CN109046461A - The method that a kind of preparation method of sulfur-bearing complex compound catalyst and its catalysis prepare spiral nanometer carbon fiber - Google Patents
The method that a kind of preparation method of sulfur-bearing complex compound catalyst and its catalysis prepare spiral nanometer carbon fiber Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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- D01F9/00—Artificial filaments or the like of other substances; Manufacture thereof; Apparatus specially adapted for the manufacture of carbon filaments
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/847—Nickel
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Abstract
The invention discloses the methods that a kind of preparation method of sulfur-bearing complex compound catalyst and its catalysis processed prepare spiral nanometer carbon fiber, the preparation method of sulfur-bearing complex compound catalyst includes that (1) prepares potassium sodium tartrate solution and nickel chloride solution respectively, and potassium sodium tartrate solution is added dropwise in nickel chloride solution under agitation；(2) after dripping, mixed liquor is transferred in reaction kettle and carries out hydro-thermal reaction；(3) after the completion of hydro-thermal reaction, mixed liquor is stood, then removes supernatant liquor, sediment is dry after being filtered, being washed, and obtains tartrate anion and Ni2+Complex compound；(4) obtained complex compound and sulphur powder 10 ~ 100:1 in mass ratio are added into ball grinder ball milling, after the completion of ball milling, dried object are milled to get the sulfur-bearing complex compound catalyst is arrived.When sulfur-bearing complex compound catalyst prepared by the present invention prepares coiled carbon fibers, without being passed through hydrogen reducing, but also it can realize and prepare spiral nanometer carbon fiber uniform, with high purity at low temperature.
Description
Technical field
The invention belongs to spiral nanometer carbon fiber preparation fields, and in particular to a kind of preparation side of sulfur-bearing complex compound catalyst
The method that method and its catalysis prepare spiral nanometer carbon fiber.
Technical background
Spiral nanometer carbon fiber possesses good mechanical property, hot property, wave absorbtion due to its unique helical structure
Energy and hydrogen storage property etc., have attracted the sight of numerous researchers.The main useization of the preparation of spiral nanometer carbon fiber at present
It learns vapour deposition process (CVD method), using the simple substance of iron, cobalt, nickel or copper or its compound as catalyst organic carbon source high temperature
(600-1200 DEG C) cracking deposition preparation.Since chemical meteorology deposition is by Multiple factors such as temperature, gas flow, heating rates
It influences, therefore the spiral nanometer carbon fiber for preparing the uniform purity is high of helical structure is still a stern challenge.Simultaneously
It is often passed through hydrogen reducing catalyst in spiral nanometer carbon fiber preparation process, causes serious security risk.
Due to factors above, spiral nanometer carbon fiber is difficult to realize industrialization production at present, is only limited to laboratory not
Stablize small lot preparation, causes its related excellent application that cannot further probe into.Liu et al. (Direct synthesis of
micro-coiled carbon fibers on graphite substrate using co-electrodeposition
of nickel and sulfur as catalysts[J]. Materials & Design, 2009, 30(3):649-
652.) the simple substance particle of nickel and sulphur is co-deposited on graphite substrate, wherein nickel is as catalyst, and sulphur is as growth promoter success
Prepared spiral nanometer carbon fiber.Although the method is in the agglomeration for alleviating nano nickle granules to a certain degree, behaviour
Make complex steps, is unfavorable for volume production；The contact area of catalyst and acetylene also reduces simultaneously, and yield is caused to reduce.Therefore pass through
It is a kind of solution nanocatalyst that the decomposition of presoma, which obtains the nano-catalyst particles of favorable dispersibility, during heat treatment
Particle agglomeration phenomenon simple effective method.
Summary of the invention
In view of the above shortcomings of the prior art, the object of the present invention is to provide a kind of systems of sulfur-bearing complex compound catalyst
Preparation Method, solving existing prepare needs to be passed through hydrogen reducing catalyst during spiral nanometer carbon fiber and nano nickle granules are easily rolled into a ball
Poly- problem.
The present invention also provides the methods that the catalyst of this method preparation is used to prepare spiral nanometer carbon fiber, solve existing
Method is difficult to the problem of preparing spiral nanometer carbon fiber uniform, with high purity.
