CN106076346B - 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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CN106076346B
CN106076346B CN201610351258.5A CN201610351258A CN106076346B CN 106076346 B CN106076346 B CN 106076346B CN 201610351258 A CN201610351258 A CN 201610351258A CN 106076346 B CN106076346 B CN 106076346B
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catalyst
zinc
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CN106076346A (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 present invention provides a kind of catalyst for methanol steam catalytically reforming hydrogen producing, the catalyst is using Cu metal oxides as active constituent, gained oxide is as catalyst carrier after roasting zinc-aluminum hydrotalcite, and the zinc-aluminum hydrotalcite is prepared using in-situ synthesis, with γ Al2O3, synthesized for silicon source；Wherein, the content of the catalyst active component accounts for the 1 30% of catalyst gross mass in terms of oxide；The content of the catalyst carrier accounts for 70% the 99% of catalyst gross mass in terms of oxide；In the catalyst carrier, Zn content accounts for 5% the 30% of zinc-aluminium gross mass in terms of oxide.Catalyst provided by the invention is prepared for zinc-aluminum hydrotalcite using the method for fabricated in situ, and the metal oxide catalyst of loaded Cu is prepared for using " structure memory " function of zinc-aluminum hydrotalcite, the catalyst is used to have high activity, low CO selectivity and high stability in hydrogen production from methanol-steam reforming reaction process.

Description

Catalyst, preparation method and application for methanol steam catalytically reforming hydrogen producing
Technical field
The invention belongs to catalysis technical fields, and in particular to a kind of hydrotalcite 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-pressures of energy and environment.Optimization fossil resource utilize, While improving energy conversion efficiency, the development and utilization of new energy, which has become, to be alleviated China's energy availability and demand contradiction, realizes the energy Diversification, the Major Strategic Demand for keeping economic environment sustainable development.The reserves of hydrogen on earth are very abundant, combustion heat value Height, and do not generate any pollution after burning, is advantageous to environmental protection, therefore is counted as 21 century ideal clean new energy. Hydrogen is the ideal energy carrier that can be obtained from number of ways, is important bridge one of of the fossil energy to regenerative resource transition.
Hydrogen is increasingly paid much attention to by people as ideal chemical fuel, energy carrier and energy storage tool.Fuel Battery technology is efficient, clean utilization Hydrogen Energy one of new technical platform, and can hydrogen electricity be easily convertible to by fuel cell And heat, there is higher transformation efficiency.However, hydrogen energy system is a huge and complicated energy resource system, in Hydrogen Energy and fuel There are many problems to need to solve on the road of battery applications.Other than economic and policy factor, Hydrogen Energy preparation, turns storage and transportation It changes and urgently overcomes using many technical barriers are still had in link.Therefore, various countries are while continuing demonstration at present, all Emphasis is turned back into applied basic research, it is desirable to by studying Hydrogen Energy and the various basic problems of fuel cell, find reality The basic method of existing Hydrogen Energy and fuel cell industrialization.Wherein, hydrogen producing technology have become fuel cell move towards market bottleneck it One.In all too many levels of hydrogen manufacturing key technology it may first have to the Discussion On Development of effective catalyst is solved, no matter from the maturation of technology Degree still from existing infrastructure can be using degree from the point of view of, it is (including methanol, gasoline, diesel oil, natural with fossil fuel Gas etc.) hydrogen manufacturing is to solve the important channel of small-scale distributing hydrogen source at this stage.But reformation hydrogen production be redox condition interweave, The reaction system of unstable state, it is desirable that reforming hydrogen-production catalyst must have excellent activity and stability, while have high temperature resistant, Anti-carbon deposit, the performance of heat shock resistance.
Currently, existing industrial catalyst can not all meet above-mentioned requirements simultaneously, therefore, research is suitable for unstable state hydrogen manufacturing The catalyst and its catalyticing mechanism of system are particularly important to breaking through distributed unstable state reformation hydrogen production key technology.Yang (Yang M, Li S, the Chen G.Applied Catalysis B such as Mei：Environmental, 2011,101 (3)：409- 416) Zn Al composite oxide catalyst is prepared for using co-precipitation, up to (GHSV=under the operation of the continuity of 200h 17930h-1, T=420 DEG C), catalyst without apparent deactivation phenomenom, stablize by product, and CO concentration is relatively low.The Bei of Michigan universities 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 simultaneously used for hydrogen production from methanol-steam reforming process, as a result, it has been found that, Mo2N Catalyst low-temperature activity is more preferable, but to CO2Selectivity it is 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 Copper cerium oxide, Copper-zinc oxide, copper Zinc-aluminium and copper aluminum oxide are synthesized, as a result, it has been found that, whole contains copper catalysis Agent shows higher catalytic activity, but cu-ce composite oxidation catalyst has relatively highest methanol conversion in low temperature Rate.
Invention content
In view of the above problems, the present invention is using hydrogen production from methanol-steam reforming system as goal in research, using copper as chief active Component, introducing hydrotalcite derivant are precursor carrier, and exploitation emphatically has high activity, low CO selectivity copper-based with high stability Catalyst.
