CN1021021C - Preparation of nitric acid rare earth nickelate catalyst with oxidized nitrogen - Google Patents
Preparation of nitric acid rare earth nickelate catalyst with oxidized nitrogen Download PDFInfo
- Publication number
- CN1021021C CN1021021C CN 89103708 CN89103708A CN1021021C CN 1021021 C CN1021021 C CN 1021021C CN 89103708 CN89103708 CN 89103708 CN 89103708 A CN89103708 A CN 89103708A CN 1021021 C CN1021021 C CN 1021021C
- Authority
- CN
- China
- Prior art keywords
- catalyst
- nitric acid
- rare earth
- preparation
- ammoxidation
- 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.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/20—Nitrogen oxides; Oxyacids of nitrogen; Salts thereof
- C01B21/24—Nitric oxide (NO)
- C01B21/26—Preparation by catalytic or non-catalytic oxidation of ammonia
- C01B21/265—Preparation by catalytic or non-catalytic oxidation of ammonia characterised by the catalyst
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/40—Nickelates
- C01G53/70—Nickelates containing rare earth, e.g. LaNiO3
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/50—Solid solutions
- C01P2002/52—Solid solutions containing elements as dopants
- C01P2002/54—Solid solutions containing elements as dopants one element only
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Catalysts (AREA)
Abstract
The present invention belongs to a method for preparing a rare earth nitrate nickelate catalyst by ammoxidation. The rare earth nitrate nickelate catalyst prepared by the ammoxidation has a general formula: La<1-x>MexNiO3, wherein Me stands for divalent alkaline earth metal, lanthanide elements and actinide elements; x is less than or equal to 0 and is greater than or equal to 1, and an industrial process by using the ammoxidation to prepare nitric acid can be realized. The present invention has the advantages of high efficiency of the catalyst, easy acquirement of raw materials, and simple and convenient preparation, and the yield of NO can reach above 97 %. The present invention can replace a precious metal platinum net and is used for a nitric acid preparing industry by the ammoxidation.
Description
The invention belongs to the method for preparation of nitric acid rare earth nickelate catalyst with oxidized nitrogen.
Ammonia is oxidation in air, and following reaction can take place:
The key reaction of system nitric acid is reaction (1).The catalyst that reaction (1) is carried out smoothly must possess two characteristics, and the one, to NH
3Conversion ratio want high, the 2nd, the NO selectivity is wanted high.
Preparing nitric acid by ammonia oxidation has used platinum guaze as catalyst since the industrialization beginning of this century always, and its performance is quite excellent, but the costliness of platinum and shortage of resources have promoted the research of catalyst cheap and easy to get.
In the research in order to the catalyst that replaces platinum guaze, initial what use is transition metal oxide, but owing to easily wave when high temperature, and activity still is lower than platinum, so fail to realize suitability for industrialized production.
ABO
3Type complex rare-earth oxidate containing valuable metal new catalyst is suitable for preparing nitric acid by ammonia oxidation.
La
1-xCa
xMnO
3(0≤x≤1) has had catalytic performance (Changchun Inst. of Applied Chemistry, Chinese Academy of Sciences's collected papers the 17th collection) preferably, but still can not replace platinum guaze.
La
1-xSr
xFeO
3The activity of (0≤x≤1) is than La
1-xCa
xMnO
3Omit, but still can not replace platinum guaze.(Chinese science B collects 1988 the 4th phases).
La
1-xSr
xCoO
3(0≤x≤1) (catalysis journal, 1985 the 4th phases) and La
0.8Ce
0.2CrO
3(Chinese patent 86108985.51989 years) demonstrated the activity suitable with platinum guaze, is expected to replace platinum guaze.
Because the price of cobalt is than the height of nickel, resource is also few than nickel, so the objective of the invention is to select rare earth nickelate ABO
3The type composite oxides are optimized catalyst with price on performance.
It is la that the present invention proposes a class general formula
1-xMe
xNiO
3(0≤x≤1) rare earth nickelate catalyst, Me is a divalent alkaline-earth metal in the formula, rare earth element, actinides.Active center element is a transiting metal nickel, and the architectural feature element is La, Me.Wherein the catalyst series of 0≤x≤1 formation is all to 4NH
3+ 5O
2=4NO+6H
2The O reaction has the high-selectivity catalyst effect.
Method for preparing catalyst of the present invention claims its preparation process of citric acid complex method (claiming explosion method again) and condition to be:
A, get nickel by chemical composition metering, lanthanum, the nitrate of Me is made into mixed solution.
B, add excessive citric acid as complexing agent.
C, heating are at a slow speed fully stirred.
Surplus yellow green jelly is accelerated firing rate behind D, the heating evaporation, and jelly deflagrates, and becomes the big superfine powder powder of specific surface concentration.
E, in 600 ℃ of powders calcined, compression molding is again in 900-1000 ℃ of following roasting.
The investigation of catalyst activity of the present invention is at current system fixed bed reactors, NH
3(volume)=10%, air speed 50,000 o'clock
-1The 8ml catalyst carries out under 700 ℃, and the yield of NO changes between 85%-98%.The yield of NO was between 91-98% when the sintering temperature of catalyst changed between 750-1100 ℃.