To achieve the above object, the present invention adopts the following technical scheme:
A kind of preparation method of sulfur-bearing complex compound catalyst, includes the following steps:
(1) potassium sodium tartrate solution and nickel chloride solution are prepared respectively, and wherein the molar ratio of sodium potassium tartrate tetrahydrate and nickel chloride is 1:
0.95 ~ 1, the potassium sodium tartrate solution of preparation is added dropwise in nickel chloride solution under agitation；
(2) after dripping, mixed liquor is transferred in reaction kettle and carries out hydro-thermal reaction；
(3) after the completion of hydro-thermal reaction, mixed liquor is stood, then removes supernatant liquor, sediment is dry after being filtered, being washed,
Obtain tartrate anion and Ni2+Complex compound；
(4) ball milling being added into ball grinder in obtained complex compound and sulphur powder 10 ~ 100:1 in mass ratio, ball milling is dry after the completion,
Obtain the sulfur-bearing complex compound catalyst.
The present invention prepares the tartrate anion and Ni of sulfur-bearing by hydro-thermal method2+Complex compound catalyst, tartrate anion and Ni2 +Complex compound in the temperature-rise period for preparing spiral nanometer carbon fiber Direct Pyrolysis be elemental nickel, catalytic action can be played, no
Use hydrogen reducing.Wherein, the molar ratio of control sodium potassium tartrate tetrahydrate and nickel chloride is 1:0.95 ~ 1 in step (1), in this way control wine
Stone acid potassium sodium molar ratio is slightly above nickel chloride, bivalent nickel ion can be made sufficiently to be complexed, since tartaric acid nickel price is apparently higher than
Sodium potassium tartrate tetrahydrate can reduce cost；The content of bivalent nickel ion in waste liquid is reduced simultaneously, reduces the pollution to environment.Step
(4) in, by obtained catalyst and sulphur powder mixing and ball milling, the catalytic effect of catalyst can be improved, make the spiral nanometer carbon of preparation
The shape of fiber is in the twisted shape being closely wound, meanwhile, sulphur powder is also used as the growth promoter of spiral nanometer carbon fiber, promotees
Into the growth of spiral nanometer carbon fiber, wherein drying condition can be 60 ~ 80 DEG C of 12 ~ 16h of vacuum drying.In step (3), mixed liquor
4 ~ 8h can be stood, the product after washing can be in 60 ~ 80 DEG C of 12 ~ 16h of vacuum drying.
Preferably, sodium potassium tartrate tetrahydrate and nickel chloride are dissolved respectively at 40 ~ 60 DEG C, and 5 ~ 10min of ultrasonic disperse.
Preferably, the mixed liquor after being added dropwise in step (2) stirs 2 ~ 4h.Solution can in this way be uniformly mixed, is conducive to
Hydro-thermal reaction mesotartaric acid root and Ni2+Complexing.
Preferably, hydrothermal temperature is 100 ~ 200 DEG C, the reaction time is 12 ~ 48h.It can be made by hydro-thermal reaction
Sodium potassium tartrate tetrahydrate and nickel chloride are substantially dissolved in solution, while the condition of 100 ~ 120 DEG C of high pressures is conducive to the formation of complex compound,
And keep the temperature 12 ~ 48h under 100 ~ 120 DEG C of high pressures and the yield of catalyst can be improved, foreign ion remaining in waste liquid is reduced, in turn
Reduce the pollution to environment.
Preferably, revolving speed is 300 ~ 500r/min, 2 ~ 4h of ball milling when ball milling.Sulphur powder and catalyst can in this way mixed equal
Even, partial size is smaller after ball milling, is conducive to the catalytic effect for improving catalyst, the growth promoting function of sulphur powder also can be improved.
The method that catalyst provided by the invention is used to prepare spiral nanometer carbon fiber are as follows: by method described above preparation
Sulfur-bearing complex compound catalyst is placed on graphite substrate, and graphite substrate is placed in tube furnace, is warming up to 377.5 under protection air-flow
~ 650 DEG C, 30 ~ 60min of acetylene is then passed to, is subsequently reduced to room temperature to get spiral nanometer carbon fiber is arrived.
The present invention obtains the nano-catalyst particles of favorable dispersibility by the decomposition of presoma during heat treatment, solves
Nano-catalyst particles of having determined problem easy to reunite, catalytic efficiency be improved, it can be achieved that prepared under lower temperature uniformly and
The spiral nanometer carbon fiber of purity is high, sulphur powder therein can be distilled at the reaction temperatures as gas, to spiral nanometer carbon fiber
Facilitation is played in growth.
