CN109694039B

CN109694039B - Reforming hydrogen production reactor, hydrogen production conversion furnace and reforming hydrogen production method

Info

Publication number: CN109694039B
Application number: CN201710985866.6A
Authority: CN
Inventors: 张旭; 戴文松
Original assignee: Sinopec Engineering Inc; Sinopec Engineering Group Co Ltd
Current assignee: Sinopec Engineering Inc; Sinopec Engineering Group Co Ltd
Priority date: 2017-10-20
Filing date: 2017-10-20
Publication date: 2021-04-23
Anticipated expiration: 2037-10-20
Also published as: CN109694039A

Abstract

The disclosure relates to a reforming hydrogen production reactor, a hydrogen production converter and a reforming hydrogen production method. The reforming hydrogen production reactor adopts a micro-catalytic reaction plate, and active components required by hydrogen production reaction are loaded on the reaction plate, so that the using amount of catalytic active metals is reduced, the catalyst is not easy to deposit carbon and deactivate, the distance from reaction gas to a catalytic activity center is shortened, the mass transfer resistance and the pressure drop of the reactor are reduced, and the conversion rate of the hydrogen production reaction is improved; the reaction gas flows outwards from the center in the reactor, the flow passage area is gradually increased, the temperature of the reaction plate is gradually increased, and the improvement of the conversion rate of the hydrogen production reaction which is used as volume increase and endothermic reaction is facilitated; the reforming hydrogen production reactor has wide application range, and can be suitable for different types of reforming furnaces as a furnace tube of a hydrogen production reforming furnace. The hydrogen production method adopting the reforming hydrogen production converter has the advantages of reduced furnace tube pressure, high space-time yield of the catalyst in unit volume in the furnace tube, high conversion rate of raw material gas treatment capacity, and capability of meeting the requirements of hydrogen production reaction.

Description

Reforming hydrogen production reactor, hydrogen production conversion furnace and reforming hydrogen production method

Technical Field

The disclosure relates to the field of hydrogen production by reforming, in particular to a hydrogen production by reforming reactor, a hydrogen production converter and a hydrogen production by reforming method.

Background

Hydrogen is not only an important chemical raw material, but also a clean fuel. Hydrogen plays an increasingly important role in modern industries, especially the petrochemical industry, fuel cells and other national economy. Under the multiple pressure of the global crude oil with the trend of increasing the weight and the deterioration of crude oil, the increasing demand of people on the quantity of clean oil products, the increasing quality standard and the stricter environmental regulations, the demand on hydrogen is also increasing, and then the higher demand on a hydrogen production device is also provided.

The hydrogen production process mainly comprises a water electrolysis method, a light hydrocarbon steam conversion method, a partial oxidation method, a methanol cracking method and the like, and the light hydrocarbon steam conversion method is most widely applied at present. The raw material for hydrogen production by the light hydrocarbon steam reforming method mainly comprises carbon-containing light hydrocarbons such as natural gas, naphtha, refinery gas and the like. The conversion process comprises the following steps: the light hydrocarbons react with water vapor under certain temperature, pressure and catalyst action to generate hydrogen and carbon monoxide, and the carbon monoxide further generates hydrogen through water gas shift reaction, so that the yield of the target product of the light hydrocarbons is further improved.

The main chemical reactions that occur during the hydrogen production reaction are:

conversion reaction C_nH_m+n H₂O→n CO+(n+m/2)H₂ △H＝206kJ/mol

Shift reaction of CO + H₂O→CO₂+H₂ △H＝-36kJ/mol

The reforming reaction is a strong endothermic reaction, and in a traditional hydrogen production furnace, the reforming furnace tube filled with the reforming catalyst is heated to 900-1000 ℃ through fuel combustion to carry out the hydrogen production reaction. Common reforming hydrogen production active components comprise group V III transition elements such as Pt, Pd, Ir, Rh and the like, and the industrial application is limited due to the high price of the elements. Currently, the most widely used active component in the hydrogen production industry by reforming is nickel. The activity of the catalyst is directly related to the axial size of the specific surface of the catalyst, and relatively, the larger the specific surface is, the better the dispersion degree of the active components is, and the more the number of active centers is, so that the catalytic activity of the catalyst is improved.

The existing hydrogen production converter is filled with a nickel-based catalyst with a certain particle size and shape in a furnace tube, so that the uneven filling often occurs, the bias flow of raw material gas is caused, the conversion rate of the raw material is low, the catalyst is easy to deposit carbon and deactivate, and the operation period of the device is shortened. In addition, the catalyst with smaller particle size is filled in the furnace tube, although the filling amount of the catalyst can be increased, the number of active centers of the catalyst is increased, and the processing capacity and the conversion rate of the raw material are improved to a certain extent.

Disclosure of Invention

The reforming hydrogen production reactor and the reformer adopting the reforming hydrogen production reactor have the advantages of pressure reduction, no gas bias flow and no short circuit phenomenon; the method adopting the reforming hydrogen production converter has high conversion rate.

In order to achieve the above object, a first aspect of the present disclosure provides a reforming hydrogen production reactor, which includes a cylindrical sealed pressure-bearing shell, an air inlet, an air outlet, a first straight pipe extending from the top of the shell to the inside of the shell, a second straight pipe extending from the bottom of the shell to the inside of the shell, and a catalytic reaction unit disposed in the shell below the first straight pipe and above the second straight pipe; the air inlet is communicated with the first straight pipe, and the air outlet is communicated with the second straight pipe; the top and the bottom of the catalytic reaction unit are respectively sealed by a top sealing plate and a bottom sealing plate, the catalytic reaction unit comprises a central tube which is axially arranged, and the central tube penetrates through the top sealing plate and is communicated with the first straight tube; an annular gap is formed between the outer side wall of the catalytic reaction unit and the inner wall of the shell; the side walls of the central tube and the catalytic reaction unit are respectively provided with an opening, so that the central tube is communicated with the annular space through the openings; a gas collection cavity communicated with the annular gap fluid is formed between the bottom sealing plate and the inner wall of the lower part of the shell, and the annular gap is communicated with the second straight pipe through the gas collection cavity; a micro-catalytic reaction plate is arranged in the catalytic reaction unit, and a reforming hydrogen production catalyst is loaded on the surface of the catalytic reaction plate.

Optionally, the micro-catalytic reaction plate extends axially and spirally around the central tube, the top end of the micro-catalytic reaction plate is connected with the top sealing plate in a sealing manner, and the bottom end of the micro-catalytic reaction plate is connected with the bottom sealing plate in a sealing manner.

Optionally, the micro-catalytic reaction plate is one or a plurality of coaxially arranged annular plates, the inner edge of the micro-catalytic reaction plate is fixedly connected with the inner side wall of the catalytic reaction unit in a sealing manner, and the outer edge of the micro-catalytic reaction plate is fixedly connected with the outer side wall of the catalytic reaction unit in a sealing manner.

Optionally, the micro-catalytic reaction plate is at least one selected from the group consisting of a flat plate, a toothed plate, a corrugated plate and a corrugated plate.

