CN111617728A - Heat exchange type reforming reactor and reforming hydrogen production system - Google Patents
Heat exchange type reforming reactor and reforming hydrogen production system Download PDFInfo
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- CN111617728A CN111617728A CN202010604726.1A CN202010604726A CN111617728A CN 111617728 A CN111617728 A CN 111617728A CN 202010604726 A CN202010604726 A CN 202010604726A CN 111617728 A CN111617728 A CN 111617728A
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- 238000002407 reforming Methods 0.000 title claims abstract description 57
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 239000001257 hydrogen Substances 0.000 title claims abstract description 19
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 19
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 54
- 239000003054 catalyst Substances 0.000 claims abstract description 49
- 238000000576 coating method Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000006057 reforming reaction Methods 0.000 claims description 35
- -1 iron-chromium-aluminum Chemical compound 0.000 claims description 32
- 239000007789 gas Substances 0.000 claims description 31
- 239000011248 coating agent Substances 0.000 claims description 11
- 229910003158 γ-Al2O3 Inorganic materials 0.000 claims description 8
- 229910007470 ZnO—Al2O3 Inorganic materials 0.000 claims description 5
- 238000005192 partition Methods 0.000 claims description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 239000000969 carrier Substances 0.000 claims description 2
- 229910052593 corundum Inorganic materials 0.000 claims description 2
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 2
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000013461 design Methods 0.000 abstract description 4
- 238000012423 maintenance Methods 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000002035 prolonged effect Effects 0.000 abstract description 2
- 230000008929 regeneration Effects 0.000 abstract description 2
- 238000011069 regeneration method Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 21
- 238000003466 welding Methods 0.000 description 6
- 238000006555 catalytic reaction Methods 0.000 description 5
- 238000010586 diagram Methods 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000010248 power generation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000001651 catalytic steam reforming of methanol Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 229910002060 Fe-Cr-Al alloy Inorganic materials 0.000 description 1
- 230000003321 amplification Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- GBMDVOWEEQVZKZ-UHFFFAOYSA-N methanol;hydrate Chemical compound O.OC GBMDVOWEEQVZKZ-UHFFFAOYSA-N 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003199 nucleic acid amplification method Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
- 239000002918 waste heat Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
- B01J19/248—Reactors comprising multiple separated flow channels
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0006—Controlling or regulating processes
- B01J19/0013—Controlling the temperature of the process
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/24—Stationary reactors without moving elements inside
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00049—Controlling or regulating processes
- B01J2219/00051—Controlling the temperature
- B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
- B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
- C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
- C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
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- General Health & Medical Sciences (AREA)
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- Combustion & Propulsion (AREA)
- Inorganic Chemistry (AREA)
- Hydrogen, Water And Hydrids (AREA)
- Fuel Cell (AREA)
Abstract
The invention provides a heat exchange type reforming reactor and a reforming hydrogen production system. The reforming reactor mainly comprises a reactor body, a first end cover and a second end cover. The reactor body has an inner cavity and is in communication with the heat-supplying medium inlet and the heat-supplying medium outlet so that the heat-supplying medium can flow through the inner cavity. The reaction part is arranged in the inner cavity and can exchange heat with a heat supply medium. The reaction part is filled with a catalyst carrier, the catalyst carrier is made of metal wires, and the surfaces of the metal wires are attached with catalyst coatings. The invention has the beneficial effects that: the whole reforming hydrogen production system adopts a detachable structural design, the metal wire can be replaced during maintenance, and the metal wire with a catalyst failure can be detached for regeneration, so that the service life of equipment is prolonged. The whole system has the advantages of simple structure, convenient assembly and disassembly, low cost, long service life, safety and reliability.
Description
Technical Field
The invention relates to a reforming hydrogen production system, in particular to a heat exchange type reforming reactor using a metal wire cluster as a catalyst carrier, and belongs to the technical field of methanol steam reforming hydrogen production.
