CN108339524A - A kind of the hypergravity preparation method and device of cellulose base magnetic Nano material - Google Patents
A kind of the hypergravity preparation method and device of cellulose base magnetic Nano material Download PDFInfo
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Abstract
The invention discloses a kind of hypergravity preparation method of cellulose base magnetic Nano material and devices, belong to technical field of nano material.Cellulose is sent into supergravity reactor by the present invention simultaneously with the mixed solution of metal salt and lye to react, after reaction Magneto separate reaction product, and deionized water and absolute ethyl alcohol are cleaned repeatedly to neutrality, and vacuum drying obtains cellulose base magnetic Nano material.This method is simple for process, the reaction time is short, it is at low cost, be produced on a large scale；Present invention introduces the large biological molecule cellulose rich in carboxyl and hydroxyl, the cellulose base magnetic Nano material grain size of preparation is small, is uniformly dispersed, and has industrial applications foreground；This method is expected to be widely used in the fields such as environmental protection, biological medicine, chemical industry.
Description
Technical field
The present invention relates to a kind of hypergravity preparation method of cellulose base magnetic Nano material and devices, belong to nano material
Preparing technical field.
Background technology
Cellulose is most abundant on the earth and reproducible natural polymer, is a kind of threadiness, the solid of multiple capillary
The high molecular polymer of regularity has porous and large specific surface area characteristic, and basic structural unit is D- glucopyranoses
For base by β-Isosorbide-5-Nitrae glucosides key connection, there are three active hydroxyls for each glucose unit in strand, and oxidation, ester easily occurs
The reactions such as change, etherificate, graft copolymerization.Therefore can according to require design cellulose chemical constitution, introduce carboxyl, sulfonic group,
The groups such as phosphate increase adsorption site (ROOH) or R (COOH) n, prepare various cellulose derivatives, wherein to adsorb a huge sum of money
The Cellulose-based Adsorbents for belonging to ion are the most notable, not only solve heavy metal ion in this way to human health and ecological environment
Harm, also solves the problems, such as that processing cost is high.Although Cellulose-based Adsorbents have many good qualities, it is applied to sewage disposal,
It is difficult to realize be separated by solid-liquid separation.
Magnetic Nano material not only has the fundamental characteristics of conventional nano material, such as a kind of special nano material
Dimensional effect, skin effect, quantum effect and macro quanta tunnel effect etc., while also having special magnetic property, magnetism is received
Rice material shows the property different from conventional material in physics, chemistry etc., and magnetic Nano material is at sewage
Reason field can solve separation problem present in water process.Cellulose is combined with magnetic Nano material, on the one hand there is magnetic
Property, it can quickly realize that the separation and recovery of magnetic composite, another aspect cellulose can also improve under externally-applied magnetic field
The dispersibility of magnetic Nano material, biocompatibility improve absorption property of the magnetic Nano material to heavy metal ion.
Currently, the most commonly used is coprecipitation, hydro-thermal method and colloidal sols to coagulate for the preparation method of cellulose base magnetic Nano material
Glue method.Wherein, coprecipitation be by soluble cellulose and dissolving metal salts in a solvent, then by precipitating reagent with certain
Speed is added dropwise, and is precipitated until each component of the metal salt in precipitating reagent and solution uniformly mixes generation, then carries out water-bath reflux
Keep precipitation complete.Due to the advantages that its preparation process is simple, operating cost is low, experiment condition is mild have become it is most commonly used
Prepare the preparation method of cellulose base magnetic Nano material, but the particle diameter distribution of prepared cellulose base magnetic nano-particle
It is uneven, and be not easy to accomplish scale production.This is because the reaction unit that coprecipitation uses is usually stirring reactor,
It is to make reaction mass Strong dispersion hybrid reaction using the shearing force of agitating paddle, belongs to intermittently operated, it is microcosmic uniformly mixed
Time is about 0.01 ~ 0.2 s.Quickly precipitation is reacted since precipitating reagent is one with reacting metal salt generation magnetic nano-particle
The characteristic time of process, nucleation is about 1ms, therefore transmission and mixing in traditional stirring reactor on molecular scale
Rate is much smaller than the nucleation rate of liquid-phase precipitation, and the uneven ring on molecular scale is in so as to cause nucleation and growth course
Thus border uses cellulose base magnetic nano-particle prepared by traditional stirring reactor uneven there are particle diameter distribution and batch
Produce the industrialness problems such as poor reproducibility, Product management model effect be big.Therefore, exploitation can prepare cellulose base magnetism with continuous batch
The new process and new method of nano material are that Cellulose-based Adsorbents apply critical problem to be solved.
