CN101530801A - Carbon nano tube supported nickel catalyst as well as preparation method and application thereof - Google Patents
Carbon nano tube supported nickel catalyst as well as preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a carbon nano tube supported nickel catalyst as well as a preparation method and application thereof. The carbon nano tube supported nickel catalyst consists of 10-35% mass percentage content of nickel and 65-90% mass percentage content of carbon nano tube. The catalyst of the invention vastly reduces the energy consumption during bio-oil hydrogen production, and improves the bio-oil conversion rate, hydrogen yield and the catalyst service life by the synergy of the active constituent, being favorable for realizing biomass fast pyrolysis bio-oil preparing technology and reforming bio-oil hydrogen production technology integration.
Description
Technical field
The present invention relates to a kind of carbon nanotube loaded Raney nickel and preparation method thereof and application.
Background technology
The energy is the mainstay of human survival and social economy's sustainable development.Along with the pressure of energy demand and environmental protection increases rapidly, utilize reproducible biomass energy to be subjected to people and pay close attention to greatly.Hydrogen is the clean energy resource of present optimal calorific value the highest (142MJ/kg), and living beings are with its aboundresources, environmental friendliness, advantage such as renewable and become a kind of up-and-coming hydrogen manufacturing raw material.Liquid bio oil (Bio-oil) is the liquid organic mixture that is produced through quick pyrolysis liquefying process by living beings, and bio oil has easily collecting, the easy advantage of storage and easily transportation aspect; Compare with the living beings direct gasification, bio oil is passed through the hydrogen-rich synthetic gas of the hydrogen content of higher hydrogen productive rate of the easier acquisition of water vapour catalytic reforming and Geng Gao, obtains pure hydrogen behind the purifying.
Bio-oil hydrogen making still is in conceptual phase in theoretical research and technology exploitation.At present existing to utilize the method for bio-oil hydrogen making be the steam reforming method, and use therein catalyst is generally nickel-base catalyst (as Ni-Al
2O
3, the Ni-Al that K or Mg mix
2O
3Deng), noble metal catalyst is (as Pt-Al
2O
3And Pd-Al
2O
3) and the nearest C12A7-O that reports
-Catalyst series is (as C12A7-O
-And C12A7-O
-/ MgO etc.).Because need in the noble metal catalyst to add expensive noble metal raw material, its production cost height should not be promoted the use of in biological oil reforming hydrogen production.Catalyst for using except that noble metal for example uses common Ni-based (Ni-Al
2O
3) situation of catalyst, mainly have two key issues: (1) reforming temperature height, energy consumption is higher.If the reforming reaction temperature is in 500-550 ℃ of scope, the bio oil conversion ratio is about 10% only, has only when the reforming reaction temperature reaches 750-850 ℃, could obtain the bio oil conversion ratio greater than 80% effect.Therefore, energy consumption is big in its whole process, and efficient is low." applied catalysis, A collects: introduction " the 320th phase in 2007 " was used C12A7-O
-Catalyst based reforming bio-oil hydrogen making " paper (Zhaoxiang Wang; Applied Catalysis A:General 320 (2007) 24-34), " energy and fuel " the 21st phase in 2007 " biological oil properties and the application in Fischer-Tropsch is synthetic " paper (Zhaoxiang Wang, Energy; Fuels 2007,21,2421-2432), and paper (the Stefan Czernik of " industry and engineering chemistry research " the 41st phase " the liquid product hydrogen manufacturing that catalyzed aqueous vapour is reformed and obtained by the biomass thermal conversion process " in 2002, Ind.Eng.Chem.Res.2002,41, all reported the particulars of relevant this respect in 4209-4215).(2) catalyst can rapid deactivation.In existing reforming catalyst, non-noble metal Ni-Al commonly used
2O
3Catalyst, its service life is very short, even under 825 ℃ of conditions of best reforming reaction temperature, after the biological oil reforming reaction is only carried out 30 minutes, hydrogen yield just is reduced to 30% from 83.8%, the report of relevant this respect was published in " applied catalysis, A collects: introduction " last the 201st phase " catalyst is formed the influence to reforming bio-oil hydrogen making " paper (LuciaGarcia, Applied Catalysis A:General201 (2000) 225-239) in visible 2000.
In view of the foregoing, how to overcome the defective of prior art, cut down the consumption of energy and the production technology cost, remain a core difficult problem in the present biomass hydrogen preparation process.
Summary of the invention
An object of the present invention is, provide a kind of can be under cryogenic conditions, improve biological oil reforming hydrogen production efficient and the carbon nanotube loaded Raney nickel in long service life arranged.
Carbon nanotube loaded Raney nickel provided by the present invention is made up of the nickel metal of 10%-35% quality percentage composition and the CNT of 65%-90% quality percentage composition.
Wherein, the quality percentage composition of nickel metal is preferably 15%-30%, and the quality percentage composition of CNT is preferably 70%-85%.
The specific surface of described catalyst is (115-130) m
2/ g, the pore volume of described catalyst are (0.28-0.30) cm
3/ g.