Background
The methanol reforming hydrogen production uses a mixture of methanol and water as a raw material, is heated and evaporated into a gaseous state, and then is subjected to catalytic conversion in a reformer to obtain reformed gas. The reforming reaction is an endothermic reaction, is sensitive to temperature, and can be continuously, efficiently and stably carried out only by continuously keeping the raw materials and the catalyst in a proper temperature range. The temperature of the reformer is kept stable, the phenomenon that a local high-temperature area is generated to cause the inactivation of a reforming catalyst is prevented, heat is continuously and stably supplied to the reformer, and the method is a hotspot for researching a methanol reforming hydrogen production fuel cell.
In the existing methanol steam reforming hydrogen production system, the forms of a tubular reactor, a plate reactor, a microchannel reactor and the like all have or have the defects of low reaction efficiency, large pressure drop, short service life, inconvenience in replacement and the like. There is a need for a new reforming reactor that overcomes the above-mentioned disadvantages.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: the existing reforming reactor has the disadvantages of low reaction efficiency, large pressure drop, short service life and inconvenient replacement.
In order to solve the above technical problems, the present invention provides a heat exchange type reforming reactor, comprising:
the reactor comprises a reactor body, a first heat exchange tube and a second heat exchange tube, wherein the reactor body is provided with a first inner cavity and a heat supply medium inlet and a heat supply medium outlet so that a heat supply medium can flow through the first inner cavity;
a first end cap connected to the first end of the reforming reactor body, the first end cap having a reformed gas inlet;
a second end cap connected to the second end of the reforming reactor body, the second end cap having a reformed gas outlet;
the reaction part is arranged in the first inner cavity and can exchange heat with a heat supply medium; the first end of the reaction part is connected with the first clapboard of the first inner cavity and is communicated with the reformed gas inlet, and the second end of the reaction part is connected with the second clapboard of the first inner cavity and is communicated with the reformed gas outlet;
a catalyst carrier filled in the reaction section; the catalyst carrier is made of metal wires, and the surfaces of the metal wires are attached with catalyst coatings.
In some embodiments, a baffle structure is disposed in the first chamber to extend the flow path of the heating medium through the first chamber.
In some embodiments, the baffle structure includes a plurality of baffles alternately staggered in sequence.
In some embodiments, the distance between two adjacent baffles is 1/5-1/2 of the diameter of the first inner cavity.
In some embodiments, the first end cap is fixedly mounted to the first end of the reactor body and the second end cap is removably mounted to the second end of the reactor body.
In some embodiments, a second interior cavity is provided between the first end cap and the first end of the reactor body, and a flow equalization plate is mounted in the second interior cavity.
In some embodiments, one heat-supplying medium outlet is disposed above the reactor body and near the second end of the reactor body, and two heat-supplying medium inlets are disposed at axially different positions below the reactor body, respectively.
In some embodiments, the outer wall of the reaction section is provided with heat exchange fins.
In some embodiments, the reaction sections comprise straight round tubes, and a plurality of catalyst carriers are densely packed in each reaction section in the axial direction.
In some embodiments, both the first end and the second end of the reaction section are provided with wire mesh baffles.
In some embodiments, the catalyst support is a cylindrical cluster made of iron-chromium-aluminum wires, and the porosity of the cylindrical cluster is 40% to 85%.
In some embodiments, each cylindrical cluster has a diameter of 15 to 30mm and a length of 15 to 30 mm.
In some embodiments, the amount of the cylindrical clusters filled in the reaction portion is 20 to 50%.
In some embodiments, the iron-chromium-aluminum wire has a diameter of 0.01 to 3 mm.
In some embodiments, the catalyst coating is Pt-In/γ -Al2O3Or Pd-ZnO/gamma-Al2O3The thickness of the catalyst coating on the surface of the iron-chromium-aluminum wire is 0.005-2 mm.
In a second aspect of the invention, a heat exchange type reforming reaction hydrogen production system is provided, which comprises the heat exchange type reforming reactor.
The invention has the beneficial effects that: the whole reforming hydrogen production system adopts a detachable structural design, the iron-chromium-aluminum wires can be replaced during maintenance, and the failed iron-chromium-aluminum wires can be detached for recycling, so that the service life of the equipment is prolonged. The whole system has the advantages of simple structure, convenient assembly and disassembly, low cost, long service life, safety and reliability.