Specifically, provided by the present invention for the catalyst of methanol steam catalytically reforming hydrogen producing, the catalyst uses Cu metal oxides are as active constituent, and gained oxide is as catalyst carrier, the zinc-aluminium water after roasting zinc-aluminum hydrotalcite Talcum is prepared using in-situ synthesis, with γ-Al2O3, synthesized for silicon source；
Wherein, the content of the catalyst active component accounts for the 1-30% of catalyst gross mass in terms of oxide；It is described to urge The content of agent carrier accounts for the 70%-99% of catalyst gross mass in terms of oxide；In the catalyst carrier, Zn content with Oxide meter accounts for the 5%-30% of zinc-aluminium gross mass.
Preferably, the content of the catalyst active component accounts for the 5-15% of catalyst gross mass in terms of oxide；It is described The content of catalyst carrier accounts for the 85-95% of catalyst gross mass in terms of oxide；In the 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 the catalyst active component in terms of oxide, accounts for the 5.89% of catalyst gross mass；Institute The content of catalyst carrier is stated in terms of oxide, accounts for the 94.11% of catalyst gross mass；In the catalyst carrier, Zn content In terms of oxide, the 18.76% of zinc-aluminium gross mass is accounted for.
It is highly preferred that provided by the present invention for the catalyst of methanol steam catalytically reforming hydrogen producing, it to be used for normal pressure, reaction 200-350 DEG C of temperature, water alcohol molar ratio is in 1-2, mass space velocity 1h-1-7h-1Under conditions of to methanol steam carry out catalysis weight Whole hydrogen manufacturing.
The present invention also provides a kind of preparation methods of the catalyst for methanol steam catalytically reforming hydrogen producing, including such as Lower step：
S1：Zn (NO are weighed respectively with the ratio that molar ratio is 1: 1: 3-6.53)2·6H2O、NH4NO3With γ-Al2O3, will γ-Al2O32-4h is roasted at 560-600 DEG C, and by Zn (NO3)2·6H2O and NH4NO3Add water mixed dissolution, then adds roasting γ-Al after burning2O3, it is uniformly mixed and forms mixed liquor, the pH value of mixed liquor is adjusted with mass fraction is 1-10% ammonium hydroxide, adjusts Section process is stirred continuously, and after pH reaches 7-10, continues to stir 0h-48h at a temperature of 40-80 DEG C, then washed, aging, wash Wash, dry after zinc-aluminum hydrotalcite；
S2：The zinc-aluminum hydrotalcite is roasted into obtain metal oxide at 350-500 DEG C；
S3：It takes the metal oxide that S2 is roasted as catalyst carrier, Cu is impregnated at 20-60 DEG C using infusion process (NO3)2·3H2Then O solution, dip time 1-2h are evaporated, after drying at 50-100 DEG C, are roasted at 350-600 DEG C Obtain oxidized catalyst；
S4：By oxidized catalyst in H2-N2In 250-280 DEG C of reductase 12-8h under the atmosphere of gaseous mixture, obtain intended catalyzed Agent.
Preferably, in S4, the H2-N2H in gaseous mixture2A concentration of 1-20%.
It is highly preferred that weighing a certain amount of Zn (NO respectively with the ratio that molar ratio is 1: 1: 53)2·6H2O、NH4NO3With γ-Al2O3, by γ-Al2O34h is roasted at 600 DEG C, and by Zn (NO3)2·6H2O and NH4NO3Add water mixed dissolution, forms Zn (NO3)2·6H2O solution concentrations are 0.2mol/L, NH4NO3Solution concentration is the lysate of 0.2mol/L, then adds roasting γ-Al afterwards2O3, it is uniformly mixed and forms mixed liquor, adjusts the pH value of mixed liquor, adjustment process for 2% ammonium hydroxide with mass fraction It is stirred continuously, after pH reaches 8, continues stirring at a temperature of 50 DEG C for 24 hours, then zinc-aluminium is obtained after washed, aging, washing, drying Hydrotalcite；
Obtained zinc-aluminum hydrotalcite is roasted into 4h at 400 DEG C and obtains metal oxide, the metal oxide that roasting obtains is taken to make For catalyst carrier, Cu (NO are impregnated at 20 DEG C using infusion process3)2·3H2O solution, dip time 1h, then exists successively It is evaporated at 80 DEG C, dry 12h under the conditions of 60 DEG C, roasts 3h at 500 DEG C, be ground to 120 mesh, compression molding is ground into 40-80 Mesh is to get oxidized catalyst；By oxidized catalyst 5%H obtained2- 95%N2Mixed gas is obtained in 280 DEG C of reductase 12 h Final catalyst.
It is applied to methanol steam reforming system provided by the present invention for the catalyst of methanol steam catalytically reforming hydrogen producing Hydrogen process can also be applied to methanol-fueled CLC and other reformation hydrogen production processes.
Catalyst provided by the invention has higher activity to hydrogen production from methanol-steam reforming reaction, in low water alcohol mole (1-2) has lower selectivity to CO than under, has preferable stability under high-speed.
Specifically, provided by the present invention for methanol steam catalytically reforming hydrogen producing catalyst reaction temperature be 260 DEG C, water alcohol molar ratio is 1-2, air speed 3.8h-1When, initial conversion reforms H in tail gas up to 90% or more2Content exists 74% or more, CO content are less than 2%.It is precursor carrier by the method synthetic hydrotalcite of fabricated in situ, must be catalyzed after fired Agent carrier.The memory effect for recycling hydrotalcite introduces active component using the method for dipping, not only improves copper species Particle size and deployment conditions on surface further improve the mechanical strength and reducing power of catalyst, and prevent copper Agglomeration of the grain species in reduction and reaction process, to improve the activity of catalyst, selectivity and stability.
