CN101780413B - Nickel-based catalyst for ammonia decomposition and preparation method and application thereof - Google Patents
Nickel-based catalyst for ammonia decomposition and preparation method and application thereof Download PDFInfo
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- CN101780413B CN101780413B CN2010101117156A CN201010111715A CN101780413B CN 101780413 B CN101780413 B CN 101780413B CN 2010101117156 A CN2010101117156 A CN 2010101117156A CN 201010111715 A CN201010111715 A CN 201010111715A CN 101780413 B CN101780413 B CN 101780413B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses nickel-based catalyst for ammonia decomposition, which is formed by gamma-aluminum oxide with specific surface area of 220-250m<2>g<-1>, nickel and lanthanum, wherein the weight percent of the nickel in the nickel-based catalyst is 10-30 percent and the weight percent of the lanthanum in the nickel-based catalyst is 1-10 percent. The invention additionally discloses the preparation method of the nickel-based catalyst. The preparation method is that the gamma-aluminum oxide is put into the mixed solution of nickel nitrate and lanthanum nitrate and is fully soaked, the gamma-aluminum oxide is naturally cooled to room temperature after the gamma-aluminum oxide is air-dried, dried and roasted, and catalyst requiring to be activated is obtained; and the catalyst requiring to be activated is activated to obtain the nickel-based catalyst. The invention additionally discloses the application of the nickel-based catalyst. The nickel-based catalyst can be used to prepare hydrogen. When pure ammonia is fed and normal-pressure reaction is conducted under 400-550 DEG C, hydrogen can be obtained.
Description
Technical field
The present invention relates to a kind of nickel-base catalyst that is used for the ammonia decomposition and its production and use.
Background technology
Along with the development of society, the energy and environmental problem have become one of countries in the world question of common concern.But traditional energy can not satisfy people's long-range demand, discharges a large amount of CO simultaneously
xAlso environment has been caused pollution, so the exploitation of new forms of energy and application are significant.Hydrogen Energy with pollution-free, can reuse, the fuel value advantages of higher enjoys favor.Simultaneously, industrial department such as chemical industry, metallurgy also needs a large amount of hydrogen as reducing gases.
Present industrial hydrogen manufacturing is mainly based on fossil fuel, brine electrolysis and ammonia decomposition method.Wherein water electrolysis hydrogen production power consumption is very big, and the electricity charge account for about 80% of whole water electrolysis hydrogen production producing cost.Fossil fuel hydrogen manufacturing widespread usage on chemical industry, but this method can produce CO in process of production inevitably
x, very easily cause catalyst poisoning and environmental pollution, and remove very difficulty, caused the raising of production cost.The hydrogen manufacturing of ammonia decomposition method is then with hydrogen purity height, occupation of land is little, simple to operate, investment is little, advantages such as cost is low, no harmful side product have been subjected to people common concern.In the time of particularly need not separating to the needs hydrogen nitrogen mixed gas or to hydrogen nitrogen, more apparent its superiority.The storage of ammonia and the operability of transportation and security are far above hydrogen.As a kind of means of storing up hydrogen, improved the feasibility of hydrogen with ammonia greatly as the raw material of industry and the energy.Ammonia decomposition reaction can also be applied to the environmental protection deamination simultaneously, for example is used to handle coke-stove gas, fuel gas, petroleum refinery's waste gas and reduction and handles NO
xRemaining ammonia in the tail gas is to protect the environment from pollution.
