CN100488867C - Steam conversion device - Google Patents
Steam conversion device Download PDFInfo
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- CN100488867C CN100488867C CNB2004800068687A CN200480006868A CN100488867C CN 100488867 C CN100488867 C CN 100488867C CN B2004800068687 A CNB2004800068687 A CN B2004800068687A CN 200480006868 A CN200480006868 A CN 200480006868A CN 100488867 C CN100488867 C CN 100488867C
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- heat passage
- pyroreaction
- inner core
- adjacent segments
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- 238000006243 chemical reaction Methods 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 claims abstract description 123
- 239000007789 gas Substances 0.000 claims abstract description 70
- 238000000629 steam reforming Methods 0.000 claims abstract description 39
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 33
- 239000001301 oxygen Substances 0.000 claims abstract description 33
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 33
- 230000008093 supporting effect Effects 0.000 claims description 58
- 238000002955 isolation Methods 0.000 claims description 35
- 239000008187 granular material Substances 0.000 claims description 13
- 238000002156 mixing Methods 0.000 claims description 5
- 230000005764 inhibitory process Effects 0.000 claims description 4
- 230000008676 import Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 3
- 238000009792 diffusion process Methods 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 abstract 3
- 239000002994 raw material Substances 0.000 description 23
- 239000000203 mixture Substances 0.000 description 19
- 238000010438 heat treatment Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 230000003321 amplification Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 229910052751 metal Inorganic materials 0.000 description 6
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 6
- 238000003199 nucleic acid amplification method Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- 238000006701 autoxidation reaction Methods 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 230000004048 modification Effects 0.000 description 5
- 239000000446 fuel Substances 0.000 description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 2
- 229910004298 SiO 2 Inorganic materials 0.000 description 2
- 238000005469 granulation Methods 0.000 description 2
- 230000003179 granulation Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910005845 NiO—SiO2—Al2O3 Inorganic materials 0.000 description 1
- UQMRAFJOBWOFNS-UHFFFAOYSA-N butyl 2-(2,4-dichlorophenoxy)acetate Chemical compound CCCCOC(=O)COC1=CC=C(Cl)C=C1Cl UQMRAFJOBWOFNS-UHFFFAOYSA-N 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 229960004643 cupric oxide Drugs 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 239000012784 inorganic fiber Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 230000000979 retarding effect Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- LENZDBCJOHFCAS-UHFFFAOYSA-N tris Chemical compound OCC(N)(CO)CO LENZDBCJOHFCAS-UHFFFAOYSA-N 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
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Abstract
A steam reformer (1) has a double structure composed of an inner cylinder (2) and an outer cylinder (3) arranged around the inner cylinder. The inner cylinder (2) has a high-temperature reaction portion (6) and an adjoining portion (7) located next to the high-temperature reaction portion. A mixed catalyst layer (4) composed of a steam reforming catalyst and an oxidation catalyst and an oxygen-containing gas introducing portion (5) are arranged in the high-temperature reaction portion (6). A heat transmission suppressing means (50) is provided for suppressing heat transmission from the high-temperature reaction portion (6) to the adjoining portion (7) or the oxygen-containing gas introducing tube (5). This heat transmission suppressing means (50) can efficiently suppress thermal diffusion from the high-temperature reaction portion (6) to the surrounding areas.
Description
Technical field
The present invention relates to a kind of steam reformer, it under the condition that has steam and oxygen, rely on autoxidation gentle-conversion of gas raw material, produce hydrogen-rich reformed gas.
Background technology
Known a kind of steam reformer, it exists under the catalyzer condition of steam reforming, and the steam reforming of carrying out gas-gas raw material and vapour mixture (hereinafter referred to as " gas raw material and vapour mixture ") produces hydrogen-rich reformed gas.The rich hydrogen reformed gas that produces in steam reformer is suitable as the fuel of fuel cell.Gas-gas the raw material that is suitable for comprises hydro carbons as methane, as the aliphatic alcohol of methyl alcohol and as the ethers of dme.
When adopting methane as gas-gas raw material, the reactional equation of steam reforming writing CH in steam reformer
4+ 2H
2O → CO
2+ 4H
2, the preferable range of wherein conversion reaction temperature is 700 ℃ to 750 ℃.
Inner heating is a system of supply reaction institute heat requirement in steam reformer.The steam reformer of inner heating has a partial oxidation reaction bed at the supply side (the perhaps upstream side of conversion system) of gas raw material and vapour mixture.The heat that in the partial oxidation reaction bed, produces be used to heat be positioned at the conversion system downstream side the steam reforming bed to the steam reforming reaction temperature.In the steam reforming catalysts bed of so heating, carry out steam reforming, to produce rich hydrogen reformed gas.Partial oxidation reaction writing CH
4+ 1/2O
2→ CO+2H
2, the preferred temperature of its partial oxidation reaction is 250 ℃ or higher.
An improved mode of the steam reformer of inner heating is the steam reformer of the inner heating of autoxidation, and Japanese Unexamined Patent Publication No 2001-192201 has announced an example.The technology of announcing according to patent in the mixed catalyst bed for preparing at mixed oxide catalyst and steam reforming catalysts, produces the heat of oxidizing reaction and steam reforming reaction respectively simultaneously.
Figure 13 is the sectional view of a signal, and it is the example of steam reformer of the inner hot type of autoxidation of inventor of the present invention exploitation.Steam reformer 1 has an inner core 2 and the urceolus 3 around inner core 2.Inner core 2 the top of portion within it comprises a pyroreaction section 6.Pyroreaction section 6 has comprised a mixed catalyst bed 4 that is prepared by mixing steam conversion catalyst and oxide catalyst, and has an oxygen-containing gas input section 5.An adjacent segments 7 that is made of heat passage bed abuts against under the pyroreaction section 6, under adjacent segments 7, has a high temperature transfer catalyst bed 8 and a low temperature shift catalyst bed 9 successively.
