CN101733130A - Amorphous copper catalyst and preparation method and application thereof - Google Patents
Amorphous copper catalyst and preparation method and application thereof Download PDFInfo
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- CN101733130A CN101733130A CN 200810226922 CN200810226922A CN101733130A CN 101733130 A CN101733130 A CN 101733130A CN 200810226922 CN200810226922 CN 200810226922 CN 200810226922 A CN200810226922 A CN 200810226922A CN 101733130 A CN101733130 A CN 101733130A
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Abstract
The invention relates to an amorphous copper catalyst and a preparation method and application thereof. The preparation method comprises the following steps: heating copper, aluminum, and an alloy consisting of a transition metal M and aluminum to melt; rapidly cooling and curing the melts; and performing extraction treatment on the cured alloy by using alkali solution so as to extract most aluminum to obtain the catalyst. The catalyst prepared by the method has high catalytic activity and stability and excellent abrasion resistance, and can be applied to catalytic dehydrogenation oxidation reaction of diethanol amine.
Description
Technical field
The present invention relates to a kind of amorphous copper catalyst and its production and application.More particularly, the present invention relates to a kind of amorphous copper catalyst and preparation method thereof and the application of this catalyst in the diethanol amine catalytic dehydrogenation processes.
Background technology
Lei Nitong is a kind of typical solid dehydrogenation; it adopts following method preparation usually: the molten alloy of copper and aluminium composition is poured in the mold; cooling is also solidified; then the alloy block that will generate is removed al composition with leachings such as NaOH thereafter with jaw crusher or ball mill crushing granulating or powder.When the raney copper catalyst of this method preparation is used for dehydrogenation reaction, can not demonstrate gratifying catalytic activity.
U.S. Pat 5367112 discloses with the dehydrogenation of thunder Buddhist nun copper catalysis primary alconol and has prepared the method for aminocarboxylate, and discloses the active and stable method that improves raney copper catalyst by metals such as interpolation chromium, titanium, niobium, tantalum, zirconium, vanadium, molybdenum, manganese, tungsten.The catalyst amount of this method is bigger, and the stability of catalyst and activity are all unsatisfactory.
Because the fast development of amorphous state technology and amorphous nickel alloy catalyst are in industrial large-scale application, amorphous copper catalyst with similar structures also will have a lot of purposes as a kind of new catalytic material at chemical field very much, and will be higher than the activity and the stability of traditional Lei Nitong or skeleton copper as dehydrogenation or oxidation catalyst.
Chinese patent CN200710107859.2 discloses a kind of preparation method of carboxylate, this method with the modified amorphous copper catalyst with contain the alkaline mixt haptoreaction of primary alconol.Amorphous copper catalyst in this method is by the preparation of rapid quench method, and one or more mixtures that add especially in metallic element, rare earth element and nonmetalloid chromium, titanium, niobium, tantalum, zirconium, vanadium, molybdenum, silicon, manganese, tungsten, cobalt, nickel, bismuth, iron, magnesium, gallium, zinc, tin, antimony, lead, germanium, boron, carbon, nitrogen, phosphorus, lanthanum, cerium, samarium, an ancient unit of weight equal to 20 or 24 *taels of silver carry out modification to the amorphous copper catalyst.This catalyst still has the following disadvantages: (1) catalyst activity and stability are also undesirable; (2) component skewness in the catalyst; (3) be difficult to accurately control the chemical composition of catalyst; (4) the energy consumption height of preparation process.
Copper-based catalysts can be used for the reaction of catalysis diethanol amine dehydrogenation oxidation, product-Iminodiacetate (IDA) is the very wide organic intermediate of a kind of application, for example can be used as broad-spectrum chelating agent and as the raw material of chelating ion exchange resin, demand is very big on synthesizing glyphosate especially.The Iminodiacetate production method is a lot, and wherein diethanol amine (DEA) catalytic dehydrogenation method generation iminodiacetic acid cost is low, pollution is little, yield is high, also is the typical method of industrial production agricultural chemicals glyphosate.
Summary of the invention
The technical problem to be solved in the present invention provides a kind of preparation method of amorphous copper catalyst, and this method can make catalyst have higher catalytic activity and stability.The present invention also provides resulting catalyst of this method and the application of this catalyst in the reaction of diethanol amine dehydrogenation oxidation.
