CN102000577B - Magnetic nanocomposite fiber and preparation method and application thereof - Google Patents
Magnetic nanocomposite fiber and preparation method and application thereof Download PDFInfo
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- CN102000577B CN102000577B CN 201010540304 CN201010540304A CN102000577B CN 102000577 B CN102000577 B CN 102000577B CN 201010540304 CN201010540304 CN 201010540304 CN 201010540304 A CN201010540304 A CN 201010540304A CN 102000577 B CN102000577 B CN 102000577B
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- silk
- fibre element
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Abstract
The invention discloses a magnetic nanocomposite fiber and a preparation method and application thereof, and relates to the technical field of inorganic nonmetallic materials and preparation thereof. The preparation method comprises the following steps of: performing chemical reaction on citric acid and metal salt of calcium and iron serving as raw materials to prepare a precursor sol; dehydrating under reduced pressure to obtain a precursor gel; spinning to obtain gel cellulose silk; and calcining the gel cellulose silk under the protection of reducing atmosphere (hydrogen and nitrogen) at aproper temperature to obtain a target product, namely a CaO/alpha-Fe nanocomposite fiber. The fiber has uniform diameter, large length-diameter ratio, high magnetism and a special hollow structure. The method has the advantages of simple process, low equipment requirement, low cost, short operating period and the like. Meanwhile, the magnetic nanocomposite fiber prepared by the method can be usedin transesterification as a solid alkaline catalyst and has high catalytic activity and long catalytic life. The existence of the alpha-Fe component makes the simplification of the separation and recovery of the catalyst possible.
Description
Technical field
The present invention relates to field of inorganic nonmetallic material, refer in particular to a kind of magnetic nano composite fibre and preparation method thereof and the purposes in ester exchange reaction.
Background technology
Solid catalyst is because it has non-volatile, free from environmental pollution, etching apparatus does not easily reclaim, reusable, the reaction condition of institute's catalysis is gentle, productive rate and selective high, incomparable advantage such as post processing traditional homogeneous catalyst such as easy grade, excellent and day by day cause widely and to pay close attention to, but solid catalyst also exists specific area little, the shortcoming that difficulty or ease fully contact in reactant, and then affected its catalytic effect.
In recent years, along with deepening continuously of nano science research, nanometer technology more and more was applied to catalyst field.The solid catalyst of nanoscale has very large specific area, can the Effective Raise catalytic effect.
CaO is widely used in industry-by-industry as one of the most common solid basic catalyst; The before this research for nanometer CaO catalyst focuses mostly in the preparation of nano particle, for the research of nano-fiber catalyst also seldom; The nano combined hollow fiber material of CaO/ α-Fe that the present invention proposes combines the advantage of high catalytic activity in the homogeneous catalysis, the characteristics of diffusion restriction in the heterogeneous catalysis process have been avoided again, also has simultaneously the larger specific area of ratio nano particle, and the good magnetic property of α-Fe will be given the magnetic stalling characteristic of catalyst uniqueness, simplified operating process, reduced running cost, and the hollow nano the regulated and control luminal structure with similar CNT, large draw ratio, the premium properties such as surface energy and Surface binding energy may have good application prospect as a kind of new catalyst.
The main preparation methods of nanofiber has hydro-thermal method, carbon fiber grouting displacement method, chemical vapour deposition technique (CVD method), Rong Jiao – gel method and organic gel-polymer derived process etc. at present, and the technical scheme that relevant CaO-iron fiber prepares the aspect does not also have report.
Summary of the invention
One of purpose of the present invention provides a kind of magnetic nano composite fibre, it is characterized in that: the component of described magnetic nano composite fibre is the mixture of CaO and α-Fe, has hollow structure, diameter 0.2 ~ 5 μ m of described magnetic nano composite fibre, fibre length 5 μ m ~ 2m.
Two of purpose of the present invention provides a kind of preparation method of described magnetic nano composite fibre.
Diameter is little in order to prepare, draw ratio large, the CaO/ α of function admirable-Fe hollow Nano fiber in use, on the basis of Rong Jiao – gel method, adopt organic gel-polymer derived process, organic salt or the inorganic salts of metal are dissolved in the suitable solvent, be configured to the solution of homogeneous transparent, reach the mixing of approximate molecular level; For making predecessor that Shui Xie – polycondensation reaction occur, should control the water yield, reaction time or add suitable catalyst in solvent; Form colloidal sol after fully stirring, the measures such as drying increase dissolved adhesiveness gradually, under suitable viscosities, are drawn into gelatinous fibre element silk, drying again, and heat treatment process obtains the nano combined doughnut of target product CaO/ α-Fe.