The second aspect of the present disclosure provides a reforming hydrogen production reformer, which includes an air inlet pipe, an air outlet pipe, a burner and a combustion chamber, and the reformer further includes the reforming hydrogen production reactor of the first aspect of the present disclosure, the reforming hydrogen production reactor is located in the combustion chamber, an air inlet of the reforming hydrogen production reactor is communicated with the air inlet pipe, and an air outlet of the reforming hydrogen production reactor is communicated with the air outlet pipe.

A third aspect of the present disclosure provides a method for performing a reforming hydrogen production reaction using the reforming hydrogen production converter of the second aspect of the present disclosure, the method comprising the steps of: (1) fuel gas and air are sprayed into the combustion chamber through the burner for combustion; (2) and enabling feed gas and steam to enter the reforming hydrogen production reactor through the air inlet pipe of the reformer, and carrying out reforming hydrogen production reaction in the catalytic reaction unit to obtain reformed gas rich in hydrogen.

Optionally, the conditions of the reforming hydrogen production reaction include: the reaction temperature is 700-1100 ℃, the reaction pressure is 1.8-5.5 MPaG, and H in the steam₂The molar ratio of O to carbon atoms in the raw material gas is (2.5-5): 1, the airspeed is 1000-100000 h^-1。

Optionally, the average flow velocity of the raw material gas in the catalytic reaction unit is 0.001-100 m/s.

Optionally, the feed gas is at least one of natural gas, liquefied petroleum gas, refinery gas, a resolved gas of reformed hydrogen-enriched PSA, and naphtha.

Optionally, the reforming hydrogen production reaction catalyst comprises a reforming hydrogen production active component comprising at least one of nickel, ruthenium, platinum, palladium, iridium, and rhodium.

Compared with the prior art, the invention has the beneficial effects that:

(1) the catalytic reaction unit of the reforming hydrogen production reactor is a radial reaction area formed by a micro-catalytic reaction plate, a catalyst for hydrogen production reaction is loaded on the reaction plate, the distance of reaction gas from a gas phase main body to a catalytic activity center is shortened, the mass transfer resistance (the diffusion resistance is almost zero) is greatly reduced, meanwhile, the generated product can be quickly diffused to a fluid main body, the retention time of the product in the reactor is short, the conversion efficiency of the hydrogen production reaction is fundamentally improved, and the purpose of improving the space-time yield of a unit catalyst product is achieved.

(2) The reaction gas is uniformly distributed from the central tube, enters the radial reaction region and flows from inside to outside, the area of the flow channel is gradually increased, and the hydrogen production reaction with increased volume is facilitated to move towards the direction of a product. In addition, as the reactant flows from inside to outside, the temperature of the outer layer micro-catalytic reaction plate is higher than that of the inner layer micro-catalytic reaction plate, the temperature of the micro-catalytic reaction plate at the annular space is the highest, and the hydrogen production reaction is an endothermic reaction, so that the hydrogen production reaction is favorably carried out.

(3) Compared with the reforming hydrogen production reactor filled with particles, the micro-catalytic reaction plate is adopted, the total amount of active metal used by the reactor is obviously reduced, and the pressure drop is low. Under the condition of the same treatment scale, the reforming hydrogen production reactor and the reformer equipment formed by the reforming hydrogen production reactor have the advantages that the size is 5-30% smaller than that of the traditional reforming reactor, and the pressure drop is 3-55% lower.

(4) Compared with a reforming hydrogen production reactor filled with particles, the micro-catalytic reaction plate of the reforming hydrogen production reactor disclosed by the invention is not easy to deposit carbon and deactivate, the service life is long, the pressure is reduced, and the bed pressure drop is lower (15-90%) than that of a reactor with the same treatment capacity;

(5) the catalytic reaction unit is composed of micro catalytic reaction plates, so that the number of active centers is increased, the uniformity of reaction gas in the catalytic reaction active centers is improved, the phenomena of reaction dead zones and gas bias flow are avoided, and the stable operation in the whole operation period can be fully ensured.

(6) The reforming hydrogen production reforming furnace tube can be suitable for reforming furnaces of different types, has wide application range, can achieve control and regulation production through an integration mode with functionalized sleeves and increase and decrease of the number according to actual industrial production requirements, is beneficial to realizing the maximum utilization efficiency of equipment, has no obvious amplification effect, shortens the processing time of the equipment and further reduces the production cost of a reactor.

Additional features and advantages of the disclosure will be set forth in the detailed description which follows.

Drawings

The accompanying drawings, which are included to provide a further understanding of the disclosure and are incorporated in and constitute a part of this specification, illustrate embodiments of the disclosure and together with the description serve to explain the disclosure without limiting the disclosure. In the drawings:

FIG. 1 is a schematic diagram of the structure of one embodiment of a reforming hydrogen production reactor of the present disclosure;

figure 2 is a cross-sectional view of one embodiment of a reforming hydrogen production reactor of the present disclosure (i.e., a cross-sectional view on the a-a plane of figure 1);

FIG. 3 is a schematic illustration of a catalytic reaction unit sidewall of one embodiment of a reforming hydrogen production reactor of the present disclosure;

FIG. 4 is a schematic view of a top seal plate of one embodiment of the reforming hydrogen production reactor of the present disclosure;

fig. 5 is a schematic structural diagram of a second embodiment of a reforming hydrogen production reactor of the present disclosure;

fig. 6 is a cross-sectional view of a second embodiment of a reforming hydrogen production reactor of the present disclosure (i.e., a cross-sectional view taken on plane a-a of fig. 5);

FIG. 7 is a schematic diagram of a triangular prism-shaped assembly for forming the sidewall of a catalytic reaction unit of a reactor according to an embodiment of the present disclosure;

FIG. 8 is a schematic structural view of a cylindrical assembly used to form the sidewall of the catalytic reaction unit of the reactor for one embodiment of the reforming hydrogen production reactor of the present disclosure;

fig. 9 is a schematic structural diagram of a third embodiment of a reforming hydrogen production reactor of the present disclosure;

fig. 10 is a sectional view of a third embodiment of a reforming hydrogen production reactor of the present disclosure (i.e., a sectional view taken on the a-a plane of fig. 9);

fig. 11 is a schematic structural diagram of a fourth embodiment of a reforming hydrogen production reactor of the present disclosure;

fig. 12 is a cross-sectional view of a fourth embodiment of a reforming hydrogen production reactor of the present disclosure (i.e., a cross-sectional view taken on plane a-a of fig. 11);

FIG. 13 is a schematic structural view of a toothed micro-catalytic reaction plate of one embodiment of a reforming hydrogen production reactor of the present disclosure;

FIG. 14 is a schematic structural view of a corrugated micro-catalytic reaction plate of one embodiment of a reforming hydrogen production reactor of the present disclosure;

FIG. 15 is a schematic structural view of a corrugated micro-catalytic reaction plate of one embodiment of a reforming hydrogen production reactor of the present disclosure;

FIG. 16 is a schematic block diagram of an embodiment of a reformer for reforming hydrogen production according to the present disclosure;

FIG. 17 is a schematic block diagram of another embodiment of a reforming hydrogen production reformer according to the present disclosure;

fig. 18 is a schematic structural diagram of a fifth embodiment of a reforming hydrogen production reactor of the present disclosure;

fig. 19 is a sectional view of a fifth embodiment of a reforming hydrogen production reactor of the present disclosure (i.e., a sectional view taken on plane a-a of fig. 18);

fig. 20 is a cross-sectional view of a sixth embodiment of a reforming hydrogen production reactor of the present disclosure;

fig. 21 is a cross-sectional view of a seventh embodiment of a reforming hydrogen production reactor of the present disclosure;

fig. 22 is a schematic structural diagram of an eighth embodiment of a reforming hydrogen production reactor of the present disclosure;

fig. 23 is a schematic structural diagram of a ninth embodiment of a reforming hydrogen production reactor of the present disclosure;

fig. 24 is a schematic structural diagram of a tenth embodiment of a reforming hydrogen production reactor of the present disclosure;

fig. 25 is a schematic diagram of an eleventh embodiment of a reforming hydrogen production reactor of the present disclosure;

FIG. 26 is a center tube schematic of an embodiment of a reforming hydrogen production reactor of the present disclosure;

figure 27 is a center tube schematic of another embodiment of a reforming hydrogen production reactor of the present disclosure.

