CN105964268A - Metal catalyst preparation method and preparation method of carbon nanotube - Google Patents
Metal catalyst preparation method and preparation method of carbon nanotube Download PDFInfo
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Abstract
The invention provides a metal catalyst preparation method which comprises the following steps: I, providing a metal salt solution, wherein a raising agent, carrier metal and active metal ions with a carbon nanotube preparation activation function are dissolved in the metal salt solution; the raising agent comprises one or more of organic acid, organic alcohol, organic aldehydes, nitrogenous organic compounds and sugar; II, adding a precipitator into the metal salt solution, and stirring so as to obtain composite metal precipitation; III, heating and calcining the composite metal precipitation, and cooling after calcining, and screening, thereby obtaining a metal catalyst. Meanwhile, the invention further discloses a carbon nanotube prepared from the metal catalyst. Problems that the metal catalyst finished product rate of a nanotube catalyst preparation method is low, the particle size is not accordant, and the quality of carbon nanotubes can be affected are solved.
Description
Technical field
The present invention relates to the metallic catalyst preparation method that a kind of applicable fluid unit produces, and carbon nanometer
The preparation method of pipe.
Background technology
CNT is a kind of nanoscale tubulose carbon material with graphite crystallization found the early 1990s in 20th century
Material.CNT finds the most to have exceeded 20 years, its technology of preparing by initial arc discharge method, hydro-thermal method and
Laser ablation method is tens kinds of representative and prepares CNT method, yet with various methods limitation but
Not having a kind of to be suitable for CNT industrialization, follow-up had catalysis method, and catalysis method is considered as most to have carbon nanometer
The preparation method of pipe industrialization prospect.
It is easily controllable that catalysis method prepares the high and low cost of CNT productivity, technological parameter.But in catalysis method
The factor affecting CNT form and productivity is the composition of catalyst, catalyst preparation conditions and activation condition
Deng, it is therefore necessary to catalyst is prepared component and condition is studied, promote that the industrialization of CNT pushes away
Extensively have great importance.Along with the maturation of preparation method of carbon nano-tube, equipment is also corresponding by horizontal reacting
Stove is upgraded to fluid bed, further promotes the development of CNT, but utilizes fluid bed to prepare carbon nanometer
Metal catalysis conditions is required harsher by pipe, and CNT prepared by fluid bed is all to use CVD, its
The CNT caliber and the width of distribution thereof that prepare are big with the composition of metallic catalyst and particle diameter thereof
Little have direct relation, and such as the bulk density of metallic catalyst, granular size (mesh number), particle diameter distribution, granule is uniform
Property has strict requirements；Or but producing is the catalyst one-pass finished rate often prepared in experimentation
Low, need secondary and repeatedly smashing to sieve, the most not only make to prepare metallic catalyst complex process difficulty and control,
Also can cause the waste of catalyst, the catalyst as having a lot of mesh number bigger than normal after smashing does not meets working condition
And cause the unfavorable problems such as catalyst cost of idleness is high to exist；How to prepare metal catalyst particle uniformly,
Narrow distribution range, the catalyst that mechanical strength is high, is that the difficult problem preparing metallic catalyst is also with fluid bed
Prepare high-crystallinity, the key problem in technology of uniform diameter CNT.
Summary of the invention
Low for there is metallic catalyst yield rate in existing carbon nano-tube catalyst preparation method, particle diameter differs
Cause, the problem affecting carbon nanotube mass, the invention provides a kind of metallic catalyst preparation method and carbon thereof
Nanotube, compared to traditional preparation methods, by activity in the metallic catalyst that this device, method prepares
Metal and carrier metal Elemental redistribution are more uniform, and granule mesh number is little, and particle diameter is consistent, improves metal catalytic
The yield rate of agent, simplifies preparation technology.
It is as follows that the present invention solves the technical scheme that above-mentioned technical problem used:
A kind of metallic catalyst preparation method is provided, comprises the following steps:
Step one: provide a kind of metal salt solution, includes bulking agent, carrier gold in described metal salt solution
Belonging to ion and have CNT and prepare the active metallic ion of catalytic action, described bulking agent includes organic acid
One or more in class, organic alcohols, organic aldehydes, itrogenous organic substance, saccharide；
Step 2: add precipitant in described metal salt solution, stirring obtains composition metal precipitation；
Step 3: composition metal precipitation heats up and calcines, cooling down after calcining is sieved, is obtained metal catalytic
Agent.