A kind of preparation method of amorphous copper catalyst, comprise: with the alloy heating and melting of copper, aluminium and transition metal M and aluminium composition, cooldown rate with 〉=1000 ℃/S is solidified fused mass, with aqueous slkali the alloy that solidifies is carried out the extracting processing and obtains catalyst to extract most aluminium out; Said transition metal M is selected from one or more in I B, II B, IIIB, IVB, VIB, VIIB and the VIII family metal.
Transition metal M is preferably one or more in molybdenum, tungsten, cobalt, cerium, titanium, zirconium, chromium, manganese, iron, platinum, ruthenium and the palladium.
Transition metal M is molybdenum more preferably, is benchmark with the Mo/A1 alloy, and the weight percentage of molybdenum is 0.5～15%.
Transition metal M is tungsten more preferably, is benchmark with the W/Al alloy, and the weight percentage of tungsten is 0.5～70%.
Weight ratio between copper, aluminium and the transition metal M is 5～100: 5～100: 1; Preferred 10～60: 10～60: 1.
Described alkali extractive process is: the alloy that solidifies is under agitation added in the alkali lye that has been heated to extraction temperature, aluminium and alkali lye in the alloy are fully reacted, obtain the black solid catalyst, extraction temperature is 10～100 ℃, preferred 40～90 ℃; Alkali concn is 2～40wt%, preferred 10～20wt%; The extracting time is 5～600min, preferred 30～120min; The alloying pellet size is 4～400 orders, preferred 80～200 orders; In copper in the alloy, with the weight ratio of alkali be 1: 1～10, preferred 1: 1.5～4.After the alkali extracting, catalyst is washed with distilled water to neutral back with the ethanol washing and be kept in the ethanol, is preferably under the condition of indifferent gas or hydrogen shield to preserve.
Described alkali is solubility highly basic, as alkali metal hydroxide and/or alkaline earth metal hydroxide, can be NaOH, KOH, Ca (OH)
2, Ba (OH)
2In a kind of, wherein preferred NaOH and/or KOH.
In the method provided by the present invention, can adopt atwirl single roller or two roller cooling molten metal, also can adopt the quick cool metal of mode at spray atomization and deposition more than 1000 ℃.
The present invention also provides the catalyst that obtains with said method, this catalyst is made up of the copper of 30～95wt%, aluminium and at least a transition metal M that is selected from period of element Table I B, II B, IIIB, IVB, VIB, VIIB or the VIII family of 0.5～30wt%, and copper mainly exists with amorphous state and nanocrystal metallic state form.
Described catalyst preferably includes the copper of 50～95wt% and the aluminium of 0.5～30wt%, more preferably comprises the copper of 60～90wt% and the aluminium of 5～20wt%.
Described transition metal M is preferably one or more in molybdenum, tungsten, cobalt, cerium, titanium, zirconium, chromium, manganese, iron, platinum, ruthenium and the palladium, more preferably one or more in molybdenum, tungsten, cobalt, platinum, manganese and the iron.
The present invention also provides above-mentioned Application of Catalyst, and described catalyst is used for the reaction of catalysis diethanol amine dehydrogenation oxidation.
In the above-mentioned application process, the ratio of reaction pressure, reaction temperature and diethanol amine and alkali metal hydroxide all can realize in the scope of prior art instruction.For catalyst of the present invention, reaction temperature is more suitable between 160～170 ℃.In the above-mentioned application process, suitable catalyst amount is 2.5～15wt% (is benchmark with the diethanol amine), is between 2.5～5.5wt% the time at catalyst amount particularly, and catalytic dehydrogenating reaction still can achieve satisfactory results.In the described application, reactor types can adopt suspended-bed reactor or fixed bed reactors.
