CN106076346A - Catalyst, preparation method and application for methanol steam catalytically reforming hydrogen producing - Google Patents

Catalyst, preparation method and application for methanol steam catalytically reforming hydrogen producing Download PDF

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CN106076346A
CN106076346A CN201610351258.5A CN201610351258A CN106076346A CN 106076346 A CN106076346 A CN 106076346A CN 201610351258 A CN201610351258 A CN 201610351258A CN 106076346 A CN106076346 A CN 106076346A
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catalyst
oxide
roasting
zinc
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CN106076346B (en
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杨占旭
张磊
贺建平
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Liaoning Shihua University
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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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/32—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of gaseous or liquid organic compounds with gasifying agents, e.g. water, carbon dioxide, air
    • C01B3/323—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents
    • 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
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/10—Constitutive chemical elements of heterogeneous catalysts of Group I (IA or IB) of the Periodic Table
    • B01J2523/17—Copper
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/20—Constitutive chemical elements of heterogeneous catalysts of Group II (IIA or IIB) of the Periodic Table
    • B01J2523/27—Zinc
    • 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
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • B01J2523/30—Constitutive chemical elements of heterogeneous catalysts of Group III (IIIA or IIIB) of the Periodic Table
    • B01J2523/31—Aluminium

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Abstract

The invention provides a kind of catalyst for methanol steam catalytically reforming hydrogen producing, described catalyst uses Cu metal-oxide as active component, after roasting zinc-aluminum hydrotalcite, gained oxide is as catalyst carrier, and described zinc-aluminum hydrotalcite uses in-situ synthesis to prepare, with γ Al2O3, synthesize for aluminum source；Wherein, the content of described catalyst active component, in terms of oxide, accounts for the 1 30% of catalyst gross mass；The content of described catalyst carrier, in terms of oxide, accounts for 70% the 99% of catalyst gross mass；In described catalyst carrier, Zn content, in terms of oxide, accounts for 5% the 30% of zinc-aluminium gross mass.The catalyst that the present invention provides utilizes the method for fabricated in situ to be prepared for zinc-aluminum hydrotalcite, and utilize " structure memory " function of zinc-aluminum hydrotalcite to be prepared for the metal oxide catalyst of loaded Cu, this catalyst has high activity, low CO selectivity and high stability in hydrogen production from methanol-steam reforming course of reaction.

Description

Catalyst, preparation method and application for methanol steam catalytically reforming hydrogen producing
Technical field
The invention belongs to catalysis technical field, be specifically related to a kind of brucite for methanol steam catalytically reforming hydrogen producing Derivative catalyst and preparation method thereof.
Background technology
Rapid development of economy makes China be faced with the dual-pressure of energy and environment.Utilize at optimization fossil resource, While improving energy conversion efficiency, the development and utilization of new forms of energy has become alleviation China energy availability and demand contradiction, has realized the energy Variation, the Major Strategic Demand of holding economic environment sustainable development.Hydrogen reserves on earth are the abundantest, combustion heat value Do not produce any pollution after height, and burning, be advantageous to environmental conservation, therefore be counted as 21 century preferably clean new forms of energy. Hydrogen is the preferable energy carrier that can obtain from number of ways, is one of fossil energy important bridge to regenerative resource transition.
Hydrogen is increasingly paid much attention to by people as preferable chemical fuel, energy carrier and energy storage instrument.Fuel Battery technology be efficiently, one of the new technical platform of clean utilization Hydrogen Energy, hydrogen can be easily convertible to electricity by fuel cell And heat, there is higher transformation efficiency.But, hydrogen energy system is a huge and complicated energy resource system, at Hydrogen Energy and fuel A lot of problems are also had to need to solve on the road of battery applications.In addition to economic and policy factor, prepared by Hydrogen Energy, accumulating, turn Change and apply link remains and urgently overcome at many technical barriers.Therefore, current various countries are while proceeding demonstration, all Emphasis is turned back to applied basic research, it is desirable to by research Hydrogen Energy and the various basic problem of fuel cell, find reality Existing Hydrogen Energy and the basic way of fuel cell industrialization.Wherein, hydrogen producing technology become fuel cell move towards market bottleneck it One.In all too many levels of hydrogen manufacturing key technology it may first have to solve the Discussion On Development of effective catalyst, no matter from the maturation of technology Degree, still from the point of view of the available degree of existing infrastructure, (includes methanol, gasoline, diesel oil, natural with Fossil fuel Gas etc.) hydrogen manufacturing is important channel present stage solving on a small scale distributing hydrogen source.But reformation hydrogen production is redox condition to interweave, Astable reaction system, it is desirable to reforming hydrogen-production catalyst must possess excellent activity and stability, have simultaneously high temperature resistant, Anti-carbon deposit, the performance of heat shock resistance.
At present, existing industrial catalyst all cannot meet above-mentioned requirements simultaneously, and therefore, research is applicable to unstable state hydrogen manufacturing Catalyst and the catalyticing mechanism thereof of system are particularly important to breaking through distributed unstable state reformation hydrogen production key technology.Yang Mei etc. (Yang M, Li S, Chen G.Applied Catalysis B:Environmental, 2011,101 (3): 409- 416) co-precipitation is used to be prepared for Zn Al composite oxide catalyst, (GHSV=under the seriality up to 200h operates 17930h-1, T=420 DEG C), catalyst is without obvious deactivation phenomenom, and product is stable, and CO concentration is relatively low.The Bei of Michigan university Deng (Bei S K, Ranganathan E S, Thompson L T. Fuel Chemistry Division Preprints, 2003,48 (1): 327-328) it is prepared for Mo2N catalyst is also used for hydrogen production from methanol-steam reforming process, it was found that Mo2N Catalyst low-temperature activity is more preferable, but to CO2Selectivity poor.Liu Yanyong etc. (Liu Y Y, Hayakawa T, Suzuki K, et al.Applied Catalysis A:General, 2002,223 (1-2): 137-145) use coprecipitation Synthesis copper cerium oxide, Copper-zinc oxide, copper Zinc-aluminium and copper aluminum oxide, it was found that whole cupric catalysis Agent all shows higher catalysis activity, but cu-ce composite oxidation catalyst has the highest methanol to convert when low temperature Rate.
