CN100431696C - Method for preparing nickel nanometer line network particle catalyst - Google Patents
Method for preparing nickel nanometer line network particle catalyst Download PDFInfo
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- CN100431696C CN100431696C CNB2007100575564A CN200710057556A CN100431696C CN 100431696 C CN100431696 C CN 100431696C CN B2007100575564 A CNB2007100575564 A CN B2007100575564A CN 200710057556 A CN200710057556 A CN 200710057556A CN 100431696 C CN100431696 C CN 100431696C
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Abstract
The invention relates to a nickel nanometer network grain accelerant. It is made in three dimensional structure, radius of the network hole 3-7nm KIT-6 as the template, adding nickel nitrate saturated solution, twisting, heating till complete water evaporation, repeatedly feeding nickel nitrate to the network hole, till the stuffing of the hole, then adding the template into the Muffle furnace, calcining in the air, cooling, exposing the grain particle into the H2 air flow, recovering under high temperature, cooling to normal temperature, keeping in the oxygen for a certain time, cleaning the template using NaOH solution or NH3. H2O solution, cleaning and drying to get the accelerant. The accelerant hole ratio is 90-99%, ratio surface being 9-12m2/g, active, stable, hard to deactivation, with good synthesis effect.
Description
Technical field
The present invention relates to a kind of preparation method of nanometer line network particle catalyst of nickel, belong to the nickel-metal catalyst preparing technical field.
Background technology
Along with the development of World Economics, the rare metal mineral resources are rare day by day, as rhodium, ruthenium, platinum, palladium etc.Because cheap and numerous reactions are had extraordinary catalytic action, nickel-metal catalyst more and more is subject to people's attention.Can have much with of the reaction of nickel metal as catalyst, mainly comprise the reaction of preparing synthetic gas by natural gas partial oxidation, the reaction of gas renormalizing preparing synthetic gas, methyl alcohol, alcohol steam reformed reaction, F-T synthetic reactions such as carbon monoxide and hydrogen synthesizing formaldehyde, methyl alcohol, methanol oxidation reaction, and multiple polymerisation.
Existing Raney nickel mainly contains granular pattern, support type and monolithic devices.Document (Applied Catalysis A:General, 2004,272:157) reported working load type Raney nickel, as Ni/Al
2O
3And Ni/TiO
2, the reaction result of catalyzing natural gas portion oxidation synthesis gas.When using fixed bed reactors, nickel catalyst carriedly under high-speed show very high activity, but inactivation very easily, and main cause is that carbon distribution has covered the supported catalyst activated centre.Document (Journal of Catalysis, 1994,146:1) reported the reaction result that uses the integral catalyst catalyzing natural gas portion oxidation synthesis gas of nickel coating.The integral catalyst of nickel coating has activity and the selectivity suitable with the rhodium integral catalyst, but very fast inactivation, main cause is the sintering or the loss of active component.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of nanometer line network particle catalyst of nickel.The nanometer line network particle catalyst porosity height of the prepared nickel of this method, specific area are big, active, good stability.
For achieving the above object, the present invention is realized by following technical proposals: a kind of preparation method of nanometer line network particle catalyst of nickel is characterized in that comprising following process:
1. be that the molecular sieve KIT-6 of 3～7nm is a template with three-dimensional cubic body structure, aperture, network hole, template is put into container, again the nickel nitrate saturated solution is slowly added the container that fills this molecular sieve template, the dripping quantity of solution reaches by the molecular sieve template and absorbs fully, after stirring, 20～100 ℃ of following heating molecular sieve KIT-6 templates, moisture is evaporated fully;
2. the process of repeating step 1 is filled up by nickel nitrate until the network hole of molecular sieve template;
3. the molecular sieve KIT-6 template of the network hole being filled up nickel nitrate adds in the Muffle furnace, is warming up to 400～900 ℃ with 1～20 ℃/minute speed from 20～30 ℃, calcines in air 3～12 hours.After being cooled to 20～30 ℃, it is 20～100ml/ minute hydrogen stream that the particulate material that obtains is placed flow velocity, is warming up to 500～900 ℃ with externally heated oven with 1～5 ℃/minute speed, and keeps 0.5～20 hour.Reducing to 20～30 ℃ then, is under 20～100ml/ minute the protection of Oxygen Flow, to keep 0.5～20 hour at flow velocity.Again with concentration be the sodium hydroxide solution of 0.1～10mol/L or concentration be 0.1～10mol/L ammonia spirit 20～90 ℃ of following dissolving molecular sieve KIT-6 templates, washing, after 40～120 ℃ of following dryings, obtain the nanometer line network particle catalyst that particle diameter is the nickel of 50～500 μ m.
The invention has the advantages that: the nanometer line network particle catalyst porosity of the prepared nickel of this method 90～99%, specific area reaches 9～12m
2/ gram, active, good stability, be difficult for inactivation, be easy to industrialization, be widely used, can be used for the reaction of catalyzing natural gas portion oxidation synthesis gas, also can be used for the reaction of catalyzing natural gas preparing synthetic gas by reforming, methyl alcohol, alcohol steam reformed reaction, F-T synthetic reactions such as carbon monoxide and hydrogen synthesizing formaldehyde, methyl alcohol, methanol oxidation reaction, and multiple polymerisation.
