CN1772614A - Prepn of nickel-base catalyst for decomposing ammonia - Google Patents
Prepn of nickel-base catalyst for decomposing ammonia Download PDFInfo
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- CN1772614A CN1772614A CNA2004100946448A CN200410094644A CN1772614A CN 1772614 A CN1772614 A CN 1772614A CN A2004100946448 A CNA2004100946448 A CN A2004100946448A CN 200410094644 A CN200410094644 A CN 200410094644A CN 1772614 A CN1772614 A CN 1772614A
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- 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
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Abstract
The present invention discloses the preparation process of nickel-base catalyst for decomposing ammonia. The preparation process includes the following steps: preparing water or alcohol solution of nitrate containing Ni, Al or Zr, with assistant La or Ce being capable of being added into the solution, and preparing stoichiometric water or alcohol solution of ammonium carboanate or ammonium bicarboanate; dropping these two kinds of solution into the same container while controlling the pH of the mixed solution in 7-10; stirring to age after finishing material feeding, separating to eliminate mother liquid, washing the precipitate with deionized water, drying and roasting at 400-900 deg.c to obtain the nickel-base catalyst. The nickel-base catalyst has high catalytic activity and high stability as well as simple preparation process and low production cost.
Description
Technical field
The present invention relates to the preparation method of the Ni-based ammonia decomposition catalyzer of a kind of efficient cryogenic, a kind of preparation method who is used for ammonia is decomposed into the nickel-base catalyst of hydrogen and nitrogen is provided specifically.
Background technology
Setting up dispersive hydrogenation station is the development trend of following Hydrogen Energy in the fuel cell field widespread use, in recent years, has abroad begun to pay attention to carry out the corresponding techniques research and development for setting up the hydrogenation station.For example, Ri Ben Toho Gas company has built a hydrogenation station for fuel cell electric vehicle filling hydrogen in the Aichi laboratory.By the end of 2004, Japanese government set up 8 hydrogenation stations in Tokyo.According to current papers in 2003 (International Journal of HydrogenEnergy 28 (2003) 743-755), the U.S. is in order to satisfy the demand of fuel cell electric vehicle, and only the fs just need be set up 4500～17700 hydrogenation stations.In addition, even the less Italy of area also need set up about 10000 hydrogenation stations (Journal of Power Sources 106 (2002) 353-363).This shows that the market business opportunity and the economic interests of following Hydrogen Energy are very huge.A fuel cell bus special line is opened at a hydrogenation station surplus China also will be before 2008 Olympic Games builds 10 in Beijing simultaneously.
Utilizing liquefied ammonia to decompose on-the-spot hydrogen manufacturing is a kind of important selection of setting up the hydrogenation station future, is the problem that raw material not only can solve the fuel transport difficulty with liquefied ammonia, can also reduce transportation cost.Adopt preparing hydrogen by ammonia decomposition in conjunction with the mineral membrane isolation technique, not only can realize the production of High Purity Hydrogen, and can realize the production and the isolation integral of hydrogen, shortened process, the economy system investment also reduces production costs.Therefore, in recent years, preparing hydrogen by ammonia decomposition technology has caused domestic and international researchist's extensive concern again.
Except that following Hydrogen Energy field has wide application prospects, the Application Areas of ammonia decomposition reaction also comprises: the environment protection deamination, electronics and metallurgy industry are with reducing gas and protect gas etc.