Compared with prior art, the present invention has the following advantages:
(1) preparation process of amorphous copper catalyst and condition are most important for catalyst performance.In the prior art, the raw material of preparation amorphous copper is a metal, with the whole fusions of these metals is very difficult, when particularly preparation contains the catalyst of high-melting-point auxiliary agents such as molybdenum, tungsten, must be heated to more than 3000 ℃, this just makes copper be in the condition of high temperature for a long time, and catalyst performance is brought very adverse effect, has also inevitably increased energy consumption simultaneously.In the prior art, the chemical composition of catalyst can not accurately be controlled, and transition metal auxiliary agent actual content always is lower than amount of calculation, and this transition metal auxiliary agent that some is described can not enter catalyst.In addition, to distribute be uneven to the component of the prepared copper catalyst of prior art.The present invention adopts the method for transition metal alloy and copper fusion, just can form more equally distributed Mo-Cu, Mo-Cu-Al alloy structure when temperature is lower than 1500 ℃, makes metallographic structure fine and close more, and bigger specific area and high mechanical strength are arranged after the activation; The transition metal auxiliary agent more is dispersed in the catalyst.In addition, method of the present invention has reduced smelting temperature, avoided copper far above the temperature of the copper fusing point boiling point of copper (even reach) contingent chemical reaction down, as oxidation reaction etc., reduced the catalyst activity adverse effect, also reduced simultaneously fused solution is carried out the initial temperature that chilling solidifies.The amorphous copper catalyst of the present invention that comprehensively makes of above factor has higher catalytic activity and longer service life.
(2) the present invention has also improved the one-tenth band rate of amorphous alloy, has reduced the catalyst cost.
(3) amorphous copper catalyst provided by the present invention is extremely effective to dehydrogenation reaction, diethanol amine catalytic dehydrogenation oxidation reaction especially, and its active and stability obviously improves, and operational stability and production efficiency also increase substantially.
The specific embodiment
Embodiment 1～5 is used to illustrate Preparation of Catalyst, and embodiment 6～10 is used to illustrate catalysis diethanol amine dehydrogenation oxidation reaction result.Subscript in embodiment and the form is represented the weight percentage of metal.
Embodiment 1
With 1.5kg copper, 1.0kg aluminium and 0.5kg Mo
10Al
90Alloy joins in the graphite crucible, it is heated to fusion in coreless induction furnace, to be sprayed onto a rotating speed from the crucible nozzle be 600 to change on～1000/ minute the copper roller to this fused solution then, logical cooling water in the copper roller, alloy liquid cools off the back fast with the cooling velocity of 1000 ℃/s and throws away along copper roller tangent line, form the flakey band, the flakey band is below 70 microns through being ground to particle diameter, obtains foundry alloy.The 50g foundry alloy is slowly joined in the there-necked flask that fills 500 gram 20wt% sodium hydrate aqueous solutions, control its temperature and be 80 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, with 100 ℃ distilled water wash to the pH value be 7.Prepared catalyst is numbered catalyst-1, and the composition of catalyst-1 sees Table 1.
Embodiment 2
With 1.5kg copper, 1.0kg aluminium and 0.5kg Mo
5Al
95Alloy joins in the graphite crucible, it is heated to fusion in coreless induction furnace, to be sprayed onto a rotating speed from the crucible nozzle be on 900 rev/mins the copper roller to this fused solution then, logical cooling water in the copper roller, alloy liquid cools off the back fast with the cooling velocity of 1000 ℃/s and throws away along copper roller tangent line, form the flakey band, the flakey band is below 70 microns through being ground to particle diameter, obtains foundry alloy.The 50g foundry alloy is slowly joined in the there-necked flask that fills 500 gram 20wt% sodium hydrate aqueous solutions, control its temperature and be 80 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, with 80 ℃ distilled water wash to the pH value be 7.Prepared catalyst is numbered catalyst-2, and the composition of catalyst-2 sees Table 1.
Embodiment 3
With 1.5kg copper, 1.0kg aluminium and 0.5kg W
10Al
90Alloy joins in the graphite crucible, and it is heated to fusion in coreless induction furnace, and it is on 900 rev/mins the copper roller that this fused solution is sprayed onto a rotating speed from the crucible nozzle, logical cooling water in the copper roller, and alloy liquid is with 10
5℃/cooling velocity of s cools off the back fast and throws away along copper roller tangent line, forms the flakey band, and the flakey band is below 70 microns through being ground to particle diameter, obtains foundry alloy.The 50g foundry alloy is slowly joined in the there-necked flask that fills 500 gram 20wt% sodium hydrate aqueous solutions, control its temperature and be 80 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, with 80 ℃ distilled water wash to the pH value be 7.Prepared catalyst is numbered catalyst-3, and the composition of catalyst-3 sees Table 1.
