CN110508315A - A kind of catalyst for preparing hydrogen by reforming methanol and water vapour and preparation method thereof - Google Patents

A kind of catalyst for preparing hydrogen by reforming methanol and water vapour and preparation method thereof Download PDF

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CN110508315A
CN110508315A CN201910651971.5A CN201910651971A CN110508315A CN 110508315 A CN110508315 A CN 110508315A CN 201910651971 A CN201910651971 A CN 201910651971A CN 110508315 A CN110508315 A CN 110508315A
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catalyst
zno
zro
methanol
water vapour
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李淇
陈秋雄
樊栓狮
杨光
陈运文
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Shenzhen Gas Corp Ltd
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Shenzhen Gas Corp Ltd
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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
    • B01J23/002—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
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
    • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
    • 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
    • C01B3/326—Catalytic reaction of gaseous or liquid organic compounds other than hydrocarbons with gasifying agents characterised by the catalyst
    • 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
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
    • B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/02—Processes for making hydrogen or synthesis gas
    • C01B2203/0205—Processes for making hydrogen or synthesis gas containing a reforming step
    • C01B2203/0227—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step
    • C01B2203/0233—Processes for making hydrogen or synthesis gas containing a reforming step containing a catalytic reforming step the reforming step being a steam reforming step
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/10—Catalysts for performing the hydrogen forming reactions
    • C01B2203/1041—Composition of the catalyst
    • C01B2203/1076—Copper or zinc-based catalysts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
    • C01B2203/12—Feeding the process for making hydrogen or synthesis gas
    • C01B2203/1205—Composition of the feed
    • C01B2203/1211—Organic compounds or organic mixtures used in the process for making hydrogen or synthesis gas
    • C01B2203/1217—Alcohols
    • C01B2203/1223—Methanol

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  • Crystallography & Structural Chemistry (AREA)
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Abstract

The invention discloses a kind of preparing hydrogen by reforming methanol catalyst and preparation method thereof, the preparing hydrogen by reforming methanol catalyst group becomes ZnO-ZrO2/ ZSM-5 molecular sieve, the ZSM-5 molecular sieve are catalyst carrier, the ZnO-ZrO2For active component, the ZnO-ZrO2For solid solution.Present invention introduces molecular sieves as carrier, increases the dispersion degree of catalyst activity component by the ZSM-5 molecular sieve, and act synergistically with active component.Catalyst of the invention reaches optimal performance at 380 DEG C, overcomes the high disadvantage of traditional zno-based catalyst reforming reaction temperature, while improving methanol conversion and H2Yield reduces CO selectivity.

Description

A kind of catalyst for preparing hydrogen by reforming methanol and water vapour and preparation method thereof
Technical field
The invention belongs to catalyst technical fields, and in particular to a kind of methanol steam catalytically reforming hydrogen producing catalyst and its Preparation method.
Background technique
With the lasting reduction of world oil reserves, ball ecological environment constantly deteriorates, energy and environmental problem at An important factor for restrict various countries' sustained economic development, therefore, develop new clear energy sources and improve the energy utilization rate oneself Through becoming 21 century letter problem to be solved.Fuel cell is a kind of novel power generation dress for directly converting chemical energy into electric energy It sets, by the concern of people due to it is with series of advantages such as high-energy conversion efficiency, low noise, zero-emissions, becomes new energy The hot fields of source material research and development.Proton Exchange Membrane Fuel Cells (PEMFC) is compared into all fuel cell studies Ripe and be most hopeful to obtain the fuel cell of industrial application, it can be applied to the electronics such as automobile, laptop and mobile phone In product.The fuel of PEMFC is hydrogen, however the commercialized biggest obstacle of PEMFC is exactly unstripped gas-hydrogen source and storage It deposits.Hydrogen is unsuitable directly vehicle-mounted since price is high, safety is poor, transport storage and filling are difficult.And it is instant with liquid fuel (on-board) hydrogen manufacturing can overcome hydrogen built-in problem.Methanol is considered as a kind of best hydrogen carrier, because it is in institute Possible with fossil fuel in have apparent advantage.
Metal-based catalyst for methanol steam reforming mainly has nickel catalyst, Cu-series catalyst and noble metal to urge Agent.Although nickel catalyst stability is good, applied widely, its low temperature active is not high and reaction exports CO too high levels, Poor selectivity.Although noble metal catalyst catalytic activity is high, good, its expensive and easy inactivation of selectivity.Cu base is urged Agent is the most widely used methanol reforming catalyst because of the advantage that its is cheap and low temperature active is good, but there is selection Property and thermal stability it is poor, under high temperature be easy sintering deactivation the problem of.
Compared with metal-based catalyst, metal oxide catalyst has using preceding without reduction, not easy-sintering, preparation side The advantages that method is simple and cheap is also widely studied application.Currently, industrial most widely used Methanol cluster system Hydrogen catalyst is CuO/ZnO/Al2O3Catalyst, due to the both sexes feature of zinc-aluminium, the additional amount of Al needs stringent control in co-precipitation System, and the surface area of the dispersion to copper, particle size and catalyst all has an impact, and then influences the activity and stabilization of catalyst Property.