Description of the reference numerals

1-air inlet 2-air outlet 3-upper end enclosure 4-lower end enclosure

5-top seal plate 6-center tube 7-annular gap 8-bottom seal plate

9-gas collecting cavity 10-micro catalytic reaction plate 11-first straight pipe

12-shell 14-second straight pipe 15-catalytic reaction unit outer side wall

16-buffer cavity 17-catalytic reaction unit inner side wall 20-reforming hydrogen production converter

21-reforming hydrogen production reactor 22-combustion chamber 23-burner

24-inlet pipe 25-outlet pipe.

Detailed Description

The following detailed description of specific embodiments of the present disclosure is provided in connection with the accompanying drawings. It should be understood that the detailed description and specific examples, while indicating the present disclosure, are given by way of illustration and explanation only, not limitation.

In the present disclosure, unless otherwise specified, use of directional words such as "upper, lower, top, bottom" generally refers to upper and lower, top and bottom of the device in normal use, and specifically refers to the orientation of the drawing in fig. 1. The "inner and outer" are with respect to the outline of the device itself. Furthermore, the terms "first", "second" and "first" are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implicitly indicating the number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present disclosure, "a plurality" means two or more unless specifically limited otherwise.

The first aspect of the present disclosure provides a reforming hydrogen production reactor, which includes a cylindrical sealed pressure-bearing shell 12, an air inlet 1, an air outlet 2, a first straight pipe 11 extending into the shell from the top of the shell 12, a second straight pipe 14 extending into the shell from the bottom of the shell 12, and a catalytic reaction unit 13 arranged in the shell 12 below the first straight pipe 11 and above the second straight pipe 14; the air inlet is communicated with the first straight pipe 11, and the air outlet 2 is communicated with the second straight pipe 14; the top and the bottom of the catalytic reaction unit 13 are respectively sealed by a top sealing plate 5 and a bottom sealing plate 8, the catalytic reaction unit 13 comprises a central pipe 6 which is axially arranged, and the central pipe 6 penetrates through the top sealing plate 5 and is communicated with the first straight pipe 11 in a fluid mode; an annular gap 7 is formed between the outer side wall 15 of the catalytic reaction unit and the inner wall of the shell 12; the side walls of the central tube 6 and the catalytic reaction unit 13 are respectively formed with openings so that the central tube 6 is in fluid communication with the annular space 7 through the openings; a gas collecting cavity 9 which is communicated with the annular gap 7 through fluid is formed between the bottom sealing plate 8 and the inner wall of the lower part of the shell 12, and the annular gap 7 is communicated with a second straight pipe 14 through the gas collecting cavity 9; a micro-catalytic reaction plate 10 is arranged in the catalytic reaction unit 13, and a reforming hydrogen production catalyst is loaded on the surface of the catalytic reaction plate.

The reforming hydrogen production reactor disclosed by the invention adopts the micro-catalytic reaction plate, and active components required by hydrogen production reaction are loaded on the reaction plate, so that the using amount of catalytic active metal is reduced, the catalyst is not easy to deposit carbon and deactivate, the distance from reaction gas to a catalytic activity center is shortened, the mass transfer resistance and the pressure drop of the reactor are reduced, and the conversion rate of the hydrogen production reaction is improved; the reaction gas flows outwards from the center in the reactor, the flow passage area is gradually increased, the temperature of the reaction plate is gradually increased, and the improvement of the conversion rate of the hydrogen production reaction which is used as volume increase and endothermic reaction is facilitated; the reforming hydrogen production reactor has wide application range, and can be suitable for different types of reforming furnaces as a furnace tube of a hydrogen production reforming furnace.

The reforming hydrogen production reactor referred to in the present disclosure is also generally referred to as hydrogen production reformer tube or reformer tube in industrial production, and the above three designations represent the same device unless otherwise specified. According to the present disclosure, the micro-catalytic reaction plate may have a reforming hydrogen production catalyst supported on an optional plate surface, or may have reforming hydrogen production catalysts supported on both plate surfaces of the micro-catalytic reaction plate, preferably, the micro-catalytic reaction plate has catalysts supported on both plate surfaces, so as to further improve the conversion rate of the hydrogen production reaction performed by the reactor. The reforming hydrogen production catalyst may employ a catalytically active component well known to those skilled in the art, for example, the supported active component may be a metal such as nickel, ruthenium, platinum, palladium, iridium, and rhodium, which has a reforming hydrogen production reaction activity; the loading means that the catalyst containing the active component can be loaded on the micro-catalytic reaction plate by a method of dipping, ion sputtering, coating or filling, and the like, or the active component can be directly loaded on the micro-catalytic reaction plate. Among them, the active metal component coating and supporting process may employ a coating method including two stages of pretreatment of a metal substrate and catalyst deposition, which are well known to those skilled in the art.

According to the present disclosure, the micro catalytic reaction plate 10 may extend axially or radially along the reactor, or the extending direction of the micro catalytic reaction plate 10 is at an angle θ from the horizontal, 0 ° < θ <90 °. The catalytic reaction unit 13 may include one or more micro catalytic reaction plates 10 therein, and the plurality of micro catalytic reaction plates 10 may be arranged in the catalytic reaction unit 13 in a conventional manner in the art, as long as it is ensured that the reaction feed gas radially moves from the center to the periphery in the catalytic reaction unit 13. In order to further enhance the contact between the reactant feedstock gas and the catalyst on the micro-catalytic reaction plate 10, in one embodiment of the present disclosure, as shown in fig. 18-21, the micro-catalytic reaction plate 10 in the catalytic reaction unit 13 may extend axially and spirally around the central tube 6, the top end of the micro-catalytic reaction plate 10 may be hermetically connected to the top sealing plate 5, and the bottom end of the micro-catalytic reaction plate 10 may be hermetically connected to the bottom sealing plate 8.

In another embodiment, as shown in fig. 1-2, in order to further reduce the pressure drop of the reactor and adapt to the increase of the volume of the hydrogen production reaction, the micro-catalytic reaction plate 10 is one or a plurality of coaxially arranged annular plates, the inner edge of the micro-catalytic reaction plate 10 may be fixedly connected with the inner sidewall 17 of the catalytic reaction unit in a sealing manner, the outer edge of the micro-catalytic reaction plate 10 may be fixedly connected with the outer sidewall 15 of the catalytic reaction unit in a sealing manner, the included angle θ between the annular micro-catalytic reaction plate 10 and the horizontal direction is preferably 0 ° to 45 °, and then the annular micro-catalytic reaction plate 10 preferably extends in the radial direction, i.e., the included angle θ is 0 °.