Embodiment 4
With 1.5kg copper, 1.0kg aluminium and 0.5kg W
20Al
80Alloy joins in the graphite crucible, it is heated to fusion in coreless induction furnace, it is on 900 rev/mins the copper roller that this fused solution is sprayed onto a rotating speed from the crucible nozzle, logical cooling water in the copper roller, alloy liquid cools off the back fast with the cooling velocity of 1000 ℃/s and throws away along copper roller tangent line, form the flakey band, the flakey band is below 70 microns through being ground to particle diameter, obtains foundry alloy.The 50g foundry alloy is slowly joined in the there-necked flask that fills 500 gram 20wt% sodium hydrate aqueous solutions, control its temperature and be 80 ℃ and constant temperature and stirred 1 hour.After stopping heating and stirring, decantation liquid, with 80 ℃ distilled water wash to the pH value be 7.Prepared catalyst is numbered catalyst-4, and the composition of catalyst-4 sees Table 1.
Embodiment 5
With 1.5kg copper, 1.0kg aluminium and 0.5kg Mo
5Al
95Alloy joins in the graphite crucible, is heated to molten state in electric arc induction furnace He under the hydrogen shield, stirs and makes it even.Use high pressure hydrogen that alloy liquid stream is atomized into a large amount of tiny molten drops, these molten drops are cooling rapidly under the effect of high velocity air, obtains the catalyst precursor particles of 100～300 micron granularities.Under hydrogen atmosphere, the NaOH solution of placing a certain amount of 25wt% concentration in advance is heated to 55 ℃ in a special container, slowly to wherein adding alloying pellet.The interpolation alloy finishes, and back maintenance reaction condition is constant to continue 90 minutes, so that the most of aluminium suction filtration in the alloy is gone out.Spend then alloying pellet that deionised water handled to the pH value near or reach 7.Prepared catalyst is numbered catalyst-5, and the composition of catalyst-5 sees Table 1.
Comparative Examples 1
Adopt the method for Chinese invention patent 200710107859.2, according to ratio (1.5kg copper, 1.45kg aluminium and 0.05kgMo) the preparation catalyst of embodiment 1, catalyst is numbered A-1, and the composition of catalyst A-1 sees Table 1.
Embodiment 6～10
In the 0.5L of belt stirrer and temperature automatically controlled heating jacket autoclave, the NaOH solution that adds 430g 30wt% adds the 4.5g catalyst, adds the diethanol amine that 160g concentration is 60wt% then, with nitrogen replacement gas reactor 3 times, then with nitrogen pressure to 1MPa.Stir, heat temperature raising is also controlled reaction temperature between 160～170 ℃.In course of reaction, the hydrogen that the emptying reaction produces keeps about still internal pressure 1MPa.After no longer including the hydrogen generation, be cooled to 100 ℃, the natural subsidence separating catalyst.Analyze the content of the amino oxalic acid in the material Central Asia, calculated yield.Reaction result sees Table 2.
Comparative Examples 2
This Comparative Examples is used to illustrate the reaction result of catalyst A-1.Except that catalyst amount was 9g, reaction condition was with embodiment 6～10, and reaction result sees Table 2.
Table 1
| Embodiment | The catalyst numbering | Catalyst is formed |
| 12345 Comparative Examples 1 | Catalyst-1 catalyst-2 catalyst-3 catalyst-4 catalyst-5 A-1 | ??Cu 85Mo 2.8Al 12.2??Cu 88Mo 1.5Al 10.5??Cu 79W 2.6Al 18.4??Cu 82.5W 5.5Al 12??Cu 88.5Mo 1.5Al 10??Cu 88.6Mo 1.4Al 10 |
Table 2
| Embodiment | The catalyst numbering | Reaction time, h | The iminodiacetic acid yield, % |
| 6789 10 Comparative Examples 2 | Catalyst-1 catalyst-2 catalyst-3 catalyst-4 catalyst-5 A-1 | ??2.0??2.0??2.0??2.0??2.0??3.2 | ??98.4??97.2??98.2??98.3??97.6??92.5 |
Claims (16)
1. the preparation method of an amorphous copper catalyst, comprise: the alloy of copper, aluminium and transition metal M and aluminium composition is heated to fusion, cooldown rate with 〉=1000 ℃/S is solidified fused mass, with aqueous slkali the alloy that solidifies is carried out the extracting processing and obtains catalyst to extract most aluminium out; Said transition metal M is selected from one or more in IB, IIB, IIIB, IVB, VIB, VIIB and the VIII family metal.
2. in accordance with the method for claim 1, it is characterized in that transition metal M is one or more in molybdenum, tungsten, cobalt, cerium, titanium, zirconium, chromium, manganese, iron, platinum, ruthenium and the palladium.
