a separate gas inlet, or via a mixing section; wherein the mixing section is arranged to receive at least the first synthesis gas stream and the second gas feed from the first and second feed lines, mix the first and second gas feeds to form a gas mixture, and feed the gas mixture to the at least one gas inlet of the reactor vessel;

[0103] - the reactor vessel is arranged to react the first synthesis gas stream with the second CO 2 gas feed, thereby providing a synthesis gas having a predetermined H 2 / CO ratio through an outlet of the reactor vessel.

[0104] The apparatus may further comprise one or more heating devices arranged to heat the second gas feed prior to mixing it with the first gas feed or prior to supplying it to the reactor vessel, wherein the heating device is a fired heater, an electric heater or a heat exchange unit. Suitably, the heating device is a heat exchange unit arranged to heat the second gas feed by exchanging heat with synthesis gas having a predetermined H2 / CO ratio from the outlet of the reactor vessel. This optimizes the use of the hot product gas.

[0105] Suitably, the steam reforming reactor is selected from an autothermal reactor (ATR), a steam methane reforming reactor (SMR) or a catalytic oxidation (CATOX) type reforming reactor, preferably an ATR.

[0106] A method for producing synthesis gas having a predetermined H2 / CO ratio from a hydrocarbon feed is provided. The method comprises the following steps:

[0107] - providing a device as described herein,

[0108] - at least partially reacting a hydrocarbon feed with steam in a steam reforming reactor to thereby produce a first

[0109] a synthesis gas stream;

[0110] - directing at least a portion of said first synthesis gas stream from a steam reforming reactor to at least one gas inlet of said reactor vessel via a first feed line,

[0111] - supplying a second CO2-rich gas feed to the reactor vessel via a second feed line;

[0112] directly through separate gas inlets, or through a mixing section; wherein the mixing section is arranged to receive at least the first synthesis gas stream and the second gas feed from the first and second feed lines, mix the first and second gas feeds to form a gas mixture, and feed the gas mixture to at least one gas inlet (121) of the reactor vessel;

[0113] - reacting the first synthesis gas stream with the second CO2 gas feed in the reactor vessel,

[0114] Thereby, a synthesis gas having a predetermined H2 / CO ratio is provided through the outlet of the reactor vessel.

[0115] The present invention has been described with reference to various aspects, embodiments and drawings. A person skilled in the art may combine elements and features from the various aspects, embodiments and drawings to modify the present invention within the scope of the appended claims.

[0116] Detailed discussion of the accompanying drawings

[0117] Figure 1 Shown is a schematic diagram of a reaction vessel according to the invention viewed from a cross section along the central axis XX.

[0118] Figures 2a-2d Various embodiments of reaction vessels having various designs of inlet end portions are illustrated.

[0119] Figure 3 and Figure 4 are cross-sectional views of two possible inlet end portions along the central axis XX.

[0120] Figure 5 A high temperature reactor section as defined herein is shown comprising:

[0121] - reactor vessel 100;

[0122] - a first feed line 301 arranged to supply a first gas feed;

[0123] - a second feed line 302 arranged to supply a second gas feed;

[0124] - Mixing section 310;

[0125] The mixing section is arranged to receive at least first and second gas feeds from first and second feed lines 301 , 302 , mix the first and second gas feeds to form a gas mixture, and feed the gas mixture to at least one gas inlet 121 of the reactor vessel 100 .

[0126] The high temperature reactor section 300 comprises a gas inlet line 311 connecting the mixing section 310 and the at least one gas inlet 121, which is arranged to feed the gas mixture from the mixing section 310 through one or more, preferably two or more, 90° angles to the at least one gas inlet 121. Typically, as described above, the first gas feed is a syngas feed and the second gas feed is a CO2-rich feed.

[0127] Figure 6 and Figure 7 A schematic diagram of an apparatus for producing synthesis gas is shown.

[0128] Figure 6 is a schematic diagram of a plant 500 for producing synthesis gas according to the present invention. The plant 500 comprises a reactor vessel in the form of an ATR reactor 10 and an adiabatic post-converter 20.