The specific embodiment
Example 1:
The P123 (poly-oxireme-poly-propylene oxide-poly-oxireme three block macromolecular surfactants) of 4.0 grams is dissolved in the distilled water of 144 grams, and adding 7.9 gram concentration is the hydrochloric acid of 35% (quality).Be to stir after 0.5 hour under 700 rev/mins the condition at 35 ℃, rotating speed, add 4.0 gram n-butanols at once.Continue to stir after 1.0 hours, add 8.6 gram ethyl orthosilicates at once.This solution is to stir 24 hours under 1400 rev/mins the condition at 35 ℃, rotating speed.Then, this solution is placed in the airtight polypropylene containers, left standstill under 100 ℃ 24 hours, obtain white depositions, need not wash, direct heat is filtered, the filter cake that obtains.100 ℃ of air dryings 24 hours, be that ethanol/hydrochloric acid mixed solution washing of 2: 1 obtains white particle with volume ratio.Put it into after the air dry in the Muffle furnace, be warming up to 550 ℃ with 10 ℃/minute speed from 20 ℃, calcining is 6 hours in air, thereby obtains the three-dimensional cubic body structure, aperture, network hole is KIT-6 molecular sieve 10.7 grams of 5.15nm.
Weighing 5 gram molecules sieve KIT-6 is placed in the container as the template agent.15 gram nickel nitrates are dissolved in the distilled water, are made into the saturated solution of nickel nitrate.The nickel nitrate saturated solution of 6ml preparation slowly is added drop-wise in the container, solution is absorbed fully by molecular sieve KIT-6.After stirring,, with the naked eye can be observed water vapour during beginning and distributed, when waiting until perusal, thought that moisture evaporates fully less than water vapour 70 ℃ of following heating molecular sieve KIT-6 templates.In container, drip 6ml nickel nitrate saturated solution again, stir, heat and evaporate moisture.Repeat said process 4 times, the network hole of molecular sieve template is filled up by nickel nitrate.The molecular sieve KIT-6 template of filling up nickel nitrate is put into Muffle furnace, be warming up to 550 ℃ with 10 ℃/minute speed from 20 ℃, calcining is 8 hours in air.After being cooled to 20 ℃, it is 30ml/ minute hydrogen stream that this particulate material is placed flow velocity, is warming up to 800 ℃ with externally heated oven with 5 ℃/minute speed, and keeps 2 hours.Reducing to 20 ℃ then, is to keep 1 hour in 30ml/ minute the Oxygen Flow at flow velocity.With concentration is the sodium hydroxide solution of 4.2mol/L, 90 ℃ of following dissolving molecular sieve KIT-6 templates, washing back 100 ℃ dry down, obtain particle diameter and be 100～120 μ m, porosity and be 95%, specific area is 9.8m
2The nanometer line network particle catalyst of the nickel of/gram.
Example 2:
The operating condition of present embodiment is identical with embodiment 1 with process, just change the technical process after the particulate material reduction, detailed process is as follows: be the ammonia spirit of 1.5mol/L with concentration, 30 ℃ of following dissolving molecular sieve KIT-6 templates, washing back 100 ℃ dry down, obtain particle diameter and be 95～110 μ m, porosity and be 97%, specific area is 10.2m
2The nanometer line network particle catalyst of the nickel of/gram.
Example 3:
The P123 (poly-oxireme-poly-propylene oxide-poly-oxireme three block macromolecular surfactants) of 2.0 grams is dissolved in the distilled water of 72 grams, and adding 3.6 gram concentration is the hydrochloric acid of 38% (quality).Be to stir after 0.5 hour under 700 rev/mins the condition at 35 ℃, rotating speed, add 2.0 gram n-butanols at once.Continue to stir after 1.0 hours, add 4.3 gram ethyl orthosilicates at once.This solution is to stir 24 hours under 1400 rev/mins the condition at 35 ℃, rotating speed.Then, this solution is placed in the airtight polypropylene containers, left standstill under 100 ℃ 24 hours, obtain white depositions, need not wash, direct heat is filtered, and obtains filter cake.100 ℃ of air dryings 24 hours, be that ethanol/hydrochloric acid mixed solution washing of 2.2: 1 obtains white particle with volume ratio.Put it into after the air dry in the Muffle furnace, be warming up to 540 ℃ with 5 ℃/minute speed from 25 ℃, calcining is 7 hours in air, obtains the three-dimensional cubic body structure, aperture, network hole is KIT-6 molecular sieve 5.2 grams of 5.2nm.
