CN1318134C - Prepn of nickel-base catalyst for decomposing ammonia - Google Patents
Prepn of nickel-base catalyst for decomposing ammonia Download PDFInfo
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- CN1318134C CN1318134C CNB2004100946448A CN200410094644A CN1318134C CN 1318134 C CN1318134 C CN 1318134C CN B2004100946448 A CNB2004100946448 A CN B2004100946448A CN 200410094644 A CN200410094644 A CN 200410094644A CN 1318134 C CN1318134 C CN 1318134C
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- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 92
- 239000003054 catalyst Substances 0.000 title claims abstract description 52
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 claims abstract description 22
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 21
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 19
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001099 ammonium carbonate Substances 0.000 claims abstract description 13
- 235000012501 ammonium carbonate Nutrition 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 229910052684 Cerium Inorganic materials 0.000 claims abstract description 6
- 229910002651 NO3 Inorganic materials 0.000 claims abstract description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 239000012452 mother liquor Substances 0.000 claims abstract description 3
- 229910000013 Ammonium bicarbonate Inorganic materials 0.000 claims abstract 3
- 235000012538 ammonium bicarbonate Nutrition 0.000 claims abstract 3
- 239000002244 precipitate Substances 0.000 claims abstract 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 56
- 230000001376 precipitating effect Effects 0.000 claims description 8
- 230000032683 aging Effects 0.000 claims description 5
- 239000012752 auxiliary agent Substances 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 4
- 239000000243 solution Substances 0.000 claims 6
- 239000007864 aqueous solution Substances 0.000 claims 2
- 239000003795 chemical substances by application Substances 0.000 claims 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 11
- 239000008367 deionised water Substances 0.000 abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 abstract description 5
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 238000003756 stirring Methods 0.000 abstract description 4
- 230000008901 benefit Effects 0.000 abstract description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 18
- 229910052739 hydrogen Inorganic materials 0.000 description 15
- 230000000694 effects Effects 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 10
- 238000005984 hydrogenation reaction Methods 0.000 description 8
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 6
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 description 5
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 5
- 239000003153 chemical reaction reagent Substances 0.000 description 5
- 239000000446 fuel Substances 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 229910000480 nickel oxide Inorganic materials 0.000 description 5
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 5
- 229910052707 ruthenium Inorganic materials 0.000 description 5
- 230000004913 activation Effects 0.000 description 4
- 125000004429 atom Chemical group 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000012545 processing Methods 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000005119 centrifugation Methods 0.000 description 3
- 230000000593 degrading effect Effects 0.000 description 3
- 235000021050 feed intake Nutrition 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000002955 isolation Methods 0.000 description 2
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 description 2
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- OERNJTNJEZOPIA-UHFFFAOYSA-N zirconium nitrate Chemical compound [Zr+4].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O OERNJTNJEZOPIA-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009615 deamination Effects 0.000 description 1
- 238000006481 deamination reaction Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000002203 pretreatment Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
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Abstract
本发明公开了一种用于氨分解的氨基催化剂的制备方法。其主要制备过程为：将含有Ni、Al或Zr的硝酸盐制成水或乙醇溶液，还可加入助剂La或Ce，用化学计量的碳酸铵或碳酸氢铵的水溶液或乙醇溶液为沉淀剂。将上述两种溶液滴加到同一容器中，控制溶液的pH值在7～10之间。进料完毕后，搅拌老化，分离除去母液，用去离子水洗涤沉淀，干燥后在400～900℃下焙烧。采用上述方法制备的催化剂对于氨分解反应具有较高的催化活性和稳定性。此外，还具有制备工艺简单和制造成本低的优点。The invention discloses a preparation method of an amino catalyst for ammonia decomposition. Its main preparation process is: make nitrate containing Ni, Al or Zr into water or ethanol solution, and additives La or Ce can also be added, and stoichiometric ammonium carbonate or ammonium bicarbonate solution or ethanol solution is used as precipitant . Add the above two solutions dropwise into the same container, and control the pH value of the solution between 7-10. After feeding, stir and age, separate and remove the mother liquor, wash the precipitate with deionized water, dry and roast at 400-900°C. The catalyst prepared by the above method has high catalytic activity and stability for ammonia decomposition reaction. In addition, it also has the advantages of simple preparation process and low manufacturing 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 the hydrogenation station that disperses is the development trend of following Hydrogen Energy in the fuel cell field extensive 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 phase I just need be set up 4500～17700 hydrogenation stations.In addition, even territory and long-pending less Italy also need set up about 10000 hydrogenation stations (Journal ofPower 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 cost of transportation.Adopt preparing hydrogen by ammonia decomposition in conjunction with the inoranic membrane isolation technics, 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 researcher's extensive concern again.