Catalyst provided by the invention has higher activity to the reaction of methanol steam catalytically reforming hydrogen producing, reforms tail gas Middle CO contents are greatly lowered relative to commercial catalysts, with good stability, and method for preparing catalyst is simple, can be into Row large-scale industrial production.
Description of the drawings
Fig. 1 is γ-Al2O3And zinc-aluminum hydrotalcite XRD diagram prepared by in-situ synthesis；
Fig. 2 is catalyst for preparing hydrogen by reforming methanol and water vapour performance evaluation figure.
Specific implementation mode
In order to enable those skilled in the art to more fully understand, technical scheme of the present invention is practiced, with reference to specific 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 (mixed solution of liquid methanol and water) and enters per hour The volume flow of reaction system divided by the volume of catalyst, are indicated with WHSV, unit h-1。
Methanol conversion of the present invention is defined as the molar percentage that methanol in raw material is converted, i.e. first in raw material Molar percentage of the difference of alcohol and unreacted methanol relative to methanol in raw material, unit %.
The activity rating of catalyst provided by the present invention carries out in homemade quartz tube reactor, takes 40-80 purposes Catalyst volume is 2mL, and alcohol-water mixture inlet amount is controlled by micro pump, reforms gas and first passes through condenser condensation, through overdrying Enter SP1000 gas-chromatography on-line analyses after dry device drying, chromatographic column is carbon molecular sieve packed column, and detector is thermal conductivity (TCD) Detector, 50 DEG C of injector temperature, 50 DEG C of detector temperature, 100 DEG C of column temperature acquire sample after stable reaction.
The present invention is described in further detail below by embodiment.
Embodiment 1
Catalyst 1：5.89%CuO/18.76%ZnO/ γ-Al2O3
Its preparation process is as follows：
1) first claim 12g γ-Al2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495gZn (NO respectively again3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, be made into the nitrate solution of a concentration of 0.2mol/L, so After add 5g γ-Al2O3, it is uniformly mixed and forms mixed solution；
2) the ammonium hydroxide 500mL that mass fraction is 2% is prepared；Under stirring at normal temperature, prepared 2% ammonium hydroxide is added dropwise to In prepared mixed solution；When the pH=8 of solution, stop be added dropwise ammonium hydroxide, temperature be raised to 50 DEG C continue stirring measure afterwards for 24 hours The pH of solution；
3) ammonium hydroxide identical with above-mentioned pH and NH are prepared respectively again4NO3, it is spare to be mixed to form mixing, washing liquid；
4) step 2) gains are filtered, the ammonium hydroxide and NH prepared in filter cake step 3)4NO3The mixing of composition is washed It washs liquid washing sample 6-7 times, then allows ammonium hydroxide and NH4NO3Mixing, washing liquid submerges filter cake aging 1h in air, then spend from Sub- water washing to neutrality, at 70 DEG C after dry 12h zinc-aluminum hydrotalcite.Zinc-aluminum hydrotalcite roasts 4h at 400 DEG C and obtains metal oxygen Compound is denoted as Zn-Al/ γ-Al as catalyst carrier2O3400, grinding pack；
5) 0.9505g Cu (NO are weighed3)2·3H2100mL deionized waters are added in beaker in O, after stirring evenly, are added 5g Zn-Al/γ-Al2O3400 in beaker, and 1h is sufficiently stirred at 20 DEG C；Then mixed solution temperature is transferred to be set as By extra water evaporation in 80 DEG C of rotary evaporimeter, 12h is dried after evaporation in 60 DEG C of baking ovens, then roasted at 500 DEG C 3h, is ground to 120 mesh, and compression molding is ground into 40-80 mesh to get oxidized catalyst.
6) by oxidized catalyst 5%H obtained above2- 95%N mixed gas obtains metal in 280 DEG C of reductase 12 h The final catalyst 1 of elemental.
γ-Al2O3And zinc-aluminum hydrotalcite XRD diagram prepared by the in-situ synthesis obtained by the present embodiment is specifically shown in Fig. 1 institutes Show, catalyst of the present invention to synthesize evaluates, specifically, first hydrogen production from methanol-steam reforming by largely testing Alcohol vapor reforming hydrogen production catalyst performance evaluation figure is shown in Fig. 2.
