CN86108985B - Catalyst for preparing rare earth cobaltate of nitric acid by ammonia oxidation - Google Patents
Catalyst for preparing rare earth cobaltate of nitric acid by ammonia oxidation Download PDFInfo
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- CN86108985B CN86108985B CN86108985A CN86108985A CN86108985B CN 86108985 B CN86108985 B CN 86108985B CN 86108985 A CN86108985 A CN 86108985A CN 86108985 A CN86108985 A CN 86108985A CN 86108985 B CN86108985 B CN 86108985B
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- nitric acid
- ammonia oxidation
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- oxalic acid
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 22
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 title claims abstract description 17
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 17
- 229910017604 nitric acid Inorganic materials 0.000 title claims abstract description 15
- 230000003647 oxidation Effects 0.000 title claims abstract description 12
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 10
- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 7
- 150000002910 rare earth metals Chemical class 0.000 title abstract description 5
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000002360 preparation method Methods 0.000 claims abstract description 10
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 29
- 238000001556 precipitation Methods 0.000 claims description 11
- 235000006408 oxalic acid Nutrition 0.000 claims description 9
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 8
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 7
- 239000003153 chemical reaction reagent Substances 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 4
- 239000002131 composite material Substances 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 2
- 150000001768 cations Chemical class 0.000 claims description 2
- 238000001914 filtration Methods 0.000 claims description 2
- 239000012452 mother liquor Substances 0.000 claims description 2
- 239000000126 substance Substances 0.000 claims description 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- 229910052723 transition metal Inorganic materials 0.000 claims 1
- 150000003624 transition metals Chemical group 0.000 claims 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 34
- 229910052697 platinum Inorganic materials 0.000 abstract description 17
- 238000006243 chemical reaction Methods 0.000 description 25
- 230000003197 catalytic effect Effects 0.000 description 14
- 229910018921 CoO 3 Inorganic materials 0.000 description 12
- 239000007789 gas Substances 0.000 description 11
- 238000012360 testing method Methods 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 238000002474 experimental method Methods 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 4
- 239000001099 ammonium carbonate Substances 0.000 description 4
- 230000009183 running Effects 0.000 description 4
- 239000012153 distilled water Substances 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000000975 co-precipitation Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 description 2
- 238000010792 warming Methods 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 1
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 1
- 229910000629 Rh alloy Inorganic materials 0.000 description 1
- ROLJWXCAVGNMAK-UHFFFAOYSA-N [Ce]=O Chemical compound [Ce]=O ROLJWXCAVGNMAK-UHFFFAOYSA-N 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000002479 acid--base titration Methods 0.000 description 1
- -1 by measuring Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- PXXKQOPKNFECSZ-UHFFFAOYSA-N platinum rhodium Chemical compound [Rh].[Pt] PXXKQOPKNFECSZ-UHFFFAOYSA-N 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000002468 redox effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 230000001052 transient effect Effects 0.000 description 1
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- Catalysts (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The general formula of the rare earth cobaltate catalyst for preparing nitric acid by ammonia oxidation is La ↓ [ 1-X ] Ce ↓ [ X ] CoO ↓ [ 3 ], X is more than or equal to 0 and less than or equal to 1, and the process of producing nitric acid by ammonia oxidation in industry can be realized. The catalyst has high efficiency and long service life, and the NO yield is still 97-98% after three months of use. The catalyst preparation does not need special equipment, and the operation is simple and easy. It is expected to replace platinum in the industry of preparing nitric acid by ammoxidation.
Description
The invention belongs to the preparing nitric acid by ammonia oxidation catalyst, its method for making and application.
Industrial by preparing nitric acid by ammonia oxidation, 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）
2NH
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 complexity of process makes that guaranteeing to react the catalyst that (1) carries out smoothly must possess two characteristics, the one, and to NH
3Conversion ratio want high; The 2nd, target reaction (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.The platinum guaze catalyst performance is quite excellent, has shown as and has made NH
3100% transforms; The selectivity (97～98%) of quite high catalysis target reaction (1); The reaction speed that is exceedingly fast; The service life of fabulous resistance to elevated temperatures and 850 ℃ long-term down (3-6 months).But the costliness of platinum and shortage of resources have promoted the research of catalyst cheap and easy to get, and replacing platinum guaze with catalyst cheap and easy to get becomes NH for a long time
3A great theoretical question and the urgent practical problems of oxidation system nitric acid catalyst research.