Steam reforming catalysts is the catalyzer that is used for steam reforming gas-gas raw material.The steam reforming catalysts that is suitable for comprises as NiO-SiO
2Al
2O
3Ni base conversion catalyst, and as WO
2-SiO
2Al
2O
3And NiO-WO
2SiO
2Al
2O
3Catalyzer.
Oxide catalyst is a kind of catalyzer, is used for oxidation and produces heat at the gas-gas raw material of gas raw material and vapour mixture, reaches the required temperature of steam reforming thus.The oxide catalyst that is suitable for comprises platinum (Pt) and palladium (Pd).According to the gas that stands steam reforming-gas type of feed, the ratio of mixture of determining oxide catalyst and steam reforming catalysts is in about 1 to 15% scope.For example,, adopt the ratio of mixture of about 5+2%,, be about 3 ± 1% for the situation of methyl alcohol as raw material for the situation of methane as gas-gas raw material.
The transfer catalyst that is used to form high temperature transfer catalyst bed 8 and low temperature shift catalyst bed 9 comprises and contains CuO-ZnO
2, Fe
2O
3, Fe
3O
4, cupric oxide and so on mixture.But,, then can adopt Cr if under 700 ℃ or higher temperature, react
2O
3
The heat passage bed that constitutes adjacent segments 7 absorbs heat from the reformed gas of leaving pyroreaction section 6, to cool off the gas that has transformed.Heat passage bed is made of the particle of filling, and this particle is as the ceramic particle for having good thermal conductivity.
Can cancel heat passage bed in some cases.For example, adopt high temperature transfer catalyst bed 8, perhaps adopt high temperature transfer catalyst bed 8 and low temperature shift catalyst bed 9 simultaneously, constitute adjacent segments 7 of the present invention.
The bottom of the mixed catalyst bed 4 in inner core 2, adjacent segments 7, high temperature transfer catalyst bed 8 and low temperature shift catalyst bed 9 is by its relevant ventilative supporting 10,11,12 and 13 supportings.
The spout part 1515 that oxygen-containing gas input section 5 has an input channel 14 and opens wide near input channel 14 front ends.Oxygen-containing gas can be an air or oxygen.For example, the pressurized air of air compressor (not shown) supply is delivered to input channel 14, can spray into mixed catalyst bed 4 to pressurized air by spout part 1515.
A steam reforming catalysts bed 16 is positioned at the top of urceolus 3 inside, and a heat passage bed 17 abuts against under the steam reforming catalysts bed 16.The bottom of steam reforming catalysts bed 16 and heat passage bed 17 is by its relevant ventilative supporting 18 and 19 supportings.The supply section 20 of gas-gas raw material and vapour mixture abuts against under the heat passage bed 17.A discharge section 21 is open on the steam reforming catalysts bed 16, and discharge section 21 is connected with supply section 22 on being positioned at pyroreaction section 6 then.In the bottom of inner core 2, a discharge section 23 that is used to discharge institute's production reformed gas abuts against under the low temperature shift catalyst bed 9.
Need remain on high temperature range to the internal temperature of pyroreaction section 6, so that carry out steam reforming reaction effectively.For this reason, should reduce unnecessary thermodiffusion as far as possible.In order to reach minimizing of thermodiffusion, isolation section 24 with hollow parts is between inner core 2 parts of laying pyroreaction section 6 and urceolus 3 parts of laying steam reforming catalysts bed 16.
Figure 14 has represented a part enlarged view that comprises isolation section 24.Isolation section 24 has an endless inner wall part 25 and a ring-type outer wall section 26.Endless inner wall part 25 is combined with ring-type outer wall section 26 in top and the bottom by relevant sidewall 27 respectively, portion has formed a ring-type hollow parts 28 within it.Inner wall section 25 is parts of inner core 2.
The method that adopts above-mentioned steam reformer 1 to carry out steam reforming is below described.When gas-gas raw material and steam mixture being delivered to supply section 20, because high temperature transfer catalyst bed 8 and low temperature shift catalyst bed 9 is heat passage, gas-gas raw material and vapour mixture are in the temperature that increased it at 17 o'clock by heat passage.Pyritous gas-gas raw material and vapour mixture enter steam reforming catalysts bed 16 then, and a part of there gas-gas raw material stands steam reforming.The gas that has transformed and remaining gas-gas raw material and vapour mixture enter inner core 2 from discharge section 21, enter pyroreaction section 6 by the supply section 22 in the inner core 2.
In pyroreaction section 6, exist under the oxide catalyst condition that constitutes mixed catalyst bed 4, some gas-gas raw material stands the oxidizing reaction from oxygen in the oxygen-containing gas of oxygen-containing gas input section 5 in the gas of inflow-gas raw material and the vapour mixture.Oxidizing reaction is increased to the required scope of conversion reaction to the temperature of gas-gas raw material and vapour mixture, for example from about 650 ℃ to about 750 ℃ (being generally about 700 ℃).That is to say, realized autoxidation and inner heating.Utilize the heat that so produces, carry out the steam reforming reaction of gas-gas raw material and vapour mixture, produce rich hydrogen reformed gas with good efficiency.Exactly, in pyroreaction section 6, carry out exothermic oxidation reaction and endothermic conversion reaction simultaneously, in pyroreaction section 6, keep uniform temperature to distribute thus.The effect of the steam reforming catalysts bed 16 in the urceolus 3 is preliminary conversion zones as pyroreaction section 6.