The preparation method of the nano combined doughnut of described CaO/ α-Fe, comprise precursor solution preparation process, with the presoma for preparing moltenly be prepared into the step of gelatinous fibre element silk, with the step of gelatinous fibre element silk roasting, it is characterized in that: in the step of gelatinous fibre element silk roasting, gelatinous fibre element silk is placed H
2And N
2Reducing atmosphere under roasting.
Among the above-mentioned preparation method, the preparation process of precursor solution is: at first with ferric nitrate as the nitrate of source of iron, calcium as the calcium source, and citric acid (CA) is dissolved in the deionized water M (Fe
3+): M (Ca
2+)=1 ~ 2:1, M(CA)=
, being stirred to evenly, the room temperature lower magnetic force stirred 8 ~ 30 hours.
Among the above-mentioned preparation method, with the molten step that is prepared into gelatinous fibre element silk of the presoma for preparing be: with the precursor solution vacuum decompression dehydration under 50 ℃ ~ 70 ℃ condition for preparing, obtain gel, through Pick Wire, reel off raw silk from cocoons, get rid of silk or wire drawing obtains gelatinous fibre element silk, subsequently gelatinous fibre element silk is dried.
Among the above-mentioned preparation method, with the step of gelatinous fibre element silk roasting be: with gelatinous fibre element silk at 900 ~ 1100 ℃ of temperature range H
2And N
2Reducing atmosphere under roasting, the ratio of the throughput of hydrogen and nitrogen is 1:4, is incubated 1 ~ 6 hour, naturally cools at last room temperature, obtains CaO/ α-Fe fiber.
Ca in the described precursor solution
2+Concentration 0.1 ~ 0.3 mol/L, Fe
3+Concentration 0.1 ~ 0.3mol/L.
Described gelatinous fibre element silk is dried to refer to gelatinous fibre element silk placed under 60 ~ 100 ℃ dry.
Three of purpose of the present invention provides the purposes of described magnetic nano composite fibre in catalyzed transesterification.
With the secondary rapeseed oil, methyl alcohol (analyzing pure) is reactant, 60 ℃ of reaction temperatures, reaction time 60min, molar ratio of methanol to oil 12:1 adds different catalyst, and wherein active ingredient CaO content is that the mass fraction that the CaO quality accounts for whole fiber among three embodiment of rapeseed oil mass fraction 5%(is respectively 50%, 40%, 33%), in order to detect the service life of catalyst, reclaims and reuse catalyst simultaneously, measure respectively the fatty acid methyl ester yield, its result is as shown in table 1 below:
The contrast of several catalyst ester exchange reaction of table 1 fatty acid methyl ester yield (%)
The nano combined doughnut catalyst of CaO/ α-Fe for preparing under 3 described conditions of embodiment is as can be seen from Table 1 compared with common CaO catalyst, all show higher catalytic activity and longer service life at catalyzed transesterification, still can obtain higher conversion ratio through reusing after 10 times fatty acid methyl ester.
In addition, because CaO is as catalytic active component among the present invention, the adding of α-Fe is in order to simplify the separation removal process of catalyst, and CaO can be used to the multiple reaction of catalysis as a kind of solid basic catalyst of function admirable, thereby the present invention can arrive among the chemical reaction of all available CaO as catalyst in the same way.
The present invention adopts organic gel-polymer derived process to prepare the nano combined doughnut of magnetic CaO/ α-Fe first, its advantage is that raw material is extensive, take metal organic salt and inorganic salts as raw material, make first the precursor solution that reaches molecule or atomic level mixing, obtain gel by the vacuum decompression dehydration, again through wire drawing, get rid of silk or reel off raw silk from cocoons and obtain gelatinous fibre element silk, then under suitable temperature and reduction protection atmosphere, carry out roasting and obtain the nano combined doughnut of CaO/ α-Fe; The present invention has at operating process Raw low price, the cycle is short, technique is simple, be easy to scale and to advantages such as ambient influnence are little.The method can also be applicable to the preparation of other various types of alkali metal oxide iron fibers.