Further, described carrier metal ion includes one or more in transition metal and lanthanide series metal
Combination.
Further, described active metallic ion include ferrum, cobalt, nickel, yttrium, molybdenum, copper, platinum, palladium, vanadium,
One or more combinations in niobium, tungsten, chromium, iridium and titanium.
Further, described carrier metal ion includes in copper, zinc, magnesium, aluminum, molybdenum, manganese, lanthanide series metal
One or more combination, described active metallic ion include in ferrum, cobalt, nickel one or more combination.
Further, the mol ratio of the active metallic ion in described metal salt solution and carrier metal ion is
0.5～5:0.5～4.
Further, on the basis of the raw material gross weight preparing metallic catalyst, the weight hundred of described bulking agent
Proportion by subtraction is 3～20%, prepares distributions of metallic elements uniform, the catalyst of uniform particle sizes.
Further, described bulking agent include organic acid, organic alcohols, organic aldehydes, itrogenous organic substance,
One or more in saccharide；Optimization citric acid, glucose, fructose, sucrose, ethylene glycol, Polyethylene Glycol,
One or more in high polyalcohols, carbamide.
Further, in described step 2, when adding precipitant, regulation metal salt solution pH value is 7～11.
Further, described precipitant is ammonia.
Further, in described step 3, the metal salt solution precipitated with composition metal is carried out intensification and forges
Burn, cooling down after calcining, sieve, obtain metallic catalyst.
Further, in described step 3, calcining heat is 400 DEG C～700 DEG C, and calcination time is 2～5h.
The preparation method of a kind of CNT, described CNT is prepared by metallic catalyst, and described metal is urged
Agent is prepared by above-mentioned metallic catalyst preparation method.
This metallic catalyst preparation method adds bulking agent on the basis of existing metal salt solution, described
Bulking agent is the material being dissolved in water, and described bulking agent is doped in compound gold forming composition metal precipitation when
Belong to precipitation internal, make composition metal precipitation form fluff structure, promote that distributions of metallic elements is more uniform, institute
State the elements such as C, H, O, N of containing in bulking agent formed during calcining carbon dioxide, steam,
The gases such as ammonia, the metallic catalyst grain obtained after composition metal precipitation is internally formed space, and then calcining
Footpath uniformity, the bulk density of catalyst is more suitable for fluid unit and prepares CNT, eliminates follow-up many
The secondary process pulverized and sieved, simplification of flowsheet, improves metallic catalyst yield.Use this metallic catalyst
Carrying out the preparation of CNT, the CNT obtained is uniform, and CNT caliber is at about 30nm, caliber
Long, CNT degree of crystallinity is high, and productivity is high；Meanwhile, this catalyst life is long, prepares catalyst and carbon is received
Mitron technique is simple, and production cost is low, is more suitable for big fluid bed and prepares the industrialization of CNT.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the metallic catalyst that the present invention provides；
Fig. 2 is the SEM mapping figure of oxygen element in the metallic catalyst that the present invention provides；
Fig. 3 is the SEM mapping figure of ferrum element in the metallic catalyst that the present invention provides；
Fig. 4 is the SEM mapping figure of magnesium elements in the metallic catalyst that the present invention provides；
Fig. 5 is the SEM mapping figure of lanthanum element in the metallic catalyst that the present invention provides；
Fig. 6 is the EDS spectrogram of the metallic catalyst that the present invention provides；
Fig. 7 is the SEM figure of the CNT that the present invention provides；
Fig. 8 is the hot weightless picture of the CNT that the present invention provides；
Fig. 9 is the Raman figure of the CNT that the present invention provides.
Detailed description of the invention
In order to make technical problem solved by the invention, technical scheme and beneficial effect clearer, with
Lower combination drawings and Examples, are further elaborated to the present invention.Should be appreciated that described herein
Specific embodiment only in order to explain the present invention, be not intended to limit the present invention.
The invention discloses a kind of metallic catalyst preparation method, comprise the following steps:
Step one: provide a kind of metal salt solution, is dissolved with bulking agent, carrier gold in described metal salt solution
Belong to and there is CNT prepare the active metallic ion of catalytic action, described bulking agent include organic acid,
One or more in organic alcohols, organic aldehydes, itrogenous organic substance, saccharide；
Step 2: add precipitant in described metal salt solution, stirring obtains composition metal precipitation；
Step 3: composition metal precipitation heats up and calcines, cooling down after calcining is sieved, is obtained metal catalytic
Agent.