Zinc based catalyst having well in hydrogen production from methanol-steam reforming reaction using zinc oxide as active component Stability and higher selectivity.But the zinc based catalyst reforming temperature using zinc oxide as active component is generally higher than 400 DEG C, preferable catalytic activity could be obtained at 450 DEG C or so, this results in reaction high energy consumptions.
Summary of the invention
In view of above-mentioned deficiencies of the prior art, the present invention provide a kind of novel carbinol steam reformed hydrogen-producing catalyst and its Preparation method, it is intended to overcome catalytic activity existing for existing Methanol cluster catalyst for preparing hydrogen is unstable, thermal stability is poor, The disadvantage that reaction selectivity is poor, reforming temperature is high.
The technical scheme adopted by the invention is as follows:
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour, wherein the group of the catalyst becomes ZnO-ZrO2/ ZSM-5 molecular sieve, The ZSM-5 molecular sieve is catalyst carrier, the ZnO-ZrO2For active component, wherein the ZnO-ZrO2For solid solution.
The catalyst for preparing hydrogen by reforming methanol and water vapour, wherein the ZnO-ZrO2ZnO molar fraction is in solid solution 10%-80%。
The catalyst for preparing hydrogen by reforming methanol and water vapour, wherein the ZnO-ZrO2With two kinds of groups of ZSM-5 molecular sieve The mass ratio divided is 0.5-5:1.
The catalyst for preparing hydrogen by reforming methanol and water vapour, wherein the partial size of the ZSM-5 molecular sieve is 6-12nm, than Surface area is 120-200m2·g-1。
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour as described above, the preparation method include following step It is rapid:
S1, using the metal salt of Zn and Zr as precursor preparation precursor solution, the precursor solution is handled to obtain ZnO-ZrO2Solid solution, wherein the method handled the precursor solution is infusion process or the precipitation method；
S2, by the ZnO-ZrO obtained2Solid solution and ZSM-5 molecular sieve are made the methanol-water by mechanical milling method and steam Gas reforming hydrogen-production catalyst.
The preparation method of the catalyst for preparing hydrogen by reforming methanol and water vapour, wherein the metal salt is soluble nitric acid One or more of salt, sulfate, hydrochloride or acetate.
The preparation method of the catalyst for preparing hydrogen by reforming methanol and water vapour, wherein the whipping temp and dipping temperature Degree is room temperature, and dip time 8-12h, the calcination temperature is 400-800 DEG C, calcination time 2-6h.
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour as described above is applied to the method for hydrogen manufacturing, comprising the following steps:
In fixing tubular reactor, ZnO-ZrO is loaded2/ ZSM-5 catalyst, with N2As carrier gas, under heating conditions It is passed through vapor and methanol is that raw material is reacted.
The catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, wherein reaction temperature 320-460 DEG C, reaction velocity 3000-8000mlgcat -1·h-1, the molar ratio of water and methanol is 0.8-2:1.
The catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, wherein reaction temperature is 380 DEG C.
The utility model has the advantages that the invention discloses a kind of preparing hydrogen by reforming methanol catalyst and preparation method thereof, the methanol recapitalization Catalyst for preparing hydrogen group becomes ZnO-ZrO2/ ZSM-5 molecular sieve, the ZSM-5 molecular sieve are catalyst carrier, the ZnO-ZrO2 For active component, the ZnO-ZrO2For solid solution.It is high that the catalyst overcomes traditional zno-based catalyst reforming reaction temperature The shortcomings that, peak optimization reaction temperature is 380 DEG C.The present invention passes through the ZSM-5 molecule by introducing molecular sieve as carrier Sieve increases the dispersion degree of active component, and and ZnO-ZrO2Solid solution acts synergistically, and improves methanol conversion and H2It produces Rate reduces CO selectivity.
Detailed description of the invention
Fig. 1 is methanol conversion in embodiment 11 with reaction time change curve.
Specific embodiment
The present invention provides a kind of catalyst for preparing hydrogen by reforming methanol and water vapour and preparation method thereof, for make the purpose of the present invention, Technical solution and effect are clearer, clear, and the present invention is described in more detail below.It should be appreciated that described herein Specific embodiment is used only for explaining the present invention, is not intended to limit the present invention.
In the present embodiment, the reaction velocity is defined as methanol and enters the volume flow of reaction system per hour divided by urging The quality of agent, unit gcat-1·h-1。
In the present embodiment, the methanol conversion be defined as in product the molar fraction of carbon monoxide and carbon dioxide it With the molar fraction of carbon atom in product with the ratio between, unit %.
Present embodiments provide a kind of catalyst for preparing hydrogen by reforming methanol and water vapour and preparation method thereof, the group of the catalyst As zinc oxide (ZnO)-zirconium oxide (ZrO2)/ZSM-5 molecular sieve.The ZnO-ZrO2For active component, ZSM-5 molecular sieve is Catalyst carrier.
