CN101579633A - Skeletal copper catalyst and preparation method thereof - Google Patents
Skeletal copper catalyst and preparation method thereof Download PDFInfo
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- CN101579633A CN101579633A CNA2009101155935A CN200910115593A CN101579633A CN 101579633 A CN101579633 A CN 101579633A CN A2009101155935 A CNA2009101155935 A CN A2009101155935A CN 200910115593 A CN200910115593 A CN 200910115593A CN 101579633 A CN101579633 A CN 101579633A
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Abstract
The invention relates to a skeletal copper catalyst and a preparation method thereof. According to the weight percentage, the raw material formulation of the skeletal copper catalyst comprises the following components of: 45-65% of metal copper, 30-50% of metal aluminium, 0.5-3% of at least one out of metal scandium and neodymium; and 1.5-2% of at least one out of cobalt, platinum, palladium, nickel, tungsten and molybdenum. The preparation method comprises the following steps of: mixing all components by the formulation proportion, and sequentially heating the mixture by section, mixing the mixture uniformly and then suddenly cooling the mixture, thus preparing an alloy block at the normal temperature; crushing and screening the alloy block to prepare the skeletal copper alloyed powder; and further activating the alloyed powder to obtain the skeletal copper catalyst. The skeletal copper catalyst has excellent catalytic performance, good stability and long service life and can be used repeatedly.
Description
Technical field
The present invention relates to a kind of skeletal copper catalyst and preparation method thereof.
Background technology
Skeleton copper or Lei Nitong (Raney Cu) are a kind of metallic copper catalyst with spongy pore structure, and it is a copper-aluminium alloy powder before activation, and physics and chemical property are stable in normal environment, are exposed to mutability inactivation in air and the water for a long time; This catalyst is the reddish black irregular particle after activation, and very strong reproducibility is arranged, and is very unstable, meeting oxidation and spontaneous combustion in air.Skeleton copper is the good catalyst in some conversion process such as dehydrogenation, oxidation dehalogenation, desulfurization, have that catalytic activity is good, mechanical strength is high,, advantage such as thermal conductivity good insensitive to poisonous substance, but there is the unit consumption height, applies mechanically deficiencies such as lot number is few, thereby cause use cost higher.
In the prior art, one of important synthetic route of PMIDA is to be raw material with the diethanol amine, obtains iminodiacetic acid through the dehydrogenation oxidation reaction, again by the synthetic PMIDA of iminodiacetic acid.In this technology, the catalyst of dehydrogenation reaction is crucial.At present owing to be subjected to the restriction of catalyst, this technology suitability for industrialized production that still is unrealized.Application number is that Chinese invention patent application that " 200410014548.8 ", name are called " preparation technology of diethanol amine dehydrogenation oxidation method synthesizing glyphosate " discloses and uses the catalyst of sodium tungstate as dehydrogenation reaction, this catalyst can not be used by recovery set, and the dehydrogenation reaction yield is also only about 90%, the cost height is unsuitable for suitability for industrialized production.
Summary of the invention
Technical problem to be solved by this invention is to overcome the deficiencies in the prior art, and a kind of skeletal copper catalyst is provided, and it is excellent catalytic effect not only, and mechanical strength and Heat stability is good, long service life, and it is many to apply mechanically lot number, and use cost is low.
The present invention also will provide a kind of preparation method of above-mentioned skeletal copper catalyst.
In order to address the above problem, the present invention takes following technical scheme:
A kind of skeletal copper catalyst, by weight percentage, its composition of raw materials comprises following component:
1. metallic copper 45%-65%;
2. metallic aluminium 30%-50%;
3. at least a 0.5%-3% in metal scandium and the neodymium;
4. at least a 1.5-2% in cobalt, platinum, palladium, nickel, tungsten and the aluminium.
As the preferred embodiments of the invention: the composition of raw materials of skeletal copper catalyst comprises following component:
1. metallic copper 50%-60%;
2. metallic aluminium 35%-45%;
3. metal scandium and neodymium 0.5%-3%;
4. at least a 1.5-2% in cobalt, platinum, palladium, nickel, tungsten and the molybdenum.
Perhaps, the composition of raw materials of skeletal copper catalyst comprises following component:
1. metallic copper 50%-60%;
2. metallic aluminium 35%-48%;
3. metal scandium or neodymium 0.5%-3%;
4. at least a 1.5-2% in cobalt, platinum, palladium, nickel, tungsten and the molybdenum.