In the research in order to the catalyst that replaces platinum guaze, transition metal oxide is owing to itself have redox property and use as catalyst in many oxidation reactions and at first be used in NH
3In the reaction of-NO, Co
3O
4, Fe
2O
3, MnO
2Goodish catalytic performance is also arranged, but its activity is still low than platinum guaze, the optimum activity warm area is narrow, actively when high temperature uses descends soon, thereby they still can not replace platinum guaze at present and are used for NH
3The industrial production of oxidation system nitric acid.
ABO
3The type composite oxides are a kind of new catalytic agent materials.We to the type catalyst at NH
3Performance in the oxidation reaction is carried out more comprehensive system research.La wherein
1-xCa
xMnO
3(0≤X≤1) is at catalyzing N H
3Demonstrated the performance (applied chemistry research institute of Chinese Academy of Sciences collected papers the 17 collection) that is better than the pure metal oxides catalyst in the → NO reaction.But from replacing the practical standpoint of platinum guaze catalyst, still there is suitable gap the aspects such as stability of this catalyst under catalytic activity and hot conditions.
The objective of the invention is to select rare earth cobaltatess ABO
3The type composite oxides are formed by catalyst, and the optimization of active component and method for making overcomes above-mentioned transition metal oxide and La
1-xCa
xMnO
3The deficiency of catalyst is used for NH with this catalyst
3-NO industrial reaction replaces the platinum guaze catalyst.
It is La that the present invention proposes a class general formula
1-xCe
xCoO
3The rare earth cobaltic trioxide catalyzer of (0≤X≤1), they are at catalyzing N H
3Use in-NO the reaction, have excellent performance, be expected to replace platinum guaze and be used for NH
3The industrial production of oxidation system nitric acid.
The selection of catalytic component of the present invention is at current system, fixed bed reactors, 8 milliliters of catalyst, carry out under the bed height 24m/m condition, the reinforcement experiment is to survey initial activity α 0% at 700 ℃, is warming up to 900 ℃ of runnings then and recovers primary condition survey active alpha after 24 hours
1%, △ α=α
0-α
1, the active mark that descends of its value representation is as the index of catalyst tolerates high-temperature behavior.Table 1 is three kinds of catalyst series experimental results under these conditions; The yield of NO is as the index of catalytic activity in the table.
The yield of three kinds of different series catalyst ns of table 1 O
(normal pressure, 50,000 o'clock
-1)
* by changing collected papers 17 described method for makings, down together
* oxalate precipitation method, down together
Composite oxides La as can be seen from Table 1
1-xCe
xCoO
3And La
1-xCa
xMnO
3Be that catalytic activity is higher than Co
3O
4; The optimum activity warm area the above two about 150 ℃, compare Co
3O
4For wide; Strengthen the result and show that also the above two resistances to elevated temperatures obviously are better than Co
3O
4Belong to ABO together
3The La of type structure
1-xCe
xCoO
3(being called for short Co system) and La
1-xCa
xMnO
3(being called for short Mn system) also has on performance than big difference, from Mn series Co system, because active center element Mn changes Co into, catalytic activity significantly improves, because the architectural feature element changes Ce into by Ca, its resistance to elevated temperatures is greatly improved, and the Co series catalysts is △ α～0 in strenuous test, show this catalyst when 900 ℃ of reactions, its structure and performance are very stable.
The best proportioning of each component of catalyst of the present invention (element) is selected to finish by contrast test, as can be seen from Table 2, in 0≤X≤0.4 scope, have high relatively activity, and have cation defect and non-stoichiometry oxygen (0.09＜λ＜0.16) in this catalyst.
Table 2 La
1-xCe
xThe catalytic activity of the different proportionings of CoO relatively
Reaction condition 8ml catalyst, fixed bed current system, NH3%～10%, air speed 50,000 o'clock
-1
Preparation of catalysts method of the present invention and condition are:
A gets by chemical composition metering and to mix as deposited components after metallic cobalt, lanthana and cerium oxide are made nitrate solution.
B, oxalic acid and ammonium carbonate make precipitating reagent after with dissolved in distilled water, and with the P in the sal volatile control precipitation process
HValue.