According to the present disclosure, the use of a micro-catalytic reaction plate 10 loaded with a reforming hydrogen production catalyst in a reforming hydrogen production reactor may reduce the total amount of catalytically active metals in the reactor, reduce the size of the reactor, and reduce the pressure drop of the reactor, wherein the micro-catalytic reaction plate 10 may be of a type conventional in the art. In order to further increase the number of catalytically active sites in the reactor, preferably, the micro catalytic reaction plate 10 may be at least one selected from the group consisting of a flat plate, a toothed plate, a corrugated plate and a corrugated plate, as shown in fig. 19, 20, 21, 13, 14 and 15, and more preferably, at least one selected from the group consisting of a toothed plate, a corrugated plate and a corrugated plate. The structures and the sizes of the toothed plate, the corrugated plate and the corrugated plate are not limited, and the requirements of loading active components and hydrogen production process conditions are met. In order to increase the number of micro catalytic reaction plates packed in the catalytic reaction unit, the same type of micro catalytic reaction plates are preferred in the reactor. Furthermore, in order to facilitate production and installation of the reaction plate, raw material gas is uniformly distributed, the size, type, density degree and the like of the tooth-shaped waveform of each micro-catalytic reaction plate are completely consistent, and the size, type and density degree of the tooth-shaped waveform are not specifically limited by the invention as long as the hydrogen production reaction process conditions are met.

According to the present disclosure, the number of catalytic reaction units 13 can increase the contact probability of the reaction gas with the catalyst, improving the conversion rate, under the same reaction conditions and reactor diameter. The number of the catalytic reaction units 13 can be adjusted according to the actual reaction conditions, for example, the number of the catalytic reaction units 13 can be 1 to 500, preferably 1 to 300. In order to improve the distribution uniformity of the reaction raw material, it is preferable that the catalytic reaction unit 13, the central tube 6 and the housing 12 are arranged coaxially, and a plurality of catalytic reaction units may be coaxially disposed. In this case, buffer cavities 16 may be formed between the inner side walls 17 of the catalytic reaction units and the wall of the central tube 6 and between the walls of two adjacent catalytic reaction units 13, so as to further uniformly distribute the reaction raw material gas in the buffer cavities. In one embodiment of the present disclosure, as shown in fig. 9, the catalytic reaction unit may include a plurality of catalytic reaction units 13 coaxially sleeved; in other embodiments, the plurality of catalytic reaction units 13 are arranged coaxially one above the other.

According to the present disclosure, in order to prolong the service life of the micro reaction plate, the central tube 6 and the micro catalytic reaction plate may be made of metal or ceramic, preferably metal that does not react with the gas in the reaction system. For extended service life, the top and

bottom seal plates

5, 8 may be provided with expansion joints, as shown in fig. 4.

The relative dimensions of the catalytic reaction unit 13 and the central tube 6 may vary within wide limits in accordance with the present disclosure, which is not particularly required. The side walls of the catalytic reaction unit 13 and the walls of the central tube 6 may be at least one of johnson mesh, perforated plate, prismatic or cylindrical wall forming surfaces, johnson mesh being well known to those skilled in the art and the present invention will not be described herein. Preferably, the side walls of the catalytic reaction unit 13 and the wall of the central tube 6 may be perforated plates, the perforated form of the perforated plates may be circular holes as shown in fig. 26 or slot type as shown in fig. 27, and the shape, size and number of the perforations (opening ratio) are not limited in the present invention as long as the reforming hydrogen production process conditions are satisfied.

According to the present disclosure, the material adopted by the shell, the upper end enclosure and the lower end enclosure of the reforming hydrogen production reactor can be the same as the material selected by the conventional reforming hydrogen production furnace tube, for example: HP-40Nb, reforming reactor shell materials are well known to those skilled in the art and the present invention is not described in detail herein. The specific dimensions of the reforming hydrogen production reactor may also vary over a wide range. Further, in order to adapt to the scale of a newly-built hydrogen production converter device or the transformation and upgrade of the existing hydrogen production converter device, the inner diameter of the reforming hydrogen production reactor can be 30-1000 mm, and preferably 50-300 mm; the length of the catalytic reaction unit in the reactor can be 1000 mm-30000 mm, preferably 3000 mm-15000 mm.

As shown in fig. 1, the flow regime of the reaction feed gas in the reforming hydrogen production reactor of the present disclosure may include: the reaction raw material gas enters a central tube 6 of a catalytic reaction unit 13 from a reactor gas inlet 1 through a first straight tube 11, enters a buffer cavity 16 through an opening of a central tube wall, is collected, continues to flow outwards under the further buffering and redistribution action of the buffer cavity 16, uniformly and radially enters the catalytic reaction unit 13, and flows radially outwards, the reaction raw material gas reacts at a catalyst active center loaded on the surface of a micro-catalytic reaction plate 10 while flowing outwards, continues to flow outwards, flows outwards through an opening of a tube wall of the catalytic reaction unit 13 to an annular gap 7, is collected, enters a gas collection cavity 9, and leaves a reforming hydrogen production reactor through a second straight tube 14 and a gas outlet 2.

As shown in fig. 16-17, a second aspect of the present disclosure provides a reforming hydrogen production reformer, which includes an air inlet pipe 24, an air outlet pipe 25, a burner 23, and a combustion chamber 22, and the reformer further includes a reforming hydrogen production reactor 21 of the first aspect of the present disclosure, the reforming hydrogen production reactor 21 is located in the combustion chamber 22, an air inlet 1 of the reforming hydrogen production reactor 21 is communicated with the air inlet pipe 24, and an air outlet 2 of the reforming hydrogen production reactor is communicated with the air outlet pipe 25.

The reforming hydrogen production reformer according to the present disclosure may be of a type conventional in the art, and for example, may be at least one of a top-fired furnace, a side-fired furnace, a bottom-fired furnace, and a trapezoidal furnace, preferably a top-fired furnace as shown in fig. 16 and/or a side-fired furnace as shown in fig. 17. The types of the burner and the fuel in the reformer are not particularly limited as long as the energy required by hydrogen production by reforming can be satisfied. In addition, the number, arrangement mode and the like of the reactors arranged between the gas inlet pipe and the gas outlet pipe of the reforming furnace are not particularly limited, and the reforming hydrogen production process can meet the requirements of the reforming hydrogen production process.

The reforming hydrogen production reformer disclosed by the invention has the advantages that the pressure of the furnace tube of the reforming hydrogen production reformer is reduced, the space-time yield of the catalyst in unit volume in the furnace tube is high, the overall size of the reformer is small, and the equipment investment and energy consumption are reduced.

A third aspect of the present disclosure provides a method for performing a reforming hydrogen production reaction using the reforming hydrogen production converter of the second aspect of the present disclosure, the method comprising the steps of: (1) fuel gas and air are sprayed into the combustion chamber through the burner for combustion; (2) the raw material gas and the steam enter a reforming hydrogen production reactor through an air inlet pipe of a reformer, and the reforming hydrogen production reaction is carried out in a catalytic reaction unit 13 to obtain reformed gas rich in hydrogen.