After reduction, it is passed through the unstripped gas of the first alcohol and water after gasification, after reaction temperature to be achieved, start recording：Reaction pressure Power P=0.1MPa, T=260 DEG C of reaction temperature, water alcohol molar ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 1。
The methanol conversion of catalyst is made in 1 embodiment 1 of table
Embodiment 2
Catalyst 2：5.89%CuO/18.76%ZnO/ γ-Al2O3
Its preparation process is as follows：
1) 12g γ-Al are first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495gZn (NO respectively again3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, be made into the nitrate solution of a concentration of 0.1mol/L, so After add 5g γ-Al2O3, it is uniformly mixed and forms mixed solution；
2) the ammonium hydroxide 500mL that mass fraction is 5% is prepared；Under stirring at normal temperature, prepared 5% ammonium hydroxide is added dropwise to In prepared mixed solution；When the pH=8 of solution, stop be added dropwise ammonium hydroxide, temperature be raised to 50 DEG C continue stirring measure afterwards for 24 hours The pH of solution；
3) ammonium hydroxide identical with above-mentioned pH and NH are prepared respectively again4NO3, it is spare to be mixed to form mixing, washing liquid；
4) step 2) gains are filtered, the ammonium hydroxide and NH prepared in filter cake step 3)4NO3The mixing of composition is washed It washs liquid washing sample 6-7 times, then allows ammonium hydroxide and NH4NO3Mixing, washing liquid submerges filter cake aging 1h in air, then spend from Sub- water washing to neutrality, at 70 DEG C after dry 12h zinc-aluminum hydrotalcite.Zinc-aluminum hydrotalcite roasts 4h at 350 DEG C and obtains metal oxygen Compound is denoted as Zn-Al/ γ-Al as catalyst carrier2O3350, grinding pack；
5) 0.9505g Cu (NO are weighed3)2·3H2100mL deionized waters are added in beaker in O, after stirring evenly, are added 5g Zn-Al/γ-Al2O3350 in beaker, and 1h is sufficiently stirred at 20 DEG C；Then mixed solution temperature is transferred to be set as By extra water evaporation in 80 DEG C of rotary evaporimeter, 12h is dried after evaporation in 60 DEG C of baking ovens, then roasted at 500 DEG C 3h, is ground to 120 mesh, and compression molding is ground into 40-80 mesh to get oxidized catalyst.
6) by oxidized catalyst 5%H obtained above2- 95%N mixed gas obtains metal in 280 DEG C of reductase 12 h The final catalyst 2 of elemental.
After reduction, it is passed through the unstripped gas of the first alcohol and water after gasification, after reaction temperature to be achieved, start recording：Reaction pressure Power P=0.1MPa, T=260 DEG C of reaction temperature, water alcohol molar ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 2。
The methanol conversion of catalyst is made in 2 embodiment 2 of table
Embodiment 3
Catalyst：3：11.13%CuO/17.71%ZnO/ γ-Al2O3
Its preparation process is as follows：
1) 12g γ-Al are first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO respectively again3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, be made into the nitrate solution of a concentration of 0.05mol/L, Then 5g γ-Al are added2O3, it is uniformly mixed and forms mixed solution；
2) the ammonium hydroxide 500mL that mass fraction is 2% is prepared；Under stirring at normal temperature, prepared 2% ammonium hydroxide is added dropwise to In prepared mixed solution；When the pH=8 of solution, stop be added dropwise ammonium hydroxide, temperature be raised to 50 DEG C continue stirring measure afterwards for 24 hours The pH of solution；
3) ammonium hydroxide identical with above-mentioned pH and NH are prepared respectively again4NO3, it is spare to be mixed to form mixing, washing liquid；
4) step 2) gains are filtered, the ammonium hydroxide and NH prepared in filter cake step 3)4NO3The mixing of composition is washed It washs liquid washing sample 6-7 times, then allows ammonium hydroxide and NH4NO3Mixing, washing liquid submerges filter cake aging 1h in air, then spend from Sub- water washing to neutrality, at 70 DEG C after dry 12h zinc-aluminum hydrotalcite.Zinc-aluminum hydrotalcite roasts 4h at 400 DEG C and obtains metal oxygen Compound is denoted as Zn-Al/ γ-Al as catalyst carrier2O3400, grinding pack；
5) 1.9009g Cu (NO are weighed3)2·3H2100mL deionized waters are added in beaker in O, after stirring evenly, are added 5g Zn-Al/γ-Al2O3400 in beaker, and 1h is sufficiently stirred at 30 DEG C；Then mixed solution temperature is transferred to be set as By extra water evaporation in 80 DEG C of rotary evaporimeter, 12h is dried after evaporation in 60 DEG C of baking ovens, then roasted at 600 DEG C 3h, is ground to 120 mesh, and compression molding is ground into 40-80 mesh to get oxidized catalyst.
6) by oxidized catalyst 5%H obtained above2- 95%N mixed gas obtains metal in 280 DEG C of reductase 12 h The final catalyst 3 of elemental.