C, oxalic acid solution adds step by step, promptly adds half oxalic acid solution in mother liquor of precipitation of ammonium earlier, and second half then adds simultaneously with deposited components (La-Ce-Co solution).
D should fully stir in the precipitation process, and strict 50～60 ℃ of pH value 6～7, the temperature of controlling.
E, powdery precipitate after filtration, the oven dry, granulating and forming after the thermal decomposition is in 900 ℃ of roastings.
The selection of two precipitating reagents makes the pH value of precipitation process solution more stable, is easy to control, and precipitates and need not wash, and it is easy to save time; The control of deposition condition can make precipitation loose, is easy to filter, and the catalytic component loss is little; It is that precipitation guarantees uniformly that substep adds precipitating reagent; 900 ℃ of roastings not only can guarantee catalyst quality but also can save energy to save time, and Preparation of catalysts method of the present invention proves the practical assurance of producing effective catalyst through a large amount of contrast experiments.
La of the present invention
1-xCe
xCoO
3Catalyst is used for the selection of preparing nitric acid by ammonia oxidation reaction condition.Although realize NH
3-NO reaction can be selected optimum condition according to different catalysts, obtain best result, but the objective of the invention is to replace existing platinum guaze catalyst, in any case therefore alternative condition, all should be principle not reduce the production target of using the platinum guaze catalyst, leading indicator has following all:
1.NH
3Be converted into once through yield (because the NH of NO
3Almost 100% transform, so the single selectivity that also can be considered NO of receiving of NO), about 97%.Have nearly 1% fluctuation according to equipment and operational circumstances difference, this index shows raw material NH
3Utilization rate.
2. NH in the unstripped gas
3: air (claims NH
3Than) be generally 10%～11%(volume ratio) this index directly influences reaction temperature, it shows catalyst treatment NH
3Ability, direct relation product (HNO on producing
3Or NH
4NO
3) output.
3. unstripped gas (NH
3Add air) by the speed of beds, 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.Industrial with linear speed or the space velocity ratio of catalyst volume (gas volume that per hour passes through with) expression, for this catalyst charge weight, the platinum guaze air speed is equivalent at 30.000 o'clock
-1According to above index, the contrast reaction condition that catalyst of the present invention is used for ammoxidation is: 750 ℃; NH
3Than～10%, air speed～50.000 o'clock
-1, consider catalyst grain size simultaneously, intensity, catalyst bed layer thickness, factors such as catalyst surface area and bulk density.
La of the present invention
1-xCe
xCoO
3Catalyst (0≤X≤1) has following characteristics:
1. adopt two precipitating reagent coprecipitation method preparations, specific surface is 1～5 meter
2/ gram, bulk density 1.5-2.0 grams per milliliter (1.5-2.0 kilogram/liter), catalyst in the form of sheets or column, hardness＞200 kilograms per centimeter
2(vertically), there are metal ion omission or oxygen defect in this catalyst series crystal.
2. catalyst is to NH
3Be oxidized to NO and have the selectivity catalytic action, when X＜0.4, NO selectivity＞97% particularly when X=0.2, shows 3 months NO selectivity on average greater than 98% through expanding test, and catalyst activity is stable, can compare with the platinum guaze catalyst that industry is used.
3. catalyst is being used for NH
3During oxidation reaction, its optimum reaction condition uses the working condition of platinum guaze to adapt to fully with industry.Experiment shows uses this catalyst not only can not reduce production target, and can improve the production capacity of equipment.
4. Preparation of Catalyst is easy, and need not special installation can make in enormous quantities, does not contain noble metal in the catalyst, and cost is low.
Embodiment 1 La
0.8Ce
0.2CoO
3Preparation of Catalyst and condition control.
To prepare 0.5 gram molecule catalyst is example, and its inventory is respectively metallic cobalt 29.5 grams, lanthanum sesquioxide 65.19 grams, cerium oxide 16.41 grams, 1500 milliliters of red fuming nitric acid (RFNA)s, oxalic acid 173.4 grams (excessive), ammonium carbonate 113.2 grams (variable), hydrogen peroxide is a small amount of, and distilled water is excessive.