Described catalyst can be arbitrary shape, and preferably particle diameter is the particle of 0.1-0.2mm.
Another object of the present invention provides a kind of method for preparing above-mentioned arbitrary described carbon nanotube loaded Raney nickel.
Preparation method provided by the present invention comprises the steps: nickel ion solution and CNT mixing, and to wherein adding urea and mixing, precipitation is reduced, and obtains carbon nanotube loaded Raney nickel again;
The proportioning of nickel ion and CNT is a 1mol nickel: (108.1-440.5) g CNT is preferably 1mol nickel: the 137.0g-333.3g CNT;
The mol ratio of nickel ion and urea is 1:(2.5-4), be preferably 1:3.
Wherein, described precipitation can be carried out under the following conditions: the rotating speed with 100-150rpm stirs, and temperature is 88-95 ℃, condensing reflux 18-24 hour; Rotating speed is preferably 120rpm, and temperature is preferably 90 ℃, and the condensing reflux time is preferably 24h.
Described method with nickel ion solution and CNT mixing can be and stirs the back sonic oscillation earlier, and the rotating speed of stirring is 100-150rpm, and the time of stirring is 0.5-1h, and the sonic oscillation time is 0.5-1h.
Also can comprise dry step before the reduction of described post precipitation, the method for described drying can be: the sediment that described post precipitation is obtained is warming up to 110-120 ℃ with the speed of (1-1.5) ℃/min earlier, keeps 10-12 hour under 110-120 ℃ condition again.
Behind nickel ion solution and CNT mixing, when the pH of solution value is 1-2, again to wherein adding urea and mixing.
The method of described reduction can be: the flow velocity with 100-150ml/min continues to feed 20%H
2/ 80%N
2Mist was at 350-400 ℃ of following reduction reaction 2-3 hour.
Described CNT before use, carry out purifying and finishing earlier, method is as follows: it is the red fuming nitric acid (RFNA) (65%-68%) of 3:1 and the mixed liquor of the concentrated sulfuric acid (95-98%) that CNT is placed volume ratio, with the rotating speed is that 100-150rpm continues mechanical agitation, and temperature is remained on 70-90 ℃ of condensing reflux processing 4-6h; CNT after the processing with deionized water wash, suction filtration 3 times, up to about filtrate pH value to 7, be washes clean; Then with the washes clean CNT 105-120 ℃ dry 10-12 hour down, wear into pulverize stand-by.
The application of above-mentioned arbitrary described carbon nanotube loaded Raney nickel in steam reforming bio-oil hydrogen making also belongs to protection scope of the present invention.
Last purpose of the present invention provides a kind of method of steam reforming bio-oil hydrogen making.
The method of steam reforming bio-oil hydrogen making provided by the present invention is to be raw material with bio oil and steam, carries out catalytic reaction with above-mentioned arbitrary described carbon nanotube loaded Raney nickel, obtains hydrogen.
Wherein, the condition of described reaction comprises as follows: temperature is 350-570 ℃, the steam pressure of water vapour is a 1.1-1.3 atmospheric pressure, per hour the mass ratio of water vapour and bio oil inlet amount is (1.5-3.0): 1 (or mol ratio 3.7-7.4/1), per hour bio oil and per hour the total inlet amount of water vapour and the mass ratio of catalyst be (10.0-28.0): 1.
The temperature of described reaction is preferably 450-550 ℃.
Bio oil is commonly used in the prior art, is raw material with various reproducible living beings such as wood chip, rice husk, stalks normally, the biomass cracked oil by using that obtains by quick cracking process.
Carbon nanotube loaded Raney nickel of the present invention, by the high degree of dispersion of active component nickel and the facilitation of carbon nanotube carrier, conversion ratio in the low-temperature biological oil electro-catalysis reformation hydrogen production process, bio-oil hydrogen making productive rate and catalyst service life have been improved significantly.Wherein, CNT has the tube wall, nanoscale duct of graphite-like structure, big specific area and high mechanical strength, is a kind of good catalyst carrier.When nickel nano particle loads on the CNT tube wall, can significantly improve its decentralization, improve catalytic effect; The adsorption-desorption performance of carbon nanotube carrier excellence can make reactant fully be reacted at catalytically active surface; And the strong metal-support interaction between the nickel nano particle of CNT and its area load makes nickel nano particle surface can reduce, and reduces that it is reunited in catalytic reaction process, the probability of sintering, thereby makes the catalyst life prolongation.
Experiment showed, that compared with prior art in 450-570 ℃ of temperature range, just can obtain high hydrogen yield with catalyst of the present invention, hydrogen yield can reach 70.7%-92.5%, the bio oil conversion ratio is 74.5%-94.9%; And normally used Ni-Al in the prior art
2O
3The biological oil reforming catalyst, in temperature was 350-400 ℃ of scope, hydrogen yield and bio oil conversion ratio were all less than 20%, even in 450-500 ℃ of scope, hydrogen yield also can only reach about 20%-40%, when only reaching more than 700 ℃ high temperature, best hydrogen yield can be arranged; Therefore with traditional steam reformation catalyst n i-γ-Al
2O
3Compare, hydrogen yield and the about high 2-3 of raw material bio oil conversion ratio are doubly during the carbon nanotube loaded Raney nickel that uses that the present invention makes, and reaction temperature has descended about 200 ℃, greatly reduce the energy consumption in the biological oil reforming hydrogen production process, reduce production cost, improved production efficiency significantly.
