CN102911061B - Method of directly synthesizing ethylene diamine with oxirane and ammonia - Google Patents
Method of directly synthesizing ethylene diamine with oxirane and ammonia Download PDFInfo
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Abstract
The invention relates to method of directly synthesizing ethylene diamine with oxirane and ammonia, which comprises the steps of filling fluidized bed catalyst to a fluidized bed reactor, mixing the oxirane, ammonia, hydrogen and complex polymer of high-boiling ethanolamine and ethylene diamine from the bottom of a rectifying still of a system, generating a mixture mainly containing ethylene diamine and containing ethanolamine and polyethylene polyamine at a certain temperature and pressure, allowing the mixture to directly enter a fixed bed reactor, filling fixed bed catalyst to a fixed bed, further ammonolyzing non-ethylene diamine substances in the mixture into ethylene diamine and auxiliarily producing polyethylene polyamine at a certain temperature and pressure, returning the excess ammonia and hydrogen to a fluidized bed by a compressor for applying, and returning the auxiliarily produced high-boiling substances to the fluidized bed for applying or for being used as an epoxy resin curing agent. The method is low in cost and energy consumption, causes little or no environmental pollution, and is suitable for large-scale industrialized production.
Description
Technical field
The present invention relates to a kind of synthetic method of quadrol, particularly a kind of synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia.
Background technology
In prior art, quadrol all adopts 1,2-ethylene dichloride ammonia metallization processes small-scale production.In this production process, need to evaporate a large amount of ammoniacal liquor, steam consumption quantity is large; Operational path is selected undesirable, generates a part quadrol by-product two molecule sodium-chlor, containing a large amount of sodium chloride waste water, almost cannot process, and environmental pollution is serious; Quadrol yield is low, and cost is high, cannot compete with external oxyethane technique.
Chinese patent literature CN 100546717C proposes to use thanomin synthesis of ethylenediamine, adopt single fixed-bed process, catalyzer is mordenite and alumina mixture containing zirconium, zinc or molybdenum, thanomin transformation efficiency 60%, quadrol yield 37.8%, catalyzer is stable in 300 hours.
Chinese patent literature CN 101622221A proposes another kind of synthetic method, utilizes aminoacetonitriles hydrogenation to carry out synthesis of ethylenediamine.Because aminoacetonitriles derives from prussic acid, limited the application of this synthetic method.
Summary of the invention
Technical problem to be solved by this invention is for the deficiencies in the prior art, provides more reasonable, easy to operate, the synthetic cost of a kind of technique low, and production energy consumption is little, by the synthetic method of oxyethane and the direct synthesis of ethylenediamine of ammonia.
Technical problem to be solved by this invention is to realize by following technical scheme.The present invention is a kind of synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia, is characterized in, its step is as follows:
(1) in fluidized-bed reactor, load fluid catalyst, by oxyethane, ammonia, hydrogen with from the complicated polymer of high boiling material thanomin and quadrol at the bottom of native system rectifying still, mix, under 370～480 ℃ of temperature, pressure 0.03～2.5MPa condition, generate and take quadrol as the main mixture containing thanomin and many ethyleneamineses; Wherein, oxyethane: ammonia: the mass ratio of hydrogen is 1: 2～100: 0.1～100, at the bottom of the rectifying still that system is applied mechanically, high boiling material amount is 0～30% of oxyethane quality;
Described fluid catalyst is comprised of the material of following mass percent:
NiO 0.5～12%； CoO 0～10% ；
Fe
2O
3 0～10%； Al
2O
3 10～70% ；
SiO
2 10～60%；
Described fluid catalyst is 20-120 object microballoon;
(2) mixture directly enters fixed-bed reactor again, loads fixed bed catalyst in fixed bed, under 370～480 ℃ of temperature, pressure 0.03～2.5MPa condition, the further ammonia solution of non-quadrol material in mixture is become to quadrol, and the many ethyleneamineses of by-product; Excess of ammonia and hydrogen return to fluidized-bed by compressor and apply mechanically; The high boiling substance of by-product returns to fluidized-bed and applies mechanically, or as epoxy curing agent;
Described fixed bed catalyst is comprised of the material of following mass percent:
NiO 0.5～10% ； CoO 0～5% ；
Fe
2O
3 0～10% ； Al
2O
3 20～70% ；
H-mordenite, HZSM-5 molecular sieve or other crystal type molecular sieve 10～60%;
Described fixed bed catalyst is particulate state.