[0129] The hydrocarbon feed stream 4 to the ATR reactor 10 of the device 500 consists of a hydrocarbon feed 1, a CO2-rich gas stream 2 (e.g., substantially pure CO2) and steam 3. The CO2-rich gas stream 2 and steam 3 are added to the first hydrocarbon gas stream 1 to form a combined stream 4, which is then introduced into the ATR reactor 10. The ATR reactor 10 contains a steam methane reforming catalyst 11. An oxygen-containing stream 5 (e.g., air, an oxygen-rich stream or substantially pure oxygen) is introduced into the combustion zone of the ATR reactor 10 through an inlet. The ATR reactor 10 produces a first synthesis gas stream 6 comprising hydrogen, carbon monoxide and carbon dioxide from the combined stream 4 and the oxygen-containing stream 5. The first synthesis gas stream 6 leaving the ATR reactor typically has a temperature of about 900°C to about 1100°C, for example, about 1000°C.

[0130] The adiabatic post-converter 20 houses particles 25 of a second catalyst active in catalytic steam methane reforming / methanation and reverse water gas shift reactions.

[0131] A first feed line 301 connects the outlet of the ATR reactor 10 to at least one gas inlet of the adiabatic post-converter 20. A second feed line 302 is arranged to provide a heated CO2-rich gas feed 7, which is added to the first synthesis gas stream 6 upstream of the adiabatic post-converter 20, thereby producing a mixed gas stream 8. This mixed gas 8 is introduced into the adiabatic post-converter, and the resulting synthesis gas 15 leaves the reactor 20 as product synthesis gas. The product synthesis gas 15 can be further processed downstream of the reactor 20.

[0132] The adiabatic post-converter 20 serves to balance the mixed gas, thereby reducing the H 2 / CO ratio of the resulting product synthesis gas 15 compared to the H 2 / CO ratio of the first synthesis gas 6 .

[0133] exist Figure 6 In the embodiment shown, the heated CO2-rich gas stream 7 is added to the first synthesis gas stream 6 to form a mixed gas stream 8, which is then provided to the adiabatic post-converter 20. Alternatively, however, the heated CO2-rich gas stream 7 and the first synthesis gas 8 can be provided separately to the adiabatic post-converter 20 for mixing therein upstream of the catalyst bed 25.

[0134] Figure 7 is a schematic diagram of an apparatus 500 for producing synthesis gas according to the present invention. The apparatus 500 comprises Figure 6 1 and 2. The units / components of the apparatus 500 are shown. Similar units are denoted by similar reference numerals and will not be described in detail here. The apparatus 500 includes a heating device 40 in the form of a heat exchanger 40a located downstream of the adiabatic post-converter 20. The CO2-rich gas stream 7' is heated by heat exchange with the hot product synthesis gas 15 leaving the adiabatic post-converter, thereby providing a heated CO2-rich gas stream 7.

[0135] Example 1

[0136] A chemical reactor according to the invention with a feed gas according to Table 1 was modelled using computational fluid dynamics.

[0137]

[0138]

[0139] Table 1

[0140] In the modeled case, two gases were mixed in a pipe with an internal diameter of 600 mm. From the mixing point to the first 90° upward bend, there was a 0.5-meter section. The pipe then extended vertically for 4.6 meters, then curved 90 degrees into a horizontal plane, traveled 2.3 meters, and then entered a vertical cylindrical section with an internal diameter of 1 m. 0.5 m below the pipe inlet, a 2-meter tapered section was placed, where the internal diameter increased from 1 m to 2.4 m.

[0141] Table 2 shows the mixing of CO2 into the synthesis at the relevant points in the reactor for two cases with different configurations of piping connections.