Drawings
FIG. 1 is a working schematic diagram of the low-temperature electric pile working condition of the reforming reaction hydrogen production system.
FIG. 2 is a working schematic diagram of the high temperature stack operating mode of the reforming reaction hydrogen production system of the present invention.
FIG. 3 is a schematic view showing the overall appearance of a heat exchange type reforming reactor according to a preferred embodiment of the present invention.
Fig. 4 is a schematic diagram of the heat exchange reforming reactor (with the first end cap removed) in a preferred embodiment of the invention.
Fig. 5 is a schematic diagram of the heat exchange reforming reactor (with the second end cap removed) in a preferred embodiment of the invention.
FIG. 6 is a schematic view showing the internal structure of a heat exchange type reforming reactor in a preferred embodiment of the present invention.
FIG. 7 is a schematic cross-sectional view of a heat exchange type reforming reactor according to a preferred embodiment of the present invention.
The reference numerals in the above figures are as follows:
100 reformer body
110 first shell
111 heat supply medium inlet
112 heat supply medium inlet
113 outlet for heat-supplying medium
114 housing flange
120 second shell
130 first partition plate
140 second partition
150 upper baffle plate
160 lower baffle plate
170 reforming reaction tube
171 front baffle
172 tailgate
173 heat exchange fin
180 flow equalizing plate
210 first end cap
211 reformed gas inlet
220 second end cap
221 reformed gas outlet
222 end cap flange
Detailed Description
Unless otherwise defined, technical or scientific terms used in the claims and the specification of this patent shall have the ordinary meaning as understood by those of ordinary skill in the art to which this patent belongs.
As used in this specification and the appended claims, the terms "first," "second," and the like do not denote any order, quantity, or importance, but rather are used to distinguish one element from another. The terms "a" or "an," and the like, do not denote a limitation of quantity, but rather denote the presence of at least one. In the description of this patent, unless otherwise indicated, "a plurality" means two or more. The word "comprising" or "having", and the like, means that the element or item appearing before "comprises" or "having" covers the element or item listed after "comprising" or "having" and its equivalent, but does not exclude other elements or items.
In the description of this patent, it is to be understood that the terms "upper," "lower," "left," "right," "horizontal," "lateral," "longitudinal," "top," "bottom," "inner," "outer," "clockwise," "axial," "radial," "circumferential," and the like are used in the orientations and positional relationships indicated in the drawings to facilitate the description of the patent and to simplify the description, but are not intended to indicate or imply that the referenced device or element must have a particular orientation, be constructed and operated in a particular orientation, and are not to be considered limiting of the patent.
The invention provides a heat exchange type reforming hydrogen production system taking a metal wire cluster as a catalyst carrier. In the reforming reactor, the Fe-Cr-Al wire cluster catalyst carrier is made into a cylindrical structure and is tightly installed. The front end of the reaction tube is limited by adopting a welding spot or a clamp spring structure; in view of exchangeability, a flange connection or a clip structure is employed at the rear end. The dividing wall type heat exchange design is adopted, the fin structure is arranged outside the reaction tube to enhance the heat transfer performance, the reforming reaction inside the reaction tube absorbs heat, and the high-temperature tail gas provides heat outside the reaction tube. Wherein the reforming reaction flow path is provided with a flow equalizing plate, a reaction pipeline and a catalyst. A high temperature tail gas flow path for supplying heat is provided with a baffling structure.
The invention adopts a cylindrical cluster body made of iron-chromium-aluminum wires coated with a catalyst, the cylindrical cluster body is plugged into a reaction tube, a plurality of reaction tubes are connected in parallel for amplification, and the number of the reaction tubes can be adjusted according to the actual required power. Introducing high-temperature tail gas of catalytic combustion reaction between the reaction tubes, offsetting heat absorption of reforming hydrogen production reaction through heat exchange, and keeping the operation at 340-380 ℃. The high-temperature tail gas flows along the baffle plate in the reforming reactor, so that the heat transfer effect is improved. The front end and the rear end of the reaction tube are provided with limiting structures, and the number of the iron-chromium-aluminum wire clusters in the reaction tube can be adjusted according to actual power and service life.