In synthetic method of the present invention: described fluidized-bed reactor is preferably shelf fluidized bed, promotes the free style fluidized-bed of tubular type fluidized-bed or built-in cyclonic separator; That described fixed bed is preferably is calandria type fixed bed, stacked fixed bed or stacked fixed bed radially.
In synthetic method of the present invention: preferably by fluidized-bed and fixed bed series connection.
In synthetic method of the present invention: in step (1), oxyethane: ammonia: the mass ratio of hydrogen is preferably 1: 25～and 30: 1～10; Fluidized-bed temperature is preferably 400～450 ℃, and pressure is preferably 0.04～1.0 MPa; In step (2), fixed bed temperature is preferably 410～430 ℃, and pressure is preferably 0.04～1.0 MPa.
In synthetic method of the present invention: in step (1), described fluid catalyst is that the preferred material by following mass percent forms:
NiO 4～8%； CoO 2～5%；
Fe
2O
3 2～5%； Al
2O
3 40～60%；
SiO
2 30～50%。
In synthetic method of the present invention: in step (2), described fixed bed catalyst is that the preferred material by following mass percent forms:
NiO 2～5%； CoO 0.5～1% ；
Fe
2O
3 0.5～2%； Al
2O
3 40～60% ；
H-mordenite, HZSM-5 molecular sieve or other crystal type molecular sieve 35～55%.
In synthetic method of the present invention: described nickel oxide preferably comes from soluble nickel salt; Cobalt oxide carrys out the excellent solubility cobalt salt that is selected from; Ferric oxide preferably comes from soluble ferric iron salt; Aluminum oxide preferably comes from Tai-Ace S 150, aluminum chloride, W 4600, pseudo-boehmite or aluminum isopropylate; Silicon oxide preferably comes from ammonia silicon sol or acidic silicasol; Mordenite silica alumina ratio 18～28; The silica alumina ratio of ZSM-5 molecular sieve is 15～80.
In synthetic method of the present invention: described nickel oxide preferably comes from nickelous nitrate, single nickel salt, nickelous chloride or nickel acetate; Cobalt oxide preferably comes from Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol or cobalt chloride; Ferric oxide preferably comes from iron nitrate, ferrous sulfate or iron(ic) chloride; The silica alumina ratio of h-mordenite is preferably 18～22; The silica alumina ratio of HZSM-5 molecular sieve is preferably 20～50.
The catalyzer relating in synthetic method of the present invention, can use currently known methods moulding, oven dry, calcining.Catalyst calcination temperature is generally 400～600 ℃, preferably 480～520 ℃.After fluid catalyst inactivation, can use water vapor and air regenesis.Catalyst microspheres can obtain by known slurry spraying or centrifugal rotation method.Granules of catalyst can obtain by known extrusion or tabletting method.Nickel oxide, cobalt oxide, ferric oxide, aluminum oxide can be by obtaining with sodium carbonate or sodium hydroxide co-precipitation.Pure water washes away soluble impurity, more composite with silicon sol or h-mordenite making beating.
The preparation method of the catalyzer relating in synthetic method of the present invention can adopt following methods to make.
1 fluid catalyst is prepared universal method
1.1 co-precipitation single nickel salts, cobalt chloride, iron(ic) chloride, Tai-Ace S 150 mixed acid solution, control 60～100 ℃ of temperature, adds saturated solution of sodium carbonate (or 30% sodium hydroxide solution), stirs neutralization in enamel still, and pH reaches 6～7 for terminal.Plate Filtration, it is qualified that pure water washing detects sodium ions content≤0.05%.
