CN105174318A - Preparation method for ferroferric oxide magnetic carrier - Google Patents
Preparation method for ferroferric oxide magnetic carrier Download PDFInfo
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- CN105174318A CN105174318A CN201510567043.2A CN201510567043A CN105174318A CN 105174318 A CN105174318 A CN 105174318A CN 201510567043 A CN201510567043 A CN 201510567043A CN 105174318 A CN105174318 A CN 105174318A
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- preparation
- magnetic carrier
- ferroferric oxide
- magnetic
- oxide magnetic
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- SZVJSHCCFOBDDC-UHFFFAOYSA-N ferrosoferric oxide Chemical compound O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 title claims abstract description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000000843 powder Substances 0.000 claims abstract description 11
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 239000012535 impurity Substances 0.000 claims abstract description 7
- 229920002565 Polyethylene Glycol 400 Polymers 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 5
- 230000004044 response Effects 0.000 claims description 5
- 238000013019 agitation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 239000013543 active substance Substances 0.000 claims description 2
- 239000006227 byproduct Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 23
- 238000006243 chemical reaction Methods 0.000 abstract description 14
- 239000002245 particle Substances 0.000 abstract description 14
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 abstract description 10
- 229910000029 sodium carbonate Inorganic materials 0.000 abstract description 5
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 abstract description 4
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000013078 crystal Substances 0.000 abstract description 2
- -1 polytetrafluoroethylene Polymers 0.000 abstract description 2
- 238000007789 sealing Methods 0.000 abstract description 2
- 235000017550 sodium carbonate Nutrition 0.000 abstract 3
- 239000011259 mixed solution Substances 0.000 abstract 2
- 238000007605 air drying Methods 0.000 abstract 1
- 239000012295 chemical reaction liquid Substances 0.000 abstract 1
- 238000007885 magnetic separation Methods 0.000 abstract 1
- 230000005389 magnetism Effects 0.000 abstract 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 abstract 1
- 239000004810 polytetrafluoroethylene Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 abstract 1
- 239000004094 surface-active agent Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 21
- 239000011734 sodium Substances 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 239000003054 catalyst Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 238000000593 microemulsion method Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000006210 lotion Substances 0.000 description 2
- 239000006247 magnetic powder Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000011358 absorbing material Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000012675 alcoholic extract Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001879 gelation Methods 0.000 description 1
- 239000008187 granular material Substances 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011553 magnetic fluid Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 230000008685 targeting Effects 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/02—Oxides; Hydroxides
- C01G49/08—Ferroso-ferric oxide [Fe3O4]
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a preparation method for a ferroferric oxide magnetic carrier. The preparation method comprises the following steps: weighing FeCl3.6H2O serving as a raw material and Na2CO3 serving as an alkali source according to a certain molar ratio, and dissolving the FeCl3.6H2O and the Na2CO3 in ethylene glycol to prepare a mixed solution; adding a proper amount of PEG-400 into the prepared mixed solution to serve as a surfactant; sealing the prepared solution in a high-pressure reaction kettle with a polytetrafluoroethylene liner; heating the high-pressure reaction kettle for a period of time in a forced air drying box; after the reaction liquid is cooled, removing non-magnetic impurities by adopting a magnetic separation method. By adopting the Na2CO3 as the alkali source, the cost is low and the OH- can be provided effectively; the powder prepared by the method is complete in crystal shape, narrow in particle size distribution range, and uniform in morphology; the Fe3O4 is separated from the non-magnetic impurities by adopting a magnet, so that the purity of a product is effectively improved, and the magnetism of the product is ensured.
Description
Technical field
The present invention relates to the preparation method of magnetic carrier, be specifically related to the preparation method as support of the catalyst and target medicine carrier bigger serface ferroferric oxide magnetic carrier, belong to functional materials preparing technical field.
Background technology
Fe
3o
4belong to isometric system, there is inverse spinel structure.Because it is cheap, magnetic is better, has absorbing property etc. again, can be widely used in the fields such as magnetic fluid, duplicating, absorbing material, vacuum-sealing.In addition, because its good biocompatibility, can as target medicine carrier; Have the advantages that easily reclaim, can support of the catalyst be used as.As magnetic carrier, the magnetic powder prepared by requirement has the features such as magnetic is good, particle diameter is less, specific surface area is large.
