CN1113832A - Catalyst for synthesizing ammonia and its preparing method - Google Patents
Catalyst for synthesizing ammonia and its preparing method Download PDFInfo
- Publication number
- CN1113832A CN1113832A CN 94106785 CN94106785A CN1113832A CN 1113832 A CN1113832 A CN 1113832A CN 94106785 CN94106785 CN 94106785 CN 94106785 A CN94106785 A CN 94106785A CN 1113832 A CN1113832 A CN 1113832A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- oxide
- iron
- characteristic
- mixed rare
- 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.)
- Granted
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 title claims abstract description 52
- 229910021529 ammonia Inorganic materials 0.000 title claims abstract description 26
- 230000002194 synthesizing effect Effects 0.000 title abstract description 3
- 238000000034 method Methods 0.000 title description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 65
- 229910052742 iron Inorganic materials 0.000 claims abstract description 20
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 16
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 claims abstract description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 5
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 5
- 238000002360 preparation method Methods 0.000 claims abstract description 5
- 238000007500 overflow downdraw method Methods 0.000 claims abstract description 3
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 claims abstract 3
- 229910001950 potassium oxide Inorganic materials 0.000 claims abstract 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 22
- 230000015572 biosynthetic process Effects 0.000 claims description 15
- 238000003786 synthesis reaction Methods 0.000 claims description 15
- 239000002994 raw material Substances 0.000 claims description 13
- 230000004927 fusion Effects 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 9
- 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 6
- 239000000126 substance Substances 0.000 claims 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 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- -1 rare earth nitrates Chemical class 0.000 claims description 4
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 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
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-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
- 229910052750 molybdenum Inorganic materials 0.000 claims description 2
- 239000011733 molybdenum 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
- 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
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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 14
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 12
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000292 calcium oxide Substances 0.000 abstract description 4
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 239000002075 main ingredient Substances 0.000 abstract 1
- 231100000572 poisoning Toxicity 0.000 abstract 1
- 230000000607 poisoning effect Effects 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
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 5
- 239000012752 auxiliary agent Substances 0.000 description 5
- 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
- FZFYOUJTOSBFPQ-UHFFFAOYSA-M dipotassium;hydroxide Chemical compound [OH-].[K+].[K+] FZFYOUJTOSBFPQ-UHFFFAOYSA-M 0.000 description 3
- 238000002474 experimental method Methods 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
- 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
- 239000000395 magnesium oxide 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
- 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
- QYTBWVFCSVDTEC-UHFFFAOYSA-N azane;iron Chemical compound N.[Fe] QYTBWVFCSVDTEC-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
- 230000003197 catalytic effect Effects 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
- 230000009977 dual effect Effects 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
- 239000000463 material Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000012768 molten material 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
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a catalyst for synthesizing ammonia and its preparation method. Said catalyst uses oxide of iron as main ingredient, and uses aluminium oxide, potassium oxide, calcium oxide, mixed rare-earth oxide and other metal oxides as assistants, and the iron ratio of said catalyst is 0.4-16, and said catalyst is prepared by using fusion method. Said catalyst has the low-temp. high catalyzing activity and good heat-resisting and poisoning resistance, and its service life is long, production cost is low. It is applicable to various ammonia plants, and can raise yield and save energy.
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 0.45-0.65.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 425 ℃ of 30.4MPa, temperature, the air speed 3.0 * 10 of pressure
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
2O
3Or other rare earth oxides can obtain higher specific activity as the structural type auxiliary agent.U.S. patent US 3992328 described a kind of interpolation cerium oxide (CeO in 1976
2) ammonia synthesis catalyst, be by making earlier through the fused iron catalyst vacuum impregnation rare-earth additive of prereduction.GB 2042921(US 4308174) be that the interpolation rare earth cerium oxide of Switzerland card Surrey company invention is made the spherical ammonia synthetic catalyst patent, 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 ZL26107630 is to be the main body composition with four iron oxide, and the iron of catalyst is than (Fe
2+/ Fe
3+) the value control range is 0.55 ± 0.22, 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 molten iron ammonia synthesis catalyst (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, adopt the raw material of single rare earth cerium salt, 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 hear resistance of a kind of low temperature active is good, raw material resources 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 ferriferous oxide, with aluminium oxide (Al
2O
3), potassium oxide (K
2O), calcium oxide (CaO) is co-catalyst, this catalyst also comprises 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
2O) 0.2-1.6, calcium oxide (CaO) 0.6-4.3, mixed rare-earth oxide 0.01-2, other metal oxide 0-7.
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.
