CN101912792B - Catalyst used in preparation of COx-free hydrogen through ammonia decomposition reaction and preparation method thereof - Google Patents
Catalyst used in preparation of COx-free hydrogen through ammonia decomposition reaction and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a catalyst used in preparation of COx-free hydrogen through ammonia decomposition reaction and a preparation method thereof. The carbon nanofibers provided by the invention are prepared by the following steps of: (1) loading a transition metal and/or an alloy thereof on the surface of a support to obtain a catalyst precursor; (2) reducing the catalyst precursor obtained in the step (1) with the mixed gas of argon gas and hydrogen gas to obtain the catalyst for growing the carbon nanofibers; and (3) contacting the catalyst for growing the carbon nanofibers obtained in the step (2) with a carbon source to obtain the carbon nanofibers, wherein the support is selected from inorganic powder or formed bodies. The carbon nanofibers provided by the invention can be directly applied to the ammonia decomposition reaction without being processed; and the particles of the transition metal and/or the alloy thereof have high ammonia decomposition activity and high stability.
Description
Technical field
The present invention relates to the energy and petrochemical industry catalysis material technical field, be specifically related to a kind of Catalysts and its preparation method for ammonia decomposition reaction preparation zero COx hydrogen.
Background technology
H
2-O
2Proton membrane fuel battery (PEMFC) is efficient, a green technology, have the advantages such as non-pollutant discharge, efficient high (＞60%), noiselessness, startup are fast, aspect the stand-by power supply of electric automobile, small-sized movable electronic equipment, family or hospital etc. huge market prospects are being arranged.Up to now, the main cause of obstruction Hydrogen Energy PEMFC acquisition large-scale application is the storage of hydrogen and the inactivation problem of electrode catalyst.The storage of hydrogen need to be used material or the liquid hydrogen-containing fuel of high weight of hydrogen.Use the hydrogen of the organic matter production of carbon containing to contain inevitably the poisonous substance CO that reduces the PEMFC life-span.Because ammonia has higher hydrogen content (17.6%), and be easy to liquefaction (liquefaction pressure of ammonia in the time of 20 ℃ only has 0.8MPa), be convenient to store and transportation, before can obtaining the anti-CO poisoned catalyst appearance of the commercial high storage material of using and permanence, producing PEMFC fuel hydrogen take ammonia as raw material will be one of effective technological approaches.The ammonia catabolite only has hydrogen and nitrogen, and nitrogen does not have negative effect to the electrode of PEMFC.Relevant technological economics evaluation shows, makes hydrogen take ammonia as raw material than making hydrogen by methanol recapitalization and has more economic advantages (R.Metkemeijer et al, Journal of Power Sources, 49 (1994) 271; Internationalof Hydrogen Energy, 19 (1994) 535).
At present, have a large amount of documents to disclose the document of the development ammonia decomposition catalyzer take hydrogen making as purpose, the catalyst activity component of reporting is mainly one pack system or the multicomponents such as Fe, Ni, Co, Mo, Ir, Pd, Pt, Rh, Ru, and carrier mostly is MgO, Al
2O
3, TiO
2, ZrO
2, SiO
2, MCM-41, SBA-15, active carbon, CNT (CNTs) and super base etc.In the research of these catalyst (227 (2004) 1. for S.F.Yin et al, Applied Catalysis A:General), take Ru as the activated centre and CNTs shown higher catalytic activity as the loaded noble metal catalyst of carrier.Yet the higher price of Ru and limited reserves have limited in the future it in the industrial applications of reality.Therefore, the development low temperature, high activity, high stability, the non-precious metal catalyst tool is of great significance cheaply.
Carbon nano-fiber (CNFs) is one of the most noticeable new material in recent years because of its unique structure and chemical characteristic.This class novel materials has higher application potential at aspects such as microelectronic component, polymeric additive, high capacity hydrogen storage catalyst carriers.Recently, bibliographical information (J.Zhang et al is arranged, ChemicalCommuni cati ons, (2007) 1916.) residual Co and the Fe nano particle of tubular carbon fiber (t-CNFs) of industry has higher ammonia degrading activity and high-temperature stability, yet metal nanoparticle most surfaces is wherein wrapped up by carbon fiber, can not fully be exposed to the surface of carbon fiber, thereby affect its catalytic activity.
Therefore, this area is in the urgent need to providing a kind of method for preparing carbon nano-fiber that can regulate and control size, pattern and the load situation of catalyst metal particles.
Summary of the invention
The present invention aims to provide a kind of preparation method of carbon nano-fiber.
In a first aspect of the present invention, a kind of preparation method of carbon nano-fiber is provided, described method comprises step:
(1) transition metal and/or its alloy are loaded to carrier surface, obtain catalyst precursor;
(2) catalyst precursor that step (1) is obtained obtains the catalyst of growing nano carbon fiber through the gaseous mixture reduction of argon gas and hydrogen; With
The catalyst of the growing nano carbon fiber that (3) step (2) is obtained contacts with carbon source, obtains carbon nano-fiber;
Described carrier is selected from inorganic particle or formed body.
In preparation method provided by the invention, described transition metal chosen from Fe, nickel; Alloy chosen from Fe-nickel, nickel-molybdenum, cobalt-molybdenum or the iron-cobalt of described transition metal; Described inorganic particle is selected from mica, imvite, silica, titanium dioxide, magnesia, aluminium oxide or carbon black; Described formed body is selected from graphite felt, carbon paper, stainless steel substrates or cordierite.