Invention content
The present invention is intended to provide the hypergravity preparation method and device of a kind of cellulose base magnetic Nano material, one-step method system
Standby cellulose base magnetic Nano material, this method have that simple for process, the reaction time is short, the at low cost, spy that is produced on a large scale
Point, and the cellulose base magnetic Nano material grain size prepared is small, is uniformly dispersed, and has industrial applications foreground.
High-gravity technology is applied in the preparation process of cellulose base magnetic Nano material by the present invention, realizes product
The optimization of energy.High-gravity technology because it strengthens microcosmic mixing and the characteristics of mass transport process, can make reaction system moment reach compared with
The high and degree of supersaturation being evenly distributed and the microcosmic mixing time less than nucleation induction time.High-gravity technology preparation is received
Rice material is short with the reaction time, formation nano particle diameter is small, particle diameter distribution is uniform, manufacturing cost is low, is easy to industrialize
Amplification production（4-20 times can be improved compared with conventional method）The advantages that.Therefore, high-gravity technology and reaction precipitation method knot are utilized
It closes, one-step synthesis good dispersion, the uniform cellulose base magnetic Nano material of particle diameter distribution, it is expected to accelerate to promote cellulose family
The sizable application of adsorbent provides important channel.
The present invention provides a kind of hypergravity preparation methods of cellulose base magnetic Nano material, include the following steps：It will
Cellulose is sent into supergravity reactor simultaneously with the mixed solution of metal salt and lye to react, and Magneto separate reacts after reaction
Product, deionized water and absolute ethyl alcohol are cleaned repeatedly to neutrality, and vacuum drying obtains cellulose base magnetic Nano material, specific to walk
It is rapid as follows：
(1) cellulose and metal mixed salt solution are prepared：Cellulose is dissolved in water and is configured to the fibre that cellulose concentration is 0.1% ~ 2%
The aqueous solution of element is tieed up, metal M is then added thereto2+Salt and Fe3+It is 0.05 ~ 1.0 mol/L's that salt, which is configured to cation concn,
The mixed solution of cellulose and metal salt, wherein Fe3+Salt and metal M2+The molar ratio of salt is 2:1~3:2, the M2+For Mn2+、
Fe2+、Ni2+、Co2+、Zn2+、Mg2+In one kind；
(2) lye is prepared：Use sodium hydroxide or ammonium hydroxide for alkali source, by cation and OH-Molar ratio be 1:2.4~1:5 prepare
Concentration of lye is the aqueous solution of 0.12 ~ 5.0 mol/L；
(3) synthetic cellulose base magnetic nano material：The mixed solution of cellulose and metal salt, lye are placed in reservoir respectively
In, 25 ~ 80 DEG C are preheating to, two strands of isometric reaction masses are delivered in supergravity reactor by liquid distribution trough and are carried out instead
It answers, is all according to isometric hybrid reaction in the mixed solution and lye of any one moment cellulose and metal salt.Control two
The volume flow of stock material liquid is 20 ~ 100 L/h, and the rotating speed of supergravity reactor is in 100 ~ 2500 rpm；
(4) after reaction, Magneto separate reaction product is cleaned repeatedly with deionized water and absolute ethyl alcohol to neutrality, vacuum drying
Obtain cellulose base magnetic Nano material.
The magnetic Nano material includes：Fe3O4、MnFe2O4、NiFe2O4、CoFe2O4、ZnFe2O4、MgFe2O4Equal iron
Oxysome.
The cellulose is cellulose derivative, including carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl fiber
Any one of element.
The M2+Salt is nitrate, sulfate and chlorate, M2+For Mn2+、Fe2+、Ni2+、Co2+、Zn2+、Mg2+In one
Kind.