1.2 making beating add coprecipitate and de-sodium silica gel in hollander, making beating at a high speed, and material becomes uniform sizing material.
1.3 make microballoon pumps into centrifugal spraying granulator by slurry.Dry-heat air temperature: 260～350 ℃ of blast inlets, 120～150 ℃ of exhaust outlets.Also can use rotary pelleting machine granulation.
1.4 dry at 110～150 ℃, and microballoon is dried.
1.5 calcine in rotary kiln, and 480～520 ℃, calcined catalyst 6～10 hours.Obtain 20～120 order microspheric catalysts.
2 fixed bed catalysts are prepared universal method
2.1 co-precipitation single nickel salts, cobalt chloride, iron(ic) chloride, Tai-Ace S 150 mixed acid solution, control 60～100 ℃ of temperature, adds saturated solution of sodium carbonate (or 30% sodium hydroxide solution), stirs neutralization in enamel still, and pH reaches 6～7 for terminal.Plate Filtration, it is qualified that pure water washing detects sodium ions content≤0.05%.
2.2 making beating add coprecipitate and mordenite (or HZSM-5 molecular sieve) in hollander, making beating at a high speed, and material becomes uniform sizing material.
2.3 sprayings are dry pumps into drying machine with centrifugal spray by slurry.Dry-heat air temperature: 260～350 ℃ of blast inlets, 120～150 ℃ of exhaust outlets.
It is wetting that 2.4 extrusion spraying dried materials add pure water, banded extruder moulding.Also available tablet machine moulding.
2.5 dry at 110～150 ℃, and particle is dried.
2.6 calcine in rotary kiln, and 480～520 ℃, calcined catalyst 6～10 hours.Obtain φ 3～6 beaded catalysts.
Working method in actual use procedure is:
1 fluidized-bed size φ 57 * 3000, loads 20～120 order catalyzer 600ml; Fixed bed size φ 38 * 2000, loads φ 3～6 catalyzer 1200ml.
2 control 410 ℃ of fluidized-beds, pressure 0.08 MPa; 420 ℃ of fixed bed temperature, pressure 0.05MPa.
3 quantitatively enter ammonia and hydrogen, deactivated catalyst 8h.
4 quantitatively enter oxyethane, add in proportion high boiling material at the bottom of rectifying still.
5 condensing trappings, gas chromatographic analysis.
(the medium: methyl-silicone oil) circulation of Venturi supercharging for 6 tail gas.
7 decline 10% time when yield, with steam: air=5～9: 1(m/m) gas mixture activating and regenerating, 480～500 ℃ of regeneration temperatures.
Compared with prior art, synthetic method of the present invention is reasonable in design, and synthetic cost is low, and production energy consumption is little, almost there is no environmental pollution, is applicable to large-scale industrial production.
Embodiment
Below further describe concrete technical scheme of the present invention, so that those skilled in the art understands the present invention further, and do not form the restriction to its right.
Embodiment 1, a kind of synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia, and its step is as follows:
(1) in fluidized-bed reactor, load fluid catalyst, by oxyethane, ammonia, hydrogen with from the complicated polymer of high boiling material thanomin and quadrol at the bottom of native system rectifying still, mix, under 370 ℃ of temperature, pressure 0.03MPa condition, generate and take quadrol as the main mixture containing thanomin and many ethyleneamineses; Wherein, oxyethane: ammonia: the mass ratio of hydrogen is 1: 2: 0.1, at the bottom of the rectifying still that system is applied mechanically, high boiling material amount is 30% of oxyethane quality;
Described fluid catalyst is comprised of the material of following mass percent:
NiO 12%； Al
2O
3 70% ；
SiO
2 18%；
Described fluid catalyst is 20 object microballoons;
(2) mixture directly enters fixed-bed reactor again, loads fixed bed catalyst in fixed bed, under 370 ℃ of temperature, pressure 0.03MPa condition, the further ammonia solution of non-quadrol material in mixture is become to quadrol, and the many ethyleneamineses of by-product; Excess of ammonia and hydrogen return to fluidized-bed by compressor and apply mechanically; The high boiling substance of by-product returns to fluidized-bed and applies mechanically, or as epoxy curing agent;
Described fixed bed catalyst is comprised of the material of following mass percent:
NiO 10% ； Al
2O
3 70% ；
H-mordenite, HZSM-5 molecular sieve or other crystal type molecular sieve 20%;
Described fixed bed catalyst is particulate state.