This method easy operating need not special installation, the easy raw material free of losses that saves time, the catalyst high degree of dispersion of making, the nearly 8m in this surface
2/ g.
La of the present invention
1-xMe
xNiO
3Catalyst is intended to replace platinum guaze, so every index is a references object with the platinum guaze catalyst all.
1, NH
3The once through yield that is converted into NO is more than 98%, NH
3Almost 100% transform, do not have 1% fluctuation according to equipment and operation.
2, unstripped gas NH
3/ air=10%(volume ratio), this index influences reaction temperature, and it shows catalyst treatment NH
3Ability.
3, unstripped gas is by the speed of beds, and its size is the sign that catalytic reaction is carried out the speed speed, and is directly related with capacity of equipment and product yield, industrially represents with air speed.For this catalyst charge weight, the platinum guaze air speed is 30,000 o'clock
-1, according to above index, the contrast condition that catalyst of the present invention is used for ammoxidation is 700 ℃, NH
3%=10%, air speed 50,000 o'clock
-1, considered the granularity of catalyst, factors such as specific surface simultaneously.
Catalyst of the present invention has following characteristics:
1, the nearly 8m of specific surface
2It is Powdered that/g, compressing tablet were in the past, and through sem observation, its microstructure in the form of sheets and column wherein has many caves.Chemical analysis thinks that Ni is divalence, trivalent, tetravalence mixed state therein, exists the zwitterion defective in the crystal.
2, catalyst NO yield when X gets appropriate value is higher than 98%, and is activity stabilized, can compare with the platinum guaze that industry is used.
3, catalyst is when being used for ammoxidation reaction, and its optimum condition uses the working condition of platinum guaze suitable fully with industry, and experiment shows, uses catalyst of the present invention not only can not reduce production target, and can improve the production capacity of equipment.
4, catalyst does not contain noble metal, and transitional technology nickel is more cheap than cobalt, and Preparation of Catalyst is easy.
Embodiment provided by the invention is as follows:
Embodiment 1:
LaNiO
3Preparation and active testing:
With preparation 40g catalyst is example, and inventory is:
Get concentration and be 43.2% lanthanum nitrate aqueous solution 122.55 grams, concentration is 11.1% nickel nitrate aqueous solution 267.62 grams, and two kinds of raw materials mix, adding distil water adds citric acid 30 grams, fully stirs, heating evaporation after becoming the yellow green jelly, improves heating-up temperature at a slow speed, jelly deflagrates, become black powder, this powder is in 600 ℃ of roastings after 1 hour, compression molding, in 900 ℃ of (air atmosphere) roastings 3 hours, catalyst got product again.
The test of catalytic performance in the ammoxidation reaction under the experiment condition.
The quartz ampoule fixed bed reactors, the about 25mm of internal diameter, interior dress thermocouple sheath, the about 106mm of beds real area
2Catalyst grain size 10-20 order, axially by beds, product is drawn by the catalyst bed bottom from top to down for dress 8ml, the high 24mm of bed, unstripped gas; The conventional acid alkali titration analytical calculation of NO individual layer yield.Select the reaction condition of platinum guaze catalyst; 700 ℃ of reaction temperatures, NH
3The %(volume)=10%, air speed is 50,000 o'clock
-1LaNiO under this condition
3Activity of such catalysts is 97.3%.
Embodiment 2:
La0.8Sr0.2NiO
3Preparation and active testing.
With preparation 40g catalyst is example, and inventory is:
Get concentration and be 43.2% lanthanum nitrate aqueous solution 102.38 grams, concentration is 11.1% nickel nitrate aqueous solution 279.45 grams, solid nitric acid strontium 7.20 grams.Three kinds of raw materials mix, adding distil water, and adding citric acid 30 grams fully stir, and heating evaporation after becoming the yellow green jelly, improves heating-up temperature at a slow speed, and jelly deflagrates, and becomes black powder.This powder is in 600 ℃ of roastings after 1 hour, compression molding, and in 9000 ℃ of (air atmosphere) roastings 3 hours, catalyst got product again.
The catalyst activity assay method is with embodiment 1, and activity is 93.1%.
Embodiment 3:
La0.6Th0.3NiO
3Preparation and activity.
With preparation 40g catalyst is example, and inventory is:
Get concentration and be 43.2% lanthanum nitrate aqueous solution 69.56 grams, concentration is 11.1 nickel nitrate aqueous solution 253.15 grams, concentration is 18.6% the thorium nitrate aqueous solution 119.06 grams, three kinds of raw materials mix, adding distil water, add citric acid 30 grams, fully stir, at a slow speed heating evaporation, after becoming the yellow green jelly, improve heating-up temperature, jelly deflagrates, and becomes black powder, this powder is in 600 ℃ of roastings after 1 hour, compression molding, in 900 ℃ of (air atmosphere) roastings 3 hours, catalyst got product again.
The catalyst activity property testing is with embodiment 1, and activity is 98.7%.
