CN105536790B - A kind of catalyst for hydrogen production from methanol-steam reforming and preparation method thereof - Google Patents
A kind of catalyst for hydrogen production from methanol-steam reforming and preparation method thereof Download PDFInfo
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- CN105536790B CN105536790B CN201510937204.2A CN201510937204A CN105536790B CN 105536790 B CN105536790 B CN 105536790B CN 201510937204 A CN201510937204 A CN 201510937204A CN 105536790 B CN105536790 B CN 105536790B
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- 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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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
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Abstract
A kind of catalyst for hydrogen production from methanol-steam reforming of the invention, by Cu and ZrO2Composition, the surface enrichment ZrO of described catalyst2, described ZrO2It is dispersed in copper component, in described catalyst, Cu molar percentage is 69.6 ~ 88.9%；Described ZrO2Molar percentage be 11.1 ~ 30.4%.Present invention also offers a kind of preparation method of above-mentioned catalyst for hydrogen production from methanol-steam reforming, first by copper nitrate solution and sodium carbonate liquor parallel-flow precipitation, then zirconyl chloride solution and sodium carbonate liquor cocurrent are continued to precipitate, produces the catalyst for hydrogen production from methanol-steam reforming.The prepared catalyst for hydrogen production from methanol-steam reforming is through H2After/He gas activations processing, high catalytic activity and stability are shown, accessory substance CO content is less than 0.3%.
Description
Technical field
The invention belongs to chemical field, is related to a kind of catalyst, specifically a kind of to be used for methanol steam reforming system
Catalyst of hydrogen and preparation method thereof.
Background technology
Fuel cell as new energy resources system, the root problem faced be reduce manufacturing cost, improve operational reliability and
Service life.Wherein, onboard hydrogen source technology moves towards one of the bottleneck in market as fuel cell.Changed using alcohols, gasoline etc.
It is that hydrogen fuel cell successfully moves towards to apply a faced key problem that stone raw material, which carries out small-scale portable hydrogen,.Methanol-water
Vapour reforming hydrogen producing is to develop faster hydrogen production process in recent years, this method compared with traditional electrolyte method, hydrocarbon steam conversion method,
Have the advantages that easy to operate, raw material is easy to get, technological process is short, reaction condition is gentle, accessory substance is few.
Mainly have for studying the catalyst that methanol steam reforming produces fuel cell hydrogen both at home and abroad at present：Noble metal
Catalyst and Cu-series catalyst, the former catalytic performance is preferable, but expensive, and the latter has preferable low temperature active and selection
Property, but less stable, poison resistance are low.Therefore, research Cu base Molecular levels, by the system for improving copper-based catalysts
Preparation Method, the different auxiliary agents of addition, and from different carrier etc. to improve its catalytic performance as universal research direction.
Although CuO/ZnO/Al2O3The application of catalyst is the most universal, but increasing researcher has found, Cu/ZrO2
Relative to CuO/ZnO/Al2O3Catalyst has more superior catalytic activity and selectivity.And copper zirconium interface interface and catalysis
The oxygen species on agent surface are the key issue of hydrogen production from methanol-steam reforming.
The content of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of for hydrogen production from methanol-steam reforming
Catalyst and preparation method thereof, the described this catalyst for hydrogen production from methanol-steam reforming and preparation method thereof solves
The ineffective technical problem of catalyst of the prior art for hydrogen production from methanol-steam reforming.
The invention provides a kind of catalyst for hydrogen production from methanol-steam reforming, by Cu and ZrO2Composition, it is described
The surface enrichment ZrO of catalyst2, described ZrO2It is dispersed in copper component, in described catalyst, Cu Mole percent
Than for 69.6~88.9%；Described ZrO2Molar percentage be 11.1~30.4%.
Further, in described catalyst, Cu molar percentage is 88.9%；Described ZrO2Moles hundred
Divide than being 11.1%.
Further, in described catalyst, Cu molar percentage is 80%；Described ZrO2Mole percent
Than for 20%.
Further, in described catalyst, Cu molar percentage is 72.7%；Described ZrO2Moles hundred
Divide than being 27.3%.
