CN1047099C - Catalyst for synthesizing ammonia and its preparing method - Google Patents
Catalyst for synthesizing ammonia and its preparing method Download PDFInfo
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- CN1047099C CN1047099C CN94106785A CN94106785A CN1047099C CN 1047099 C CN1047099 C CN 1047099C CN 94106785 A CN94106785 A CN 94106785A CN 94106785 A CN94106785 A CN 94106785A CN 1047099 C CN1047099 C CN 1047099C
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- oxide
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- iron
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- earth
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Abstract
The present invention relates to an ammonia synthesis catalyst and a preparation method. The ammonia synthesis catalyst uses iron oxide as the main component and uses alumina, potassium oxide, calcium oxide, mixed rare earth oxide and other metal oxide as auxiliary agents, the iron ratio of the catalyst is from 0.4 to 16, and the catalyst is prepared by a melting method. The present invention has the advantages of high catalytic activity at low temperature, good heat and toxicity resistance, long service life, lower manufacture cost, yield increase, energy saving, obvious consumption reduction effect, larger economic benefit and larger social benefit, and is suitable for various ammonia factories.
Description
The present invention relates to ammonia synthesis catalyst and preparation method, be applicable to the occasion of hydrogen and nitrogen synthetic ammonia.
Before the present invention made, both at home and abroad the industrial ammonia synthesis catalyst that uses was normally mixed by selected magnetic iron ore and auxiliary agent raw material, made through fusion, cooling.The co-catalyst that is adopted has aluminium oxide (Al
2O
3), potassium oxide (K
2O), calcium oxide (CaO), magnesia (MgO), cobalt oxide etc.The iron of the existing industrial ammonia synthesis catalyst in countries in the world is than (Fe
2+/ Fe
3+) value is all in the 0.4-0.8 scope, and the overwhelming majority is controlled between 0.45-0.55.Existing advanced both at home and abroad industrial ammonia synthesis catalyst, as the A110 catalyst series of China, the KM catalyst of rope company of Denmark Top (Topsoe), the S6-10 catalyst of BASF Aktiengesellschaft (BASF), the 35-4 catalyst of Britain's ICI Imperial Chemical Industries (ICI), the AS-4 catalyst of Norsk Hydro A.S (Horsk Hydro), iron cobalt type catalyst both domestic and external (the A201 type of the 74-1 type of ICI, China) etc., they are in pressure 30.4MPa, 425 ℃ of temperature, air speed 3.0 * 10
4The time
-1, catalyst grain size 1.0-1.4 millimeter experiment condition under, catalyst activity, reactor outlet concentration are 23-26%.For the auxiliary agent of rare earth oxide, report is arranged also as ammonia synthesis catalyst.Reported interpolation Se as the former Soviet Union
3O
3Or other rare earth oxides can obtain higher specific activity as the structural type auxiliary agent.The U.S. described a kind of interpolation cerium oxide (CaO of patent IS3992328 in 1976
2) ammonia synthesis catalyst, be by making earlier through the fused iron catalyst vacuum impregnation rare-earth additive of prereduction.GB2042921 (US4308174) is that the interpolation rare earth cerium oxide of Switzerland card Surrey company invention is made the spherical ammonia synthetic catalyst patent, and this catalyst is through batch mixing, fusion, cool off, grind, balling-up and sintering form.Above-mentioned patented technology is the manufacture method complexity not only, and it is also unsatisfactory to get institute's activity of such catalysts.The described catalyst containing rare earth element for synthesis of ammonia that contains of Chinese patent ZL86107630 is to be the main body composition with the tri-iron tetroxide, and the iron of catalyst is than (Fe
2+/ Fe
3+) the value control range is 0.55 ± 0.02, contained oxygen is to be that raw material adds with cerous nitrate or cerous carbonate or cerium oxalate than cerium, cerium oxide content is 0.4-1.0% (weight %).In pressure 30.4MPa, 425 ℃ of temperature, air speed 3.0 * 10
4The time
-1Under the experiment condition, this catalyst activity (outlet ammonia concentration) is 26.0%, compare with industrial existing advanced person's Fused-iron Catalyst for Ammonia Synthesis (activity is 24.3%) and iron cobalt type catalyst (activity is 25.3%), the outlet ammonia concentration of this catalyst has improved 1.7 and 0.7 percentage points respectively.In the prior art, adopting single rare earth cerium salt is raw material, and cost is higher, and catalyst iron ratio all is controlled in traditional classical scope (0.5-0.7), and catalyst activity is difficult to obtain bigger raising.