When preparing described metal salt solution, weigh active metal salt and carrier metal salt in catalytic component ratio,
And be dissolved in deionized water, it is filtrated to get the first solution；Bulking agent is weighed in calculating ratio, and will
It is dissolved in deionized water, is filtrated to get the second solution；Described first solution and the second solution are mixed i.e.
Obtain the metal salt solution described in step one.Another embodiment of the invention is: by catalytic component
Ratio weighs active metal salt and carrier metal salt, and is dissolved in deionized water, then weighs bulking agent
It is dissolved in this solution, obtains the metal salt solution described in step one.
The solvent that this metal salt solution uses is deionized water, and described deionized water is i.e. without other metal ion
Water, can avoid introducing foreign ion in the solution, so avoid to composition metal precipitation composition produce shadow
Ring.
The present invention adds bulking agent, active metallic ion and carrier metal ion in metal salt solution, when
When adding precipitant in metallic solution, active metallic ion, carrier metal ion and bulking agent are formed coprecipitated
Forming sediment, stirring obtains the composition metal precipitation with bulking agent doping, and described bulking agent is incendivity or pyrolysis
Organic substance, when calcining this composition metal precipitation, composition metal precipitation calcining forms composition metal oxygen
Compound catalyst, described bulking agent burns or is pyrolyzed into gas effusion, forming hole in metal composite oxide
Gap, thus form open structure, this metallic catalyst is the powder of molecule, by metallic catalyst mistake
100～200 mesh sieves, it is possible to obtain the one-pass finished rate of more than 95%, it is to avoid follow-up pulverizing and sieving repeatedly
Process, simplifies production procedure, improves production efficiency, the metallic catalyst mesh number distribution simultaneously obtained
Narrow, be conducive to improving its catalytic effect in CNT preparation process.
In the present invention, the kind for carrier metal ion is not particularly limited, described carrier metal
Ion includes one or more combinations in transition metal and lanthanide series metal.One as the present invention is preferred
Embodiment, described carrier metal ion includes the transition metal such as copper, zinc, magnesium, aluminum, molybdenum, manganese, with
And one or more combinations in lanthanide series metal.
Described active metallic ion i.e. CNT can be prepared produce catalytic action active metal from
Sub-form, described active metallic ion include active metallic ion include ferrum, cobalt, nickel, yttrium, molybdenum, copper,
One or more combinations in platinum, palladium, vanadium, niobium, tungsten, chromium, iridium and titanium.One as the present invention is excellent
The embodiment of choosing, described active metallic ion includes one or more combinations in ferrum, cobalt, nickel.
Described metal salt solution calculates according to active component and carrier component mol ratio, further preferred institute
The mol ratio stating the active metallic ion in metal salt solution and carrier metal ion is 0.5～5:0.5～4.
To prepare metal catalyst weight benchmark, the percentage by weight of described bulking agent is 3～20%.
Described bulking agent includes in organic acid, organic alcohols, organic aldehydes, itrogenous organic substance, saccharide
One or more；As citric acid, glucose, fructose, sucrose, ethylene glycol, Polyethylene Glycol, high polyalcohols,
One or more in carbamide.During preparing metallic catalyst, introduce bulking agent, the most do not affect catalysis
The metal component ratio of agent, also will not produce harmful effect to its preparation technology, otherwise, compared to not introducing
The existing technique of catalyst, catalyst activity metal and carrier metal that present invention process prepares are distributed more
Uniformly, substantially increase the yield rate of metallic catalyst, simplify preparation technology, reduce production cost, follow-up
Prepare CNT degree of crystallinity high.
Described precipitant is ammonia, containing a large amount of OH in ammonia-, after adding ammonia in above-mentioned metal salt solution,
Carrier metal ion and active metallic ion respectively with OH-Ions binding forms precipitated metal；
NH in the most described ammonia3·H2The amount of the material of O is total with the electric charge of metal cation in metal salt solution
Number is equal.With the OH that offer is enough-Ion and the active metallic ion in metal salt solution and carrier metal ion
Coordinate, avoid excess of ammonia water to produce complexing with some metal ion simultaneously, cause resolution of precipitate.
When adding precipitant, regulation metal salt solution pH value is 7～11, may advantageously facilitate active metallic ion
Precipitate with carrier metal ion.