Another technical scheme that the present invention takes is: a kind of preparation method of above-mentioned skeletal copper catalyst comprises the steps:
(1) 3. 4. the part of the component of getting formula ratio in 2., the component of formula ratio reach component, place in the stove, and roasting to 750 ℃-850 ℃, and constant temperature stirred 1-2 hour under this temperature; Continue to be warming up to 1200 ℃-1400 ℃ then, roasting 1-2 hour, be warming up to 1700 ℃-1900 ℃ at last, roasting 1-2 hour, make metal liquid A;
(2), get remaining component and 2. 1. place in the stove with the component of formula ratio, be warming up to 900 ℃-1100 ℃, roasting 1-2 hour, continue to be warming up to 1300 ℃-1400 ℃, make metallic solution B;
(3), described metallic solution A and metallic solution B are mixed, be warming up to 1700 ℃-1900 ℃, constant temperature stirred 0.5-1 hour, made the mixed liquor quenching obtain alloy block then, this alloy block through pulverize, screening obtains the skeleton copper alloy powder;
(4), the described skeleton copper alloy powder of activation promptly obtains described skeletal copper catalyst.
As further embodiment of the present invention: concrete steps are in the step (4): be that the caustic solution of 2%-40% dissolves the metallic aluminium in the skeleton copper alloy powder and removes with mass percent concentration at first, described caustic solution consumption is 0.5-4 a times of skeleton copper alloy powder quality, solution temperature is 40 ℃-100 ℃, then, with the deoxidation deionized water wash to cleaning solution pH be 7-8, promptly obtain described skeletal copper catalyst.
The skeletal copper catalyst that as above makes can be kept in the sodium hydroxide solution of deionized water, absolute ethyl alcohol or 0.1mol/L.
Because the enforcement of above technical scheme, the present invention compared with prior art has following advantage:
The present invention introduces at least a in rare earth metal scandium and the neodymium in traditional skeletal copper catalyst, on the one hand, the crystal structure of scandium and neodymium is more stable, can improve the stability of skeletal copper catalyst, prolongs the service life of catalyst; On the other hand, the catalytic effect of catalyst strengthens, when the present invention is used for the diethanol amine dehydrogenation oxidation and prepares the reaction of iminodiacetic acid, the conversion ratio of diethanol amine is about 95-97%, can apply mechanically 35-40 criticizes, greatly reduce production cost, making diethanol amine is that the industrialization of the route of the synthetic PMIDA of raw material becomes possibility.
The specific embodiment
The present invention will be further described in detail below in conjunction with specific embodiment.
Embodiment 1
According to the skeletal copper catalyst of present embodiment, its raw material is 1000g altogether, and composition of raw materials is: copper 58%, aluminium 39.5%, scandium 0.25%, neodymium 0.25%, cobalt 0.5%, platinum 0.5%, palladium 0.5% and nickel 0.5%.
Skeletal copper catalyst prepares according to following steps:
Take by weighing aluminium flake 150g, cobalt, platinum, palladium, each 5g of nickel, each 2.5g of scandium and neodymium (1), earlier, mix when being placed in the intermediate frequency furnace roasting to 800 ℃, constant temperature stirred 1 hour, continued to be warming up to 1300 ℃ of constant temperature calcinings 1 hour, be warming up to 1800 ℃ of constant temperature calcinings at last 2 hours, and made metallic solution A.
(2), again take by weighing aluminium flake 245g and copper sheet 580g, roasting was 1 hour after mixing placed and is warming up to 1000 ℃ in the intermediate frequency furnace, made metallic solution B when continuing to be warming up to 1300 ℃.
(3), metallic solution A and metallic solution B are mixed, be warming up to 1800 ℃, constant temperature stirred 0.5 hour, with special quenching granulation this mixed liquor was made alloy block under the normal temperature, pulverized at last, sieved and obtain the skeleton copper alloy powder.
(4), the skeleton copper alloy powder that makes is put into the sodium hydroxide solution of 4000ml 10% (quality), be warming up to 65 ℃ of insulations 3 hours, with the deoxygenation deionized water wash to the pH value be 7-8, repetition of activation is operated once, makes the catalyst of present embodiment.