The present invention provides a kind of hypergravity preparation facilities of cellulose base magnetic Nano material, including hypergravity to react
Device, cellulose and metal mixed salt solution storage tank, lye storage tank, cellulose and metal mixed salt solution storage tank, lye storage tank point
Supergravity reactor is not connected, pump and spinner flowmeter are respectively equipped on connecting line, by pumping control fiber element and metal salt
The flow of mixed solution and lye is equal；Liquid distribution trough is equipped in supergravity reactor, control fiber element is mixed with metal salt
Solution and lye are mixed；Connection product storage tank below supergravity reactor.
In above-mentioned apparatus, the supergravity reactor is Impinging Stream-Rotating Packed Bed, rotary packed bed or helical duct type
Any one of revolving bed.
When supergravity reactor used is Impinging Stream-Rotating Packed Bed, principle is two strands of reaction masses by liquid distribution
Two opposite nozzles spray to form jet stream on device, and the circle perpendicular to jet direction is formed after hitting（Fan）Shape film
（Mist）Face, two strands of reaction masses are realized in the process mixes, reacts for the first time.The weaker shock cloudy surface edge of mixing enters rotation
Turn the inner cavity of packed bed, under the influence of centrifugal force along the outside edge flowing of filler hole, and liquid is multiple by filler during this period
Second of mixing, reaction are completed in cutting, coalescence and dispersion.Finally, reaction product is under the influence of centrifugal force from the outer rim of filler
It is thrown on shell, is pooled to outlet discharge under gravity.
Supergravity reactor used is rotary packed bed, and principle is two strands of reaction masses by trepanning on liquid distribution trough
Nozzle is sprayed onto on filler, and liquid is flowed along filler hole from rotor inner edge to rotor periphery under the influence of centrifugal force.In this phase
Between, material liquid repeatedly cut by filler, coalescence and dispersion, and reaction is mutually mixed in packing layer.Finally, reaction product is centrifuging
It is thrown on shell from filler outer rim under the action of power, is pooled to outlet discharge under the effect of gravity.
Supergravity reactor used is rotating bed with helix channel, principle be two strands of reaction masses by liquid distribution trough into
Enter in helical duct, liquid acts on from inside to outside centrifugal force along the rotor stream with spiral of Archimedes shape channel
Go out.During this period, material liquid is mutually mixed in helical duct, reacts.Finally, reaction product under the influence of centrifugal force from turn
Sub- outer rim is thrown on shell, is pooled to outlet discharge under gravity.
For the present invention by the magnetic Nano material of supergravity reactor one-step synthesis cellulose modifying, utilization is high-speed rotating
Filler is acutely sheared and is crushed to fluid process, generates huge and quick newer boundary so that microcosmic to mix and mass transfer mistake
Journey has obtained great reinforcing, and the microcosmic uniformly mixed characteristic time is 10-100 μ s in supergravity reactor, much smaller than tradition
The induction Nucleation characteristics time of liquid-phase precipitation reaction.That is, by hypergravity reaction technology, magnetic Nano material is crystallizing
Uniform degree of supersaturation is had reached before nucleation, in reactor, therefore the nucleation of prepared magnetic Nano material and growth are equal
It is carried out under conditions of a uniform degree of supersaturation, meets desired homogeneous into nuclear environment, control nucleation process, particle is made to present
Go out relatively narrow distribution thus prepared by nano material grain size is smaller, particle diameter distribution is uniform；In addition, continuously being prepared by hypergravity
Method, magnetic Nano material production efficiency can reach 0.068-7.95 kg/h, this is that common stirred tank method is difficult to realize
, industrial applications foreground outclass traditional reaction kettle paddling process.Hypergravity reaction coprecipitation of the present invention is logical
The control magnetic nano-particle nucleation and crystallization time is spent to control the forming process of nano material.
Beneficial effects of the present invention：
The present invention reacts the supergravity reactor with powerful microcosmic composite character applied to quick chemical precipitation, while profit
Use the cellulose of biomass as the dispersant and surface modifier of magnetic Nano material, the magnetic Nano material of preparation has grain
Diameter is small, particle diameter distribution is uniform, preparation method is simple, manufacturing cost is low, can continuous batch prepare, therefore have industrialization outstanding
Application prospect.It is expected to be widely used in the fields such as sewage disposal, heavy metal analysis, magnetic catalysis, magnetic recording, biomedicine.