Wherein, protection air-flow can be able to be 100 ~ 200mL/min with argon stream or stream of nitrogen gas, air-flow velocity.Protect gas
Body can be effectively protected that catalyst is not oxidized during heating, maintain the catalytic action of catalyst
Preferably, heating rate is 1 ~ 5 DEG C/min.The elemental nickel particle diameter that heating rate obtains after decomposing for complex compound
Have a direct impact, and the partial size of catalyst is related to partial size to the pattern of the spiral nanometer carbon fiber of catalytic growth, 1 ~ 5
DEG C/min heating rate under, catalyst pyrolytic impurity can be made few, partial size is small, and catalytic effect is more preferable.
Preferably, acetylene is passed through in tube furnace with 80 ~ 300mL/min.Flow by controlling acetylene can make acetylene
Utilization reach maximization, be passed through excessive acetylene and will lead to acetylene decomposition and be not thorough and cause to waste, it is too small to be passed through acetylene flow
The efficiency that will lead to catalyst again is not in full use, so needing to select acetylene flow appropriate.
Compared with prior art, the invention has the following beneficial effects:
The present invention prepares tartrate anion and Ni using hydro-thermal method2+Complex compound, then by complex compound and sulphur powder mixing and ball milling, effectively
The catalytic efficiency for improving catalyst, is used to prepare during spiral nanometer carbon fiber, tartrate anion and Ni2+Complex compound can be straight
It connects and is cracked into elemental nickel performance catalytic action, prepare uniform, purity at low temperature without being passed through hydrogen reducing, but also can realize
High spiral nanometer carbon fiber.The yield and purity of complex compound catalyst can be greatly improved in hydro-thermal method；With sulphur powder together ball milling
The more tiny complex compound catalyst of available partial size, while the sulphur powder being added can also promote the life of spiral nanometer carbon fiber
It is long.
Detailed description of the invention
Fig. 1 is tartrate anion and Ni prepared by embodiment 12+The TG of complex compound schemes；
Fig. 2 is tartrate anion and Ni prepared by embodiment 12+The XRD diagram of complex compound；
Fig. 3 is the SEM figure of spiral nanometer carbon fiber prepared by embodiment 1；
Fig. 4 is spiral nanometer carbon fiber prepared by embodiment 1.
Specific embodiment
The present invention is further explained in the light of specific embodiments.
Embodiment 1:
It is the tartrate anion and Ni of sulfur-bearing first2+Complex compound preparation: 1. weigh 0.05 mol sodium potassium tartrate tetrahydrate and 0.05
Mol nickel chloride is dissolved separately in 100 mL deionized waters, and two kinds of solution are stirred well to solute at 60 DEG C and are completely dissolved, then
Potassium sodium tartrate solution, is then added drop-wise in nickel chloride solution by ultrasonic 5min under agitation, after being added dropwise to complete, control strip
Part is constant to be continued to stir 2 h, is sufficiently mixed two kinds of solution uniformly；2. mixed solution is transferred in hydrothermal reaction kettle, 125
DEG C 12 h of hydro-thermal reaction.After the completion of hydro-thermal reaction, by static 4 h of turbid solution after abundant complexing, supernatant liquor is then outwelled, is used
It is filtered after deionized water washing, product is milled into powder after 60 DEG C of 12 h of vacuum drying after being repeated 3 times, obtains tartrate anion
And Ni2+Complex catalyst precursor.3. ball grinder is added in the ratio of catalyst precursor and sulphur powder 80:1 in mass ratio
In, the ball milling 2h under the revolving speed of 300r/min is sufficiently mixed sulphur powder and precursor powder, dry in 60 DEG C of vacuum after ball milling
It is milled into powder after dry 12 h, obtains sulfur-bearing complex compound catalyst.
The followed by preparation of spiral nanometer carbon fiber: take 0.2 g of sulfur-bearing catalyst precursor of above-mentioned preparation in graphite-based
Graphite substrate is placed in tube furnace by piece, with the heating rate of 2 DEG C/min under the protection atmosphere of argon gas (100 mL/min)
After rising to 500 DEG C, acetylene (120 mL/min) 30 min are passed through under 500 DEG C of heat preservations, acetylene continues after being passed through in argon gas
The protection atmosphere of (80 mL/min) drops to room temperature, obtains spiral nanometer carbon fiber product.
