CN102489311B - Catalyst for hydrogen production through catalytic cracking of methane and its preparation method - Google Patents
Catalyst for hydrogen production through catalytic cracking of methane and its preparation method Download PDFInfo
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Abstract
Belonging to the technical field of catalysts for hydrogen production through catalytic cracking of methane, the invention relates to a catalyst for hydrogen production through catalytic cracking of methane and its preparation method. The catalyst in the invention is composed of a nickel salt, copper oxide, a precious metal catalytic promoter, an alkaline earth metal catalytic promoter, and a nanometer ZrO-ZnO composite carrier. The method in the invention comprises: taking the nickel salt, the copper oxide, the precious metal catalytic promoter, the alkaline earth metal catalytic promoter, a zirconium salt, a zinc salt, and an alkaline precipitating agent as raw materials, first preparing a nanometer ZrO-ZnO composite carrier, then implementing the simple processes of mixing, ultrasonic dispersion, roasting, and moulding, thus obtaining a product. The method in the invention has the advantages of simple process, mild reaction condition, energy saving, sufficient material and liquid utilization, and no discharge of ''three wastes''. The product prepared by the method of the invention has the characteristics of high activity, good dispersibility, and strong temperature resistance, etc. The catalyst prepared by the method provided in the invention can be widely applied in catalytic cracking of methane, ethane and other low carbon alkanes, and is especially suitable for catalytic cracking of methane in a fluidized bed for hydrogen production.
Description
Technical field
The invention belongs to methane catalytic decomposition catalyst for preparing hydrogen technical field, being specifically related to the nano zircite zinc complexes is the Ni-based methane cracking hydrogen production Catalysts and its preparation method of carrier.
Background technology
Hydrogen Energy is a kind of desirable secondary energy sources, because during its burning pollution-free (product is water), the fuel value height, the unit mass fuel value is 121061kJ/kg, all more much higher than methane (50054kJ/kg), gasoline (44467kJ/kg), methyl alcohol (20254kJ/kg) etc., thereby paid close attention to widely in recent years.Large-scale natural gas hydrogen preparation mainly is to adopt steam reforming, traditional steam reforming needs at high temperature just can carry out, and can produce a large amount of hydrocarbon (30% volume) in hydrogen manufacturing, and the concentration of hydrogen is not high, about 60%, follow-up segregational load is very big.In order to obtain the higher hydrogen of purity, generally need carry out series of process processes such as high and low temperature shift, decarbonylation reaction and cryogenic separation or transformation adsorbing separation, long flow path, equipment investment is big, the operating cost height.
Along with development and the application of fuel cell technology, the act as a fuel fuel of battery of hydrogen, the status in the future source of energy structure will be more important.But fuel cell has strict demand to CO content in the hydrogen, and concentration is less than 10-6.Methane cracking prepares hydrogen and contains hydrocarbon hardly, it is the fuel cell ideal raw material, the directly charging of pure hydrogen raw material, do not need fuel reforming hydrogen manufacturing system, battery structure is simple, starting rapidly and with hydrogen when being the fuel cell operation of raw material and discharge a spot of clean water, is real zero to pollute.
Existing methane cracking hydrogen production Catalysts and its preparation method, as on May 27th, 2009 disclosed publication number be " catalyst for hydrogen production from catalytic pyrolysis of natural gas and preparation method thereof " patent of CN101439287A, component and the weight fraction thereof of disclosed catalyst for preparing hydrogen are: Ni element 10～15, MOy 5～20, and CNFs 2～45; Wherein MOy is SiO
2, ZrO
2, TiO
2, Ce
(1-x)Zr
xO
2In a kind of, x=0.2～0.8 wherein; CNFs is carbon nano-fiber.Disclosed method is: with MO
y/ CNFs is carrier loaded active component Ni, adds in the nickel salt aqueous solution with MOy with through pretreated CNFs, and adding alkali lye then, to regulate pH be 6～8, leave standstill after the stirring, at last to sediment after filtration, washing, dry and product.The major defect of this patent is: (1) adopts metal oxide supported at CNT MO
y/ CNFs, though this good catalyst activity, and since CNT water-soluble relatively poor, Yi Jutuan, and the active component in the aqueous solution is disperseed uneven at catalyst surface, can not give full play to the activity of such catalysts effect; (2) this catalyst activity component is single, and the catalyst combination property is poor, and the nickel of one pack system at high temperature runs off easily, also lacks co-catalyst fortifying catalytic performance, thereby causes activity of such catalysts stable inadequately.