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 straight iron powder 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, CaO 1.4, mixed rare-earth oxide 0.8, MgO 0.4, and all the other are the oxide of iron, is 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 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, all the other 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 30 * 10
4The time
-1, under the sample granularity 1.0-1.4 millimeter, 425 ℃ of experiment conditions of temperature, this catalyst activity (outlet ammonia concentration) is 29.2%.
Embodiment 2:
Press catalyst chemical and form (weight %) Al
2O
33.2, K
2O 1.4, and CaO 2.0, 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, all the other 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 activity (outlet ammonia concentration) is 29.4%.
Embodiment 3:
Press catalyst chemical and form (weight %) Al
2O
31.8, K
2O 0.5, and CaO 1.6, 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 mixture fusion in the electric smelter of packing into, control iron ratio, make or the iron of catalyst than (Fe
2+/ Fe
3+) be 0.5, when fusion finishes, molten material is cooled off fast, 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 advantage of catalyst of the present invention is that catalyst has very high catalytic activity, in pressure 30.4MPa, air speed 30 * 104The time-1, under 425 ℃ of the sample granularity 1.0-1.4mm, temperature, the reactor outlet gas ammonia content can reach 30.1%, the activity of existing industrial advanced person's ammonia synthesis catalyst improves 4～5 percentage points, and the at low temperatures active amplitude that improves is bigger. This catalyst is used for large, medium and small synthesis ammonia plant, its volume increase, energy-conservation, the consumption reduction effect is remarkable.
Another outstanding advantage of the present invention is that the antitoxin and heat-resisting performance of catalyst is good. In catalyst of the present invention, the mixed rare-earth oxide auxiliary agent high degree of dispersion of adding catalyst body mutually in, have the dual effect of electron type auxiliary agent and Structure promoter concurrently, not only active good, low temperature active height, and antitoxin and fine heat-resisting performance. The employing mixed rare earth compound is raw material, and production cost is lower.
Catalyst of the present invention relatively sees the following form with the existing domestic and international advanced level A110-2 type of industrial tool catalyst performance.
Table, catalyst of the present invention and A110-2 type catalyst performance are relatively
* pressure 30.4MPa, air speed 30 * 104hr
-1, the activity under the sample granularity 1.0-1.4mm condition;
The heat-resisting condition of *: 500 ℃ heat-resisting 20 hours.
Claims (6)
1, a kind of ammonia synthesis catalyst is a main component with the oxide of iron, with aluminium oxide (Al
2O
3), potassium oxide (X
2O), calcium oxide (CaO) is co-catalyst, its characteristic is that 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 (X
2O) 0.2-1.6, calcium oxide (CaO) 0.6-4.8, mixed rare-earth oxide 0.01-2, other metal oxide 0-7.
2, catalyst as claimed in claim 1, its characteristic are in the oxide of iron of catalyst, ferrous iron and ferric ratio (Fe
2+/ Fe
3+) be 0.4-16.
3, catalyst as claimed in claim 1, its characteristic are that 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.
4, other metal oxide promoters that catalyst as claimed in claim 1, its characteristic are 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.
5, as claim 1 or 3 described catalyst, its characteristic be mixed rare-earth oxide can mixed rare-earth oxide or mishmetal oxalates or mishmetal carbonate or mixed rare earth nitrates be raw material.
6, the preparation method of ammonia synthesis catalyst as claimed in claim 1, adopt fusion method, its characteristic 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 straight iron powder 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 true CN1113832A (en) | 1995-12-27 |
| CN1047099C 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) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010031247A1 (en) * | 2008-09-18 | 2010-03-25 | 中国石油天然气股份有限公司 | Iron-based ammonia synthesis catalyst and method for preparing the same |
| CN102909030A (en) * | 2012-09-12 | 2013-02-06 | 浙江工业大学 | Ferrous oxide-based ammonia synthesis catalyst |
| CN110280268A (en) * | 2019-07-03 | 2019-09-27 | 北京氦舶科技有限责任公司 | A kind of synthetic ammonia catalyst and preparation method thereof |