Metal salt solution by the composition metal obtained precipitation or with composition metal precipitation is calcined, calcining
Temperature is 400 DEG C～700 DEG C, and calcination time is 2～5h, remove composition metal precipitation in water be easily pyrolyzed into
Point, obtain black metal catalyst particles；If calcining heat is less than 400 DEG C, then cannot be to composition metal
Crystal effectively decomposes, if calcining heat is more than 700 DEG C, then easily produces the form of the metallic catalyst generated
Raw impact.
It should be noted that in step 3 of the present invention, can be composition metal precipitation mistake from metal salt solution
Calcine after filter, it is also possible to be directly the metal salt solution precipitated with composition metal to be calcined, make
For the present invention one preferred embodiment, in metal salt solution produce composition metal precipitation after, will
Metal salt solution with composition metal precipitation puts into heating in Muffle furnace, and during calcining, slaine is molten
Liquid moisture evaporates so that bulking agent decomposes, and improves bulking agent and active metallic ion, carrier metal ion
In conjunction with ratio, improve the fluffy degree of the metallic catalyst generated, improve active metallic ion, carrier metal
The utilization rate of ion；Metallic catalyst is obtained after calcining.
The invention also discloses a kind of CNT, described CNT uses metallic catalyst as above
The metallic catalyst that preparation method prepares, is prepared especially by fluidized-bed chemical vapor deposition method,
Comprise the following steps:
Step one: put into metallic catalyst in fluid unit, be passed through nitrogen and protect, heat up, treat
Temperature reaches 460～800 DEG C and keeps constant, is passed through hydrogen and reduces metallic catalyst, and the recovery time is
25～50min, stop after having reduced being passed through hydrogen；
Step 2: being passed through carbon-source gas and react in fluid bed, the response time is 40～140min, stops
Stop-pass enters carbon-source gas, and fluid bed is cooled to room temperature under nitrogen protection, obtains granular carbon nano tube and slightly produces
Product, carry out test and characterize the CNT obtained.
It is experimentally confirmed, is fluidized by the highly crystallineization metallic catalyst using the inventive method to obtain
Bed vapour deposition process prepares CNT, and the CNT obtained is in many aspects performance excellence, and such as carbon is received
The uniform diameter of mitron, degree of graphitization are high, configuration state stable and consistent etc..
By the following examples the present invention is further detailed.
Embodiment 1
The present embodiment, for the preparation method of metallic catalyst disclosed by the invention and CNT thereof is described, wraps
Include following steps:
Step one: configuration metal salt solution, example 2:1.25:0.25 weighs Fe (NO respectively in molar ratio3)3·6H2O、
Mg(NO3)2·6H2O、La(NO3)3·6H2O, and be dissolved in deionized water, add gross weight 5%
Sucrose, stirring, after slaine and sucrose all dissolve, impurity screening obtains metal salt solution；
Step 2: add ammonia in described metal salt solution, carry out catalyst precipitation, in described ammonia
NH3·H2The amount of the material of O is equal with the electric charge sum of metal cation in metal salt solution, and regulation pH value is
10, stirring obtains composition metal precipitation, speed of agitator 2000 revs/min；
Step 3: the composition metal prepared precipitation is put into together with metal salt solution the Muffle of 500 DEG C
Calcining in stove, calcination time is 3h, obtains the metal catalyst particles of black；Metallic catalyst is crossed 100～200
Mesh sieve, obtains 95% one-pass finished rate of metallic catalyst, the metallic catalyst obtained is scanned Electronic Speculum
Scanning, element distribution analysis, EDS energy spectrum analysis, obtain result as shown in Fig. 1～Fig. 6；
Step 4: put into 1g metallic catalyst in fluid unit, be passed through nitrogen and protect, heat up,
Treat that temperature reaches 750 DEG C and keeps constant, be passed through hydrogen and metallic catalyst is carried out reduction activation,
VH2:VN2=2:8, the recovery time is 30min, stops being passed through hydrogen after having reduced；
Step 5: be passed through carbon source methane and react in fluid bed, VCH4:VN2=4:6, the response time is 60
Min, stops being passed through carbon source methane, and fluid bed is cooled to room temperature under nitrogen protection, obtains graininess carbon nanometer
Manage thick product 80g.Characterizing the CNT obtained, result is as shown in Fig. 7～Fig. 9.
Embodiment 2
The present embodiment, for the preparation method of metallic catalyst disclosed by the invention and CNT thereof is described, wraps
Include following steps:
Step one: configuration metal salt solution, example 2:1.25:0.25 weighs Ni (NO respectively in molar ratio3)2·6H2O、
Al(NO3)3·6H2O、La(NO3)3·6H2O, and be dissolved in deionized water, add gross weight 5%
Sucrose, stirring, after slaine and sucrose all dissolve, impurity screening obtains metal salt solution；
Step 2: add ammonia in described metal salt solution, carry out catalyst precipitation, in described ammonia
NH3·H2The amount of the material of O is equal with the electric charge sum of metal cation in metal salt solution, and regulation pH value is
10, stirring obtains composition metal precipitation, speed of agitator 2000 revs/min；
Step 3: the composition metal prepared precipitation is put into together with metal salt solution the Muffle of 500 DEG C
Calcining in stove, calcination time is 3h, obtains the metal catalyst particles of black；Metallic catalyst is crossed 100～200
Mesh sieve, obtains 95% one-pass finished rate of metallic catalyst；
Step 4: put into 1g metallic catalyst in fluid unit, be passed through nitrogen and protect, heat up,
Treat that temperature reaches 750 DEG C and keeps constant, be passed through hydrogen and metallic catalyst is carried out reduction activation,
VH2:VN2=2:8, the recovery time is 30min, stops being passed through hydrogen after having reduced；
Step 5: be passed through carbon source methane and react in fluid bed, VCH4:VN2=4:6, the response time is 60
Min, stops being passed through carbon source methane, and fluid bed is cooled to room temperature under nitrogen protection, obtains graininess carbon nanometer
Manage thick product 40g.
Embodiment 3
The present embodiment, for the preparation method of metallic catalyst disclosed by the invention and CNT thereof is described, wraps
Include following steps:
Step one: configuration metal salt solution, example 2:1.25:0.25 weighs Co (NO respectively in molar ratio3)2·6H2O、
Mg(NO3)2·6H2O、Mn(NO3)2·6H2O, and be dissolved in deionized water, add gross weight 5%
Sucrose, stirring, after slaine and sucrose all dissolve, impurity screening obtains metal salt solution；
Step 2: add ammonia in described metal salt solution, carry out catalyst precipitation, in described ammonia
NH3·H2The amount of the material of O is equal with the electric charge sum of metal cation in metal salt solution, and regulation pH value is
10, stirring obtains composition metal precipitation, speed of agitator 2000 revs/min；
Step 3: the composition metal prepared precipitation is put into together with metal salt solution the Muffle of 500 DEG C
Calcining in stove, calcination time is 3h, obtains the metal catalyst particles of black；Metallic catalyst is crossed 100～200
Mesh sieve, obtains 95% one-pass finished rate of metallic catalyst；
Step 4: put into 1g metallic catalyst in fluid unit, be passed through nitrogen and protect, heat up,
Treat that temperature reaches 750 DEG C and keeps constant, be passed through hydrogen and metallic catalyst is carried out reduction activation,
VH2:VN2=2:8, the recovery time is 30min, stops being passed through hydrogen after having reduced；
Step 5: be passed through carbon source methane and react in fluid bed, VCH4:VN2=4:6, the response time is 60
Min, stops being passed through carbon source methane, and fluid bed is cooled to room temperature under nitrogen protection, obtains graininess carbon nanometer
Manage thick product 50g.
Performance test
The metallic catalyst preparing embodiment 1 and CNT carry out performance test:
As it is shown in figure 1, be SEM figure (SEM, the scanning electron of metallic catalyst in embodiment 1
Microscope, scanning electron microscope), from image, this metallic catalyst has in microstructure
Loose porous structure, form is disperseed, is not likely to produce condensation.
Fig. 2 is the SEM mapping figure of oxygen element in metallic catalyst, and Fig. 3 is ferrum unit in metallic catalyst
The SEM mapping figure of element, Fig. 4 is the SEM mapping figure of magnesium elements in metallic catalyst, and Fig. 5 is
The SEM mapping figure of lanthanum element in metallic catalyst；Shown by the test result of Fig. 2～Fig. 5, this enforcement
In the metallic catalyst that example obtains, each Elemental redistribution region essentially coincides, and illustrates that each the content distribution of elements is uniform.