Yet the use temperature of the ammonia decomposition catalyzer of present industrial application is too high, and generally more than 800 ℃, not only energy consumption is higher, and equipment corrosion is serious.Therefore, exploitation efficient cryogenic ammonia decomposition catalyzer is the important development direction.Document shows that 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 (Yin, et al., J.Catal.224,384,2004; Xu, et al., CN 1456491A), but content of metal generally higher (＞5%) in the existing efficient ruthenium catalyst has increased the cost of catalyzer.Carbon-based material such as gac, carbon nanotube is the optimum carrier of ruthenium, and methanation reaction takes place under the high temperature of ammonia decomposition reaction, rich hydrogen condition easily, has reduced the stability of ruthenium catalyst.Studies show that the nickel that reserves are abundant, market value is low also is that a kind of ammonia preferably decomposes catalytic active component (Choudhary, et al., Catal.Lett.72,197,2001:Ganley, et al., Catal.Lett.96,117,2004).But the research and development of nickel-base catalyst for a long time lack than quantum jump, show that mainly the low temperature active of catalyzer is poor, processing power is low.For example, document shows (A.S.Chellappa etal., Appl.Catal.A 227,231,2002), and several commercial ammonia decomposition catalyzers are being lower than under 700 ℃ the temperature, and its catalytic activity is all lower.
| Catalyzer | Main chemical | Producer | Temperature (℃) | Transformation efficiency (%) |
| G43-A 2800 146 | Ni，Al，＜1wt.％Pt 93.8％Ni，0.3％Fe，5.9％Al 0.5％Ru，Al | United Catalyst Grace Davison Johnson Matthey | 500 600 600 700 550 600 | 14.5 78.1 18.8 81.6 12.9 23.6 |
At present, the preparation method of Ni-based ammonia decomposition catalyzer is based on the pickling process of routine, and the nickel species mainly exist with the free state form, with carrier interactions a little less than.Therefore, nickel crystallite in pre-treatment (roasting, the reduction etc.) process of catalyzer very easily sintering grow up, this is to cause the active low major cause of existing nickel-base catalyst.In addition,, suppressed amino molecule and contacted, so cold condition is difficult to realize the high conversion of ammonia down with the catalyst activity component because the absorption occupy-place takes place on the catalyst activity component product hydrogen easily.
Summary of the invention
The object of the present invention is to provide a kind of preparation method who is used for the nickel-base catalyst of ammonia decomposition, have the characteristics of high reactivity, high stability, active ingredient high dispersive by the nickel-base catalyst of the present invention's preparation
For achieving the above object, the preparation method who is used for the nickel-base catalyst of ammonia decomposition reaction provided by the invention, concrete steps are as follows:
The nitrate of active constituent Ni, carrier A l or Zr is made solution in the water-soluble or dehydrated alcohol, stoichiometric volatile salt or bicarbonate of ammonia are dissolved in water or the ethanol form solution.Above-mentioned two kinds of drips of solution are added in the same container, and the pH value of control solution is between 7～10.After charging finishes, stirred aging 2-6 hour, separate and remove mother liquor, with the deionized water wash precipitation, dry back obtained the target catalyzer at 400～900 ℃ of following roasting 4-8 hours, wherein the mass percent of active constituent Ni is 10-70%, is preferably 300-60%, preferred 40-60%.The present invention can also add auxiliary agent La or Ce, and its mass percent is 0-30%.
The present invention has following advantage:
1. strong, the good stability of catalyst activity height, processing power.Use the nickel-base catalyst of method preparation provided by the present invention, its key character is that catalytic activity is higher than the existing related Ni-based ammonia decomposition catalyzer of document.Because the present invention has used unconventional coprecipitation method to prepare nickel-base catalyst, active component nickel is high dispersion state, and active ingredient has less median size after the activation treatment.Experimental result shows that the transformation efficiency of ammonia can reach 99.8% when temperature of reaction was 500 ℃.Temperature of reaction is that 550 ℃, ammonia charging air speed are 20000h
-1The time, the transformation efficiency of ammonia is up to 99.9%.Catalyst stability experiment shows, under 550 ℃, the reaction conditions of 5atm, laboratory scale ammonia decomposition device safe handling is after 1000 hours, and transformation efficiency maintains more than 99.9% all the time.This explanation, the nickel-base catalyst of method preparation provided by the present invention is a kind of efficient, stable ammonia decomposition catalyzer.
2. technology is simple.The present invention only needs general Preparation of Catalyst condition, and easy control of reaction and technological process are simple relatively, can satisfy the requirement that large-scale industrialization is produced fully.
3. preparation cost is low.The raw materials used cheapness of the present invention, preparation flow is short, and equipment requirements is simple.