Embodiment 2, a kind of synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia, and its step is as follows:
(1) in fluidized-bed reactor, load fluid catalyst, the complicated polymer of oxyethane, ammonia, hydrogen and quadrol is mixed, under 480 ℃ of temperature, pressure 2.5MPa condition, generate and take quadrol as the main mixture containing thanomin and many ethyleneamineses; Wherein, oxyethane: ammonia: the mass ratio of hydrogen is 1: 100: 100;
Described fluid catalyst is comprised of the material of following mass percent:
NiO 0.5%； Al
2O
3 39.5% ；
SiO
2 60%；
Described fluid catalyst is 120 object microballoons;
(2) mixture directly enters fixed-bed reactor again, loads fixed bed catalyst in fixed bed, under 480 ℃ of temperature, pressure 2.5MPa condition, the further ammonia solution of non-quadrol material in mixture is become to quadrol, and the many ethyleneamineses of by-product; Excess of ammonia and hydrogen return to fluidized-bed by compressor and apply mechanically; The high boiling substance of by-product returns to fluidized-bed and applies mechanically, or as epoxy curing agent;
Described fixed bed catalyst is comprised of the material of following mass percent:
NiO 0.5% ； Al
2O
3 39.5% ；
H-mordenite, HZSM-5 molecular sieve or other crystal type molecular sieve 60%;
Described fixed bed catalyst is particulate state.
Embodiment 3, a kind of synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia, and its step is as follows:
(1) in fluidized-bed reactor, load fluid catalyst, by oxyethane, ammonia, hydrogen with from the complicated polymer of high boiling material thanomin and quadrol at the bottom of native system rectifying still, mix, under 420 ℃ of temperature, pressure 1MPa condition, generate and take quadrol as the main mixture containing thanomin and many ethyleneamineses; Wherein, oxyethane: ammonia: the mass ratio of hydrogen is 1: 25: 10; Fluidized-bed temperature is 420 ℃, and pressure is 0.5 MPa; At the bottom of the rectifying still that system is applied mechanically, high boiling material amount is 5% of oxyethane quality;
Described fluid catalyst is comprised of the material of following mass percent:
NiO 10%； CoO 0.1% ；
Al
2O
3 60% ； SiO
2 29.9%；
Described fluid catalyst is 30 object microballoons;
(2) mixture directly enters fixed-bed reactor again, loads fixed bed catalyst in fixed bed, in temperature, is 410 ℃, and pressure is under 0.04MPa condition, and the further ammonia solution of non-quadrol material in mixture is become to quadrol, and the many ethyleneamineses of by-product; Excess of ammonia and hydrogen return to fluidized-bed by compressor and apply mechanically; The high boiling substance of by-product returns to fluidized-bed and applies mechanically, or as epoxy curing agent;
Described fixed bed catalyst is comprised of the material of following mass percent:
NiO 8.9% ；
Fe
2O
3 0.1% ； Al
2O
3 61% ；
H-mordenite, HZSM-5 molecular sieve or other crystal type molecular sieve 30%;
Described fixed bed catalyst is particulate state.
Described fluidized-bed reactor is shelf fluidized bed, the free style fluidized-bed that promotes tubular type fluidized-bed or built-in cyclonic separator; Described fixed bed is calandria type fixed bed, stacked fixed bed or stacked fixed bed radially.Described fluidized-bed and fixed bed series connection.