Summary of the invention
The objective of the invention is the deficiency at existing methane cracking hydrogen production Catalysts and its preparation method, a kind of methane catalytic decomposition catalyst for preparing hydrogen and preparation method thereof is provided, has that active component is uniformly dispersed, characteristics such as good stability, catalyst strength height, catalytic activity are good.
Mechanism of the present invention: by a large amount of experiments, determine best component prescription, make catalyst have lasting high activity.Adopt that surface treated nano metal oxide compound of the present invention is dispersed in water, stability is all fine, be conducive to the catalyst activity component and evenly disperse and obtain dispersed catalysts at catalyst surface, give full play to the activity of such catalysts effect.Nickel-based compound is loaded on the catalyst of making on the ZrO-ZnO carrier, do not contain CO in the hydrogen of catalytic cracking methane preparation, purity height, and methane conversion height in the reaction, catalyst stability is good.
The technical scheme that realizes the object of the invention is: a kind of component of methane catalytic decomposition catalyst for preparing hydrogen and weight fraction thereof are:
Wherein: nickel salt is nickel nitrate or nickel acetate or nickel oxalate or nickel chloride; The precious metal catalyst auxiliary agent is ruthenium (Ru) or platinum (Pt) or palladium (Pd) or rhodium (Rh) or gold (Au), also can be wherein several; Base earth metal promoter is lithium (Li) or sodium (Na) or calcium (Ca) or barium (Ba), also can be wherein several; Nano zircite zinc complexes carrier diameter is 10～60 nanometers, and the mole (mol) of element zirconium (Zr): the ratio of the mole (mol) of element zinc (Zn) is 1: 2～10.
A kind of preparation method of methane catalytic decomposition catalyst for preparing hydrogen, be raw material with nickel salt, cupric oxide, precious metal catalyst auxiliary agent, base earth metal promoter, zirconates, zinc salt, alkaline precipitating agent, first preparation nano zircite zinc complexes carrier makes product by the simple process of mixing, ultrasonic dispersion, roasting, moulding.Its concrete steps are as follows:
(1) preparation nano zircite zinc complexes carrier
First mole (mol) in zirconium ion in the zirconates (being zirconium oxychloride or zirconium nitrate or zirconium sulfate or zirconium chloride): the mole (mol) of zinc ion in the zinc salt (being zinc acetate or zinc nitrate or zinc sulfate): the ratio of the hydroxyl mole (mol) of alkaline precipitating agent (being ammoniacal liquor or ammonium carbonate or carbonic hydroammonium or ammonium oxalate or NaOH or sodium acid carbonate or urea) is 1: 2～10: 4～12 ratio, zirconates and zinc salt are joined in the alkaline precipitating agent, and to regulate its pH value with NaOH be 8～10, till being stirred to precipitation and dissolving fully.Behind still aging 10～24h, pump into and carry out the centrifugation first time in the centrifuge again, collect primary centrifugate and centrifugal sediment respectively.Reusable after purifying for the centrifugate of collecting for the first time; Be positioned in the drying box for the centrifugal sediment of collecting for the first time, the water with in drying medium (ethanol) the displacement centrifugal sediment at 80～150 ℃ of drying 4～12h, and makes the zirconia zinc complexes.
Again in the quality of zirconia zinc complexes: the ratio of the quality of distilled water is 1: 50 ratio, and the zirconia zinc complexes is added in the distilled water, stirs and evenly mixs and makes the zirconia zinc complexes aqueous solution (abbreviation compound water solution).