The reformed gas that obtains in pyroreaction section 6 enters near the adjacent segments 7 below it, and the temperature of reformed gas reduces there, and by high temperature transfer catalyst bed 8 and low temperature shift catalyst bed 9.During by high temperature transfer catalyst bed 8 and low temperature shift catalyst bed 9, most of carbon monoxide of staying in the reformed gas are converted into hydrogen.Leave the high purity reformed gas of low temperature shift catalyst bed 9 and discharge, deliver to an input unit (not shown) then, as the fuel cell of vehicle and the fuel cell of domestic power supply from discharge section 23.
As mentioned above, isolation section 24 has suppressed heat diffusion in the pyroreaction section 6 to urceolus 3.However, shown in arrow A among Figure 14, the heat in the pyroreaction section 6 is diffused into the downstream side of inner core 2 from the inner wall section 25 of isolation section 24, perhaps is diffused into adjacent segments 7, in addition, a part of heat also is diffused into the outer wall section 26 of isolation section 24 from inner wall section 25 by sidewall sections 27.The result is that the heat energy that heating pyroreaction section 6 is consumed increases, and has reduced the thermo-efficiency and the reaction efficiency of steam reformer 1.
Therefore, owing to only can not fully suppress from pyroreaction section 6 to adjacent segments 7 or the thermodiffusion of oxygen-containing gas input channel 14 by isolation section shown in Figure 14 24, it is not enough improving the thermo-efficiency of steam reformer 1 and the effect of reaction efficiency.
Summary of the invention
For this reason, a problem of the present invention is the thermodiffusion shortcoming that further solves in the pyroreaction section.
That is to say, an object of the present invention is to improve the ability of inhibition from the pyroreaction section to the adjacent segments thermodiffusion.
Another object of the present invention is to improve to suppress from the pyroreaction section to the ability that contains the thermodiffusion of gas oxygen input channel section.
Another purpose of the present invention is to improve to suppress from the pyroreaction section to the adjacent segments thermodiffusion simultaneously and the ability from the pyroreaction section to the thermodiffusion of oxygen-containing gas input channel section.
It is to adopt a simple structure of steam reformer to improve inhibition from the pyroreaction section to adjacent segments with the ability of oxygen-containing gas input channel section thermodiffusion that the present invention also has another purpose.
It is to improve the thermo-efficiency and the reaction efficiency of steam reformer that the present invention also has another purpose.
Steam reformer 1 of the present invention comprises a double-barrel structure, has an inner core 2 and the urceolus 3 around inner core 2.Inner core 2 comprises a pyroreaction section 6 and the adjacent segments 7 near pyroreaction section 6.Pyroreaction section 6 comprises the mixed catalyst bed 4 that is prepared by mixing steam conversion catalyst and oxide catalyst, and has an oxygen-containing gas input section 5.Urceolus 3 comprises a steam reforming catalysts bed 16.Steam reformer 1 of the present invention has a heat passage suppressor 50, and its suppresses from pyroreaction section 6 to adjacent segments 7 or heat passage to oxygen-containing gas input section 5.
As mentioned above, according to the present invention, heat passage suppressor 50 in steam reformer 1 has suppressed effectively from pyroreaction section 6 to adjacent segments 7 or to the thermodiffusion of oxygen-containing gas input channel section 5, has improved thermo-efficiency and reaction efficiency in pyroreaction section 6 thus.
In steam reformer 1, the isolation section 24 with hollow parts is located at inner core 2 parts that contain pyroreaction section 6 and faces between urceolus 3 parts of inner core 2 parts, forms an opening portion 30 that opens wide in the inner wall section 25 that constitutes hollow parts.Adopt this configuration, opening portion 30 has constituted heat passage suppressor 50, suppress from pyroreaction section 6 to adjacent segments 7 heat passage.Opening portion 30 can be formed by many slits 31, is arranged on the inner wall section 25 by the ring-type pattern.
So the heat passage suppressor 50 that constitutes can adopt simple structure to suppress from pyroreaction section 6 to adjacent segments 7 thermodiffusion effectively.
In addition, in steam reformer 1, form a dead level 40, on a specific range pyroreaction section 6 and adjacent segments 7 are isolated, dead level 40 has constituted heat passage suppressor 50 thus, suppress from pyroreaction section 6 to adjacent segments 7 heat passage.
Oxygen-containing gas input section 5 has an input channel 14 that extends along inner core 2 axis, and one is positioned near the spout part 15 of pipeline 14 front ends.Input channel 14 has one from the outwards outstanding supporting member 42 of pipeline, and facing to outwards outstanding supporting member 42, inner core 2 has one from the inwardly outstanding supporting member 41 of inner core, therefore the bottom supporting of mixed catalyst bed 4 forms dead level 40 thus between supporting 43 and adjacent segments 7 in a ventilative supporting 43 that is positioned on these supporting members 41 and 42.
Adopt simple structure, the heat passage suppressor 50 that is made of dead level 40 also can suppress effectively from pyroreaction section 6 to adjacent segments 7 thermodiffusion.
In addition, in steam reformer 1, isolation section 24 with hollow parts is located at inner core 2 parts that comprise pyroreaction section 6 and in the face of between urceolus 3 parts of inner core 2 parts, form an opening portion 30, this opening portion 30 opens wide in the inner wall section 25 that constitutes hollow parts, opening portion 30 constitutes heat passage suppressor 50 thus, suppressed from pyroreaction section 6 to adjacent segments 7 heat passage.In addition, form a dead level 40, on a specific range pyroreaction section 6 and adjacent segments 7 are isolated, dead level 40 constitutes heat passage suppressor 50 thus, suppressed from pyroreaction section 6 to adjacent segments 7 heat passage.