Description of drawings
Fig. 1 is Ni/Al
2 O
31000 hours stability result of catalyzer.
Embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
155g nickelous nitrate, 74g aluminum nitrate are dissolved in the 500ml deionized water, and it is standby to be configured to mixed solution.Get stoichiometric volatile salt and be dissolved in the 500ml deionized water, standby as precipitation agent.Under stirring above-mentioned two drips of solution are added in the same vessel, the pH value of control solution is 8.After charging finishes, stirred aging 2 hours, deionized water wash is used in centrifugation, obtains gel.After 120 ℃ of dryings, temperature programming to 600 ℃, roasting is 8 hours in air.Make nickel oxide content and be 80% Ni/Al
2O
3Catalyzer.
According to the method described above, will feed intake changes 117g nickelous nitrate, 147g aluminum nitrate into, makes nickel oxide content and be 63% Ni/Al
2O
3Catalyzer.
According to the method described above, will feed intake changes 7.8g nickelous nitrate, 280g aluminum nitrate into, makes nickel oxide content and be 5% Ni/Al
2O
3Catalyzer.
Get above-mentioned each catalyzer of 1.0g respectively and place stainless steel reactor, use 50%H
2-He reducing gas (100ml/min) feeds pure ammonia and carries out synthesis under normal pressure at 550 ℃ 600 ℃ of activation treatment 3 hours, and the ammonia flow velocity is 333ml/min.Experimental result is as shown in table 1.
Table 1: nickel content is to the influence of catalytic activity
| Numbering | Nickel oxide (wt.%) | Nickel/al atomic ratio | 550℃，20000h -1Following ammonia transformation efficiency (%) | Reduction back Ni 0Crystal grain d XRD(nm) |
| 1 2 3 | 80 63 5.0 | 2.8 1.2 0.04 | 90.2 91.3 17.6 | 5.9 3.6 - |
This shows that the nickel oxide percentage composition is 63% Ni/Al
2O
3Catalyzer possesses the highest ammonia degrading activity.Select this catalyzer to carry out the investigation of catalyst stability, setting the ammonia air speed is 5000h
-1, temperature of reaction is 620 ℃, reaction pressure is 5atm.After the system steady running 1000 hours, the ammonia transformation efficiency maintains (accompanying drawing 1) more than 99.9% all the time.The prepared Ni/Al of this explanation the present invention
2O
3Have good high temperature resistance stability, industrial prospect is wide.
Embodiment 2
46g nickelous nitrate, 59g aluminum nitrate, 9g lanthanum nitrate are dissolved in the 200ml deionized water, and it is standby to be mixed with mixed solution.Get stoichiometric volatile salt and be dissolved in the 200ml deionized water, standby as precipitation agent.Under stirring above-mentioned two drips of solution are added in the same vessel, the pH value of control solution is 8.After charging finishes, stirred aging 6 hours, deionized water wash is used in centrifugation, obtains gel.After 120 ℃ of dryings, temperature programming to 600 ℃, roasting is 4 hours in air.Making the nickel al atomic ratio is 1.2, and the lanthanum nickle atom is than the Ni/La-Al that is 0.22
2O
3Catalyzer.
According to the method described above, will feed intake changes 46g nickelous nitrate, 59g zirconium nitrate, 11g cerous nitrate into, and making the nickel al atomic ratio is 1.2, and the cerium nickle atom is than the Ni/Ce-ZrO that is 0.23
2Catalyzer.
Get above-mentioned each catalyzer of 1.0g respectively and place stainless steel reactor, use 50%H
2-He reducing gas (100ml/min) feeds pure ammonia and carries out synthesis under normal pressure at 550 ℃ 600 ℃ of activation treatment 3 hours, and the ammonia flow velocity is 333ml/min.Experimental result is as shown in table 2.