The reforming hydrogen production reaction method disclosed by the invention has the advantages that the internal pressure of the reforming furnace tube is reduced, the conversion rate of the raw material gas is high, and the hydrogen production reaction requirement can be met.

In the reforming hydrogen production reaction method disclosed by the disclosure, the conditions of the reforming hydrogen production reaction can be changed within a large range, and preferably, the reaction temperature in the reforming hydrogen production reactor can be 700-1100 ℃, and preferably 800-950 ℃; the reaction pressure may be 1.8 to 5.5MPaG, preferably 1.8 to 3.5MPaG, H in steam₂The molar ratio of O to carbon atoms in the feed gas can be (2.5-5): 1, preferably (2.5-4): 1. the reforming hydrogen production reaction of the present disclosure has a higher conversion rate under the above preferred reaction conditions.

Further, in order to improve the conversion rate of the raw material gas, the space velocity of the raw material gas can be 1000-100000 h^-1More preferably 3000 to 90000h^-1Most preferably 8000-70000 h^-1。

In order to improve the conversion rate of the raw material gas, the average flow velocity of the raw material gas in the catalytic reaction unit can be 0.3-90 m/s. Further, in the embodiment that the micro-catalytic reaction plate extends along the axial direction and is spirally distributed around the central tube 6, the average flow velocity of the feed gas passing through the spiral structure of the micro-catalytic reaction plate may be 0.003-90 m/s, preferably 0.1-75 m/s; in the embodiment where a plurality of annular micro catalytic reaction plates 10 are axially spaced, the average flow velocity of the raw material gas may be 0.001 to 100m/s, preferably 0.3 to 90 m/s.

In the reforming hydrogen production reaction method according to the present disclosure, the reaction raw material gas may be at least one of natural gas, liquefied petroleum gas, refinery gas, a resolved gas of reforming hydrogen concentration PSA, and naphtha. The natural gas mainly becomes methane, contains a small amount of micromolecular hydrocarbons such as ethane and the like, carbon dioxide, nitrogen and the like, has low sulfur content, mainly comprises hydrogen sulfide, mercaptan, hydroxyl sulfur and the like, and can be easily removed through simple hydrotreatment; refinery gas mainly refers to non-condensable gas, catalytic dry gas, coking dry gas, hydrogenation dry gas, reforming dry gas and the like of a crude oil distillation unit; the main components of the liquefied petroleum gas are propane, propylene, butane and butylene, can be a mixture of one or more of the above hydrocarbons, and contains a small amount of pentane, pentene and trace sulfide impurities, wherein carbonyl sulfide is removed by an alcohol amine absorption tower, and sulfides are removed by an alkali washing method; the desorption gas of the reformed hydrogen-enriched PSA contains about a large amount of hydrogen and some small-molecule hydrocarbons; the preferred order of naphtha is: straight-run light naphtha (reforming topped oil) with a dry point of 70 ℃, refinery narrow-cut reforming raffinate oil, full-cut straight-run gasoline with a dry point of 146 ℃ and single-pass hydrocracked naphtha.

In the reforming hydrogen production reaction method according to the present disclosure, the steam refers to medium-pressure steam, the temperature of the steam may be about 420 ℃, the pressure of the steam may be about 3.5Mpa, and the temperature and the pressure of the steam may fluctuate in the actual gas distribution process.

In the reforming hydrogen production reaction method according to the present disclosure, the reforming hydrogen production reaction catalyst may be of a type conventional in the art, for example, the reforming hydrogen production reaction catalyst may include a reforming hydrogen production active component, and the reforming hydrogen production active component may include at least one of nickel, ruthenium, platinum, palladium, iridium, and rhodium.

The invention will be further illustrated by way of example with reference to the accompanying drawings, without the disclosure being limited thereto in any way.

Example 1

As shown in fig. 1, 2, 3, 4, and 15, the reforming hydrogen production reactor used in this embodiment includes a pressure-bearing housing 12 having a first straight pipe 11 at an upper end and a second straight pipe 14 at a lower end, a cylindrical catalytic reaction unit 13 is disposed in the housing, the catalytic reaction unit 13 includes a central pipe 6 disposed axially, an air inlet 1 is disposed at an upper portion of the first straight pipe 11, and an air outlet 2 is disposed at a lower portion of the second straight pipe 14. The catalytic reaction unit is composed of a horizontal parallel waveform catalytic reaction plate, and the central tube 6, the cylindrical catalytic reaction unit 13 and the shell 12 are coaxially arranged; the micro-catalytic reaction plate 10 of the catalytic reaction unit 13 is fixedly connected with the outer side wall 15 of the catalytic reaction unit and the inner side wall 17 of the catalytic reaction unit; the outer side wall 15 of the catalytic reaction unit and the inner side wall 17 of the catalytic reaction unit are respectively connected and fixed with the top sealing plate 5 and the bottom sealing plate 8; the central tube 6 adopts a circular hole with the opening rate of 16.8 percent, and the two sides of the micro-catalytic reaction plate 10 are loaded with a catalytic active component NiO required by the reforming hydrogen production reaction.

The internal diameter of the reforming hydrogen production reactor is 130mm, the tangent length is 11500mm, the internal diameter of the central tube is 25mm, the height of the radial catalytic reaction unit is 9500mm, the distance between two adjacent micro catalytic reaction plates of the catalytic reaction unit 13 at the position of one half of the diameter of the catalytic reaction unit 13 is 1mm, the annular space distance is 5mm, and the average flow speed between the adjacent micro reaction plates of the catalytic reaction unit 13 is 0.02 m/s.

The material of the reactor shell adopts HP40-Nb (containing elements such as Cr, Ni, Nb, W, Mo and Ti), and the micro-catalytic reaction plate 10 adopts Fe-Cr-Al/Al₂O₃The material is a catalytic load substrate and a waveform substrate, the distance between the wave crest and the wave trough is 2.5mm, the distance between two adjacent wave crests or adjacent wave troughs on the same micro-catalytic reaction plate is 5mm, the load active metal on the two sides of the substrate is NiO, and the content is 17.5 percent.

As shown in fig. 16, the reforming hydrogen production reformer of this embodiment includes the reforming hydrogen production reactor 21, an air inlet pipe 24, an air outlet pipe 25, a burner 23, and a combustion chamber 22, where the reforming hydrogen production reactor 21 is located in the combustion chamber 22, an air inlet 1 of the reforming hydrogen production reactor 21 is communicated with the air inlet pipe 24, and an air outlet 2 of the reforming hydrogen production reactor is communicated with the air outlet pipe 25.

