CN105536790A - Catalyst for hydrogen production from steam reforming of methanol and preparation method thereof - Google Patents
Catalyst for hydrogen production from steam reforming of methanol and preparation method thereof Download PDFInfo
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- CN105536790A CN105536790A CN201510937204.2A CN201510937204A CN105536790A CN 105536790 A CN105536790 A CN 105536790A CN 201510937204 A CN201510937204 A CN 201510937204A CN 105536790 A CN105536790 A CN 105536790A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/03—Precipitation; Co-precipitation
- B01J37/031—Precipitation
- B01J37/033—Using Hydrolysis
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
- C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
- C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
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Abstract
The invention discloses a catalyst for hydrogen production from steam reforming of methanol. The catalyst is composed of Cu and ZrO2. ZrO2 is enriched on surface of the catalyst and dispersed in a copper component, wherein the mole percentage of Cu is 69.6-88.9%; the mole percentage of ZrO2 is 11.1-30.4%. The invention also provides a preparation method of the catalyst for hydrogen production from steam reforming of methanol. A cupric nitrate solution and a sodium carbonate solution are parallelly and dropwise added for precipitation, a zirconium oxychloride solution and a sodium carbonate solution are parallelly and dropwise added for precipitation, and the catalyst for hydrogen production from steam reforming of methanol is obtained. After the prepared catalyst for hydrogen production from steam reforming of methanol is activated by H2/He gas, high catalytic activity and stability of the catalyst are shown, and the content of by-product CO is lower than 0.3%.
Description
Technical field
The invention belongs to chemical field, relate to a kind of catalyst, specifically a kind of Catalysts and its preparation method for hydrogen production from methanol-steam reforming.
Background technology
Fuel cell is as new energy resources system, and the root problem faced reduces manufacturing cost, improves operational reliability and service life.Wherein, onboard hydrogen source technology has become one of fuel cell bottleneck moving towards market.Utilizing the fossil feedstock such as alcohols, gasoline to carry out portable hydrogen is on a small scale that hydrogen fuel cell successfully moves towards to apply the key problem faced.Hydrogen production from methanol-steam reforming is development in recent years hydrogen production process faster, and the method, compared with traditional electrical solution, hydrocarbon steam conversion method, has the advantages such as easy to operate, raw material is easy to get, technological process is short, reaction condition is gentle, accessory substance is few.
The domestic and international catalyst producing fuel cell hydrogen for studying methanol steam reforming mainly contains at present: noble metal catalyst and Cu-series catalyst, the former catalytic performance is better, but expensive, and the latter has good low temperature active and selective, but less stable, poison resistance is low.For this reason, research Cu catalyst based structure-activity relationship, by improve copper-based catalysts preparation method, add different auxiliary agent, and select different carrier etc. to be general research direction to improve its catalytic performance.
Although CuO/ZnO/Al
2o
3the application of catalyst is the most general, but increasing researcher finds, Cu/ZrO
2relative to CuO/ZnO/Al
2o
3catalyst has more superior catalytic activity and selective.And the oxygenate kind of interface, copper zirconium interface and catalyst surface is the key issue of hydrogen production from methanol-steam reforming.
Summary of the invention
For above-mentioned technical problem of the prior art, the invention provides a kind of Catalysts and its preparation method for hydrogen production from methanol-steam reforming, the described this Catalysts and its preparation method for hydrogen production from methanol-steam reforming solves the technical problem of the catalyst poor effect for hydrogen production from methanol-steam reforming of the prior art.
The invention provides a kind of catalyst for hydrogen production from methanol-steam reforming, by Cu and ZrO
2composition, the surface enrichment ZrO of described catalyst
2, described ZrO
2be dispersed in copper component, in described catalyst, the molar percentage of Cu is 69.6 ~ 88.9%; Described ZrO
2molar percentage be 11.1 ~ 30.4%.
Further, in described catalyst, the molar percentage of Cu is 88.9%; Described ZrO
2molar percentage be 11.1%.
Further, in described catalyst, the molar percentage of Cu is 80%; Described ZrO
2molar percentage be 20%.