The method preparing nano ferriferrous oxide powder at present mainly contains air oxidation process, microemulsion method, thermal decomposition method, solvent-thermal method etc.Often kind of method all has respective relative merits.Such as, air oxidation process technique is simple, and cost is lower, is applicable to suitability for industrialized production.But influence factor is numerous in reaction process, grain-size, product purity etc. are difficult to control; Microemulsion method effectively can avoid particle agglomeration, Control granularity, but its productive rate is lower, and solvent load is larger; Sol-gel method can prepare height single dispersing, the powder of narrow diameter distribution.But high cost.Gelation process is slow simultaneously, and the production cycle is long; Solvent-thermal method reaction conditions is gentle, and pattern, particle diameter are all controlled.The current industrial prepared most particle diameter of Z 250 is comparatively large, and specific surface area is less, is about 4 ~ 12m
2/ g, is difficult to meet the requirement as magnetic carrier.And some use unorthodox method (as microemulsion method, sol-gel method etc.) although the product prepared can meet as the requirement of magnetic carrier to particle diameter and specific surface area, its high cost, is not suitable for scale operation.
Summary of the invention
The object of the invention is to, for deficiency of the prior art, provide use solvent-thermal method, with the Na that lattice are lower
2cO
3as alkali source, preparation Fe
3o
4the method of magnetic carrier, prepared magnetic powder has larger specific surface area, less particle diameter, preferably magnetic property, to meet the requirement as magnetic carrier contrast table area, particle diameter, magnetic.
For solving the problems of the technologies described above, the present invention adopts following technical scheme to realize:
With FeCl
36H
2o is raw material, with Na
2cO
3as alkali source, take Iron trichloride hexahydrate and sodium carbonate according to certain mol proportion example and be dissolved in ethylene glycol and be configured to mixing solutions, in the mixing solutions prepared, add appropriate PEG-400 as tensio-active agent; Then joined solution is sealed in teflon-lined autoclave, puts into air dry oven and heat for some time; After question response liquid cooling but, the removing of magnet separation method is adopted not have magnetic impurity.
The present invention selects Na
2cO
3as alkali source, lower cost, its price is only about 1/3rd of NaAc price used in other document.And it is as strong base-weak acid salt, by hydrolysis reaction:
CO
3 2-+H
2O→HCO
3-+OH
-(1)
HCO
3-+H
2O→H
2CO
3+OH
-(2)
Produce a large amount of OH
-, thus play the effect of precipitation agent.
The present invention adopts ethylene glycol as solvent.Ethylene glycol has lower boiling point, produces larger pressure at the same temperature, is conducive to the mineralising nucleation of Z 250.Meanwhile, ethylene glycol contains two alcoholic extract hydroxyl groups, has stronger reductibility.Can by Fe under solvent thermal system
3+partial reduction becomes Fe
2+.Concrete reaction formula is as follows:
2Fe
3++OHCH
2CH
2OH+2H
+→2Fe
2++CH
3CHO+2H
2O(3)
2Fe
3++Fe
2++8OH
-→Fe
3O
4+4H
2O(4)
The present invention is because adopting Na
2cO
3make alkali source, side reaction can occur in reaction process:
CO
3 2-+Fe
2+→FeCO
3(5)
In order to remove FeCO
3impurity, improves product purity, needs the method adopting magnet to be separated after the completion of reaction.
Concrete steps of the present invention are as follows:
1) by Iron trichloride hexahydrate and sodium carbonate mixing, be dissolved in ethylene glycol, magnetic agitation is to dissolving completely.Then add PEG-400, mix.
2) solution prepared is sealed in teflon-lined autoclave.Then put into air dry oven and heat for some time.
3) after question response liquid cooling but, utilize magnet by product separation, removing does not have magnetic impurity.And with ethanol: water=1: the mixing solutions of 1 washes residual organism off.
4) gained magnetic substance is put into loft drier to dry, and oven dry product is ground.