It is an endothermic reaction that ammonia decomposes, and can judge that from the thermodynamics angle ammonia decomposition catalyzer catalyst for preparing hydrogen of developing low temperature high activity is fully feasible.Even under lower temperature, the hydrogen that the ammonia incomplete decomposing produces can be used for the protective gas in the industrial production, protects the materials such as catalyst of easy oxidation.The active component of Bao Dao ammonia decomposition catalyzer is mainly one pack system or multicomponent metals such as Fe, Ni, Ti, Mo, Co, Ru up to now, and carrier is mainly MgO, the SiO of conventional method preparation
2, Al
2O
3With active carbon etc.The research of ammonia decomposition catalyzer mainly biases toward highly active ruthenium base of exploitation or nickel-base catalyst.Though ruthenium-based catalyst possesses higher ammonia degrading activity, the load capacity generally higher (＞5%) of metal Ru in the efficient ruthenium catalyst has increased the cost of catalyst.The nickel that reserves are abundant, price is lower also is that a kind of ammonia preferably decomposes catalytic active component, but the nickel-base catalyst low temperature active is poor, disposal ability is low.The preparation method of Ni-based ammonia decomposition catalyzer is based on the infusion process (only adopting nickel nitrate) of routine, and nickel mainly exists with the free state form, with carrier interactions a little less than.Therefore, nickel crystallite in pre-treatment (roasting, the reduction etc.) process of catalyst very easily sintering grow up, this is the main cause that causes existing nickel-base catalyst poor activity.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of nickel-base catalyst with high activity, high stability, active component polymolecularity and preparation method thereof, and the purposes of this kind nickel-base catalyst.
In order to solve the problems of the technologies described above, the invention provides a kind of nickel-base catalyst that ammonia decomposes that is used for, this nickel-base catalyst is by specific area 220-250m
2g
-1Gama-alumina, nickel and lanthanum form, the percentage by weight of nickel is 10%～30% in the nickel-base catalyst, the percentage by weight of lanthanum is 1%～10%.
The present invention also provides the above-mentioned preparation method who is used for the nickel-base catalyst of ammonia decomposition simultaneously, may further comprise the steps: with specific area 220-250m
2g
-1The gama-alumina mixed solution of putting into nickel nitrate and lanthanum nitrate fully flood, dry the back at 110～130 ℃ of drying 4.5～5.5h, at 400 ℃～450 ℃ roasting 3.5～4.5h, be cooled to room temperature naturally again, must need the catalyst that activates; The catalyst that will activate carries out activation processing then, gets nickel-base catalyst.
As the improvement that is used for the preparation method of the nickel-base catalyst that ammonia decomposes of the present invention: the time of activation processing is 24 hours, carries out following steps successively:
At 0-4h, be the N of 60L/h at flow
2Effect activates in 25-180 ℃ down;
At 4-6h, be the N of 60L/h at flow
2With flow be the H of 1.8L/h
2Acting in conjunction under, activate in 180-210 ℃;
At 6-8h, be the N of 60L/h at flow
2With flow be the H of 3L/h
2Acting in conjunction under, activate in 210-230 ℃;
At 8-10h, be the N of 56L/h at flow
2With flow be the H of 10L/h
2Acting in conjunction under, activate in 230-250 ℃;
At 10-14h, be the N of 40L/h at flow
2With flow be the H of 20L/h
2Acting in conjunction under, activate in 250-270 ℃;
At 14-18h, be the N of 20L/h at flow
2With flow be the H of 40L/h
2Acting in conjunction under, activate in 270-285 ℃;
At 18-20h, be the H of 60L/h at flow
2Effect activates in 280-290 ℃ down;
At 20-24h, be the H of 60L/h at flow
2Effect activates in 280-290 ℃ down.
The present invention also discloses the method for utilizing this nickel-base catalyst to prepare hydrogen simultaneously: under the effect of nickel-base catalyst, feed pure ammonia and carry out synthesis under normal pressure at 400 ℃～550 ℃, ammonia air speed scope is 1000～20000h
-1
In the present invention, nitrate is all resolved into metal oxide in roasting process, and metal oxide is activated to be become metal simple-substance by Restore All.
Of the present inventionly being used for the nickel-base catalyst that ammonia decomposes, is to be catalyst precursor with nickel nitrate and lanthanum nitrate, a kind of loaded catalyst that adopts immersion process for preparing to form; Its main active component is Ni, and carrier is Al
2O
3, auxiliary agent is La, is applicable to preparing hydrogen by ammonia decomposition under the low temperature.
The present invention has following advantage:
1, catalyst activity height, good stability, active component decentralization height, long service life.The adding of auxiliary agent La has formed La-O-Ni construction unit closely, has improved the heat-resisting ability of catalyst crystal, has improved activity of such catalysts, and has reduced the temperature that ammonia decomposes fully.