Further, in described catalyst, the molar percentage of Cu is 72.7%; Described ZrO
2molar percentage be 27.3%.
Further, in described catalyst, the molar percentage of Cu is 69.6%; Described ZrO
2molar percentage be 30.4%.
Present invention also offers the preparation method of above-mentioned a kind of catalyst for hydrogen production from methanol-steam reforming, comprise the steps:
1) step of a cement copper component, by the Cu (NO of 0.7 ~ 1.3mol/L
3)
2the Na of solution and 0.4 ~ 0.6mol/L
2cO
3solution drip is added to the Na that 0.2mol/L is housed
2cO
3in the reaction vessel of solution, the Cu (NO of 0.7 described ~ 1.3mol/L
3)
2the Na of solution and 0.2mol/L
2cO
3the volume ratio of solution is 3 ~ 6:1, and controlling the amount that also drip added-time every dropping liquid drips is 0.05-0.07ml, by regulating the Na of 0.4 ~ 0.6mol/L
2cO
3suspension pH value controls within the scope of 7.3-7.8 by the drop rate of solution, and controlling speed of agitator in dropping process is 200-300r/min, and temperature 50 ~ 65 DEG C, terminates the dropping of sodium carbonate liquor after copper nitrate solution dropwises;
2) step of a precipitation zirconium component, by 0.3 ~ 0.6mol/L zirconyl chloride solution and the Na with 0.4 ~ 0.6mol/L
2cO
3solution drip is added in above-mentioned reaction vessel, the Cu (NO of 0.7 described ~ 1.3mol/L
3)
2the volume ratio of solution and 0.3 ~ 0.6mol/L zirconyl chloride solution is 1.5 ~ 4:1, and to control and the amount that the every dropping liquid flowed drips is 0.05-0.07ml, controlling speed of agitator in dropping process is 200-300r/min, temperature 50 ~ 65 DEG C, by regulating the Na of 0.4 ~ 0.6mol/L
2cO
3suspension pH value controls within the scope of 9.3-9.8 by the drop rate of solution, at 50 ~ 65 DEG C of ageing 0.5 ~ 2h after end to be precipitated, and suction filtration, the filter cake of gained is with after distilled water washing, again filter cake is dried 5 ~ 20h through 100 ~ 120 DEG C, then in 400 ~ 500 DEG C of roasting 2 ~ 6h, the catalyst for hydrogen production from methanol-steam reforming is obtained.
Further, the prepared catalyst for hydrogen production from methanol-steam reforming is through H
2/ He gas activation process.
As everyone knows, zirconia (ZrO
2) because have acid, alkalescence simultaneously and be oxidized, reproducibility, and be again P-type semiconductor, easily produce hole, be therefore widely used as catalyst carrier.As catalyst carrier, ZrO
2stronger interaction is produced with active component, not only can the high dispersion state of stabilized copper, and and copper component between there is stronger electronic action and cooperative effect, itself has stronger activation capacity to methyl alcohol and hydrone in addition, and therefore copper and zirconia interface are the key factor affecting catalyst.
At present, infusion process and coprecipitation method are industrially prepare one of copper-based catalysts main method, versus dip method, coprecipitation method due to catalyst activity component and the mutual degree of scatter of carrier higher and present higher activity and stability.For Cu/ZrO
2catalyst, due to Cu (OH)
2with Zr (OH)
4k
spdiffer larger, adopt same pH value (generally choosing pH is 9-10) that Cu component can be caused first to precipitate formation nucleus in coprecipitation process, then zirconium component crystal grain rapid precipitation is in zirconium precipitate nucleation, not only cause the gathering of copper component, Zr component is also difficult forms colloidal sol, thus causes copper zirconium interface smaller.
Found by catalyst characterization, ZrO
2component not only can Dissociative state methyl alcohol effectively, and efficient solution can form surface hydroxyl from adsorbed water molecule, and this surface hydroxyl can overflow to copper surface and form surface oxygen species and Cu through the dehydrogenation of copper component further
+species, therefore catalyst surface ZrO
2enrichment advantageously in methanol steam reforming reaction catalytic activity.