After reduction, it is passed through the unstripped gas of the first alcohol and water after gasification, after reaction temperature to be achieved, start recording：Reaction pressure Power P=0.1MPa, T=260 DEG C of reaction temperature, water alcohol molar ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 3。
The methanol conversion of catalyst is made in 3 embodiment 3 of table
Embodiment 4
Catalyst 4：11.13%CuO/17.71%ZnO/ γ-Al2O3
Its preparation process is as follows：
1) 12g γ-Al are first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO respectively again3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, be made into the nitrate solution of a concentration of 0.2mol/L, so After add 5g γ-Al2O3, it is uniformly mixed and forms mixed solution；
2) the ammonium hydroxide 500mL that mass fraction is 2% is prepared；Under stirring at normal temperature, prepared 2% ammonium hydroxide is added dropwise to In prepared mixed solution；When the pH=9 of solution, stop be added dropwise ammonium hydroxide, temperature be raised to 60 DEG C continue stirring measure afterwards for 24 hours The pH of solution；
3) ammonium hydroxide identical with above-mentioned pH and NH are prepared respectively again4NO3, it is spare to be mixed to form mixing, washing liquid；
4) step 2) gains are filtered, the ammonium hydroxide and NH prepared in filter cake step 3)4NO3The mixing of composition is washed It washs liquid washing sample 6-7 times, then allows ammonium hydroxide and NH4NO3Mixing, washing liquid submerges filter cake aging 1h in air, then spend from Sub- water washing to neutrality, at 70 DEG C after dry 12h zinc-aluminum hydrotalcite.Zinc-aluminum hydrotalcite roasts 4h at 400 DEG C and obtains metal oxygen Compound is denoted as Zn-Al/ γ-Al as catalyst carrier2O3400, grinding pack；
5) 1.9009Cu (NO are weighed3)2·3H2100mL deionized waters are added in beaker in O, and after stirring evenly, 5g is added Zn-Al/γ-Al2O3400 in beaker, and 1h is sufficiently stirred at 20 DEG C；Then mixed solution is transferred to temperature and is set as 80 DEG C Rotary evaporimeter in by extra water evaporation, after evaporation in 60 DEG C of baking ovens dry 12h, then roast 3h at 500 DEG C, grind 120 mesh are milled to, compression molding is ground into 40-80 mesh to get oxidized catalyst.
6) by oxidized catalyst 5%H obtained above2- 95%N mixed gas obtains metal in 280 DEG C of reductase 12 h The final catalyst 4 of elemental.
After reduction, it is passed through the unstripped gas of the first alcohol and water after gasification, after reaction temperature to be achieved, start recording：Reaction pressure Power P=0.1MPa, T=260 DEG C of reaction temperature, water alcohol molar ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 4。
The methanol conversion of catalyst is made in 4 embodiment 4 of table
Embodiment 5
Catalyst 5：11.13%CuO/9.84%ZnO/ γ-Al2O3
Its preparation process is as follows：
1) 12g γ-Al are first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO respectively again3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, be made into the nitrate solution of a concentration of 0.2mol/L, so After add 10g γ-Al2O3, it is uniformly mixed and forms mixed solution；
2) the ammonium hydroxide 500mL that mass fraction is 2% is prepared；Under stirring at normal temperature, prepared 2% ammonium hydroxide is added dropwise to In prepared mixed solution；When the pH=8 of solution, stop that ammonium hydroxide is added dropwise, temperature is raised to 60 DEG C and continues to measure after stirring 48h The pH of solution；
3) ammonium hydroxide identical with above-mentioned pH and NH are prepared respectively again4NO3, it is spare to be mixed to form mixing, washing liquid；
4) step 2) gains are filtered, the ammonium hydroxide and NH prepared in filter cake step 3)4NO3The mixing of composition is washed It washs liquid washing sample 6-7 times, then allows ammonium hydroxide and NH4NO3Mixing, washing liquid submerges filter cake aging 1h in air, then spend from Sub- water washing to neutrality, at 70 DEG C after dry 12h zinc-aluminum hydrotalcite.Zinc-aluminum hydrotalcite roasts 4h at 400 DEG C and obtains metal oxygen Compound is denoted as Zn-Al/ γ-Al as catalyst carrier2O3400, grinding pack；
5) 1.9009Cu (NO are weighed3)2·3H2100mL deionized waters are added in beaker in O, and after stirring evenly, 5g is added Zn-Al/γ-Al2O3400 in beaker, and 1h is sufficiently stirred at 20 DEG C；Then mixed solution is transferred to temperature and is set as 80 DEG C Rotary evaporimeter in by extra water evaporation, after evaporation in 60 DEG C of baking ovens dry 12h, then roast 3h at 500 DEG C, grind 120 mesh are milled to, compression molding is ground into 40-80 mesh to get oxidized catalyst.
6) by oxidized catalyst 5%H obtained above2- 95%N mixed gas obtains metal in 280 DEG C of reductase 12 h The final catalyst 5 of elemental.
After reduction, it is passed through the unstripped gas of the first alcohol and water after gasification, after reaction temperature to be achieved, start recording：Reaction pressure Power P=0.1MPa, T=260 DEG C of reaction temperature, water alcohol molar ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 5。
The methanol conversion of catalyst is made in 5 embodiment 5 of table
Embodiment 6
Catalyst 6：20.02%CuO/15.94%ZnO/ γ-Al2O3
Its preparation process is as follows：
1) 12g γ-Al are first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO respectively again3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, be made into the nitrate solution of a concentration of 0.1mol/L, so After add 10g γ-Al2O3, it is uniformly mixed and forms mixed solution；
2) the ammonium hydroxide 500mL that mass fraction is 2% is prepared；Under stirring at normal temperature, prepared 2% ammonium hydroxide is added dropwise to In prepared mixed solution；When the pH=8 of solution, stop be added dropwise ammonium hydroxide, temperature be raised to 70 DEG C continue stirring measure afterwards for 24 hours The pH of solution；
3) ammonium hydroxide identical with above-mentioned pH and NH are prepared respectively again4NO3, it is spare to be mixed to form mixing, washing liquid；
4) step 2) gains are filtered, the ammonium hydroxide and NH prepared in filter cake step 3)4NO3The mixing of composition is washed It washs liquid washing sample 6-7 times, then allows ammonium hydroxide and NH4NO3Mixing, washing liquid submerges filter cake aging 1h in air, then spend from Sub- water washing to neutrality, at 70 DEG C after dry 12h zinc-aluminum hydrotalcite.Zinc-aluminum hydrotalcite roasts 4h at 400 DEG C and obtains metal oxygen Compound is denoted as Zn-Al/ γ-Al as catalyst carrier2O3400, grinding pack；
5) 3.8019Cu (NO are weighed3)2·3H2100mL deionized waters are added in beaker in O, after stirring evenly, are added 10g Zn-Al/γ-Al2O3400 in beaker, and 2h is sufficiently stirred at 30 DEG C；Then mixed solution temperature is transferred to be set as By extra water evaporation in 80 DEG C of rotary evaporimeter, 12h is dried after evaporation in 60 DEG C of baking ovens, then roasted at 500 DEG C 3h, is ground to 120 mesh, and compression molding is ground into 40-80 mesh to get oxidized catalyst.