Table 2: auxiliary agent is to the influence of catalytic activity
| Numbering | Catalyzer | Nickel/al atomic ratio | Nickel/auxiliary agent atomic ratio | 550℃，20000h -1Ammonia transformation efficiency (%) |
| 1 2 3 | Ni/Al 2O 3 Ni/La-Al 2O 3 Ni/Ce-ZrO 2 | 1.2 1.2 1.2 | - 0.22 0.23 | 91.3 99.9 96.8 |
As shown in Table 2, add rare-earth elements of lanthanum, cerium can effectively improve the ammonia degrading activity of nickel-alumina catalyst, and it is active best wherein to add lanthanum trioxide.Therefore, The effect Ni/La-Al
2O
3The activity of catalyzer under the differential responses condition.Experimental result is as shown in table 3.
Table 3:Ni/La-Al
2O
3Ammonia decomposition reaction transformation efficiency (%) on the catalyzer
| Temperature of reaction (℃) | Ammonia charging air speed (h -1) | ||||
| 1000 | 2000 | 5000 | 10000 | 20000 | |
| 400 450 500 550 | 51.9 97.4 99.9 ＞99.9 | 37.5 91.9 99.8 ＞99.9 | 21.5 67.3 99.4 ＞99.9 | 14.1 51.4 95.3 ＞99.9 | 9.6 37.0 78.0 99.9 |
Embodiment 3
According to embodiment 2 described preparation methods, change volatile salt into bicarbonate of ammonia, making the nickel al atomic ratio is 1.2, the lanthanum nickle atom is than the Ni/La-Al that is 0.21
2O
3Catalyzer.
Get this catalyzer of 1.0g, carry out activity rating according to the condition described in the embodiment 2.Experimental result: 550 ℃, when the ammonia flow velocity was 333ml/min, the ammonia transformation efficiency was 99.7%.
Ni/La-Al with gained among the embodiment 2
2O
3Catalyzer is compared, and selects for use bicarbonate of ammonia or volatile salt suitable as the prepared catalyst activity of precipitation agent.This explanation prepares the Ni-based ammonia decomposition catalyzer technology of high reactivity for coprecipitation method, and volatile salt and bicarbonate of ammonia all are precipitation agents preferably.
Embodiment 4
46g nickelous nitrate, 59g aluminum nitrate, 9g lanthanum nitrate are dissolved in the 200ml dehydrated alcohol, and it is standby to be mixed with mixed solution.Get stoichiometric volatile salt and be dissolved in 200ml ethanol water (1: the 1) solution, standby as precipitation agent.Under stirring above-mentioned two drips of solution are added in the same vessel, the pH value of control solution is 8.After charging finishes, stirred aging 4 hours, deionized water wash is used in centrifugation, obtains gel.After 120 ℃ of dryings, temperature programming to 600 ℃, roasting is 6 hours in air.Making the nickel al atomic ratio is 1.2, and the lanthanum nickle atom is than the Ni/La-Al that is 0.22
2O
3Catalyzer.
Get the above-mentioned catalyzer of 1.0g and place stainless steel reactor, use 50%H
2-He reducing gas (100ml/min) feeds pure ammonia and carries out synthesis under normal pressure at 550 ℃ 600 ℃ of activation treatment 3 hours, and the ammonia flow velocity is 333ml/min.Experimental result: the ammonia transformation efficiency is 98.9%.
Ni/La-Al with gained among the embodiment 2
2O
3Catalyzer is compared, and the catalyst activity of present embodiment gained is suitable.
Claims (6)
1, a kind of preparation method who is used for the nickel-base catalyst of ammonia decomposition, key step is:
A) with the nitrate solution mixing of active ingredient Ni, carrier A l or Zr;
B) with stoichiometric precipitation agent precipitation, pH is 7-10;
C) aging 2-6 hour, separate and remove mother liquor, washing precipitation, drying;
D) 400～900 ℃ roasting 4-8 hour;
Wherein the quality percentage composition of Ni is 10～70%;
Precipitation agent is volatile salt or ammonium bicarbonate soln.
2. the preparation method of claim 1 is characterized in that, adds the nitrate solution of auxiliary agent La or Ce among the step a, and the quality percentage composition of auxiliary agent La or Ce is 0～30%.