Then in the quality of zirconia zinc in the compound water solution: the quality of little molecular surface modifier (being polyethylene glycol): the mass ratio of dispersant (being neopelex or Arlacel-60 APEO (polysorbate60) or polysorbate (Tween 80) or sorbitol anhydride oleate (Span80)) is 1: 0.01～0.1: 0.01～0.1 ratio, earlier compound water solution is carried out ultrasonic dispersion 30～120min, add little molecular surface modifier and dispersant again, at 60～80 ℃ of following stirring reaction 2～6h, pump into then and carry out the centrifugation second time in the centrifuge, collect secondary centrifugate and centrifugal sediment (being nano zircite zinc complexes carrier) respectively.For the centrifugate of collecting for the second time, after separating, can be recycled; Be placed in the vacuum drying chamber for the centrifugal sediment of collecting for the second time, at 400～750 ℃ of vacuum drying 2～24h, make nano zircite zinc complexes powder.
(2) preparation methane catalytic decomposition catalyst for preparing hydrogen product
(1) step finish after, earlier by (1) quality that goes on foot the nano zircite zinc complexes powder that makes: the quality of cupric oxide: the quality of precious metal catalyst auxiliary agent: the quality of alkaline-earth metal catalyst aid: the ratio of the quality of distilled water is 1: 0.07～0.22: 0.03～0.11: 0.03～0.22: 2～5 ratio, nano zircite zinc complexes powder and cupric oxide that (1) step was made join in the there-necked flask that fills distilled water, carry out ultrasonic dispersion 30～120min.Add nickel salt (being nickel nitrate or nickel acetate or nickel oxalate or nickel chloride) solution, precious metal catalyst auxiliary agent (ruthenium or platinum or palladium or rhodium or gold), alkaline-earth metal catalyst aid (lithium or sodium or calcium or barium) successively, the quality of the nickel salt in the nickel salt solution of adding is 0.1～0.66 times of nano zircite zinc complexes powder quality.Stir 2～6h down at 40～80 ℃, behind still aging 8～12h, be positioned in the vacuum drying chamber then, under 100～180 ℃, carry out vacuum drying 8～12h.Be placed at last on the Muffle furnace, make methane catalytic decomposition catalyst for preparing hydrogen powder at 500～800 ℃ of following roasting 2～10h.Again by tablet press machine compacting in flakes, through pulverizing, sieve then, make particle diameter and be 40～200 microns granular methane catalyst for hydrogen production from catalytic pyrolysis finished product.
The use of catalyst of the present invention: the methane catalytic decomposition catalyst for preparing hydrogen that will adopt the present invention to make is loaded in the fluid bed, as fluid bed diameter 20mm, and during high 500mm, loaded catalyst 5～20mL., before carrying out the methane catalytic decomposition hydrogen production reaction, must under 400～500 ℃, feed hydrogen and carry out reductase 12～4h with this catalyst.Catalyst after the reduction has advantages of high catalytic activity, and under 600 ℃ of reaction temperatures, the initial conversion of methane is up to 65.7%, and the simple substance carbon of generation is carried away by air-flow, recycles after gas solid separation.
After the present invention adopts technique scheme, mainly contain following effect:
1 catalyst of the present invention can keep the high activity of catalyst, can guarantee that again catalyst has stronger resistance to elevated temperatures, has enlarged the accommodation of catalyst, and is flexible and convenient to use, is convenient to promote the use of.
The particle diameter of 2 catalyst carriers of the present invention is very little, is the particle of 10～60 nanometers, bigger specific area is provided for the activity of such catalysts component, can improve activity of such catalysts.
Nano zircite in 3 catalyst of the present invention has stronger mechanical strength, has guaranteed the higher anti-wear performance of catalyst; Nano zine oxide is a kind of dispersed preferred metal nano-oxide, and it is dispersed preferably to have guaranteed that catalyst granules has.Therefore, the wear-resisting property of catalyst of the present invention height, good dispersion.
4 the inventive method reduce the nano grain surface energy by composite Nano metal oxide carrier is carried out surface modification, reduce the poly-group of nano particle, and the active component that is conducive in the aqueous solution evenly spreads to catalyst surface, obtain the catalyst of polymolecularity.
5 preparation technologies are simple, reaction condition gentleness, energy savings.In process of production, take full advantage of thing liquid, do not have " three wastes " discharging, be conducive to environmental protection.
The methane catalytic decomposition catalyst for preparing hydrogen that adopts the inventive method to prepare can be widely used in the low-carbon alkanes such as catalytic cracking methane, ethane, is specially adapted to catalytic cracking methane hydrogen manufacturing in the fluid bed.