Further, in described catalyst, Cu molar percentage is 69.6%；Described ZrO2Moles hundred
Divide than being 30.4%.
Present invention also offers a kind of preparation method of above-mentioned catalyst for hydrogen production from methanol-steam reforming, including
Following steps：
1) the step of cement copper component, by 0.7~1.3mol/L Cu (NO3)2Solution and 0.4~0.6mol/L's
Na2CO3Solution cocurrent is added drop-wise to the Na equipped with 0.2mol/L2CO3In the reaction vessel of solution, 0.7 described~1.3mol/L's
Cu(NO3)2The Na of solution and 0.2mol/L2CO3The volume ratio of solution is 3~6:1, the amount of each of the droplets when control cocurrent is added dropwise
For 0.05-0.07ml, pass through 0.4~0.6mol/L of regulation Na2CO3The drop rate of solution controls suspension pH value
It is 200-300r/min that speed of agitator is controlled in the range of 7.3-7.8, during dropwise addition, 50~65 DEG C of temperature, treats copper nitrate solution
Terminate the dropwise addition of sodium carbonate liquor after being added dropwise；
2) the step of precipitation zirconium component, by 0.3~0.6mol/L zirconyl chloride solutions and with 0.4~0.6mol/L's
Na2CO3Solution cocurrent is added drop-wise in above-mentioned reaction vessel, the Cu (NO of 0.7 described~1.3mol/L3)2Solution and 0.3~
The volume ratio of 0.6mol/L zirconyl chloride solutions is 1.5~4:1, and it is 0.05-0.07ml to control the amount of each of the droplets of cocurrent,
It is 200-300r/min that speed of agitator is controlled during dropwise addition, 50~65 DEG C of temperature, passes through 0.4~0.6mol/L's of regulation
Na2CO3The drop rate of solution controls suspension pH value in the range of 9.3-9.8, in 50~65 DEG C of ageings after end to be precipitated
0.5~2h, and filter, after the filter cake use distillation water washing of gained, then by filter cake through 100~120 DEG C of bakings 5~20h, Ran Houyu
400~500 DEG C of 2~6h of roasting, produce the catalyst for hydrogen production from methanol-steam reforming.
Further, the prepared catalyst for hydrogen production from methanol-steam reforming is through H2/ He gas activations are handled.
It is well known that zirconium oxide (ZrO2) because possess acid, alkalescence and oxidation, reproducibility simultaneously, and be that p-type is partly led again
Body, hole is also easy to produce, therefore is widely used as catalyst carrier.As catalyst carrier, ZrO2With active component produce compared with
Strong interaction, not only can with the high dispersion state of stabilized copper, and between copper component exist stronger electronic action with
And cooperative effect, itself there is stronger activation capacity, therefore copper and zirconium oxide interface to methanol and hydrone in addition
To influence the key factor of catalyst.
At present, infusion process and coprecipitation method are industrially to prepare one of copper-based catalysts main method, versus dip
Method, coprecipitation method are higher and show higher activity and steady due to catalyst activity component and the mutual degree of scatter of carrier
It is qualitative.For Cu/ZrO2Catalyst, due to Cu (OH)2With Zr (OH)4KspDiffer bigger, using same in coprecipitation process
PH value (the general pH that chooses is 9-10) can cause Cu components to precipitate to form nucleus first, and then zirconium component crystal grain rapid precipitation is in zirconium
In precipitate nucleation, the aggregation of copper component is not only caused, Zr components are also difficult to form colloidal sol, so as to cause copper zirconium interface smaller.
Found by catalyst characterization, ZrO2Component not only can effectively Dissociative state methanol, and can be effective
Dissociative hydrone forms surface hydroxyl, and the surface hydroxyl can overflow to copper surface and further be formed through copper component dehydrogenation
Surface oxygen species and Cu+Species, therefore catalyst surface ZrO2Enrichment advantageously in methanol steam reforming reaction urging
Change activity.