Step 1) in, PEG-400 add-on is 1/15 of overall solution volume, and CO3 in solution joins in institute
2-and Fe
3+mol ratio be 5: 3 ~ 10: 3;
Step 2) in, arranging air dry oven Heating temperature is 180 DEG C, and the reaction times is 9 hours ~ 24 hours.
Step 4) in, arrange bake out temperature 60 DEG C, drying time is 8 hours.
Beneficial effect of the present invention: method raw materials cost provided by the invention is lower, reaction conditions is gentle, is easy to control.Prepared Z 250 powder granule size is less, and specific surface area is large, and magnetic property is better, is mainly reflected in:
1, this experiment adopts the Na that price is lower
2cO
3as alkali source, its price is only and uses 1/3rd of NaAc price, and it is strong base-weak acid salt, can effectively provide reaction required OH
-.
2, prepared powder crystal formation is complete, and particle size distribution range is narrow, and pattern is homogeneous.Prepared diameter of particle is all less than 100nm, and is all the honeycombed spherical bodies of the nanocrystalline reunion being about 5nm by particle diameter.This body structure surface slipperiness is poor, forms rough step, adds the contact surface of chemical reaction.The Fe that this legal system is standby
3o
4powder has relatively large specific surface area, is about 30m
2/ g, significantly can increase its appendix amount as drug targeting carrier or support of the catalyst.
3, the present invention adopts the Fe in magnet separated product
3o
4with non-magnetic impurity, effectively raise the purity of product, ensure that the magnetic of product.
Accompanying drawing illustrates:
Fig. 1 is that solvent-thermal method prepares Fe
3o
4reacting flow chart.
Fig. 2 is that solvent-thermal method prepares Fe
3o
4sample XRD figure is composed.
Fig. 3 is that solvent-thermal method prepares Fe
3o
4sample TEM photo.
Fig. 4 is that solvent-thermal method prepares Fe
3o
4sample XRD figure is composed.
Fig. 5 is that solvent-thermal method prepares Fe
3o
4sample TEM photo.
Embodiment
Below in conjunction with specific embodiment, the present invention is elaborated.
Example 1
1) FeCl that quality is 2.4327g is taken
36H
2o and quality are the Na of 1.59g
2cO
3be dissolved in 70ml ethylene glycol, magnetic agitation is to dissolving completely; Measure 5mlPEG-400 to be slowly added drop-wise in above-mentioned solution.Fe in solution
3+concentration be 0.12M, CO
3 2-concentration be 0.2M, i.e. CO
3 2-and Fe
3+mol ratio be 5: 3.
2) the above-mentioned solution prepared is sealed in 100ml teflon-lined autoclave; Then be transferred in air dry oven and heat, temperature of reaction is set to 180 DEG C, and the reaction times is 24 hours.
3), after question response terminates, cooling for some time, autoclave is opened, by the reaction solution beaker of falling people.Use magnet near beaker side, to adsorb magnetic substance; After 2 minutes, by solution and do not outwelled by the material of magnet adsorption, with ethanol: water=1: the solution of 1 washs, and uses attraction simultaneously, after 2 minutes, again outwell solution.Repeat this lotion process 3 times.
4) material after washing is put into air dry oven to dry, bake out temperature is set to 60 DEG C, dries 8 hours; Ground by material after drying, gained powder main component is Fe
3o
4, purity is higher, well-crystallized's (as shown in Figure 2).Powder is the honeycombed spherical body (as shown in Figure 3) of about the 70nm ~ 80nm of the nanocrystalline reunion of about 5nm by particle diameter.
Example 2
1) FeCl that quality is 2.4327g is taken
36H
2o and quality are the Na of 3.18g
2cO
3be dissolved in 70ml ethylene glycol, magnetic agitation is to dissolving completely; Measure 5mlPEG-400 to be slowly added drop-wise in above-mentioned solution.Fe in solution
3+concentration be 0.12M, CO
3 2-concentration be 0.4M, i.e. CO
3 2-and Fe
3+mol ratio be 10: 3.
2) the above-mentioned solution prepared is sealed in 100ml teflon-lined autoclave; Then be transferred in air dry oven and heat, temperature of reaction is set to 180 DEG C, and the reaction times is 9 hours.