Summary of the invention
For problem above, the present invention is with hydrogen production from methanol-steam reforming system as goal in research, with copper as chief active Component, introducing hydrotalcite derivant is precursor carrier, and exploitation has high activity, low CO selectivity and the cuprio of high stability emphatically Catalyst.
Concrete, the catalyst for methanol steam catalytically reforming hydrogen producing of present invention offer, described catalyst uses Cu metal-oxide is as active component, and after roasting zinc-aluminum hydrotalcite, gained oxide is as catalyst carrier, described zinc-aluminium water Talcum uses in-situ synthesis to prepare, with γ-Al2O3, synthesize for aluminum source；
Wherein, the content of described catalyst active component, in terms of oxide, accounts for the 1-30% of catalyst gross mass；Described urge The content of agent carrier, in terms of oxide, accounts for the 70%-99% of catalyst gross mass；In described catalyst carrier, Zn content with Oxide meter, accounts for the 5%-30% of zinc-aluminium gross mass.
Preferably, the content of described catalyst active component, in terms of oxide, accounts for the 5-15% of catalyst gross mass；Described The content of catalyst carrier, in terms of oxide, accounts for the 85-95% of catalyst gross mass；In described catalyst carrier, Zn content with Oxide meter, accounts for the 10-20% of zinc-aluminium gross mass.
It is highly preferred that the content of described catalyst active component is in terms of oxide, account for the 5.89% of catalyst gross mass；Institute State the content of catalyst carrier in terms of oxide, account for the 94.11% of catalyst gross mass；In described catalyst carrier, Zn content In terms of oxide, account for the 18.76% of zinc-aluminium gross mass.
It is highly preferred that the catalyst for methanol steam catalytically reforming hydrogen producing that the present invention provides, for normal pressure, reaction Temperature 200-350 DEG C, water alcohol mol ratio is at 1-2, mass space velocity 1h-1-7h-1Under conditions of methanol steam carried out catalysis weight Whole hydrogen manufacturing.
Present invention also offers the preparation method of a kind of catalyst for methanol steam catalytically reforming hydrogen producing, including such as Lower step:
S1: weigh Zn (NO respectively with the ratio that mol ratio is 1: 1: 3-6.53)2·6H2O、NH4NO3With γ-Al2O3, will γ-Al2O3At 560-600 DEG C of roasting 2-4h, and by Zn (NO3)2·6H2O and NH4NO3Add water mixed dissolution, then adds roasting γ-Al after burning2O3, mix homogeneously forms mixed liquor, is the pH value that 1-10% ammonia regulates mixed liquor with mass fraction, adjusts Joint process is stirred continuously, after pH reaches 7-10, at a temperature of 40-80 DEG C continue stirring 0h-48h, more scrubbed, aging, wash Wash, dried zinc-aluminum hydrotalcite；
S2: described zinc-aluminum hydrotalcite is obtained metal-oxide 350-500 DEG C of roasting；
S3: take metal-oxide that S2 roasting obtains as catalyst carrier, use infusion process to impregnate Cu at 20-60 DEG C (NO3)2·3H2O solution, dip time is 1-2h, then evaporates at 50-100 DEG C, dried, roasting at 350-600 DEG C Obtain oxidized catalyst；
S4: by oxidized catalyst at H2-N2At 250-280 DEG C of reductase 12-8h under the atmosphere of gaseous mixture, obtain intended catalyzed Agent.
Preferably, in S4, described H2-N2H in gaseous mixture2Concentration is 1-20%.
It is highly preferred that weigh a certain amount of Zn (NO respectively with the ratio that mol ratio is 1: 1: 53)2·6H2O、NH4NO3With γ-Al2O3, by γ-Al2O3At 600 DEG C of roasting 4h, and by Zn (NO3)2·6H2O and NH4NO3Add water mixed dissolution, forms Zn (NO3)2·6H2O solution concentration is 0.2mol/L, NH4NO3Solution concentration is the lysate of 0.2mol/L, then adds roasting After γ-Al2O3, mix homogeneously forms mixed liquor, is the pH value that 2% ammonia regulates mixed liquor with mass fraction, regulates process It is stirred continuously, after pH reaches 8, at a temperature of 50 DEG C, continues stirring 24h, more scrubbed, aging, washing, dried zinc-aluminium Brucite；
The zinc-aluminum hydrotalcite obtained is obtained metal-oxide at 400 DEG C of roasting 4h, takes the metal-oxide work that roasting obtains For catalyst carrier, infusion process is used to impregnate Cu (NO at 20 DEG C3)2·3H2O solution, dip time is 1h, exists the most successively Evaporate at 80 DEG C, be dried 12h, roasting 3h at 500 DEG C under the conditions of 60 DEG C, be ground to 120 mesh, compression molding, be ground into 40-80 Mesh, obtains oxidized catalyst；By prepared oxidized catalyst 5%H2-95%N2Mixed gas, at 280 DEG C of reductase 12 h, obtains Final catalyst.