2, technology is simple.The present invention only needs general Preparation of Catalyst condition, and easy control of reaction and technology are simple relatively, can satisfy the requirement that large-scale industrialization is produced fully.
3, preparation cost is low.The present invention is raw materials used inexpensive, and preparation flow is short, and equipment requires simple.
The specific embodiment
Embodiment 1, a kind of nickel-base catalyst that is used for the ammonia decomposition, preparation process is as follows:
With 4.96gNi (NO
3)
26H
2O and 0.31g La (NO
3)
36H
2O is dissolved in the water of 20ml, gets maceration extract, puts into gama-alumina (the specific area 220-250m of 8.9g then
2g
-1) carry out abundant hybrid infusion, absorbed fully by gama-alumina until maceration extract.At 120 ℃ of dry 5h, at 400 ℃～450 ℃ roasting 4h, be cooled to room temperature naturally more then, must need the catalyst of activation.
It is that the stainless steel reaction pipe of 700mm carries out activation processing that the above-mentioned catalyst 100g that needs activation is put into an internal diameter Φ=7.5mm, length, the activation processing time amounts to 24 hours, and the duration of ventilation of different soak time sections, ventilation flow rate and heating-up temperature are as shown in table 1.
Table 1, catalyst activation condition
| 14-18 | 20 | 33.3 | 40 | 66.7 | 270-285 |
| 18-20 | 0 | 0 | 60 | 100 | 285 |
| 20-24 | 0 | 0 | 60 | 100 | 285 |
(annotate: what this table 1 was represented is: when the catalyst that need activate activated in 24 hours, in the process conditions of different time periods.)
The nickel-base catalyst of gained contains 10% Ni and 1% La; This % is weight percentage.
Embodiment 2, with 4.96gNi (NO
3)
26H
2O and 1.56g La (NO
3)
36H
2O is dissolved in the water of 20ml, gets maceration extract, puts into gama-alumina (the specific area 220-250m of 8.5g then
2g
-1) carry out abundant hybrid infusion, absorbed fully by gama-alumina until maceration extract.All the other contents are with embodiment 1.
The nickel-base catalyst of gained contains 10% Ni and 5% La.
Embodiment 3, with 4.96gNi (NO
3)
26H
2O and 3.12g La (NO
3)
36H
2O is dissolved in the water of 20ml, gets maceration extract, puts into gama-alumina (the specific area 220-250m of 8.0g then
2g
-1) carry out abundant hybrid infusion, absorbed fully by gama-alumina until maceration extract.All the other contents are with embodiment 1.
The nickel-base catalyst of gained contains 10% Ni and 10% La.
Embodiment 4, with nickel nitrate and the 1.56g La (NO of 9.92g
3)
36H
2O is dissolved in the water of 20ml, gets maceration extract, puts into gama-alumina (the specific area 220-250m of 7.5g then
2g
-1) carry out abundant hybrid infusion, absorbed fully by gama-alumina until maceration extract.All the other contents are with embodiment 1.
The nickel-base catalyst of gained contains 20% Ni and 5% La.
Embodiment 5, with nickel nitrate and the 3.12g La (NO of 14.9g
3)
36H
2O is dissolved in the water of 20ml, gets maceration extract, puts into gama-alumina (the specific area 220-250m of 6.0g then
2g
-1) carry out abundant hybrid infusion, absorbed fully by gama-alumina until maceration extract.All the other contents are with embodiment 1.
The nickel-base catalyst of gained contains 30% Ni and 10%La.
Called after catalyst A～catalyst the E of the foregoing description 1～embodiment 5 described nickel-base catalyst correspondences.
In order to verify the activity of catalyst A～catalyst E, done following experiment:
Experiment 1, to select volume for use be the stainless steel reactor of 50mL, and 1.0g catalyst A (embodiment 1 gained) is placed above-mentioned stainless steel reactor, feeds pure ammonia and carry out synthesis under normal pressure at 300 ℃～450 ℃ and be used to prepare hydrogen, and ammonia air speed scope is 1000～10000h
-1, experiment condition and experimental result are as shown in table 2.