[0142] Case 1 2 Syngas velocity before mixing [m / s] 18.6 18.6 <![CDATA[CO2 velocity before mixing [m / s]]]> 2.48 18.6 <![CDATA[CO2 molar concentration span in the relative stage [mol%]]]> Before entering the reactor 10.4-18.3 13.2-17 Top of the tapered section 13.5-15.8 15.7-16.7 300mm above the catalyst bed 13.5-15.8 14.8-15.6 Above the catalyst bed 14.3-15.5 14.6-15.3 Maximum velocity in the plane above the catalyst [m / s] 9 7.9

[0143] Table 2

[0144] As can be seen in Case 1, the configuration of the vortex inlet and the tapered section helps reduce the relative standard deviation of the CO2 concentration from 15.1% before entering the reactor to 2.1% just above the catalyst. In Case 2, the CO2 velocity is increased at the mixing point, and the relative standard deviation at the reactor inlet can be reduced to 5.9%, and then further reduced to 0.8% by the vortex inlet arrangement.

[0145] Overall, it has been shown that the configuration according to the invention has a significant impact on achieving good mixing of CO 2 into the synthesis gas.

[0146] This example also shows the maximum velocity in the plane just above the catalyst. Note that the numbers are not exact, and the results for Case 1 are not significantly different from those for Case 2. When using a 20 mm diameter, 1800 kg / m 3 When the alumina balls are used as the top layer of the catalyst, the terminal velocity can be calculated according to the following formula:

[0147]

[0148] Here g is the acceleration due to gravity, d is the diameter of the particle, Cd is the drag coefficient (assumed to be 0.6), and ρ s is the density of the particle, and ρ is the density of the gas (5.73 kg / m in this case 3 ). For a given alumina particle, the final velocity will be 11.7 m / s, which is above the maximum velocity where grinding / fluidization of the particles does not occur and the gas can already be sufficiently decelerated by the configuration of the present invention.

[0149] Example 2

[0150] Exemplary calculations for this method are given in Table 3 below. Figure 6 As shown, a hydrocarbon feed stream 4 comprising a hydrocarbon gas 1, a CO2-rich stream 2, and steam 3 and having an S / C ratio of 0.6 is fed to an ATR reactor 10. The hydrocarbon feed stream 4 is heated to 650°C before entering the ATR reactor 10. The ATR reactor 10 produces a first synthesis gas stream 6. An oxidant gas stream 5 of oxygen is added to the ATR reactor 10 and its amount is adjusted so that the temperature of the first synthesis gas stream 6 is 1050°C.

[0151] The total flow rates of all components in all inlet streams to the ATR reactor and the flow rates of all components in the first synthesis gas stream 5 are given in Table 3 in the column headed "ATR 10".

[0152] The CO2 rich gas stream is heated to a heated CO2 rich gas stream having a temperature of 650°C, and the combined gas (first synthesis gas stream and heated CO2 rich gas stream) enters the adiabatic post-converter 20 at a temperature of 969°C.

[0153] Within the adiabatic post-reformer 20, the combined stream is balanced, meaning it undergoes reverse water-gas shift, methanation, and reforming reactions. The total amount of carbon monoxide, steam, and methane output from the adiabatic post-reformer 20 is increased compared to the gas entering the adiabatic post-reformer 20. The outlet temperature of the product gas stream exiting the adiabatic post-reformer 20 is 951°C, well below the gas's methane decomposition equilibrium temperature of 1195°C and above its Boudouard temperature of 850°C. Therefore, the product gas stream has no potential for carbon formation.

[0154] In this context, the methane decomposition temperature (T(MDC)) is calculated as the equilibrium constant for the decomposition of methane to graphite The temperature at which the reaction quotient of the gas is equal to the reaction quotient. When the temperature is higher than this temperature, the formation of graphite carbon can occur. The reaction quotient QC is defined as the ratio of the square of the hydrogen partial pressure to the methane partial pressure, that is, QC = P 2 H2 / P CH4 .

[0155] The Boudouard equilibrium temperature (T(BOU)) is calculated in a similar manner, but based on the Boudouard reaction In this case, when the temperature is lower than the Boudouard equilibrium temperature, the formation of graphitic carbon may occur.