Except that following Hydrogen Energy field has wide application prospects, the application of ammonia decomposition reaction also comprises: the environmental protection deamination, electronics and metallurgy industry are with reducing gases and protect gas etc.
Yet the serviceability 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 catalyst.Carbon-based material such as active carbon, CNT 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, the market price 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 catalyst is poor, disposal ability 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 the tool catalytic activity is all lower.
| Catalyst | Main chemical | Producer | Temperature (℃) | Conversion ratio (%) |
| 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 infusion 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 catalyst very easily sintering grow up, this is to cause the active low main cause of existing nickel-base catalyst.In addition,, suppressed amino molecule and contacted, so cryogenic conditions 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 activity, high stability, active component 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 absolute ethyl alcohol, stoichiometric ammonium carbonate or carbonic hydroammonium 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, spend the deionised water precipitation, dry back obtained the target catalyst at 400～900 ℃ of following roasting 4-8 hours, wherein the mass percent of active constituent Ni is 10-70%, is preferably 30-60%, 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, disposal ability.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 to prepare nickel-base catalyst, active component nickel is high dispersion state, and active component has less average grain diameter after the activation processing.Experimental result shows that the conversion ratio of ammonia can reach 99.8% when reaction temperature was 500 ℃.Reaction temperature is that 550 ℃, ammonia charging air speed are 20000h
-1The time, the conversion ratio of ammonia is up to 99.9%.Catalyst stability experiment shows, under 550 ℃, the reaction condition of 5atm, laboratory scale ammonia decomposition device safe handling is after 1000 hours, and conversion ratio 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 technical 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 requires simple.
Description of drawings
Fig. 1 is Ni/Al
2 O
31000 hours stability result of catalyst.
The specific embodiment
The present invention will be further described below in conjunction with embodiment.
Embodiment 1
155g nickel nitrate, 74g aluminum nitrate are dissolved in the 500ml deionized water, and it is standby to be configured to mixed liquor.Get stoichiometric ammonium carbonate and be dissolved in the 500ml deionized water, standby as precipitating reagent.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, centrifugation spends deionised water, 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
3Catalyst.
According to the method described above, will feed intake changes 117g nickel nitrate, 147g aluminum nitrate into, makes nickel oxide content and be 63% Ni/Al
2O
3Catalyst.
According to the method described above, will feed intake changes 7.8g nickel nitrate, 280g aluminum nitrate into, makes nickel oxide content and be 5% Ni/Al
2O
3Catalyst.
Get above-mentioned each catalyst of 1.0g respectively and place stainless steel reactor, use 50%H
2-He reducing gases (100ml/min) feeds pure ammonia and carries out synthesis under normal pressure at 550 ℃ 600 ℃ of activation processing 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 conversion ratio (%) | 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
3Catalyst possesses the highest ammonia degrading activity.Select this catalyst to carry out the investigation of catalyst stability, setting the ammonia air speed is 5000h
-1, reaction temperature is 620 ℃, reaction pressure is 5atm.After the system steady running 1000 hours, the ammonia conversion ratio 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 nickel nitrate, 59g aluminum nitrate, 9g lanthanum nitrate are dissolved in the 200ml deionized water, and it is standby to be mixed with mixed liquor.Get stoichiometric ammonium carbonate and be dissolved in the 200ml deionized water, standby as precipitating reagent.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, centrifugation spends deionised water, 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
3Catalyst.
According to the method described above, will feed intake changes 46g nickel 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
2Catalyst.