| CN113976134A (en) * | 2021-11-15 | 2022-01-28 | 浙江工业大学 | Ferrous oxide-based catalyst and preparation method and application thereof |
| WO2023108907A1 (en) * | 2021-12-14 | 2023-06-22 | 上海兖矿能源科技研发有限公司 | FUSED IRON CATALYST FOR PREPARING HIGH-CARBON α OLEFIN FROM SYNTHESIS GAS, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1479310A (en) * | 1974-10-30 | 1977-07-13 | Lummus Co | Process for the preparation of ammonia catalyst |
| IT1114730B (en) * | 1979-02-07 | 1986-01-27 | Ammonia Casale Sa | SPHERICAL CATALYST ACTIVATED WITH CERIUM FOR THE SUMMARY OF AMMONIA AND THE PROCEDURE FOR ITS PRODUCTION |
| CN85101605B (en) * | 1985-04-01 | 1988-05-25 | 郑州大学 | High activity spherule catalyst for lower temp. synthesis of ammonla |
| CN85101604B (en) * | 1985-04-01 | 1988-05-25 | 郑州大学 | Mechanical dispersing method for manufacturing high strengh ball catalyst in ammonia synthesizing |
| CN1008439B (en) * | 1985-08-13 | 1990-06-20 | 国际标准电气公司 | Preparation method of slender glass especially prefabricated component used in light guide |
-
1994
- 1994-06-21 CN CN94106785A patent/CN1047099C/en not_active Expired - Lifetime
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010031247A1 (en) * | 2008-09-18 | 2010-03-25 | 中国石油天然气股份有限公司 | Iron-based ammonia synthesis catalyst and method for preparing the same |
| 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 |
| CN102909030A (en) * | 2012-09-12 | 2013-02-06 | 浙江工业大学 | Ferrous oxide-based ammonia synthesis catalyst |
| CN102909030B (en) * | 2012-09-12 | 2015-01-28 | 浙江工业大学 | Ferrous oxide-based ammonia synthesis catalyst |
| CN110280268A (en) * | 2019-07-03 | 2019-09-27 | 北京氦舶科技有限责任公司 | A kind of synthetic ammonia catalyst and preparation method thereof |
| CN113976134A (en) * | 2021-11-15 | 2022-01-28 | 浙江工业大学 | Ferrous oxide-based catalyst and preparation method and application 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 |
| WO2023108907A1 (en) * | 2021-12-14 | 2023-06-22 | 上海兖矿能源科技研发有限公司 | FUSED IRON CATALYST FOR PREPARING HIGH-CARBON α OLEFIN FROM SYNTHESIS GAS, PREPARATION METHOD THEREFOR AND APPLICATION THEREOF |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1047099C (en) | 1999-12-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| EP0763379B1 (en) | Fe 1-x O-BASED CATALYST FOR AMMONIA SYNTHESIS | |
| US5834394A (en) | Fluidized-bed catalyst for propylene ammoxidation to acrylonitrile | |
| CN1028495C (en) | Deoxidized catalyst for alkyl hydrocarbon | |
| EP0956899B1 (en) | A catalyst for manufacturing alkyl aromatics and production method and use thereof | |
| CN1030571A (en) | The preparation method of Tetra hydro Phthalic anhydride | |
| CN1169709A (en) | Large particle dehydrogenation catalyst and process | |
| CN102909030B (en) | Ferrous oxide-based ammonia synthesis catalyst | |
| US4604375A (en) | Manganese-spinel catalysts in CO/H2 olefin synthesis | |
| US3839229A (en) | Ammonia-synthesis catalyst | |
| CN1047099C (en) | Catalyst for synthesizing ammonia and its preparing method | |
| US4997802A (en) | Catalyst for preparation of hydrocarbons | |
| KR20000075903A (en) | USE OF Ce/Zr MIXED OXIDE PHASE FOR THE MANUFACTURE OF STYRENE BY DEHYDROGENATION OF ETHYLBENZENE | |
| CA1262124A (en) | Catalysts | |
| CN101993362B (en) | Method for producing oxalic ester through coupling CO | |
| WO2010031247A1 (en) | Iron-based ammonia synthesis catalyst and method for preparing the same | |
| EP0174080B1 (en) | Catalystsfor the synthesis of ammonia | |
| US3951862A (en) | Process for the preparation of ammonia synthesis catalyst | |
| US3980584A (en) | Carrier and catalyst for chemical processes and method of preparing said catalyst | |
| CN1091997A (en) | Ferrous oxide catalyst for amino synthesis and preparation method | |
| CN1193827C (en) | Catalyst for ultralow temperature high activity ammonia synthesis | |
| CN112958143A (en) | Catalyst for preparing low-carbon olefin by carbon monoxide hydrogenation | |
| CN1235800C (en) | High-activity ferrous oxide base amonia synthesis catalyst and its preparation method | |
| CN1047098C (en) | Pre-reduction type ammonia synthesis catalyst and preparing process | |
| CN1121844A (en) | Catalyst for preparing ethylene by oxidation and dehydrogenation of ethane and process thereof | |
| CN113976134B (en) | Ferrous oxide-based catalyst and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C06 | Publication | ||
| PB01 | Publication | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| C17 | Cessation of patent right | ||
| CX01 | Expiry of patent term |
Expiration termination date: 20140621 Granted publication date: 19991208 |