In the present embodiment, the ZnO-ZrO2For solid solution, and in the ZnO-ZrO2It is ZnO moles in solid solution Score is 10%-80%, the ZnO, ZnO-ZrO for being 10%-80% by using molar fraction2Solid solution can play preferable reaction Activity, in the ZnO-ZrO for being 10%-80% by the ZnO molar fraction2Solid solution is made the hydrogen production from methanol-steam reforming and urges Agent is applied in the reaction of hydrogen manufacturing, and the conversion ratio of methanol can achieve 80% or more.In addition, one in the present embodiment is excellent It selects in implementation, the molar fraction of the ZnO is preferably 15%, is using 15%ZnO-ZrO2Solid solution prepares the methanol-water Vapour reforming hydrogen producing catalyst is applied in the reaction of hydrogen manufacturing, and methanol conversion can achieve nearly 100%, while H2Yield is high Selectively low up to 99%, CO, the catalyst for preparing hydrogen by reforming methanol and water vapour is optimal performance.
Further, ZSM-5 molecular sieve is a kind of aluminosilicate molecular sieves material with MFI structure, ZSM-5 molecular sieve Aperture is 0.5-0.6 nanometers, and has excellent thermal stability and highly acid.Therefore, ZSM-5 molecular sieve can be as load Body will be carried on the ZnO-ZrO on its surface2Solid solution is dispersed, and ZnO-ZrO is increased2The reactivity of solid solution, and can make For solid acid catalyst, catalysis enters the reaction that the small molecules such as the first alcohol and water inside ZSM-5 molecular sieve structure occur, with institute State ZnO-ZrO2Solid solution acts synergistically, it is made to play better catalytic effect.In the present embodiment, ZSM-5 molecular sieve Partial size is 6-12nm, and specific surface area is 120-200 m2·g-1, increase active component ZnO-ZrO2The dispersion degree of solid solution, and It acts synergistically with active component, improves the catalytic effect of catalyst.
Based on above-mentioned methanol steam catalytically reforming hydrogen producing catalyst, the present embodiment additionally provides a kind of methanol steam weight The preparation method of whole catalyst for preparing hydrogen, the preparation method comprises the following steps:
S10, using the metal salt of Zn and Zr as precursor preparation precursor solution, the precursor solution is handled to obtain ZnO-ZrO2Solid solution, wherein the method handled the precursor solution is infusion process or the precipitation method.
Specifically, the method handled to the precursor solution is the precipitation method, the precipitation method the following steps are included: First being calculated according to default ZnO molar fraction needs the metal salt of weighed preset quality Zn and Zr as presoma and deionized water It is mixedly configured into the precursor solution of preset concentration, while weighing the (NH of preset quality4)2CO3Configure (the NH of preset concentration4)2CO3Solution, under 60 DEG C of stirring conditions, by the preset concentration (NH4)2CO3Solution is slowly dropped to the precursor solution Middle formation precipitating, the pH value for controlling solution is 7.0-9.0, continues to stir 2 h, be cooled to room temperature, filters, deionized water washing 5 It is secondary；The sediment is placed in Muffle furnace by gained sediment after drying in air atmosphere 5 h of lower 100 DEG C of dryings 500 DEG C of 3 h of constant temperature calcining obtain the catalyst activity component ZnO-ZrO of default molar fraction2Solid solution.
Further, in an implementation of the present embodiment, the method that the precursor solution is handled is dipping Method, the infusion process is the following steps are included: first preset the weighed Zn's and Zr of ZnO molar fraction calculating needs according to by active component The preset quality of metal salt, the metal salt for accurately weighing preset quality Zn and Zr is presoma, and deionized water dissolving configuration is added dropwise At the precursor solution of preset concentration；The precursor solution is stirred at room temperature after impregnating 8-24 h and is heated under uniform stirring It is evaporated, 2-6 hour is calcined at 400-800 DEG C, obtain the active component ZnO-ZrO of default molar fraction2.In addition, described Metal salt is soluble one or more of nitrate, sulfate, hydrochloride or acetate.One of the present embodiment is excellent It selects in embodiment, the metal salt uses nitrate.
S20, by the ZnO-ZrO obtained2The methanol is made by mechanical milling method in solid solution and ZSM-5 molecular sieve Vapor reforming hydrogen production catalyst.
Specifically, the mechanical milling method is the following steps are included: by ZnO-ZrO obtained2Solid solution and ZSM-5 molecular sieve It is uniformly mixed by preset quality ratio by mechanical lapping, tabletting, which is sieved, is made hydrogen production from methanol-steam reforming described in 40-60 purpose Catalyst.In the present embodiment, the ZnO-ZrO2Solid solution and the mass ratio of two kinds of components of ZSM-5 molecular sieve are 0.5-5:1, According to the ratio that mass ratio is 0.5-5:1 by ZnO-ZrO2Solid solution be carried on ZSM-5 molecular sieve carrier can increase it is described Catalyst activity component ZnO-ZrO2The dispersion degree of solid solution, while the amount for controlling ZSM-5 molecular sieve avoids ZnO-ZrO2Solid solution The active site on surface is covered by excessive ZSM-5 molecular sieve and its activity is caused to reduce.One in the present embodiment is preferred real In existing mode, using ZnO-ZrO2Solid solution and the mass ratio of two kinds of components of ZSM-5 molecular sieve are 2:1, can make ZnO-ZrO2 Solid solution obtains optimum dispersion degree and keeps its activity unaffected simultaneously, so that the hydrogen production from methanol-steam reforming is catalyzed Agent is optimal performance.
