CN101612581A - Be used for mesopore-macropore integral catalyzer and preparation that hydrogen-rich gas CO purifies - Google Patents
Be used for mesopore-macropore integral catalyzer and preparation that hydrogen-rich gas CO purifies Download PDFInfo
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- CN101612581A CN101612581A CN200910069436A CN200910069436A CN101612581A CN 101612581 A CN101612581 A CN 101612581A CN 200910069436 A CN200910069436 A CN 200910069436A CN 200910069436 A CN200910069436 A CN 200910069436A CN 101612581 A CN101612581 A CN 101612581A
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Abstract
The present invention is a kind of mesopore-macropore integral catalyzer and preparation that hydrogen-rich gas CO purifies that be used for.This catalyst comprises macroporous integral α-Al
2O
3Carrier loads on macroporous integral α-Al
2O
3Coating γ on the carrier hole wall-Al
2O
3, load on active component Pt and co-catalyst Ni on the coating.Big hole dimension is about 5～100 μ m, and mesoporous most probable bore dia is 2.8～4.9nm on the hole wall, and the wall thickness in hole is 0.1～2.5 μ m, and Kong Yukong connects mutually, is linked to each other by the hole window.The mass percent of Pt, Ni shared quality percentage composition Pt in catalyst is 0.5～2%, and Pt is 1: 3～10 with the atomic molar ratio of Ni.It is little that catalyst provided by the invention has a volume, active high, anti-water and CO that selectivity is better and certain
2Ability can be reduced to the carbon monoxide in the hydrogen rich gas below the 10ppm, and this catalyst mechanical strength height, has dwindled the volume of carbon monoxide preferential oxidation reactor in the hydrogen rich gas effectively, is particularly suitable for small-sized on-the-spot hydrogen supply device and uses.
Description
Technical field
The present invention relates to be used for mesopore-macropore integral catalyzer and the preparation that hydrogen-rich gas CO purifies, belong to CO preferential oxidation technology in the hydrogen-rich gas.
Background technology
Fuel cell particularly Proton Exchange Membrane Fuel Cells (PEMFCs) is used to drive automobile and huge as the market prospects of small-size energy facility.The fuel of PEMFCs is pure hydrogen gas, and the feasible way of producing hydrogen at present is liquid organic-fuel, gas renormalizing or partial oxidation, and is auxiliary with water gas shift reaction etc.Hydrogen source system research and development wherein is one of technical bottleneck, and the key problem that the hydrogen source system need solve is miniaturization, and therefore small-sized hydrogen generating system research and development are focuses both domestic and external in recent years.
Reformation gas-conversion gas composition from fuel is generally 45%～75%H
2, 15%～25%CO
2, 0.5%～2%CO and a spot of H
2O and N
2Because of the hydrogen fuel cell electrode material is noble metals such as Pt, CO not only can poison noble metal electrodes such as Pt, and very easily is adsorbed in the surface of catalyst, hinder the catalytic oxidation of fuel, so the content of CO must be controlled at below the 10ppm electrode 50ppm following or that anti-CO is poisoned in the hydrogen-rich gas.And the preferential oxidation of CO is a most effectual way of removing CO in the hydrogen-rich gas, and the miniaturization that therefore realizes the preferential oxidation reactor volume of CO is one of key technology of fuel cell unstripped gas preparation.
At present, correlative study and exploitation can be divided into following several respects: research and development of (1) effective catalyst and related basic research; (2) the granular pattern oxide catalyst is directly used in the reactor of miniaturization; (3) be the integral catalyzer of carrier with traditional cordierite etc.; (4) metal etc. is the micro passage reaction or the microreactor of carrier.The research of catalyst has had significant progress, the catalyst based particularly Fe of Pt wherein, and Co or Ni doped P t catalyst show catalytic performance preferably.Therefore later emphasis is the H of miniaturization
2The relevant research of middle CO-PROX reactor.The beaded catalyst reactor of the Small-sized C O-PROX reactor of having reported exists pressure to fall bigger problem; By contrast, integral catalyzer particularly microreactor has clear superiority, but its volume is still bigger.The aperture of microreactor and hole wall are at micron order (100～500 μ m), and the corresponding data of monoblock type ceramic monolith is then bigger.Compare with micro passage reaction, foam metal carrier can reduced bore and increasing specific surface area/volume ratio, and has the advantage of micro passage reaction.The volume that integral catalyzer will significantly dwindle catalytic reactor then in nanoscale scope (tens nanometers are to the hundreds of nanometer), is therefore made with large pore material in the hole wall of large pore material and aperture, can realize miniaturization.
