CN101513611A - Catalyst for oxidation of ammonia gas and method for preparing same - Google Patents
Catalyst for oxidation of ammonia gas and method for preparing same Download PDFInfo
- Publication number
- CN101513611A CN101513611A CNA2009100970613A CN200910097061A CN101513611A CN 101513611 A CN101513611 A CN 101513611A CN A2009100970613 A CNA2009100970613 A CN A2009100970613A CN 200910097061 A CN200910097061 A CN 200910097061A CN 101513611 A CN101513611 A CN 101513611A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxidation
- ammonia gas
- temperature
- selectivity
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 37
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 23
- 230000003647 oxidation Effects 0.000 title claims abstract description 15
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 6
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- 229910052720 vanadium Inorganic materials 0.000 claims abstract description 5
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- DHEQXMRUPNDRPG-UHFFFAOYSA-N strontium nitrate Chemical compound [Sr+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O DHEQXMRUPNDRPG-UHFFFAOYSA-N 0.000 claims description 8
- 229910002651 NO3 Inorganic materials 0.000 claims description 6
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 239000008139 complexing agent Substances 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 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 claims description 4
- 150000003624 transition metals Chemical class 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 22
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910021529 ammonia Inorganic materials 0.000 abstract description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 229910017604 nitric acid Inorganic materials 0.000 abstract description 4
- 229910052697 platinum Inorganic materials 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract 1
- 238000003980 solgel method Methods 0.000 abstract 1
- 229910002204 La0.8Sr0.2MnO3 Inorganic materials 0.000 description 4
- 239000003708 ampul Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011572 manganese Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a catalyst for the oxidation of ammonia gas, having the general formula: La1-xSrxBO3, wherein x is more than 0 and less than 1, B is Mn or V transition metal element. The catalyst is prepared by using the sol-gel processing, the preparing process is simple, the reagent is easy to obtain, the reacting temperature is lower, the catalyst is in industrial production. The catalyst has high catalytic effect at the temperature of 400 DEG C, at the temperature of 600 DEG C, the conversion rate of ammonia gas exceeds 90% and the selectivity for NO exceeds 90%. The catalyst has higher activity and selectivity, and can be used for replacing platinum in the preparation of nitric acid by the oxidation of ammonia.
Description
Technical field
The present invention relates to the Catalysts and its preparation method of a class catalysis oxidation of ammonia gas.
Background technology
Industrially make nitric acid by ammoxidation and relate to series of parallel reaction and successive reaction:
4NH
3+5O
2＝4NO+6H
2O (1)
4NH
3+4O
2＝2N
2O+6H
2O (2)
4NH
3+3O
2＝2N
2+6H
2O (3)
NH
3 ＝N
2+3H
2 (4)
2NO ＝N
2+O
2 (5)
2NO+O
2 ＝2NO
2 (6)
4NH
3+6NO＝5N
2+6H
2O (7)
The catalyst that the complexity of process makes assurance reaction equation (1) carry out smoothly must possess two characteristics, and the one, to NH
3Conversion ratio want high; The 2nd, reaction equation (1) is had the selection catalytic action, promptly the selectivity of NO wants high.
Preparing nitric acid by ammonia oxidation has used the platinum-rhodium alloy net as catalyst since the industrialization beginning of this century always, and the platinum guaze catalyst performance is quite excellent, has shown as and has made NH
3100% transforms; Reaction equation (1) there is quite high selectivity (97-98%); The reaction speed that is exceedingly fast; The service life of long under fabulous resistance to elevated temperatures and 850 ℃ (3-6 month).But it is not only very expensive that shortcoming is this catalyst, the reaction temperature height, and under reaction temperature, this metal show sizable volatility and gradually the loss enter in the air-flow, thereby though known recyclable these metals of device that the metal that captures volatilization can be set in the downstream, but because constantly volatilization, life of catalyst is short and need frequent replacement.In addition, relate to sizable circulating fund distribution by the trap recovery metal in downstream and the regeneration of catalyst screen or silk screen.Thereby, be desirable to provide the substitute of this noble metal catalyst.
Summary of the invention
It is simple to the purpose of this invention is to provide a kind of technology, and cost is low, is easy to the Catalysts and its preparation method that is used for oxidation of ammonia gas of suitability for industrialized production.
The catalyst that is used for oxidation of ammonia gas of the present invention, it forms general formula is La
1-xSr
xBO
3, 0＜X＜1, wherein B is Mn or V transition metal.