Based on above-mentioned methanol steam catalytically reforming hydrogen producing catalyst, the present embodiment additionally provides a kind of such as above-described embodiment The catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, the described method comprises the following steps:
M10, in fixing tubular reactor, load ZnO-ZrO2/ ZSM-5 catalyst, with N2As carrier gas, in the item of heating It is passed through vapor under part and methanol is that raw material is reacted.
Specifically, the catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and its step are as follows, takes default The catalyst for preparing hydrogen by reforming methanol and water vapour ZnO-ZrO of quality and mesh number2/ ZSM-5 is placed in quartz ampoule, under normal pressure described in heating Quartz ampoule carries out the reaction at a certain temperature, with N2It is logical to reactor under default reaction velocity as carrier gas The vapor and methanol for entering default molar ratio are reacted, and terminate sampling analysis after reacting one section of preset time.
Further, the method that the catalyst for preparing hydrogen by reforming methanol and water vapour is applied to hydrogen manufacturing is divided into the progress of two steps:
Step 1: CH3OH→CO+2H2
Step 2: CO+2H2O→CO2+H2
Catalyst poisoning is made due to the CO in reaction, is needed in hydrogen production from methanol-steam reforming reaction process described in strict control The content of the CO of generation, eventually by detection CH3Conversion ratio, the H of OH2Yield and the selectivity of CO can be urged with overall merit The performance of agent.
In the present embodiment, the catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and reaction temperature is 320-460 DEG C, temperature is higher, and the catalytic activity of catalyst is consequently increased, and the content of another aspect CO by-product also increases, CO Selectivity increase will lead to the catalyst for preparing hydrogen by reforming methanol and water vapour poisoning and deactivation, to reduce its catalytic effect.In In one preferred implementation of the present embodiment, the catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the anti-of the method for hydrogen manufacturing Answering temperature is 380 DEG C, and at such a temperature, methanol conversion can achieve nearly 100%, while H2Yield is up to 99%, CO selection Property is low, and the catalyst for preparing hydrogen by reforming methanol and water vapour is optimal performance.
In the present embodiment, the catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and reaction velocity is 3000-8000ml·gcat -1·h-1, the molar ratio of water and methanol is 0.8-2:1.It specifically, is 380 DEG C in reaction temperature, water The molar ratio of steam and methanol is 1.2:1, and reaction velocity is 4500 mlgcat -1·h-1Under conditions of, the methanol steam Reforming hydrogen-production catalyst is optimal performance.
Further, in the case where the catalyst for preparing hydrogen by reforming methanol and water vapour is optimal the reaction condition of performance, the first Alcohol vapor reforming hydrogen production catalyst is applied to the method for hydrogen manufacturing during the reaction every sampling analysis in 1 hour, Therapy lasted 9 After hour, the catalyst for preparing hydrogen by reforming methanol and water vapour still keeps higher activity, and methanol conversion still can achieve 90% or more.
Further, in the case where the catalyst for preparing hydrogen by reforming methanol and water vapour is optimal the reaction condition of performance, this implementation By the catalyst for preparing hydrogen by reforming methanol and water vapour ZnO-ZrO in example2/ ZSM-5 is substituted for without ZSM-5 molecular sieve and has phase With the ZnO-ZrO of ZnO molar fraction2Catalyst, only with active component ZnO-ZrO2Solid solution is not being used as catalyst In the case where catalyst carrier, compared to the catalyst for preparing hydrogen by reforming methanol and water vapour ZnO-ZrO2/ ZSM-5, ZnO-ZrO2It urges The catalytic performance of agent substantially reduces.The present invention is with ZnO-ZrO2Solid solution is to reform active component, is to carry with ZSM-5 molecular sieve Body increases active component ZnO- using its cellular structure with 0.5-0.6 nanometers of medium micropore, excellent thermal stability ZrO2The dispersion degree of solid solution, and and ZnO-ZrO2Solid solution acts synergistically, and improves hydrogen production from methanol-steam reforming catalysis Agent activity, reduces the reforming temperature of hydrogen production from methanol-steam reforming.
Below by specific embodiment, the invention will be further described.
Embodiment 1
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 1.0 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4·5H2O It is dissolved in 100 ml deionized waters, weighs 5.10 g (NH4)2CO3It is configured to 100ml solution.It, will under 60 DEG C of stirring conditions (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, continues to stir 2 h are mixed, are cooled to room temperature, are filtered, deionized water is washed 5 times；Gained sediment is done in air atmosphere 5 h of lower 100 DEG C of dryings Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after dry, obtains catalyst activity component ZnO-ZrO2Gu Solution, wherein the molar fraction of ZnO is 15%, i.e. 15% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 15% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The reaction that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40-60 mesh methanol-water Vapour reforming hydrogen producing catalyst Z nO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, under normal pressure Reaction temperature is 380 DEG C, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of be passed through to reactor Molar ratio is that the vapor of 1.2:1 and methanol are reacted, and reacts about 2 hours end sampling analyses, experimental result is shown in Table 1.