Embodiment 2:
It is the tartrate anion and Ni of sulfur-bearing first2+Complex compound preparation: 1. weigh 0.05 mol sodium potassium tartrate tetrahydrate and 0.0495
Mol nickel chloride is dissolved separately in 100 mL deionized waters, and two kinds of solution are stirred well to solute at 40 DEG C and are completely dissolved, then
Potassium sodium tartrate solution, is then added drop-wise in nickel chloride solution by ultrasonic 5min under agitation, after being added dropwise to complete, control strip
Part is constant to be continued to stir 2 h, is sufficiently mixed two kinds of solution uniformly；2. mixed solution is transferred in hydrothermal reaction kettle, 150
DEG C 24 h of hydro-thermal reaction.After the completion of hydro-thermal reaction, by static 4 h of turbid solution after abundant complexing, supernatant liquor is then outwelled, is used
It is filtered after deionized water washing, product is milled into powder after 60 DEG C of 12 h of vacuum drying after being repeated 3 times, obtains tartrate anion
And Ni2+Complex catalyst precursor.3. ball grinder is added in the ratio of catalyst precursor and sulphur powder 60:1 in mass ratio
In, the ball milling 4h under the revolving speed of 400r/min is sufficiently mixed sulphur powder and precursor powder, dry in 70 DEG C of vacuum after ball milling
It is milled into powder after dry 12 h, obtains the catalyst precursor powder of sulfur-bearing.
The followed by preparation of spiral nanometer carbon fiber: taking 0.3 g of catalyst precursor of above-mentioned preparation on graphite substrate,
Graphite substrate is placed in tube furnace, is risen under the protection atmosphere of argon gas (120 mL/min) with the heating rate of 3 DEG C/min
After 600 DEG C, acetylene (160 mL/min) 60 min are passed through under 600 DEG C of heat preservations, acetylene continues after being passed through in argon gas (100
ML/min protection atmosphere) drops to room temperature, obtains spiral nanometer carbon fiber product.
Embodiment 3:
It is the tartrate anion and Ni of sulfur-bearing first2+Complex compound preparation: 1. weigh 0.05 mol sodium potassium tartrate tetrahydrate and 0.049
Mol nickel chloride is dissolved separately in 100 mL deionized waters, and two kinds of solution are stirred well to solute at 50 DEG C and are completely dissolved, then
Potassium sodium tartrate solution, is then added drop-wise in nickel chloride solution by ultrasonic 5min under agitation, after being added dropwise to complete, control strip
Part is constant to be continued to stir 2 h, is sufficiently mixed two kinds of solution uniformly；2. mixed solution is transferred in hydrothermal reaction kettle, 175
DEG C 36 h of hydro-thermal reaction.After the completion of hydro-thermal reaction, by static 4 h of turbid solution after abundant complexing, supernatant liquor is then outwelled, is used
It is filtered after deionized water washing, product is milled into powder after 80 DEG C of 12 h of vacuum drying after being repeated 3 times, obtains tartrate anion
And Ni2+Complex catalyst precursor.3. ball grinder is added in the ratio of catalyst precursor and sulphur powder 40:1 in mass ratio
In, the ball milling 6h under the revolving speed of 500r/min is sufficiently mixed sulphur powder and precursor powder, dry in 80 DEG C of vacuum after ball milling
It is milled into powder after dry 12h, obtains the catalyst precursor powder of sulfur-bearing.
The preparation of spiral nanometer carbon fiber: 0.4 g of catalyst precursor of above-mentioned preparation is taken on graphite substrate, by graphite
Substrate is placed in tube furnace, rises to 650 DEG C under the protection atmosphere of argon gas (100 mL/min) with the heating rate of 4 DEG C/min
Afterwards, acetylene (200 mL/min) 50 min are passed through under 650 DEG C of heat preservations, acetylene continues after being passed through in argon gas (100 mL/
Min protection atmosphere) drops to room temperature, obtains spiral nanometer carbon fiber product.
Fig. 1 is tartrate anion and Ni prepared by embodiment 12+The TG of complex compound schemes, and Fig. 2 is tartaric acid prepared by embodiment 1
Root and Ni2+The XRD diagram of complex compound, as shown in Figure 1, tartrate anion and Ni2+Complex compound has decomposed after temperature is higher than 377.5 DEG C
Entirely, by the XRD diagram of Fig. 2 decomposition product it is found that decomposition product is in the strongest several crystal faces (111) of diffraction, (200), (220) and Ni
(PDF 04-0850's) mutually has good matching degree, illustrates that decomposition product is nickel simple substance, and crystallinity is good.Scheme simultaneously
Occur in spectrum without apparent impurity peaks, illustrates there is no impurity in decomposition product.