The present invention uses step-by-step precipitation method, i.e., copper nitrate solution and sodium carbonate liquor parallel-flow precipitation is formed copper and sunk first
Form sediment, zirconyl chloride solution and sodium carbonate liquor cocurrent are then formed into zirconium colloidal sol again, in this process, zirconium colloidal sol can be effectively
Copper component is fully wrapped in, the caused aggregation in catalyst last handling process of copper component is effectively prevent, so as to increase copper zirconium
The contact interface of component, while the process contributes to ZrO2Component to the enrichment in catalyst surface, so as to play to methanol with
And the pre-activate of the reaction molecular of water, it is stable so as to further increase the activity of the methanol steam reforming of catalyst and catalysis
Property.The prepared catalyst for hydrogen production from methanol-steam reforming is through H2After/He gas activations processing, high catalysis is shown
Activity and stability, accessory substance CO content are less than 0.3%.
The present invention compares with prior art, and its technological progress is significant.One kind of the present invention is used for methanol steam weight
The catalyst of whole hydrogen manufacturing, due to using fractional precipitation, being not only effectively improved Cu/ZrO2Copper and point of zirconium component in catalyst
Divergence, and reached enrichment of the zirconium component on copper surface, and price is total to compared with the zirconates content of mantoquita costliness compared with traditional
Catalyst prepared by the precipitation method is significantly reduced, therefore the preparation expense of catalyst significantly reduces, simultaneously as ZrO2Component exists
The enrichment of catalyst surface, can effectively facilitate the pre-activate of water and methanol in catalyst surface, therefore catalyst activity and steady
It is qualitative to dramatically increase.In addition, the method for preparing catalyst is simple, industrial amplification is easily carried out.
Embodiment
The present invention is described further, it is necessary to which what is illustrated is this specific embodiment not structure below by specific embodiment
The limitation of the paired claimed scope of the invention.
Embodiment 1
A kind of catalyst for hydrogen production from methanol-steam reforming, fractional precipitation is taken to prepare, i.e. first step cement copper group
Divide, second step precipitation zirconium component, the molar percentage of contained each metallic atom calculates in catalyst, specific as follows：
Cu 88.9%
Zr 11.1%.
A kind of above-mentioned preparation method for hydrogen production from methanol-steam reforming, specifically comprises the following steps：
1) by 357mL 0.7mol/L Cu (NO3)2The Na of solution I and 0.4mol/L2CO3Cocurrent is added dropwise solution II dropwise
To the Na of the 0.2mol/L equipped with 50mL2CO3In the beaker III of solution, and it is 0.05- to control the amount of each of the droplets of cocurrent
0.07ml, by the Na for adjusting 0.5mol/L2CO3The drop rate of solution II is controlled suspension pH value in 7.3- using pH meter
It is 200-300r/min that speed of agitator is controlled in the range of 7.8, during dropwise addition, temperature 60 C, by treating that copper nitrate solution I is added dropwise
Terminate；
2) by 104mL 0.3mol/L zirconyl chloride solutions IV and 0.4mol/L Na2CO3Solution II presses condition above
Further cocurrent is added drop-wise in beaker III, by the Na for adjusting 0.4~0.6mol/L2CO3The drop rate of solution is by suspension
PH value is controlled in the range of 9.3-9.8, is aged 1h, and is filtered, and the filter cake of gained is with after distillation water washing 6-7 times, then by filter cake
Through 120 DEG C of baking 12h, 4h then is calcined in 450 DEG C, produces the catalyst A for hydrogen production from methanol-steam reforming.
The above-mentioned 0.2mol/L equipped with 50mL in beaker III Na2CO3The amount of solution is according to the stirring of mechanical agitator
Head rest is near but without impinging on bottom of the beaker and can touch 0.2mol/L Na2CO3Solution is defined.
Embodiment 2
A kind of catalyst for hydrogen production from methanol-steam reforming, fractional precipitation is taken to prepare, i.e. first step cement copper group
Divide, second step precipitation zirconium component, the molar percentage of contained each metallic atom calculates in catalyst, specific as follows：
Cu 80%
Zr 20%.