Get above-mentioned each catalyst of 1.0g respectively and place stainless steel reactor, use 50%H
2-He reducing gases (100ml/min) feeds pure ammonia and carries out synthesis under normal pressure at 550 ℃ 600 ℃ of activation processing 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 | Catalyst | Nickel/al atomic ratio | Nickel/auxiliary agent atomic ratio | 550℃，20000h -1Ammonia conversion ratio (%) |
| 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 lanthana.Therefore, The effect Ni/La-Al
2O
3The activity of catalyst under the differential responses condition.Experimental result is as shown in table 3.
Table 3:Ni/La-Al
2O
3Ammonia decomposition reaction conversion ratio (%) on the catalyst
| Reaction temperature (℃) | 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 ammonium carbonate into carbonic hydroammonium, making the nickel al atomic ratio is 1.2, the lanthanum nickle atom is than the Ni/La-Al that is 0.21
2O
3Catalyst.
Get this catalyst 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 conversion ratio was 99.7%.
Ni/La-Al with gained among the embodiment 2
2O
3Catalyst is compared, and selects for use carbonic hydroammonium or ammonium carbonate suitable as the prepared catalyst activity of precipitating reagent.This explanation prepares the Ni-based ammonia decomposition catalyzer technology of high activity for coprecipitation, and ammonium carbonate and carbonic hydroammonium all are precipitating reagents preferably.
Embodiment 4
46g nickel nitrate, 59g aluminum nitrate, 9g lanthanum nitrate are dissolved in the 200ml absolute ethyl alcohol, and it is standby to be mixed with mixed liquor.Get stoichiometric ammonium carbonate and be dissolved in 200ml ethanol water (1: the 1) solution, standby as precipitating reagent.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, centrifugation spends deionised water, 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
3Catalyst.
Get the above-mentioned catalyst of 1.0g and place stainless steel reactor, use 50%H
2-He reducing gases (100ml/min) feeds pure ammonia and carries out synthesis under normal pressure at 550 ℃ 600 ℃ of activation processing 3 hours, and the ammonia flow velocity is 333ml/min.Experimental result: the ammonia conversion ratio is 98.9%.
Ni/La-Al with gained among the embodiment 2
2O
3Catalyst is compared, and the catalyst activity of present embodiment gained is suitable.
Claims (6)
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| EP3145860A1 (en) * | 2014-05-22 | 2017-03-29 | SABIC Global Technologies B.V. | Mixed metal oxide catalysts for ammonia decomposition |
| MX2017009789A (en) * | 2015-02-03 | 2017-12-04 | Gencell Ltd | NICKEL BASED CATALYST FOR THE DECOMPOSITION OF AMMONIA. |
| US10450192B2 (en) * | 2015-07-22 | 2019-10-22 | Gencell Ltd. | Process for the thermal decomposition of ammonia and reactor for carrying out said process |
| CN114160150B (en) * | 2021-12-31 | 2023-01-10 | 西南化工研究设计院有限公司 | A large-scale high-pressure ammonia decomposition catalyst and its preparation method |
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6113871A (en) * | 1998-01-08 | 2000-09-05 | Basf Aktiengesellschaft | Catalytic decomposition of ammonia and hydrogen cyanide in coke-oven gas |
| CN1506299A (en) * | 2002-12-12 | 2004-06-23 | 中国科学院大连化学物理研究所 | Preparation method and application of a nickel-based catalyst for ammonia decomposition to produce hydrogen-nitrogen mixed gas |
| CN1528657A (en) * | 2003-09-26 | 2004-09-15 | 清华大学 | Catalyst for producing hydrogen by low-temperature ammonia decomposition and its preparation method |
-
2004
- 2004-11-11 CN CNB2004100946448A patent/CN1318134C/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6113871A (en) * | 1998-01-08 | 2000-09-05 | Basf Aktiengesellschaft | Catalytic decomposition of ammonia and hydrogen cyanide in coke-oven gas |
| CN1506299A (en) * | 2002-12-12 | 2004-06-23 | 中国科学院大连化学物理研究所 | Preparation method and application of a nickel-based catalyst for ammonia decomposition to produce hydrogen-nitrogen mixed gas |
| CN1528657A (en) * | 2003-09-26 | 2004-09-15 | 清华大学 | Catalyst for producing hydrogen by low-temperature ammonia decomposition and its preparation method |
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