Description of drawings
Fig. 1: the preparation flow figure of ferrite fibre;
Fig. 2: the XRD diffraction pattern of the nano combined doughnut of CaO/ α-Fe;
Fig. 3: the nano combined doughnut SEM of CaO/ α-Fe scanned photograph;
Fig. 4: the nano combined doughnut hollow structure of CaO/ α-Fe SEM scanning electron microscope (SEM) photograph (a) and TEM transmission electron microscope picture (b).
The specific embodiment
Embodiment 1(CaO/ α-Fe
Fiber M (CaO): M(α-Fe)=1:1
):
Step 1: get 5.618g calcium nitrate (Ca (NO
3)
24H
2O), 9.612g ferric nitrate (Fe (NO
3)
3.9H
2O), 15g citric acid (CA:C
6H
8O
7H
2O), in the 150ml deionized water, mix Ca
2+Molar concentration be 0.159mol/L, Fe
3+Molar concentration be 0.159mol/L, material molar ratio is: CA:Fe
3+: Ca
2+Then=3:1:1 carried out magnetic agitation 20 hours;
Step 2: subsequently precursor solution is put in the vacuum rotary evaporator, reduced pressure in 60 ℃, pressure is less than 0.1Mpa, and dehydration approximately 30 minutes, obtains gelatinous colloidal substance;
Step 3: the gel that step 2 is obtained is put among the baking oven, carries out drying and dewatering in 60 ℃, places in baking oven approximately 1 hour, then gel is drawn into gelatinous fibre element silk, and cellulose silk is placed the inherent 100 ℃ of dryings of crucible.
Step 4: with Precursors of Fibers at H
2, N
2Heating rate with 3 ℃/min in the atmosphere furnace is warmed up to 900 ℃, insulation 2h; Naturally cooling obtains diameter and reaches micron-sized target product CaO/ α-Fe fiber.
Embodiment 2(CaO/ α-Fe
Fiber M (CaO): M(α-Fe)=1:1.5
):
Step 1: get 4.214g calcium nitrate (Ca (NO
3)
24H
2O), 10.814g ferric nitrate (Fe (NO
3)
39H
2O), 15g citric acid (CA:C
6H
8O
7H
2O), in the 150ml deionized water, mix Ca
2+Molar concentration be 0.119mol/L, Fe
3+Molar concentration be 0.178mol/L, material molar ratio is: CA:Fe
3+: Ca
2+Then=3:1.5:1 carried out magnetic agitation 20 hours;
Step 2: subsequently precursor solution is put in the vacuum rotary evaporator, reduced pressure in 60 ℃, pressure is less than 0.1Mpa, and dehydration approximately 30 minutes, obtains gelatinous colloidal substance;
Step 3: the gel that step 2 is obtained is put among the baking oven, carries out drying and dewatering in 60 ℃, places in baking oven approximately 1 hour, then gel is drawn into gelatinous fibre element silk, and cellulose silk is placed the inherent 100 ℃ of dryings of crucible;
Step 4: with Precursors of Fibers at H
2, N
2Heating rate with 3 ℃/min in the atmosphere furnace is warmed up to 1000 ℃, insulation 2h; Naturally cooling obtains diameter and reaches micron-sized target product CaO/ α-Fe fiber.
Embodiment 3(CaO/ α-Fe
Fiber M (CaO): M(α-Fe)=1:2
):
Step 1: get 3.746g calcium nitrate (Ca (NO
3)
24H
2O), 12.817g ferric nitrate (Fe (NO
3)
3.9H
2O), 15g citric acid (CA:C
6H
8O
7H
2O), in the 150ml deionized water, mix Ca
2+Molar concentration be 0.106mol/L, Fe
3+Molar concentration be 0.212mol/L, material molar ratio is: CA:Fe
3+: Ca
2+Then=4.5:2:1 carried out magnetic agitation 20 hours;
Step 2: subsequently precursor solution is put in the vacuum rotary evaporator, reduced pressure in 60 ℃, pressure is less than 0.1Mpa, and dehydration approximately 30 minutes, obtains gelatinous colloidal substance;
Step 3: the gel that step 2 is obtained is put among the baking oven, carries out drying and dewatering in 60 ℃, places in baking oven approximately 1 hour, then gel is drawn into gelatinous fibre element silk, and cellulose silk is placed the inherent 100 ℃ of dryings of crucible;
Step 4: with Precursors of Fibers at H
2, N
2Heating rate with 3 ℃/min in the atmosphere furnace is warmed up to 1100 ℃, insulation 2h; Naturally cooling obtains diameter and reaches micron-sized target product CaO/ α-Fe fiber.