A kind of above-mentioned preparation method for hydrogen production from methanol-steam reforming, specifically comprises the following steps：
1) by 190mL 1.3mol/L Cu (NO3)2The Na of solution I and 0.6mol/L2CO3Solution II is added drop-wise to dress dropwise
There is 50mL 0.2mol/L Na2CO3In the beaker III of solution, and it is 0.05-0.07ml to control the amount of each of the droplets of cocurrent,
By the Na for adjusting 0.5mol/L2CO3The drop rate of solution II is controlled suspension pH value in 7.3-7.8 scopes using pH meter
Interior, it is 200-300r/min that speed of agitator is controlled during dropwise addition, temperature 60 C, treats copper nitrate solution I completion of dropwise addition；
2) by 104mL 0.6mol/L zirconyl chloride solutions IV and 0.6mol/L Na2CO3Solution II presses condition above
Further cocurrent is added drop-wise in beaker III, by the Na for adjusting 0.4~0.6mol/L2CO3The drop rate of solution is by suspension
PH value is controlled in the range of 9.3-9.8, is aged 1h, and is filtered, and the filter cake of gained is with after distillation water washing 6-7 times, then by filter cake
Through 120 DEG C of baking 12h, 4h then is calcined in 450 DEG C, produces the catalyst B for hydrogen production from methanol-steam reforming.
The above-mentioned 0.2mol/L equipped with 50mL in beaker III Na2CO3The amount of solution is according to the stirring of mechanical agitator
Head rest is near but without impinging on bottom of the beaker and can touch 0.2mol/L Na2CO3Solution is defined.
Embodiment 3
A kind of catalyst for hydrogen production from methanol-steam reforming, fractional precipitation is taken to prepare, i.e. first step cement copper group
Divide, second step precipitation zirconium component, the molar percentage of contained each metallic atom calculates in catalyst, specific as follows：
Cu 72.7%
Zr 27.3%.
A kind of above-mentioned preparation method for hydrogen production from methanol-steam reforming, specifically comprises the following steps：
1) by 250mL 1mol/L Cu (NO3)2The Na of solution I and 0.5mol/L2CO3Solution II is added drop-wise to is equipped with dropwise
50mL 0.2mol/L Na2CO3In the beaker III of solution, and it is 0.05-0.07ml to control the amount of each of the droplets of cocurrent, is led to
Overregulate 0.5mol/L Na2CO3The drop rate of solution II is controlled suspension pH value in the range of 7.3-7.8 using pH meter,
It is 200-300r/min that speed of agitator is controlled during dropwise addition, temperature 60 C, treats copper nitrate solution I completion of dropwise addition；
2) by 234mL 0.4mol/L zirconyl chloride solutions IV and 0.5mol/L Na2CO3Solution II presses condition above
Further cocurrent is added drop-wise in beaker III, by the Na for adjusting 0.4~0.6mol/L2CO3The drop rate of solution is by suspension
PH value is controlled in the range of 9.3-9.8, is aged 1h, and is filtered, and the filter cake of gained is with after distillation water washing 6-7 times, then by filter cake
Through 120 DEG C of baking 12h, 4h then is calcined in 450 DEG C, produces the catalyst C for hydrogen production from methanol-steam reforming.
The above-mentioned 0.2mol/L equipped with 50mL in beaker III Na2CO3The amount of solution is according to the stirring of mechanical agitator
Head rest is near but without impinging on bottom of the beaker and can touch 0.2mol/L Na2CO3Solution is defined.
Embodiment 4
A kind of catalyst for hydrogen production from methanol-steam reforming, fractional precipitation is taken to prepare, i.e. first step cement copper group
Divide, second step precipitation zirconium component, the molar percentage of contained each metallic atom calculates in catalyst, specific as follows：
Cu 69.6%
Zr 30.4%.