Owing to formed heat passage suppressor 50 that adopts hollow parts 30 and the heat passage suppressor 50 that adopts dead level 40 simultaneously, can more effectively suppress from pyroreaction section 6 to adjacent segments 7 thermodiffusion.
In addition, in steam reformer 1, oxygen-containing gas input section 5 has an input channel 14 that extends along inner core 2 axis and one and is positioned near pipeline 14 front ends spout part 15.Input channel 14 has a cylindrical shell 40a, this opening portion 30 forms a clearance layer 41a in input channel 14 outsides, perhaps has a thermofin 43a, cover input channel 14 outsides, cylindrical shell 40a or thermofin 43a have constituted heat passage suppressor 50 thus, and the heat passage of section 5 imported in inhibition from pyroreaction section 6 to oxygen-containing gas.
The heat passage suppressor 50 that is made of cylindrical shell 40a or thermofin 43a can suppress effectively to import the heat passage of section 5 from pyroreaction section 6 to oxygen-containing gas with simple structure, has improved the thermo-efficiency and the reaction efficiency of pyroreaction section 6 thus.
In addition, in steam reformer 1, except the heat passage suppressor 50 that is made of cylindrical shell 40a or thermofin 43a, they have suppressed to import the heat passage of section 5 from pyroreaction section 6 to oxygen-containing gas, can also constitute:
(1) isolation section 24 with hollow parts is located at inner core 2 parts that comprise pyroreaction section 6 and in the face of between urceolus 3 parts of inner core 2 parts, form an opening portion 30, it opens wide in the inner wall section 25 that constitutes hollow parts, opening portion 30 constitutes heat passage suppressor 50 thus, suppressed from pyroreaction section 6 to adjacent segments 7 heat passage;
(2) form a dead level 40, on a specific range pyroreaction section 6 and adjacent segments 7 are isolated, dead level 40 constitutes heat passage suppressor 50 thus, suppressed from pyroreaction section 6 to adjacent segments 7 heat passage; Perhaps
(3) be used for the heat passage suppressor 50 of above-mentioned (1) and (2) simultaneously.
Because so the heat passage suppressor 50 that forms can suppress from pyroreaction section 6 to oxygen-containing gas input section 5 effectively and to the thermodiffusion of adjacent segments 7, can further improve the thermo-efficiency and the reaction efficiency of pyroreaction section 6.
In addition, in any one of above-mentioned steam reformer 1, inner core 2 also comprises a high temperature transfer catalyst bed 8 and a low temperature shift catalyst bed 9 except comprising mixed catalyst bed 4; Urceolus 3 comprises a steam reforming catalysts bed 16; Each of high temperature transfer catalyst bed 8, low temperature shift catalyst bed 9 and steam reforming catalysts bed 16 adopts granular catalyzer 44a filling; The inner wall surface of at least one forms a corrugated surface 45 in the mixed catalyst bed 4 that contacts with catalyzer 44a, high temperature transfer catalyst bed 8, low temperature shift catalyst bed 9 and the steam reforming catalysts bed 16, wherein many pits evenly are arranged to the morphology of two dimension continuously, have set up the face contact between granules of catalyst 44a and pit thus.
Adopt said structure, improved the filling efficient of granules of catalyst 44a, improved the heat transfer efficiencies in the catalyst bed thus.The result is to improve the reaction efficiency of steam reformer 1.
Description of drawings
Fig. 1 has represented the isolation section of steam reformer of the present invention and the part amplification view of neighboring area.
Fig. 2 has represented the part enlarged perspective of an example of Fig. 1 split shed part 30.
Fig. 3 has represented the part enlarged perspective of another example of Fig. 1 split shed part 30.
Fig. 4 has represented another embodiment of steam reformer of the present invention, has represented the part amplification view of isolation section and neighboring area.
Fig. 5 has represented the part amplification view of the modification example of Fig. 4.
Fig. 6 has represented the part enlarged perspective of another modification of Fig. 4.
Fig. 7 is another embodiment of steam reformer of the present invention, has represented the isolation section of taking apart and the part enlarged perspective of neighboring area.
Fig. 8 has represented the part amplification view after Fig. 7 assembling.
Fig. 9 has represented another embodiment of steam reformer of the present invention, has represented the part amplification view of isolation section and neighboring area.
Figure 10 has represented the isolation section of the heat passage suppressor 50 that Fig. 9 revises and the part enlarged perspective of neighboring area.
Figure 11 has represented another embodiment of steam reformer of the present invention, has represented the part skeleton view of pyroreaction section and neighboring area.
Figure 12 is the part enlarged view of the signal of pyroreaction section internal surface and adjacent mixed catalyst bed among Figure 11.
Figure 13 is the schematic sectional view of an example of autoxidation steam reformer of the present invention.
Figure 14 has represented the part enlarged view of isolation section 24 and neighboring area among Figure 13.
Embodiment
Below describe each embodiment of the present invention with reference to the accompanying drawings.In Fig. 1, what provide among the steam reformer major portion of embodiment and catalyzer and Figure 13 is identical, therefore same section is provided identical numbering, and omits to this further describe, to avoid repetition.