When the present embodiment catalyst was used for the diethanol amine dehydrogenation oxidation and prepares the reaction of iminodiacetic acid, the conversion ratio of diethanol amine can be applied mechanically 35-40 and criticize about 95-97%, and the wear rate of catalyst is 6.0-6.1.
Embodiment 2
According to the skeletal copper catalyst of present embodiment, its raw material is 1000g altogether, and composition of raw materials is: copper 60%, aluminium 37%, scandium 1.0%, cobalt 0.4%, platinum 0.4%, palladium 0.4%, nickel 0.4% and molybdenum 0.4%.
The skeletal copper catalyst of present embodiment can be with reference to the method preparation of embodiment, when it is used for the diethanol amine dehydrogenation oxidation and prepares the reaction of iminodiacetic acid, the conversion ratio of diethanol amine can be applied mechanically 33-37 and criticize about 94-96%, and the wear rate of catalyst is 5.9-6.1.
Embodiment 3
According to the skeletal copper catalyst of present embodiment, its raw material is 1000g altogether, and composition of raw materials is: copper 60%, aluminium 37%, neodymium 1.0%, cobalt 0.4%, platinum 0.4%, palladium 0.4%, nickel 0.4% and molybdenum 0.4%.
The skeletal copper catalyst of present embodiment can be with reference to the method preparation of embodiment, when it is used for the diethanol amine dehydrogenation oxidation and prepares the reaction of iminodiacetic acid, the conversion ratio of diethanol amine can be applied mechanically 34-38 and criticize about 94-96%, and the wear rate of catalyst is 5.8-6.0.
Embodiment 4
According to the skeletal copper catalyst of present embodiment, its raw material is 1000g altogether, and composition of raw materials is: copper 60%, aluminium 35%, neodymium 3%, cobalt 0.4%, platinum 0.4%, palladium 0.4%, nickel 0.4% and molybdenum 0.4%.
The skeletal copper catalyst of present embodiment can be with reference to the method preparation of embodiment, when it is used for the diethanol amine dehydrogenation oxidation and prepares the reaction of iminodiacetic acid, the conversion ratio of diethanol amine can be applied mechanically 33-37 and criticize about 93-94%, and the wear rate of catalyst is 5.8-6.0.
Comparative Examples
A kind of skeletal copper catalyst, its raw material be 1000g altogether, comprises copper 60%, aluminium 38%, and cobalt 0.4%, platinum 0.4%, palladium 0.4%, nickel 0.4% and molybdenum 0.4% make according to the preparation method of traditional skeletal copper catalyst.
When this catalyst was used for the diethanol amine dehydrogenation oxidation and prepares the reaction of iminodiacetic acid, the conversion ratio of diethanol amine can be applied mechanically 20-22 and criticize about 92%, and the wear rate of catalyst is below 5.0.
By comparing embodiment 1-4 and Comparative Examples as seen, skeletal copper catalyst of the present invention is used for the reaction that the diethanol amine dehydrogenation oxidation prepares iminodiacetic acid, shown more excellent catalytic performance, and, because the lot number that catalyst can be applied mechanically increases, significantly reduce production cost, be suitable for suitability for industrialized production.
Skeletal copper catalyst of the present invention is not limited to the above embodiments.All equivalences of doing according to spiritual essence of the present invention change or modify, and all should be encompassed in protection scope of the present invention.
Claims (6)
1, a kind of skeletal copper catalyst, by weight percentage, its composition of raw materials comprises following component:
1. metallic copper 45%-65%;
2. metallic aluminium 30%-50%;
3. at least a 0.5%-3% in metal scandium and the neodymium;
4. at least a 1.5-2% in cobalt, platinum, palladium, nickel, tungsten and the molybdenum.
2, a kind of skeletal copper catalyst according to claim 1, it is characterized in that: the composition of raw materials of skeletal copper catalyst comprises following component:
1. metallic copper 50%-60%;
2. metallic aluminium 35%-45%;
3. metal scandium and neodymium 0.5%-3%;
4. at least a 1.5-2% in cobalt, platinum, palladium, nickel, tungsten and the molybdenum.
3, a kind of skeletal copper catalyst according to claim 1, it is characterized in that: the composition of raw materials of skeletal copper catalyst comprises following component:
1. metallic copper 50%-60%;
2. metallic aluminium 35%-48%;
3. metal scandium or neodymium 0.5%-3%;
4. at least a 1.5-2% in cobalt, platinum, palladium, nickel, tungsten and the aluminium.