The present invention adopts step-by-step precipitation method, namely first by copper nitrate solution and sodium carbonate liquor parallel-flow precipitation, formation copper precipitates, and then by zirconyl chloride solution and sodium carbonate liquor also stream formation zirconium colloidal sol, in this process, zirconium colloidal sol can fully be wrapped in copper component effectively, effectively prevent the gathering that copper component produces in catalyst last handling process, thus increasing the contact interface of copper zirconium component, this process helps is in ZrO simultaneously
2component to the enrichment at catalyst surface, thus plays the pre-activate of the reaction molecular to methyl alcohol and water, thus further increases activity and the catalytic stability of the methanol steam reforming of catalyst.The prepared catalyst for hydrogen production from methanol-steam reforming is through H
2after/He gas activation process, show high catalytic activity and stability, the content of accessory substance CO is lower than 0.3%.
The present invention compares with prior art, and its technological progress is significant.A kind of catalyst for hydrogen production from methanol-steam reforming of the present invention, owing to adopting fractional precipitation, not only improves Cu/ZrO effectively
2the decentralization of copper and zirconium component in catalyst, and reach the enrichment of zirconium component on copper surface, and the catalyst that price is prepared compared with traditional coprecipitation compared with the zirconates content of mantoquita costliness also significantly reduces, and therefore the preparation expense of catalyst significantly reduces, meanwhile, due to ZrO
2component is in the enrichment of catalyst surface, and effectively can promote that water and methyl alcohol are in the pre-activate of catalyst surface, therefore catalyst activity and stability all significantly increase.In addition, this method for preparing catalyst is simple, easily carries out industry and amplifies.
Detailed description of the invention
Below by specific embodiment, the present invention is described further, it should be noted that this specific embodiment does not form the restriction to application claims protection domain.
Embodiment 1
For a catalyst for hydrogen production from methanol-steam reforming, take fractional precipitation to prepare, i.e. first step cement copper component, second step precipitation zirconium component, the molar percentage of each metallic atom contained in catalyst calculates, specific as follows:
Cu88.9％
Zr11.1％。
Above-mentioned a kind of preparation method for hydrogen production from methanol-steam reforming, specifically comprises the steps:
1) by the Cu (NO of the 0.7mol/L of 357mL
3)
2the Na of solution I and 0.4mol/L
2cO
3solution II dropwise and drip is added to the Na of the 0.2mol/L that 50mL is housed
2cO
3in the beaker III of solution, and to control and the amount that the every dropping liquid flowed drips is 0.05-0.07ml, by regulating the Na of 0.5mol/L
2cO
3the drop rate of solution II adopts pH meter to control within the scope of 7.3-7.8 by suspension pH value, and controlling speed of agitator in dropping process is 200-300r/min, temperature 60 C, terminates by treating that copper nitrate solution I drips;
2) by the Na of 0.3mol/L zirconyl chloride solution IV and 0.4mol/L of 104mL
2cO
3solution II is added in beaker III, by regulating the Na of 0.4 ~ 0.6mol/L by the further also drip of condition above
2cO
3suspension pH value controls within the scope of 9.3-9.8 by the drop rate of solution, ageing 1h, and suction filtration, the filter cake of gained is with after distilled water washing 6-7 time, again filter cake is dried 12h through 120 DEG C, then in 450 DEG C of roasting 4h, obtain the catalyst A for hydrogen production from methanol-steam reforming.
The above-mentioned Na that the 0.2mol/L of 50mL is housed in beaker III
2cO
3the amount of solution according to the stirring-head of mechanical agitator near but not encounter at the bottom of beaker and the Na of 0.2mol/L can be touched
2cO
3solution is as the criterion.