10 gram nickel nitrates are dissolved in the distilled water, are made into the saturated solution of nickel nitrate.3.5ml nickel nitrate saturated solution is slowly added in the container that 3 gram molecules sieve KIT-6 is housed, solution is absorbed fully by the molecular sieve template, after stirring, 90 ℃ of following heating molecular sieve KIT-6 templates, with the naked eye having can be observed water vapour during beginning distributes, by the time perusal thinks that moisture evaporates fully during less than water vapour.In container, drip 3.5ml nickel nitrate saturated solution again, stir, heat and evaporate moisture.Repeat said process 5 times, the network hole of molecular sieve template is filled up by nickel nitrate.The network hole is filled up the molecular sieve KIT-6 template of nickel nitrate and put into Muffle furnace, be warming up to 540 ℃ with 5 ℃/minute speed from 25 ℃, calcining is 10 hours in air.After being cooled to 25 ℃, it is 20ml/ minute hydrogen stream that this particulate material is placed flow velocity, is warming up to 850 ℃ with externally heated oven with 3 ℃/minute speed, and keeps 4 hours.Reducing to 25 ℃ then, is to keep 4 hours in 20ml/ minute the Oxygen Flow at flow velocity.With concentration is the sodium hydroxide solution of 3.5mol/L, 95 ℃ of following dissolving molecular sieve KIT-6 templates, washing back 100 ℃ dry down, obtain particle diameter and be 105～125 μ m, porosity and be 99%, specific area is 11m
2The nanometer line network particle catalyst of the nickel of/gram.
Example 4:
The operating condition of present embodiment is identical with embodiment 3 with process, just change the technical process after the particulate material reduction, detailed process is as follows: be the ammonia spirit of 1.3mol/L with concentration, 35 ℃ of following dissolving molecular sieve KIT-6 templates, washing back 100 ℃ dry down, obtain particle diameter and be 110～130 μ m, porosity and be 98%, specific area is 10m
2The nanometer line network particle catalyst of the nickel of/gram.
Claims (1)
1. the preparation method of the nanometer line network particle catalyst of a nickel is characterized in that comprising following process:
1). with three-dimensional cubic body structure, aperture, network hole is that the molecular sieve KIT-6 of 3～7nm is a template, template is put into container, again the nickel nitrate saturated solution is slowly added the container that fills this molecular sieve template, the dripping quantity of solution reaches by the molecular sieve template and absorbs fully, after stirring, 20～100 ℃ of following heating molecular sieve KIT-6 templates, moisture is evaporated fully;
2). repeating step 1) process, filled up by nickel nitrate until the network hole of molecular sieve template;
3). the molecular sieve KIT-6 template of the network hole being filled up nickel nitrate adds in the Muffle furnace, be warming up to 400～900 ℃ with 1～20 ℃/minute speed from 20～30 ℃, in air, calcined 3～12 hours, after being cooled to 20～30 ℃, it is 20～100ml/ minute hydrogen stream that the particulate material that obtains is placed flow velocity, be warming up to 500～900 ℃ with externally heated oven with 1～5 ℃/minute speed, and kept 0.5～20 hour, reduce to 20～30 ℃ then, in being 20～100ml/ minute Oxygen Flow, flow velocity kept 0.5～20 hour, again with concentration be the sodium hydroxide solution of 0.1～10mol/L or concentration be 0.1～10mol/L ammonia spirit 20～90 ℃ of following dissolving molecular sieve KIT-6 templates, washing, after 40～120 ℃ of following dryings, obtain the nanometer line network particle catalyst that particle diameter is the nickel of 50～500 μ m.
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| CNB2007100575564A CN100431696C (en) | 2007-06-06 | 2007-06-06 | Method for preparing nickel nanometer line network particle catalyst |
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| CN100431696C true CN100431696C (en) | 2008-11-12 |
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| CN101444737B (en) * | 2008-12-22 | 2011-07-20 | 长沙星纳气凝胶有限公司 | Nickel-based catalyst for hydrogen production by ethanol steam reforming and preparation method thereof |
| CN101462056B (en) * | 2009-01-13 | 2010-09-15 | 天津大学 | Method for preparing porous nickel metal integral type catalyst |
| CN106082346A (en) * | 2016-06-21 | 2016-11-09 | 苏州帝瀚环保科技股份有限公司 | The preparation method of meso-porous titanium dioxide manganese |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491744A (en) * | 2003-08-27 | 2004-04-28 | 天津大学 | Process for preparing carbon nano fiber knitting macro-particles containing high active nickel catalyst |
| WO2006001648A1 (en) * | 2004-06-23 | 2006-01-05 | Industry-University Cooperation Foundation Sogang University | The method ofprepaeing substrates - molecular sieve layer complex using ultrasound and apparatuses used therein |
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2007
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1491744A (en) * | 2003-08-27 | 2004-04-28 | 天津大学 | Process for preparing carbon nano fiber knitting macro-particles containing high active nickel catalyst |
| WO2006001648A1 (en) * | 2004-06-23 | 2006-01-05 | Industry-University Cooperation Foundation Sogang University | The method ofprepaeing substrates - molecular sieve layer complex using ultrasound and apparatuses used therein |
Non-Patent Citations (4)
| Title |
|---|
| . Applied Catalysis A: General,Vol.272 No.157. 2004 |
| . Journal of Catalysis,Vol.146 No.1. 1994 |
| . Applied Catalysis A: General,Vol.272 No.157. 2004 * |
| . Journal of Catalysis,Vol.146 No.1. 1994 * |
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