In preparation method's provided by the invention step (2), the gaseous mixture of catalyst precursor process argon gas and hydrogen obtains the catalyst of growing nano carbon fiber at 500-700 ℃ of reduction 0.5-5h.
The catalyst of the growing nano carbon fiber that obtains in preparation method's provided by the invention step (2), in its gross weight, wherein the percentage by weight of the transition metal of load and/or its alloy is 0.5-20.0%.
In preparation method's provided by the invention step (3), the catalyst of growing nano carbon fiber is contacted with carbon source, 500-700 ℃ of reaction 0.5-20 hour, obtain carbon nano-fiber.
In preparation method provided by the invention, described carbon source is carbon monoxide or ethene.
In preparation method provided by the invention, described load is finished by following step:
(a) precursor water solution and the carrier with transition metal and/or its alloy mix, leave standstill, dry after at 500-700 ℃ of roasting 2-5 hour.
In another preference, the precursor water solution of step (a) is in its gross weight, and the percentage by weight of transition metal wherein and/or the presoma of its alloy is 3.2-42.5%.
In preparation method provided by the invention, described load also can be finished by following step:
(i) with presoma, urea, carrier and the water of transition metal and/or its alloy 85-90 ℃ of mixing, obtain suspension i; With
(ii) suspension i is filtered, behind the filtration cakes torrefaction at 500-700 ℃ of roasting 2-5 hour.
In another preference, in the step (i), in the gross weight of the suspension i that obtains, the percentage by weight of transition metal wherein and/or the presoma of its alloy is 0.7-24.8%.
In a second aspect of the present invention, a kind of purposes of carbon nano-fiber is provided, prepare the catalyst of hydrogen as ammonia decomposition reaction; The weight ratio of described Nano carbon fibers peacekeeping catalyst wherein is 0.1-5.0: 1; Described catalyst is transition metal and/or its alloy.
Described carbon nano-fiber is carbon nanofibers.
In another preference, described carbon nano-fiber is to obtain by preparation method provided by the invention.
Accordingly, the invention provides a kind of method for preparing carbon nano-fiber that can regulate and control size, pattern and the load situation of catalyst metal particles.
Description of drawings
Fig. 1 has shown Fe particle size distribution situation in the carbon nanofibers provided by the invention (Fe particle size range 20-160nm).
Fig. 2 has shown powerful carbon nanofibers among Fig. 1 provided by the invention.
Fig. 3 has shown Fe particle size distribution situation in the plshy bone open carbon nano-fiber provided by the invention (Fe particle size range 50-300nm).
Fig. 4 has shown powerful plshy bone open carbon nano-fiber among Fig. 3 provided by the invention.
Fig. 5 has shown the stability of carbon nanofibers CAT-5 provided by the invention.
Fig. 6 has shown the carbon nanofibers CAT-5 for preparing among the embodiment 5 and the X-ray diffractogram (XRD) of CAT-19.
Fig. 7 has shown carbon nanofibers CAT-5 and the steadiness of CAT-19 under oxidation (TG-DTG) for preparing among the embodiment 5.
Fig. 8 has shown that the carbon nanofibers CAT-5 for preparing among the embodiment 5 and CAT-19 are at reducing atmosphere (H
2-steadiness under TPR).
The specific embodiment
The inventor finds with γ-Al through extensive and deep research
2O
3, SiO
2, MgO, MMT, TiO
2, mica, carbon black, graphite felt, cordierite, carbon paper, stainless steel substrates etc. be carrier, utilize equi-volume impregnating or (with) (transition metal or its alloy are such as but not limited to Fe, Ni, Fe-Ni, Ni-Mo, Co-Mo or Fe-Co for the deposition-precipitation method load active component; Preferred Fe, Ni or Fe-Ni), obtain catalyst precursor after roasting, the reduction, again with the gaseous mixture reduction of this catalyst precursor through argon gas and hydrogen, obtain the catalyst of growing nano carbon fiber, then the catalyst of growing nano carbon fiber is used for the growth of carbon nano-fiber, thereby obtains with ammonia decomposition reaction preparation zero CO
xThe catalyst of hydrogen.Finished on this basis the present invention.
As used herein, " catalyst precursor " refers to that its area load has the material of transition metal oxide or its alloyed oxide take inorganic particle or formed body as carrier.
As used herein, " catalyst of growing nano carbon fiber " refers to that catalyst precursor is through the reduction of argon gas and hydrogen gas mixture, the material of the inorganic particle that obtains or formed body carrying transition metal or its alloy.
As used herein, " carbon nano-fiber " refers to that with the material of inorganic particle or formed body carrying transition metal or its alloy and the material of carbon source contact preparation, without any processing, its area load has transition metal or its alloying pellet.
In the present invention, catalyst precursor can prepare by equi-volume impregnating or deposition-precipitation method, such as but not limited to the disclosed method of document (G.Ertl etc. compile " Handbook of Heterogeneous Catalysis ", Wiley, 2008).Specifically can prepare by following step:
(a) precursor water solution and the carrier with transition metal and/or its alloy mixes, leaves standstill, obtained at 500-700 ℃ of roasting 2-5 hour after dry.
In the step (a), to implement the gross weight of the aqueous solution, wherein the percentage by weight of the presoma of transition metal and/or its alloy is 3.2-42.5%; The weight of the described aqueous solution equals the saturated water adsorptive value of different carriers; Time of repose is 10-14 hour.Preferably, the roasting in the step (a) is carried out in air, obtains catalyst precursor in 0.5-4 hour 500-700 ℃ of reduction again after the roasting.