Steam reformer 1 has a double-barrel structure, comprises an inner core 2 and a urceolus 3 that is positioned at inner core 2 outsides.Inner core 2 comprises a pyroreaction section 6.Pyroreaction section 6 comprises the mixed catalyst bed 4 of the mixture that is prepared by mixing steam conversion catalyst and oxide catalyst, and has an oxygen-containing gas input section 5.The annular gas permeable supporting 10 that the bottom of the mixed catalyst bed 4 in the pyroreaction bed 6 is made by punch metal and so on is supported.Be positioned at the downstream side (bottom of Fig. 1) of supporting 10 by heat passage adjacent segments 7 that constitutes.Supporting 10 is placed on the supporting member 10a and supporting member 10b who is formed on the inner wall section 25 who is formed on the input channel 14.Steam reforming catalysts bed 16 is arranged in urceolus 3.
In order to suppress from pyroreaction section 6 to urceolus 3 thermodiffusion, be positioned at the outside of pyroreaction section 6 similar in appearance to the isolation section 24 of Figure 13.Isolation section 24 forms hollow shape, and it is centered on by endless inner wall part 25, ring-type outer wall section 26 and the sidewall sections 27 that connects its relevant top and bottom.Adopt this configuration, the internal space of Xing Chenging has constituted ring-type hollow parts 28 thus.Inner wall section 25 is parts of inner core 2.
The opening portion 30 that constitutes heat passage suppressor 50 is formed between inner wall section 25 and the adjacent segments 7.The heat that opening portion 30 suppresses pyroreaction section 6 is diffused into adjacent segments 7 from inwall 2 parts.In addition, opening portion 30 has suppressed a part of heat effectively and has been diffused into outer wall section 26 by sidewall sections 27.Because these heat passage retarding effects have reduced the heat energy that consumes in pyroreaction section 6, and have improved thermo-efficiency and the reaction efficiency in the conversion reaction.
Fig. 2 and 3 has represented the example of opening portion 30.Opening portion 30 is made of many short slits 31, and they are arranged to the ring-type pattern discontinuously along the periphery of inner wall section 25.Fig. 2 has represented the example of single slit 31, and Fig. 3 has represented the example of the double slit 31 that is crisscross arranged.Spacing between the slit 31 is preferably as far as possible little to suppress thermodiffusion, but the lower limit of its spacing is subjected to the restriction of requirement of strength.
Except opening portion 30, the top in inner wall section 25 embodiment illustrated in fig. 1 has an additional opening portion 32.Opening portion 32 can be similar in appearance to the slit 31 shown in Fig. 2 and 3.Opening portion 32 can suppress by upper side wall part 27 thermodiffusion of 26 from inner wall section 25 to outer wall section.But, can cancel opening portion 32 in some cases.
Steam reformer 1 shown in Figure 4 is characterised in that and has formed a dead level 40, on a specific range adjacent segments in the bottom of pyroreaction section 6 and the inner core 27 is isolated.Dead level 40 has constituted heat passage suppressor 50, has suppressed from pyroreaction section 6 to adjacent segments 7 thermodiffusion that caused by thermal conduction.Heat passage suppressor 50 can be saved the heat energy of pyroreaction section 6 and thermo-efficiency and the reaction efficiency in the raising conversion reaction.
The bottom of inner wall section 25 in isolation section 24 is provided with inwardly outstanding supporting member 41, and in the face of supporting member 41 parts, supporting member 42 is outwards outstanding from input channel 14 parts that constitute oxygen-containing gas input section 5.These supporting members 41 and 42 can form the ring-type continuous structure along periphery, perhaps form the discontinuous shape along periphery.Ventilative supporting 43 is placed on each supporting member 41 and 42.
Fig. 5 is the modification of Fig. 4.According to this embodiment, the supporting 43 that constitutes dead level 40 is only made by the porous annular bearing plate of making by punch metal and so on 44, and the shank of not seeing in Fig. 4 example divides 45a.With the difference of Fig. 4 be: from the inwardly outstanding supporting member 41 in the bottom of isolation section 24 inner wall section 25, and face supporting member 41, all divide the length of 45a to be positioned at the higher position according to shank among Fig. 4 from the outwards outstanding supporting members 42 of input channel 14.
Fig. 6 is another modification of Fig. 4.According to this embodiment, the supporting 43 that constitutes dead level 40 divides 45a to constitute by porous annular bearing plate 44 and the many shanks made by punch metal and so on.But shank divides 45a to be connected with supporting plate 44 integral body as seeing among Fig. 4, but separates with supporting 43.Many shanks for the thin strip of rectangle divide 45a with the stationkeeping of its vertical surface on the outside surface of input channel 14.Then supporting plate 44 being placed on these shanks divides on the 45a.The vertical range of dead level 40 is divided the vertical length decision of 45a by shank.
Fig. 7 is another embodiment of steam reformer of the present invention, has represented the isolation section of taking apart and the part enlarged perspective of neighboring area.Fig. 8 has represented the sectional view after Fig. 7 isolation section and the neighboring area assembling.The embodiment that Fig. 7 and 8 provides has two heat passage suppressors 50, or the dead level 40 that provides of the opening portion 30 that provides in Fig. 1 example and Fig. 4.These two heat passage suppressors 50 have further suppressed effectively from pyroreaction section 6 to adjacent segments 7 thermodiffusion.
This embodiment has widened the sectional area on inner core 2 tops.When the direction of arrow in Fig. 7 is inserted isolation section 24 those widened sections and assigned to they are assembled together, set up state shown in Figure 8.The vertical wall of the widened section of inner core 2 constitutes the outer wall section 26 of isolation section 24, and the horizontal wall of its widened section has constituted the sidewall sections 27 on isolation section 24 bottoms.In addition, between sidewall sections 27 and inner wall section 25 lower ends, formed opening portion 30.If desired, another opening portion (slit) 32 can be located at the top of inner wall section 25.