The catalyst for methanol steam catalytically reforming hydrogen producing that the present invention provides is applied to methanol steam reforming system Hydrogen process, can also be applied to methanol-fueled CLC and other reformation hydrogen production processes.
The catalyst that the present invention provides has higher activity, at low water alcohol mole to hydrogen production from methanol-steam reforming reaction Under Bi, (1-2) has relatively low selectivity to CO, has preferable stability under high-speed.
Concrete, the catalyst for methanol steam catalytically reforming hydrogen producing that the present invention provides is 260 in reaction temperature DEG C, water alcohol mol ratio is 1-2, and air speed is 3.8h-1Time, initial conversion up to more than 90%, H in reformation tail gas2Content exists More than 74%, CO content is less than 2%.Be precursor carrier by the method synthetic hydrotalcite of fabricated in situ, fired after must be catalyzed Agent carrier.The memory effect of recycling brucite, uses the method for dipping to introduce active component, not only improves copper species Size and deployment conditions on surface further improve mechanical strength and the reducing power of catalyst, and prevent copper Grain species agglomeration in reduction and course of reaction, thus improve the activity of catalyst, selectivity and stability.
The catalyst that the present invention provides has higher activity, reformation tail gas to the reaction of methanol steam catalytically reforming hydrogen producing Middle CO content is greatly lowered relative to commercial catalysts, has good stability, and method for preparing catalyst is simple, can enter Row large-scale industrial production.
Accompanying drawing explanation
Fig. 1 is γ-Al2O3And zinc-aluminum hydrotalcite XRD figure prepared by in-situ synthesis；
Fig. 2 is catalyst for preparing hydrogen by reforming methanol and water vapour performance evaluation figure.
Detailed description of the invention
In order to make those skilled in the art be more fully understood that, technical scheme can be practiced, below in conjunction with specifically The invention will be further described for embodiment, but illustrated embodiment is not as a limitation of the invention.
Reaction velocity of the present invention is defined as reaction raw materials (liquid methanol and the mixed solution of water) and enters per hour The volume flow of response system, divided by the volume of catalyst, represents with WHSV, unit h-1。
Methanol conversion of the present invention is defined as the first in the molar percentage that methanol in raw material is converted, i.e. raw material The difference of alcohol and unreacted methanol is relative to the molar percentage of methanol in raw material, and unit is %.
Activity rating of catalyst provided by the present invention, is carried out in homemade quartz tube reactor, takes 40-80 purpose Catalyst volume is 2mL, and alcohol-water mixture inlet amount is by micro pump control, and reformation gas first passes through condenser condensation, through overdrying Dry device enters SP1000 gas chromatogram on-line analysis after drying, and chromatographic column is carbon molecular sieve packed column, and detector is thermal conductance (TCD) Detector, injector temperature 50 DEG C, detector temperature 50 DEG C, column temperature 100 DEG C, after question response is stable, gather sample.
Below by embodiment, the present invention is described in further detail.
Embodiment 1
Catalyst 1:5.89%CuO/18.76%ZnO/ γ-Al2O3
Its preparation process is as follows:
1) 12g γ-Al is first claimed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495gZn (NO the most respectively3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, is made into the nitrate solution that concentration is 0.2mol/L, so After add 5g γ-Al2O3, mix homogeneously forms mixed solution；
2) preparation mass fraction is the ammonia 500mL of 2%；Under stirring at normal temperature, the ammonia of prepare 2% is added dropwise to In the mixed solution prepared；When the pH=8 of solution, stopping dropping ammonia, temperature is raised to 50 DEG C and continues measurement after stirring 24h The pH of solution；
3) ammonia identical with above-mentioned pH and NH are prepared the most respectively4NO3, it is mixed to form mixing, washing liquid standby；
4) by step 2) gains carry out sucking filtration, filter cake step 3) in the ammonia for preparing and NH4NO3The mixing of composition is washed Wash liquid washing sample 6-7 time, then allow ammonia and NH4NO3Mixing, washing immersion there is not the most aging 1h of filter cake, then spend from The washing of sub-water, to neutral, obtains zinc-aluminum hydrotalcite after being dried 12h at 70 DEG C.Zinc-aluminum hydrotalcite roasting 4h at 400 DEG C obtains metal oxygen Compound, as catalyst carrier, is designated as Zn-Al/ γ-Al2O3400, grind pack；
5) 0.9505g Cu (NO is weighed3)2·3H2O, in beaker, adds 100mL deionized water, after stirring, adds 5g Zn-Al/γ-Al2O3400 in beaker, is sufficiently stirred for 1h at 20 DEG C；Then mixed solution is transferred to temperature be set as By unnecessary water evaporation in the rotary evaporimeter of 80 DEG C, in 60 DEG C of baking ovens, after evaporation, it is dried 12h, then roasting at 500 DEG C 3h, is ground to 120 mesh, compression molding, is ground into 40-80 mesh, obtains oxidized catalyst.
6) by above-mentioned prepared oxidized catalyst 5%H2-95%N mixed gas, at 280 DEG C of reductase 12 h, obtains metal The final catalyst 1 of elemental.
γ-Al2O3And zinc-aluminum hydrotalcite XRD figure prepared by the in-situ synthesis obtained by the present embodiment is specifically shown in Fig. 1 institute Show, the present invention with synthesis catalyst to hydrogen production from methanol-steam reforming, be evaluated through substantial amounts of test, concrete, first Alcohol vapor reforming hydrogen production catalyst performance evaluation figure is shown in Fig. 2.
