CN1491744A - Process for preparing carbon nano fiber knitting macro-particles containing high active nickel catalyst - Google Patents
Process for preparing carbon nano fiber knitting macro-particles containing high active nickel catalyst Download PDFInfo
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- CN1491744A CN1491744A CNA031441963A CN03144196A CN1491744A CN 1491744 A CN1491744 A CN 1491744A CN A031441963 A CNA031441963 A CN A031441963A CN 03144196 A CN03144196 A CN 03144196A CN 1491744 A CN1491744 A CN 1491744A
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Abstract
The present invention discloses a preparation process of woven nano carbon fiber macro particle containing high activity nickel catalyst for industrial application. The preparation process includes the following steps: preparing nitrate solution with Ni, Cu and Al ions of 0.4-1 M concentration; heating the solution to 55-65 deg.c and dropping 1 M concentration Na2CO3 solution; filtering and washing the precipitate with deionized water in 55-65 deg.c for 2-8 times; drying the precipitate at 120 deg.c for 5 hr; crushing the precipitate, incinerating at 350-550 deg.c and reduction in reactor; introducing methane for reaction at 450-750 deg.c. The particle thus obtained has high mechanical strength, high conducting capacity and excellent antioxidant ability.
Description
Technical field
The present invention relates to catalytic field, more particularly, relate to the preparation method that a kind of carbon nano-fiber weaves macroscopical porous particle.
Background technology
At catalytic field, traditional active carbon is widely used in the production of dyestuff, pigment and pharmaceutical intermediate as the carrier of noble metal catalyst (Pt, Pd and Rh etc.), in the liquid phase reactor of these strong mixings, and very easily efflorescence of active carbon, the noble metal of load is lost with material, thereby cause significant wastage.
Carbon nano-fiber and nanotube are novel material with carbon elements, mechanical strength is good, degree of graphitization is high, and conduction and oxidation resistance are good, have overcome the shortcoming of active carbon as carrier, it can with the metal generation strong interaction of load, make catalyst have high activity or high selectivity.In addition, to some gas, as NO, CO and organic matter, as alcohols, hydro carbons and phenols etc. suction-operated preferably, these material with carbon elements being arranged is hydrophobicity, can be used for adsorbing the organic matter in the industries generation waste water such as chemical industry, pharmacy.But the material of report use at present mostly is carbon nano-fiber or nanotube aggregated particle, yardstick is micron-sized, use in breadboard microreactor as catalyst carrier to be fine, but undersized particle causes easily and runs off and stop up reactor pipeline when using in industrial reactor.The Industrial Catalysis reactor all has certain requirement to the macro-size of catalyst granules, require catalyst granules at least at a hundreds of micron as the stirred tank batch reactor, fixed bed reactors then require particle at least more than 2.5-5.0mm, require catalyst that good individual particle intensity is arranged simultaneously, can stand the impact that strong mixing and high-pressure flow cause mutually.
The Hoogenraad of Holland and Jong etc. [Catal Rev-Sci Eng 42 (2000) 481] are because the catalyst activity that adopts is low; so must adopt the way that strengthens catalyst granules active component density and restriction carbon growing space; prepared macro-size and be the carbon nano-fiber aggregated particle about the hundreds of micron; its whole crushing strength is suitable with the general industrial catalyst; but original catalyst accounts for about 10wt% greatly in the aggregation; must remove before using, can cause very big infringement to granule strength like this.Muscovite Kuvshinov etc. [Carbon 37 (1999) 1239] have also prepared the aggregated particle of size about 1mm; but only reported their tear strength; up to now; can important indicator-individual particle mechanical strength that commercial Application to it does not have open report so far as yet, and that is to say does not have to such an extent that reach macroscopical carbon granule of industrial requirements.
Summary of the invention
The objective of the invention is in order to overcome the deficiencies in the prior art, a kind of preparation method that can satisfy the carbon nano-fiber braiding macroscopic particles that contains highly active ni catalysts of commercial Application is provided.
The present invention contains the preparation method of the carbon nano-fiber braiding macroscopic particles of highly active ni catalysts, is achieved by following technical proposals, comprises the steps:
(1) selects for use and contain Ni
2+, Cu
2+, Al
3+Nitrate solution, its concentration is 0.4～1M;
(2) above-mentioned solution is warming up to 55～65 ℃, dripping concentration is the Na of 1M
2CO
3Solution;
(3) with above-mentioned reacting liquid filtering;
(4) precipitation after the above-mentioned filtration is washed 2～8 times with 55～65 ℃ of deionized waters;
(5) be deposited in 120 ℃ of down dry 5h with above-mentioned;
(6) dried precipitation is ground, screening is the particle of 10～60 order sizes;
(7) above-mentioned particle is calcined and reduced in reactor at 350～550 ℃;
(8) in above-mentioned reactor, under 450～750 ℃, feed methane gas, react.