Embodiment 4, a kind of synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia, and its step is as follows:
(1) in fluidized-bed reactor, load fluid catalyst, by oxyethane, ammonia, hydrogen with from the complicated polymer of high boiling material thanomin and quadrol at the bottom of native system rectifying still, mix, under 450 ℃ of temperature, pressure 0.5MPa condition, generate and take quadrol as the main mixture containing thanomin and many ethyleneamineses; Wherein, oxyethane: ammonia: the mass ratio of hydrogen is 1: 30: 5; Fluidized-bed temperature is 430 ℃, and pressure is 0.1MPa; At the bottom of the rectifying still that system is applied mechanically, high boiling material amount is 10% of oxyethane quality;
Described fluid catalyst is comprised of the material of following mass percent:
NiO 10%； CoO 10% ；
Al
2O
3 70% ；
SiO
2 10%；
Described fluid catalyst is 50 object microballoons;
(2) mixture directly enters fixed-bed reactor again, loads fixed bed catalyst in fixed bed, in temperature, is 430 ℃, and pressure is under 0.1 MPa condition, and the further ammonia solution of non-quadrol material in mixture is become to quadrol, and the many ethyleneamineses of by-product; Excess of ammonia and hydrogen return to fluidized-bed by compressor and apply mechanically; The high boiling substance of by-product returns to fluidized-bed and applies mechanically, or as epoxy curing agent;
Described fixed bed catalyst is comprised of the material of following mass percent:
NiO 10% ；
Fe
2O
3 10% ； Al
2O
3 70% ；
H-mordenite, HZSM-5 molecular sieve or other crystal type molecular sieve 10%;
Described fixed bed catalyst is particulate state.
Described fluidized-bed reactor is shelf fluidized bed, the free style fluidized-bed that promotes tubular type fluidized-bed or built-in cyclonic separator; Described fixed bed is calandria type fixed bed, stacked fixed bed or stacked fixed bed radially.Described fluidized-bed and fixed bed series connection.
Embodiment 5, a kind of synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia, and wherein said fluid catalyst is comprised of the material of following mass percent:
NiO 4%； CoO 2%；
Fe
2O
3 2%； Al
2O
3 52%；
SiO
2 40%；
Described fixed bed catalyst is comprised of the material of following mass percent:
NiO 2%； CoO 0.5% ；
Fe
2O
3 0.5%； Al
2O
3 42% ；
H-mordenite, HZSM-5 molecular sieve or other crystal type molecular sieve 55%.
All the other are all identical with embodiment 3.
Embodiment 6, and dissolve a kind of side with oxyethane and the direct synthesis of ethylenediamine of ammonia, and wherein said fluid catalyst is comprised of the material of following mass percent:
NiO 8%； CoO 5%；
Fe
2O
3 5%； Al
2O
3 47%；
SiO
2 35%；
Described fixed bed catalyst is comprised of the material of following mass percent:
NiO 5%； CoO 1% ；
Fe
2O
3 2%； Al
2O
3 50% ；
H-mordenite, HZSM-5 molecular sieve or other crystal type molecular sieve 42%.
All the other are all identical with embodiment 4.
Embodiment 7, the method with oxyethane and ammonia direct synthesis of ethylenediamine of embodiment 1-6 described in any one: described nickel oxide comes from soluble nickel salt; Cobalt oxide comes from solubility cobalt salt; Ferric oxide comes from soluble ferric iron salt; Aluminum oxide comes from Tai-Ace S 150, aluminum chloride, W 4600, pseudo-boehmite or aluminum isopropylate; Silicon oxide comes from ammonia silicon sol or acidic silicasol; Mordenite silica alumina ratio 18～28; The silica alumina ratio of ZSM-5 molecular sieve is 15～80.