Summary of the invention
The object of the present invention is to provide a kind of mesopore-macropore integral catalyzer and preparation that hydrogen-rich gas CO purifies that be used for, be used to dwindle the volume of CO preferential oxidation reactor under the rich hydrogen condition.
The mesopore-macropore integral catalyzer that is used for hydrogen-rich gas CO purification provided by the invention comprises macroporous integral α-Al
2O
3Carrier loads on macroporous integral α-Al
2O
3Coating γ on the carrier hole wall-Al
2O
3, load on active component Pt and co-catalyst Ni on the coating.
Big hole dimension is about 5～100 μ m, and mesoporous most probable bore dia is 2.8～4.9nm on the hole wall, and the wall thickness in hole is 0.1～2.5 μ m, and Kong Yukong connects mutually, is linked to each other by the hole window.
Pt, Ni shared quality percentage composition in catalyst, wherein the mass percent of Pt is 0.5～2%, Pt is 1: 3～10 with the atomic molar ratio of Ni.
The preparation method who is used for the mesopore-macropore integral catalyzer of hydrogen-rich gas CO purification comprises following process:
(1) be monomer (volume ratio V (DVB)/V (styrene)=1: 3.8～4.4) with styrene (styrene) and divinylbenzene (DVB), adding quality is the class of surfactant department 80 of total monomer quality 2%～20%, and quality is that evenly to mix the back be oil phase for the initator azodiisobutyronitrile (AIBN) of total monomer quality 0.1%～2%.Under agitation add in oil phase and remove ionized water, the volume fraction that makes water obtains anti-phase concentrated emulsions 80%～90%.Concentrated emulsions is poured in the mould, 50～80 ℃ of sealing polymerization 24～48h, 60～90 ℃ of drying 24～48h obtain the organic macropore template of monolithic devices;
(2) preparation of the aluminium hydrosol is predecessor with the boehmite, will add in 60～90mL deionized water behind 3～6mg boehmite porphyrize in batches, stirs 0.5～2h it is uniformly dispersed, and slowly dripping concentration in boehmite suspension is 0.5～1mol L
-1Rare nitric acid peptization, regulate pH=3～4, stir 3～7h under the room temperature, obtain Al
2O
3The hydrosol;
(3) polystyrene moulding of preparation in (1) is put into the container of sealing, in vacuum is that the aluminium hydrosol that under 0.06～0.1MPa condition (2) is prepared is pumped on the hole wall of polystyrene moulding, 60～90 ℃ of down dry 12～24h, so repeat to fill drying several times, 400～700 ℃ of preroast 3～6h, heating rate are 0.5～1 ℃/min, then 1200～1300 ℃ of roasting 2～4h, heating rate is 5～10 ℃/min, promptly obtains macroporous integral α-Al
2O
3Carrier.With macroporous integral α-Al
2O
3Put into the container of sealing, under the vacuum condition aluminium hydrosol is filled into macroporous integral α-Al
2O
3Hole wall on, 60～90 ℃ of down dry 12～24h so repeat to fill dry 2～4 times, 400～600 ℃ of roasting 2～4h, heating rate are 5～10 ℃/min, obtain coating γ-Al
2O
3, the carrier M-γ/α-Al that so obtains
2O
3Has mesopore-macropore double-hole structure.
(4) adopted the volume infusion process will be filled into mesopore-macropore monoblock type α-Al
2O
3On the carrier, impregnated in 12～24h in the precursor liquid of active component Pt and auxiliary agent Ni, freeze drying 12～24h, 300～500 ℃ of following roasting 2～4h.Wherein with Pt (NH
3)
2(NO
3)
2And Ni (NO
3)
26H
2O is that predecessor is dissolved in the precursor liquid that makes catalyst in an amount of distilled water.