After reduction, it is passed through the unstripped gas of first alcohol and water after gasification, after reaction temperature to be achieved, starts record: reaction pressure Power P=0.1MPa, reaction temperature T=260 DEG C, water alcohol mol ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 1。
Table 1 embodiment 1 prepares the methanol conversion of catalyst
Embodiment 2
Catalyst 2:5.89%CuO/18.76%ZnO/ γ-Al2O3
Its preparation process is as follows:
1) 12g γ-Al is first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495gZn (NO the most respectively3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, is made into the nitrate solution that concentration is 0.1mol/L, so After add 5g γ-Al2O3, mix homogeneously forms mixed solution；
2) preparation mass fraction is the ammonia 500mL of 5%；Under stirring at normal temperature, the ammonia of prepare 5% is added dropwise to In the mixed solution prepared；When the pH=8 of solution, stopping dropping ammonia, temperature is raised to 50 DEG C and continues measurement after stirring 24h The pH of solution；
3) ammonia identical with above-mentioned pH and NH are prepared the most respectively4NO3, it is mixed to form mixing, washing liquid standby；
4) by step 2) gains carry out sucking filtration, filter cake step 3) in the ammonia for preparing and NH4NO3The mixing of composition is washed Wash liquid washing sample 6-7 time, then allow ammonia and NH4NO3Mixing, washing immersion there is not the most aging 1h of filter cake, then spend from The washing of sub-water, to neutral, obtains zinc-aluminum hydrotalcite after being dried 12h at 70 DEG C.Zinc-aluminum hydrotalcite roasting 4h at 350 DEG C obtains metal oxygen Compound, as catalyst carrier, is designated as Zn-Al/ γ-Al2O3350, grind pack；
5) 0.9505g Cu (NO is weighed3)2·3H2O, in beaker, adds 100mL deionized water, after stirring, adds 5g Zn-Al/γ-Al2O3350 in beaker, is sufficiently stirred for 1h at 20 DEG C；Then mixed solution is transferred to temperature be set as By unnecessary water evaporation in the rotary evaporimeter of 80 DEG C, in 60 DEG C of baking ovens, after evaporation, it is dried 12h, then roasting at 500 DEG C 3h, is ground to 120 mesh, compression molding, is ground into 40-80 mesh, obtains oxidized catalyst.
6) by above-mentioned prepared oxidized catalyst 5%H2-95%N mixed gas, at 280 DEG C of reductase 12 h, obtains metal The final catalyst 2 of elemental.
After reduction, it is passed through the unstripped gas of first alcohol and water after gasification, after reaction temperature to be achieved, starts record: reaction pressure Power P=0.1MPa, reaction temperature T=260 DEG C, water alcohol mol ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 2。
Table 2 embodiment 2 prepares the methanol conversion of catalyst
Embodiment 3
Catalyst: 3:11.13%CuO/17.71%ZnO/ γ-Al2O3
Its preparation process is as follows:
1) 12g γ-Al is first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO the most respectively3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, is made into the nitrate solution that concentration is 0.05mol/L, Then 5g γ-Al is added2O3, mix homogeneously forms mixed solution；
2) preparation mass fraction is the ammonia 500mL of 2%；Under stirring at normal temperature, the ammonia of prepare 2% is added dropwise to In the mixed solution prepared；When the pH=8 of solution, stopping dropping ammonia, temperature is raised to 50 DEG C and continues measurement after stirring 24h The pH of solution；
3) ammonia identical with above-mentioned pH and NH are prepared the most respectively4NO3, it is mixed to form mixing, washing liquid standby；
4) by step 2) gains carry out sucking filtration, filter cake step 3) in the ammonia for preparing and NH4NO3The mixing of composition is washed Wash liquid washing sample 6-7 time, then allow ammonia and NH4NO3Mixing, washing immersion there is not the most aging 1h of filter cake, then spend from The washing of sub-water, to neutral, obtains zinc-aluminum hydrotalcite after being dried 12h at 70 DEG C.Zinc-aluminum hydrotalcite roasting 4h at 400 DEG C obtains metal oxygen Compound, as catalyst carrier, is designated as Zn-Al/ γ-Al2O3400, grind pack；
5) 1.9009g Cu (NO is weighed3)2·3H2O, in beaker, adds 100mL deionized water, after stirring, adds 5g Zn-Al/γ-Al2O3400 in beaker, is sufficiently stirred for 1h at 30 DEG C；Then mixed solution is transferred to temperature be set as By unnecessary water evaporation in the rotary evaporimeter of 80 DEG C, in 60 DEG C of baking ovens, after evaporation, it is dried 12h, then roasting at 600 DEG C 3h, is ground to 120 mesh, compression molding, is ground into 40-80 mesh, obtains oxidized catalyst.
6) by above-mentioned prepared oxidized catalyst 5%H2-95%N mixed gas, at 280 DEG C of reductase 12 h, obtains metal The final catalyst 3 of elemental.