The Preparation of catalysts method that is used for oxidation of ammonia gas, employing be sol-gal process, may further comprise the steps:
(1) presses catalyst and form La
1-xSr
xBO
3, 0＜X＜1 takes by weighing lanthanum nitrate, strontium nitrate and B element salt, mixes back adding deionized water and makes nitrate solution, and B is Mn or V transition metal;
(2) be that complexing agent joins in the nitrate solution with the citric acid, and regulate the pH value to 2-10 with ammoniacal liquor, the mol ratio of citric acid and B element is 1: 1～5: 1;
(3) in 50-100 ℃ water-bath, be incubated 1-10h, form gel, dry down at 100-150 ℃ then;
(4) calcine 2-6h under 600-800 ℃ of condition in the air.
The prepared catalyst of the present invention is used for oxidation of ammonia gas, and condition is as follows:
Adopt fixed bed reactors, atmospheric operation, operating temperature is 400-600 ℃; The operation air speed is 60000h
-1
Beneficial effect of the present invention is:
Preparation process of the present invention is simple, and required reagent is easy to get, and reaction temperature is low, is easy to suitability for industrialized production.Very high catalytic efficiency is just arranged in 400 ℃, and the catalytic efficiency height reaches the ammonia conversion ratio more than 90% in the time of 600 ℃, and the NO selectivity is surpassed 90%.And the catalyst that makes has higher activity and selectivity, is expected to replace the industry that platinum is used for preparing nitric acid by ammonia oxidation.
Description of drawings
Fig. 1 is La
0.8Sr
0.2MnO
3Transmission electron microscope (TEM) figure;
Fig. 2 is La
0.8Sr
0.2MnO
3XRD figure;
Fig. 3 is La
0.8Sr
0.2VO
3Transmission electron microscope (TEM) figure;
Fig. 4 is La
0.8Sr
0.2VO
3XRD figure.
The specific embodiment
Embodiment 1
Take by weighing the lanthanum nitrate of 0.0032mol, the strontium nitrate of 0.0008mol and the manganese nitrate of 0.004mol, mix the deionized water of back adding 100ml and make nitrate solution.The citric acid that adds 0.016mol dropwise adds the pH=5 value of ammoniacal liquor control solution as complexing agent, is incubated 6h then in 80 ℃ water-bath, forms gel; Dry 2h in 120 ℃ baking oven; Calcine 3h under 800 ℃ of conditions in the air, get La
0.8Sr
0.2MnO
3Catalyst.The La that makes
0.8Sr
0.2MnO
3Catalyst transmission electron microscope (TEM) photo is seen Fig. 1, and the X-ray diffraction picture is seen Fig. 2, as seen from Figure 1, and the La that makes
0.8Sr
0.2MnO
3It is netted that catalyst is, and as seen from Figure 2, catalyst is a Ca-Ti ore type.
Get above-mentioned La
0.8Sr
0.2MnO
3Catalyst carries out oxidation of ammonia gas in quartz ampoule fixed bed reactors (ф 12mm), catalyst shared length in quartz ampoule is 4-6 centimetre.
Reaction condition is: 0.5vol%NH
3, 10vol%O
2, N
2Be balanced gas, temperature is 400 ℃, air speed 60000h
-1NH
3Conversion ratio be 34.5%, the selectivity of NO is 88.2%.
Reaction condition is: 0.5vol%NH
3, 10vol%O
2, N
2Be balanced gas, temperature is 500 ℃, air speed 60000h
-1NH
3Conversion ratio be 72.3%, the selectivity of NO is 90.5%.
Reaction condition is: 0.5vol%NH
3, 10vol%O
2, N
2Be balanced gas, temperature is 600 ℃, air speed 60000h
-1NH
3Conversion ratio be 94.6%, the selectivity of NO is 95.2%.
Embodiment 2
Take by weighing the lanthanum nitrate of 0.0032mol, the strontium nitrate of 0.0008mol and the metavanadic acid ammonia of 0.004mol, mix the deionized water of back adding 100ml and make nitrate solution.The citric acid that adds 0.016mol dropwise adds the pH=5 value of ammoniacal liquor control solution as complexing agent, is incubated 6h then in 80 ℃ water-bath, forms gel; Dry 2h in 120 ℃ baking oven; Calcine 3h under 800 ℃ of conditions in the air, can get La
0.8Sr
0.2VO
3Catalyst.The La that makes
0.8Sr
0.2VO
3Catalyst transmission electron microscope (TEM) photo is seen Fig. 3, and the X-ray diffraction picture is seen Fig. 4, as seen from Figure 3, and the La that makes
0.8Sr
0.2VO
3It is netted that catalyst is, and as seen from Figure 4, catalyst is a Ca-Ti ore type.