Preferred embodiments of the present invention will be described in detail below with reference to the accompanying drawings.
Fig. 1 and 2 are schematic diagrams illustrating the operation of a reforming hydrogen production system. The surface of the iron-chromium-aluminum wire cluster catalyst carrier is coated with Pt-In/gamma-Al2O3Or Pd-ZnO/gamma-Al2O3The mixed liquid of the catalyst, the methanol and the water vapor is gasified by the evaporator and then enters the reactor for reaction, the generated gas is discharged from the outlet of the reactor, and enters the low-temperature electric pile for reaction power generation after CO is removed by PROX or directly enters the high-temperature electric pile for power generation. The optimal molar ratio of methanol to water in the mixed solution of methanol and water vapor is 4: 6, the optimal temperature for the reforming reaction is 350 ℃.
Fig. 3 shows a heat exchange type reforming reactor provided in this embodiment, which mainly comprises a reactor body 100, a first end cap 210, and a second end cap 220. The first end cap 200 is coupled to an axial first end of the reforming reactor body 100, and the first end cap 210 is provided with a reformed gas inlet 211. The second end cap 220 is coupled to the second axial end of the reforming reactor body 100, and the second end cap 220 is provided with a reformed gas outlet 221. The mixture of methanol and steam is vaporized by the evaporator, and then enters the reactor body 100 through the reformed gas inlet 211 to undergo a reforming reaction, and the gas generated by the reaction is discharged from the reformed gas outlet 221. The reforming reaction requires the absorption of heat from heat exchange.
The internal structure of the reactor body 100 is shown in fig. 5, and these internal structures are installed in the reactor shell formed by the combination of the first shell 110, the second shell 120, the first end cap 210 and the second end cap 220. The first and second partitions 130 and 140 in the reactor body 100 form an inner chamber with the first shell 110. The reforming reaction tubes 170 are installed in the inner chamber, the gas inlets of the reforming reaction tubes 170 are located at the first separation plate 130, and the outlets of the reforming reaction tubes 170 are located at the second separation plate 140. The gas inlet of the reforming reaction tube 170 communicates with the reformed gas inlet 211; preferably, a flow equalization plate 180 is provided between them. The second housing 120 is connected to the first housing 110 as an extension thereof by welding, and the flow equalizing plate 180 is disposed inside the second housing 120, as shown in fig. 3. The first end cap 210 is also connected to the second housing 120 by welding, ensuring good air tightness.
As shown in fig. 3, the first case 110 is provided with a heat supply medium inlet 111, a heat supply medium inlet 112, and a heat supply medium outlet 113. The heat supply medium inlet 111 is arranged close to the first end of the first shell 110, and the heat supply medium inlet 112 is arranged at 1/3-2/3 along the axial direction and serves as a heat compensation inlet. The heat supply medium is usually hot air, and the heat is released by the combustion of methanol water, and can also be generated by waste heat generated during the power generation of the electric pile, and the like. The hot air flowing into the cavity from the heat supply medium inlet 111 and the heat supply medium inlet 112 is adjusted according to space and time according to the requirements of the reforming reaction, the temperature of the reforming reaction is kept constant, and the suitable working temperature of the reforming reactor is 340-380 ℃. The heat supply medium inlet 111 may be opened first, and the heat supply medium inlet 111 may be opened later; or alternatively. The two can be opened simultaneously, but the flow of the heat supply medium inlet 111 is larger, and the flow of the heat supply medium inlet 112 is smaller, so as to be used as a supplementary source of heat. The heating medium outlet 113 is disposed above the first housing 110 at a position near the second end.