The specific embodiment
The following examples are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment 1
A kind of component of methane catalytic decomposition catalyst for preparing hydrogen and weight fraction thereof are:
Wherein: nickel salt is nickel acetate; The precious metal catalyst auxiliary agent is palladium; Base earth metal promoter is lithium; Nano zircite zinc complexes carrier diameter is 40 nanometers, and the mole of element zirconium: the ratio of the mole of element zinc is 1: 4.
A kind of preparation method's concrete steps of methane catalytic decomposition catalyst for preparing hydrogen are as follows:
(1) preparation nano zircite zinc complexes carrier
First mole (mol) in zirconium ion in the zirconium nitrate: the mole of zinc ion (mol) in the zinc acetate: the ratio of the hydroxyl mole (mol) of NaOH is 1: 4: 6 ratio, earlier zirconium nitrate and zinc acetate are joined in the alkaline precipitating agent, and to regulate its pH value with NaOH be 8, till being stirred to precipitation and dissolving fully.Behind the still aging 10h, pump into and carry out the centrifugation first time in the centrifuge again, collect primary centrifugate and centrifugal sediment respectively.Reusable after purifying for the centrifugate of collecting for the first time; Be positioned in the drying box for the centrifugal sediment of collecting for the first time, the water with in drying medium (ethanol) the displacement centrifugal sediment at 80 ℃ of dry 12h, and makes the zirconia zinc complexes.
Again in the quality of zirconia zinc complexes: the ratio of the quality of distilled water is 1: 50 ratio, and the zirconia zinc complexes is added in the distilled water, stirs and evenly mixs and makes the zirconia zinc complexes aqueous solution (abbreviation compound water solution).
Then in the quality of zirconia zinc in the compound water solution: the quality of little molecular surface modifier (being polyethylene glycol): the mass ratio of dispersant (being sorbitol anhydride oleate (Span80)) is 1: 0.03: 0.03 ratio, earlier compound water solution is carried out ultrasonic dispersion 60min, add polyethylene glycol and sorbitol anhydride oleate again, at 70 ℃ of following stirring reaction 4h, pump into then and carry out the centrifugation second time in the centrifuge, collect secondary centrifugate and centrifugal sediment (being nano zircite zinc complexes carrier) respectively.For the centrifugate of collecting for the second time, after separating, can be recycled; Be placed in the vacuum drying chamber for the centrifugal sediment of collecting for the second time, at 500 ℃ of vacuum drying 12h, make nano zircite zinc complexes powder.
(2) preparation methane catalytic decomposition catalyst for preparing hydrogen product
(1) step finish after, earlier by (1) quality that goes on foot the nano zircite zinc complexes powder that makes: the quality of cupric oxide: the quality of precious metal catalyst auxiliary agent: the quality of alkaline-earth metal catalyst aid: the ratio of the quality of distilled water is 1: 0.08: 0.06: 0.07: 4 ratio, nano zircite zinc complexes powder and cupric oxide that (1) step was made join in the there-necked flask that fills distilled water, carry out ultrasonic dispersion 60min.Add nickel acetate solution more successively, precious metal catalyst auxiliary agent palladium, alkaline-earth metal catalyst aid lithium, the quality of the nickel salt in the nickel acetate solution of adding is 0.2 times of nano zircite zinc complexes powder quality.Stir 6h down at 40 ℃, behind the still aging 8h, be positioned in the vacuum drying chamber then, under 100 ℃, carry out vacuum drying 12h.Be placed at last on the Muffle furnace, make methane catalytic decomposition catalyst for preparing hydrogen powder at 500 ℃ of following roasting 10h.Again by tablet press machine compacting in flakes, through pulverizing, sieve then, make particle diameter and be 60～200 microns granular methane catalyst for hydrogen production from catalytic pyrolysis finished product.
Embodiment 2
A kind of component of methane catalytic decomposition catalyst for preparing hydrogen and weight fraction thereof are:
Wherein: nickel salt is nickel nitrate; The precious metal catalyst auxiliary agent is platinum; Base earth metal promoter is calcium; Nano zircite zinc complexes carrier diameter is 30 nanometers, and the mole of element zirconium: the ratio of the mole of element zinc is 1: 3.