After reduction, it is passed through the unstripped gas of first alcohol and water after gasification, after reaction temperature to be achieved, starts record: reaction pressure Power P=0.1MPa, reaction temperature T=260 DEG C, water alcohol mol ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 3。
Table 3 embodiment 3 prepares the methanol conversion of catalyst
Embodiment 4
Catalyst 4:11.13%CuO/17.71%ZnO/ γ-Al2O3
Its preparation process is as follows:
1) 12g γ-Al is first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO the most respectively3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, is made into the nitrate solution that concentration is 0.2mol/L, so After add 5g γ-Al2O3, mix homogeneously forms mixed solution；
2) preparation mass fraction is the ammonia 500mL of 2%；Under stirring at normal temperature, the ammonia of prepare 2% is added dropwise to In the mixed solution prepared；When the pH=9 of solution, stopping dropping ammonia, temperature is raised to 60 DEG C and continues measurement after stirring 24h The pH of solution；
3) ammonia identical with above-mentioned pH and NH are prepared the most respectively4NO3, it is mixed to form mixing, washing liquid standby；
4) by step 2) gains carry out sucking filtration, filter cake step 3) in the ammonia for preparing and NH4NO3The mixing of composition is washed Wash liquid washing sample 6-7 time, then allow ammonia and NH4NO3Mixing, washing immersion there is not the most aging 1h of filter cake, then spend from The washing of sub-water, to neutral, obtains zinc-aluminum hydrotalcite after being dried 12h at 70 DEG C.Zinc-aluminum hydrotalcite roasting 4h at 400 DEG C obtains metal oxygen Compound, as catalyst carrier, is designated as Zn-Al/ γ-Al2O3400, grind pack；
5) 1.9009Cu (NO is weighed3)2·3H2O, in beaker, adds 100mL deionized water, after stirring, adds 5g Zn-Al/γ-Al2O3400 in beaker, is sufficiently stirred for 1h at 20 DEG C；Then mixed solution is transferred to temperature and is set as 80 DEG C Rotary evaporimeter in by unnecessary water evaporation, in 60 DEG C of baking oven, be dried 12h, then roasting 3h at 500 DEG C after evaporation, grind It is milled to 120 mesh, compression molding, is ground into 40-80 mesh, obtains oxidized catalyst.
6) by above-mentioned prepared oxidized catalyst 5%H2-95%N mixed gas, at 280 DEG C of reductase 12 h, obtains metal The final catalyst 4 of elemental.
After reduction, it is passed through the unstripped gas of first alcohol and water after gasification, after reaction temperature to be achieved, starts record: reaction pressure Power P=0.1MPa, reaction temperature T=260 DEG C, water alcohol mol ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 4。
Table 4 embodiment 4 prepares the methanol conversion of catalyst
Embodiment 5
Catalyst 5:11.13%CuO/9.84%ZnO/ γ-Al2O3
Its preparation process is as follows:
1) 12g γ-Al is first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO the most respectively3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, is made into the nitrate solution that concentration is 0.2mol/L, so After add 10g γ-Al2O3, mix homogeneously forms mixed solution；
2) preparation mass fraction is the ammonia 500mL of 2%；Under stirring at normal temperature, the ammonia of prepare 2% is added dropwise to In the mixed solution prepared；When the pH=8 of solution, stopping dropping ammonia, temperature is raised to 60 DEG C and continues measurement after stirring 48h The pH of solution；
3) ammonia identical with above-mentioned pH and NH are prepared the most respectively4NO3, it is mixed to form mixing, washing liquid standby；
4) by step 2) gains carry out sucking filtration, filter cake step 3) in the ammonia for preparing and NH4NO3The mixing of composition is washed Wash liquid washing sample 6-7 time, then allow ammonia and NH4NO3Mixing, washing immersion there is not the most aging 1h of filter cake, then spend from The washing of sub-water, to neutral, obtains zinc-aluminum hydrotalcite after being dried 12h at 70 DEG C.Zinc-aluminum hydrotalcite roasting 4h at 400 DEG C obtains metal oxygen Compound, as catalyst carrier, is designated as Zn-Al/ γ-Al2O3400, grind pack；
5) 1.9009Cu (NO is weighed3)2·3H2O, in beaker, adds 100mL deionized water, after stirring, adds 5g Zn-Al/γ-Al2O3400 in beaker, is sufficiently stirred for 1h at 20 DEG C；Then mixed solution is transferred to temperature and is set as 80 DEG C Rotary evaporimeter in by unnecessary water evaporation, in 60 DEG C of baking oven, be dried 12h, then roasting 3h at 500 DEG C after evaporation, grind It is milled to 120 mesh, compression molding, is ground into 40-80 mesh, obtains oxidized catalyst.
6) by above-mentioned prepared oxidized catalyst 5%H2-95%N mixed gas, at 280 DEG C of reductase 12 h, obtains metal The final catalyst 5 of elemental.
After reduction, it is passed through the unstripped gas of first alcohol and water after gasification, after reaction temperature to be achieved, starts record: reaction pressure Power P=0.1MPa, reaction temperature T=260 DEG C, water alcohol mol ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 5。
Table 5 embodiment 5 prepares the methanol conversion of catalyst
Embodiment 6
Catalyst 6:20.02%CuO/15.94%ZnO/ γ-Al2O3
Its preparation process is as follows:
1) 12g γ-Al is first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO the most respectively3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, is made into the nitrate solution that concentration is 0.1mol/L, so After add 10g γ-Al2O3, mix homogeneously forms mixed solution；
2) preparation mass fraction is the ammonia 500mL of 2%；Under stirring at normal temperature, the ammonia of prepare 2% is added dropwise to In the mixed solution prepared；When the pH=8 of solution, stopping dropping ammonia, temperature is raised to 70 DEG C and continues measurement after stirring 24h The pH of solution；
3) ammonia identical with above-mentioned pH and NH are prepared the most respectively4NO3, it is mixed to form mixing, washing liquid standby；
4) by step 2) gains carry out sucking filtration, filter cake step 3) in the ammonia for preparing and NH4NO3The mixing of composition is washed Wash liquid washing sample 6-7 time, then allow ammonia and NH4NO3Mixing, washing immersion there is not the most aging 1h of filter cake, then spend from The washing of sub-water, to neutral, obtains zinc-aluminum hydrotalcite after being dried 12h at 70 DEG C.Zinc-aluminum hydrotalcite roasting 4h at 400 DEG C obtains metal oxygen Compound, as catalyst carrier, is designated as Zn-Al/ γ-Al2O3400, grind pack；
5) 3.8019Cu (NO is weighed3)2·3H2O, in beaker, adds 100mL deionized water, after stirring, adds 10g Zn-Al/γ-Al2O3400 in beaker, is sufficiently stirred for 2h at 30 DEG C；Then mixed solution is transferred to temperature be set as By unnecessary water evaporation in the rotary evaporimeter of 80 DEG C, in 60 DEG C of baking ovens, after evaporation, it is dried 12h, then roasting at 500 DEG C 3h, is ground to 120 mesh, compression molding, is ground into 40-80 mesh, obtains oxidized catalyst.