The reforming hydrogen production reactor and the reformer of the embodiment are applied to the natural gas steam reforming hydrogen production reaction, and the main steps comprise:

1) fuel gas and air are sprayed into a combustion chamber 22 through a burner 23 of the reformer, the fuel is combusted in the combustion chamber of the reformer to provide heat required by hydrogen production reaction, and the temperature of the reactor is 910 ℃;

2) by mixing water vapor with CH₄The mixed gas with the molar ratio of 3.1 (the temperature is 500 ℃, the pressure is 3.0MPaG), the flow rate is 30kmol/h, and the space velocity is 42300h^-1After fully mixed, the mixture enters an air inlet pipe of a converter, passes through a first straight pipe 11 of a reactor, then sequentially enters a micro-catalytic reaction plate of a central pipe 6, a buffer cavity 16 and a sleeve 15 to carry out reforming hydrogen production reaction, and the reacted converted gas leaves the reactor through an annular gap 7, a gas collection cavity 9 and a second straight pipe 14, enters an air outlet pipe 25 of the converter and is discharged to the outside of the converter. The detection proves that the outlet methane content (without water vapor) is 0.2%.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 1. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 1 the reforming reactor of this example is compared to a conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.06	≥99	42300

Example 2

As shown in fig. 2, fig. 3, fig. 4 and fig. 5, the reforming hydrogen production reactor and the reformer of the present example have the same reactor size, the distance between two adjacent catalytic reaction plates, the annular space distance, the matrix material of the micro reaction plates and the loading capacity of the active component NiO per unit area as those of example 1. The difference from example 1 is that the micro-catalytic reaction plate in this example is a planar micro-reaction plate. The reactor and the reformer of the embodiment are applied to the hydrogen production reaction by natural gas steam reforming in the same way. The hydrogen production process conditions were the same as in example 1, and it was determined that the outlet methane content (containing no water vapor) was 1.3%.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 2. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 2 the reforming reactor of this example is compared to a conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.05	≥97	42300

Example 3

As shown in fig. 5, fig. 6 and fig. 7, the reforming hydrogen production reactor and the reformer of this example have the same reactor size, the distance between two adjacent catalytic reaction plates, the annular space distance, the matrix material of the micro reaction plates and the loading parameters of the active component NiO per unit area as those of example 2. The difference from embodiment 2 is that in this embodiment, the inner sidewall 17 of the catalytic reaction unit and the outer sidewall 15 of the catalytic reaction unit are made of a material of regular triangular prism HP40-Nb, the side length of each triangular prism is 9.5mm, and the gap distance between adjacent triangular prisms is 1.5 mm.

The reactor and the reformer of the embodiment are applied to the hydrogen production reaction by natural gas steam reforming in the same way. The hydrogen production process conditions were the same as in example 1, and it was determined that the outlet methane content (containing no water vapor) was 1.5%.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 3. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 3 comparison of reforming reactor of this example with conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.04	≥97.5	42300

Example 4

As shown in fig. 9 and 10, the reforming hydrogen production reactor and the reformer, and the hydrogen production process conditions and the like in this example are the same as those in example 2. The difference from the embodiment 2 is that the embodiment adopts a radial catalytic reaction unit composed of two sleeves, the radial sizes of the two sleeves are the same, and other parameters of the sleeves are the same as those of the embodiment 2.

The hydrogen production process conditions were the same as in example 1, and it was determined that the outlet methane content (containing no water vapor) was 1.0%.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 4. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 4 the reforming reactor of this example is compared to a conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.07	≥98	42300

Example 5

As shown in fig. 11 and 12, the reforming hydrogen production reactor and the reformer, the hydrogen production process conditions, and the like of this example are the same as those of example 1. The difference from the embodiment 1 is that the inner side of the micro-catalytic reaction plate of the sleeve 13 of the embodiment is directly connected and fixed with the outer wall of the central tube 6, and the buffer chamber 16 and the inner side wall 17 of the catalytic reaction unit are omitted.

The reforming hydrogen production reactor and the reformer of the embodiment are applied to the hydrogen production reaction by reforming natural gas steam in the same way. The hydrogen production process conditions were the same except that the space velocity was different from that in example 1, and the space velocity in this example was 48600. The detection proves that the outlet methane content (without water vapor) is 1.2%.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 5. From the reactionPressure drop in bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 5 the reforming reactor of this example is compared to a conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.1	≥98	48600

Example 6

As shown in fig. 11 and 12, the reforming hydrogen production reactor and the reformer of the present example are the same as those of example 5. The difference from example 5 is that this example uses a reformed hydrogen-enriched PSA stripping gas as a reaction raw material, and the stripping gas composition is shown in table 6. The fuel is burnt in the combustion chamber of the reformer to provide the heat required by the hydrogen production reaction, and the temperature of the reactor is 905 DEG C. Steam and CH₄The mixed gas with the molar ratio of 2.5 (the temperature is 500 ℃, the pressure is 3.05MPaG), the flow rate is 35kmol/h, and the space velocity is 49300h^-1The fully mixed gas enters the gas inlet pipe of the converter, enters the catalytic reaction unit through the first straight pipe 11 of the reactor to carry out reforming hydrogen production reaction, and the reacted converted gas leaves the reactor through the annular gap 7, the gas collection cavity 9 and the second straight pipe 14, enters the gas outlet pipe of the converter and is discharged to the outside of the converter. The detection proves that the outlet methane content (without water vapor) is 0.75%.

Using the reactor provided in example 5, the reaction raw materials and process conditions were different from those of the example, and the reaction results obtained were compared with those obtained in a conventional reactor under the same reaction raw materials and process conditions, as shown in Table 7. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

TABLE 6 reformate hydrogen enrichment PSA desorption gas composition

Table 7 hydrogen production process reactor of this example is compared to a conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.38	97	4400
Reactor of this example	0.13	≥99	49300

Example 7

As shown in fig. 18 and 19, the reforming hydrogen production reactor used in this embodiment includes a pressure-bearing housing 12 having a first straight pipe 11 at an upper end and a second straight pipe 14 at a lower end, a catalytic reaction unit 13 including a central pipe 6 is disposed in the housing, an air inlet 1 is disposed at an upper portion of the first straight pipe 11, and an air outlet 2 is disposed at a lower portion of the second straight pipe 14. The catalytic reaction unit 13 is formed by spirally arranging a micro-catalytic reaction plate 10 around a central pipe 6, and the central pipe 6 and the shell 12 are coaxially arranged; the upper edge of the micro-catalytic reaction plate 10 is hermetically fixed with a catalytic reaction unit top sealing plate 5, and the lower edge of the micro-catalytic reaction plate 10 is hermetically fixed with a catalytic reaction unit bottom sealing plate 8; the two sides of the micro-catalytic reaction plate 10 are loaded with a catalytic active component NiO required by the reforming hydrogen production reaction.

The inner diameter of the reforming hydrogen production reactor is 110mm, the tangent length is 12500mm, the inner diameter of the central tube is 30mm, the length of the micro-catalytic reaction plate 10 is 10000mm, the central tube adopts a circular opening, and the aperture size is 10000mm

The holes are uniformly opened, the opening rate is 17.5 percent, the distance between two adjacent catalytic reaction plates is 1mm, the annular gap distance between the outermost micro catalytic reaction plate and the inner wall of the shell is 3mm, and the average flow speed between the micro reaction plates is 1.3 m/s.

The material of the reactor shell adopts HP40-Nb (containing elements such as Cr, Ni, Nb, W, Mo and Ti) and a micro-catalytic reaction plate10 adopts Fe-Cr-Al/Al₂O₃The material is a catalytic loading substrate and is a plane substrate, and the loading active metal on the two sides of the substrate is NiO, and the content is 13.5%.