[0156] ATR 10 Adiabatic post-converter 20 Inlet T[℃] 650 969 Outlet T[℃] 1050 951 <![CDATA[Inlet P [kg / cm 2 g]]]> 35.5 34.5 <![CDATA[Outlet P [kg / cm 2 g]]]> 34.5 34 Export T (MDC) [℃] - 1195 Export T (BOU) [℃] 892 850 Entrance: <![CDATA[N2[Nm 3 / h]]]> 27 251 <![CDATA[CO2[Nm 3 / h]]]> 8515 19356 <![CDATA[CH4[Nm 3 / h]]]> 19222 391 <![CDATA[H2[Nm 3 / h]]]> 405 32380 <![CDATA[H2O[Nm 3 / h]]]> 11639 17327 <![CDATA[CO[Nm 3 / h]]]> 0 21315 Oxygen feed: <![CDATA[O2[Nm 3 / h]]]> 11018 <![CDATA[N2[Nm 3 / h]]]> 224 Oxygen feed T[℃] 371 exit: <![CDATA[N2[Nm 3 / h]]]> 251 251 <![CDATA[CO2[Nm 3 / h]]]> 6032 14597 <![CDATA[CH4[Nm 3 / h]]]> 391 779 <![CDATA[H2[Nm 3 / h]]]> 32380 26455 <![CDATA[H2O[Nm 3 / h]]]> 17327 22475 <![CDATA[CO[Nm 3 / h]]]> 21315 25685 <![CDATA[Total outlet flow rate [Nm 3 / h]]]> 77696 90242

[0157] Table 3

[0158] Thus, when using the process of the present invention, a product gas stream in the form of synthesis gas having a relatively high amount of CO can be provided.

[0159] Example 3

[0160] This example relates to and provides further information on the same studies as Example 1. Using two different reactor geometries of an adiabatic post-converter (APOC), CFD (computational fluid dynamics) analysis was performed under three cases with different process parameters to analyze the gas flow patterns, including mixing and velocity at the point of impact with the catalyst bed.

[0161] Reactor geometry

[0162] parameter Reactor 1 (m) Reactor 2 (m) Process gas inlet diameter 0.6 0.6 <![CDATA[Inlet diameter of CO2 gas to process gas pipe]]> 0.6 0.218 Catalyst bed height 2.6 2.6 Reaction zone cross section 2.4 2.4 Outlet diameter 0.5 0.5 Height of the frustum 2.0 2.0

[0163] Both reactors have the form of a larger diameter cylinder (main body) connected to a smaller diameter cylinder by the side wall of a diverging frustoconical section, wherein the gas inlet is introduced into the smaller diameter cylinder, and wherein the smaller diameter cylinder together with the diverging frustoconical section constitutes the gas inlet portion.

[0164] Process parameters

[0165]

[0166]

[0167]

[0168] Results – Relative standard deviation of CO2 mole fraction at different levels in the reactor

[0169]

[0170] As can be seen from the results, the relative standard deviation of the CO2 mole fraction decreases significantly along the flow path from entering the reactor sidewall through the top of the frustoconical section to just above the catalyst bed, remaining within ±2% of the mean value above the catalyst bed in all cases. Therefore, mixing of the CO2 stream and the process gas stream is very effective.

[0171] Results – Gas velocity at the point of collision with the catalyst bed

[0172] Particle diameter (mm) <![CDATA[Particle density (kg / m 2 )]]> Disturbance threshold speed (m / s) 20 1800 11.67 25.4 (1 inch alumina ball) 3600 18.62 50-8 (2-inch alumina ball) 3600 26.34

[0173] The velocities of the mixed gas stream at the point of collision with the catalyst bed were calculated to be 9.0, 7.9, and 7.1 m / s, respectively, for Cases 1, 2, and 3. Therefore, in all cases, the velocity of the mixed gas stream was well below the minimum velocity at which catalyst bed disturbance would occur.