The reforming reaction tube 170 is provided with a heat exchange structure on an outer surface thereof, and the heat exchange fins 173 having a spiral shape shown in fig. 6 are only one type, and may be other types, such as straight fins or parallel circular ring-shaped heat exchange fins, for enhancing heat exchange. Be provided with baffling structure in the cavity in order to prolong the flow of heating medium through first inner chamber, do benefit to more abundant heat transfer. One preferred form of baffle arrangement is a plurality of baffles in an alternating sequence and offset arrangement as shown in figure 6. Preferably, the distance between two adjacent baffle plates is 1/5-1/2 of the inner diameter of the inner cavity. In fig. 6, both the upper baffle 150 and the lower baffle 160 are single-arcuate baffles, and may take other forms, such as other arcuate (double arcuate, multiple arcuate) or disc-annular baffles. The hot gas flows in the space between the baffles in a zigzag manner, so that the medium is forced to convect and fully contacts with each heat exchange surface of the heat exchange fin 173.
A second end cap 220 is attached to the second end of the reactor body 100. The second end cap 220 has a reformed gas outlet 221, and the outlet of the reforming reaction tube 170 communicates with the reformed gas outlet 221. To facilitate maintenance and replacement of the internal structure, the second end cap 220 is flanged to the reactor body 100. The bottom of the second end cap 220 extends outwardly to form an end cap flange 222 and the second end of the reactor body 100 also extends outwardly to form the shell flange 114. The end cover flange 222 and the housing flange 114 are provided with corresponding screw holes, respectively, and are fixed by bolts, as shown in fig. 4. In the present embodiment, the first end cap 210 and the second end cap 220 are spherical, but may be made in other shapes, such as a cone shape.
The reforming reaction tube 170 has a cylindrical shape and houses a catalyst carrier (not shown). The catalyst carrier adopts a cylindrical cluster body made of iron-chromium-aluminum wires, and the diameter of the iron-chromium-aluminum wires is 0.01-3 mm, preferably 0.02-0.3 mm.
The surface of the iron-chromium-aluminum wire is coated with a catalyst In advance, and the catalyst coating comprises but is not limited to Pt-In/gamma-Al2O3Or Pd-ZnO/gamma-Al2O3The thickness of the catalyst coating is 0.005-2 mm, and the thickness of the preferable catalyst coating is 0.02-0.8 mm. The iron chromium aluminum wire is adopted because the iron chromium aluminum wire is high temperature resistant and low in cost, and other metal wires can be adopted to replace the iron chromium aluminum wire. In order to further enhance the catalytic efficiency, the same catalyst is also coated on the inner wall of the reforming reaction tube 170, and the thickness of the inner wall catalyst coating is 0.005-2 mm. Preferably, the thickness of the inner wall catalyst coating is 0.01-1 mm.
The surface and the interior of the cylindrical cluster body are porous, the porosity is 40% -85%, preferably, the porosity is 60-75%, the reformed gas raw material can be conveniently and fully contacted with the catalyst when passing through, and the catalytic conversion efficiency is improved.
Preferably, a plurality of cylindrical clusters are densely packed in each reforming reaction tube 170 in the axial direction. The length of the single reforming reaction tube 170 is 15-30 cm. The diameter of each cylindrical cluster body is 15-30 mm, the length is 15-30 mm, and preferably, the diameter of each cylindrical cluster body is 20-25 mm, and the length is 20-25 mm. More preferably, each cylindrical cluster has a diameter of 20mm and a length of 20 mm. A stopper (not shown) is provided in the reforming reaction tube 170. The limiting part can be a welding spot protrusion or a clamp spring structure and is used for hooking the cluster body to limit the sliding of the cluster body in the reforming reaction tube 170. The inlet end of the reforming reaction tube 170 is provided with a front baffle 171, the outlet end is provided with a rear baffle 172 for preventing the cluster from sliding out of the reforming reaction tube 170, and the front baffle 171 and the rear baffle 172 are both provided with densely distributed small holes for facilitating smooth gas passage.