Description of the drawings
Fig. 1 is the flow chart of the hypergravity preparation facilities of cellulose base magnetic Nano material.
Fig. 2 is the Fe of 1 obtained carboxymethyl cellulose of embodiment modification3O4The TEM of magnetic nano-particle schemes.
Fig. 3 is the Fe of 1 obtained carboxymethyl cellulose of embodiment modification3O4The X-ray diffractogram of magnetic nano-particle,
Wherein (a) is Fe3O4Magnetic nano-particle；(b) it is the Fe of carboxymethyl cellulose modification3O4Magnetic nano-particle.
Fig. 4 is the Fe of 1 obtained carboxymethyl cellulose of embodiment modification3O4The infrared spectrogram of magnetic nano-particle,
In (a) be Fe3O4Magnetic nano-particle；(b) it is the Fe of carboxymethyl cellulose modification3O4Magnetic nano-particle；(c) it is carboxymethyl
Cellulose.
Fig. 5 is the Fe of 1 obtained carboxymethyl cellulose of embodiment modification3O4The hysteresis loop figure of magnetic nano-particle,
In (a) be Fe3O4Magnetic nano-particle；(b) it is the Fe of carboxymethyl cellulose modification3O4Magnetic nano-particle.
In figure, 1- celluloses and metal mixed salt solution storage tank；2- centrifugal pumps；3- valves；4- spinner flowmeters；5- is overweight
Power reactor；6- product storage tanks；7- lye storage tanks.
Specific implementation mode
It is further illustrated the present invention below by embodiment, but is not limited to following embodiment.
Fig. 1 be cellulose base magnetic Nano material hypergravity preparation facilities, including supergravity reactor 5, cellulose with
Metal mixed salt solution storage tank 1, lye storage tank 7, cellulose are separately connected super with metal mixed salt solution storage tank 1, lye storage tank 7
Gravity reactor is respectively equipped with centrifugal pump 2 and spinner flowmeter 4 on connecting line, passes through centrifugal pump control fiber element and metal
The flow of mixed salt solution and lye is equal；Liquid distribution trough is equipped in supergravity reactor, control fiber element is mixed with metal salt
It closes solution and lye is mixed；5 lower section connection product storage tank 6 of supergravity reactor.
Specific experiment step is：The mixed solution and lye of cellulose and metal salt are added separately to cellulose and metal
In mixed salt solution storage tank 1 and lye storage tank 7,25 ~ 80 °C are preheating to, starts centrifugal pump material liquid is defeated through spinner flowmeter 4
It is sent into supergravity reactor 5, two strands of material liquids of constant speed enter the rotor of rotation by liquid distribution trough, and liquid is in centrifugal force
Under the action of flow through the rotor of rotation, and the hybrid reaction in rotor from inside to outside.Effect of the final reaction product in centrifugal force
Under be thrown on shell, be pooled under gravity outlet discharge.
Embodiment 1：
A kind of hypergravity preparation method of cellulose base magnetic Nano material, the miscible fluid and lye of cellulose and metal salt is same
When be sent into supergravity reactor in react, Magneto separate reaction product, deionized water and absolute ethyl alcohol clean repeatedly after reaction
To neutrality, vacuum drying obtains cellulose base magnetic Nano material, is as follows：
The carboxymethyl cellulose for weighing 2 g is dissolved in the aqueous solution that carboxymethyl cellulose a concentration of 0.2% is configured in 1L water, Xiang Qi
Middle addition FeCl2•4H2O (36.16 g, 0.179 mol) and FeCl3•6H2O (88.56g, 0.321 mol) be configured to sun from
The iron salt solutions of a concentration of 0.5 mol/L of son, wherein Fe3+Salt and Fe2+The molar ratio of salt is 1.8:1；In addition, according to cation
And OH-Molar ratio be 1:3.86, it is the water-soluble of 1.93 mol/L to weigh 77.6 g sodium hydroxides and be configured to naoh concentration
Liquid；Above-mentioned carboxymethyl cellulose and molysite mixed solution are added separately to NaOH aqueous solutions in storage tank, 80 DEG C is preheating to, opens
Liquid is conveyed into through spinner in Impinging Stream-Rotating Packed Bed agent set by dynamic centrifugal pump, two strands of isometric reactants
Material is ejected into after being hit by the nozzle constant speed of liquid distribution trough on rotary packed bed inner edge, and edge is filled out under the influence of centrifugal force
Expect that hole is flowed to outer rim, and is mutually mixed reaction in packing layer.Finally, reaction product is under the influence of centrifugal force from filler
Outer rim be thrown on shell, be pooled to exit under gravity, through outlet be discharged.Two kinds of raw materials are adjusted in the process
The volume flow of liquid is 60 L/h, and the rotating speed for controlling Impinging Stream-Rotating Packed Bed is 1000 rpm；After reaction, it uses
Magnetic separation technique collecting reaction product is cleaned with deionized water repeatedly to neutrality, and vacuum drying obtains carboxymethyl cellulose modification
Fe3O4Magnetic nano-particle.