Embodiment 2
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 2.426 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4· 5H2O is dissolved in 100 ml deionized waters, weighs 6.458 g (NH4)2CO3It is configured to 100ml solution.In 60 DEG C of stirring conditions Under, by (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, Continue to stir 2 h, be cooled to room temperature, filter, deionized water is washed 5 times；Gained sediment is in the lower 100 DEG C of dryings 5 of air atmosphere Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after drying, obtains catalyst activity component ZnO- by h ZrO2Solid solution, wherein the molar fraction of ZnO is 30%, i.e. 30% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 30% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The reaction that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40-60 mesh methanol-water Vapour reforming hydrogen producing catalyst Z nO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, under normal pressure Reaction temperature is 380 DEG C, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of be passed through to reactor Molar ratio is that the vapor of 1.2:1 and methanol are reacted, and reacts about 2 hours end sampling analyses, experimental result is shown in Table 1.
Embodiment 3
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 5.669 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4· 5H2O is dissolved in 100 ml deionized waters, weighs 8.666 g (NH4)2CO3It is configured to 100ml solution.In 60 DEG C of stirring conditions Under, by (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, Continue to stir 2 h, be cooled to room temperature, filter, deionized water is washed 5 times；Gained sediment is in the lower 100 DEG C of dryings 5 of air atmosphere Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after drying, obtains catalyst activity component ZnO- by h ZrO2Solid solution, wherein the molar fraction of ZnO is 50%, i.e. 50% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 50% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The catalysts evaluation that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40- 60 mesh catalyst for preparing hydrogen by reforming methanol and water vapour ZnO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm In, reaction temperature is 380 DEG C under normal pressure, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of to anti- It answers device to be passed through molar ratio to be reacted for the vapor and methanol of 1.2:1, reacts about 2 hours end sampling analyses, experimental result It is shown in Table 1.
Embodiment 4
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 13.228 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4· 5H2O is dissolved in 100 ml deionized waters, weighs 14.223 g (NH4)2CO3It is configured to 100ml solution.In 60 DEG C of stirring conditions Under, by (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, Continue to stir 2 h, be cooled to room temperature, filter, deionized water is washed 5 times；Gained sediment is in the lower 100 DEG C of dryings 5 of air atmosphere Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after drying, obtains catalyst activity component ZnO- by h ZrO2Solid solution, wherein the molar fraction of ZnO is 70%, i.e. 70% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 70% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The reaction that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40-60 mesh methanol-water Vapour reforming hydrogen producing catalyst Z nO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, under normal pressure Reaction temperature is 380 DEG C, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of be passed through to reactor Molar ratio is that the vapor of 1.2:1 and methanol are reacted, and reacts about 2 hours end sampling analyses, experimental result is shown in Table 1.
Embodiment 5
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 22.676 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4· 5H2O is dissolved in 100 ml deionized waters, weighs 21.635 g (NH4)2CO3It is configured to 100ml solution.In 60 DEG C of stirring conditions Under, by (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, Continue to stir 2 h, be cooled to room temperature, filter, deionized water is washed 5 times；Gained sediment is in the lower 100 DEG C of dryings 5 of air atmosphere Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after drying, obtains catalyst activity component ZnO- by h ZrO2Solid solution, wherein the molar fraction of ZnO is 80%, i.e. 80% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 80% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The reaction that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40-60 mesh methanol-water Vapour reforming hydrogen producing catalyst Z nO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, under normal pressure Reaction temperature is 380 DEG C, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of be passed through to reactor Molar ratio is that the vapor of 1.2:1 and methanol are reacted, and reacts about 2 hours end sampling analyses, experimental result is shown in Table 1.
Influence of the 1 ZnO molar fraction of table to catalyst for preparing hydrogen by reforming methanol and water vapour performance
Number Methanol conversion/% H2Yield/% CO selectivity/%
Embodiment 1 96.73 99.25 6.34
Embodiment 2 91.25 93.36 11..63
Embodiment 3 92.37 94.74 12.86
Embodiment 4 84.59 89.31 13.97
Embodiment 5 80.62 82.16 4.92
By embodiment 1 ~ 5 in table 1 it can be concluded that ZnO-ZrO2Difference molar fraction ZnO is to the methanol steam weight in solid solution The conclusion of the influence of whole catalyst for preparing hydrogen: for the ZnO-ZrO of molar fraction ZnO10% ~ 80%2Solid solution, in a certain range, ZnO molar fraction increases, ZnO-ZrO2Solid solution catalytic activity increases, methanol conversion and H2Yield increases, and is more than certain model It encloses, ZnO molar fraction increases, ZnO-ZrO2Solid solution catalytic activity declines instead.In the present embodiment, so that the methanol-water steams The ZnO molar fraction that gas reforming hydrogen-production catalyst is optimal performance is 15%.