A kind of preparation method of methane catalytic decomposition catalyst for preparing hydrogen, with embodiment 1, wherein:
In (1) step, zirconates is zirconium oxychloride, zinc salt is zinc nitrate, alkaline precipitating agent is ammonium carbonate, the mole of zirconium ion (mol) in the zirconium oxychloride: the mole of zinc ion (mol) in the zinc nitrate: the ratio of the hydroxyl mole (mol) of ammonium carbonate is 1: 3: 10, and the pH value is 9, and the still aging time is 15h, the baking temperature of centrifugal sediment is 120 ℃, and be 8h drying time.
Dispersant is Arlacel-60 APEO (polysorbate60), the quality of zirconia zinc in the compound water solution: the quality of little molecular surface modifier (being polyethylene glycol): the mass ratio of dispersant (being Arlacel-60 APEO (polysorbate60)) is 1: 0.05: 0.05, the time of the ultrasonic dispersion of compound water solution is 90min, the whipping temp that adds behind little molecular surface modifier and the dispersant is 60 ℃, mixing time is 6h, the baking temperature that the centrifugal sediment of collecting the second time is placed in the vacuum drying chamber is 600 ℃, and the vacuum drying time is 8h.
The quality of nano zircite zinc complexes powder in (2) step: the quality of cupric oxide: the quality of precious metal catalyst auxiliary agent: the quality of alkaline-earth metal catalyst aid: the ratio of the quality of distilled water is 1: 0.22: 0.03: 0.12: 3, the time of ultrasonic dispersion was 90min.The quality of the nickel salt in the nickel nitrate solution that adds is 0.1 times of nano zircite zinc complexes powder quality.Whipping temp is 60 ℃, and mixing time is 4h, and the still aging time is 10h, and vacuum drying temperature is 140 ℃, and the vacuum drying time is 10h.The temperature that is placed on roasting on the Muffle furnace at last is 600 ℃, and roasting time is 6h.
Embodiment 3
A kind of component of methane catalytic decomposition catalyst for preparing hydrogen and weight fraction thereof are:
Wherein: nickel salt is nickel chloride; The precious metal catalyst auxiliary agent is ruthenium and gold; Base earth metal promoter is sodium and barium; Nano zircite zinc complexes carrier diameter is 60 nanometers, and the mole of element zirconium: the ratio of the mole of element zinc is 1: 10.
A kind of preparation method of methane catalytic decomposition catalyst for preparing hydrogen, with embodiment 1, wherein:
In (1) step, zirconates is zirconium chloride, zinc salt is zinc sulfate, alkaline precipitating agent is urea, the mole of zirconium ion (mol) in the zirconium chloride: the mole of zinc ion (mol) in the zinc sulfate: the ratio of the hydroxyl mole (mol) of urea is 1: 10: 12, and the pH value of regulating with NaOH is 10, and the still aging time is 24h, the baking temperature of centrifugal sediment is 150 ℃, and be 4h drying time.
Dispersant is neopelex, the quality of zirconia zinc in the compound water solution: the quality of little molecular surface modifier (being polyethylene glycol): the mass ratio of dispersant (being neopelex) is 1: 0.1: 0.1, the time of the ultrasonic dispersion of compound water solution is 120min, the whipping temp that adds behind little molecular surface modifier and the dispersant is 80 ℃, mixing time is 2h, the baking temperature of centrifugal sediment in vacuum drying chamber of collecting is 750 ℃ for the second time, and the vacuum drying time is 2h.
In (2) step, the quality of nano zircite zinc complexes powder: the quality of cupric oxide: the quality of precious metal catalyst auxiliary agent: the quality of alkaline-earth metal catalyst aid: the ratio of the quality of distilled water is 1: 0.07: 0.11: 0.03: 5, the time of ultrasonic dispersion was 120min.The quality of the nickel salt in the nickel chloride solution that adds is 0.13 times of nano zircite zinc complexes powder quality.Whipping temp is 80 ℃, and mixing time is 2h, and the still aging time is 12h, and vacuum drying temperature is 180 ℃, and the vacuum drying time is 8h.The temperature that is placed on roasting on the Muffle furnace at last is 800 ℃, and roasting time is 2h.