Fig. 3 is the SEM figure of spiral nanometer carbon fiber prepared by embodiment 1, and Fig. 4 is spiral nanometer carbon prepared by embodiment 1
Fiber original graph, can be seen that by Fig. 3 and Fig. 4, and coiled carbon fibers shape is in the twisted shape being closely wound, and be commonly spiral in product
Shape fiber, does not find fibers straight, has good helix degree.Product is paved with entire graphite substrate simultaneously, with higher
Yield
Finally, it is stated that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although referring to preferable reality
Example is applied to describe the invention in detail, those skilled in the art should understand that, it can be to technical side of the invention
Case is modified or replaced equivalently, and without departing from the objective and range of technical solution of the present invention, should all be covered in the present invention
Scope of the claims in.
Claims (8)
1. a kind of preparation method of sulfur-bearing complex compound catalyst, which comprises the steps of:
(1) potassium sodium tartrate solution and nickel chloride solution are prepared respectively, and wherein the molar ratio of sodium potassium tartrate tetrahydrate and nickel chloride is 1:
0.95 ~ 1, the potassium sodium tartrate solution of preparation is added dropwise in nickel chloride solution under agitation；
(2) after dripping, mixed liquor is transferred in reaction kettle and carries out hydro-thermal reaction；
(3) after the completion of hydro-thermal reaction, mixed liquor is stood, then removes supernatant liquor, sediment is dry after being filtered, being washed,
Obtain tartrate anion and Ni2+Complex compound；
(4) ball milling being added into ball grinder in obtained complex compound and sulphur powder 10 ~ 100:1 in mass ratio, ball milling is dry after the completion,
Obtain the sulfur-bearing complex compound catalyst.
2. the preparation method of sulfur-bearing complex compound catalyst according to claim 1, which is characterized in that sodium potassium tartrate tetrahydrate and chlorine
Change nickel to dissolve respectively at 40 ~ 60 DEG C, and 5 ~ 10min of ultrasonic disperse.
3. the preparation method of sulfur-bearing complex compound catalyst according to claim 1, which is characterized in that be added dropwise in step (2)
Mixed liquor afterwards stirs 2 ~ 4h.
4. the preparation method of sulfur-bearing complex compound catalyst according to claim 1, which is characterized in that hydrothermal temperature is
100 ~ 200 DEG C, the reaction time is 12 ~ 48h.
5. the preparation method of sulfur-bearing complex compound catalyst according to claim 1, which is characterized in that revolving speed is when ball milling
300 ~ 500r/min, 2 ~ 4h of ball milling.
6. a kind of preparation method of spiral nanometer carbon fiber, which is characterized in that by any one of claim 1 to 5 the method system
Standby sulfur-bearing complex compound catalyst is placed on graphite substrate, and graphite substrate is placed in tube furnace, is warming up under protection air-flow
377.5 ~ 650 DEG C, 30 ~ 60min of acetylene is then passed to, is subsequently reduced to room temperature to get spiral nanometer carbon fiber is arrived.
7. the preparation method of spiral nanometer carbon fiber according to claim 6, which is characterized in that heating rate be 1 ~ 5 DEG C/
min。
8. the preparation method of spiral nanometer carbon fiber according to claim 6, which is characterized in that acetylene is with 80 ~ 300mL/
Min is passed through in tube furnace.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517458A (en) * | 2003-01-13 | 2004-08-04 | 中国科学院金属研究所 | Method of preparing carbon fiber and nanometer carbon pipe |
| CN104386668A (en) * | 2014-11-10 | 2015-03-04 | 电子科技大学 | Method for preparing coiled carbon nano material under nickel nano catalytic actions |
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2018
- 2018-08-07 CN CN201810890923.7A patent/CN109046461B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1517458A (en) * | 2003-01-13 | 2004-08-04 | 中国科学院金属研究所 | Method of preparing carbon fiber and nanometer carbon pipe |
| CN104386668A (en) * | 2014-11-10 | 2015-03-04 | 电子科技大学 | Method for preparing coiled carbon nano material under nickel nano catalytic actions |
Non-Patent Citations (3)
| Title |
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| QIAN YANG ET AL.: "High yield synthesis of helical carbon nanotubes catalyzed by porous precursor with terrace morphology", 《DIAMOND & RELATED MATERIALS》 * |
| 李红: "螺旋形碳纤维的制备及其生长机理的研究", 《化工新型材料》 * |
| 董丽红: "《两亲分子在纳米技术领域中的应用》", 30 October 2013, 吉林大学出版社 * |
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