Embodiment 2
For a catalyst for hydrogen production from methanol-steam reforming, take fractional precipitation to prepare, i.e. first step cement copper component, second step precipitation zirconium component, the molar percentage of each metallic atom contained in catalyst calculates, specific as follows:
Cu80％
Zr20％。
Above-mentioned a kind of preparation method for hydrogen production from methanol-steam reforming, specifically comprises the steps:
1) by the Cu (NO of the 1.3mol/L of 190mL
3)
2the Na of solution I and 0.6mol/L
2cO
3solution II is dropwise added drop-wise to the Na of the 0.2mol/L that 50mL is housed
2cO
3in the beaker III of solution, and to control and the amount that the every dropping liquid flowed drips is 0.05-0.07ml, by regulating the Na of 0.5mol/L
2cO
3the drop rate of solution II adopts pH meter to control within the scope of 7.3-7.8 by suspension pH value, and controlling speed of agitator in dropping process is 200-300r/min, temperature 60 C, treats that copper nitrate solution I drips and terminates;
2) by the Na of 0.6mol/L zirconyl chloride solution IV and 0.6mol/L of 104mL
2cO
3solution II is added in beaker III, by regulating the Na of 0.4 ~ 0.6mol/L by the further also drip of condition above
2cO
3suspension pH value controls within the scope of 9.3-9.8 by the drop rate of solution, ageing 1h, and suction filtration, the filter cake of gained is with after distilled water washing 6-7 time, again filter cake is dried 12h through 120 DEG C, then in 450 DEG C of roasting 4h, obtain the catalyst B for hydrogen production from methanol-steam reforming.
The above-mentioned Na that the 0.2mol/L of 50mL is housed in beaker III
2cO
3the amount of solution according to the stirring-head of mechanical agitator near but not encounter at the bottom of beaker and the Na of 0.2mol/L can be touched
2cO
3solution is as the criterion.
Embodiment 3
For a catalyst for hydrogen production from methanol-steam reforming, take fractional precipitation to prepare, i.e. first step cement copper component, second step precipitation zirconium component, the molar percentage of each metallic atom contained in catalyst calculates, specific as follows:
Cu72.7％
Zr27.3％。
Above-mentioned a kind of preparation method for hydrogen production from methanol-steam reforming, specifically comprises the steps:
1) by the Cu (NO of the 1mol/L of 250mL
3)
2the Na of solution I and 0.5mol/L
2cO
3solution II is dropwise added drop-wise to the Na of the 0.2mol/L that 50mL is housed
2cO
3in the beaker III of solution, and to control and the amount that the every dropping liquid flowed drips is 0.05-0.07ml, by regulating the Na of 0.5mol/L
2cO
3the drop rate of solution II adopts pH meter to control within the scope of 7.3-7.8 by suspension pH value, and controlling speed of agitator in dropping process is 200-300r/min, temperature 60 C, treats that copper nitrate solution I drips and terminates;
2) by the Na of 0.4mol/L zirconyl chloride solution IV and 0.5mol/L of 234mL
2cO
3solution II is added in beaker III, by regulating the Na of 0.4 ~ 0.6mol/L by the further also drip of condition above
2cO
3suspension pH value controls within the scope of 9.3-9.8 by the drop rate of solution, ageing 1h, and suction filtration, the filter cake of gained is with after distilled water washing 6-7 time, again filter cake is dried 12h through 120 DEG C, then in 450 DEG C of roasting 4h, obtain the catalyst C for hydrogen production from methanol-steam reforming.
The above-mentioned Na that the 0.2mol/L of 50mL is housed in beaker III
2cO
3the amount of solution according to the stirring-head of mechanical agitator near but not encounter at the bottom of beaker and the Na of 0.2mol/L can be touched
2cO
3solution is as the criterion.