Claims

1. A reactor vessel (100) for high temperature catalytic reactions, the reactor (100) comprising a main body portion (110), an inlet end portion (120) and an outlet end portion (130), wherein the main body portion (110) extends between the inlet end portion (120) and the outlet end portion (130) along a central axis XX of the reactor vessel (100), and wherein the main body portion (110), the inlet end portion (120) and the outlet end portion (130) together define a reactor chamber (101); The main body portion (110) has a cylindrical form around a central axis XX of the reactor vessel (100); A catalyst bed (200) of catalyst particles (201) is located within the reactor chamber (101) in the main body portion (110); The inlet end portion (120) includes one or more gas inlets (121); The outlet end portion (130) includes one or more gas outlets (131); Its characteristics are: The inlet end portion (120) includes at least one side wall (125); the side wall (125) includes a diverging section A, wherein the side wall (125) is connected to the main body portion (110), and wherein the gas inlets (121) are arranged only in the side wall (125) of the inlet end portion (120); each gas inlet (121) defines a main gas inlet flow direction vector V along which gas enters the reactor chamber (101), wherein the gas inlets are arranged such that the main gas inlet flow direction vector V does not intersect the central axis XX, and wherein the interior space of the inlet end portion is configured such that the cross-sectional area available for gas flow is constant or increases along the central axis XX in a direction from the gas inlet to the main body portion, And wherein the inlet end portion does not include any gas distributor in the form of a perforated plate disposed at the lower end of the inlet end portion upstream of the main body portion.

2. The reactor vessel (100) according to claim 1, wherein all inner surfaces of the reactor vessel in contact with the gas are coated or lined with a layer of ceramic material.

3. The reactor vessel (100) according to claim 1 or 2, wherein the inlet end portion (120) and the outlet end portion (130) have a circular cross-section around a central axis XX of the reactor vessel (100).

4. A reactor vessel (100) according to claim 1 or 2, wherein the diverging section A has a truncated conical form, wherein the side wall of the inlet end portion (120) diverges from the main body portion (110) in the direction of the central axis XX, the inlet end portion (120) further comprising an end wall (126), and wherein the side wall of the inlet end portion extends between the main body portion (110) and the end wall (126).

5. The reactor vessel (100) according to claim 1 or 2, wherein the side wall (125) of the inlet end portion (120) comprises the diverging section A and a non-diverging section B adjacent to the diverging section A, wherein In the non-diverging section B, the side walls (125) of the inlet end portion (120) extend in a direction parallel to the central axis XX.

6. The reactor vessel (100) according to claim 5, wherein the gas inlet (121) is arranged in a side wall (125) of the non-diverging section B of the inlet end portion (120).

7. The reactor vessel (100) according to claim 1 or 2, wherein the side wall (125) of the inlet end portion (120) is composed of the diverging section A so that the inlet end portion (120) has a conical form that narrows from the main body portion (110) along the central axis XX.

8. The reactor vessel (100) according to claim 1 or 2, wherein the gas inlets (121) are arranged such that each gas flow direction vector V lies in a plane perpendicular to the central axis XX.

9. A reactor vessel (100) according to claim 1 or 2, wherein the gas inlet (121) comprises an inlet pipe (128) having an inlet side wall (129) defining a circular hollow cylinder, wherein the main gas inlet flow direction vector V constitutes the central axis of the hollow cylinder, and wherein the inlet side wall (129) is arranged in an extension of the tangent T of the side wall (125) of the inlet end portion (120).

10. The reactor vessel (100) of claim 1 or 2, wherein the inlet end portion (120) comprises two or more gas inlets (121) and is arranged such that each inlet provides a different gas flow to the reactor vessel (100).

11. A reactor vessel (100) according to claim 10, wherein the reactor vessel is an adiabatic post-converter; one gas inlet (121) is arranged to provide synthesis gas to the reactor vessel (100), and at least one other gas inlet (121) is arranged to provide a CO2-rich gas feed to the reactor vessel (100).

12. The reactor vessel (100) according to claim 1 or 2, wherein the inlet end portion (120) comprises one gas inlet (121) arranged to provide a mixture of different gases to the reactor vessel (100) through the one gas inlet (121).

13. The reactor vessel (100) of claim 1 or 2, which is an adiabatic post-converter.

14. The reactor vessel (100) according to claim 1 or 2, which is a water-gas shift reactor.

15. The reactor vessel (100) of claim 1 or 2, wherein the catalyst particles (201) comprise a ceramic material.

16. The reactor vessel (100) of claim 15, wherein the ceramic material is coated and / or impregnated with a catalytically active metal or metal salt.