3. in accordance with the method for claim 2, it is characterized in that transition metal M is a molybdenum, is benchmark with the Mo/Al alloy, and the weight percentage of molybdenum is 0.5～15%.
4. in accordance with the method for claim 2, it is characterized in that transition metal M is a tungsten, is benchmark with the W/Al alloy, and the weight percentage of tungsten is 0.5～70%.
5. in accordance with the method for claim 1, it is characterized in that the weight ratio between copper, aluminium and the transition metal M is 5～100: 5～100: 1.
6. in accordance with the method for claim 5, it is characterized in that the weight ratio between copper, aluminium and the transition metal M is 10～60: 10～60: 1.
7. in accordance with the method for claim 1, it is characterized in that when with aqueous slkali the alloy that solidifies being carried out the extracting processing, the granular size of solidified alloy is 4～400 orders.
8. in accordance with the method for claim 7, it is characterized in that the granular size of solidified alloy is 80～200 orders.
9. in accordance with the method for claim 1, it is characterized in that described alkali is alkali metal hydroxide and/or alkaline earth metal hydroxide.
10. in accordance with the method for claim 1, it is characterized in that, adopt atwirl single roller or two roller cooling molten metal, or with the quick cool metal of the mode of spray atomization and deposition.
11. the catalyst of the described method preparation of claim 1, it is characterized in that, this catalyst is made up of the copper of 30～95wt%, aluminium and at least a transition metal M that is selected from periodic table of elements IB, IIB, IIIB, IVB, VIB, VIIB or the VIII family of 0.5～30wt%, and copper mainly exists with amorphous state and nanocrystal metallic state form.
12., it is characterized in that described transition metal M is one or more in molybdenum, tungsten, cobalt, cerium, titanium, zirconium, chromium, manganese, iron, platinum, ruthenium and the palladium according to the described catalyst of claim 11.
13. the described Application of Catalyst of claim 11 is used for the reaction of catalysis diethanol amine dehydrogenation oxidation with described catalyst.
14., it is characterized in that reaction temperature is between 160～170 ℃ according to the described application of claim 13.
15., it is characterized in that according to the described application of claim 13, with the diethanol amine benchmark, catalyst amount is 2.5～15wt%.
16., it is characterized in that according to the described application of claim 13, with the diethanol amine benchmark, catalyst amount is 2.5～5.5wt%.
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Cited By (4)
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| CN103801303A (en) * | 2014-02-20 | 2014-05-21 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate, as well as preparation method and application of catalyst |
| CN106892496A (en) * | 2017-03-31 | 2017-06-27 | 中国科学院金属研究所 | Application of the cu-base amorphous alloy state alloy as catalysis material in the treatment of waste water |
| CN112316948A (en) * | 2020-11-10 | 2021-02-05 | 大唐国际化工技术研究院有限公司 | Method for preparing amorphous catalyst for methanation |
| CN115722184A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Adsorption desulfurizing agent and preparation method and application thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101134731A (en) * | 2007-05-21 | 2008-03-05 | 江苏扬农化工股份有限公司 | Method for preparing carboxylate by dehydrogenating carbinol with modified amorphous copper metal catalyst |
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2008
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103801303A (en) * | 2014-02-20 | 2014-05-21 | 中国科学院山西煤炭化学研究所 | Catalyst for synthesizing methyl glycolate by hydrogenating dimethyl oxalate, as well as preparation method and application of catalyst |
| CN103801303B (en) * | 2014-02-20 | 2016-01-20 | 中国科学院山西煤炭化学研究所 | The catalyst of Hydrogenation of Dimethyl Oxalate synthesizing methyl glycolate and method for making and application |
| CN106892496A (en) * | 2017-03-31 | 2017-06-27 | 中国科学院金属研究所 | Application of the cu-base amorphous alloy state alloy as catalysis material in the treatment of waste water |
| CN112316948A (en) * | 2020-11-10 | 2021-02-05 | 大唐国际化工技术研究院有限公司 | Method for preparing amorphous catalyst for methanation |
| CN115722184A (en) * | 2021-08-31 | 2023-03-03 | 中国石油化工股份有限公司 | Adsorption desulfurizing agent and preparation method and application thereof |
| CN115722184B (en) * | 2021-08-31 | 2024-04-02 | 中国石油化工股份有限公司 | Adsorption desulfurizing agent and preparation method and application thereof |
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