Embodiment 4
For a catalyst for hydrogen production from methanol-steam reforming, take fractional precipitation to prepare, i.e. first step cement copper component, second step precipitation zirconium component, the molar percentage of each metallic atom contained in catalyst calculates, specific as follows:
Cu69.6％
Zr30.4％。
Above-mentioned a kind of preparation method for hydrogen production from methanol-steam reforming, specifically comprises the steps:
1) by the Cu (NO of the 1mol/L of 250mL
3)
2the Na of solution I and 0.5mol/L
2cO
3solution II is dropwise added drop-wise to the Na of the 0.2mol/L that 50mL is housed
2cO
3in the beaker III of solution, and to control and the amount that the every dropping liquid flowed drips is 0.05-0.07ml, by regulating the Na of 0.5mol/L
2cO
3the drop rate of solution II adopts pH meter to control within the scope of 7.3-7.8 by suspension pH value, and controlling speed of agitator in dropping process is 200-300r/min, temperature 60 C, treats that copper nitrate solution I drips and terminates;
2) by the Na of 0.4mol/L zirconyl chloride solution IV and 0.5mol/L of 274mL
2cO
3solution II is added in beaker III, by regulating the Na of 0.4 ~ 0.6mol/L by the further also drip of condition above
2cO
3suspension pH value controls within the scope of 9.3-9.8 by the drop rate of solution, ageing 1h, and suction filtration, the filter cake of gained is with after distilled water washing 6-7 time, again filter cake is dried 12h through 120 DEG C, then in 450 DEG C of roasting 4h, obtain the catalyst D for hydrogen production from methanol-steam reforming.
The above-mentioned Na that the 0.2mol/L of 50mL is housed in beaker III
2cO
3the amount of solution according to the stirring-head of mechanical agitator near but not encounter at the bottom of beaker and the Na of 0.2mol/L can be touched
2cO
3solution is as the criterion.
Embodiment 5
By the catalyst A compressing tablet being used for hydrogen production from methanol-steam reforming of above-described embodiment 1 gained and to be crushed to 40-60 order for subsequent use.
Active testing for the catalyst A of hydrogen production from methanol-steam reforming carries out in quartz ampoule fixed bed reactors, the catalyst A (40-60 order) 0.3g being used for hydrogen production from methanol-steam reforming with etc. the quartz sand of quality mix after be fixed to the interlude of reaction tube, 5%H
2/ N
2gaseous mixture (flow 80mL/min) passes into reactor, 2 DEG C/min temperature programming to 250 DEG C reduction activation catalyst 8h, then reacting furnace temperature is dropped to setting reaction temperature, switch nitrogen (flow 30mL/min), the mixed liquor introducing reaction system of water and methyl alcohol is started reaction by nitrogen stream. and react and stablize the analysis of 2h post-sampling in setting reaction temperature, reaction tube out gas is first detected by thermal conductivity detector (TCD) (TCD) after condenser cooling, controls sampling process and carry out data processing with work station.
Reaction condition: H
2o/CH
3oH=1.1/1 (mol ratio); WHSV=4.8ml.gcat
-1h
-1t=230 DEG C; P=0.1MPa
Embodiment 6
By the catalyst B compressing tablet being used for hydrogen production from methanol-steam reforming of above-described embodiment 2 gained and to be crushed to 40-60 order for subsequent use.
Active testing for the catalyst A of hydrogen production from methanol-steam reforming carries out in quartz ampoule fixed bed reactors, the catalyst B (40-60 order) 0.3g being used for hydrogen production from methanol-steam reforming with etc. the quartz sand of quality mix after be fixed to the interlude of reaction tube, 5%H
2/ N
2gaseous mixture (flow 80mL/min) passes into reactor, 2 DEG C/min temperature programming to 250 DEG C reduction activation catalyst 8h, then reacting furnace temperature is dropped to setting reaction temperature, switch nitrogen (flow 30mL/min), the mixed liquor introducing reaction system of water and methyl alcohol is started reaction by nitrogen stream. and react and stablize the analysis of 2h post-sampling in setting reaction temperature, reaction tube out gas is first detected by thermal conductivity detector (TCD) (TCD) after condenser cooling, controls sampling process and carry out data processing with work station.
Reaction condition: H
2o/CH
3oH=1.1/1 (mol ratio); WHSV=4.8ml.gcat
-1h
-1; T=230 DEG C; P=0.1MPa
Embodiment 7
By the catalyst C compressing tablet being used for hydrogen production from methanol-steam reforming of above-described embodiment 3 gained and to be crushed to 40-60 order for subsequent use.