Task of the present invention is the shortcoming that overcomes prior art, and good, the antitoxin fine heat-resisting performance of a kind of low temperature active, raw material resources are abundant, manufacturing cost is lower ammonia synthesis catalyst and preparation method are provided.
Ammonia synthesis catalyst of the present invention is a main component with the oxide of iron, with aluminium oxide (Al
2O
3), potassium oxide (K
2O), calcium oxide (CaO) is co-catalyst, this catalyst also includes mixed rare-earth oxide and other oxide, the chemical composition of this catalyst (weight %) is: iron (II) oxide (in FeO) 23-90, iron (III) oxide is (with Fe
2O
3Meter) 5-71, aluminium oxide (Al
2O
3) 0.8-5.2, potassium oxide (K
3O) 0.2-1.6, calcium oxide (CaO) 0.6-4.8, mixed rare-earth oxide 0.01-2, other metal oxide 0-7.
In the oxide of the iron of catalyst, ferrous iron and ferric ratio (Fe
2+/ Fe
3+) be 0.4-16.
The mixed rare-earth oxide of catalyst is meant the several or whole of scandium, yttrium and 17 kinds of element oxides of group of the lanthanides.
Other metal oxide promoters of catalyst is meant a kind of in the oxide of molybdenum, cobalt, zirconium, barium, magnesium, titanium, vanadium, silicon, tungsten, niobium, nickel, chromium, manganese or several.
Mixed rare-earth oxide can mixed rare-earth oxide or mishmetal oxalates or mishmetal carbonate or mixed rare earth nitrates be raw material.
The preparation method of ammonia synthesis catalyst of the present invention, adopting fusion method is that a certain amount of co-catalyst raw material is mixed with magnetite powder, pure iron, or with a certain amount of co-catalyst raw material, magnetite powder with pure iron or/and carbon mix, through fusion, cool off and form.
Embodiment 1:
Press chemical composition (weight %) Al of catalyst
2O
32.4, K
2O0.6, CaO1.4, mixed rare-earth oxide 0.8, MgO0.4, all the other are the oxide of iron, are selected magnetite powder 100 with raw material (by weight), iron powder 28, aluminium oxide 3.25, potassium nitrate 1.74, calcium carbonate 3.40, mixed light rare earth oxide 1.09, the ratio of magnesia 0.54 batching, mix after, with the mixed material fusion in the electric smelter of packing into, 2000 ℃ of melt temperatures, when fusion finishes, melt is put into the cooling bath that has water-cooling jacket cool off fast,, get varigrained product again with cooled frit fragmentation, screening.The iron of this catalyst is than (Fe
2+/ Fe
3+) be 9.2, its iron (II) oxide (in FeO weight %) is 84.2, iron (III) oxide is (with Fe
2O
3Weight % meter) be 10.2, in pressure 30.4MPa, air speed 3.0 * 10
4The time
-1, under the sample granularity 1.0-1.4 millimeter, 425 ℃ of experiment conditions of temperature, this drawing together property of catalyst (outlet ammonia concentration) is 29.2%.
Embodiment 2:
Press catalyst chemical and form (weight %) Al
2O
33.2, K
2O1.4, CaO2.0, mixed rare-earth oxide 1.2, V
2O
50.4, all the other are the oxide of iron, are selected magnetite powder 100 with raw material (by weight), iron powder 22, aluminium oxide 4.29, potassium nitrate 3.04, calcium carbonate 4.81, mishmetal oxalates 3.01, after the ratio of ammonium metavanadate 0.81 is prepared burden, is mixed, the interior fusion of the electric smelter of packing into, 1600 ℃ of melt temperatures, surplus with embodiment 1.The iron of this catalyst is than (Fe
2+/ Fe
3+) be 4.5, its iron (II) oxide (in FeO weight %) is 73.6, iron (III) oxide is (with Fe
2O
3Weight % meter) be 18.2, under embodiment 1 described condition, its drawing together property (outlet ammonia concentration) is 29.4%.