4, the preparation method of any described skeletal copper catalyst in a kind of claim 1 to 3 is characterized in that: comprise the steps:
(1) 3. 4. the part of the component of getting formula ratio in 2., the component of formula ratio reach component, place in the stove, and roasting to 750 ℃-850 ℃, and constant temperature stirred 1-2 hour under this temperature; Continue to be warming up to 1200-1400 ℃ then, roasting 1-2 hour, be warming up to 1700 ℃-1900 ℃ at last, roasting 1-2 hour, make metal liquid A;
(2), get remaining component and 2. 1. place in the stove with the component of formula ratio, be warming up to 900 ℃-1100 ℃, roasting 1-2 hour, continue to be warming up to 1300 ℃-1400 ℃, make metallic solution B;
(3), described metallic solution A and metallic solution B are mixed, be warming up to 1700 ℃-1900 ℃, constant temperature stirred 0.5-1 hour, made the mixed liquor quenching obtain alloy block, alloy block through pulverize, screening obtains the skeleton copper alloy powder;
(4), the described skeleton copper alloy powder of activation promptly gets described skeletal copper catalyst.
5, the preparation method of skeletal copper catalyst according to claim 4, it is characterized in that: concrete steps are in the step (4): be that the caustic solution of 2%-40% dissolves the metallic aluminium in the skeleton copper alloy powder and removes with mass percent concentration at first, described caustic solution consumption is 0.5-4 a times of skeleton copper alloy powder quality, solution temperature is 40 ℃-100 ℃, then, with the deoxidation deionized water wash to cleaning solution pH be 7-8, promptly obtain described skeletal copper catalyst.
6, any one skeletal copper catalyst is used for the purposes of catalysis diethanol amine dehydrogenation oxidation prepared in reaction iminodiacetic acid among a kind of claim 1-3.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2009101155935A CN101579633B (en) | 2009-06-23 | 2009-06-23 | Skeletal copper catalyst and preparation method thereof |
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| CN2009101155935A CN101579633B (en) | 2009-06-23 | 2009-06-23 | Skeletal copper catalyst and preparation method thereof |
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| CN101579633A true CN101579633A (en) | 2009-11-18 |
| CN101579633B CN101579633B (en) | 2011-01-05 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275250A (en) * | 2013-05-13 | 2013-09-04 | 太仓市方亮精细合金厂 | Metallocene metal alloy catalyst and preparation method thereof |
| CN106423185A (en) * | 2016-08-19 | 2017-02-22 | 万华化学集团股份有限公司 | Preparation method and application of coated skeleton Co catalyst |
| CN106946763A (en) * | 2017-04-26 | 2017-07-14 | 宿迁万康新材料有限公司 | Prepare method, catalyst of hexamethylene diamine piperidines and preparation method thereof |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292936A (en) * | 1993-04-12 | 1994-03-08 | Monsanto Company | Process to prepare amino carboxylic acid salts |
| CN1136979C (en) * | 2001-07-20 | 2004-02-04 | 中国石油化工股份有限公司 | Catalyst for preparing iminodiacetate |
| CN1187319C (en) * | 2001-07-20 | 2005-02-02 | 中国石油化工股份有限公司 | Diethanolamine dehydrogendting process of preparing imino diacetate |
-
2009
- 2009-06-23 CN CN2009101155935A patent/CN101579633B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103275250A (en) * | 2013-05-13 | 2013-09-04 | 太仓市方亮精细合金厂 | Metallocene metal alloy catalyst and preparation method thereof |
| CN103275250B (en) * | 2013-05-13 | 2016-08-10 | 太仓市方亮精细合金厂 | Metallocene metal alloy catalyst and preparation method thereof |
| CN106423185A (en) * | 2016-08-19 | 2017-02-22 | 万华化学集团股份有限公司 | Preparation method and application of coated skeleton Co catalyst |
| CN106423185B (en) * | 2016-08-19 | 2018-10-16 | 万华化学集团股份有限公司 | A kind of cladded type skeleton Co method for preparing catalyst and its application |
| CN106946763A (en) * | 2017-04-26 | 2017-07-14 | 宿迁万康新材料有限公司 | Prepare method, catalyst of hexamethylene diamine piperidines and preparation method thereof |
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| CN101579633B (en) | 2011-01-05 |
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