Experiment shows that also catalyst of the present invention did not almost change with interior its catalyzing manufacturing of hydrogen performance at 12 hours, and Ni-γ Al of the prior art
2O
3Catalyst, just serious inactivation (LuciaGarcia, Applied Catalysis A:General 201 (2000) 225-239) after 0.5-2 hour usually.
Catalyst of the present invention, going for the bio oil that various reproducible living beings obtain by quick cracking is the reformation hydrogen production reaction of raw material, that its raw material has is renewable, easily collecting, the easy advantage of storage and easily transportation aspect, has realized sustainability recycling of resource-energy-environmental integration.Particularly, catalyst of the present invention can carry out hydrogen manufacturing operation under 350-400 ℃ of cryogenic conditions, the biomass flash pyrolysis system bio oil technology (cracking reaction temperature: 480-550 ℃) that realizes researching and developing and the integrated and integrated technical guarantee that provides of reforming bio-oil hydrogen making technology (reforming reaction temperature: 350-400 ℃) are provided.
In sum, catalyst of the present invention has reduced the energy consumption in the bio-oil hydrogen making process significantly, and the synergy by active component, improve bio oil conversion ratio, hydrogen manufacturing productive rate and catalyst service life, helped realizing the integrated of biomass flash pyrolysis system bio oil technology and reforming bio-oil hydrogen making technology.
The specific embodiment
Employed experimental technique is conventional method if no special instructions among the following embodiment.
Used material, reagent etc. if no special instructions, all can obtain from commercial channels among the following embodiment.
Nickel nitrate: analyze purely, available from Chinese Medicine Shanghai chemical reagents corporation, catalog number is 10014318;
Urea: analyze purely, available from Chinese Medicine Shanghai chemical reagents corporation, catalog number is 10023218;
γ-alundum (Al: analyze pure, available from Xinyuan Group Col, Wu Xi;
CNT: available from Chengdu Organical Chemical Co., Ltd., Chinese Academy of Sciences, catalog number is IM6.
Embodiment 1, the carbon nanotube loaded Raney nickel of employing hydrolysis of urea Preparation by Uniform Precipitation
One, adopts the carbon nanotube loaded Raney nickel I of hydrolysis of urea Preparation by Uniform Precipitation
(1) CNT purifying and finishing: the 30g CNT is inserted in the mixed liquor of the red fuming nitric acid (RFNA) (65%-68%) that the volume ratio that fills 500ml is 3:1 and the concentrated sulfuric acid (98%), rotating speed with 150rpm continues mechanical agitation, and temperature remained on 90 ℃, condensing reflux is handled 6h; CNT after the processing with deionized water wash, suction filtration 3 times, be washes clean up to filtrate pH value to 7; CNT with washes clean descended dry 10 hours at 110 ℃ then, ground stand-by;
(2) weighing 8.74g nickel nitrate (molecular formula: Ni (NO
3)
26H
2O, purity: analyze pure AR) dissolve in that (nickel nitrate and distilled water mass ratio are: 1/57.2) in the 500ml distilled water, (proportioning of nickel and CNT is a 1mol nickel: the 333.3g CNT) by step (1) processed carbon nanotubes to add 10g simultaneously, under room temperature (25 ℃), continue to stir 0.5h with rotating speed 120rpm, after stirring, sonic oscillation 1h, CNT is fully disperseed in solution, and the pH value of mixed solution is adjusted to 1 with rare nitric acid, add 5.40g urea stir (mol ratio of nickel and urea is 1:3) then.
(3) precipitation: the mixed solution that step (2) is obtained continues to stir with rotating speed 120rpm, and heating remains on 90 ℃, carries out condensing reflux 24h simultaneously, reaches 6.5 reactions until pH value and finishes;
(4) drying: the sediment after the said hydrolyzed is spent deionised water 30min and carries out suction filtration 1 time; Sediment after the washing is inserted that the speed with 1 ℃/min is warming up to 120 ℃ in the drying box, and remain under 120 ℃ the condition and reduce to room temperature after dry 10 hours;
(5) dried mixture is ground to sieve obtain the particle that particle diameter is 0.1-0.2mm (80-100 order).Particle is inserted in the quartz reaction chamber, and continuing to feed flow velocity is the 20%H of 100ml/min
2/ 80%N
2Mist 400 ℃ of following reduction reactions 3 hours, is cooled to room temperature then, obtains the about 12g of carbon nanotube loaded Raney nickel, is named as the Ni-CNT-I catalyst.After tested, this catalyst specific surface and pore volume are respectively 122.0m
2/ g and 0.29cm
3/ g, each composition weight percentage composition is respectively: the content of Ni is 15%; CNT promoter is 85%.