6) by above-mentioned prepared oxidized catalyst 5%H2-95%N mixed gas, at 280 DEG C of reductase 12 h, obtains metal The final catalyst 6 of elemental.
After reduction, it is passed through the unstripped gas of first alcohol and water after gasification, after reaction temperature to be achieved, starts record: reaction pressure Power P=0.1MPa, reaction temperature T=260 DEG C, water alcohol mol ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 6。
Table 6 embodiment 6 prepares the methanol conversion of catalyst
Embodiment 7
Catalyst 7:20.02%CuO/15.94%ZnO/ γ Al2O3
Its preparation process is as follows:
1) 12g γ-Al is first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO the most respectively3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, is made into the nitrate solution that concentration is 0.2mol/L, so After add 10g γ-Al2O3, mix homogeneously forms mixed solution；
2) preparation mass fraction is the ammonia 500mL of 2%；Under stirring at normal temperature, the ammonia of prepare 2% is added dropwise to In the mixed solution prepared；When the pH=8 of solution, stopping dropping ammonia, temperature is raised to 50 DEG C and continues measurement after stirring 24h The pH of solution；
3) ammonia identical with above-mentioned pH and NH are prepared the most respectively4NO3, it is mixed to form mixing, washing liquid standby；
4) by step 2) gains carry out sucking filtration, filter cake step 3) in the ammonia for preparing and NH4NO3The mixing of composition is washed Wash liquid washing sample 6-7 time, then allow ammonia and NH4NO3Mixing, washing immersion there is not the most aging 1h of filter cake, then spend from The washing of sub-water, to neutral, obtains zinc-aluminum hydrotalcite after being dried 12h at 70 DEG C.Zinc-aluminum hydrotalcite roasting 4h at 400 DEG C obtains metal oxygen Compound, as catalyst carrier, is designated as Zn-Al/ γ-Al2O3400, grind pack；
5) 3.8019Cu (NO is weighed3)2·3H2O, in beaker, adds 100mL deionized water, after stirring, adds 10g Zn-Al/γ-Al2O3400 in beaker, is sufficiently stirred for 2h at 30 DEG C；Then mixed solution is transferred to temperature be set as By unnecessary water evaporation in the rotary evaporimeter of 80 DEG C, in 60 DEG C of baking ovens, after evaporation, it is dried 12h, then roasting at 500 DEG C 3h, is ground to 120 mesh, compression molding, is ground into 40-80 mesh, obtains oxidized catalyst.
6) by above-mentioned prepared oxidized catalyst 5%H2-95%N mixed gas, at 280 DEG C of reductase 12 h, obtains metal The final catalyst 7 of elemental.
After reduction, it is passed through the unstripped gas of first alcohol and water after gasification, after reaction temperature to be achieved, starts record: reaction pressure Power P=0.1MPa, reaction temperature T=260 DEG C, water alcohol mol ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 7。
Table 7 embodiment 7 prepares the methanol conversion of catalyst
Embodiment 8
Catalyst 8:20.02%CuO/15.94%ZnO/ γ-Al2O
Its preparation process is as follows:
1) 12g γ-Al is first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO the most respectively3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, is made into the nitrate solution that concentration is 0.2mol/L, so After add 10g γ-Al2O3, mix homogeneously forms mixed solution；
2) preparation mass fraction is the ammonia 500mL of 2%；Under stirring at normal temperature, the ammonia of prepare 2% is added dropwise to In the mixed solution prepared；When the pH=8 of solution, stopping dropping ammonia, temperature is raised to 60 DEG C and continues measurement after stirring 24h The pH of solution；
3) ammonia identical with above-mentioned pH and NH are prepared the most respectively4NO3, it is mixed to form mixing, washing liquid standby；
4) by step 2) gains carry out sucking filtration, filter cake step 3) in the ammonia for preparing and NH4NO3The mixing of composition is washed Wash liquid washing sample 6-7 time, then allow ammonia and NH4NO3Mixing, washing immersion there is not the most aging 1h of filter cake, then spend from The washing of sub-water, to neutral, obtains zinc-aluminum hydrotalcite after being dried 12h at 70 DEG C.Zinc-aluminum hydrotalcite roasting 4h at 400 DEG C obtains metal oxygen Compound, as catalyst carrier, is designated as Zn-Al/ γ-Al2O3400, grind pack；
5) 3.8019Cu (NO is weighed3)2·3H2O, in beaker, adds 100mL deionized water, after stirring, adds 10g Zn-Al/γ-Al2O3400 in beaker, is sufficiently stirred for 2h at 30 DEG C；Then mixed solution is transferred to temperature be set as By unnecessary water evaporation in the rotary evaporimeter of 90 DEG C, in 60 DEG C of baking ovens, after evaporation, it is dried 12h, then roasting at 500 DEG C 3h, is ground to 120 mesh, compression molding, is ground into 40-80 mesh, obtains oxidized catalyst.