A kind of above-mentioned preparation method for hydrogen production from methanol-steam reforming, specifically comprises the following steps：
1) by 250mL 1mol/L Cu (NO3)2The Na of solution I and 0.5mol/L2CO3Solution II is added drop-wise to is equipped with dropwise
50mL 0.2mol/L Na2CO3In the beaker III of solution, and it is 0.05-0.07ml to control the amount of each of the droplets of cocurrent, is led to
Overregulate 0.5mol/L Na2CO3The drop rate of solution II is controlled suspension pH value in the range of 7.3-7.8 using pH meter,
It is 200-300r/min that speed of agitator is controlled during dropwise addition, temperature 60 C, treats copper nitrate solution I completion of dropwise addition；
2) by 274mL 0.4mol/L zirconyl chloride solutions IV and 0.5mol/L Na2CO3Solution II presses condition above
Further cocurrent is added drop-wise in beaker III, by the Na for adjusting 0.4~0.6mol/L2CO3The drop rate of solution is by suspension
PH value is controlled in the range of 9.3-9.8, is aged 1h, and is filtered, and the filter cake of gained is with after distillation water washing 6-7 times, then by filter cake
Through 120 DEG C of baking 12h, 4h then is calcined in 450 DEG C, produces the catalyst D for hydrogen production from methanol-steam reforming.
The above-mentioned 0.2mol/L equipped with 50mL in beaker III Na2CO3The amount of solution is according to the stirring of mechanical agitator
Head rest is near but without impinging on bottom of the beaker and can touch 0.2mol/L Na2CO3Solution is defined.
Embodiment 5
Above-described embodiment 1 gained for the catalyst A tablettings of hydrogen production from methanol-steam reforming and is crushed to 40-60 mesh
It is standby.
Active testing for the catalyst A of hydrogen production from methanol-steam reforming is carried out in quartz ampoule fixed bed reactors,
By 0.3g be used for hydrogen production from methanol-steam reforming catalyst A (40-60 mesh) with etc. quality quartz sand mix after fixed to instead
Should pipe interlude, 5%H2/N2Gaseous mixture (flow 80mL/min) is passed through reactor, 2 DEG C/min temperature programmings to 250 DEG C of reduction
Activated catalyst 8h, reacting furnace temperature is then dropped into setting reaction temperature, switching nitrogen (flow 30mL/min), nitrogen stream will
The mixed liquor of water and methanol introduces reaction system and starts to react reactions in the stable 2h post-samplings analysis of setting reaction temperature, reaction
Pipe comes out after gas first passes through condenser cooling and detected by thermal conductivity detector (TCD) (TCD), with work stand control sampling process and carries out
Data processing
Reaction condition：H2O/CH3OH=1.1/1 (mol ratio)；WHSV=4.8ml.gcat-1h-1T=230 DEG C；P=
0.1MPa
Embodiment 6
Above-described embodiment 2 gained for the catalyst B tablettings of hydrogen production from methanol-steam reforming and is crushed to 40-60 mesh
It is standby.
Active testing for the catalyst A of hydrogen production from methanol-steam reforming is carried out in quartz ampoule fixed bed reactors,
By 0.3g be used for hydrogen production from methanol-steam reforming catalyst B (40-60 mesh) with etc. quality quartz sand mix after fixed to instead
Should pipe interlude, 5%H2/N2Gaseous mixture (flow 80mL/min) is passed through reactor, 2 DEG C/min temperature programmings to 250 DEG C of reduction
Activated catalyst 8h, reacting furnace temperature is then dropped into setting reaction temperature, switching nitrogen (flow 30mL/min), nitrogen stream will
The mixed liquor of water and methanol introduces reaction system and starts to react reactions in the stable 2h post-samplings analysis of setting reaction temperature, reaction
Pipe comes out after gas first passes through condenser cooling and detected by thermal conductivity detector (TCD) (TCD), with work stand control sampling process and carries out
Data processing
Reaction condition：H2O/CH3OH=1.1/1 (mol ratio)；WHSV=4.8ml.gcat-1h-1；T=230 DEG C；P=
0.1MPa
Embodiment 7
Above-described embodiment 3 gained for the catalyst C tablettings of hydrogen production from methanol-steam reforming and is crushed to 40-60 mesh
It is standby.