Two, adopt the carbon nanotube loaded Raney nickel II of hydrolysis of urea Preparation by Uniform Precipitation
(1) CNT purifying and finishing: the 30g CNT being inserted in the mixed liquor of the red fuming nitric acid (RFNA) (65%-68%) that the volume ratio that fills 500ml is 3:1 and the concentrated sulfuric acid (98%) with the rotating speed is that 140rpm continues mechanical agitation, and temperature is remained on 90 ℃ of left and right sides condensing refluxes handles 6h; CNT after the processing with deionized water wash, suction filtration 3 times, be washes clean up to filtrate pH value to 7; Then with the washes clean CNT 110 ℃ dry 10 hours down, wear into pulverize stand-by;
(2) weighing 21.24g nickel nitrate (molecular formula: Ni (NO
3)
26H
2O, purity: analyze pure AR) dissolve in that (nickel nitrate and distilled water mass ratio are: 1/23.5) in the 500ml distilled water, (proportioning of nickel and CNT is a 1mol nickel: the 137.0g CNT) by step (1) processed carbon nanotubes to add 10g simultaneously, under room temperature (25 ℃), continue to stir 0.5h with rotating speed 120rpm, after stirring, sonic oscillation 30 minutes, CNT is fully disperseed in solution, and the pH value of mixed solution is adjusted to 1 with rare nitric acid, add 13.15g urea stir (mol ratio of nickel and urea is 1:3) then.
(3) precipitation: the mixed solution that step (2) is obtained continues to stir with rotating speed 120rpm, and heating remains on 90 ℃, carries out condensing reflux 24h simultaneously, reaches 6 reactions until pH value and finishes;
(4) drying: the sediment after the said hydrolyzed is spent deionised water 30min and carries out suction filtration 1 time; Sediment after the washing is inserted that the speed with 1 ℃/min is warming up to 120 ℃ in the drying box, and remain under 120 ℃ the condition and reduce to room temperature after dry 10 hours;
(5) dried mixture is ground to sieve obtain the particle that particle diameter is 0.1-0.2mm (80-100 order).Particle is inserted in the quartz reaction chamber, and continuing to feed flow velocity is the 20%H of 100ml/min
2/ 80%N
2Mist 400 ℃ of following reduction reactions 3 hours, is cooled to room temperature then, obtains carbon nanotube loaded nickel-base catalyst 15g, is named as the Ni-CNT-II catalyst.After tested, this catalyst specific surface and pore volume are respectively 116.6m
2/ g and 0.28cm
3/ g, each constituent mass percentage composition is respectively: the content of Ni is 30%; CNT promoter is 70%.
Three, adopt the carbon nanotube loaded Raney nickel III of hydrolysis of urea Preparation by Uniform Precipitation
(1) CNT purifying and finishing: it is that 130rpm continues mechanical agitation that the 30g CNT is inserted in the mixed liquor that the volume ratio that fills 500ml is 3: 1 the red fuming nitric acid (RFNA) (65%-68%) and the concentrated sulfuric acid (98%) with the rotating speed, and temperature is remained on 85 ℃ of left and right sides condensing refluxes handles 6h; CNT after the processing with deionized water wash, suction filtration 3 times, be washes clean up to filtrate pH value to 7; Then with the washes clean CNT 115 ℃ dry 11 hours down, wear into pulverize stand-by;
(2) weighing 12.4g nickel nitrate (molecular formula: Ni (NO
3)
26H
2O, purity: analyze pure AR) dissolve in that (nickel nitrate and distilled water mass ratio are: 1/40.3) in the 500ml distilled water, (proportioning of nickel and CNT is a 1mol nickel: the 234.7g CNT) by step (1) processed carbon nanotubes to add 10g simultaneously, under room temperature (25 ℃), continue to stir 0.5h with rotating speed 135rpm, after stirring, sonic oscillation 40 minutes, CNT is fully disperseed in solution, and the pH value of mixed solution is adjusted to 2 with rare nitric acid, add 7.67g urea stir (mol ratio of nickel and urea is 1: 3) then.
(3) precipitation: the mixed solution that step (2) is obtained continues to stir with rotating speed 135rpm, and heating remains on 92 ℃, carries out condensing reflux 20h simultaneously, reaches 6 reactions until pH value and finishes;
(4) drying: the sediment after the said hydrolyzed is spent deionised water 30min and carries out suction filtration 1 time; Sediment after the washing is inserted that the speed with 1 ℃/min is warming up to 115 ℃ in the drying box, and remain under 115 ℃ the condition and reduce to room temperature after dry 11 hours;
(5) dried mixture is ground to sieve obtain the particle that particle diameter is 0.1-0.2mm (80-100 order).Particle is inserted in the quartz reaction chamber, and continuing to feed flow velocity is the 20%H of 120ml/min
2/ 80%N
2Mist 370 ℃ of following reduction reactions 3 hours, is cooled to room temperature then, obtains carbon nanotube loaded nickel-base catalyst 15g, is named as the Ni-CNT-III catalyst.After tested, this catalyst specific surface and pore volume are respectively 119.5m
2/ g and 0.29cm
3/ g, each constituent mass percentage composition is respectively: the content of Ni is 20wt%; CNT promoter is 80wt%.
Four, adopt the carbon nanotube loaded Raney nickel IV of hydrolysis of urea Preparation by Uniform Precipitation
(1) CNT purifying and finishing: it is that 100rpm continues mechanical agitation that the 30g CNT is inserted in the mixed liquor that the volume ratio that fills 500ml is 3: 1 the red fuming nitric acid (RFNA) (65%-68%) and the concentrated sulfuric acid (98%) with the rotating speed, and temperature is remained on 70 ℃ of left and right sides condensing refluxes handles 6h; CNT after the processing with deionized water wash, suction filtration 3 times, be washes clean up to filtrate pH value to 7; Then with the washes clean CNT 105 ℃ dry 10 hours down, wear into pulverize stand-by;
(2) weighing 6.6g nickel nitrate (molecular formula: Ni (NO
3)
26H
2O, purity: analyze pure AR) dissolve in that (nickel nitrate and distilled water mass ratio are: 1/75.8) in the 500ml distilled water, (proportioning of nickel and CNT is a 1mol nickel: the 440.5g CNT) by step (1) processed carbon nanotubes to add 10g simultaneously, under room temperature (25 ℃), continue to stir 0.5h with rotating speed 100rpm, after stirring, sonic oscillation 50 minutes, CNT is fully disperseed in solution, and the pH value of mixed solution is adjusted to 2 with rare nitric acid, add 3.41g urea stir (mol ratio of nickel and urea is 1:2.5) then;
(3) precipitation: the mixed solution that step (2) is obtained continues to stir with rotating speed 100rpm, and heating remains on 88 ℃, carries out condensing reflux 18h simultaneously, reaches 7 reactions until pH value and finishes;
(4) drying: the sediment after the said hydrolyzed is spent deionised water 30min and carries out suction filtration 1 time; Sediment after the washing is inserted that the speed with 1 ℃/min is warming up to 110 ℃ in the drying box, and remain under 110 ℃ the condition and reduce to room temperature after dry 10 hours;
(5) dried mixture is ground to sieve obtain the particle that particle diameter is 0.1-0.2mm (80-100 order).Particle is inserted in the quartz reaction chamber, and continuing to feed flow velocity is the 20%H of 130ml/min
2/ 80%N
2Mist 350 ℃ of following reduction reactions 2 hours, is cooled to room temperature then, obtains carbon nanotube loaded nickel-base catalyst 15g, is named as the Ni-CNT-I catalyst.After tested, this catalyst specific surface and pore volume are respectively 129.7m
2/ g and 0.30cm
3/ g, each constituent mass percentage composition is respectively: the content of Ni is 10%; CNT promoter is 90%.
Five, adopt the carbon nanotube loaded Raney nickel V of hydrolysis of urea Preparation by Uniform Precipitation
(1) CNT purifying and finishing: it is that 120rpm continues mechanical agitation that the 30g CNT is inserted in the mixed liquor that the volume ratio that fills 500ml is 3: 1 the red fuming nitric acid (RFNA) (65%-68%) and the concentrated sulfuric acid (98%) with the rotating speed, and temperature is remained on 80 ℃ of left and right sides condensing refluxes handles 6h; CNT after the processing with deionized water wash, suction filtration 3 times, be washes clean up to filtrate pH value to 7; Then with the washes clean CNT 120 ℃ dry 12 hours down, wear into pulverize stand-by;
(2) weighing 26.9g nickel nitrate (molecular formula: Ni (NO
3)
26H
2O, purity: analyze pure AR) dissolve in that (nickel nitrate and distilled water mass ratio are: 1/18.6) in the 500ml distilled water, (proportioning of nickel and CNT is a 1mol nickel: the 108.1g CNT) by step (1) processed carbon nanotubes to add 10g simultaneously, under room temperature (25 ℃), continue to stir 1h with rotating speed 150rpm, after stirring, sonic oscillation 45 minutes, CNT is fully disperseed in solution, and the pH value of mixed solution is adjusted to 2 with rare nitric acid, add 22.2g urea stir (mol ratio of nickel and urea is 1:4) then.
(3) precipitation: the mixed solution that step (2) is obtained continues to stir with rotating speed 150rpm, and heating remains on 95 ℃, carries out condensing reflux 22h simultaneously, reaches 7 reactions until pH value and finishes;
(4) drying: the sediment after the said hydrolyzed is spent deionised water 30min and carries out suction filtration 1 time; Sediment after the washing is inserted that the speed with 1.5 ℃/min is warming up to 110 ℃ in the drying box, and remain under 110 ℃ the condition and reduce to room temperature after dry 12 hours;
(5) dried mixture is ground to sieve obtain the particle that particle diameter is 0.1-0.2mm (80-100 order).Particle is inserted in the quartz reaction chamber, and continuing to feed flow velocity is the 20%H of 150ml/min
2/ 80%N
2Mist 390 ℃ of following reduction reactions 2.5 hours, is cooled to room temperature then, obtains carbon nanotube loaded nickel-base catalyst 15g, is named as the Ni-CNT-I catalyst.After tested, this catalyst specific surface and pore volume are respectively 115.2m
2/ g and 0.28cm
3/ g, each constituent mass percentage composition is respectively: the content of Ni is 35%; CNT promoter is 65%.
Embodiment 2, employing hydrolysis of urea Preparation by Uniform Precipitation Ni-γ-Al
2O
3Catalyst
(1) weighing 8.74g nickel nitrate (molecular formula: Ni (NO
3)
26H
2O, purity: analyze pure AR) dissolve in the 500ml distilled water, add 10g γ-Al simultaneously
2O
3, sonic oscillation is 10 minutes after stirring, and is adjusted between the 1-2 with the pH value of red fuming nitric acid (RFNA) with mixed solution, adds 5.4g urea then, keeps continuing to stir;
(2) above-mentioned mixed solution heating is remained on about 90 ℃, carry out condensing reflux 24h simultaneously, to about 6-7, react end until pH value;
(3) sediment after the said hydrolyzed is carried out suction filtration, and spend deionised water; Sediment after the washing was inserted in the drying box under 120 ℃ condition dry 10 hours;
(4) dried sediment slowly is heated to 500 ℃ with the programming rate of 1 ℃/min, and roasting 3 hours in 500 ℃ of air atmospheres;
(5) mixed oxide after the roasting is ground to sieve obtain the mixed oxide particle that particle diameter is 0.1-0.2mm (80-100 order).Particle is inserted in the quartz reaction chamber, and continuing to feed flow velocity is the 20%H of 100ml/min
2-80%N
2Mist, 400 ℃ of following reduction reactions 3 hours, it was stand-by to be cooled to room temperature then.After tested, its specific surface and pore volume are respectively 115.1m
2/ g and 0.28cm
3/ g.Wherein, each composition weight percentage composition is respectively: Ni is 15%; γ-Al
2O
3Be 85%.
Embodiment 3, the application of carbon nanotube loaded Raney nickel in bio-oil hydrogen making
The evaluation of catalytic activity is carried out on quartzy flow reactor of fixed bed-gas-chromatography (GC) combined system.
Reaction unit is quartzy flow reactor of fixed bed, it comprise one have the tubular quartz tube reactor that adds electrothermal stove (internal diameter: Φ 2.5mm, length: 40cm) and the reactant (bio oil and steam) that is connected both ends feed pipeline and reaction end gas output channel; Bio oil holding vessel, steam generator are connected with feeding pipeline respectively, and are respectively equipped with control valve and reactant flow controller, and the access tube pipeline outer wall is provided with the outer heater that is used for preheating; On output channel, be connected with in turn and comprise water vapor condensation device, CO
2Chemical absorbing device and drier are at interior exhaust collection purification system; Send into the gas-chromatography six-way valve from the reaction end gas of reactor outlet discharging after through the condensation drying and take a sample, carry out on-line analysis by the GC-6890 gas chromatograph.
One, carries out bio-oil hydrogen making with experiment one catalyst I that obtains among the embodiment 1
The preparation of bio oil: with the wood chip is raw material, and cracking process obtains bio oil fast.
Concrete grammar is as follows:
The catalyst I that embodiment 1 is made is filled in the quartz reactor, by reactor external heat stove catalyst is heated to different temperatures in 350-570 ℃; Raw material bio oil and water vapour are passed in the tubular reforming reactor inlet tube preheating zone, enter in the tubular electrocatalysis water vapour biological oil reforming reactor after making the two mixing, preheating, making bio oil carry out reforming reaction (bio oil dissociation reaction, catalytic steam reforming reaction and water gas shift reaction) under water vapour atmosphere and 350-570 ℃ of environment, is hydrogen and carbon dioxide mix gas with the carbon containing in the bio oil-hydrogen-oxygen organic matter transformation; Reacted mist process is comprised condenser, CO
2Chemical absorbing device, drier obtain pure hydrogen behind interior exhaust collection purification system.Reaction condition: the steam pressure of water vapour is 1.1 atmospheric pressure, steam rates 60.0g/h, bio oil 25.0g/h, mass ratio is 2.4:1 (corresponding mol ratio is 6/1), catalyst amount is 5g (per hour bio oil and per hour the total inlet amount of water vapour and the mass ratio of catalyst are 17:1), stable reaction afterreaction 12 hours is measured hydrogen yield and bio oil conversion ratio in following 12 hours of different reforming reaction temperature (350-570 ℃).
The computing formula of hydrogen yield is:
The computing formula of bio oil conversion ratio is:
3 repetitions are established in experiment, and the result takes the mean.The result is as shown in table 1.As can be seen, in temperature was 350570 ℃ of scopes, hydrogen yield reached 43.6%-92.5%; The bio oil conversion ratio is 52.9%-94.9%.The holdup time of bio oil steam in the tubular reforming reactor is 0.05-0.2 second.
Table 1, catalyst I are carried out hydrogen yield and bio oil conversion ratio in the hydrogen manufacturing
Two, carry out bio-oil hydrogen making with the experiment two catalyst I I that obtain among the embodiment 1
The preparation of bio oil: with the wood chip is raw material, and cracking process obtains bio oil fast.
Apparatus structure that uses and hydrogen production process, reaction condition are filled by the experiment two catalyst I I that obtain among the embodiment 1 all with identical described in one, record hydrogen yield and bio oil conversion ratio under different reforming reaction temperature (350-570 ℃).
3 repetitions are established in experiment, and the result is as shown in table 2.As can be seen, in temperature was 350-570 ℃ of scope, hydrogen yield reached 46.3%-93.8%; The bio oil conversion ratio is 56.2%-95.1%.Because the increase of active component Ni content in the catalyst, every index slightly increases, but amplification is very little, and therefore Ni content increases to 30% from 15% as can be seen, and little to the influence of catalyst performance, 15%-30%Ni content proportioning is all within suitable interval.
Table 2, catalyst I I carry out hydrogen yield and bio oil conversion ratio in the hydrogen manufacturing
Three, carry out bio-oil hydrogen making with the catalyst I II that makes among the embodiment 1, catalyst I V, catalyst V respectively
The preparation of bio oil: with the wood chip is raw material, and cracking process obtains bio oil fast.
Apparatus structure that uses and hydrogen production process are filled respectively by the catalyst I II that obtains among the embodiment 1, catalyst I V, catalyst V with identical described in one, record hydrogen yield and bio oil conversion ratio under different reforming reaction temperature (350-570 ℃).
The reaction condition of different catalysts correspondence is as follows:
Catalyst I II: the steam pressure of water vapour is 1.1 atmospheric pressure, steam rates 60g/h, bio oil 40g/h, mass ratio is 1.5:1 (corresponding mol ratio is 3.7/1), and catalyst amount is 10g (per hour bio oil and per hour the total inlet amount of water vapour and the mass ratio of catalyst are 10.0:1).
Catalyst I V: the steam pressure of water vapour is 1.2 atmospheric pressure, steam rates 80g/h, bio oil 40g/h, mass ratio is 2.0:1 (corresponding mol ratio is 5.6/1), and catalyst amount is 6g (per hour bio oil and per hour the total inlet amount of water vapour and the mass ratio of catalyst are 20.0:1).
Catalyst V: the steam pressure of water vapour is 1.3 atmospheric pressure, steam rates 105g/h, bio oil 35g/h, mass ratio is 3.0:1 (corresponding mol ratio is 7.4/1), and catalyst amount is 5g (per hour bio oil and per hour the total inlet amount of water vapour and the mass ratio of catalyst are 28:1).
3 repetitions are established in experiment, and the result of the experiment two of hydrogen yield and bio oil conversion ratio and present embodiment is basic identical as a result.
The comparison of embodiment 4, several catalyst effect
The preparation of bio oil: with the wood chip is raw material, and cracking process obtains bio oil fast.
Apparatus structure that uses and hydrogen production process all with embodiment 3 in one described identical, (embodiment 1 tests Ni-γ-Al that a catalyst I that obtains, embodiment 2 prepare to fill 3 kinds of different catalyst respectively
2O
3, pure nano-carbon tube), survey down hydrogen yield and bio oil conversion ratio in different reforming reaction temperature (400-570 ℃).
3 repetitions are established in experiment, and the result takes the mean.The result is as shown in table 3.As can be seen, hydrogen yield and the raw material bio oil conversion ratio that uses pure nano-carbon tube to obtain in the temperature range of test is zero substantially; With traditional steam reformation catalyst n i-γ-Al
2O
3Compare, the high 2-3 of effect (hydrogen yield and raw material bio oil conversion ratio) of the carbon nanotube loaded nickel-base catalyst that use the present invention makes doubly.
The catalytic effect of table 3, three kinds of different catalysts
The service life of embodiment 5, test catalyst of the present invention
With experiment one catalyst I that obtains among the embodiment 1 is example, is described in detail experimental technique, and the method for other catalyst I I-V is identical.
Apparatus structure that uses and hydrogen production process are all with identical described in the embodiment 3 one.Test condition: steam rates 60.0g/h, bio oil 25.0g/h, corresponding mol ratio is 6/1, catalyst amount is 5g, particle diameter is 0.1-0.2mm, under temperature T=500 ± 5 ℃ permanence condition in guaranteeing the reforming reactor inner chamber, normal pressure is measured when the steam reforming bio-oil hydrogen making reactor is worked hydrogen yield down with the variation of reforming reaction time.
3 repetitions are established in experiment, and the result is taken the mean.The result of catalyst I is as shown in table 4.As can be seen from Table 4, after the catalyst continuous operation 12 hours, hydrogen yield and raw material bio oil conversion ratio almost do not change, and under lower temperature, its life-span is higher than traditional steam reformation catalyst n i-γ-Al203 (just serious inactivation after 0.5-2 hour usually) far away.The result of catalyst I I-V is identical therewith.
Detect the service life of table 4, catalyst
Claims (10)
1, a kind of carbon nanotube loaded Raney nickel is made up of the nickel metal of 10%-35% quality percentage composition and the CNT of 65%-90% quality percentage composition.