6) by oxidized catalyst 5%H obtained above2- 95%N mixed gas obtains metal in 280 DEG C of reductase 12 h The final catalyst 6 of elemental.
After reduction, it is passed through the unstripped gas of the first alcohol and water after gasification, after reaction temperature to be achieved, start recording：Reaction pressure Power P=0.1MPa, T=260 DEG C of reaction temperature, water alcohol molar ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 6。
The methanol conversion of catalyst is made in 6 embodiment 6 of table
Embodiment 7
Catalyst 7：20.02%CuO/15.94%ZnO/ γ Al2O3
Its preparation process is as follows：
1) 12g γ-Al are first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO respectively again3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, be made into the nitrate solution of a concentration of 0.2mol/L, so After add 10g γ-Al2O3, it is uniformly mixed and forms mixed solution；
2) the ammonium hydroxide 500mL that mass fraction is 2% is prepared；Under stirring at normal temperature, prepared 2% ammonium hydroxide is added dropwise to In prepared mixed solution；When the pH=8 of solution, stop be added dropwise ammonium hydroxide, temperature be raised to 50 DEG C continue stirring measure afterwards for 24 hours The pH of solution；
3) ammonium hydroxide identical with above-mentioned pH and NH are prepared respectively again4NO3, it is spare to be mixed to form mixing, washing liquid；
4) step 2) gains are filtered, the ammonium hydroxide and NH prepared in filter cake step 3)4NO3The mixing of composition is washed It washs liquid washing sample 6-7 times, then allows ammonium hydroxide and NH4NO3Mixing, washing liquid submerges filter cake aging 1h in air, then spend from Sub- water washing to neutrality, at 70 DEG C after dry 12h zinc-aluminum hydrotalcite.Zinc-aluminum hydrotalcite roasts 4h at 400 DEG C and obtains metal oxygen Compound is denoted as Zn-Al/ γ-Al as catalyst carrier2O3400, grinding pack；
5) 3.8019Cu (NO are weighed3)2·3H2100mL deionized waters are added in beaker in O, after stirring evenly, are added 10g Zn-Al/γ-Al2O3400 in beaker, and 2h is sufficiently stirred at 30 DEG C；Then mixed solution temperature is transferred to be set as By extra water evaporation in 80 DEG C of rotary evaporimeter, 12h is dried after evaporation in 60 DEG C of baking ovens, then roasted at 500 DEG C 3h, is ground to 120 mesh, and compression molding is ground into 40-80 mesh to get oxidized catalyst.
6) by oxidized catalyst 5%H obtained above2- 95%N mixed gas obtains metal in 280 DEG C of reductase 12 h The final catalyst 7 of elemental.
After reduction, it is passed through the unstripped gas of the first alcohol and water after gasification, after reaction temperature to be achieved, start recording：Reaction pressure Power P=0.1MPa, T=260 DEG C of reaction temperature, water alcohol molar ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 7。
The methanol conversion of catalyst is made in 7 embodiment 7 of table
Embodiment 8
Catalyst 8：20.02%CuO/15.94%ZnO/ γ-Al2O
Its preparation process is as follows：
1) 12g γ-Al are first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO respectively again3)2· 6H2O, 1.2242g NH4NO3, the two mixes and adds deionized water dissolving, be made into the nitrate solution of a concentration of 0.2mol/L, so After add 10g γ-Al2O3, it is uniformly mixed and forms mixed solution；
2) the ammonium hydroxide 500mL that mass fraction is 2% is prepared；Under stirring at normal temperature, prepared 2% ammonium hydroxide is added dropwise to In prepared mixed solution；When the pH=8 of solution, stop be added dropwise ammonium hydroxide, temperature be raised to 60 DEG C continue stirring measure afterwards for 24 hours The pH of solution；
3) ammonium hydroxide identical with above-mentioned pH and NH are prepared respectively again4NO3, it is spare to be mixed to form mixing, washing liquid；
4) step 2) gains are filtered, the ammonium hydroxide and NH prepared in filter cake step 3)4NO3The mixing of composition is washed It washs liquid washing sample 6-7 times, then allows ammonium hydroxide and NH4NO3Mixing, washing liquid submerges filter cake aging 1h in air, then spend from Sub- water washing to neutrality, at 70 DEG C after dry 12h zinc-aluminum hydrotalcite.Zinc-aluminum hydrotalcite roasts 4h at 400 DEG C and obtains metal oxygen Compound is denoted as Zn-Al/ γ-Al as catalyst carrier2O3400, grinding pack；
5) 3.8019Cu (NO are weighed3)2·3H2100mL deionized waters are added in beaker in O, after stirring evenly, are added 10g Zn-Al/γ-Al2O3400 in beaker, and 2h is sufficiently stirred at 30 DEG C；Then mixed solution temperature is transferred to be set as By extra water evaporation in 90 DEG C of rotary evaporimeter, 12h is dried after evaporation in 60 DEG C of baking ovens, then roasted at 500 DEG C 3h, is ground to 120 mesh, and compression molding is ground into 40-80 mesh to get oxidized catalyst.