More preferably, 9 fe-cr-al wire clusters are built in each reforming reaction tube 170. At the inlet of the reforming reaction tube 170, the degree of catalytic reaction is high, where the catalyst on the surface of the fe-cr-al wire cluster participates sufficiently in the catalytic reaction. The more to the rear end, the lower the extent of the catalytic reaction. Therefore, the catalyst used in different positions is different in degree of use, and the service life thereof is also different. According to the experimental verification, the first 6 of 9 iron chromium aluminum wire clusters mainly participate in the reaction, the reforming reaction is almost completed when the gas reaches the 7 th or later, and the 7 th to 9 th iron chromium aluminum wire clusters are used as the standby ones. That is, the surplus of the number of the fe-cr-al wire clusters filled in the reforming reaction tube 170 is 50%. The suitable range of the amount of the iron-chromium-aluminum wire cluster is 20-50%. If the surplus is too small, the improvement on the operation life of the reforming reactor is limited; if the margin is too large, it is uneconomical.
With the gradual use, the catalyst of the 1 st iron chromium aluminum wire cluster will be completely failed, and the 2 nd to 7 th (total 6) iron chromium aluminum wire clusters participate in the catalytic reaction, and the 8 th and 9 th are still idle. When the 2 nd iron-chromium-aluminum wire cluster also fails, the 3 rd to 8 th (6 in total) iron-chromium-aluminum wire clusters participate in catalytic reaction, the 9 th iron-chromium-aluminum wire cluster is idle, and the rest is repeated, so that the operation life of the reforming reactor is guaranteed to be 2000-5000 h.
Example 1
Is the design of a 1000W reforming reactor. The inside adopts 7 reforming reaction pipes to evenly arrange, and the reforming reaction pipe both ends opening, reforming reaction pipe diameter are 20mm, and length is 180 mm. The diameter of the entire reactor was 150 mm. The front end cover, the cavity section and the reaction section are connected into a whole by adopting a welding structure. The reforming reaction tube and the baffle plate adopt a welding structure. The reaction section is connected with the rear end cover through a flange, and the threaded holes are 6M 6. Both the reformed gas inlet and outlet had an inner diameter of 50 mm. The inner diameter of the heat supply medium inlet is 30mm, and the inner diameter of the heat supply medium outlet is 30 mm.
The front inlet of the reactor is provided with a flow equalizing plate for evenly distributing fluid. The reaction section adopts single bow-shaped baffle plates which are arranged in a staggered way in opposite directions, and the number of the baffle plates is 5.
The front end and the rear end of the reaction tube are limited by the screen snap springs, so that the iron-chromium-aluminum wire column is ensured to be inactive and detachable while the smoothness of a flow channel is ensured. The inner side of the reaction tube is coated with a catalyst, and the outer side of the reaction tube adopts a fin with a screw pitch of 10 and the height of 3 mm.
6 iron-chromium-aluminum wire clusters are connected in series, 3 residues are added, 9 single reaction tubes are arranged, and the total number of the whole reactor is 63. The diameter of the cluster is 20mm, the height is 20mm, and the porosity is 70%. The wire diameter of the iron-chromium-aluminum wire is 1mm, and the thickness of the coated catalyst is 0.04 mm.
The reaction tube adopts Pt-In/gamma-Al2O3Or Pd-ZnO/gamma-Al2O3The iron-chromium-aluminum wire clusters of the catalyst are arranged in a specific arrangement mode.
Compared with the prior art, the reforming hydrogen production system provided by the embodiment has the following characteristics:
(1) the iron-chromium-aluminum wire cluster not only has reliability of the coated catalyst, but also has considerable advantages in economy;
(2) the total surface area of the iron-chromium-aluminum wire cluster is large, the coverage rate of a catalyst is high, and the catalytic effect and efficiency of hydrogen production reaction are high;
(3) the binding force of the catalyst coating and the iron-chromium-aluminum wire is high, and the catalyst coating is not easy to crack and fall off;
(4) the number of the reaction tubes can be adjusted as required;
(5) the number of the iron-chromium-aluminum wire clusters can be adjusted in the reaction tube as required;
(6) the reaction temperature can be adjusted by the flow, flow rate, temperature and the like of a heat supply medium;
(7) the reforming reactor and the reaction tube can be amplified in parallel according to the power requirement;
(8) the maintenance and the replacement are convenient, and the catalyst on the iron-chromium-aluminum wire cluster body can be detached for regeneration after the catalyst fails.