Fig. 2 shows the Fe of the carboxymethyl cellulose modification of the embodiment 1 synthesis3O4The TEM of magnetic nano-particle schemes, from
The Fe of it can be seen from the figure that carboxymethyl cellulose modification3O4The grain size of magnetic nano-particle is about 11 nm, and particle size is uniform, point
It is good to dissipate property.
Fig. 3 is the Fe for the carboxymethyl cellulose modification that the embodiment 1 obtains3O4The X-ray diffractogram of magnetic nano-particle.
It can be seen from the figure that the Fe of carboxymethyl cellulose modification3O4Magnetic nano-particle at 30.1 °, 35.4 °, 43.1 °, 53.4 °,
57.0 ° and 62.6 ° there is Fe3O4The characteristic diffraction peak of magnetic nano-particle, respectively corresponding (220), (311), (400), (422),
(511) and (440) crystal face, and diffraction peak intensity is high, almost without other miscellaneous peaks, illustrates prepared carboxymethyl cellulose modification
Fe3O4Nano-particle is cubic phase, and carboxymethyl cellulose modification does not influence Fe3O4The crystalline phase of magnetic nano-particle, and crystallinity
Preferably, grain size is smaller, purity is higher.
Fig. 4 shows the carboxymethyl cellulose-based Fe of embodiment synthesis3O4Infrared spectrum (Fig. 4 of magnetic nano-particle
(b)) Fe that, as can be seen from the figure carboxymethyl cellulose is modified3O4The infrared spectrum of magnetic nano-particle is in 572 cm-1It is corresponding
The characteristic peak of Fe-O, in 1612 and 1392 cm-1Corresponding to the asymmetry and symmetrical stretching vibration of the-COO of carboxymethyl cellulose
Peak, in 1131 cm-1The stretching vibration peak of the C-O-C of corresponding carboxymethyl cellulose.Illustrating carboxymethyl cellulose, successfully modification exists
Fe3O4Magnetic nano-particle surface.
Fig. 5 shows that the embodiment obtains carboxymethyl cellulose modification Fe3O4The hysteresis loop figure of magnetic nano-particle.From
It can be seen from the figure that modifies front and back Fe3O4The coercivity and remanent magnetism of nano-particle can hardly be surveyed, and illustrate prepared sample table
It is now superparamagnetism.Fe after modification carboxymethyl cellulose3O4The saturation magnetization of magnetic nano-particle（M s）For 45.1 emu/
G, purer Fe3O4Nano-particleM s(60.5 emu/g) is slightly lower, and this is mainly due to carboxymethyl celluloses to modify Fe3O4Magnetism is received
There are a large amount of diamagnetic carboxymethyl celluloses in rice corpuscles, the dipolar interaction between magnetic particle is reduced, to makeM sIt reduces.