Claims (5)
1. magnetic nano composite fibre, it is characterized in that: the component of described magnetic nano composite fibre is the mixture of CaO and α-Fe, has hollow structure, diameter 0.2 ~ 5 μ m of described magnetic nano composite fibre, fibre length 5 μ m ~ 2m; Described magnetic nano composite fibre adopts the preparation of following method: described method comprise precursor solution preparation process, with the precursor solution for preparing be prepared into the step of gelatinous fibre element silk, with the step of gelatinous fibre element silk roasting, it is characterized in that: the preparation process of described precursor solution is: at first with ferric nitrate as the nitrate of source of iron, calcium as the calcium source, and citric acid (CA) is dissolved in the deionized water M (Fe
3+): M (Ca
2+)=1 ~ 2:1, the M(citric acid)=
, being stirred to evenly, the room temperature lower magnetic force stirred 8 ~ 30 hours; The described step that the precursor solution for preparing is prepared into gelatinous fibre element silk is: with the precursor solution vacuum decompression dehydration under 50 ℃ ~ 70 ℃ condition for preparing, obtain gel, through Pick Wire, reel off raw silk from cocoons, get rid of silk or wire drawing obtains gelatinous fibre element silk, subsequently gelatinous fibre element silk is dried; Described step with the roasting of gelatinous fibre element silk is: with gelatinous fibre element silk at 900 ~ 1100 ℃ of temperature range H
2And N
2Reducing atmosphere under roasting, the ratio of the throughput of hydrogen and nitrogen is 1:4, is incubated 1 ~ 6 hour, naturally cools at last room temperature, obtains CaO/ α-Fe fiber.
2. the preparation method of a kind of magnetic nano composite fibre as claimed in claim 1, comprise precursor solution preparation process, with the precursor solution for preparing be prepared into the step of gelatinous fibre element silk, with the step of gelatinous fibre element silk roasting, it is characterized in that: the preparation process of described precursor solution is: at first with ferric nitrate as the nitrate of source of iron, calcium as the calcium source, and citric acid (CA) is dissolved in the deionized water M (Fe
3+): M (Ca
2+)=1 ~ 2:1, the M(citric acid)=
, being stirred to evenly, the room temperature lower magnetic force stirred 8 ~ 30 hours; The described step that the precursor solution for preparing is prepared into gelatinous fibre element silk is: with the precursor solution vacuum decompression dehydration under 50 ℃ ~ 70 ℃ condition for preparing, obtain gel, through Pick Wire, reel off raw silk from cocoons, get rid of silk or wire drawing obtains gelatinous fibre element silk, subsequently gelatinous fibre element silk is dried; Described step with the roasting of gelatinous fibre element silk is: with gelatinous fibre element silk at 900 ~ 1100 ℃ of temperature range H
2And N
2Reducing atmosphere under roasting, the ratio of the throughput of hydrogen and nitrogen is 1:4, is incubated 1 ~ 6 hour, naturally cools at last room temperature, obtains CaO/ α-Fe fiber.
3. the preparation method of a kind of magnetic nano composite fibre as claimed in claim 2 is characterized in that: the Ca in the described precursor solution
2+Concentration 0.1 ~ 0.3 mol/L, Fe
3+Concentration 0.1 ~ 0.3mol/L.
4. the preparation method of a kind of magnetic nano composite fibre as claimed in claim 2 is characterized in that: described gelatinous fibre element silk is dried to refer to gelatinous fibre element silk placed under 60 ~ 100 ℃ dry.
5. the purposes of magnetic nano composite fibre as claimed in claim 1 in catalyzed transesterification.
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| CN103145201B (en) * | 2012-12-04 | 2015-08-05 | 江苏大学 | A kind of cellular perovskite typed microfibre and preparation method thereof |
| CN106400185B (en) * | 2016-09-21 | 2018-11-23 | 东华大学 | A kind of preparation method of magnetic cellulose composite fibre |
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