Described step (7) is reduced for using feeding hydrogen.Described step (8) feeds methane and the nitrogen mixture volume ratio is 2: 1 or pure methane gas.Described step (8) reaction time is relevant with catalyst and reaction condition, is generally 10-100h.
The carbon nano-fiber braiding macroscopic particles that uses the present invention to obtain, as Fig. 1 is its pore size distribution, its most probable pore size distribution appears at about 16.6-22.0nm, hole proportion less than 6nm is very little, the average pore size of whole particle is 11.2nm, total pore volume is 0.211ml/g, and the BET specific area is 71.7m
2/ g.Because the overwhelming majority is a mesopore in the particle, when it was used as carrier, the diffusion effect in the catalytic reaction just can effectively be weakened, thereby has improved the efficient of course of reaction.Fig. 2 be the carbon granule crushing strength and the crushing probability, can find, when pressure when 16kgf is following, the crushing probability is no more than 5%, and the crushing strength of most particles is at 16-25kgf, and average crushing strength is 20 ± 4kgf, suitable with the performance of most Industrial Catalysis agent carriers, as γ-Al
2O
3, be much better than active carbon.
Description of drawings
Fig. 1 is a carbon granule pore-size distribution of the present invention,
Fig. 2 is carbon granule crushing strength of the present invention and crushing probability.
The specific embodiment
Below in conjunction with embodiment the present invention is further described.
Get Ni
2+, Cu
2+, Al
3+The about 300ml of mixed nitrate solution, mol ratio is: Ni: Cu: Al=75: 2: 23, the metal ion total concentration was 1M; Be warming up to 55 ℃ in water bath with thermostatic control, dripping concentration is the Na of 1M
2CO
3The about 220ml of solution; Fully after the reaction above-mentioned reactant liquor is filtered; Precipitation after the filtration is washed 5 times with 65 ℃ of deionized waters; With the 120 ℃ of dry 5h down that are deposited in after the washing; Dried precipitation is ground, and screening obtains the particle of 10 order sizes; Above-mentioned particle is obtained mol ratio at 450 ℃ of calcining 10h is: Ni: Cu: Al=75: 2: 23 Ni-Cu/Al
2O
3Catalyst; Getting the above-mentioned catalyst granules of 100mg, to place an internal diameter be the horizontal tube reactor of 38mm, catalyst is used hydrogen reducing 4h down at 750 ℃ earlier, then under nitrogen protection, be cooled to 500 ℃, the feeding volume ratio is that 2: 1 methane and nitrogen mixture reacts, the gaseous mixture total flow is 100ml/min (STP); Reaction keeps about 60h.After reaction stopped, the carbon nanofibers grow amount was 135g carbon/g catalyst, generated the carbon granule smooth surface, and size has reached the requirement of industrial reactor.
Embodiment 2
Get Ni
2+, Cu
2+, Al
3+The about 300ml of mixed nitrate solution, mol ratio is: Ni: Cu: Al=75: 15: 10, the metal ion total concentration was 1M; Be warming up to 60 ℃ in water bath with thermostatic control, dripping concentration is the Na of 1M
2CO
3The about 170ml of solution; Fully after the reaction above-mentioned reactant liquor is filtered; Precipitation after the filtration is washed 3 times with 60 ℃ of deionized waters; With the 120 ℃ of dry 5h down that are deposited in after the washing; Dried precipitation is ground, and screening obtains the particle of 20-40 order size; It is Ni: Cu: Al=75 that above-mentioned particle is obtained mol ratio at 450 ℃ of calcining 10h: 15: 10 Ni-Cu/Al
2O
3Catalyst; Getting the above-mentioned catalyst granules of 100mg, to place an internal diameter be the horizontal tube reactor of 38mm, and catalyst use hydrogen reducing 2h down at 700 ℃ earlier, then is cooled to 600 ℃ under nitrogen protection, feeds pure methane and react, and flow is 68ml/min (STP); Reaction keeps 100h.After reaction stopped, the carbon nanofibers grow amount was 380g carbon/g catalyst, generated the carbon granule smooth surface, and size has reached the requirement of industrial reactor.