Embodiment 4
A kind of component of methane catalytic decomposition catalyst for preparing hydrogen and weight fraction thereof are:
Wherein: nickel salt is nickel chloride; The precious metal catalyst auxiliary agent is ruthenium and gold; Base earth metal promoter is sodium and barium; Nano zircite zinc complexes carrier diameter is 10 nanometers, and the mole of element zirconium: the ratio of the mole of element zinc is 1: 2.
A kind of preparation method of methane catalytic decomposition catalyst for preparing hydrogen, with embodiment 1, wherein:
In (1) step, zirconates is zirconium chloride, zinc salt is zinc sulfate, alkaline precipitating agent is urea, the mole of zirconium ion (mol) in the zirconium chloride: the mole of zinc ion (mol) in the zinc sulfate: the ratio of the hydroxyl mole (mol) of urea is 1: 2: 4, and the pH value is 8, and the still aging time is 12h, the baking temperature of centrifugal sediment is 100 ℃, and be 10h drying time.
Dispersant is polysorbate (Tween 80), the quality of zirconia zinc in the compound water solution: the quality of little molecular surface modifier (being polyethylene glycol): the mass ratio of dispersant (being polysorbate) is 1: 0.01: 0.01, the time of the ultrasonic dispersion of compound water solution is 30min, the whipping temp that adds behind little molecular surface modifier and the dispersant is 65 ℃, mixing time is 5h, the baking temperature of centrifugal sediment in vacuum drying chamber of collecting is 400 ℃ for the second time, and the vacuum drying time is 24h.
In (2) step, the quality of nano zircite zinc complexes powder: the quality of cupric oxide: the quality of precious metal catalyst auxiliary agent: the quality of alkaline-earth metal catalyst aid: the ratio of the quality of distilled water is 1: 0.22: 0.11: 0.22: 2, the time of ultrasonic dispersion was 30min.The quality of the nickel salt in the nickel chloride solution that adds is 0.66 times of nano zircite zinc complexes powder quality.Whipping temp is 50 ℃, and mixing time is 5h, and the still aging time is 9h, and vacuum drying temperature is 120 ℃, and the vacuum drying time is 8h.The temperature that is placed on roasting on the Muffle furnace at last is 500 ℃, and roasting time is 8h.
Claims (2)
1. the preparation method of a methane catalytic decomposition catalyst for preparing hydrogen is characterized in that its concrete steps are as follows:
(1) preparation nano zircite zinc complexes carrier
Be the mole of zirconium ion in zirconium oxychloride or zirconium nitrate or zirconium sulfate or the zirconium chloride in zirconates earlier: zinc salt is the mole of zinc ion in zinc acetate or zinc nitrate or the zinc sulfate: alkaline precipitating agent is that the ratio of the hydroxyl mole of ammoniacal liquor or ammonium carbonate or carbonic hydroammonium or ammonium oxalate or NaOH or sodium acid carbonate or urea is 1: 2～10: 4～12 ratio, earlier zirconates and zinc salt are joined in the alkaline precipitating agent, and to regulate its pH value with NaOH be 8～10, till being stirred to precipitation and dissolving fully; Again behind still aging 10～24h, pump into and carry out the centrifugation first time in the centrifuge, collect primary centrifugate and centrifugal sediment respectively, purify for the centrifugate of collecting for the first time, be positioned in the drying box for the centrifugal sediment of collecting for the first time, with the water in the ethanol drying medium displacement centrifugal sediment, at 80～150 ℃ of drying 4～12h;
Again in the quality of zirconia zinc complexes: the ratio of the quality of distilled water is 1: 50 ratio, and the zirconia zinc complexes is added in the distilled water, stirs and evenly mixs and makes compound water solution;
Then in the quality of zirconia zinc in the compound water solution: the quality of the little molecular surface modifier of polyethylene glycol: dispersant is that the mass ratio of neopelex or Arlacel-60 APEO or polysorbate or sorbitol anhydride oleate is 1: 0.01～0.1: 0.01～0.1 ratio, earlier compound water solution is carried out ultrasonic dispersion 30～120min, add little molecular surface modifier and dispersant again, at 60～80 ℃ of following stirring reaction 2～6h, pump into then and carry out the centrifugation second time in the centrifuge, collect secondary centrifugate and centrifugal sediment respectively, separate for the centrifugate of collecting for the second time, be placed in the vacuum drying chamber for the centrifugal sediment of collecting for the second time, at 400～750 ℃ of vacuum drying 2～24h;