Embodiment 8, the method with oxyethane and ammonia direct synthesis of ethylenediamine of embodiment 1-6 described in any one: described nickel oxide comes from nickelous nitrate, single nickel salt, nickelous chloride or nickel acetate; Cobalt oxide comes from Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol or cobalt chloride; Ferric oxide comes from iron nitrate, ferrous sulfate or iron(ic) chloride; The silica alumina ratio of h-mordenite is 18～22; The silica alumina ratio of HZSM-5 molecular sieve is 20～50.
Embodiment 9, a kind of experiment of the synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia one.
Experimental technique is with embodiment 2, and wherein, catalyzer composition sees the following form:
Analytical results sees the following form:
# disregards moisture, is only quadrol and thanomin relative mass ratio.
## quadrol is to oxyethane molar yield 80%.
Embodiment 10, a kind of experiment of the synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia two.
Experimental technique is with embodiment 3, and wherein, catalyzer composition sees the following form:
Analytical results sees the following form:
# disregards moisture, is only quadrol and thanomin relative mass ratio.
## quadrol is to oxyethane molar yield 79.3%.
Embodiment 11, a kind of experiment of the synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia three.
Experimental technique is with embodiment 4, and wherein, catalyzer composition sees the following form:
Analytical results sees the following form:
# disregards moisture, is only quadrol and thanomin relative mass ratio.
## quadrol is to oxyethane molar yield 78.2%.
Embodiment 12, a kind of experiment of the synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia four.
Experimental technique is with embodiment 4, and wherein, catalyzer composition sees the following form:
Analytical results sees the following form:
# disregards moisture, is only quadrol and thanomin relative mass ratio.
## quadrol is to oxyethane molar yield 77%.
Embodiment 13, a kind of experiment of the synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia five.
Experimental technique is with embodiment 4, and wherein, catalyzer composition sees the following form:
Analytical results sees the following form:
# disregards moisture, is only quadrol and thanomin relative mass ratio.
## quadrol is to oxyethane molar yield 62%.
Embodiment 14, a kind of experiment of the synthetic method with oxyethane and the direct synthesis of ethylenediamine of ammonia six.
Experimental technique is with embodiment 4, and wherein, catalyzer composition sees the following form:
Move after 240 hours, quadrol drops to 73% to oxyethane molar yield, uses steam: air=8: 1(m/m) gas mixture activating and regenerating, 480～500 ℃ of regeneration temperatures, recovery time 6h.
Analytical results sees the following form:
# disregards moisture, is only quadrol and thanomin relative mass ratio.
## quadrol, to oxyethane molar yield 79.6%, does not almost decline.
Claims (8)
1. by a synthetic method for oxyethane and the direct synthesis of ethylenediamine of ammonia, it is characterized in that, its step is as follows:
(1) in fluidized-bed reactor, load fluid catalyst, by oxyethane, ammonia, hydrogen with from the complicated polymer of high boiling material thanomin and quadrol at the bottom of native system rectifying still, mix, under 370～480 ℃ of temperature, pressure 0.03～2.5MPa condition, generate and take quadrol as the main mixture containing thanomin and many ethyleneamineses; Wherein, oxyethane: ammonia: the mass ratio of hydrogen is 1: 2～100: 0.1～100, at the bottom of the rectifying still that system is applied mechanically, high boiling material amount is 0～30% of oxyethane quality;
Described fluid catalyst is comprised of the material of following mass percent:
NiO 0.5～12%； CoO 0～10%；
Fe
2O
3 0～10%； Al
2O
3 10～70%；
SiO
2 10～60%；
Described fluid catalyst is 20-120 object microballoon;
(2) mixture directly enters fixed-bed reactor again, loads fixed bed catalyst in fixed bed, under 370～480 ℃ of temperature, pressure 0.03～2.5MPa condition, the further ammonia solution of non-quadrol material in mixture is become to quadrol, and the many ethyleneamineses of by-product; Excess of ammonia and hydrogen return to fluidized-bed by compressor and apply mechanically; The high boiling substance of by-product returns to fluidized-bed and applies mechanically, or as epoxy curing agent;
Described fixed bed catalyst is comprised of the material of following mass percent:
NiO 0.5～10% ； CoO 0～5%；
Fe
2O
3 0～10% ； Al
2O
3 20～70%；
H-mordenite, HZSM-5 molecular sieve or other crystal type molecular sieve 10～60%;
Described fixed bed catalyst is particulate state.