Embodiment 4:
La0.9Ce0.1NiO
3Preparation and activity.
Be example with preparation 40g catalyst still, inventory is:
Get concentration and be 43.2% lanthanum nitrate aqueous solution 110.29 grams, concentration is 11.1 nickel nitrate aqueous solution 267.62 grams, solid Ce(NO
3)
36H
2The O7.07 gram, three kinds of raw materials mix, and adding distil water adds citric acid 30 grams, fully stirs, and heating evaporation after becoming the yellow green jelly, improves heating-up temperature at a slow speed, and jelly deflagrates, and becomes black powder.This powder is in 600 ℃ of roastings after 1 hour, compression molding, and in 900 ℃ of (air atmosphere) roastings 3 hours, catalyst got product again.
The catalyst activity property testing is with embodiment 1, and activity is 97.0%.
Claims (1)
1, a kind of rare-earth composite oxide catalyst that is used for preparing nitric acid by ammonia oxidation is characterized in that catalyst consists of La
0.6Th
0.3NiO
3, adopt following step to make:
1. get the nitrate of each composition by the chemical composition metering, be made into mixed solution,
2. add excessive citric acid as complexing agent,
3. surplus yellow green jelly behind the heating evaporation deflagrates through Fast Heating, becomes the very big superfine powder powder thing of specific surface,
4. Powdered thing is through 600 ℃ of roastings, compression molding, and in 900～1000 ℃ of following roastings, catalyst gets product again.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89103708 CN1021021C (en) | 1989-05-31 | 1989-05-31 | Preparation of nitric acid rare earth nickelate catalyst with oxidized nitrogen |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 89103708 CN1021021C (en) | 1989-05-31 | 1989-05-31 | Preparation of nitric acid rare earth nickelate catalyst with oxidized nitrogen |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1047633A CN1047633A (en) | 1990-12-12 |
| CN1021021C true CN1021021C (en) | 1993-06-02 |
Family
ID=4855245
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 89103708 Expired - Fee Related CN1021021C (en) | 1989-05-31 | 1989-05-31 | Preparation of nitric acid rare earth nickelate catalyst with oxidized nitrogen |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1021021C (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039193C (en) * | 1994-03-21 | 1998-07-22 | 常敏毅 | Chinese-medicinal bath lotion and its preparation |
-
1989
- 1989-05-31 CN CN 89103708 patent/CN1021021C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1039193C (en) * | 1994-03-21 | 1998-07-22 | 常敏毅 | Chinese-medicinal bath lotion and its preparation |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1047633A (en) | 1990-12-12 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US3929670A (en) | Catalyst | |
| US5977017A (en) | Perovskite-type metal oxide compounds | |
| CN1269566C (en) | Catalyst for decomposing nitrous oxide and method for performing processes comprising formation of nitrous oxide | |
| DE69917746T2 (en) | three-way | |
| US8361925B2 (en) | Exhaust gas-purifying catalyst | |
| CN101637725B (en) | Honeycomb ceramic type monolithic catalyst using mayenite as coating layer, preparation method and application thereof | |
| NZ210549A (en) | Modified copper- and zinc- containing catalyst and methanol production | |
| CN103182308B (en) | Perovskite/metal composite oxide catalyst and preparation method thereof | |
| JP3260148B2 (en) | Exhaust gas purification catalyst | |
| CN102989448A (en) | Preparation method and application of lanthanum-manganese perovskite type NOx removing catalyst | |
| CN110856817B (en) | Catalyst for producing methyl glycolate and preparation method and application thereof | |
| CN110339840A (en) | A kind of preparation method preparing Ni and/or Ru base ammonia decomposition catalyzer using houghite | |
| CN113996305A (en) | Medium-low temperature catalytic decomposition of N2O composite oxide catalyst and preparation method and application thereof | |
| CN103374430A (en) | High-stability oxygen carrier, preparation method and applications | |
| Vaz et al. | Preparation, characterization and catalytic CO oxidation studies on LaNi1− xCoxO3 system | |
| CN1021021C (en) | Preparation of nitric acid rare earth nickelate catalyst with oxidized nitrogen | |
| CN112604701B (en) | Composite oxide catalyst, preparation method and application thereof | |
| CN102862956B (en) | The application of a kind of oxygen carrier with perovskite structure in hydrogen production of chemical chain and preparation | |
| CN102442640B (en) | Application of composite metal oxide oxygen carrier to recycle chemistry chain hydrogen production and preparation thereof | |
| JP2620624B2 (en) | Exhaust gas purification catalyst | |
| JP2003080072A (en) | Co shift catalyst and method for producing the same | |
| CN86108985A (en) | Rare earth cobaltic trioxide catalyzer for preparing nitric acid by ammonia oxidation | |
| CN1114955A (en) | Catalyzer for methanation of carbon dioxide and its preparation method | |
| CN1052431C (en) | Catalyst for preparing ethylene by oxidation and dehydrogenation of ethane and process thereof | |
| CN102864007A (en) | Oxygen carrier for chemical-looping combustion technology and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C19 | Lapse of patent right due to non-payment of the annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |