CN1204967C - Ammoxidation catalyst and the application method thereof - Google Patents
Ammoxidation catalyst and the application method thereof Download PDFInfo
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- CN1204967C CN1204967C CN 03148814 CN03148814A CN1204967C CN 1204967 C CN1204967 C CN 1204967C CN 03148814 CN03148814 CN 03148814 CN 03148814 A CN03148814 A CN 03148814A CN 1204967 C CN1204967 C CN 1204967C
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- ammoxidation
- catalyzer
- catalyst
- transition metal
- selectivity
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Abstract
The present invention relates to an ammoxidation catalyst which uses Al2O3 as carriers to load transition metal oxides and uses alkali metal oxides as adjutants. Under the conditions of operative temperature of 450 to 600 DEG C and air speed of 3500 to 56000h<-1>, the catalyst has very high catalytic activity for ammoxidation; the conversion rate of ammonia is as high as 94% or more; and the selectivity of NO can be as high as 92% or more. The catalyst has the advantages of great ammoxidation temperature reduction, easy raw material obtainment and simple preparation, and is suitable for replacing noble metal Pt nets in ammoxidation nitric acid making industry.
Description
Technical field:
The invention belongs to a kind of preparation and the application on the system nitric acid industry thereof of ammoxidation catalyst.
Background technology:
Learn (two) according to inorganic chemical technology, sulfuric acid and nitric acid: 241-259 (Chemical Industry Press) report, ammonia is oxidation in air, and following reaction can take place:
The principal reaction of system nitric acid is reaction (1).The catalyzer that reaction (1) is carried out smoothly must possess high NH
3Characteristics such as transformation efficiency and NO selectivity.
Preparing nitric acid by ammonia oxidation is since the earlier 1900s industrialization, use platinum guaze as catalyzer always, its performance is quite excellent, but platinum must carry out being higher than under 800 ℃ the temperature condition the catalytic oxidation of ammonia, so high temperature causes the generation of above-mentioned (2)-side reactions such as (6) easily, reducing reactive behavior and selectivity, therefore is that the oxidative ammonolysis of catalyzer is quite harsh to the requirement of reaction conditionss such as air speed, oxygen concn with platinum.In addition, the shortage of resources of platinum costs an arm and a leg.Therefore, the gentle non-platinum ammoxidation catalyst of cheap and easy to get and reaction conditions is the focus of research always.
In in order to the catalyst research that replaces platinum guaze, non-platinum catalysts such as ferric oxide, copper, cobalt, manganese, chromium, cerium present higher ammonia catalytic activity under 700 ℃ of left and right sides temperature condition, but owing to catalyst structure instability under hot conditions, catalytic activity descends easily, fails to realize industrialization.At present, to the study on the modification of transition metal oxide, as the La of Chinese patent 86108985 reports
0.8Ce
0.2CoO
3With Kinetics and Catalysis, 2002 (1), the Fe of 95-98 report
2O
3-Bi
2O
3Catalyzer, though increased the stability of catalytic activity, but do not solve high temperature problem.
Summary of the invention:
The purpose of this invention is to provide a kind of preparation and application of the cheap and easy to get and non-platinum ammoxidation catalyst that reaction conditions is gentle.
Ammoxidation catalyst of the present invention is with Al
2O
3Be carrier, the carrying transition metal oxide compound is an auxiliary agent with an alkali metal salt, is expressed as AxBy/Al
2O
3, wherein A represents transition metal, and loading (x) is 3～8wt%, and B represents basic metal, and loading (y) is 1～5wt%.Transition metal and basic metal exist with the metal oxide form in catalyzer.
Above-mentioned transition metal comprises Cu, Fe, Mn etc.
Above-mentioned basic metal comprises Na, K etc.
Preparation of catalysts of the present invention adopts the pore volume co-impregnation.With the catalyst precursor aqueous solution and carrier A l
2O
3Press catalyzer proportion of composing incipient impregnation.Dipping back sample drying and calcine finished catalyst.
The prepared catalyzer of the present invention carries out oxidative ammonolysis under the following conditions:
Adopt fixed-bed reactor, atmospheric operation; Service temperature is 450～600 ℃; The operation air speed is 3500～56000h
-1
The present invention has following advantage:
1. activity of such catalysts temperature of the present invention is low, the reaction conditions gentleness, and the selectivity height, activity stabilized;
2. catalyzer of the present invention is with the Al of high-specific surface area
2O
3Be carrier, active in the carrier surface high dispersing;
3. this catalyzer does not contain precious metal, and is cheap and easy to get;
4. Preparation of Catalyst is easy, need not specific installation, easy handling.
Embodiment:
Embodiment 1
Take by weighing 3.025g Cu (NO
3)
2.3H
2O and 0.370gNaNO
3Be dissolved in and be mixed with the aqueous solution in the distilled water.Take by weighing 10gAl
2O
3(30-60 order) incipient impregnation is in above-mentioned solution, drying and calcine to such an extent that copper content is 8wt%, and sodium content is the Cu8Na1/Al of 1wt%
2O
3Catalyzer.Get this catalyzer of 1g and in silica tube fixed-bed reactor (φ 10mm), carry out ammonia oxidation.Reaction conditions is: 0.5vol%NH
3, 5.0vol%O
2, Ar is a balance gas, and temperature is 450 ℃, and air speed is 28000h
-1NH
3Transformation efficiency be 98.2%, the NO selectivity is 92%.