Get above-mentioned La
0.8Sr
0.2VO
3Catalyst carries out oxidation of ammonia gas in quartz ampoule fixed bed reactors (ф 12mm), catalyst shared length in quartz ampoule is 4-6 centimetre.
Reaction condition is: 0.5vol%NH
3, 10vol%O
2, N
2Be balanced gas, temperature is 400 ℃, air speed 60000h
-1NH
3Conversion ratio be 30.7%, the selectivity of NO is 86.5%.
The condition of answering is: 0.5vol%NH
3, 10vol%O
2, N
2Be balanced gas, temperature is 500 ℃, air speed 60000h
-1NH
3Conversion ratio be 70.4%, the selectivity of NO is 88.9%.
Reaction condition is: 0.5vol%NH
3, 10vol%O
2, N
2Be balanced gas, temperature is 600 ℃, air speed 60000h
-1NH
3Conversion ratio be 93.8%, the selectivity of NO is 92.6%.
Claims (2)
1. the catalyst that is used for oxidation of ammonia gas is characterized in that it is La that this catalyst is formed general formula
1-xSr
xBO
3, 0＜X＜1, wherein B is Mn or V transition metal.
2. the Preparation of catalysts method that is used for oxidation of ammonia gas according to claim 1 may further comprise the steps:
(1) presses catalyst and form La
1-xSr
xBO
3, 0＜X＜1 takes by weighing lanthanum nitrate, strontium nitrate and B element salt, mixes back adding deionized water and makes nitrate solution, and B is Mn or V transition metal;
(2) be that complexing agent joins in the nitrate solution with the citric acid, and regulate the pH value to 2-10 with ammoniacal liquor, the mol ratio of citric acid and B element is 1: 1～5: 1;
(3) in 50-100 ℃ water-bath, be incubated 1-10h, form gel, dry down at 100-150 ℃ then;
(4) calcine 2-6h under 600-800 ℃ of condition in the air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100970613A CN101513611A (en) | 2009-03-30 | 2009-03-30 | Catalyst for oxidation of ammonia gas and method for preparing same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2009100970613A CN101513611A (en) | 2009-03-30 | 2009-03-30 | Catalyst for oxidation of ammonia gas and method for preparing same |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN101513611A true CN101513611A (en) | 2009-08-26 |
Family
ID=41038323
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNA2009100970613A Pending CN101513611A (en) | 2009-03-30 | 2009-03-30 | Catalyst for oxidation of ammonia gas and method for preparing same |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN101513611A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102583279A (en) * | 2011-01-14 | 2012-07-18 | 通用汽车环球科技运作有限责任公司 | Low temperature oxidation of ammonia in nitric acid production |
| CN103209927A (en) * | 2010-11-04 | 2013-07-17 | 日产自动车株式会社 | Layered complex oxide, oxidation catalyst, and diesel particulate filter |
| CN109046378A (en) * | 2018-09-29 | 2018-12-21 | 浙江树人学院 | A kind of catalyst and preparation method thereof for ammonia of degrading |
| CN112569968A (en) * | 2020-12-10 | 2021-03-30 | 浙江新和成股份有限公司 | Modified perovskite type catalyst and preparation method and application thereof |
-
2009
- 2009-03-30 CN CNA2009100970613A patent/CN101513611A/en active Pending
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103209927A (en) * | 2010-11-04 | 2013-07-17 | 日产自动车株式会社 | Layered complex oxide, oxidation catalyst, and diesel particulate filter |
| CN102583279A (en) * | 2011-01-14 | 2012-07-18 | 通用汽车环球科技运作有限责任公司 | Low temperature oxidation of ammonia in nitric acid production |
| US20120183467A1 (en) * | 2011-01-14 | 2012-07-19 | GM Global Technology Operations LLC | Low temperature oxidation of ammonia in nitric acid production |
| CN109046378A (en) * | 2018-09-29 | 2018-12-21 | 浙江树人学院 | A kind of catalyst and preparation method thereof for ammonia of degrading |
| CN112569968A (en) * | 2020-12-10 | 2021-03-30 | 浙江新和成股份有限公司 | Modified perovskite type catalyst and preparation method and application thereof |
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| PB01 | Publication | ||
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Open date: 20090826 |