Embodiment 3:
Press catalyst chemical and form (weight %) Al
2O
31.8, K
2O0.5, CaO1.6, mixed rare-earth oxide 0.3, V
2O
50.4, all the other are the oxide of iron, with raw material (by weight) is selected magnetite powder 100, aluminium oxide 1.91, potassium nitrate 1.13, calcium carbonate 3.05, mishmetal oxalates 0.59, the ratio of vanadic anhydride 0.43 batching, mix after, with the mixed material fusion in the electric smelter of packing into, control iron ratio, the iron that makes finished catalyst is than (Fe
2+/ Fe
3+) value is 0.5, when fusion finishes, melt cooled off fast, and is surplus with embodiment 1.The iron of this catalyst is than (Fe
2+/ Fe
3+) be 0.5, iron (II) oxide (in FeO weight %) is 29.6, iron (III) oxide is (with Fe
2O
3Weight % meter) be 65.8, under embodiment 1 described condition, its activity (outlet ammonia concentration) is 27.4%.
The outstanding advantages of catalyst of the present invention is that catalyst has very high catalytic activity, at pressure 30.4MP3, air speed 3.0 * 104The time-1, under 425 ℃ of the sample granularity 1.0～1.4mm, temperature, The reactor outlet gas ammonia content can reach 30.1%, existing industrial advanced person's ammonia synthesis catalysis The activity of agent improves 4～5 percentage points, and the dawn, the at low temperatures active amplitude that improves was bigger. This is urged Change agent with sub large, medium and small synthesis ammonia plant, its volume increase, energy-conservation, the effect that lowers consumption is remarkable.
Another outstanding advantages of the present invention is that the antitoxin and heat resistance of catalyst is good. At this In the bright catalyst, add as mixed rare-earth oxide auxiliary agent high degree of dispersion in the catalyst body phase In, have the double action of electron type auxiliary agent and Structure promoter concurrently, not only active good, low temperature is lived Property height, and antitoxin and fine heat-resisting performance. The employing mixed rare earth compound is raw material, produces This is lower.
Catalyst of the present invention and the Al10-2 type catalyst that has the domestic and international advanced level of industrial tool now Performance Ratio sees the following form.
Table, catalyst of the present invention and A110-2 type catalyst performance are relatively
* pressure 30.4MP1, air speed 3.0 * 104hr
-1, sample granularity is 1.0～1.4mm Activity under the condition;
The heat-resisting condition of *: 500 ℃ heat-resisting 20 hours.
Claims (4)
1, a kind of ammonia synthesis catalyst, oxide with iron is a main component, with aluminium oxide, potassium oxide, calcium oxide is a co-catalyst, it is characterized in that this catalyst also includes mixed rare-earth oxide and other oxides, the chemical composition of this catalyst (weight %) is: ferrous oxide or ferrous oxide 23-90, ferric oxide or di-iron trioxide 5-71, aluminium oxide 0.8-5.2, potassium oxide 0.2-1.6, calcium oxide 0.6-4.8, mixed rare-earth oxide 0.01-2, other metal oxide 0-7, the mixed rare-earth oxide of catalyst is meant scandium, yttrium and 17 kinds of element oxides of group of the lanthanides several or whole, other metal oxide promoters of catalyst is meant aluminium, cobalt, zirconium, barium, magnesium, titanium, vanadium, silicon, tungsten, niobium, nickel, chromium, a kind of in the oxide of manganese or several.
2, catalyst as claimed in claim 1 is characterized in that ferrous iron and ferric ratio are 0.4-16 in the oxide of iron of catalyst.