The reforming hydrogen production reactor and the reformer of the embodiment are applied to the natural gas steam reforming hydrogen production reaction, and the main steps comprise: 1) fuel gas and air are sprayed into a combustion chamber 22 through a burner 23 of the reformer, the fuel is combusted in the combustion chamber of the reformer to provide heat required by hydrogen production reaction, and the temperature of the reactor is 950 ℃; 2) by mixing water vapor with CH₄The mixed gas with the molar ratio of 3.2 (the temperature is 500 ℃, the pressure is 3.2MPaG), the flow rate is 44.91kmol/h, and the space velocity is 63230h^-1The fully mixed gas enters the air inlet pipe of the converter, enters the micro catalytic reaction plate through the first straight pipe 11 and the central pipe 6 of the reactor to carry out reforming hydrogen production reaction, and the reacted converted gas leaves the reactor through the gas outlet 15 of the catalytic reaction unit, the annular gap 7, the gas collecting cavity 9 and the second straight pipe 14, enters the air outlet pipe of the converter and is discharged to the outside of the converter. The detection proves that the outlet methane content (without water vapor) is 1.45 percent.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 8. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 8 comparison of a reforming reactor of this example with a conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.05	≥95.5	63230

Example 8

As shown in fig. 18, 20 and 13, the reforming hydrogen production reactor and the reformer of this example have the same reactor size, the distance between two adjacent catalytic reaction plates, the annular space distance between the outermost micro catalytic reaction plate and the inner wall of the shell, the matrix material of the micro reaction plates, and the loading amount of the active component NiO per unit area as those of example 7. The difference from example 7 is that the micro-catalytic reaction plate in this embodiment is a toothed micro-reaction plate, and the direction of the teeth may be along the radial direction of the reactor. For the castellated plate, the distance between the wave crest and the wave trough is 4mm, and the distance between two adjacent wave crests or adjacent wave troughs of the same micro-plate is 6.5 mm.

The reforming hydrogen production reactor and the reformer of the embodiment are applied to the hydrogen production reaction by reforming natural gas steam in the same way. The hydrogen production process conditions were the same as in example 7, and it was determined that the exit methane content (no water vapor) was 1.2%.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 9. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 9 another reforming reactor of this example is compared to a conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.062	≥96	63230

Example 9

As shown in fig. 18, 21 and 15, the reforming hydrogen production reactor and the reformer of this example have the same reactor size, the distance between two adjacent catalytic reaction plates, the annular space distance between the outermost micro catalytic reaction plate and the inner wall of the shell, the matrix material of the micro reaction plates, and the loading amount of the active component NiO per unit area as those of example 8. The difference from example 8 is that the micro-catalytic reaction plate in this example is a corrugated micro-reaction plate, and the corrugated direction is along the radial direction of the reactor. For the corrugated plate, the distance between the wave crest and the wave trough is 4mm, and the distance between two adjacent wave crests or adjacent wave troughs of the same micro-plate is 6.5 mm.

The reactor of the embodiment is applied to the hydrogen production reaction by natural gas steam reforming in the same way. The hydrogen production process conditions were the same as in example 7, and it was determined that the exit methane content (no water vapor) was 1.30%.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 10. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 10 comparison of reforming reactor of this example with conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.06	≥96	63230

Example 10

As shown in fig. 19 and 22, the reforming hydrogen production reactor and the reformer, the hydrogen production process conditions, and the like of this example are the same as those of example 9. The difference from example 9 is that the micro-catalytic reaction plate in this example is corrugated along the axial direction of the reactor and is a corrugated plate.

The reforming hydrogen production reactor and the reformer of the embodiment are applied to the hydrogen production reaction by reforming natural gas steam in the same way. The hydrogen production process conditions were the same as in example 7, and it was determined that the exit methane content (no water vapor) was 0.05%.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 11. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 11 the reforming reactor of this example is compared to a conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.05	≥99	63230

Example 11

As shown in fig. 19, 23 and 14, the reforming hydrogen production reactor and the reformer, the hydrogen production process conditions, the micro-catalytic reaction plate wave direction, the structural parameters and the like of the present example are the same as those of example 10. The difference from example 10 is that the micro reaction plate in this example is a corrugated plate.

The reforming hydrogen production reactor and the reformer of the embodiment are applied to the hydrogen production reaction by reforming natural gas steam in the same way. The hydrogen production process conditions were the same as in example 10, and it was determined that the outlet methane content (containing no water vapor) was 0.05%.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 12. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 12 the reforming reactor of this example is compared to a conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.05	≥99.3	63230

Example 12

As shown in fig. 19, 24 and 13, the reforming hydrogen production reactor and the reformer, the hydrogen production process conditions, the micro-catalytic reaction plate wave direction, the structural parameters and the like of the present embodiment are the same as those of embodiment 10. The difference from example 10 is that the micro-reaction plate in this example is a castellated plate.

The reforming hydrogen production reactor and the reformer of the embodiment are applied to the hydrogen production reaction by reforming natural gas steam in the same way. The hydrogen production process conditions were the same as in example 10, and it was found that the outlet methane content (containing no water vapor) was 0.08%.

Table 13 shows the reforming hydrogen production reactor of this example and the prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit sizeAnd (6) comparing the conditions. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 13 comparison of reforming reactor of this example with conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.055	≥99	63230

Example 13

As shown in fig. 19 and 25, the reforming hydrogen production reactor and the hydrogen production process conditions of this example are the same as those of example 7. The difference from the embodiment 7 is that the embodiment comprises five coaxially arranged micro-catalytic reaction units with the same structure size, and the height of the catalytic reaction unit is 2000 mm. Except for the uppermost catalytic reaction unit and the lowermost catalytic reaction unit, the top sealing plate 5 and the bottom sealing plate 8 of the adjacent catalytic reaction unit are fixed in a sealing way, and the central pipe 6 is fixedly connected and communicated.

As shown in fig. 17, the reforming hydrogen production reformer of this embodiment is a side-firing reformer, and includes the reforming hydrogen production reactor 21, an air inlet pipe 24, an air outlet pipe 25, a burner 23, and a combustion chamber 22, where the reforming hydrogen production reactor 21 is located in the combustion chamber 22, an air inlet 1 of the reforming hydrogen production reactor 21 is communicated with the air inlet pipe 24, and an air outlet 2 of the reforming hydrogen production reactor is communicated with the air outlet pipe 25.

The reforming hydrogen production reactor and the reformer of the embodiment are applied to the hydrogen production reaction by natural gas steam reforming. The hydrogen production process conditions were the same as in example 7. The detection proves that the outlet methane content (without water vapor) is 1.2%.