Further, take " spectrogram 29 " and " spectrogram 30 " two points in FIG to carry out
EDS (Energydispersive X-ray spectroscopy) energy spectrum analysis, Fig. 6 is the EDS at " spectrogram 29 " place
Spectrogram, following table is " spectrogram 29 " and " spectrogram 30 " place EDS energy spectrum analysis table:
As seen from the above table, basically identical at the content of each element of " spectrogram 29 " and " spectrogram 30 " place, explanation
Metal catalyst particles size and tenor are uniform, and the quality conformance of metallic catalyst is high.
As it is shown in fig. 7, be in embodiment 1 prepare CNT SEM figure, as can be seen from Figure, this
The diameter of bright middle CNT is consistent, i.e. molecular structure is uniform, and CNT degree of crystallinity is high, average pipe range.
Fig. 8 is the hot weightless picture of the CNT prepared in embodiment 1, and as seen from the figure, CNT is connecing
Starting weightlessness when of nearly 470 DEG C, its weightless temperature is 560 DEG C, and 700 DEG C when, weightlessness terminates.
Fig. 9 is the Raman figure of the CNT prepared in embodiment 1；In figure, the ratio at G peak and D peak is more than
1, and miscellaneous peak is few, illustrates that this CNT degree of graphitization is high, structure is consistent.
In sum, technical scheme original prepare metallic catalyst technique on the basis of, add
Bulking agent；Original technique can't be had a negative impact by this bulking agent, and compared to prior art, this
The advantage that invention possesses has:
1, the Elemental redistribution in metallic catalyst is uniform；
2, catalyst grain size narrow distribution range, in mesh manifold；
3, metallic catalyst bulk density is improved so that it is be more suitable for fluid unit and prepare the technique need of CNT
Ask；
4, technique is simple, prepares carbon pipe crystallinity high.
The foregoing is only presently preferred embodiments of the present invention, not in order to limit the present invention, all at this
Any amendment, equivalent and the improvement etc. made within bright spirit and principle, should be included in the present invention
Protection domain within.
Claims (12)
1. a metallic catalyst preparation method, it is characterised in that comprise the following steps:
Step one: provide a kind of metal salt solution, includes bulking agent, carrier gold in described metal salt solution
Belonging to ion and have CNT and prepare the active metallic ion of activation, described bulking agent includes organic acid
One or more in class, organic alcohols, organic aldehydes, itrogenous organic substance, saccharide；
Step 2: add precipitant in described metal salt solution, stirring obtains composition metal precipitation；
Step 3: composition metal precipitation heats up and calcines, cooling down after calcining is sieved, is obtained metal catalytic
Agent.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described load
Body metal ion includes one or more combinations in transition metal and lanthanide series metal.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described work
Property metal ion includes ferrum, cobalt, nickel, yttrium, molybdenum, copper, platinum, palladium, vanadium, niobium, tungsten, chromium, iridium and titanium
In one or more combination.
4. according to a kind of metallic catalyst preparation method described in Claims 2 or 3, it is characterised in that institute
State one or more combinations that carrier metal ion includes in copper, zinc, magnesium, aluminum, molybdenum, manganese, lanthanide series metal,
Described active metallic ion includes one or more combinations in ferrum, cobalt, nickel.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described gold
The mol ratio belonging to the active metallic ion in saline solution and carrier metal ion is 0.5～5:0.5～4.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that with preparation
On the basis of the raw material gross weight of metallic catalyst, the 3～20% of the percentage by weight of described bulking agent.
7. according to a kind of metallic catalyst preparation method described in claim 1 or 6, it is characterised in that institute
State bulking agent and include citric acid, glucose, fructose, sucrose, ethylene glycol, Polyethylene Glycol, high polyalcohols, urine
One or more in element.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described step
In rapid two, when adding precipitant, regulation metal salt solution pH value is 7～11.
9. according to a kind of metallic catalyst preparation method described in claim 1 or 8, it is characterised in that institute
Stating precipitant is ammonia.
A kind of metallic catalyst preparation method the most according to claim 1, it is characterised in that described
In step 3, carry out the metal salt solution precipitated with composition metal heating up and calcine, cooling down after calcining,
Sieve, obtain metallic catalyst.
11. according to a kind of metallic catalyst preparation method described in claim 1 or 10, it is characterised in that
In described step 3, calcining heat is 400 DEG C～700 DEG C, and calcination time is 2～5h.
The preparation method of 12. 1 kinds of CNTs, it is characterised in that described CNT is by metallic catalyst
Preparing, described metallic catalyst is by the metallic catalyst preparation method described in any one in claim 1～11
Prepare.
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