Embodiment 6
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 1.0 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4·5H2O It is dissolved in 100 ml deionized waters, weighs 5.10 g (NH4)2CO3It is configured to 100ml solution.It, will under 60 DEG C of stirring conditions (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, continues to stir 2 h, be cooled to room temperature, filters, go Ion water washing 5 times；Catalyst is placed in horse after drying in air atmosphere 5 h of lower 100 DEG C of dryings by gained sediment Not catalyst activity component ZnO-ZrO is obtained in 500 DEG C of 3 h of constant temperature calcining in furnace2Solid solution, wherein the molar fraction of ZnO be 15%, i.e. 15% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 15% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The reaction that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40-60 mesh methanol-water Vapour reforming hydrogen producing catalyst Z nO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, under normal pressure Reaction temperature is 360 DEG C, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of be passed through to reactor Molar ratio is that the vapor of 1.2:1 and methanol are reacted, and reacts about 2 hours end sampling analyses, experimental result is shown in Table 2.
Embodiment 7
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 1.0 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4·5H2O It is dissolved in 100 ml deionized waters, weighs 5.10 g (NH4)2CO3It is configured to 100ml solution.It, will under 60 DEG C of stirring conditions (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, continues to stir 2 h are mixed, are cooled to room temperature, are filtered, deionized water is washed 5 times；Gained sediment is done in air atmosphere 5 h of lower 100 DEG C of dryings Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after dry, obtains catalyst activity component ZnO-ZrO2Gu Solution, wherein the molar fraction of ZnO is 15%, i.e. 15% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 15% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The reaction that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40-60 mesh methanol-water Vapour reforming hydrogen producing catalyst Z nO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, under normal pressure Reaction temperature is 400 DEG C, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of be passed through to reactor Molar ratio is that the vapor of 1.2:1 and methanol are reacted, and reacts about 2 hours end sampling analyses, experimental result is shown in Table 2.
Embodiment 8
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 1.0 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4·5H2O It is dissolved in 100 ml deionized waters, weighs 5.10 g (NH4)2CO3It is configured to 100ml solution.It, will under 60 DEG C of stirring conditions (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, continues to stir 2 h are mixed, are cooled to room temperature, are filtered, deionized water is washed 5 times；Gained sediment is done in air atmosphere 5 h of lower 100 DEG C of dryings Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after dry, obtains catalyst activity component ZnO-ZrO2Gu Solution, wherein the molar fraction of ZnO is 15%, i.e. 15% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 15% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The reaction that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40-60 mesh methanol-water Vapour reforming hydrogen producing catalyst Z nO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, under normal pressure Reaction temperature is 420 DEG C, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of be passed through to reactor Molar ratio is that the vapor of 1.2:1 and methanol are reacted, and reacts about 2 hours end sampling analyses, experimental result is shown in Table 2.
Embodiment 9
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 1.0 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4·5H2O It is dissolved in 100 ml deionized waters, weighs 5.10 g (NH4)2CO3It is configured to 100ml solution.It, will under 60 DEG C of stirring conditions (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, continues to stir 2 h are mixed, are cooled to room temperature, are filtered, deionized water is washed 5 times；Gained sediment is done in air atmosphere 5 h of lower 100 DEG C of dryings Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after dry, obtains catalyst activity component ZnO-ZrO2Gu Solution, wherein the molar fraction of ZnO is 15%, i.e. 15% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 15% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The reaction that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40-60 mesh methanol-water Vapour reforming hydrogen producing catalyst Z nO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, under normal pressure Reaction temperature is 440 DEG C, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of be passed through to reactor Molar ratio is that the vapor of 1.2:1 and methanol are reacted, and reacts about 2 hours end sampling analyses, experimental result is shown in Table 2.
Embodiment 10
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 1.0 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4·5H2O It is dissolved in 100 ml deionized waters, weighs 5.10 g (NH4)2CO3It is configured to 100ml solution.It, will under 60 DEG C of stirring conditions (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, continues to stir 2 h are mixed, are cooled to room temperature, are filtered, deionized water is washed 5 times；Gained sediment is done in air atmosphere 5 h of lower 100 DEG C of dryings Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after dry, obtains catalyst activity component ZnO-ZrO2Gu Solution, wherein the molar fraction of ZnO is 15%, i.e. 15% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 15% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The reaction that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40-60 mesh methanol-water Vapour reforming hydrogen producing catalyst Z nO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, under normal pressure Reaction temperature is 460 DEG C, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of be passed through to reactor Molar ratio is that the vapor of 1.2:1 and methanol are reacted, and reacts about 2 hours end sampling analyses, experimental result is shown in Table 2.