The foregoing detailed description of the preferred embodiments of the invention has been presented. It should be understood that numerous modifications and variations could be devised by those skilled in the art in light of the present teachings without departing from the inventive concepts. Therefore, the technical solutions available to those skilled in the art through logic analysis, reasoning and limited experiments based on the prior art according to the concept of the present invention should be within the scope of protection defined by the claims.
Claims (16)
1. A heat exchange reforming reactor, comprising:
a reactor body having a first interior cavity with a heat supply medium inlet and a heat supply medium outlet to enable a heat supply medium to flow through the first interior cavity;
a first end cap coupled to a first end of the reforming reactor body, the first end cap having a reformed gas inlet;
a second end cap coupled to a second end of the reforming reactor body, the second end cap having a reformed gas outlet;
the reaction part is arranged in the first inner cavity and can exchange heat with the heat supply medium; the first end of the reaction part is connected to the first partition plate of the first inner cavity and communicated with the reformed gas inlet, and the second end of the reaction part is connected to the second partition plate of the first inner cavity and communicated with the reformed gas outlet;
a catalyst carrier filled in the reaction part; the catalyst carrier is made of metal wires, and the surfaces of the metal wires are attached with catalyst coatings.
2. A heat exchange reforming reactor in accordance with claim 1, wherein a baffle structure is provided in said first chamber for extending the flow path of said heat-supplying medium through said first chamber.
3. A heat exchange reforming reactor in accordance with claim 2, wherein said baffle structure comprises a plurality of baffles arranged alternately in staggered relationship in sequence.
4. A heat exchange reforming reactor in accordance with claim 3, wherein the distance between adjacent baffles is 1/5-1/2 of the diameter of the first interior cavity.
5. A heat exchange reforming reactor in accordance with claim 1, wherein said first end cap is fixedly secured to a first end of said reactor body and said second end cap is removably secured to a second end of said reactor body.
6. The heat exchange reforming reactor according to claim 5, wherein a second chamber is defined between the first end cap and the first end of the reactor body, and wherein a flow equalization plate is disposed in the second chamber.
7. A heat exchange reforming reactor in accordance with claim 1, wherein one of said heat-supplying medium outlets is disposed above said reactor body near said second end of said reactor body, and two of said heat-supplying medium inlets are disposed at axially different positions below said reactor body.
8. A heat exchange reforming reactor according to claim 1, wherein the outer wall of the reaction part is provided with heat exchange fins.
9. A heat exchange reforming reactor in accordance with claim 1, wherein said reaction section comprises a straight circular tube, and a plurality of said catalyst carriers are packed tightly in each of said reaction sections in the axial direction.
10. A heat exchange reforming reactor according to claim 9, wherein the first and second ends of the reaction section are provided with wire mesh baffles.
11. The heat exchange reforming reactor according to claim 9, wherein the catalyst support is a cylindrical cluster made of fe-cr-al wires, and the porosity of the cylindrical cluster is 40% to 85%.
12. The heat exchange reforming reactor according to claim 11, wherein each of the cylindrical clusters has a diameter of 15 to 30mm and a length of 15 to 30 mm.
13. The heat exchange reforming reactor according to claim 11, wherein the margin of the number of the cylindrical clusters filled in the reaction part is 20 to 50%.
14. The heat exchange reforming reactor according to claim 11, wherein the fe-cr-al wires have a diameter of 0.01 to 3 mm.
15. The heat exchange reforming reactor as defined In claim 11, wherein the catalyst coating is Pt-In/γ -Al2O3Or Pd-ZnO/gamma-Al2O3And the thickness of the catalyst coating on the surface of the iron-chromium-aluminum wire is 0.005-2 mm.
16. A heat exchange reforming reaction hydrogen production system, characterized by comprising a heat exchange reforming reactor according to any one of claims 1 to 15.
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