6) by oxidized catalyst 5%H obtained above2- 95%N mixed gas in 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 the first alcohol and water after gasification, after reaction temperature to be achieved, start recording：Reaction pressure Power P=0.1MPa, T=260 DEG C of reaction temperature, water alcohol molar ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 8。
The methanol conversion of catalyst is made in 8 embodiment 8 of table
Comparative example 1
Catalyst I：11.13%CuO/17.71%ZnO/ γ-Al2O3
Its preparation process is as follows：
1) 12g γ-Al are first weighed2O3600 DEG C of roasting 4h in Muffle furnace；Weigh 4.5495g Zn (NO respectively again3)2· 6H2O, adds 100mL deionized water dissolvings, then adds 10g γ-Al2O3, it is uniformly mixed；12h is sufficiently stirred at 20 DEG C, so Mixed solution temperature is transferred to afterwards to be set as that product being then placed on to extra water evaporation in 80 DEG C of rotary evaporimeter Dry 12h, is denoted as Zn/ γ-Al in 70 DEG C of baking ovens2O3
2) 1.9010Cu (NO are weighed3)2·3H2O is added 100mL deionized water dissolvings, 5g is then added in beaker Zn-Al/γ-Al2O3, it is uniformly mixed at 20 DEG C and is sufficiently stirred 12h, mixed solution, which is then transferred to temperature, is set as 80 DEG C By extra water evaporation in rotary evaporimeter, 12h is dried after evaporation in 70 DEG C of baking ovens, then 3h is roasted at 500 DEG C, ground To 120 mesh, compression molding is ground into 40-80 mesh to get oxidized catalyst.
3) by oxidized catalyst 5%H obtained above2- 95%N mixed gas obtains metal in 280 DEG C of reductase 12 h The final catalyst I of elemental.
After reduction, it is passed through the unstripped gas of the first alcohol and water after gasification, after reaction temperature to be achieved, start recording：Reaction pressure Power P=0.1MPa, T=260 DEG C of reaction temperature, water alcohol molar ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 9。
The methanol conversion of catalyst is made in 9 comparative example 1 of table
Comparative example 2
Catalyst II：17.26%CuO/58.36%ZnO/Al2O3
Its preparation process is as follows：
1) NaOH and Na that 100mL concentration is 1.0mol/L are prepared2CO3Aqueous solution it is spare；
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 is uniformly mixed；Under 60 DEG C of stirrings, by the 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 that NaOH and Na is added dropwise2CO3Aqueous solution, continue anti- It should for 24 hours；Precipitation is filtered, is washed with deionized to neutrality, 4h is roasted at 400 DEG C after dry 12h at 70 DEG C, is denoted as Zn- Al 400, grinding pack；
3) 1.9010g Cu (NO are weighed3)2·3H2100mL deionized waters are added in beaker in O, after stirring evenly, are added 3g Zn-Al 400 are sufficiently stirred 1h in beaker at 20 DEG C, mixed solution is then transferred to the rotation that temperature is set as 90 DEG C By extra water evaporation in rotatable evaporimeter, 12h is dried after evaporation in 60 DEG C of baking ovens, then 3h is roasted at 500 DEG C, be ground to 120 mesh, compression molding are ground into 40-80 mesh to get oxidized catalyst；
4) by oxidized catalyst 5%H obtained above2- 95%N mixed gas obtains metal in 280 DEG C of reductase 12 h The final catalyst II of elemental.
After reduction, it is passed through the unstripped gas of the first alcohol and water after gasification, after reaction temperature to be achieved, start recording；Reaction pressure Power P=0.1MPa, T=260 DEG C of reaction temperature, water alcohol molar ratio W/M=1.2, air speed WHSV=3.8h-1, evaluation result is shown in Table 10。
The methanol conversion of catalyst is made in 10 comparative example 2 of table
Embodiment described above is only to absolutely prove that preferred embodiment that is of the invention and being lifted, protection domain are unlimited In this.Those skilled in the art on the basis of the present invention made by equivalent substitute or transformation, the present invention protection Within the scope of, protection scope of the present invention is subject to claims.