Active testing for the catalyst C of hydrogen production from methanol-steam reforming carries out in quartz ampoule fixed bed reactors, the catalyst C (40-60 order) 0.3g being used for hydrogen production from methanol-steam reforming with etc. the quartz sand of quality mix after be fixed to the interlude of reaction tube, 5%H
2/ N
2gaseous mixture (flow 80mL/min) passes into reactor, 2 DEG C/min temperature programming to 250 DEG C reduction activation catalyst 8h, then reacting furnace temperature is dropped to setting reaction temperature, switch nitrogen (flow 30mL/min), the mixed liquor introducing reaction system of water and methyl alcohol is started reaction by nitrogen stream. and react and stablize the analysis of 2h post-sampling in setting reaction temperature, reaction tube out gas is first detected by thermal conductivity detector (TCD) (TCD) after condenser cooling, controls sampling process and carry out data processing with work station.
Reaction condition: H
2o/CH
3oH=1.1/1 (mol ratio); WHSV=4.8ml.gcat
-1h
-1; T=230 DEG C; P=0.1MPa
Embodiment 8
By the catalyst D compressing tablet being used for hydrogen production from methanol-steam reforming of above-described embodiment 4 gained and to be crushed to 40-60 order for subsequent use.
Active testing for the catalyst D of hydrogen production from methanol-steam reforming carries out in quartz ampoule fixed bed reactors, the catalyst C (40-60 order) 0.3g being used for hydrogen production from methanol-steam reforming with etc. the quartz sand of quality mix after be fixed to the interlude of reaction tube, 5%H
2/ N
2gaseous mixture (flow 80mL/min) passes into reactor, 2 DEG C/min temperature programming to 250 DEG C reduction activation catalyst 8h, then reacting furnace temperature is dropped to setting reaction temperature, switch nitrogen (flow 30mL/min), the mixed liquor introducing reaction system of water and methyl alcohol is started reaction by nitrogen stream. and react and stablize the analysis of 2h post-sampling in setting reaction temperature, reaction tube out gas is first detected by thermal conductivity detector (TCD) (TCD) after condenser cooling, controls sampling process and carry out data processing with work station.
Reaction condition: H
2o/CH
3oH=1.1/1 (mol ratio); WHSV=4.8ml.gcat
-1h
-1; T=230 DEG C; P=0.1MPa
Embodiment 9
The catalyst C being used for indoor HCHO catalytic oxidation of embodiment 3 gained is adopted the activity rating method with Application Example 3, and keeps reaction temperature constant, the conversion ratio of the methyl alcohol of its corresponding different time and H
2generating rate see the following form:
Reaction condition: H
2o/CH
3oH=1.1/1 (mol ratio); WHSV=4.8ml.gcat
-1h
-1; T=230 DEG C; P=0.1MPa
The Cu/ZrO by the precipitation that distributes can be drawn by above result
2catalyst activity is high, and CO content is low, and optimum proportioning catalyst C methanol conversion can reach 92%, CO content and only account for 0.25%, and catalyst was through 24 hours, and continuous running does not find active reduction.
In sum, step-by-step precipitation method is prepared Cu/ZrO2 catalyst and is shown more excellent catalytic activity to hydrogen production from methanol-steam reforming.This catalyst reaction mild condition, has higher reactivity, and accessory substance CO content is less.By literature search, do not meet similar catalyst system and catalyzing report, belonged to innovative works.
Above said content be only the present invention conceive under basic explanation, and according to any equivalent transformation that technical scheme of the present invention is done, all should protection scope of the present invention be belonged to.
Claims (7)
1. for a catalyst for hydrogen production from methanol-steam reforming, it is characterized in that: by Cu and ZrO
2composition, the surface enrichment ZrO of described catalyst
2, described ZrO
2be dispersed in copper component, in described catalyst, the molar percentage of Cu is 69.6 ~ 88.9%; Described ZrO
2molar percentage be 11.1 ~ 30.4%.
2. a kind of catalyst for hydrogen production from methanol-steam reforming according to claim 1, is characterized in that: in described catalyst, the molar percentage of Cu is 88.9%; Described ZrO
2molar percentage be 11.1%.
3. a kind of catalyst for hydrogen production from methanol-steam reforming according to claim 1, is characterized in that: in described catalyst, the molar percentage of Cu is 80%; Described ZrO
2molar percentage be 20%.