3. claim 1 or 2 preparation method is characterized in that nitrate solution is meant the aqueous solution or the ethanolic soln of nitrate.
4. the preparation method of claim 1 is characterized in that, precipitation agent is meant the aqueous solution or the ethanolic soln of volatile salt or bicarbonate of ammonia.
5. the preparation method of claim 1 is characterized in that, the quality percentage composition of active ingredient Ni is 30～60%.
6. the preparation method of claim 1 is characterized in that, the quality percentage composition of active ingredient Ni is 40～60%.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2016126576A1 (en) * | 2015-02-03 | 2016-08-11 | Gencell Ltd. | Nickel-based catalyst for the decomposition of ammonia |
| CN106457222A (en) * | 2014-05-22 | 2017-02-22 | 沙特基础工业全球技术有限公司 | Mixed metal oxide catalysts for ammonia decomposition |
| CN114160150A (en) * | 2021-12-31 | 2022-03-11 | 西南化工研究设计院有限公司 | Large-scale high-pressure ammonia decomposition catalyst and preparation method thereof |
| CN115646500A (en) * | 2022-10-31 | 2023-01-31 | 上海簇睿低碳能源技术有限公司 | Catalyst for preparing hydrogen by decomposing ammonia and preparation method and application thereof |
| IL257019B1 (en) * | 2015-07-22 | 2023-06-01 | Gencell Ltd | Process for the thermal decomposition of ammonia and reactor for carrying out said process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE19800449A1 (en) * | 1998-01-08 | 1999-07-15 | Basf Ag | Process for the catalytic destruction of ammonia and hydrogen cyanide from coke oven emissions |
| 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 |
| CN1528657A (en) * | 2003-09-26 | 2004-09-15 | 清华大学 | Low-temperature ammonia decomposition hydrogen preparation catalyst and preparing method thereof |
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106457222A (en) * | 2014-05-22 | 2017-02-22 | 沙特基础工业全球技术有限公司 | Mixed metal oxide catalysts for ammonia decomposition |
| WO2016126576A1 (en) * | 2015-02-03 | 2016-08-11 | Gencell Ltd. | Nickel-based catalyst for the decomposition of ammonia |
| EP3253487A4 (en) * | 2015-02-03 | 2018-08-01 | Gencell Ltd. | Nickel-based catalyst for the decomposition of ammonia |
| IL257019B1 (en) * | 2015-07-22 | 2023-06-01 | Gencell Ltd | Process for the thermal decomposition of ammonia and reactor for carrying out said process |
| CN114160150A (en) * | 2021-12-31 | 2022-03-11 | 西南化工研究设计院有限公司 | Large-scale high-pressure ammonia decomposition catalyst and preparation method thereof |
| CN114160150B (en) * | 2021-12-31 | 2023-01-10 | 西南化工研究设计院有限公司 | Large-scale high-pressure ammonia decomposition catalyst and preparation method thereof |
| CN115646500A (en) * | 2022-10-31 | 2023-01-31 | 上海簇睿低碳能源技术有限公司 | Catalyst for preparing hydrogen by decomposing ammonia and preparation method and application thereof |
| CN115646500B (en) * | 2022-10-31 | 2024-01-30 | 上海簇睿低碳能源技术有限公司 | Catalyst for producing hydrogen by ammonia decomposition and preparation method and application thereof |
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Owner name: DALIAN HUAHAI HYDROGEN MANUFACTURE EQUIPMENT CO., Free format text: FORMER OWNER: DALIAN INST OF CHEMICOPHYSICS, CHINESE ACADEMY OF SCIENCES Effective date: 20091218 |
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Effective date of registration: 20091218 Address after: Hi tech Industrial Park, Dalian, Liaoning Patentee after: Dalian Huahy Hydrogen Production Equipment Co., Ltd. Address before: No. 457, Zhongshan Road, Liaoning, Dalian Patentee before: Dalian Institute of Chemical Physics, Chinese Academy of Sciences |
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