Embodiment 2：
A kind of hypergravity preparation method of cellulose base magnetic Nano material, includes the following steps：
The hydroxyethyl cellulose for weighing 1 g is dissolved in the aqueous solution that hydroxyethyl cellulose a concentration of 0.1% is configured in 1L water, Xiang Qi
Middle addition Mn (NO3)2(3.58 g, 0.02 mol), Fe2(SO4)3(12.0 g, 0.03 mol), being configured to cation concn is
The metal salt solution of 0.05 mol/L, wherein Fe3+Salt and Mn2+The molar ratio of salt is 3:2；In addition, according to cation and OH-Rub
You are than being 1:5, it weighs 8.76 g ammonium hydroxide and is configured to the aqueous solution that ammonia concn is 0.25 mol/L；By above-mentioned hydroxyethyl cellulose
It is added separately in storage tank with metal mixed salt solution and ammonia aqueous solution, is preheating to 25 DEG C, start centrifugal pump by two kinds of raw materials
Liquid respectively by liquid distribution trough be delivered to it is rotary packed bed in, material liquid is sprayed onto the filler of rotation by the trepanning on liquid distribution trough
On, flow through the hole of filler from inside to outside under the influence of centrifugal force, and reaction is mutually mixed in packing layer.Finally, it reacts
Product is thrown to from the outer rim of filler on shell under the influence of centrifugal force, is pooled to exit under gravity, through outlet
Discharge.It is 20 L/h to adjust the volume flow of two kinds of material liquids in the process, and it is 100 to control rotary packed bed rotating speed
rpm；After reaction, it using magnetic separation technique collecting reaction product, is cleaned repeatedly to neutrality, is dried in vacuo with deionized water
The ferrite MnFe modified to hydroxyethyl cellulose2O4Magnetic nano-particle
Embodiment 3：
A kind of hypergravity preparation method of cellulose base magnetic Nano material, includes the following steps：
The hydroxypropyl methyl cellulose for weighing 20 g is dissolved in the aqueous solution that hypromellose a concentration of 2% is configured in 1L water,
NiSO is added thereto4•6H2O (93.34 g, 0.33 mol), Fe (NO3)3•9H2O (270.68 g, 0.37 mol), is configured to
Cation concn is the metal salt solution of 1.0 mol/L, wherein Fe3+Salt and Ni2+The molar ratio of salt is 2:1；In addition, according to sun
Ion and OH-Molar ratio be 1:2.4, it is the water-soluble of 2.4 mol/L to weigh 96 g sodium hydroxides and be configured to naoh concentration
Liquid；Above-mentioned hydroxypropyl methyl cellulose and metal mixed salt solution are added to lye in storage tank, are preheating to 60 DEG C, start from
Two kinds of material liquids are delivered to by liquid distribution trough in rotating bed with helix channel by heart pump respectively, and liquid is entered by liquid distribution trough
It is flowed out from inside to outside along the rotor with spiral of Archimedes shape channel in the effect of centrifugal force in helical duct.Herein
Period, material liquid are mutually mixed in helical duct, react.Finally, reaction product is under the influence of centrifugal force from rotor periphery
It is thrown on shell, is pooled to outlet discharge under gravity.The volume flow for adjusting two kinds of material liquids in the process is equal
For 100 L/h, the rotating speed for controlling rotating bed with helix channel is 2500 rpm；After reaction, Magneto separate reaction product is spent
Ionized water and absolute ethyl alcohol are cleaned repeatedly to neutrality, and vacuum drying obtains the ferrite NiFe of hydroxypropyl methyl cellulose modification2O4
Magnetic nano-particle.
Embodiment 4：
A kind of hypergravity preparation method of cellulose base magnetic Nano material, includes the following steps：
The carboxymethyl cellulose for weighing 10 g is dissolved in the aqueous solution that a concentration of 1.0 % of carboxymethyl cellulose is configured in 1L water, to
Co (NO are wherein added3)2•6H2O (29.11 g, 0.10 mol), Fe (NO3)3•9H2O (60.6 g, 0.15 mol), is configured to sun
Ion concentration is the metal salt solution of 0.25 mol/L, wherein Fe3+Salt and Co2+The molar ratio of salt is 3:2；In addition, according to sun from
Son and OH-Molar ratio be 1:5, it weighs 43.81 g ammonium hydroxide and is configured to the aqueous solution that ammonia concn is 1.25 mol/L；It will be above-mentioned
Carboxymethyl cellulose and metal mixed salt solution are added separately to ammonia aqueous solution in storage tank, are preheating to 40 DEG C, start centrifugation
Pump by two kinds of material liquids respectively by liquid distribution trough be delivered to it is rotary packed bed in, material liquid by liquid distribution trough trepanning spray
Onto the filler of rotation, the hole of filler is flowed through from inside to outside under the influence of centrifugal force, and be mutually mixed instead in packing layer
It answers.Finally, reaction product is thrown to from the outer rim of filler on shell under the influence of centrifugal force, is pooled to out under gravity
At mouthful, it is discharged through outlet.It is 80 L/h to adjust the volume flow of two kinds of material liquids in the process, is controlled rotary packed bed
Rotating speed is 1500 rpm；After reaction, it using magnetic separation technique collecting reaction product, is cleaned repeatedly into deionized water
Property, vacuum drying obtains the ferrite CoFe of carboxymethyl cellulose modification2O4Magnetic nano-particle.