2. synthetic method according to claim 1, is characterized in that: described fluidized-bed reactor is shelf fluidized bed, the free style fluidized-bed that promotes tubular type fluidized-bed or built-in cyclonic separator; Described fixed bed is calandria type fixed bed or stacked fixed bed.
3. synthetic method according to claim 1, is characterized in that: described fluidized-bed and fixed bed series connection.
4. synthetic method according to claim 1, is characterized in that: in step (1), and oxyethane: ammonia: the mass ratio of hydrogen is 1: 25～30: 1～10; Fluidized-bed temperature is 400～450 ℃, and pressure is 0.04～1.0 MPa; In step (2), fixed bed temperature is 410～430 ℃, and pressure is 0.04～1.0MPa.
5. synthetic method according to claim 1, is characterized in that: in step (1), described fluid catalyst is comprised of the material of following mass percent:
NiO 4～8%； CoO 2～5%；
Fe
2O
3 2～5%； Al
2O
3 40～60%；
SiO
2 30～50%。
6. synthetic method according to claim 1, is characterized in that: in step (2), described fixed bed catalyst is comprised of the material of following mass percent:
NiO 2～5%； CoO 0.5～1%；
Fe
2O
3 0.5～2%； Al
2O
3 40～60%；
H-mordenite, HZSM-5 molecular sieve or other crystal type molecular sieve 35～55%.
7. according to the synthetic method described in claim 1 or 5 or 6, it is characterized in that: described nickel oxide comes from soluble nickel salt; Cobalt oxide comes from solubility cobalt salt; Ferric oxide comes from soluble ferric iron salt; Aluminum oxide comes from Tai-Ace S 150, aluminum chloride, W 4600, pseudo-boehmite or aluminum isopropylate; Silicon oxide comes from ammonia silicon sol or acidic silicasol; H-mordenite silica alumina ratio 18～28; The silica alumina ratio of HZSM-5 molecular sieve is 15～80.
8. synthetic method according to claim 7, is characterized in that: described nickel oxide comes from nickelous nitrate, single nickel salt, nickelous chloride or nickel acetate; Cobalt oxide comes from Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, rose vitriol or cobalt chloride; Ferric oxide comes from iron nitrate, ferrous sulfate or iron(ic) chloride; The silica alumina ratio of h-mordenite is 18～22; The silica alumina ratio of HZSM-5 molecular sieve is 20～50.
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| CN113831250B (en) * | 2020-06-23 | 2024-05-03 | 中国科学院过程工程研究所 | Method, device and catalyst for preparing 1, 2-butanediamine |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400539A (en) * | 1981-09-30 | 1983-08-23 | Union Carbide Corporation | Process for the manufacture of ethylenediamine |
| CN1962058A (en) * | 2006-12-19 | 2007-05-16 | 西安近代化学研究所 | Catalyst for gas phase synthesis of ethylenediamine and preparation method thereof |
| CN101622221A (en) * | 2007-03-01 | 2010-01-06 | 巴斯夫欧洲公司 | Method for producing ethylenediamine |
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2012
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4400539A (en) * | 1981-09-30 | 1983-08-23 | Union Carbide Corporation | Process for the manufacture of ethylenediamine |
| CN1962058A (en) * | 2006-12-19 | 2007-05-16 | 西安近代化学研究所 | Catalyst for gas phase synthesis of ethylenediamine and preparation method thereof |
| CN101622221A (en) * | 2007-03-01 | 2010-01-06 | 巴斯夫欧洲公司 | Method for producing ethylenediamine |
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