4. a kind of catalyst for hydrogen production from methanol-steam reforming according to claim 1, is characterized in that: in described catalyst, the molar percentage of Cu is 72.7%; Described ZrO
2molar percentage be 27.3%.
5. a kind of catalyst for hydrogen production from methanol-steam reforming according to claim 1, is characterized in that: in described catalyst, the molar percentage of Cu is 69.6%; Described ZrO
2molar percentage be 30.4%.
6. the preparation method of a kind of catalyst for hydrogen production from methanol-steam reforming according to claim 1, is characterized in that comprising the steps:
1) step of a cement copper component, by the Cu (NO of 0.7 ~ 1.3mol/L
3)
2the Na of solution and 0.4 ~ 0.6mol/L
2cO
3solution drip is added to the Na that 0.2mol/L is housed
2cO
3in the reaction vessel of solution, the Cu (NO of 0.7 described ~ 1.3mol/L
3)
2the Na of solution and 0.2mol/L
2cO
3the volume ratio of solution is 3 ~ 6:1, and controlling the amount that also drip added-time every dropping liquid drips is 0.05-0.07ml, by regulating the Na of 0.4 ~ 0.6mol/L
2cO
3suspension pH value controls within the scope of 7.3-7.8 by the drop rate of solution, and controlling speed of agitator in dropping process is 200-300r/min, and temperature 50 ~ 65 DEG C, terminates the dropping of sodium carbonate liquor after copper nitrate solution dropwises;
2) step of a precipitation zirconium component, by 0.3 ~ 0.6mol/L zirconyl chloride solution and the Na with 0.4 ~ 0.6mol/L
2cO
3solution drip is added in above-mentioned reaction vessel, the Cu (NO of 0.7 described ~ 1.3mol/L
3)
2the volume ratio of solution and 0.3 ~ 0.6mol/L zirconyl chloride solution is 1.5 ~ 4:1, and controls and the amount that the every dropping liquid flowed drips is 0.05-0.07ml, and controlling speed of agitator in dropping process is 200-300r/min, temperature 50 ~ 65 DEG C, by regulating the Na of 0.4 ~ 0.6mol/L
2cO
3suspension pH value controls within the scope of 9.3-9.8 by the drop rate of solution, at 50 ~ 65 DEG C of ageing 0.5 ~ 2h after end to be precipitated, and suction filtration, the filter cake of gained is with after distilled water washing, again filter cake is dried 5 ~ 20h through 100 ~ 120 DEG C, then in 400 ~ 500 DEG C of roasting 2 ~ 6h, the catalyst for hydrogen production from methanol-steam reforming is obtained.
7. the preparation method of a kind of catalyst for hydrogen production from methanol-steam reforming according to claim 6, is characterized in that: the prepared catalyst for hydrogen production from methanol-steam reforming is through H
2/ He gas activation process.
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| CN109603834A (en) * | 2018-12-17 | 2019-04-12 | 上海应用技术大学 | A kind of catalyst and preparation method thereof for hydrogen production from methanol-steam reforming |
| CN111068681A (en) * | 2019-11-28 | 2020-04-28 | 上海应用技术大学 | Catalyst for methanol steam reforming hydrogen production and preparation method and application thereof |
| CN112986047A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Method for measuring steam content in reformed gas and method for evaluating and measuring reforming fuel conversion rate |
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| 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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| 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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| CN109603834A (en) * | 2018-12-17 | 2019-04-12 | 上海应用技术大学 | A kind of catalyst and preparation method thereof for hydrogen production from methanol-steam reforming |
| CN111068681A (en) * | 2019-11-28 | 2020-04-28 | 上海应用技术大学 | Catalyst for methanol steam reforming hydrogen production and preparation method and application thereof |
| CN112986047A (en) * | 2019-12-12 | 2021-06-18 | 中国科学院大连化学物理研究所 | Method for measuring steam content in reformed gas and method for evaluating and measuring reforming fuel conversion rate |
| CN112986047B (en) * | 2019-12-12 | 2022-02-01 | 中国科学院大连化学物理研究所 | Method for measuring steam content in reformed gas and method for evaluating and measuring reforming fuel conversion rate |
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