The ammonia decomposition reaction conversion ratio of table 2, catalyst A
The experiment 2, with catalyst B (embodiment 2 gained) alternative catalysts A, all the other contents with the experiment 1.Experiment condition and experimental result are as shown in table 3.
The ammonia decomposition reaction conversion ratio of table 3, catalyst B
The experiment 3, with catalyst C (embodiment 3 gained) alternative catalysts A, all the other contents with the experiment 1.Experiment condition and experimental result are as shown in table 4.
The ammonia decomposition reaction conversion ratio of table 4, catalyst C
The experiment 4, with catalyst D (embodiment 4 gained) alternative catalysts A, all the other contents with the experiment 1.Experiment condition and experimental result are as shown in table 5.
The ammonia decomposition reaction conversion ratio of table 5, catalyst D
The experiment 5, with catalyst E (embodiment 5 gained) alternative catalysts A, all the other contents with the experiment 1.Experiment condition and experimental result are as shown in table 6.
The ammonia decomposition reaction conversion ratio of table 6, catalyst E
The contrast experiment: the Ni-based ammonia decomposition catalyzer after activating with infusion process (only the adopting nickel nitrate) gained of the routine of informing in the background technology and as the described activation condition of table 1 is catalyst (weight percentage of nickel is 30%) as a comparison, with this comparative catalyst's alternative catalysts A, all the other contents are with experiment 1.Experiment condition and experimental result are as shown in table 7.
Table 7 comparative catalyst's ammonia decomposition reaction conversion ratio
At last, it is also to be noted that what more than enumerate only is several instantiations of the present invention.Obviously, the invention is not restricted to above example, many distortion can also be arranged.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention all should be thought protection scope of the present invention.
Claims (1)
1. preparation method who is used for the nickel-base catalyst that ammonia decomposes, it is characterized in that: described nickel-base catalyst is by specific area 220-250m
2g
-1Gama-alumina, nickel and lanthanum form, the percentage by weight of nickel is 10%～30% in the described nickel-base catalyst, the percentage by weight of lanthanum is 1%～10%; May further comprise the steps: with specific area 220-250m
2g
-1The gama-alumina mixed solution of putting into nickel nitrate and lanthanum nitrate fully flood, dry the back at 110～130 ℃ of drying 4.5～5.5h, at 400 ℃～450 ℃ roasting 3.5～4.5h, be cooled to room temperature naturally again, must need the catalyst that activates; The catalyst that will activate carries out activation processing then, gets nickel-base catalyst;
The time of described activation processing is 24 hours, carries out following steps successively:
At 0-4h, be the N of 60L/h at flow
2Effect activates in 25-180 ℃ down;
At 4-6h, be the N of 60L/h at flow
2With flow be the H of 1.8L/h
2Acting in conjunction under, activate in 180-210 ℃;
At 6-8h, be the N of 60L/h at flow
2With flow be the H of 3L/h
2Acting in conjunction under, activate in 210-230 ℃;
At 8-10h, be the N of 56L/h at flow
2With flow be the H of 10L/h
2Acting in conjunction under, activate in 230-250 ℃;
At 10-14h, be the N of 40L/h at flow
2With flow be the H of 20L/h
2Acting in conjunction under, activate in 250-270 ℃;
At 14-18h, be the N of 20L/h at flow
2With flow be the H of 40L/h
2Acting in conjunction under, activate in 270-285 ℃;
At 18-20h, be the H of 60L/h at flow
2Effect activates in 280-290 ℃ down;
At 20-24h, be the H of 60L/h at flow
2Effect activates in 280-290 ℃ down.
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|---|---|---|---|---|
| CN1506299A (en) * | 2002-12-12 | 2004-06-23 | 中国科学院大连化学物理研究所 | Prepn and application of nickel-based catalyst for decomposing ammonia to prepare mixed H2-N2 gas |
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| CN1506299A (en) * | 2002-12-12 | 2004-06-23 | 中国科学院大连化学物理研究所 | Prepn and application of nickel-based catalyst for decomposing ammonia to prepare mixed H2-N2 gas |
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Granted publication date: 20111228 Termination date: 20120212 |