In a preference of the present invention, described equi-volume impregnating is: the saturated water absorption of at first measuring insoluble carrier mica is the 0.65g/g mica, then according to preparing 10.0000g0.5wt%Fe/ mica catalyst, the quality of required mica is 9.9500g, (the presoma quality of iron is 0.3607 to dispose the precursor water solution of corresponding iron, the quality of water is 6.3229g), and be added dropwise to uniform stirring on the mica carrier.After static 12 hours, 120 ℃ of dryings 12 hours, then roasting 3 hours in 600 ℃ of air, it is for subsequent use at last the gained catalyst precursor to be ground encapsulation.
Catalyst precursor among the present invention also can prepare by following step:
(i) with presoma, urea, carrier and the water of transition metal and/or its alloy 85-90 ℃ of mixing, obtain suspension i; With
(ii) will obtain at 500-700 ℃ of roasting 2-5 hour behind suspension i filtration, the filtration cakes torrefaction.
Preferably, suspension i obtains by following step:
(i ') mixes carrier and water, obtains carrier suspension;
(i ") will contain the aqueous solution of the presoma of transition metal and/or its alloy and urea and carrier suspension that step (i ') obtains 85-90 ℃ of mixing, obtain suspension i.
In a preference of the present invention, described deposition-precipitation method is: at first add 300mL distilled water in there-necked flask, then add 9.9500g mica carrier, dripping the nitre acid for adjusting pH value is 5-6, and at 90 ℃ of stirred in water bath 2-3 hours.And then add 0.3607g ferric nitrate and a certain amount of urea, continue to stir 12 hours.Filter and after distilled water repeatedly washs with filter cake 120 ℃ of dryings 12 hours, then roasting 3 hours in 600 ℃ of air, it is for subsequent use at last the gained catalyst precursor to be ground encapsulation.
Growing nano carbon fiber catalyst in the present invention prepares by following step:
To advance with the catalyst precursor of equi-volume impregnating and deposition-precipitation method preparation the gaseous mixture of argon gas and hydrogen at 500-700 ℃ of reduction 0.5-5h.Preferably, the volume ratio of argon gas and hydrogen is 4: 1-3: it is 1h with the recovery time that 1 (preferred 3: 1) and temperature are 600 ℃.
In the present invention, the presoma of transition metal is selected from the nitrate such as but not limited to iron, the nitrate of nickel; The presoma of transition metal alloy is selected from such as but not limited to the nitrate of iron and the nitrate of nickel.
As used herein, be selected from mica, imvite, silica, titanium dioxide, magnesia, gama-alumina or carbon black as " inorganic particle " of the carrier of catalyst precursor; " formed body " as the carrier of catalyst precursor is selected from graphite felt, carbon paper, stainless steel substrates or cordierite.
Preferably, be tabular as the carrier of catalyst precursor among the present invention, and have smooth surface.
As used herein, " mica (mica) " refers to a kind of rock-forming mineral, and the general name of the layer structure aluminosilicates such as potassium, aluminium, magnesium, iron, lithium is tabular, sheet, the column crystalline form of false six sides or rhombus usually.
As used herein, " imvite " main component montmorillonite is octahedra by two-layer Si-O tetrahedron and one deck Al-O, the phyllosilicate crystal of composition, and it mainly is sodium ion that layer contains cation, magnesium ion, calcium ion, next has potassium ion, lithium ion etc." imvite " refers to that smectite clay (comprising that calcium base, sodium base, Sodium/Calcium base, magnesium base cover clay) forms through the dispersion of delaminating, the remodeling of purifying, super-fine classified, special organic composite, average wafer thickness can be used as inorganic polymer class thickener less than 25nm.
As used herein, " carbon black (carbon black) " refers to a kind of amorphous carbon.Gently, the pine and superfine black powder, specific area is very large, scope is from 10-3000m
2/ g, be organic matter (natural gas, heavy oil, fuel wet goods) under the condition of lack of air through imperfect combustion or decomposes and product, molecular weight 12.01.Outward appearance is particulate or the powder of ater.The depth of color, the fineness of particle, the size of proportion, all different and variant with raw materials used and manufacture method.Carbon black is water insoluble, sour, alkali; Can become carbon dioxide at combustion synthesis in air.The chief component thing of carbon black is carbon, also contains a small amount of hydrogen, oxygen, sulphur, ash content, tar and moisture.
As used herein, " graphite felt " refers to that acupuncture becomes felt take the PAN fiber as raw material, through production processes such as pre-oxidation, carbonization, graphitizations and get, is the new type high temperature heat-barrier material.
As used herein, " cordierite " refers to a kind of silicate mineral (2MgO2Al
2O
35SiO
2), pleochroism has glassy lustre, claims again water sapphire.
The invention provides a kind of preparation method of carbon nano-fiber, described method is that the catalyst with growing nano carbon fiber provided by the invention contacts with carbon source, obtains carbon nano-fiber.Described carbon source is selected from carbon monoxide or ethene.Mode with the carbon source contact can be this area routine, such as but not limited to, 500-700 ℃ of reaction 0.5-20 hour.
The carbon nano-fiber that the present invention obtains is selected from tubular carbon fiber, plshy bone open carbon fiber or plate-type carbon fiber; Preferred plate-type carbon fiber, wherein take carbon monoxide as carbon source and Fe be active component, as the carrier of catalyst precursor, can prepare the monoblock type plate-type carbon fiber with stainless steel substrates or carbon paper; Take ethene as carbon source and Ni be active component, as the carrier of catalyst precursor, also can prepare the monoblock type plate-type carbon fiber with graphite felt and cordierite.
The preferred mist of carbon source of the present invention contains carbon monoxide and hydrogen in the mist, or contains ethene and hydrogen, more preferably, also contains argon gas in the mist.The volume ratio of various gases can be the conventional use in this area in the mist.
In the present invention, " tubular carbon fiber (t-CNFs) ", " plshy bone open carbon fiber (f-CNFs) " and " plate-type carbon fiber (p-CNFs) " refer to that respectively the graphite flake layer of carbon fiber and the angle between the growth axis are 0 °, 0 °-90 ° and 90 °.
In the present invention, the degree of graphitization of carbon fiber (Graphitic degree, referred to as G, unit is %) expression has the probability of ideal graphite crystal structure.G is the model G=100 (0.3440-d that proposes according to Maire and Mering (J.Maire, J.Mering, Chemistry and physics of Carbon, 6 (1970) 125)
002)/(0.3440-0.3354) calculates.D wherein
002Obtained by Bragg formula d=λ/(2sin θ).0.3440 be the complete interlamellar spacing of graphitized carbon material (nm) not; 0.3354 be the interlamellar spacing (nm) of desirable single crystal graphite.The G value is higher, and the degree of graphitization that represents carbon fiber is higher.
That method provided by the invention prepares is the higher p-CNFs of degree of graphitization.
Carbon nano-fiber provided by the invention can be used as the catalyst that ammonia decomposition reaction prepares hydrogen; The weight ratio of described Nano carbon fibers peacekeeping catalyst wherein is 0.1-5.0: 1; Described catalyst is transition metal and/or its alloy.
The above-mentioned feature that the present invention mentions, or the feature that embodiment mentions can any combination.All features that this case specification discloses can with any composition forms and usefulness, each feature that discloses in the specification can anyly provide the alternative characteristics of identical, impartial or similar purpose to replace.Therefore except special instruction is arranged, the feature that discloses only is the general example of equalization or similar features.
Major advantage of the present invention is:
1, the catalyst in the carbon nano-fiber provided by the invention (transition metal or its alloy) is globoid, and at the top of carbon nano-fiber, thereby can fully expose, improve catalytic capability.
2, it is even to be positioned at the catalyst granules particle diameter at carbon nano-fiber of the present invention top, and specific area is large.
3, the method for preparing carbon nano-fiber provided by the invention can be regulated and control size and the pattern of catalyst granules wherein.
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.The experimental technique of unreceipted actual conditions in the following example is usually according to normal condition or the condition of advising according to manufacturer.Unless otherwise indicated, otherwise all percentage, ratio, ratio or umber by weight.
Unit in the percent weight in volume among the present invention is well-known to those skilled in the art, for example refers to the weight of solute in 100 milliliters solution.
Unless otherwise defined, employed all specialties are identical with the meaning that scientific words and one skilled in the art are familiar with in the literary composition.In addition, any method similar or impartial to described content and material all can be applicable in the inventive method.The usefulness that better implementation method described in the literary composition and material only present a demonstration.
The activity of catalyst represents with the conversion ratio of ammonia in the embodiment of the invention.
The mica that relates in the embodiment of the invention is available from Junjiang Science and Technology Co Ltd, Shanghai.
The ferric nitrate that relates in the embodiment of the invention and nickel nitrate are all available from Chemical Reagent Co., Ltd., Sinopharm Group.
The quartz boat that relates in the embodiment of the invention is available from glass apparatus processing factory of East China University of Science.
The fixed-bed quartz reactor that relates in the embodiment of the invention is available from Shanghai experimental electric furnace factory.
The change modulation CNFs of I, carrier is p-CNFs
Embodiment 1 to embodiment 8, and the carbon source of preparation nanometer CNFs is CO, CO/H
2=800/200mL/min, reaction temperature is 600 ℃.
Embodiment 1
The catalyst S-1 of preparation growing nano carbon fiber is to S-5
Utilize equi-volume impregnating, get 0.3607gFe (NO
3)
39H
2O is dissolved in wiring solution-forming in the 6.3229g water, then this solution dropwise is added drop-wise on the 9.9500g commodity mica, behind the strong agitation 1h, the sample that makes, after static (12h under the room temperature) and dry (120 ℃ of lower 12h), 600 ℃ of roasting 3h in air atmosphere are then at H
2600 ℃ of reduction 1h in/Ar (200/600mL/min) atmosphere, wherein, the content of Fe is the Fe/ mica catalyst of 0.5wt%, is expressed as S-1.
By same method, the load capacity of the Fe that obtains is respectively the Fe/ mica catalyst of 1.0wt%, 4.0wt%, 7.0wt% and 10.0wt%, is expressed as respectively S-2, S-3, S-4 and S-5.
Embodiment 2
The catalyst S-6 of preparation growing nano carbon fiber is to S-8
In the above-mentioned case study on implementation, used preparation method changes deposition-precipitation method into.At first add 300mL distilled water in there-necked flask, then add 9.9500g mica carrier, dripping the nitre acid for adjusting pH value is 5-6, and at 90 ℃ of stirred in water bath 2-3 hours.And then add 0.3607g ferric nitrate and a certain amount of urea, continue to stir 12 hours.Filter and after distilled water repeatedly washs with filter cake 120 ℃ of dryings 12 hours, then roasting 3 hours in 600 ℃ of air is then at H
2600 ℃ of reduction 1h in/Ar (200/600mL/min) atmosphere, wherein, the content of Fe is the Fe/ mica catalyst of 0.5wt%, is expressed as S-6.
By same method, the load capacity of the Fe that obtains is respectively the Fe/ mica catalyst of 10.0wt% and 20.0wt%, is expressed as respectively S-7 and S-8.
Embodiment 3
The catalyst S-9 of preparation growing nano carbon fiber is to S-16
Use is with embodiment 2 similar deposition-precipitation method load 20.0wt%Fe active components, change the type (seeing table 1 for details) of carrier, the catalyst that makes is expressed as respectively S-9, S-10, S-11, S-12, S-13, S-14, S-15, S-16, S-17 and S-18.Can realize microstructure modulation in plshy bone open and board-like scope of the graphite unit arrangement mode of carbon nano-fiber by the change of carrier.Carrier (mica, imvite, SiO with platen surface
2, MgO, TiO
2, carbon paper, stainless steel substrates) load Fe particle, the dull and stereotyped interface that is in contact with one another with Fe is smooth flat board, this interface can provide template mechanism to be used for growth p-CNFs.And the carrier (γ-Al of non-tablet
2O
3, carbon black, graphite felt, cordierite) load Fe particle, the carbon fiber that grows is f-CNFs.
Embodiment 4
The catalyst S-19 of preparation growing nano carbon fiber
Do not use any carrier, directly utilize Fe
3O
4Powder (purity is greater than 99.8%, granular size 20-30nm, Alfa Aesar company produces) reduction obtains the Fe particle, at H
2600 ℃ of reduction 1h in/Ar (200/600mL/min) atmosphere, the Fe catalyst of preparation is expressed as S-19.
Table 1 has shown the situation of the catalyst of the growing nano carbon fiber that embodiment 1-4 prepares:
Composition and the constituent content of the catalyst of the made growing nano carbon fiber of table 1 embodiment 1-4
| Sample | Carrier | The load capacity of Fe (wt%) | The preparation method |
| S-1 | Mica | 0.5 | Equi-volume impregnating |
| S-2 | Mica | 1.0 | Equi-volume impregnating |
| S-3 | Mica | 4.0 | Equi-volume impregnating |
| S-4 | Mica | 7.0 | Equi-volume impregnating |
| S-5 | Mica | 10.0 | Equi-volume impregnating |
| S-6 | Mica | 0.5 | Deposition-precipitation method |
| S-7 | Mica | 10.0 | Deposition-precipitation method |
| S-8 | Mica | 20.0 | Deposition-precipitation method |
| S-9 | Imvite | 20.0 | Deposition-precipitation method |
| S-10 | Silica | 20.0 | Deposition-precipitation method |
| S-11 | Titanium dioxide | 20.0 | Deposition-precipitation method |
| S-12 | Magnesia | 20.0 | Deposition-precipitation method |
| S-13 | Gama-alumina | 20.0 | Deposition-precipitation method |
| S-14 | Carbon black | 20.0 | Deposition-precipitation method |
| S-15 | Graphite felt | 20.0 | Deposition-precipitation method |
| S-16 | Cordierite | 20.0 | Deposition-precipitation method |
| S-17 | Carbon paper | 20.0 | Deposition-precipitation method |
| S-18 | Stainless steel substrates | 20.0 | Deposition-precipitation method |
| S-19 | Nothing | 100.0 |
Preparation carbon nano-fiber CAT-1 to CAT-17
Take by weighing the catalyst of the S-1 growing nano carbon fiber that obtains among the 6.0000g embodiment 1, it evenly is tiled in the quartz boat, then quartz boat is placed the fixed-bed quartz reactor middle part of being furnished with heating furnace, pass into CO/H
2Gaseous mixture (800/200mL/min) in 600 ℃ of reaction 1.5h, carries out the preparation of carbon nano-fiber, and the protective atmosphere at argon gas drops to room temperature at last, and the carbon nano-fiber that obtains is expressed as CAT-1.
As stated above, change the carbon fibre growth time into 0.5h, 3.5h, 7.0h and 16h, the carbon nano-fiber that obtains is expressed as respectively CAT-20, CAT-21, CAT-22 and CAT-23.
As stated above, with the growth of S-2 ~ S-18 for carbon fiber, the prepared carbon nano-fiber that obtains is expressed as respectively CAT-2 ~ CAT-18.
As stated above, take by weighing the growth that 1.2000g S-19 is used for carbon fiber, the prepared carbon nano-fiber that obtains is expressed as respectively CAT-19.
Table 2 is composition and constituent contents of prepared carbon nano-fiber:
Table 2
Wherein the carbon nano-fiber of the preparation of the catalyst take S-1 ~ S-12 and S17 ~ S-18 as growing nano carbon fiber is p-CNFs (CAT-1 ~ CAT-12 and CAT-17 ~ CAT-18), the Fe particle size distribution is more even pattern homogeneous, as depicted in figs. 1 and 2 (take CAT-5 as example, the Fe particle size distribution also has similar result with pattern in other plate-type carbon fiber catalyst);
The carbon nano-fiber of the catalyst preparation take S-13 ~ S-16 and S-19 as growing nano carbon fiber is as f-CNFs (CAT-13 ~ CAT-16 and CAT-19), Fe granule-morphology homogeneous, but the most of crystal face of the particle diameter wider distribution of Fe particle and Fe particle is wrapped by f-CNFs, as shown in Figure 3 and Figure 4 (take CAT-19 as example, the Fe particle size distribution also has similar result with pattern in other plshy bone open carbon fiber catalyst).
Embodiment 6
Ammonia decomposition reaction hydrogen manufacturing
Get in 0.1000gCAT-1 ~ CAT-23 catalyst wherein a kind of, be put in the quartz reactor, under argon gas atmosphere, be warming up to 600 ℃ with 16 ℃/min, and under this temperature, stop 3h, then pass into high-purity ammonia and react at 600 ℃, the GHSV=36000mL/ (hg of ammonia
Cat).The result of ammonia conversion ratio is as shown in table 2, can find out that Fe particle ammonia rates of decomposing and transforming with this understanding is 88.7%-98.4% among the p-CNFs, be higher than that Fe particle ammonia rates of decomposing and transforming with this understanding is 49.6%-79.6% among the f-CNFs, more be higher than the activity (as shown in table 3) of industrial ammonia decomposition catalyzer.In addition, for the Fe particle among the p-CNFs, the Fe particle of mica load has higher ammonia degrading activity.
Table 3
(
aJ.Zhang et al，Chemical Communications，(2007)1916；
bA.S.Chellappa et al，Applied Catalysis A：General，227(2002)231；
cC.H.Liang et al，Industrial & Engineering Chemistry Research，39(2000)3964.)
Embodiment 7
Preparation carbon nano-fiber CAT-24 to CAT-26 and ammonia decomposition reaction hydrogen manufacturing
Press the method for the catalyst of above-mentioned preparation S-6 growing nano carbon fiber, take mica as carrier, presoma take nickel nitrate as Ni, the load capacity of preparation Ni is respectively the catalyst of 0.5wt%, 10.0wt% and 20.0wt%, is expressed as respectively S-20, S-21 and S-22.
Then, take by weighing respectively 6.0000g S-20, S-21 or S-22 catalyst, it evenly be tiled in the quartz boat, then with quartz boat as for the fixed-bed quartz reactor middle part of being furnished with heating furnace, pass into CO/H
2Gaseous mixture (800/200mL/min) in 600 ℃ of reaction 1.5h, carries out the preparation of carbon nano-fiber, and the protective atmosphere at argon gas drops to room temperature at last, and the carbon nano-fiber that obtains is expressed as respectively CAT-24, CAT-25 and CAT-26 (seeing Table 4).
Table 4
Get among 0.1000g catalyst CAT-24 ~ CAT-26 wherein a kind of, be put in the quartz reactor, under argon gas atmosphere, be warming up to 600 ℃ with 16 ℃/min, and under this temperature, stop 3h, then pass into high-purity ammonia and react at 600 ℃, the GHSV=36000mL/ (hg of ammonia
Cat).The result of ammonia conversion ratio is as shown in table 4, can find out that Ni particle ammonia rates of decomposing and transforming with this understanding is 91.2%-99.9% among the f-CNFs, is higher than that Fe particle ammonia rates of decomposing and transforming with this understanding is 49.6%-79.6% among the f-CNFs.
For carbon nano-fiber CAT-24～CAT-26, when reactive metal changes Ni into, when using CO as carbon source, CO/H
2=800/200ml/min, reaction temperature is 600 ℃, utilizes mica as carrier (carbon fiber of other board-like carrier loaded Ni preparations also has similar character), can prepare the higher p-CNFs of degree of graphitization.
Embodiment 8
Preparation carbon nano-fiber CAT-27 to CAT-30 and ammonia decomposition reaction hydrogen manufacturing
Press the method for the catalyst of above-mentioned preparation S-6 growing nano carbon fiber, take mica as carrier, presoma take nickel nitrate and ferric nitrate as Ni and Fe, prepare the alloy catalyst of three kinds of 10.0wt%Ni-Fe (Ni/Fe=5/5), Fe-Co (Fe/Co=5/5), Co-Mo (Co/Mo=5/5) and Ni-Mo (Ni/Mo=5/5) growing nano carbon fiber, be expressed as respectively S-23, S-24, S-25 and S-26.
Then, take by weighing respectively the catalyst of 6.0000g S-23, S-24, S-25 and S-26 growing nano carbon fiber, it evenly be tiled in the quartz boat, then with quartz boat as for the fixed-bed quartz reactor middle part of being furnished with heating furnace, pass into CO/H
2Gaseous mixture (800/200mL/min) in 600 ℃ of reaction 1.5h, carries out the preparation of carbon nano-fiber, and the protective atmosphere at argon gas drops to room temperature at last, and the carbon nano-fiber that obtains is expressed as respectively CAT-27, CAT-28, CAT-29 and CAT-30.
Table 5
Get among 0.1000g catalyst CAT-27 ~ CAT-30 wherein a kind of, be put in the quartz reactor, under argon gas atmosphere, be warming up to 600 ℃ with 16 ℃/min, and under this temperature, stop 3h, then pass into high-purity ammonia and react at 600 ℃, the GHSV=36000mL/ (hg of ammonia
Cat).The result of ammonia conversion ratio is as shown in table 4, can find out that alloy catalyst has preferably ammonia degrading activity among the CNFs, and the ammonia rates of decomposing and transforming is 98.0%-99.8%.
For carbon nano-fiber CAT-27～CAT-30, when reactive metal changes alloy into, when using CO as carbon source, CO/H
2=800/200ml/min, reaction temperature is 600 ℃, utilizes mica as carrier (carbon fiber of other board-like carrier loaded Ni preparations also has similar character), can prepare the higher p-CNFs of degree of graphitization.
The change modulation CNFs of II, carbon source is p-CNFs
Embodiment 9
Preparation carbon nano-fiber CAT-31 to CAT-32 and ammonia decomposition reaction hydrogen manufacturing
Take by weighing the S-15 that obtains among the 6.0000g embodiment 1 and the catalyst of S-16 growing nano carbon fiber, it evenly is tiled in the quartz boat, then quartz boat is placed the fixed-bed quartz reactor middle part of being furnished with heating furnace, pass into C
2H
4/ H
2Gaseous mixture (800/200mL/min) in 600 ℃ of reaction 1.5h, carries out the preparation of carbon nano-fiber, and the protective atmosphere at argon gas drops to room temperature at last, and the p-CNFs that obtains is expressed as respectively CAT-31 and CAT-32.
Table 6
Get among 0.1000g catalyst CAT-31 ~ CAT-32 wherein a kind of, be put in the quartz reactor, under argon gas atmosphere, be warming up to 600 ℃ with 16 ℃/min, and under this temperature, stop 3h, then pass into high-purity ammonia and react at 600 ℃, the GHSV=36000mL/ (hg of ammonia
Cat).The result of ammonia conversion ratio is as shown in table 6, can find out that alloy catalyst has preferably ammonia degrading activity among the CNFs, and the ammonia rates of decomposing and transforming is 97.9%-98.1%.
For carbon nano-fiber CAT-31～CAT-32, when reactive metal changed Ni into, reaction temperature was 600 ℃, utilized S-15 and S-16 as carrier, also can prepare the higher monoblock type p-CNFs of degree of graphitization.
III, growth conditions (reaction temperature and CO/H
2Proportioning) change modulation CNFs is p-CNFs
Preparation carbon nano-fiber CAT-33 to CAT-36 and ammonia decomposition reaction hydrogen manufacturing
Take by weighing the catalyst of 6.0000g S-9 growing nano carbon fiber, it evenly be tiled in the quartz boat, then with quartz boat as for the fixed-bed quartz reactor middle part of being furnished with heating furnace, pass into C
2H
4/ H
2Gaseous mixture (800/200mL/min); respectively at 450 ℃, 570 ℃, 600 ℃, 800 ℃ reaction 1.5h; carry out the preparation of carbon nano-fiber; protective atmosphere at argon gas drops to room temperature at last, and the carbon nano-fiber that obtains is expressed as respectively CAT-33, CAT-34, CAT-35 and CAT-36 (seeing Table 4).
Table 7
Get among 0.1000g catalyst CAT-33 ~ CAT-36 wherein a kind of, be put in the quartz reactor, under argon gas atmosphere, be warming up to 600 ℃ with 16 ℃/min, and under this temperature, stop 3h, then pass into high-purity ammonia and react at 600 ℃, the GHSV=36000mL/ (hg of ammonia
Cat).The result of ammonia conversion ratio is as shown in table 6, can find out that the Fe catalyst has preferably ammonia degrading activity among the CAT-33, and the ammonia rates of decomposing and transforming is 96.7%, far above CAT-34 ~ CAT-36.
Embodiment 11
Preparation carbon nano-fiber CAT-37 to CAT-38 and ammonia decomposition reaction hydrogen manufacturing
Take by weighing the catalyst of 0.0500g S-19 growing nano carbon fiber, it evenly be tiled in the quartz boat, then with quartz boat as for the fixed-bed quartz reactor middle part of being furnished with heating furnace, pass into CO/H
2The gaseous mixture of/Ar, wherein CO and H
2(be expressed as Q, unit is m to the flow of mixture
3/ hour kilogram catalyst), in 600 ℃ of reaction 1.5h, carry out the preparation of carbon nano-fiber, the protective atmosphere at argon gas drops to room temperature at last, and the carbon nano-fiber that obtains is expressed as respectively CAT-37 and CAT-38 (seeing Table 8).
Table 8
Get among 0.1000g catalyst CAT-37 ~ CAT-38 wherein a kind of, be put in the quartz reactor, under argon gas atmosphere, be warming up to 600 ℃ with 16 ℃/min, and under this temperature, stop 3h, then pass into high-purity ammonia and react at 600 ℃, the GHSV=36000mL/ (hg of ammonia
Cat).The result of ammonia conversion ratio is as shown in table 6, can find out that the Fe catalyst has preferably ammonia degrading activity among the CAT-38, and the ammonia rates of decomposing and transforming is 94.2%, far above CAT-37.
Test example 1
Stability test
In order to further specify the superiority of catalyst of the present invention, select carbon nano-fiber CAT-5 as the catalyst of preparing hydrogen by ammonia decomposition, (reaction temperature is 600 ℃, GHSV to have carried out the stability of 100h
NH3=36000mL/ (hg
Cat)) investigate, the result is as shown in Figure 5.Can find out that the CAT-5 ammonia decomposition catalyzer has preferably structural stability.
Test example 2
The stability test of carbon fiber under degree of graphitization test and the oxidation-reducing atmosphere
The CAT-5 for preparing in above-described embodiment is as example, and the CAT-19 for preparing in above-described embodiment is as Comparative Examples, and the characterization result of the XRD of two kinds of carbon nano-fibers is seen Fig. 6 and table 9.The result shows that the p-CNFs (CAT-5) that the catalyst of use S-5 growing nano carbon fiber prepares has higher degree of graphitization, and other plate-type carbon fibers also have similar rule.
Table 9
| Sample | The microstructure of CNFs | G(％) |
| CAT-5 | Board-like | 95.1 |
| CAT-19 | Plshy bone open | 74.4 |
Then investigate CAT-5 and CAT-19 in the difference of oxidation-reducing atmosphere stability inferior, the results are shown in Figure 7 and Fig. 8.The stability test of carbon nano-fiber carries out on TA SDT-Q600 (TA company, the U.S.) differential scanning calorimetric analysis instrument under the oxidizing atmosphere, and as carrier gas, sample is warming up to 800 ℃ with 10 ℃/min under this atmosphere with air.The stability test of carbon nano-fiber carries out on Autochem II 2920 (Micromeritics company, the U.S.) temperature programmed reduction instrument under the reducing atmosphere, with 10%H
2-Ar gaseous mixture, sample are warming up to 700 ℃ with 10 ℃/min under this atmosphere.The result shows that CAT-5 is at oxidation (Fig. 7, TG-DTG) or reducing atmosphere (Fig. 8, H
2-TPR) under, all have higher stability, other plate-type carbon fibers also have similar rule.
The above only is preferred embodiment of the present invention, be not to limit essence technology contents scope of the present invention, essence technology contents of the present invention is broadly to be defined in the claim scope of application, any technology entity or method that other people finish, if defined identical with the claim scope of application, also or a kind of change of equivalence, all will be regarded as being covered by among this claim scope.
Claims (10)
1. the preparation method of a carbon nano-fiber is characterized in that, described method comprises step:
(1) transition metal and/or its alloy are loaded to carrier surface, obtain catalyst precursor;
(2) catalyst precursor that step (1) is obtained obtains the catalyst of growing nano carbon fiber through the gaseous mixture reduction of argon gas and hydrogen; With
The catalyst of the growing nano carbon fiber that (3) step (2) is obtained contacts with carbon source, obtains carbon nano-fiber;
Described carrier is selected from inorganic particle or formed body; Described carrier is tabular, and has smooth surface.
2. preparation method as claimed in claim 1 is characterized in that, described transition metal chosen from Fe, nickel; Alloy chosen from Fe-nickel, nickel-molybdenum, cobalt-molybdenum or the iron-cobalt of described transition metal; Described inorganic particle is selected from mica, imvite, silica, titanium dioxide, magnesia, aluminium oxide or carbon black; Described formed body is selected from graphite felt, carbon paper, stainless steel substrates or cordierite.
3. preparation method as claimed in claim 1 is characterized in that, described load is finished by following step:
(a) precursor water solution and the carrier with transition metal and/or its alloy mix, leave standstill, dry after at 500-700 ℃ of roasting 2-5 hour; Or
(i) with presoma, urea, carrier and the water of transition metal and/or its alloy 85-90 ℃ of mixing, obtain suspension i; With
(ii) suspension i is filtered, behind the filtration cakes torrefaction at 500-700 ℃ of roasting 2-5 hour.
4. preparation method as claimed in claim 3 is characterized in that, the precursor water solution of step (a) is in its gross weight, and the percentage by weight of transition metal wherein and/or the presoma of its alloy is 3.2-42.5%; In the step (i), in the gross weight of the suspension i that obtains, the percentage by weight of transition metal wherein and/or the presoma of its alloy is 0.7-24.8%.
5. preparation method as claimed in claim 1 is characterized in that, catalyst precursor at 500-700 ℃ of reduction 0.5-5h, obtains the catalyst of growing nano carbon fiber through the gaseous mixture of argon gas and hydrogen in the step (2).
6. such as the arbitrary described preparation method of claim 1-5, it is characterized in that the catalyst of the growing nano carbon fiber that step (2) obtains is in its gross weight, wherein the percentage by weight of the transition metal of load and/or its alloy is 0.5-20.0%.
7. preparation method as claimed in claim 1 is characterized in that, step (3) is that the catalyst with growing nano carbon fiber contacts with carbon source, 500-700 ℃ of reaction 0.5-20 hour, obtains carbon nano-fiber.
8. preparation method as claimed in claim 7 is characterized in that, described carbon source is carbon monoxide or ethene.
9. the purposes of a carbon nano-fiber is characterized in that, prepares the catalyst of hydrogen as ammonia decomposition reaction; The weight ratio of described Nano carbon fibers peacekeeping catalyst wherein is 0.1-5.0: 1; Described catalyst is transition metal and/or its alloy;
Described carbon nano-fiber is by obtaining such as the arbitrary described preparation method of claim 1-8.
10. purposes as claimed in claim 9 is characterized in that, described carbon nano-fiber is carbon nanofibers.
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| CN111215086A (en) * | 2018-11-25 | 2020-06-02 | 中国科学院大连化学物理研究所 | Application of rare earth oxide loaded transition metal catalyst in ammonia decomposition reaction |
| CN115155594B (en) * | 2022-07-15 | 2024-02-20 | 东南大学 | Preparation method and application of graphite alkyne-loaded metal ammonia decomposition catalyst |
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| CN1389295A (en) * | 2002-06-10 | 2003-01-08 | 中国科学院大连化学物理研究所 | Ru-based ammonia synthesizing catalyst carried by nano carbon fiber and its prepn. |
| CN1793451A (en) * | 2006-01-10 | 2006-06-28 | 华东理工大学 | Process for preparing plate type nano carbon fibre |
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| CN1793451A (en) * | 2006-01-10 | 2006-06-28 | 华东理工大学 | Process for preparing plate type nano carbon fibre |
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