Similar in appearance to the example of Fig. 5, dead level 40 is formed by supporting 43, and it only is made of the porous annular bearing plate of making by punch metal and so on.From the inwardly outstanding supporting member 41 in the bottom of isolation section 24 inner wall section 25, and face supporting member 41, all divide the length of 45a to be positioned at the higher position according to shank among Fig. 4 from the outwards outstanding supporting members 42 of input channel 14.Then supporting 43 is placed on these supporting members 41 and 42.
Fig. 9 is another embodiment of steam reformer 1 of the present invention.The pyroreaction section 2 similar and the part enlarged view of neighboring area have been provided to Fig. 1.The major portion of the steam reformer 1 of this embodiment is identical with Fig. 1.
Steam reformer 1 has a double-barrel structure, comprises an inner core 2 and the adjacent segments 7 near pyroreaction section 6 that comprises pyroreaction section 6, and the urceolus 3 around inner core 2.Pyroreaction section 6 comprises the mixed catalyst bed 4 that is prepared by mixing steam conversion catalyst and oxide catalyst, and and has an oxygen-containing gas input section 5.Urceolus 3 comprises steam reforming catalysts bed 16.Isolation section 24 with ring-type hollow parts is located at the outside of inner core 2.
Vertical wall in inner core 2 widened sections has constituted the outer wall section 26 of isolation section 24, and has constituted the sidewall sections 27 of isolation section 24 bottoms in the zone of widened section flange shape.
Oxygen-containing gas input section 5 has along inner core 2 axially extended input channels 14, and is positioned near the spout part 15 its front end.Internal diameter is positioned to center on the periphery of input channel 14 greater than the cylindrical shell 40a of input channel 14 external diameters.The top of cylindrical shell 40a is connected with the top of input channel 14, perhaps directly abuts against under the spout part 15.Clearance layer 41a with Rack is formed between input channel 14 and the cylindrical shell 40a.Clearance layer 41a extends to the lower position of inner wall section from above-mentioned tie point, and has opened wide its lower end.Adopt the cylindrical shell 40 that constitutes clearance layer 41a, formed thermodiffusion suppressor 50, suppress thermodiffusion from pyroreaction section 6 to oxygen-containing gas input channel 14.
Inner periphery surface by the bottom of the mixed catalyst bed 4 of supporting plate 10 supporting contacts with the outside surface of cylindrical shell 40a, and does not contact with input channel 14.Therefore, suppressed heat passage significantly, increased the thermo-efficiency of pyroreaction section 6 from pyroreaction section 6 (mixed catalyst bed 4) to input channel 14.
According to this embodiment, two heat passage and suppressors 50 thermodiffusion are installed are suppressed from pyroreaction section 6 to adjacent segments 7 heat passage and thermodiffusion.One of them heat passage and thermodiffusion suppressor 50 is made of opening portion 30, and it forms ring-type in the bottom of the inner wall section 25 that constitutes isolation section 24.
The suppressor 50 of another heat passage and thermodiffusion is made of dead level.That is to say, prepared from the inwardly outstanding annular support spare 41 in the lower end of inner wall section 25, and in the face of the supporting member 41 annular support spare 42 outwards outstanding from cylindrical shell 40a lower end, the annular gas permeable supporting 10 of being made by punch metal and so on is supported on supporting member 41 and 42.The bottom of mixed catalyst bed 4 in the pyroreaction section 6 is supported in supporting 10, and the adjacent segments 7 that is made of heat passage bed is positioned at its downstream side (Fig. 9 bottom).Therefore, the dead level 40 that constitutes heat passage suppressor 50 is formed between mixed catalyst bed 4 bottom surfaces and adjacent segments 7 end faces.
Like this, this embodiment has three heat passage suppressors: i.e. cylindrical shell 40a, opening portion 30 and dead level 33.Because the optimum synergistic effect of these three heat passage suppressors 50, the utmost point has suppressed the thermodiffusion from pyroreaction section 6 to the neighboring area effectively.In some cases, can cancel any one of opening portion 30 and dead level 40.
Embodiment shown in Figure 9 has opening portion 30a, and it is in the flange shape extension between inner wall section 25 top margins and outer wall section 26 top margins short slit to be set and to form, and inner and outer wall has partly constituted isolation section 24.The effect of opening portion 30a is to suppress heat passage from the top margin of inner wall section 25 to outer wall section 26, and opening portion 30a can cancel in some cases.
Figure 10 is the modification of Fig. 9.The difference of this embodiment and Fig. 9 example only is heat passage suppressor 50, and other parts have the configuration similar to Fig. 9.The tubular thermofin 43a that covers input channel 14 outsides has constituted heat passage suppressor 50.The inorganic fibers as glass fibre with thermal resistance and heat-insulating properties is configured as a tubular, inserts along the neighboring of input channel 14 then, constitute thermofin 43a thus.
Similar in appearance to the example of Fig. 9, the top of thermofin 43a extends to the top of input channel 14, perhaps directly abut against under the spout part 15, and its bottom extends to the position, base that constitutes isolation section 24 inner wall section 25.Similar in appearance to the example of Fig. 9, the ventilative supporting plate 10 of ring-type is supported on the annular support spare 41 that is positioned at inner wall section 25 bases, and is supported on the annular support spare that is positioned at input channel 14 neighborings 42 in the face of supporting member 41.But, because the inner peripheral surface of supporting plate 10 contact with the periphery of thermofin 43a, and owing to it does not directly contact with input channel 14, suppressed effectively to pass through supporting plate 10 from mixed catalyst bed 4 to input channel 14 heat passage.