2 temperature of table is on the active influence of catalyst for preparing hydrogen by reforming methanol and water vapour
Number Methanol conversion/% H2Yield/% CO selectivity/%
Embodiment 6 81.38 85.16 1.39
Embodiment 7 99.12 99.13 16.57
Embodiment 8 99.73 99.97 23.62
Embodiment 9 97.58 97.33 25.56
Embodiment 10 95.14 95.01 31.71
By embodiment 6-10 in table 2 it can be concluded that different temperatures is on the active influence of the catalyst for preparing hydrogen by reforming methanol and water vapour Conclusion: temperature be 320 ~ 460 DEG C in the range of, the catalyst for preparing hydrogen by reforming methanol and water vapour, which can achieve, preferably urges Change activity, the catalyst for preparing hydrogen by reforming methanol and water vapour be applied to the conversion ratio of methanol that hydrogen manufacturing obtains can reach 80% with On, H2For yield 85% or more, temperature is higher, and methanol conversion is higher, but excessively high temperature will lead to CO and selectively increase, So as to cause catalyst poisoning to inactivate.In the present embodiment, so that the catalyst for preparing hydrogen by reforming methanol and water vapour reaches most The reaction temperature of dominance energy is 380 DEG C.
Embodiment 11
A kind of preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour, the preparation method include the precipitation method and mechanical lapping Method, steps are as follows for the preparation method:
Steps are as follows for the precipitation method: by 1.0 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4·5H2O It is dissolved in 100 ml deionized waters, weighs 5.10 g (NH4)2CO3It is configured to 100ml solution.It, will under 60 DEG C of stirring conditions (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, continues to stir 2 h are mixed, are cooled to room temperature, are filtered, deionized water is washed 5 times；Gained sediment is done in air atmosphere 5 h of lower 100 DEG C of dryings Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after dry, obtains catalyst activity component ZnO-ZrO2Gu Solution, wherein the molar fraction of ZnO is 15%, i.e. 15% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: by 15% ZnO-ZrO2It is in mass ratio that 2:1 carries out mechanical lapping with ZSM-5 It is uniformly mixed, tabletting screening is 40-60 mesh, and methanol steam reforming catalyst Z nO-ZrO is made2/ZSM-5。
A kind of catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The reaction that the catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5 g 40-60 mesh methanol-water Vapour reforming hydrogen producing catalyst Z nO-ZrO2/ ZSM-5 is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, under normal pressure Reaction temperature is 380 DEG C, with N2As carrier gas, in reaction velocity 4500mlgcat-1·h-1Under the conditions of be passed through to reactor Molar ratio is that the vapor of 1.2:1 and methanol are reacted, after stable reaction, every sampling analysis in 1 hour, Therapy lasted 9 Hour, experimental result is shown in Fig. 1.
As shown in Figure 1, after reaction continues 9 hours, the catalyst for preparing hydrogen by reforming methanol and water vapour is obtained applied to hydrogen manufacturing The conversion ratio of methanol be still maintained at 90% or more, illustrate catalyst for preparing hydrogen by reforming methanol and water vapour tool provided in this embodiment There is excellent stability.
Comparative example 1
ZnO-ZrO2The preparation method of catalyst, the preparation method include the precipitation method and mechanical milling method, the preparation method Steps are as follows:
Steps are as follows for the precipitation method: by 1.0 g zinc nitrate Zn (NO3)2·6H2O and 8.18 g zirconium nitrate Zr (NO3)4·5H2O It is dissolved in 100 ml deionized waters, weighs 5.10 g (NH4)2CO3It is configured to 100ml solution.It, will under 60 DEG C of stirring conditions (NH4)2CO3Solution, which is slowly dropped in mixed nitrate solution, forms precipitating, and the pH value for controlling solution is 7.0-9.0, continues to stir 2 h are mixed, are cooled to room temperature, are filtered, deionized water is washed 5 times；Gained sediment is done in air atmosphere 5 h of lower 100 DEG C of dryings Catalyst is placed in Muffle furnace in 500 DEG C of 3 h of constant temperature calcining after dry, obtains catalyst activity component ZnO-ZrO2Gu Solution, wherein the molar fraction of ZnO is 15%, i.e. 15% ZnO-ZrO2。
Steps are as follows for the mechanical milling method: 15% ZnO-ZrO of 40-60 mesh is sieved to obtain in above-mentioned made catalyst tabletting2 Catalyst.
ZnO-ZrO2Catalyst is applied to the method for hydrogen manufacturing, and preparation step is as follows:
The ZnO-ZrO2The reaction that catalyst is applied to hydrogen manufacturing carries out in fixed-bed tube reactor, takes 0.5g 40-60 mesh ZnO-ZrO2Catalyst is placed in the quartz ampoule that internal diameter is 6 mm, length is 280 mm, and reaction temperature is 380 DEG C under normal pressure, is made Use N2As carrier gas, in 4500 mlg of reaction velocitycat -1·h-1It is lower to reactor be passed through molar ratio be 1.2:1 vapor and Methanol is reacted, and is about reacted sampling analysis after 2 hours stabilizations, be the results are shown in Table 3.