3, catalyst as claimed in claim 1 or 2 is characterized in that mixed rare-earth oxide is is feedstock production by mishmetal oxalates or mishmetal carbonate or mixed rare earth nitrates.
4, the preparation method of ammonia synthesis catalyst as claimed in claim 1, adopt fusion method, it is characterized in that a certain amount of co-catalyst raw material is mixed with magnetite powder, pure iron, or with a certain amount of co-catalyst raw material, magnetite powder with pure iron or/and carbon mix, through fusion, the cooling form.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94106785A CN1047099C (en) | 1994-06-21 | 1994-06-21 | Catalyst for synthesizing ammonia and its preparing method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN94106785A CN1047099C (en) | 1994-06-21 | 1994-06-21 | Catalyst for synthesizing ammonia and its preparing method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1113832A CN1113832A (en) | 1995-12-27 |
| CN1047099C true CN1047099C (en) | 1999-12-08 |
Family
ID=5032667
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN94106785A Expired - Lifetime CN1047099C (en) | 1994-06-21 | 1994-06-21 | Catalyst for synthesizing ammonia and its preparing method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1047099C (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101676026B (en) * | 2008-09-18 | 2011-12-07 | 中国石油天然气股份有限公司 | Iron ammonia synthesis catalyst and preparation method |
| CN102909030B (en) * | 2012-09-12 | 2015-01-28 | 浙江工业大学 | Ferrous oxide-based ammonia synthesis catalyst |
| CN110280268B (en) * | 2019-07-03 | 2023-04-07 | 北京氦舶科技有限责任公司 | Synthetic ammonia catalyst and preparation method thereof |
| CN113976134B (en) * | 2021-11-15 | 2024-04-09 | 浙江工业大学 | Ferrous oxide-based catalyst and preparation method and application thereof |
| CN114130406A (en) * | 2021-12-14 | 2022-03-04 | 上海兖矿能源科技研发有限公司 | Molten iron catalyst for preparing high-carbon alpha olefin from synthesis gas and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992328A (en) * | 1974-10-30 | 1976-11-16 | The Lummus Company | Process for the preparation of ammonia synthesis catalyst and catalyst prepared by the process |
| US4308174A (en) * | 1979-02-07 | 1981-12-29 | Ammonia Casale S.A. | Spherical cerium-activated catalyst for ammonia synthesis and process for its manufacture |
| CN85101604A (en) * | 1985-04-01 | 1986-03-10 | 郑州大学 | Mechanical dispersing method for manufacturing high strengh ball catalyst in ammonia synthesizing |
| CN85101605A (en) * | 1985-04-01 | 1986-09-17 | 郑州大学 | The low temperature high activity ball catalyst in ammonia synthesizing |
| CN85106106A (en) * | 1985-08-13 | 1987-03-04 | 国际标准电气公司 | Slender glass is the preparation method of the prefabricated component used of optical waveguides particularly |
-
1994
- 1994-06-21 CN CN94106785A patent/CN1047099C/en not_active Expired - Lifetime
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3992328A (en) * | 1974-10-30 | 1976-11-16 | The Lummus Company | Process for the preparation of ammonia synthesis catalyst and catalyst prepared by the process |
| US4308174A (en) * | 1979-02-07 | 1981-12-29 | Ammonia Casale S.A. | Spherical cerium-activated catalyst for ammonia synthesis and process for its manufacture |
| CN85101604A (en) * | 1985-04-01 | 1986-03-10 | 郑州大学 | Mechanical dispersing method for manufacturing high strengh ball catalyst in ammonia synthesizing |
| CN85101605A (en) * | 1985-04-01 | 1986-09-17 | 郑州大学 | The low temperature high activity ball catalyst in ammonia synthesizing |
| CN85106106A (en) * | 1985-08-13 | 1987-03-04 | 国际标准电气公司 | Slender glass is the preparation method of the prefabricated component used of optical waveguides particularly |
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| Publication number | Publication date |
|---|---|
| CN1113832A (en) | 1995-12-27 |
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Expiration termination date: 20140621 Granted publication date: 19991208 |