Figure 11 is another embodiment of steam reformer of the present invention.This embodiment is characterised in that: the wall that contacts with catalyst bed in the steam reformer 1 is designed to a specific shape.Specific shape goes for the inner core 2 of the various embodiments described above and the wall of urceolus 3.
Figure 11 has represented the example of interior perimeter surface of the pyroreaction section 6 of inner core 2, is configured as specific shape.Be arranged in catalyst particle 44a (mixture of steam reforming catalysts particle and the oxidation catalyst particles) formation of the mixed catalyst bed 4 of pyroreaction section 6 by close packing.At least the internal surface 2a that contacts with mixed catalyst bed 4 in inner core 2 is a corrugated surface 45, and it is by equally spaced forming countless pits by two-dimensional model and making.The a part of neighboring that constitutes the granules of catalyst 44a of mixed catalyst bed 4 contacts with inner surface portion 2a, makes granules of catalyst enter ripple.
Each pit on the corrugated surface 45 has identical radius-of-curvature, and the size of preparation radius-of-curvature equals the catalyzer 44a particulate radius-of-curvature of even granulation, and perhaps size is a bit larger tham (for example several percentage points) catalyzer 44a particulate radius-of-curvature.In general, be known catalyzer by the used steam reforming catalysts of granulation preparation, oxide catalyst, transfer catalyst and so on, the pit that prepared corrugated surface 45 has, its radius-of-curvature is consistent with the granules of catalyst diameter of preparation.
Figure 12 has represented the synoptic diagram of the amplification profile of contact condition between catalyzer 44a and the corrugated surface 45.As mentioned above, because each pit formation has the essentially identical radius-of-curvature with granules of catalyst 44a on the corrugated surface 45, it is surface contact state that the granules of catalyst 44a that contacts with inner core 2 internal surface 2a is arranged to each pit.Therefore, the hole B that forms between internal surface 2a and granules of catalyst 44a becomes very little, and hole B is substantially equal to second row and follow-up row goes up the hole C that forms between the close mutually granules of catalyst 44a thus.
As mentioned above, when hole B and hole C became mutually much at one, blended catalyst bed 4 had hole part fully uniformly, and it allows that gas-gas raw material and vapour mixture keep mobile uniformly, and does not produce the separated flow pattern.The result is, at the gas-gas raw material by mixed catalyst bed 4 and become evenly the duration of contact between vapour mixture and the catalyzer, it has caused the raising of reaction efficiency in the pyroreaction section 6.In addition, because granules of catalyst 44a can load into the tightst filling of ideal, can load the granules of catalyst 44a quantity that further increases in same space, it has also improved reaction efficiency.
In case the hole B between granules of catalyst 44a and internal surface 2a reduces, the amount corresponding to hole B reduces increases to the heat passage and thermodiffusion of outside by internal surface 2a.But, suppress the increase of heat passage and thermodiffusion by heat passage suppressor 50.Therefore, according to having the shape that above-mentioned heat passage and embodiment thermodiffusion suppressor 50 makes up wall, can suppress the decline of thermo-efficiency effectively, and keep high reaction efficiency.
Above embodiment has described the internal surface 2a of inner core 2, and this internal surface 2a contacts with mixed catalyst bed 4.But, the present invention is not limited to this configuration, the present invention also can similarly be applicable to the internal surface of the urceolus 3 that contacts with steam reforming catalysts bed 16, perhaps is applicable to the internal surface 2a of the inner core 2 that contacts with low temperature shift catalyst bed 9 with high temperature transfer catalyst bed 8.
Claims (9)
1. steam reformer that comprises double-barrel structure, described double-barrel structure have an inner core (2) and the urceolus (3) around inner core (2); Inner core (2) comprises a pyroreaction section (6) and the adjacent segments (7) near pyroreaction section (6); Pyroreaction section (6) comprises the mixed catalyst bed (4) that is prepared by mixing steam conversion catalyst and oxide catalyst, and has an oxygen-containing gas input section (5); Urceolus (3) comprises a steam reforming catalysts bed (16), forms the steam reformer (1) of double-barrel structure thus; Wherein constitute a heat passage suppressor (50) in steam reformer (1), it suppresses to import the heat passage of section (5) from pyroreaction section (6) to adjacent segments (7) or to oxygen-containing gas.
2. steam reformer as claimed in claim 1, an isolation section (24) that wherein has hollow parts is located between inner core (2) part and urceolus (3) part in the face of inner core (2) part that contains pyroreaction section (6), form an opening portion (30) that in the inner wall section (25) that constitutes hollow parts, opens wide, opening portion (30) has constituted heat passage suppressor (50) thus, suppresses heat passage from pyroreaction section (6) to adjacent segments (7).
3. steam reformer as claimed in claim 2, wherein opening portion (30) is formed by many slits (31), and these many slits (31) are arranged on the inner wall section (25) by the ring-type pattern.
4. steam reformer as claimed in claim 1, wherein form a dead level (40), its pyroreaction section (6) and adjacent segments (7) are isolated, and dead level (40) has constituted heat passage suppressor (50) thus, suppress heat passage from pyroreaction section (6) to adjacent segments (7).
5. steam reformer as claimed in claim 4, wherein oxygen-containing gas input section (5) has an input channel (14) that extends along inner core (2) axis, near and spout part (15) that is positioned at pipeline (14) front end, input channel (14) has one from the outwards outstanding supporting member (42) of pipeline, and facing to outwards outstanding supporting member (42), inner core (2) has one from the inwardly outstanding supporting member (41) of inner core, therefore the bottom supporting of mixed catalyst bed (4) forms dead level (40) thus between supporting (43) and adjacent segments (7) in a ventilative supporting (43) that is positioned on these supporting members (41) and (42).