3 ZSM-5 molecular sieve of table is on the active influence of catalyst for preparing hydrogen by reforming methanol and water vapour
Number Methanol conversion/% H2Yield/% CO selectivity/%
Embodiment 1 96.73 99.25 6.34
Comparative example 1 82.63 84.31 8.62
By embodiment 1 in table 3 and comparative example 1 it can be concluded that ZSM-5 molecular sieve as catalyst carrier to the methanol steam The conclusion of the active influence of reforming hydrogen-production catalyst: in the case where no ZSM-5 molecular sieve is as carrier, only with ZnO-ZrO2 Solid solution is as catalyst, compared to the catalyst for preparing hydrogen by reforming methanol and water vapour ZnO-ZrO2/ ZSM-5, ZnO-ZrO2Catalysis Agent activity substantially reduces, ZnO-ZrO2Catalyst is applied to the methanol conversion and H that the method for hydrogen manufacturing obtains2Yield reduces Nearly 15%.
In conclusion methanol steam reforming catalyst provided by the invention, with ZnO-ZrO2Solid solution is reforming activity Component compared with traditional zno-based catalyst, can reach optimality at 380 DEG C using ZSM-5 molecular sieve as catalyst carrier Can, catalyst stability is high, overcomes the high disadvantage of traditional zno-based catalyst reforming reaction temperature.Methanol steam of the present invention Reforming hydrogen-production catalyst, under the reaction condition for being optimal performance, methanol conversion is close to 100%, H2Yield is up to 99%, CO Selectivity is low, and catalyst stability is good.
It should be understood that the application of the present invention is not limited to the above for those of ordinary skills can With improvement or transformation based on the above description, all these modifications and variations all should belong to the guarantor of appended claims of the present invention Protect range.

Claims (10)

1. a kind of catalyst for preparing hydrogen by reforming methanol and water vapour, which is characterized in that the group of the catalyst becomes ZnO-ZrO2/ZSM-5 Molecular sieve, the ZSM-5 molecular sieve are catalyst carrier, the ZnO-ZrO2For active component, wherein the ZnO-ZrO2For Solid solution.
2. a kind of catalyst for preparing hydrogen by reforming methanol and water vapour according to claim 1, which is characterized in that the ZnO-ZrO2Gu ZnO molar fraction is 10%-80% in solution.
3. a kind of catalyst for preparing hydrogen by reforming methanol and water vapour according to claim 1, which is characterized in that the ZnO-ZrO2With The mass ratio of two kinds of components of ZSM-5 molecular sieve is 0.5-5:1.
4. a kind of catalyst for preparing hydrogen by reforming methanol and water vapour according to claim 1, which is characterized in that the ZSM-5 molecule The partial size of sieve is 6-12nm, specific surface area 120-200m2·g-1。
5. a kind of preparation method of the catalyst for preparing hydrogen by reforming methanol and water vapour as described in claim 1-4 is any, which is characterized in that The preparation method comprises the following steps:
Using the metal salt of Zn and Zr as precursor preparation precursor solution, the precursor solution is handled to obtain ZnO- ZrO2Solid solution, wherein the method handled the precursor solution is infusion process or the precipitation method；
By the ZnO-ZrO obtained2The methanol steam weight is made by mechanical milling method in solid solution and ZSM-5 molecular sieve Whole catalyst for preparing hydrogen.
6. the preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour according to claim 5, which is characterized in that the metal Salt is soluble one or more of nitrate, sulfate, hydrochloride or acetate.
7. the preparation method of catalyst for preparing hydrogen by reforming methanol and water vapour according to claim 5, which is characterized in that the stirring Temperature and the dipping temperature are room temperature, and dip time 8-12h, the calcination temperature is 400-800 DEG C, and calcination time is 2-6h。
8. a kind of catalyst for preparing hydrogen by reforming methanol and water vapour as described in claim 1-4 is applied to the method for hydrogen manufacturing, feature exists In, comprising the following steps:
In fixing tubular reactor, ZnO-ZrO is loaded2/ ZSM-5 catalyst, with N2As carrier gas, under heating conditions It is passed through vapor and methanol is that raw material is reacted.
9. catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing according to claim 8, which is characterized in that institute Stating reaction temperature is 320-460 DEG C, reaction velocity 3000-8000mlgcat -1·h-1, the molar ratio of water and methanol is 0.8- 2:1。
10. catalyst for preparing hydrogen by reforming methanol and water vapour is applied to the method for hydrogen manufacturing according to claim 9, which is characterized in that The reaction temperature is 380 DEG C.
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CN114506816A (en) * 2020-11-17 2022-05-17 中国科学院大连化学物理研究所 Method for preparing hydrogen by reforming methanol
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CN115770563B (en) * 2021-09-06 2024-02-02 中国科学院大连化学物理研究所 Bimetallic catalyst for high-temperature methanol steam reforming hydrogen production and preparation method and application thereof
CN114160182A (en) * 2021-12-03 2022-03-11 江苏三吉利化工股份有限公司 Catalyst for methanol steam reforming hydrogen production and preparation and hydrogen production methods thereof
CN114405496A (en) * 2022-01-10 2022-04-29 四川亚联高科技股份有限公司 Methanol reforming hydrogen production catalyst, and preparation method, evaluation method and application thereof

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