A comparison of the reforming hydrogen production reactor of this example with a prior art hydrogen production reactor of the same reactor size and the same catalytic reaction unit size is given in table 14. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

Table 14 comparison of the reforming reactor of this example with a conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.33	95	3400
Reactor of this example	0.075	≥97.5	63230

Example 14

As shown in fig. 18 and 19, the reforming hydrogen production reactor and the reformer of the present example have the same parameters as those of example 7. The difference from example 7 is that this example uses a reformed hydrogen-enriched PSA stripping gas as the reaction raw material, and the stripping gas group is shown in table 15, the fuel is combusted in the combustion chamber of the reformer to provide the heat required for the hydrogen production reaction, and the reactor temperature is 930 ℃. Steam and CH₄The mixed gas (temperature 500 ℃, pressure 3MPaG) with the molar ratio of 2.8 has the flow rate of 48.52kmol/h and the space velocity of 68310h^-1The fully mixed gas enters the air inlet pipe of the converter, enters the micro catalytic reaction plate through the first straight pipe 11 and the central pipe 6 of the reactor to carry out reforming hydrogen production reaction, and the reacted converted gas leaves the reactor through the annular gap 7, the gas collection cavity 9 and the second straight pipe 14, enters the air outlet pipe of the converter and is discharged to the outside of the converter. The detection proves that the outlet methane content (without water vapor) is 0.08%.

Using the reactor provided in example 7, reaction raw materials and process conditions were different from those of the example, and the reaction results obtained were compared with those obtained in a conventional reactor under the same reaction raw materials and process conditions, as shown in Table 16. Pressure drop from reactor bed, CH₄As can be seen from the three indexes of conversion rate and space velocity, the reactor of the embodiment shows excellent performance, and particularly has the advantages of reducing the pressure drop of the reactor and improving the space velocity of the reactor.

TABLE 15 reformate hydrogen enrichment PSA desorption gas composition

Table 16 comparison of reforming reactor of this example with conventional hydrogen production reactor

Reactor type	Pressure drop, MPa	CH₄Conversion/(%)	Space velocity, h^-1
				Conventional reactor	0.38	97	4400
Reactor of this example	0.1	≥99	68310

The reforming hydrogen production reactor and the reformer provided by the disclosure have compact structures and low active metal consumption; when the reactor is used for reforming hydrogen production reaction, the pressure drop of a bed layer is small, the production intensity of a catalyst in unit volume is high, the diffusion path of reactants is short, the conversion rate of raw materials is high, and the reactor has no phenomena of gas bias flow and short circuit, and can meet the requirement of the existing production process of reforming hydrogen production by water vapor.

As can be seen from the data of examples 1-14, the bed pressure from the reactorDescending and CH₄Three indexes of conversion rate and space velocity can be seen, the reforming hydrogen production reactor and the reformer of the present disclosure exhibit excellent performance, and especially have outstanding advantages in reducing the pressure drop of the reactor and increasing the space velocity of the reactor.

The preferred embodiments of the present disclosure are described in detail with reference to the accompanying drawings, however, the present disclosure is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present disclosure within the technical idea of the present disclosure, and these simple modifications all belong to the protection scope of the present disclosure.

It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. In order to avoid unnecessary repetition, various possible combinations will not be separately described in this disclosure.

In addition, any combination of various embodiments of the present disclosure may be made, and the same should be considered as the disclosure of the present disclosure, as long as it does not depart from the spirit of the present disclosure.

Claims

1. A reforming hydrogen production reactor is characterized by comprising a cylindrical sealed pressure-bearing shell (12), an air inlet (1), an air outlet (2), a first straight pipe (11) extending into the shell from the top of the shell (12), a second straight pipe (14) extending into the shell from the bottom of the shell (12), and a catalytic reaction unit (13) arranged in the shell (12) below the first straight pipe (11) and above the second straight pipe (14); the air inlet is communicated with the first straight pipe (11), and the air outlet (2) is communicated with the second straight pipe (14);

the top and the bottom of the catalytic reaction unit (13) are respectively sealed by a top sealing plate (5) and a bottom sealing plate (8), the catalytic reaction unit (13) comprises a central tube (6) which is axially arranged, and the central tube (6) penetrates through the top sealing plate (5) and is in fluid communication with the first straight tube (11); an annular gap (7) is formed between the outer side wall (15) of the catalytic reaction unit and the inner wall of the shell (12); the side walls of the central tube (6) and the catalytic reaction unit (13) are respectively formed with an opening so that the central tube (6) is in fluid communication with the annular space (7) through the openings; a gas collection cavity (9) communicated with the annular gap (7) in a fluid manner is formed between the bottom sealing plate (8) and the inner wall of the lower part of the shell (12), and the annular gap (7) is communicated with the second straight pipe (14) through the gas collection cavity (9); a micro-catalytic reaction plate (10) is arranged in the catalytic reaction unit (13), and a reforming hydrogen production catalyst is loaded on the surface of the micro-catalytic reaction plate (10);

the micro-catalytic reaction plate (10) extends along the axial direction and is spirally distributed around the central pipe (6), the top end of the micro-catalytic reaction plate (10) is hermetically connected with the top sealing plate (5), and the bottom end of the micro-catalytic reaction plate (10) is hermetically connected with the bottom sealing plate (8);

the micro-catalytic reaction plate (10) is an annular plate or a plurality of annular plates which are coaxially arranged; the inner edge of the micro-catalytic reaction plate (10) is fixedly connected with the inner side wall (17) of the catalytic reaction unit in a sealing manner, and the outer edge of the micro-catalytic reaction plate (10) is fixedly connected with the outer side wall (15) of the catalytic reaction unit in a sealing manner.

2. A reforming hydrogen production reactor according to claim 1, characterized in that the micro-catalytic reaction plate (10) is at least one selected from the group consisting of a flat plate, a toothed plate and a corrugated plate.

3. A reforming hydrogen production reactor according to claim 1, characterized in that the micro-catalytic reaction plate (10) is a corrugated plate.

4. A reforming hydrogen production reformer comprises an air inlet pipe (24), an air outlet pipe (25), a burner (23) and a combustion chamber (22), and is characterized in that the reformer further comprises the reforming hydrogen production reactor (21) as claimed in any one of claims 1 to 3, the reforming hydrogen production reactor (21) is located in the combustion chamber (22), the air inlet (1) of the reforming hydrogen production reactor (21) is communicated with the air inlet pipe (24), and the air outlet (2) of the reforming hydrogen production reactor is communicated with the air outlet pipe (25).

5. The method for reforming hydrogen production reaction by using the reforming hydrogen production reformer of claim 4, characterized by comprising the steps of:

(1) fuel gas and air are sprayed into the combustion chamber (22) through the burner (23) to be combusted;

(2) and enabling feed gas and steam to enter the reforming hydrogen production reactor (21) through an air inlet pipe (24) of the reforming furnace, and carrying out reforming hydrogen production reaction in the catalytic reaction unit (13) to obtain reformed gas rich in hydrogen.

6. The method of claim 5, wherein the reforming hydrogen production reaction conditions comprise: the reaction temperature is 700-1100 ℃, the reaction pressure is 1.8-5.5 MPaG, and H in the steam₂The molar ratio of O to carbon atoms in the raw material gas is (2.5-5): 1, the airspeed is 1000-100000 h^-1。

7. The method according to claim 5, wherein the average flow velocity of the feed gas in the catalytic reaction unit (13) is 0.001 to 100 m/s.

8. The method of claim 5, wherein the feed gas is at least one of natural gas, liquefied petroleum gas, refinery gas, a resolved gas of reforming hydrogen-concentrated PSA, and naphtha.

9. The method of claim 5, wherein the reforming hydrogen production reaction catalyst comprises a reforming hydrogen production active component comprising at least one of nickel, ruthenium, platinum, palladium, iridium, and rhodium.