2, catalyst according to claim 1 is characterized in that: in the described catalyst, the quality percentage composition of nickel metal is 15%-30%, and the quality percentage composition of CNT is 70%-85%.
3, catalyst according to claim 1 and 2 is characterized in that: the specific surface of described catalyst is (115-130) m
2/ g, the pore volume of described catalyst are (0.28-0.30) cm
3/ g.
4, a kind of method for preparing carbon nanotube loaded Raney nickel comprises the steps: nickel ion solution and CNT mixing, and to wherein adding urea and mixing, precipitation is reduced, and obtains carbon nanotube loaded Raney nickel again;
The proportioning of nickel ion and CNT is a 1mol nickel: (108.1-440.5) g CNT is preferably 1mol nickel: (137.0-333.3) g CNT;
The mol ratio of nickel ion and urea is 1:(2.5-4), be preferably 1:3.
5, method according to claim 4 is characterized in that: described precipitation is carried out under the following conditions: the rotating speed with 100-150rpm stirs, and temperature is 88-95 ℃, condensing reflux 18-24 hour; Rotating speed is preferably 120rpm, and temperature is preferably 90 ℃, and the condensing reflux time is preferably 24h.
6, according to claim 4 or 5 described methods, it is characterized in that: described method with nickel ion solution and CNT mixing is sonic oscillation after stirring earlier, the rotating speed that stirs is 100-150rpm, and the time of stirring is 0.5-1h, and the sonic oscillation time is 0.5-1h.
7, the application of arbitrary described carbon nanotube loaded Raney nickel in steam reforming bio-oil hydrogen making among the claim 1-3.
8, a kind of method of steam reforming bio-oil hydrogen making is to be raw material with bio oil and steam, carries out catalytic reaction with arbitrary described carbon nanotube loaded Raney nickel among the claim 1-3, obtains hydrogen.
9, method according to claim 8, it is characterized in that: the condition of described reaction comprises as follows: temperature is 350-570 ℃, the steam pressure of water vapour is a 1.1-1.3 atmospheric pressure, per hour the mass ratio of water vapour and bio oil inlet amount is (1.5-3.0): 1, per hour bio oil and per hour the total inlet amount of water vapour and the mass ratio of described catalyst be (10.0-28.0): 1.
10, method according to claim 9 is characterized in that: the temperature of described reaction is 450-550 ℃.
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| CN102161000A (en) * | 2010-12-24 | 2011-08-24 | 黑龙江大学 | Method for preparing carbon nano tube loaded nano nickel powder material by liquid-phase reduction method |
| CN102634355A (en) * | 2011-12-20 | 2012-08-15 | 华北电力大学 | Method for cracking biomass pyrolytic tar catalytically using nickel-carrying carbon nano tube |
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| CN106853372A (en) * | 2015-12-16 | 2017-06-16 | 中国科学技术大学 | A kind of nickel-base catalyst and the method that hydrogen is prepared using bio oil |
| CN108187683A (en) * | 2018-01-12 | 2018-06-22 | 安徽理工大学 | Nickel-copper catalyst of attapulgite load that a kind of calcium oxide is modified and its preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102161000A (en) * | 2010-12-24 | 2011-08-24 | 黑龙江大学 | Method for preparing carbon nano tube loaded nano nickel powder material by liquid-phase reduction method |
| CN102634355A (en) * | 2011-12-20 | 2012-08-15 | 华北电力大学 | Method for cracking biomass pyrolytic tar catalytically using nickel-carrying carbon nano tube |
| CN102634355B (en) * | 2011-12-20 | 2014-04-23 | 华北电力大学 | Method for cracking biomass pyrolytic tar catalytically using nickel-carrying carbon nano tube |
| CN106853372A (en) * | 2015-12-16 | 2017-06-16 | 中国科学技术大学 | A kind of nickel-base catalyst and the method that hydrogen is prepared using bio oil |
| CN106521550A (en) * | 2016-12-09 | 2017-03-22 | 济南大学 | Method for preparing foamed nickel/ layer-by-layer self-assembled carbon nano tube / nickel composite material used for hydrogen production by electrolysis |
| CN106521550B (en) * | 2016-12-09 | 2018-09-25 | 济南大学 | Nickel foam/LBL self-assembly carbon nanotube/nickel composite material preparation method for electrolytic hydrogen production |
| CN108187683A (en) * | 2018-01-12 | 2018-06-22 | 安徽理工大学 | Nickel-copper catalyst of attapulgite load that a kind of calcium oxide is modified and its preparation method and application |
| CN113164918A (en) * | 2018-08-09 | 2021-07-23 | 巴西石油公司 | Method for gasifying low-value carbonaceous feedstocks as fuels using nanocatalysts |
| CN113164918B (en) * | 2018-08-09 | 2024-04-26 | 巴西石油公司 | Method for gasifying low-value carbon-containing raw materials as fuel by using nano catalyst |
| CN113174612A (en) * | 2021-03-30 | 2021-07-27 | 江苏大学 | Carbon tube composite material loaded with Ni nano-particles and preparation method and application thereof |
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