Embodiment 2
Take by weighing 3.025g Cu (NO
3)
2.3H
2O and 1.850gNaNO
3Making copper content by embodiment 1 described method is 8wt%, and sodium content is the Cu8Na5/Al of 5wt%
2O
3Catalyzer is got this catalyzer of 1g and carry out ammonia oxidation in the silica tube fixed-bed reactor.Reaction conditions is: 0.5vol%NH
3, 5.0vol%O
2, Ar is a balance gas, and temperature is 450 ℃, and air speed is 28000h
-1NH
3Transformation efficiency be 98.7%, the selectivity of NO is 96.4%.
Embodiment 3
Take by weighing 0.756g Cu (NO
3)
2.3H
2O and 1.109gNaNO
3Making copper content by embodiment 1 described method is 2wt%, and sodium content is the Cu2Na3/Al of 3wt%
2O
3Catalyzer is got this catalyzer of 1g and carry out ammonia oxidation in the silica tube fixed-bed reactor.Reaction conditions is: 0.5vol%NH
3, 5.0vol%O
2, Ar is a balance gas, and temperature is 450 ℃, and air speed is 28000h
-1NH
3Transformation efficiency be 94.6%, the selectivity of NO is 94.4%.
Embodiment 4
Taking by weighing the 1g copper content is 8wt%, contains the Cu8Na3/Al that the sodium amount is 3wt%
2O
3Catalyzer carries out ammonia oxidation in the silica tube fixed-bed reactor.Reaction conditions is: 0.5vol%NH
3, 5.0vol%O
2, Ar is a balance gas, and temperature is 600 ℃, and air speed is 28000h
-1NH
3Transformation efficiency be 99.8%, the selectivity of NO is 95.3.%.
Embodiment 5
Taking by weighing the 8g copper content is 8wt%, contains the Cu8Na3/Al that the sodium amount is 3wt%
2O
3Catalyzer carries out ammonia oxidation in the silica tube fixed-bed reactor.Reaction conditions is: 0.5vol%NH
3, 5.0vol%O
2, Ar is a balance gas, and temperature is 500 ℃, and air speed is 3500h
-1NH
3Transformation efficiency be 99.6%, the selectivity of NO is 92.9%.
Embodiment 6
Taking by weighing the 0.5g copper content is 8wt%, contains the Cu8Na3/Al that the sodium amount is 3wt%
2O
3Catalyzer carries out ammonia oxidation in the silica tube fixed-bed reactor.Reaction conditions is: 0.5vol%NH
3, 5.0vol%O
2, Ar is a balance gas, and temperature is 500 ℃, and air speed is 56000h
-1NH
3Transformation efficiency be 96.5%, the selectivity of NO is 95.8%.
Embodiment 7
Taking by weighing the 2.0g copper content is 8wt%, contains the Cu8Na5/Al that the sodium amount is 3wt%
2O
3Catalyzer carries out ammonia oxidation in the silica tube fixed-bed reactor.Reaction conditions is: 5.0vol%NH
3, 20vol%O
2, Ar is a balance gas, and temperature is 600 ℃, and air speed is 28000h
-1NH
3Transformation efficiency be 99.8%, the selectivity of NO is 95%.
Embodiment 8
Take by weighing 3.610g Fe (NO
3)
3.9H
2O and 0.776gKNO
3Making iron level by embodiment 1 described method is 5wt%, and potassium content is the Fe5K3/Al of 3wt%
2O
3Catalyzer is got this catalyzer of 1g and carry out ammonia oxidation in the silica tube fixed-bed reactor.Reaction conditions is: 10.0vol%NH
3, 20vol%O
2, Ar is a balance gas, and temperature is 500 ℃, and air speed is 28000h
-1NH
3Transformation efficiency be 99.8%, the selectivity of NO is 95.4%.
Claims (3)
1. a method for ammoxidation is characterized in that adopting with Al
2O
3Be carrier, the carrying transition metal oxide compound, with the alkalimetal oxide is auxiliary agent, wherein the loading of transition metal is 3～8wt%, alkali-metal loading is 1～5wt%, the catalyzer that transition metal and basic metal exist with the metal oxide form in catalyzer is used for fixing bed bioreactor, atmospheric operation; Service temperature is 450～600 ℃; The operation air speed is 3500～56000h
-1
2. a kind of method for ammoxidation as claimed in claim 1 is characterized in that described transition metal is Cu, Fe, Mn.
3. a kind of method for ammoxidation as claimed in claim 1 is characterized in that described basic metal is Na, K.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03148814 CN1204967C (en) | 2003-06-12 | 2003-06-12 | Ammoxidation catalyst and the application method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 03148814 CN1204967C (en) | 2003-06-12 | 2003-06-12 | Ammoxidation catalyst and the application method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1485134A CN1485134A (en) | 2004-03-31 |
| CN1204967C true CN1204967C (en) | 2005-06-08 |
Family
ID=34156280
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 03148814 Expired - Fee Related CN1204967C (en) | 2003-06-12 | 2003-06-12 | Ammoxidation catalyst and the application method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1204967C (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104399476B (en) * | 2014-10-17 | 2018-09-18 | 乐山东承新材料有限公司 | The preparation method of nitric acid rare earth catalyst |
| CN105107503A (en) * | 2015-09-01 | 2015-12-02 | 黎明化工研究设计院有限责任公司 | Loaded catalyst for burning treatment of waste gas containing amine |
| CN110102338A (en) * | 2019-04-30 | 2019-08-09 | 昆明贵研催化剂有限责任公司 | A kind of ammoxidation catalyst and preparation method thereof of high nitrogen selective |
-
2003
- 2003-06-12 CN CN 03148814 patent/CN1204967C/en not_active Expired - Fee Related
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| Publication number | Publication date |
|---|---|
| CN1485134A (en) | 2004-03-31 |
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Granted publication date: 20050608 Termination date: 20100612 |