3), after question response terminates, cooling for some time, open autoclave, reaction solution is poured in beaker.Use magnet near beaker side, to adsorb magnetic substance; After 2 minutes, by solution and do not outwelled by the material of magnet adsorption.Wash with the solution of ethanol/water=1/1, use attraction simultaneously, after 2 minutes, again outwell solution.Repeat this lotion process 3 times.
4) material after washing is put into air dry oven to dry, bake out temperature is set to 60 DEG C, dries 8 hours.Ground by material after drying, gained powder main component is Fe
3o
4, purity is higher, well-crystallized's (as shown in Figure 4).Powder is the honeycombed spherical body (as shown in Figure 5) that the particle diameter being the nanocrystalline reunion of 5nm by particle diameter is about 100nm.
Above-described embodiment is only in order to illustrate technical scheme of the present invention; but not design of the present invention and protection domain are limited; those of ordinary skill of the present invention is modified to technical scheme of the present invention or equivalent replacement; and not departing from aim and the scope of technical scheme, it all should be encompassed in right of the present invention.
Claims (4)
1. the preparation method of ferroferric oxide magnetic carrier, is characterized in that: comprise the steps:
1) with FeCl
36H
2o is raw material, with Na
2cO
3as alkali source, both mixing are dissolved in ethylene glycol prepares mixing solutions, and magnetic agitation, to dissolving completely, then adds PEG-400 as tensio-active agent, mixes;
2) solution prepared is sealed in teflon-lined autoclave, then puts into air dry oven and heat;
3) after question response liquid cooling but, utilize magnet by product separation, removing does not have magnetic impurity, and with ethanol: water=1: the mixing solutions of 1 washes residual organism off;
4) powder obtained is put into air dry oven to dry, oven dry product is ground.
2. the preparation method of ferroferric oxide magnetic carrier according to claim 1, is characterized in that: described step 1) CO in solution
3 2-with Fe
3+mol ratio be 5: 3 ~ 10: 3, PEG-400 add-on be 1/15 of overall solution volume.
3. the preparation method of ferroferric oxide magnetic carrier according to claim 1, is characterized in that: described step 2) in air dry oven heating temperature be set to 180 DEG C, 9 hours ~ 24 hours reaction times.
4. the preparation method of ferroferric oxide magnetic carrier according to claim 1, is characterized in that: described step 4) in, bake out temperature is set to 60 DEG C, and drying time is 8 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510567043.2A CN105174318A (en) | 2015-09-08 | 2015-09-08 | Preparation method for ferroferric oxide magnetic carrier |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510567043.2A CN105174318A (en) | 2015-09-08 | 2015-09-08 | Preparation method for ferroferric oxide magnetic carrier |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN105174318A true CN105174318A (en) | 2015-12-23 |
Family
ID=54896859
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510567043.2A Pending CN105174318A (en) | 2015-09-08 | 2015-09-08 | Preparation method for ferroferric oxide magnetic carrier |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105174318A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186081A (en) * | 2016-07-13 | 2016-12-07 | 南通中兴多元复合钢管有限公司 | The preparation method of ferroferric oxide magnetic carrier |
| CN106927511A (en) * | 2017-04-17 | 2017-07-07 | 吉林大学 | A kind of high-energy ball milling preparation method of magnetic ferroferric oxide nanometer powder |
| CN114538524A (en) * | 2022-03-19 | 2022-05-27 | 合肥中镓纳米技术有限公司 | Preparation method and application of ferroferric oxide octahedral nanocrystal |
-
2015
- 2015-09-08 CN CN201510567043.2A patent/CN105174318A/en active Pending
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106186081A (en) * | 2016-07-13 | 2016-12-07 | 南通中兴多元复合钢管有限公司 | The preparation method of ferroferric oxide magnetic carrier |
| CN106927511A (en) * | 2017-04-17 | 2017-07-07 | 吉林大学 | A kind of high-energy ball milling preparation method of magnetic ferroferric oxide nanometer powder |
| CN114538524A (en) * | 2022-03-19 | 2022-05-27 | 合肥中镓纳米技术有限公司 | Preparation method and application of ferroferric oxide octahedral nanocrystal |
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Application publication date: 20151223 |