6) by above-mentioned prepared oxidized catalyst 5%H2-95%N mixed gas at 280 DEG C of reductase 12 h,
Obtain the final catalyst 8 of metal simple-substance state.
After reduction, it is passed through the unstripped gas of first alcohol and water after gasification, after reaction temperature to be achieved, starts record: reaction pressure Power P=0.1MPa, reaction temperature T=260 DEG C, water alcohol mol ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 8。
Table 8 embodiment 8 prepares the methanol conversion of catalyst
Comparative example 1
Catalyst I:11.13%CuO/17.71%ZnO/ γ-Al2O3
Its preparation process is as follows:
1) 12g γ-Al is first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO the most respectively3)2· 6H2O, adds 100mL deionized water dissolving, then adds 10g γ-Al2O3, mix homogeneously；It is sufficiently stirred for 12h, so at 20 DEG C After mixed solution transferred to temperature be set as in the rotary evaporimeter of 80 DEG C, by unnecessary water evaporation, being then placed on by product 70 DEG C of baking ovens are dried 12h, are designated as Zn/ γ-Al2O3
2) 1.9010Cu (NO is weighed3)2·3H2O, in beaker, adds 100mL deionized water dissolving, is subsequently adding 5g Zn-Al/γ-Al2O3, it is sufficiently stirred for 12h at mix homogeneously 20 DEG C, subsequently mixed solution is transferred to temperature and is set as 80 DEG C By unnecessary water evaporation in rotary evaporimeter, in 70 DEG C of baking ovens, it is dried 12h, then roasting 3h at 500 DEG C after evaporation, grinds To 120 mesh, compression molding, it is ground into 40-80 mesh, obtains oxidized catalyst.
3) by above-mentioned prepared oxidized catalyst 5%H2-95%N mixed gas, at 280 DEG C of reductase 12 h, obtains metal The final catalyst I of elemental.
After reduction, it is passed through the unstripped gas of first alcohol and water after gasification, after reaction temperature to be achieved, starts record: reaction pressure Power P=0.1MPa, reaction temperature T=260 DEG C, water alcohol mol ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 9。
Table 9 comparative example 1 prepares the methanol conversion of catalyst
Comparative example 2
Catalyst II:17.26%CuO/58.36%ZnO/Al2O3
Its preparation process is as follows:
1) preparation 100mL concentration is NaOH and Na of 1.0mol/L2CO3Aqueous solution standby；
2)8.9248g Zn(NO3)2·6H2O, 3.7514g Al (NO3)3·9H2O, adds deionized water dissolving, is made into The nitrate solution of 0.2mol/L, mix homogeneously；Under 60 DEG C of stirrings, by NaOH and Na of above-mentioned preparation2CO3Aqueous solution dropwise It is added drop-wise in the nitrate solution prepared；When the pH=10 of solution, stop dropping NaOH and Na2CO3Aqueous solution, continue anti- Answer 24h；Sucking filtration will be precipitated, be washed with deionized to neutrality, and be dried after 12h roasting 4h at 400 DEG C at 70 DEG C, be designated as Zn- Al 400, grinds pack；
3) 1.9010g Cu (NO is weighed3)2·3H2O, in beaker, adds 100mL deionized water, after stirring, adds 3g Zn-Al 400, in beaker, is sufficiently stirred for 1h at 20 DEG C, then mixed solution is transferred to temperature and is set as the rotation of 90 DEG C By unnecessary water evaporation in rotatable evaporimeter, in 60 DEG C of baking ovens, it is dried 12h, then roasting 3h at 500 DEG C after evaporation, is ground to 120 mesh, compression molding, it is ground into 40-80 mesh, obtains oxidized catalyst；
4) by above-mentioned prepared oxidized catalyst 5%H2-95%N mixed gas, at 280 DEG C of reductase 12 h, obtains metal The final catalyst II of elemental.
After reduction, it is passed through the unstripped gas of first alcohol and water after gasification, after reaction temperature to be achieved, starts record；Reaction pressure Power P=0.1MPa, reaction temperature T=260 DEG C, water alcohol mol ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 10。
Table 10 comparative example 2 prepares the methanol conversion of catalyst
Embodiment described above is only the preferred embodiment lifted by absolutely proving the present invention, and its protection domain does not limits In this.The equivalent that those skilled in the art are made on the basis of the present invention substitutes or conversion, all in the protection of the present invention Within the scope of, protection scope of the present invention is as the criterion with claims.

Claims (8)

1. the catalyst for methanol steam catalytically reforming hydrogen producing, it is characterised in that described catalyst uses Cu metal Oxide is as active component, and after roasting zinc-aluminum hydrotalcite, gained oxide is as catalyst carrier, and described zinc-aluminum hydrotalcite is adopted Prepare with in-situ synthesis, with γ-Al2O3, synthesize for aluminum source；
Wherein, the content of described catalyst active component, in terms of oxide, accounts for the 1-30% of catalyst gross mass；Described catalyst The content of carrier, in terms of oxide, accounts for the 70%-99% of catalyst gross mass；In described catalyst carrier, Zn content is with oxidation Thing meter, accounts for the 5%-30% of zinc-aluminium gross mass.