6. steam reformer as claimed in claim 1, one of them isolation section 24 with hollow parts is located between inner core (2) part and urceolus (3) part in the face of inner core (2) part that comprises pyroreaction section (6), form an opening portion (30), this opening portion (30) opens wide in the inner wall section (25) that constitutes hollow parts, opening portion (30) constitutes heat passage suppressor (50) thus, to suppress heat passage from pyroreaction section (6) to adjacent segments (7), in addition, form a dead level (40), its pyroreaction section (6) is isolated with adjacent segments (7), dead level (40) constitutes heat passage suppressor (50) thus, to suppress heat passage from pyroreaction section (6) to adjacent segments (7).
7. steam reformer as claimed in claim 1, wherein oxygen-containing gas input section (5) has an input channel (14) that extends along inner core (2) axis and one and is positioned near the spout part (15) of pipeline (14) front end, input channel (14) has a cylindrical shell (40a), it forms a clearance layer (41a) in input channel (14) outside, perhaps has a thermofin (43a), cover input channel (14) outside, cylindrical shell (40a) or thermofin (43a) have constituted heat passage suppressor (50) thus, and the heat passage of section (5) imported in inhibition from pyroreaction section (6) to oxygen-containing gas.
8. steam reformer as claimed in claim 7 except cylindrical shell (40a) or thermofin (43a), also comprises:
(1) isolation section (24) with hollow parts is located between inner core (2) part and urceolus (3) part in the face of inner core (2) part that comprises pyroreaction section (6), form an opening portion (30), this opening portion (30) opens wide in the inner wall section (25) that constitutes hollow parts, opening portion (30) constitutes heat passage suppressor (50) thus, to suppress heat passage from pyroreaction section (6) to adjacent segments (7);
(2) form a dead level (40), pyroreaction section (6) and adjacent segments (7) are isolated, dead level (40) constitutes heat passage suppressor (50) thus, has suppressed heat passage from pyroreaction section (6) to adjacent segments (7); Perhaps
(3) be used for the heat passage suppressor (50) of above-mentioned (1) and (2) simultaneously.
9. as any one steam reformer among the claim 1-8, wherein inner core (2) also comprises a high temperature transfer catalyst bed (8) and a low temperature shift catalyst bed (9) except comprising mixed catalyst bed (4); Urceolus (3) comprises a steam reforming catalysts bed (16); Each of high temperature transfer catalyst bed (8), low temperature shift catalyst bed (9) and steam reforming catalysts bed (16) adopts granular catalyzer (44a) filling; The inner wall surface of at least one forms a corrugated surface (45) in the mixed catalyst bed (4) that contacts with catalyzer (44a), high temperature transfer catalyst bed (8), low temperature shift catalyst bed (9) and the steam reforming catalysts bed (16), wherein many pits evenly are arranged to the morphology of two dimension continuously, have set up the face contact between granules of catalyst (44a) and pit thus.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2003068286A JP4387677B2 (en) | 2003-03-13 | 2003-03-13 | Steam reformer |
| JP68286/2003 | 2003-03-13 | ||
| JP89208/2003 | 2003-03-27 | ||
| JP89211/2003 | 2003-03-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1761613A CN1761613A (en) | 2006-04-19 |
| CN100488867C true CN100488867C (en) | 2009-05-20 |
Family
ID=33285674
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2004800068687A Expired - Fee Related CN100488867C (en) | 2003-03-13 | 2004-03-11 | Steam conversion device |
Country Status (2)
| Country | Link |
|---|---|
| JP (1) | JP4387677B2 (en) |
| CN (1) | CN100488867C (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039774A (en) * | 1988-07-22 | 1990-02-21 | 帝国化学工业公司 | Hydrogen |
| CN1321136A (en) * | 1999-09-10 | 2001-11-07 | 大金工业株式会社 | Apparatus for producing hydrogen gas and fuel cell system using same |
| US6506359B1 (en) * | 1999-10-20 | 2003-01-14 | Nippon Chemical Plant Consultant Co., Ltd. | Auto-oxidation and internal heating type reforming method and apparatus for hydrogen production |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6089235U (en) * | 1983-11-24 | 1985-06-19 | 三菱重工業株式会社 | fuel reformer |
| DE68905891T2 (en) * | 1988-07-22 | 1993-10-14 | Ici Plc | Generation of hydrogen which includes carbon monoxide conversion using water vapor. |
| JPH11199201A (en) * | 1998-01-09 | 1999-07-27 | Ishikawajima Harima Heavy Ind Co Ltd | Partial oxidation reformer |
-
2003
- 2003-03-13 JP JP2003068286A patent/JP4387677B2/en not_active Expired - Fee Related
-
2004
- 2004-03-11 CN CNB2004800068687A patent/CN100488867C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039774A (en) * | 1988-07-22 | 1990-02-21 | 帝国化学工业公司 | Hydrogen |
| CN1321136A (en) * | 1999-09-10 | 2001-11-07 | 大金工业株式会社 | Apparatus for producing hydrogen gas and fuel cell system using same |
| US6506359B1 (en) * | 1999-10-20 | 2003-01-14 | Nippon Chemical Plant Consultant Co., Ltd. | Auto-oxidation and internal heating type reforming method and apparatus for hydrogen production |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2004277198A (en) | 2004-10-07 |
| JP4387677B2 (en) | 2009-12-16 |
| CN1761613A (en) | 2006-04-19 |
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