Embodiment 3
Get Ni
2+, Cu
2+, Al
3+The about 300ml of mixed nitrate solution, mol ratio is: Ni: Cu: Al=75: 30: 45, the metal ion total concentration was 0.5M; Be warming up to 65 ℃ in water bath with thermostatic control, dripping concentration is the Na of 1M
2CO
3The about 260ml of solution; Fully after the reaction above-mentioned reactant liquor is filtered; Precipitation after the filtration is washed 7 times with 55 ℃ of deionized waters; With the 120 ℃ of dry 5h down that are deposited in after the washing; Dried precipitation is ground, and screening obtains the particle of 10-20 order size; It is Ni: Cu: Al=75 that above-mentioned particle is obtained mol ratio at 450 ℃ of calcining 10h: 30: 45 Ni-Cu/Al
2O
3Catalyst; Getting the above-mentioned catalyst granules of 250mg, to place an internal diameter be the horizontal tube reactor of 38mm, and catalyst use hydrogen reducing 4h down at 750 ℃ earlier, then is cooled to 700 ℃ under nitrogen protection, feeds pure methane gas and react, and flow is 68ml/min (STP); Reaction keeps 25h.After reaction stopped, the carbon nanofibers grow amount was 120g carbon/g catalyst, generated the carbon granule smooth surface, and size has reached the requirement of industrial reactor.
Embodiment 4
Get Ni
2+, Cu
2+, Al
3+The about 300ml of mixed nitrate solution, mol ratio is: Ni: Cu: Al=75: 37.5: 37.5, the metal ion total concentration was 0.5M; Be warming up to 55 ℃ in water bath with thermostatic control, dripping concentration is the Na of 1M
2CO
3The about 250ml of solution; Fully after the reaction above-mentioned reactant liquor is filtered; Precipitation after the filtration is washed 8 times with 65 ℃ of deionized waters; With the 120 ℃ of dry 5h down that are deposited in after the washing; Dried precipitation is ground, and screening obtains the particle of 10-20 order size; It is Ni: Cu: Al=75 that above-mentioned particle is obtained mol ratio at 450 ℃ of calcining 10h: 37.5: 37.5 Ni-Cu/Al
2O
3Catalyst; Getting the above-mentioned catalyst granules of 100mg, to place an internal diameter be the horizontal tube reactor of 38mm, and catalyst use hydrogen reducing 4h down at 700 ℃ earlier, then is cooled to 740 ℃ under nitrogen protection, feeds pure methane and react, and total flow is 68ml/min (STP); Reaction keeps 18h.After reaction stopped, the carbon nanofibers grow amount was 150g carbon/g catalyst, generated the carbon granule smooth surface, and size has reached the requirement of industrial reactor.
Embodiment 5
Get Ni
2+, Cu
2+, Al
3+The about 300ml of mixed nitrate solution, mol ratio is: Ni: Cu: Al=75: 75: 75, the metal ion total concentration was 0.5M; Be warming up to 55 ℃ in water bath with thermostatic control, dripping concentration is the Na of 1M
2CO
3Solution 280ml; Fully after the reaction above-mentioned reactant liquor is filtered; Precipitation after the filtration is washed 8 times with 65 ℃ of deionized waters; With the 120 ℃ of dry 5h down that are deposited in after the washing; Dried precipitation is ground, and screening obtains the particle of 10-20 order size; It is Ni: Cu: Al=75 that above-mentioned particle is obtained mol ratio at 450 ℃ of calcining 10h: 75: 75 Ni-Cu/Al
2O
3Catalyst; Getting the above-mentioned catalyst granules of 100mg, to place an internal diameter be the horizontal tube reactor of 38mm, and catalyst use hydrogen reducing 4h down at 750 ℃ earlier, then is cooled to 500 ℃ under nitrogen protection, feeds pure methane gas and react, and flow is 68ml/min (STP); Reaction keeps 10h.After reaction stopped, the carbon nanofibers grow amount was 40g carbon/g catalyst, generated the carbon granule smooth surface, and size has reached the requirement of industrial reactor.
Embodiment 6
Get Ni
2+, Al
3+The about 300ml of mixed nitrate solution, mol ratio is: Ni: Al=1: 1, the metal ion total concentration is 1M; Be warming up to 55 ℃ in water bath with thermostatic control, dripping concentration is the Na of 1M
2CO
3Solution 220ml; Fully after the reaction above-mentioned reactant liquor is filtered; Precipitation after the filtration is washed 3 times with 65 ℃ of deionized waters; With the 120 ℃ of dry 5h down that are deposited in after the washing; Dried precipitation is ground, and screening obtains the particle of 10-20 order size; It is Ni: Al=1 that above-mentioned particle is obtained mol ratio at 450 ℃ of calcining 10h: 1 Ni/Al
2O
3Catalyst; Getting the above-mentioned catalyst granules of 100mg, to place an internal diameter be the horizontal tube reactor of 38mm, catalyst is used hydrogen reducing 2h down at 750 ℃ earlier, then under nitrogen protection, be cooled to 500 ℃, the feeding volume ratio is that 2: 1 methane and nitrogen mixture reacts, and the gaseous mixture total flow is 100ml/min (STP); Reaction keeps about 30h.After reaction stopped, the carbon nanofibers grow amount was 70g carbon/g catalyst, generated the carbon granule smooth surface, and size has reached the requirement of industrial reactor.