(2) preparation methane catalytic decomposition catalyst for preparing hydrogen product
(1) step finish after, earlier by (1) quality that goes on foot the nano zircite zinc complexes powder that makes: the quality of cupric oxide: the quality of precious metal catalyst auxiliary agent: the quality of alkaline-earth metal catalyst aid: the ratio of the quality of distilled water is 1: 0.07～0.22: 0.03～0.11: 0.03～0.22: 2～5 ratio, nano zircite zinc complexes powder and cupric oxide are joined in the there-necked flask that fills distilled water, carry out ultrasonic dispersion 30～120min; Adding nickel salt successively is nickel nitrate or nickel acetate or nickel oxalate or nickel chloride solution, precious metal catalyst auxiliary agent ruthenium or platinum or palladium or rhodium or gold, alkaline-earth metal catalyst aid calcium or barium, and the quality of the nickel salt in the nickel salt solution of adding is 0.1～0.66 times of nano zircite zinc complexes powder quality; Stir 2～6h down at 40～80 ℃, behind still aging 8～12h, be positioned in the vacuum drying chamber then, under 100～180 ℃, carry out vacuum drying 8～12h, be placed at last on the Muffle furnace, make methane catalytic decomposition catalyst for preparing hydrogen powder at 500～800 ℃ of following roasting 2～10h; Again by tablet press machine compacting in flakes, through pulverizing, sieve then, make particle diameter and be 40～200 microns granular methane catalyst for hydrogen production from catalytic pyrolysis finished product.
2. according to the catalyst of the preparation method of the described a kind of methane catalytic decomposition catalyst for preparing hydrogen of claim 1 preparation, it is characterized in that the component of described catalyst and weight fraction thereof are:
Wherein: nickel salt is nickel nitrate or nickel acetate or nickel oxalate or nickel chloride; The precious metal catalyst auxiliary agent is ruthenium or platinum or palladium or rhodium or gold; Base earth metal promoter is calcium or barium; Nano zircite zinc complexes carrier diameter is 10～60 nanometers, and the mole of element zirconium: the ratio of the mole of element zinc is 1: 2～10.
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| CN105214673A (en) * | 2014-05-27 | 2016-01-06 | 中国科学院大连化学物理研究所 | The application of a kind of nickel-base catalyst in hydrazine decomposing hydrogen-production |
| CN104399485B (en) * | 2014-11-03 | 2016-08-24 | 新奥科技发展有限公司 | A kind of methane vapor low-temperature reformate catalyst and preparation method thereof |
| CN105618065A (en) * | 2014-11-07 | 2016-06-01 | 中国科学院大连化学物理研究所 | Applications of catalyst in hydrogen production through hydrazine decomposition |
| CN104437570A (en) * | 2014-11-28 | 2015-03-25 | 西安近代化学研究所 | Preparation method of catalyst applied to intra-molecular dehydration of amino alcohol compounds |
| CN105013506B (en) * | 2015-06-25 | 2017-12-12 | 中国石油天然气集团公司 | Bifunctional catalyst and its preparation method and hydrogen production process for methane catalytic decomposition |
| CN104998654B (en) * | 2015-06-25 | 2018-05-01 | 中国石油天然气集团公司 | The method of nickel-base catalyst and preparation method thereof and methane catalytic decomposition production hydrogen |
| CN110550603B (en) * | 2018-05-31 | 2022-07-19 | 上海康碳复合材料科技有限公司 | Device and method for treating alkane tail gas |
| CN111097447A (en) * | 2018-10-29 | 2020-05-05 | 中国石油天然气股份有限公司 | Catalyst for low-temperature catalytic cracking of methane to produce hydrogen, preparation method thereof and low-temperature catalytic cracking method for methane to produce hydrogen |
| CN110721691B (en) * | 2019-11-12 | 2020-07-24 | 中南大学 | CFAN catalyst, preparation thereof and application thereof in methane hydrogen production |
| CN116237030A (en) * | 2022-12-26 | 2023-06-09 | 安徽理工大学 | Nickel-ruthenium-zirconium/attapulgite-based molecular sieve catalyst and application thereof |
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