Active testing for the catalyst C of hydrogen production from methanol-steam reforming is carried out in quartz ampoule fixed bed reactors,
By 0.3g be used for hydrogen production from methanol-steam reforming catalyst C (40-60 mesh) with etc. quality quartz sand mix after fixed to instead
Should pipe interlude, 5%H2/N2Gaseous mixture (flow 80mL/min) is passed through reactor, 2 DEG C/min temperature programmings to 250 DEG C of reduction
Activated catalyst 8h, reacting furnace temperature is then dropped into setting reaction temperature, switching nitrogen (flow 30mL/min), nitrogen stream will
The mixed liquor of water and methanol introduces reaction system and starts to react reactions in the stable 2h post-samplings analysis of setting reaction temperature, reaction
Pipe comes out after gas first passes through condenser cooling and detected by thermal conductivity detector (TCD) (TCD), with work stand control sampling process and carries out
Data processing
Reaction condition：H2O/CH3OH=1.1/1 (mol ratio)；WHSV=4.8ml.gcat-1h-1；T=230 DEG C；P=
0.1MPa
Embodiment 8
Above-described embodiment 4 gained for the catalyst D tablettings of hydrogen production from methanol-steam reforming and is crushed to 40-60 mesh
It is standby.
Active testing for the catalyst D of hydrogen production from methanol-steam reforming is carried out in quartz ampoule fixed bed reactors,
By 0.3g be used for hydrogen production from methanol-steam reforming catalyst C (40-60 mesh) with etc. quality quartz sand mix after fixed to instead
Should pipe interlude, 5%H2/N2Gaseous mixture (flow 80mL/min) is passed through reactor, 2 DEG C/min temperature programmings to 250 DEG C of reduction
Activated catalyst 8h, reacting furnace temperature is then dropped into setting reaction temperature, switching nitrogen (flow 30mL/min), nitrogen stream will
The mixed liquor of water and methanol introduces reaction system and starts to react reactions in the stable 2h post-samplings analysis of setting reaction temperature, reaction
Pipe comes out after gas first passes through condenser cooling and detected by thermal conductivity detector (TCD) (TCD), with work stand control sampling process and carries out
Data processing
Reaction condition：H2O/CH3OH=1.1/1 (mol ratio)；WHSV=4.8ml.gcat-1h-1；T=230 DEG C；P=
0.1MPa
Embodiment 9
The activity with Application Example 3 is used to comment the catalyst C for indoor HCHO catalysis oxidations of the gained of embodiment 3
Valency method, and keep reaction temperature constant, the conversion ratio and H of the methanol of its corresponding different time2Generating rate see the table below：
Reaction condition：H2O/CH3OH=1.1/1 (mol ratio)；WHSV=4.8ml.gcat-1h-1；T=230 DEG C；P=
0.1MPa
The Cu/ZrO prepared by being distributed precipitation can be drawn by result above2Catalyst activity is high, and CO contents are low, most preferably
Catalyst ratio C methanol conversions can reach 92%, CO contents and only account for 0.25%, and catalyst was by 24 hours continuous fortune
Turn to reduce without discovery activity.
In summary, step-by-step precipitation method prepares Cu/ZrO2 catalyst and hydrogen production from methanol-steam reforming is shown to compare
Excellent catalytic activity.The catalyst reaction mild condition, there is higher reactivity, and accessory substance CO contents are less.
By literature search, similar catalyst system and catalyzing was not met to report, belonged to innovative works.
Above said content is only the basic explanation under present inventive concept, and is appointed according to what technical scheme was made
What equivalent transformation, all should belong to protection scope of the present invention.
