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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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title abstract description 3
- 230000002194 synthesizing effect Effects 0.000 title 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 66
- 229910052742 iron Inorganic materials 0.000 claims abstract description 24
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims abstract description 23
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 18
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 18
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000002360 preparation method Methods 0.000 claims abstract description 6
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000000292 calcium oxide Substances 0.000 claims abstract description 4
- 238000004519 manufacturing process Methods 0.000 claims abstract description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims description 13
- 230000004927 fusion Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 239000003426 co-catalyst Substances 0.000 claims description 7
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 7
- -1 rare earth nitrates Chemical class 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 150000003891 oxalate salts Chemical class 0.000 claims description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 239000011651 chromium Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052747 lanthanoid Inorganic materials 0.000 claims description 2
- 150000002602 lanthanoids Chemical class 0.000 claims description 2
- 229910052749 magnesium Inorganic materials 0.000 claims description 2
- 239000011777 magnesium Substances 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 239000010955 niobium Substances 0.000 claims description 2
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 2
- 238000007500 overflow downdraw method Methods 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052710 silicon Inorganic materials 0.000 claims description 2
- 239000010703 silicon Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 2
- 229910052721 tungsten Inorganic materials 0.000 claims description 2
- 239000010937 tungsten Substances 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 229910052727 yttrium Inorganic materials 0.000 claims description 2
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- DQMUQFUTDWISTM-UHFFFAOYSA-N O.[O-2].[Fe+2].[Fe+2].[O-2] Chemical compound O.[O-2].[Fe+2].[Fe+2].[O-2] DQMUQFUTDWISTM-UHFFFAOYSA-N 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims 1
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 12
- 239000012752 auxiliary agent Substances 0.000 abstract description 6
- 230000008901 benefit Effects 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 230000001988 toxicity Effects 0.000 abstract 1
- 231100000419 toxicity Toxicity 0.000 abstract 1
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 6
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 6
- LIKBJVNGSGBSGK-UHFFFAOYSA-N iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Fe+3].[Fe+3] LIKBJVNGSGBSGK-UHFFFAOYSA-N 0.000 description 4
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 3
- 230000001147 anti-toxic effect Effects 0.000 description 3
- 229910000019 calcium carbonate Inorganic materials 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- 235000010333 potassium nitrate Nutrition 0.000 description 3
- 239000004323 potassium nitrate Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 2
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical compound C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 description 1
- 229960001759 cerium oxalate Drugs 0.000 description 1
- ZMZNLKYXLARXFY-UHFFFAOYSA-H cerium(3+);oxalate Chemical compound [Ce+3].[Ce+3].[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O.[O-]C(=O)C([O-])=O ZMZNLKYXLARXFY-UHFFFAOYSA-H 0.000 description 1
- GHLITDDQOMIBFS-UHFFFAOYSA-H cerium(3+);tricarbonate Chemical compound [Ce+3].[Ce+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O GHLITDDQOMIBFS-UHFFFAOYSA-H 0.000 description 1
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000005470 impregnation Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
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- Catalysts (AREA)
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 |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101676026B (en) * | 2008-09-18 | 2011-12-07 | 中国石油天然气股份有限公司 | Iron-based ammonia synthesis catalyst and preparation method thereof |
| 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 |
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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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| CN1113832A (en) | 1995-12-27 |
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