Claims (8)

1. a kind of catalyst for methanol steam catalytically reforming hydrogen producing, which is characterized in that the catalyst uses Cu metals Oxide is introduced as active constituent, the active constituent using the method for dipping, and gained oxide after zinc-aluminum hydrotalcite is roasted As catalyst carrier, the zinc-aluminum hydrotalcite is prepared using in-situ synthesis, with γ-Al2O3, synthesized for silicon source；
Wherein, the content of the catalyst active component accounts for the 1-30% of catalyst gross mass in terms of oxide；The catalyst The content of carrier accounts for the 70%-99% of catalyst gross mass in terms of oxide；In the catalyst carrier, Zn content is to aoxidize Object meter accounts for the 5%-30% of zinc-aluminium gross mass.
2. the catalyst according to claim 1 for methanol steam catalytically reforming hydrogen producing, which is characterized in that described to urge The content of agent active constituent accounts for the 5-15% of catalyst gross mass in terms of oxide；The content of the catalyst carrier is with oxygen Compound meter accounts for the 85-95% of catalyst gross mass；In the catalyst carrier, Zn content accounts for zinc-aluminium gross mass in terms of oxide 10-20%.
3. the catalyst according to claim 2 for methanol steam catalytically reforming hydrogen producing, which is characterized in that described to urge The content of agent active constituent accounts for the 5.89% of catalyst gross mass in terms of oxide；The content of the catalyst carrier is with oxygen Compound meter accounts for the 94.11% of catalyst gross mass；In the catalyst carrier, Zn content accounts for zinc-aluminium gross mass in terms of oxide 18.76%.
4. being used for the catalyst of methanol steam catalytically reforming hydrogen producing according to claim 1-3 any one of them, feature exists In the catalyst is suitable for normal pressure, and 200-350 DEG C of reaction temperature, water alcohol molar ratio is in 1-2, mass space velocity 1h-1-7h-1's Under the conditions of to methanol steam carry out catalytically reforming hydrogen producing.
5. the preparation method of the catalyst according to claim 1 for methanol steam catalytically reforming hydrogen producing, feature It is, includes the following steps：
S1：Zn (NO are weighed respectively with the ratio that molar ratio is 1: 1: 3-6.53)2·6H2O、NH4NO3With γ-Al2O3, by γ- Al2O32-4h is roasted at 560-600 DEG C, and by Zn (NO3)2·6H2O and NH4NO3Add water mixed dissolution, then adds roasting γ-Al afterwards2O3, it is uniformly mixed and forms mixed liquor, the pH value of mixed liquor is adjusted with mass fraction is 1-10% ammonium hydroxide, adjusts Process is stirred continuously, after pH reaches 7-10, continue at a temperature of 40-80 DEG C stir 0h-48h, then washed, aging, washing, Zinc-aluminum hydrotalcite is obtained after drying；
S2：The zinc-aluminum hydrotalcite is roasted into obtain metal oxide at 350-500 DEG C；
S3：It takes the metal oxide that S2 is roasted as catalyst carrier, Cu is impregnated at 20-60 DEG C using infusion process (NO3)2·3H2Then O solution, dip time 1-2h are evaporated, after drying at 50-100 DEG C, are roasted at 350-600 DEG C Obtain oxidized catalyst；
S4：By oxidized catalyst in H2-N2In 250-280 DEG C of reductase 12-8h under the atmosphere of gaseous mixture, final catalyst is obtained.
6. the preparation method of the catalyst according to claim 5 for methanol steam catalytically reforming hydrogen producing, feature It is, in S4, the H2-N2H in gaseous mixture2A concentration of 1-20%.
7. the preparation method of the catalyst according to claim 6 for methanol steam catalytically reforming hydrogen producing, feature It is,
A certain amount of Zn (NO are weighed respectively with the ratio that molar ratio is 1: 1: 53)2·6H2O、NH4NO3With γ-Al2O3, by γ- Al2O34h is roasted at 600 DEG C, and by Zn (NO3)2·6H2O and NH4NO3Add water mixed dissolution, forms Zn (NO3)2·6H2O solution A concentration of 0.2mol/L, NH4NO3Solution concentration is the lysate of 0.2mol/L, then adds the γ-Al after roasting2O3, mix Conjunction is formed uniformly mixed liquor, adjusts the pH value of mixed liquor for 2% ammonium hydroxide with mass fraction, and adjustment process is stirred continuously, and waits for pH After reaching 8, continue stirring at a temperature of 50 DEG C for 24 hours, then zinc-aluminum hydrotalcite is obtained after washed, aging, washing, drying；
Obtained zinc-aluminum hydrotalcite is roasted into 4h at 400 DEG C and obtains metal oxide, takes the metal oxide that roasting obtains to be used as and urges Agent carrier impregnates Cu (NO using infusion process at 20 DEG C3)2·3H2O solution, dip time 1h, then successively at 80 DEG C Lower evaporation, dry 12h under the conditions of 60 DEG C roast 3h at 500 DEG C, are ground to 120 mesh, compression molding is ground into 40-80 mesh, i.e., Obtain oxidized catalyst；By oxidized catalyst 5%H obtained2- 95%N2Mixed gas obtains target in 280 DEG C of reductase 12 h Catalyst.
8. the catalyst according to claim 1 for methanol steam catalytically reforming hydrogen producing, which is characterized in that described to urge Agent is applied to hydrogen production from methanol-steam reforming process, or applied to methanol-fueled CLC and other reformation hydrogen production processes.
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