Adopt oxalic acid, the two precipitating reagent coprecipitations of ammonium carbonate, preparation process is as follows: A, and with metallic cobalt, lanthana, cerium oxide, by measuring, mix respectively as feed liquid (A) B with (during the dissolved oxygen cerium, adding an amount of hydrogen peroxide and heating) behind the nitric acid dissolve, dissolving oxalic acid and ammonium carbonate are respectively as feed liquid (B
1) and (B
2) C, with (B
1) half put into settling vessel, under fully stirring, keep adding (B under 50-60 ℃ of condition of feed liquid
2), make feed liquid PH keep 6-7, add (A) and (B afterwards simultaneously
2), the control feed liquid adds speed, makes pH value be stabilized in 6-7, treats that (A) adds a half (volume), again that second half is standby (B
1) add simultaneously, D till (A) adds after stopping to feed in raw material, continues to stir 3-5 minute, forms sediment and falls 15 minutes time.E, take out sediment and filter (pink) in 6 hours extremely dried F of 120 ℃ of bakings, block after the oven dry is in 600 ℃ of thermal decompositions, 5 hours (being dirty-green) G, product after the pyrolysis adds 30-35% distilled water, rolls oven dry, granulation, moulding H, the product after the moulding was in 900 ℃ of oxygen (or in air) roasting 5 hours, and catalyst gets product.
This preparation method expands as 5 gram molecule scales (every batch system 1.23 kilograms of catalyst) by 0.5 gram molecule scale, 32 batches of sample testings, and NO is single to be received on average 98.9%, and worst error 0.6% repeatability is fine.
Catalytic performance and test in the ammoxidation reaction under embodiment 2 laboratory conditions.
Quartzy battalion fixed bed reactors, internal diameter～25mm, interior dress thermocouple sheath, the about 106mm of catalyst layer real area
2; Catalyst grain size 10～20 orders, dress 8ml, the about 24mm of floor height; Axially by beds, by catalyst bed bottom drawn from top to bottom by product for unstripped gas; Conventional acid-base titration analytical calculation, the reaction condition of selection platinum guaze catalyst: 750 ℃ of reaction temperatures, NH used of NO once through yield
3Than～10%, air speed 50,000 o'clock
-1Also tested reaction temperature and gas space velocity to the single influence of receiving of NO on said apparatus, it the results are shown in Table 3.Test shows, at 650-850 ℃, during 5-10 ten thousand
-1Air speed under, the single receipts of NO all can be greater than 98%.
Table 3 temperature and air speed are to La
0.8Ce
0.2CoO
3The influence of catalytic activity
Embodiment 3 strengthens experiment, 700 ℃ of initial activities of surveying catalyst with α
0Expression is warming up to 900 ℃ of runnings 24 hours then, recovers primary condition again and surveys active alpha
1, △ α=α
0-α
1Represent the active percentage that descends as the catalyst tolerates r, catalyst La of the present invention
0.8Ce
0.2CoO
3With comparative catalyst La
1-xCa
xMnO
3, Co
3O
4Strengthen the experiment comparing result and list following table 4 in.Strengthen the result and show 900 ℃ of runnings of high temperature 24 hours, La
0.8Ce
0.2CoO
3Catalytic performance is influenced hardly.
Several catalyst of table 4 are strengthened experimental result relatively
* by " should change collected papers 17 " method for making
* oxalate precipitation method
4 life-spans of embodiment are examined or check test, under laboratory condition, carry out 500 hours life tests, result such as following table 5:
Table 5 La
0.8Ce
0.2CoO
3Laboratory examination in 500 hours result
Catalyst La
0.8Ce
0.2CoO
3, catalytic amount 8ml, air speed 50,000 o'clock
-1, 700 ℃ of reaction temperatures, NH
3The %(volume)=10-11%
* this experiment is heated with outer because of carrying out under 700 ℃, and the temperature minor fluctuations is not by NH
3Amount control.