Claims (5)
1. the preparation method of a kind of catalyst for hydrogen production from methanol-steam reforming, it is characterised in that comprise the following steps：
1）The step of one cement copper component, by 0.7 ~ 1.3 mol/L Cu (NO3)2Solution and 0.4 ~ 0.6 mol/L's
Na2CO3Solution cocurrent is added drop-wise to the Na equipped with 0.2mol/L2CO3In the reaction vessel of solution, 0.7 ~ 1.3 described mol/L
Cu (NO3)2The Na of solution and 0.2mol/L2CO3The volume ratio of solution is 3 ~ 6:1, the amount of each of the droplets when control cocurrent is added dropwise
For 0.05-0.07 ml, pass through 0.4 ~ 0.6mol/L of regulation Na2CO3The drop rate of solution controls suspension pH value
It is 200-300r/min that speed of agitator is controlled in the range of 7.3-7.8, during dropwise addition, 50 ~ 65 DEG C of temperature, treats that copper nitrate solution drips
Terminate the dropwise addition of sodium carbonate liquor after adding；
2）The step of one precipitation zirconium component, by 0.3 ~ 0.6 mol/L zirconyl chloride solutions and Na with 0.4 ~ 0.6mol/L2CO3
Solution cocurrent is added drop-wise in above-mentioned reaction vessel, the Cu (NO of 0.7 ~ 1.3 described mol/L3)2Solution and 0.3 ~ 0.6
The volume ratio of mol/L zirconyl chloride solutions is 1.5 ~ 4:1, and it is 0.05-0.07 ml to control the amount of each of the droplets of cocurrent, drop
It is 200-300r/min that speed of agitator is controlled during adding, and 50 ~ 65 DEG C of temperature, passes through 0.4 ~ 0.6mol/L of regulation Na2CO3It is molten
The drop rate of liquid controls suspension pH value in the range of 9.3-9.8, and 0.5 ~ 2h is aged at 50 ~ 65 DEG C after end to be precipitated,
And filter, after the filter cake use distillation water washing of gained, then by filter cake through 100 ~ 120 DEG C of 5 ~ 20h of baking, then in 400 ~ 500 DEG C of roastings
2 ~ 6h is burnt, produces the catalyst for hydrogen production from methanol-steam reforming；The described catalysis for hydrogen production from methanol-steam reforming
Agent is made up of Cu and ZrO2, and the surface enrichment ZrO2 of described catalyst, described ZrO2 is dispersed in copper component, described
In catalyst, Cu molar percentage is 69.6 ~ 88.9%；Described ZrO2Molar percentage be 11.1 ~ 30.4%；It is prepared
The catalyst for hydrogen production from methanol-steam reforming through H2/ He gas activations are handled.
2. a kind of preparation method of catalyst for hydrogen production from methanol-steam reforming as claimed in claim 1, its feature exist
In：In described catalyst, Cu molar percentage is 88.9%；Described ZrO2 molar percentage is 11.1%.
3. a kind of preparation method of catalyst for hydrogen production from methanol-steam reforming as claimed in claim 1, its feature exist
In：In described catalyst, Cu molar percentage is 80%；Described ZrO2Molar percentage be 20%.
4. a kind of preparation method of catalyst for hydrogen production from methanol-steam reforming as claimed in claim 1, its feature exist
In：In described catalyst, Cu molar percentage is 72.7%；Described ZrO2Molar percentage be 27.3%.
5. a kind of preparation method of catalyst for hydrogen production from methanol-steam reforming as claimed in claim 1, its feature exist
In：In described catalyst, Cu molar percentage is 69.6%；Described ZrO2Molar percentage be 30.4%.
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| CN101474563A (en) * | 2009-01-13 | 2009-07-08 | 上海应用技术学院 | Preparation method of catalyst for hydrogen production from methanol-steam reforming |
| CN103566941A (en) * | 2013-02-04 | 2014-02-12 | 中国科学院大连化学物理研究所 | Methanol steam catalytic reforming hydrogen production catalyst and preparation method thereof |
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| US474357A (en) * | 1892-05-10 | Refrigerator | ||
| CN1772378A (en) * | 2005-11-03 | 2006-05-17 | 复旦大学 | Cu-Zr catalyst for steam reforming of methanol to prepare hydrogen and its prepn |
| CN101474563A (en) * | 2009-01-13 | 2009-07-08 | 上海应用技术学院 | Preparation method of catalyst for hydrogen production from methanol-steam reforming |
| CN103566941A (en) * | 2013-02-04 | 2014-02-12 | 中国科学院大连化学物理研究所 | Methanol steam catalytic reforming hydrogen production catalyst and preparation method thereof |
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