In addition, this catalyst is used for comprising of hydrogen rich gas carbon monooxide oxidized purifying process: the mesopore-macropore integral catalyzer of in fixed reactor, packing into, and for the rich H that contains 0.1～2.0vol.%CO
2Gas wherein can contain N
2Deng inert gas, 0～25vol.%CO
2With 0～20vol.%H
2O normal pressure and 50～200 ℃, feeds 0.3～2.0vol.%O
2, can realize that the CO preferential oxidation purifies in the hydrogen rich gas, the volume space velocity maximum can reach 24,000h
-1, make the CO that is cleaned in the gas be converted into CO
2
It is little that catalyst provided by the invention has a volume, active high, anti-water and CO that selectivity is better and certain
2Ability can be reduced to the carbon monoxide in the hydrogen rich gas below the 10ppm, and this catalyst mechanical strength height, has dwindled the volume of carbon monoxide preferential oxidation reactor in the hydrogen rich gas effectively, is particularly suitable for vehicle-mounted and small-sized on-the-spot hydrogen supply device and uses.
Description of drawings
Fig. 1 is polystyrene monoblock type template, M-γ/α-Al
2O
3Carrier and M-Pt-Ni/Al
2O
3(1: 5) catalyst.
Fig. 2 is polystyrene monoblock type template, M-γ/α-Al
2O
3Carrier and M-Pt-Ni/Al
2O
3The SEM figure of (1: 5) catalyst.
Fig. 3 is M-γ/α-Al
2O
3The BJH pore size distribution curve figure of carrier.
The specific embodiment
Embodiment 1:
Preparation mesopore-macropore monoblock type M-Pt-Ni/Al
2O
3(1: 5) catalyst
The preparation of mesopore-macropore integral catalyzer: the preparation styrene of (1) polystyrene moulding and divinylbenzene monomer be with the NaOH solution washing of equal-volume 0.2mol/L 4 times, and be standby with equal-volume deionized water washing 4 times again.Accurately take by weighing washed styrene 6mL and divinylbenzene 1.5mL, put into the 100mL there-necked flask.To wherein adding class of 0.062g initator azodiisobutyronitrile and 0.54g surfactant department 80, stirring it is mixed.Under agitation dropwise slowly drip deionized water 33.9mL (being that the water volume fraction is 82.0%) in there-necked flask, the dropping time is controlled at 60min, forms anti-phase concentrated emulsions.After continuing to stir 30min, concentrated emulsions is moved in the mould, put into 60 ℃ of insulating box polymerization 24h.Template after the polymerization obtains the integral macropore polystyrene moulding at 60 ℃ of dry 48h.(2) preparation of the aluminium hydrosol is predecessor with the boehmite, will add in the 60mL deionized water behind the 4mg boehmite porphyrize in batches, stirs 1h it is uniformly dispersed, and slowly dripping concentration in boehmite suspension is 1mol L
-1Rare nitric acid peptization, regulate pH=3～4, stir 5h under the room temperature, obtain Al
2O
3The hydrosol.(3) polystyrene moulding of preparation in (1) is put into the container of sealing, in vacuum is under the 0.098MPa condition, the aluminium hydrosol of (2) preparation is pumped on the hole wall of polystyrene moulding, dry 12h under 60 ℃, it is inferior so to repeat to fill dry 2 (2-4), 600 ℃ of preroast 4h, heating rate is 1 ℃/min, 1300 ℃ of roasting 2h then, heating rate is 10 ℃/min, promptly obtains macroporous integral α-Al
2O
3Carrier.With macroporous integral α-Al
2O
3Put into the container of sealing, under the vacuum condition aluminium hydrosol is filled into macroporous integral α-Al
2O
3Hole wall on, 60 ℃ of following dry 12h so repeat to fill dry 2 times, 600 ℃ of roasting 2h, heating rate are 10 ℃/min, obtain coating γ-Al
2O
3, the carrier that so obtains (abbreviates M-γ/α-Al as
2O
3) have a mesopore-macropore double-hole structure.(4) adopted the volume infusion process that the precursor liquid of active component Pt and auxiliary agent Ni is filled into mesopore-macropore monoblock type α-Al
2O
3On the carrier, dipping 12h, freeze drying 12h, 300 ℃ of following roasting 2h.Prepared catalyst cartridge is written as M-Pt-Ni/Al
2O
3(1: 5).Wherein with Pt (NH
3)
2(NO
3)
2And Ni (NO
3)
26H
2O is that predecessor is dissolved in the precursor liquid that makes catalyst in an amount of distilled water.The consumption of predecessor is pressed Pt, Ni respectively in catalyst shared quality percentage composition promptly 1%, 1.5% calculate, corresponding Pt is 1: 5 with the atomic molar ratio of Ni.Dry run adopts Vacuum Freezing ﹠ Drying Technology, and vacuum is 10Pa, and condenser temperature is-50 ℃.Prepared polystyrene moulding, M-γ/α-Al
2O
3Carrier and M-Pt-Ni/Al
2O
3(1: 5) catalyst and SEM figure are respectively as Fig. 1, and be shown in Figure 2, Fig. 1 (a) polystyrene monoblock type template; (b) M-γ/α-Al
2O
3Carrier; (c) M-Pt-Ni/Al
2O
3The optical photograph of catalyst.Fig. 2 (a) polystyrene monoblock type template; (b) M-γ/α-Al
2O
3Carrier; (c, d) M-Pt-Ni/Al
2O
3SEM figure .Scale bar:50 μ m for (a, b, c) and 5 μ m for (the d mesopore-macropore monoblock type M-γ/α-Al of catalyst
2O
3The BJH pore size distribution curve figure of carrier as shown in Figure 3.