Embodiment 7
Get Ni
2+, Al
3+The about 300ml of mixed nitrate solution, mol ratio is: Ni: Al=3: 1, the metal ion total concentration is 1M; Be warming up to 55 ℃ in water bath with thermostatic control, dripping concentration is the Na of 1M
2CO
3The about 250ml of solution; Fully after the reaction above-mentioned reactant liquor is filtered; Precipitation after the filtration is washed 8 times with 65 ℃ of deionized waters; With the 120 ℃ of dry 5h down that are deposited in after the washing; Dried precipitation is ground, and screening obtains the particle of 10-20 order size; Above-mentioned particle is obtained mol ratio at 450 ℃ of calcining 10h is: Ni: Al=3: 1 Ni/Al
2O
3Catalyst; Getting the above-mentioned catalyst granules of 100mg, to place an internal diameter be the horizontal tube reactor of 38mm, catalyst is used hydrogen reducing 2h down at 750 ℃ earlier, then under nitrogen protection, be cooled to 500 ℃, the feeding volume ratio is that 2: 1 methane and nitrogen mixture reacts, and the gaseous mixture total flow is 100ml/min (STP); Reaction keeps 40h.After reaction stopped, the carbon nanofibers grow amount was 90g carbon/g catalyst, generated the carbon granule smooth surface, and size has reached the requirement of industrial reactor.
Get Ni
2+, Al
3+The about 300ml of mixed nitrate solution, mol ratio is: Ni: Al=9: 1, the metal ion total concentration is 1M; Be warming up to 55 ℃ in water bath with thermostatic control, dripping concentration is the Na of 1M
2CO
3The about 180ml of solution; Fully after the reaction above-mentioned reactant liquor is filtered; Precipitation after the filtration is washed 3 times with 65 ℃ of deionized waters; With the 120 ℃ of dry 5h down that are deposited in after the washing; Dried precipitation is ground, and screening obtains the particle of 20-40 order size; Above-mentioned particle is obtained mol ratio at 450 ℃ of calcining 10h is: Ni: Al=9: 1 Ni/Al
2O
3Catalyst; Getting the above-mentioned catalyst granules of 250mg, to place an internal diameter be the horizontal tube reactor of 38mm, catalyst is used hydrogen reducing 4h down at 750 ℃ earlier, then under nitrogen protection, be cooled to 500 ℃, the feeding volume ratio is that 2: 1 methane and nitrogen mixture reacts, and the gaseous mixture total flow is 100ml/min (STP); Reaction keeps 90h.After reaction stopped, the carbon nanofibers grow amount was 163g carbon/g catalyst, generated the carbon granule smooth surface, and size has reached the requirement of industrial reactor.
Claims (4)
1. a preparation method who contains the carbon nano-fiber braiding macroscopic particles of highly active ni catalysts is characterized in that, comprises the steps:
(1) selects for use and contain Ni
2+, Cu
2+, Al
3+Nitrate solution, its concentration is 0.4～1M;
(2) above-mentioned solution is warming up to 55～65 ℃, dripping concentration is the Na of 1M
2CO
3Solution;
(3) with above-mentioned reacting liquid filtering;
(4) precipitation after the above-mentioned filtration is washed 2～8 times with 55～65 ℃ of deionized waters;
(5) be deposited in 120 ℃ of down dry 5h with above-mentioned;
(6) dried precipitation is ground, screening is the particle of 10～60 order sizes;
(7) above-mentioned particle is calcined and reduced in reactor at 350～550 ℃;
(8) in above-mentioned reactor, under 450～750 ℃, feed methane gas, reaction keeps in the 70h.
2. the preparation method who contains the carbon nano-fiber braiding macroscopic particles of highly active ni catalysts according to claim 1 is characterized in that described step (7) is reduced for using feeding hydrogen.
3. the preparation method who contains the carbon nano-fiber braiding macroscopic particles of highly active ni catalysts according to claim 1 is characterized in that described step (8) feeds methane and the nitrogen mixture volume ratio is 2: 1.
4. the preparation method who contains the carbon nano-fiber braiding macroscopic particles of highly active ni catalysts according to claim 1 is characterized in that described step (8) reaction time is 10～100h.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431696C (en) * | 2007-06-06 | 2008-11-12 | 天津大学 | Method for preparing nickel nanometer line network particle catalyst |
| CN101462056B (en) * | 2009-01-13 | 2010-09-15 | 天津大学 | Method for preparing porous nickel metal integral type catalyst |
-
2003
- 2003-08-27 CN CNA031441963A patent/CN1491744A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100431696C (en) * | 2007-06-06 | 2008-11-12 | 天津大学 | Method for preparing nickel nanometer line network particle catalyst |
| CN101462056B (en) * | 2009-01-13 | 2010-09-15 | 天津大学 | Method for preparing porous nickel metal integral type catalyst |
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