Catalyst for methanol steam catalytically reforming hydrogen producing the most according to claim 1, it is characterised in that described in urge The content of agent active component, in terms of oxide, accounts for the 5-15% of catalyst gross mass；The content of described catalyst carrier is with oxygen Compound meter, accounts for the 85-95% of catalyst gross mass；In described catalyst carrier, Zn content, in terms of oxide, accounts for zinc-aluminium gross mass 10-20%.
Catalyst for methanol steam catalytically reforming hydrogen producing the most according to claim 2, it is characterised in that described in urge The content of agent active component, in terms of oxide, accounts for the 5.89% of catalyst gross mass；The content of described catalyst carrier is with oxygen Compound meter, accounts for the 94.11% of catalyst gross mass；In described catalyst carrier, Zn content, in terms of oxide, accounts for zinc-aluminium gross mass 18.76%.
4., according to the catalyst for methanol steam catalytically reforming hydrogen producing described in any one of claim 1-3, its feature exists In, described catalyst is applicable to normal pressure, reaction temperature 200-350 DEG C, and water alcohol mol ratio is at 1-2, mass space velocity 1h-1-7h-1's Under the conditions of methanol steam is carried out catalytically reforming hydrogen producing.
The preparation method of the catalyst for methanol steam catalytically reforming hydrogen producing the most according to claim 1, its feature It is, comprises the steps:
S1: weigh Zn (NO respectively with the ratio that mol ratio is 1: 1: 3-6.53)2·6H2O、NH4NO3With γ-Al2O3, by γ- Al2O3At 560-600 DEG C of roasting 2-4h, and by Zn (NO3)2·6H2O and NH4NO3Add water mixed dissolution, then adds roasting After γ-Al2O3, mix homogeneously forms mixed liquor, is the pH value that 1-10% ammonia regulates mixed liquor with mass fraction, regulation Process is stirred continuously, after pH reaches 7-10, at a temperature of 40-80 DEG C continue stirring 0h-48h, more scrubbed, aging, washing, Dried zinc-aluminum hydrotalcite；
S2: described zinc-aluminum hydrotalcite is obtained metal-oxide 350-500 DEG C of roasting；
S3: take metal-oxide that S2 roasting obtains as catalyst carrier, use infusion process to impregnate Cu at 20-60 DEG C (NO3)2·3H2O solution, dip time is 1-2h, then evaporates at 50-100 DEG C, dried, roasting at 350-600 DEG C Obtain oxidized catalyst；
S4: by oxidized catalyst at H2-N2At 250-280 DEG C of reductase 12-8h under the atmosphere of gaseous mixture, obtain final catalyst.
The preparation method of the catalyst for methanol steam catalytically reforming hydrogen producing the most according to claim 5, its feature It is, in S4, described H2-N2H in gaseous mixture2Concentration is 1-20%.
The preparation method of the catalyst for methanol steam catalytically reforming hydrogen producing the most according to claim 6, its feature It is,
A certain amount of Zn (NO is weighed respectively with the ratio that mol ratio is 1: 1: 53)2·6H2O、NH4NO3With γ-Al2O3, by γ- Al2O3At 600 DEG C of roasting 4h, and by Zn (NO3)2·6H2O and NH4NO3Add water mixed dissolution, forms Zn (NO3)2·6H2O solution Concentration is 0.2mol/L, NH4NO3Solution concentration is the lysate of 0.2mol/L, then adds the γ-Al after roasting2O3, mixed Conjunction is formed uniformly mixed liquor, is the pH value that 2% ammonia regulates mixed liquor with mass fraction, and regulation process is stirred continuously, and treats pH After reaching 8, at a temperature of 50 DEG C, continue stirring 24h, more scrubbed, aging, washing, dried zinc-aluminum hydrotalcite；
The zinc-aluminum hydrotalcite obtained is obtained metal-oxide at 400 DEG C of roasting 4h, takes metal-oxide that roasting obtains as urging Agent carrier, uses infusion process to impregnate Cu (NO at 20 DEG C3)2·3H2O solution, dip time is 1h, the most successively at 80 DEG C Lower evaporation, is dried 12h, roasting 3h at 500 DEG C, is ground to 120 mesh, compression molding, is ground into 40-80 mesh, i.e. under the conditions of 60 DEG C Obtain oxidized catalyst；By prepared oxidized catalyst 5%H2-95%N2Mixed gas, at 280 DEG C of reductase 12 h, obtains target Catalyst.
Catalyst for methanol steam catalytically reforming hydrogen producing the most according to claim 1, it is characterised in that described in urge Agent is applied to hydrogen production from methanol-steam reforming process, or is applied to methanol-fueled CLC and other reformation hydrogen production processes.
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CN111215084A (en) * 2018-11-25 2020-06-02 中国科学院大连化学物理研究所 Copper-based catalyst for preparing methanol by carbon dioxide hydrogenation, preparation and application thereof
CN112108148A (en) * 2020-09-24 2020-12-22 华东理工大学 Supported copper-based catalyst for hydrogen production by methanol steam reforming, and preparation method and application thereof
CN112403492A (en) * 2020-12-01 2021-02-26 中科院过程工程研究所南京绿色制造产业创新研究院 Catalyst with good low-temperature activity and high efficiency and stability, and preparation method and application thereof
CN112403492B (en) * 2020-12-01 2023-03-21 中科南京绿色制造产业创新研究院 Catalyst with good low-temperature activity and high efficiency and stability, and preparation method and application thereof
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CN116328775A (en) * 2023-01-05 2023-06-27 大连理工大学 Preparation method and application of core-shell catalyst for preparing fatty alcohol by deoxidizing and hydrogenating fatty acid methyl ester

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