The mesopore-macropore monoblock type M-Pt-Ni/Al that adopts said method to make
2O
3(1: 5) catalyst is used for the preferential oxidation process of hydrogen rich gas CO: this is reflected in the normal pressure isothermal fixed bed continuous-flow reaction system and carries out, integral catalyzer is filled in one section high temperature resistant silicon sebific duct, fill a small amount of silica wool up and down at catalyst, connect two sections crystal reaction tubes again.Use the H of 10vol.% before the reaction
2/ N
2Gaseous mixture reduces 1h at a certain temperature, and reaction gas is formed: 1vol.%O
2, 1vol.%CO, 50vol.%H
2, N
2Balance, air speed are 16,000h
-1Establish a temperature spot since 50 ℃ per 25 ℃, to 200 ℃.Each temperature spot reaction 1 hour.Tail gas is removed water and CO through silica gel and ascarite
2, chromatographic column is the 5A molecular sieve, H
2Do carrier gas, flow rate of carrier gas is 30mLmin
-1, thermal conductance (TCD) detects, and is used for analyzing O
2, N
2And CO; The methane conversion stove is used for amplifying the signal of CO, and hydrogen flame (FID) detects, and is used for analyzing CH
4With the signal of the CO that amplifies, be 1ppm to the accuracy of detection of CO.
The result of CO preferential oxidation is as follows under these conditions: in the time of 50 ℃, and CO conversion ratio 29.42%, selectivity 100%; In the time of 75 ℃, CO conversion ratio 87.25%, selectivity 76.04%; In the time of 100 ℃～150 ℃, CO conversion ratio 100%, selectivity remains on about 57.97%; In the time of 175 ℃, CO conversion ratio 99.62%, selectivity 56.81%; In the time of 200 ℃, CO conversion ratio 96.63%, selectivity 48.13%.
Embodiment 2:
Press the catalyst preparation step of embodiment 1, preparation mesopore-macropore monoblock type M-Pt-Ni/Al
2O
3(1: 3) catalyst carries out the preferential oxidation of CO in the hydrogen rich gas with this catalyst, and the preferential oxidation condition is with embodiment 1, and its result is: in the time of 50 ℃, and CO conversion ratio 2.48%, selectivity 100%; In the time of 75 ℃, CO conversion ratio 11.29%, selectivity 81.98%; In the time of 100 ℃, CO conversion ratio 30.96%, selectivity 71.02%; In the time of 125 ℃, CO conversion ratio 88.82%, selectivity 62.95%; In the time of 150 ℃, CO conversion ratio 98.52%, selectivity 57.72%; In the time of 175 ℃, CO conversion ratio 92.81%, selectivity 48.73%; In the time of 200 ℃, CO conversion ratio 80.59%, selectivity 46.73%.
Embodiment 3:
Press the catalyst preparation step of embodiment 1, preparation mesopore-macropore monoblock type M-Pt-Ni/Al
2O
3(1: 8) catalyst carries out the preferential oxidation of CO in the hydrogen rich gas with this catalyst, and the preferential oxidation condition is with embodiment 1, and its result is: in the time of 50 ℃, and CO conversion ratio 5.15%, selectivity 100%; In the time of 75 ℃, CO conversion ratio 20.15%, selectivity 80.01%; In the time of 100 ℃, CO conversion ratio 25.15%, selectivity 62.91%; In the time of 125 ℃, CO conversion ratio 56.41%, selectivity 57.44%; In the time of 150 ℃, CO conversion ratio 83.01%, selectivity 56.02%; In the time of 175 ℃, CO conversion ratio 85.52%, selectivity 49.11%; In the time of 200 ℃, CO conversion ratio 80.18%, selectivity 42.91%.