17. The reactor vessel (100) of claim 1 or 2, wherein the catalyst bed comprises two or more layers of different catalyst particles (201).

18. The reactor vessel (100) according to claim 1 or 2, wherein the main body portion (110) further comprises a catalytically inert particle layer (202) arranged at one surface of the catalyst bed (200).

19. The reactor vessel (100) according to claim 1 or 2, wherein the reactor vessel is suitable for a pressure between 15 and 45 barg.

20. A method for high temperature catalytic reaction, comprising the following steps - introducing a gas having a temperature of at least 750° C. into at least one gas inlet ( 121 ) of a reactor vessel ( 110 ) according to any one of claims 1 to 18, and - subjecting the gas to a catalytic reaction in said reactor vessel.

21. An apparatus (500) for producing synthesis gas (15) having a predetermined H2 / CO ratio from a hydrocarbon feed (501), the apparatus (500) comprising: a steam reforming reactor (510) comprising a first catalyst and arranged to at least partially react the hydrocarbon feed (1) with steam (3) to produce a first synthesis gas stream (6); - A reactor vessel (100) according to any one of claims 1 to 19, wherein the catalyst particles (25) comprise catalysts active for steam reforming, methanation and reverse water gas shift reactions; a first feed line (301) arranged to direct at least a portion of the first synthesis gas stream (6) from a steam reforming reactor (510) to at least one gas inlet (121) of the reactor vessel (100); a second feed line (302) arranged to supply a second gas feed (7) rich in CO2 to the reactor vessel (100); directly via a separate gas inlet (121), or via a mixing section (310); wherein the mixing section is arranged to receive at least the first synthesis gas stream and the second gas feed from the first and second feed lines (301, 302), mix the first synthesis gas stream and the second gas feed to form a gas mixture, and feed the gas mixture to at least one gas inlet (121) of the reactor vessel (100); - the reactor vessel (100) being arranged to react the first synthesis gas stream (6) with the second gas feed (7) enriched in CO2, thereby providing a synthesis gas (15) having a predetermined H2 / CO ratio through an outlet of the reactor vessel (100).

22. The apparatus (500) according to claim 21 further comprises one or more heating devices (40), wherein the heating devices (40) are arranged to heat the second gas feed before mixing it with the first synthesis gas flow or before supplying the second gas feed to the reactor vessel (100), wherein the heating devices (40) are fired heaters, electric heaters or heat exchange units.

23. Apparatus (500) according to claim 22, wherein the heating device (40) is a heat exchange unit (40a) arranged to heat the second gas feed by heat exchange with synthesis gas (15) having a predetermined H2 / CO ratio from the outlet of the reactor vessel (100).

24. The apparatus (500) according to any one of claims 21 to 23, wherein the steam reforming reactor (510) is selected from an autothermal reactor, a steam methane reforming reactor or a catalytic oxidation reforming reactor.

25. A method for producing synthesis gas having a predetermined H2 / CO ratio from a hydrocarbon feed (501), the method comprising the steps of: - providing an apparatus (500) according to any one of claims 21 to 24; - at least partially reacting a hydrocarbon feed (501) with steam (502) in a steam reforming reactor (510) and thereby producing a first synthesis gas stream (511); - directing at least a portion of the first synthesis gas stream (511) from the steam reforming reactor (510) to at least one gas inlet (121) of the reactor vessel (100) via a first feed line (301), - supplying a second gas feed rich in CO2 to the reactor vessel (100) via a second feed line (302); directly via a separate gas inlet (121), or via a mixing section (310); wherein the mixing section is arranged to receive at least the first synthesis gas stream and the second gas feed from the first and second feed lines (301, 302), mix the first synthesis gas stream and the second gas feed to form a gas mixture, and feed the gas mixture to at least one gas inlet (121) of the reactor vessel (100); - reacting a first synthesis gas stream (511) with a second gas feed enriched in CO2 in the reactor vessel (100) to provide a synthesis gas having a predetermined H2 / CO ratio through an outlet of the reactor vessel (100).

Images