Embodiment 5 La
0.8Ce
0.2CoO
3Expanding test under the catalyst industrial condition
Directly quote unstripped gas in factory, in stainless steel fixed bed reactors (adorn 1 liter catalyst, catalyst is φ 6.5 * 4m/m sheet, and this reactor is similar to platinum guaze oxidation furnace structure), real-world operation 93 days.Reaction condition is: catalyst bed layer height 4-8Cm, select 6Cm
Reacting system pressure 0.1Kg/Cm
2
During unstripped gas air speed 4.5-5 ten thousand
-1
Unstripped gas gives 60 ℃～120 ℃ of hot temperature
Unstripped gas proportioning NH
3: air=10-11%(volume)
Reaction temperature 720-850 ℃
400 data average N O yields 98.1% are got in reaction beginning initial activity (NO yield) running in 97.8%, 93 day.Whole active 98.2%.Expanding test shows: 1.NH
3Ratio is basicly stable for the 9-12% activity.2. unstripped gas can be refused heat, and it is better to give heat＞60 ℃ reaction effect.3. the air speed of unstripped gas is when 3-8 ten thousand
-1The interval, the equal tool greater activity of catalyst.4. reaction temperature: once occurring temporary transient 900-1000 ℃ high temperature during test does not have influence to catalyst performance.5. the catalyst height of bed does not have big difference 4-8Cm result, active 98% the yield that all reaches.
6. the reacting system pressure influence is more obvious, 0-2.0Kg/Cm
2Between yield all can be greater than 90%, system pressure is less than 0.5Kg/Cm
2, active＞98%.
Claims (3)
1, a class composite oxide of rare-earth elements for preparation of nitric acid by oxidation of Ammonia catalyst is characterized in that catalyst group general formula is La
1-xCe
xCOO
3, active center element is a transition metals cobalt, the architectural feature element is rare-earth elements of lanthanum and cerium, wherein 0≤x≤1; The Preparation of catalysts method is as follows: (1) gets metallic cobalt by the chemical composition metering, lanthana and cerium oxide mix as deposited components after making salpeter solution, (2) oxalic acid and sal volatile are as precipitating reagent, and with the pH value in the sal volatile control precipitation process, (3) oxalic acid solution adds step by step, promptly in mother liquor of precipitation of ammonium, add half oxalic acid solution earlier, second half and deposited components (La-Ce-Co solution) add simultaneously, (4) fully stir in the precipitation process, and strict control pH value is 6～7,50～60 ℃ of temperature, (5) powdery precipitate is after filtration, oven dry, granulating and forming after the thermal decomposition is in 900 ℃ of roastings.
2, as the described catalyst of claim 1, the optimum value that it is characterized in that forming x in the general formula is best with x=0.2 between 0≤x≤0.4 especially, and it can exist cation defect and non-stoichiometry oxygen in forming.
3, as claim 1,2 described catalyst, it is characterized in that being successfully used to the preparing nitric acid by ammonia oxidation reaction,
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86108985A CN86108985B (en) | 1986-10-04 | 1986-10-04 | Catalyst for preparing rare earth cobaltate of nitric acid by ammonia oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN86108985A CN86108985B (en) | 1986-10-04 | 1986-10-04 | Catalyst for preparing rare earth cobaltate of nitric acid by ammonia oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN86108985A CN86108985A (en) | 1988-04-20 |
| CN86108985B true CN86108985B (en) | 1988-11-23 |
Family
ID=4804129
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN86108985A Expired CN86108985B (en) | 1986-10-04 | 1986-10-04 | Catalyst for preparing rare earth cobaltate of nitric acid by ammonia oxidation |
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|---|---|
| CN (1) | CN86108985B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095398C (en) * | 1996-12-20 | 2002-12-04 | 帝国化学工业公司 | Ammonia oxidation catalyst |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB9724310D0 (en) * | 1997-11-19 | 1998-01-14 | Ici Plc | Ammonia oxidation catalysts |
| CN100335168C (en) * | 2005-07-14 | 2007-09-05 | 浙江大学 | Preparation method of cerium lanthanium complex oxide |
| CN101327432B (en) * | 2008-07-22 | 2011-07-20 | 太原华宝贵金属回收有限公司 | Rare-earth composite oxide catalyst for preparation of nitric acid by ammoxidation |
| DK2202201T3 (en) | 2008-12-23 | 2016-08-01 | Clariant Prod (Italia) Spa | Ammoniakoxidationskatalysatorer |
| CN103803514A (en) * | 2014-01-28 | 2014-05-21 | 中海油太原贵金属有限公司 | Method for producing nitric acid |
| 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 |
-
1986
- 1986-10-04 CN CN86108985A patent/CN86108985B/en not_active Expired
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1095398C (en) * | 1996-12-20 | 2002-12-04 | 帝国化学工业公司 | Ammonia oxidation catalyst |
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| Publication number | Publication date |
|---|---|
| CN86108985A (en) | 1988-04-20 |
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