Embodiment 4:
Press the catalyst preparation step of embodiment 1, preparation mesopore-macropore monoblock type M-Pt-Ni/Al
2O
3(1: 10) catalyst carries out the preferential oxidation of CO in the hydrogen rich gas with this catalyst, and the preferential oxidation condition is with embodiment 1, and its result is: in the time of 50 ℃, and CO conversion ratio 10.66%, selectivity 100%; In the time of 75 ℃, CO conversion ratio 17.80%, selectivity 75.02%; In the time of 100 ℃, CO conversion ratio 43.40%, selectivity 62.93%; In the time of 125 ℃, CO conversion ratio 90.51%, selectivity 58.91%; In the time of 150 ℃, CO conversion ratio 95.74%, selectivity 54.34%; In the time of 175 ℃, CO conversion ratio 95.17%, selectivity 52.06%; In the time of 200 ℃, CO conversion ratio 91.14%, selectivity 45.91%.
Embodiment 5:
Press the catalyst preparation step of embodiment 1, change the deionized water 33.9mL that adds in the step (1) into 42.5mL (being that the water volume fraction is 85.0%), the mesopore-macropore monoblock type M-Pt-Ni/Al that makes
2O
3(1: 5) catalyst carries out the preferential oxidation of CO in the hydrogen rich gas with this catalyst, and the preferential oxidation condition is with embodiment 1, and its result is: in the time of 50 ℃, and CO conversion ratio 20.03%, selectivity 100%; In the time of 75 ℃, CO conversion ratio 40.24%, selectivity 79.41%; In the time of 100 ℃, CO conversion ratio 80.99%, selectivity 61.43%; In the time of 125 ℃, CO conversion ratio 100%, selectivity 57.82%; In the time of 150 ℃, CO conversion ratio 99.63%, selectivity 53.91%; In the time of 175 ℃, CO conversion ratio 99.42%, selectivity 51.94%; In the time of 200 ℃, CO conversion ratio 90.16%, selectivity 44.98%.
Embodiment 6:
Press the catalyst preparation step of embodiment 1, change the deionized water 33.9mL that adds in the step (1) into 67.5mL (being that the water volume fraction is 90.0%), the mesopore-macropore monoblock type M-Pt-Ni/Al that makes
2O
3(1: 5) catalyst carries out the preferential oxidation of CO in the hydrogen rich gas with this catalyst, and the preferential oxidation condition is with embodiment 1, and its result is: in the time of 50 ℃, and CO conversion ratio 19.02%, selectivity 100%; In the time of 75 ℃, CO conversion ratio 56.74%, selectivity 76.63%; In the time of 100 ℃, CO conversion ratio 70.16%, selectivity 60.22%; In the time of 125 ℃, CO conversion ratio 89.61%, selectivity 55.84%; In the time of 150 ℃, CO conversion ratio 100%, selectivity 52.14%; In the time of 175 ℃, CO conversion ratio 99.32%, selectivity 50.86%; In the time of 200 ℃, CO conversion ratio 93.27%, selectivity 47.88%.
Embodiment 7:
The composition that is cleaned gas is become: 1vol.%O
2, 1vol.%CO, 50vol.%H
2, 15vol.%H
2O, 12.5vol.%CO
2, N
2Balance.Establish a temperature spot since 100 ℃ per 20 ℃, to 200 ℃.Each temperature spot reaction 1 hour.The preferential oxidation condition of other CO is with embodiment 1.Use the mesopore-macropore integral catalyzer M-Pt-Ni/Al of embodiment 1 preparation
2O
3(1: 5), CO preferential oxidation result is: in the time of 100 ℃, CO conversion ratio 48.65%, selectivity 66.05%; In the time of 120 ℃, CO conversion ratio 90.61%, selectivity 61.32%; In the time of 140 ℃, CO conversion ratio 99.95%, selectivity 51.83%; In the time of 160 ℃, CO conversion ratio 99.78%, selectivity 51.51%; In the time of 180 ℃, CO conversion ratio 99.06%, selectivity 51.30%; In the time of 200 ℃, CO conversion ratio 98.38%, selectivity 49.29%.
Claims (7)
1, a kind of mesopore-macropore integral catalyzer that is used for hydrogen-rich gas CO purification is characterized in that it comprises macroporous integral α-Al
2O
3Carrier loads on macroporous integral α-Al
2O
3Coating γ on the carrier hole wall-Al
2O
3, load on active component Pt and co-catalyst Ni on the coating.
2, according to the described catalyst of claim 1, it is characterized in that the macropore of this catalyst is of a size of 5～100 μ m, mesoporous most probable bore dia is 2.8～4.9nm on the hole wall, and the wall thickness in hole is 0.1～2.5 μ m, and Kong Yukong connects mutually, is linked to each other by the hole window.
3, according to the described catalyst of claim 1, it is characterized in that described Pt, Ni shared quality percentage composition in catalyst: the mass percent of Pt is 0.5～2%, and Pt is 1: 3～10 with the atomic molar ratio of Ni.
4, a kind of preparation method who is used for the mesopore-macropore integral catalyzer of hydrogen-rich gas CO purification is characterized in that the step that it comprises:
(1) be monomer with styrene and divinylbenzene, volume ratio=1: 3.8～4.4, adding quality is the class of surfactant department 80 of total monomer quality 2%～20%, and quality is that the initator azodiisobutyronitrile of total monomer quality 0.1%～2% evenly mixes the back and is oil phase, under agitation in oil phase, add and remove ionized water, the volume fraction that makes water obtains anti-phase concentrated emulsions 80%～90%.Concentrated emulsions is poured in the mould, 50～80 ℃ of sealing polymerization 24～48h, 60～90 ℃ of drying 24～48h obtain the organic macropore template of monolithic devices;
(2) preparation of the aluminium hydrosol is predecessor with the boehmite, will add in 60～90mL deionized water behind 3～6mg boehmite porphyrize in batches, stirs 0.5～2h it is uniformly dispersed, and slowly dripping concentration in boehmite suspension is 0.5～1mol L
-1Rare nitric acid peptization, regulate pH=3～4, stir 3～7h under the room temperature, obtain Al
2O
3The hydrosol;
(3) polystyrene moulding of preparation in the step (1) is put into the container of sealing, be pumped on the hole wall of polystyrene moulding at the aluminium hydrosol that under certain vacuum condition step (2) is prepared, 60～90 ℃ of down dry 12～24h, so repeat to fill drying several times, 400～700 ℃ of preroast 3～6h, heating rate are 0.5～1 ℃/min, then 1200～1300 ℃ of roasting 2～4h, heating rate is 5～10 ℃/min, promptly obtains macroporous integral α-Al
2O
3Carrier; With macroporous integral α-Al
2O
3Putting into the container of sealing, is under 0.06～0.1MPa condition the aluminium hydrosol to be filled into macroporous integral α-Al in vacuum
2O
3Hole wall on, 60～90 ℃ of down dry 12～24h so repeat to fill dry 2～4 times, 400～600 ℃ of roasting 2～4h, heating rate are 5～10 ℃/min, obtain coating γ-Al
2O
3, the carrier M-γ/α-Al that so obtains
2O
3Has mesopore-macropore double-hole structure;
(4) adopted the volume infusion process will be filled into mesopore-macropore monoblock type α-Al
2O
3On the carrier, impregnated in 12～24h in the precursor liquid of active component Pt and auxiliary agent Ni, freeze drying 12～24h, 300～500 ℃ of following roasting 2～4h.
5, according to the described preparation method of claim 4, the precursor liquid thing that it is characterized in that described Pt and auxiliary agent Ni is with Pt (NH
3)
2(NO
3)
2And Ni (NO
3)
26H
2O is the predecessor precursor liquid that makes soluble in water.
6, according to the described preparation method of claim 4, it is characterized in that the described freeze drying of step (4) is is 5～20Pa in vacuum, condenser temperature is freeze drying 12～24h under-55～-40 ℃ the condition.
7, a kind of application process that is used for the mesopore-macropore integral catalyzer of hydrogen-rich gas CO purification is characterized in that the step that it comprises:
The mesopore-macropore integral catalyzer of packing in fixed reactor is for the rich H that contains 0.1～2.0vol.%CO
2Gas wherein can contain N
2Deng inert gas, 0～25vol.%CO
2With 0～20vol.%H
2O normal pressure and 50～200 ℃, feeds 0.3～2.0vol.%O
2, can realize that the CO preferential oxidation purifies in the hydrogen rich gas, the volume space velocity maximum can reach 24,000h
-1, make the CO that is cleaned in the gas be converted into CO
2
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