Embodiment 5：
A kind of hypergravity preparation method of cellulose base magnetic Nano material, includes the following steps：
The hypromellose for weighing 5 g is dissolved in the aqueous solution that hypromellose a concentration of 0.5% is configured in 1L water,
ZnCl is added thereto2(2.32 g, 0.017 mol), FeCl3•6H2It is dense that O (9.01 g, 0.033 mol) is configured to cation
Degree is the metal salt solution of 0.05 mol/L, wherein Fe3+Salt and Zn2+The molar ratio of salt is 2:1；In addition, according to cation and OH-
Molar ratio be 1:2.4, it weighs 4.8 g sodium hydroxides and is configured to the aqueous solution that naoh concentration is 0.12 mol/L；It will be upper
It states hypromellose and metal mixed salt solution to be added separately in storage tank with NaOH aqueous solutions, is preheating to 50 DEG C, start
Liquid is conveyed into through spinner in Impinging Stream-Rotating Packed Bed agent set by centrifugal pump, two strands of isometric reaction masses
It is ejected on rotary packed bed inner edge after being hit by the nozzle constant speed of liquid distribution trough, under the influence of centrifugal force along filler
Hole is flowed to outer rim, and reaction is mutually mixed in packing layer.Finally, reaction product is under the influence of centrifugal force from filler
Outer rim is thrown on shell, is pooled to exit under gravity, is discharged through outlet.Two kinds of material liquids are adjusted in the process
Volume flow be 70 L/h, control Impinging Stream-Rotating Packed Bed rotating speed be 1200 rpm；After reaction, using magnetic
Isolation technics collecting reaction product is cleaned with deionized water repeatedly to neutrality, and vacuum drying obtains hypromellose modification
Ferrite ZnFe2O4Magnetic nano-particle.
Embodiment 6：
A kind of hypergravity preparation method of cellulose base magnetic Nano material, includes the following steps：
The hydroxyethyl cellulose for weighing 15 g is dissolved in the aqueous solution that hydroxyethyl cellulose a concentration of 1.5% is configured in 1L water, Xiang Qi
Middle addition MgSO4(36.12 g, 0.3 mol), Fe2(SO4)3(180g, 0.45 mol), it is 0.75 to be configured to cation concn
The metal salt solution of mol/L, wherein Fe3+Salt and Mg2+The molar ratio of salt is 3:2；In addition, according to cation and OH-Molar ratio
It is 1:4, it weighs 105.15 g ammonium hydroxide and is configured to the aqueous solution that ammonia concn is 3.0 mol/L；By above-mentioned hydroxyethyl cellulose and
Metal mixed salt solution is added to lye in storage tank, is preheating to 70 DEG C, starts centrifugal pump by two kinds of material liquids respectively by liquid
Distributor is delivered in rotating bed with helix channel, and liquid enters the effect in helical duct in centrifugal force certainly by liquid distribution trough
It is flowed out from inside to outside along the rotor with spiral of Archimedes shape channel.During this period, material liquid phase in helical duct
Mutually mixing, reaction.Finally, reaction product is thrown to from rotor periphery on shell under the influence of centrifugal force, under gravity
It is pooled to outlet discharge.It is 40 L/h to adjust the volume flow of two kinds of material liquids in the process, control helical duct type rotation
The rotating speed of rotated bed is 800 rpm；After reaction, Magneto separate reaction product, with deionized water and absolute ethyl alcohol clean repeatedly to
Neutrality, vacuum drying obtain the ferrite MgFe of hydroxyethyl cellulose modification2O4Magnetic nano-particle.
Claims (10)
1. a kind of hypergravity preparation method of cellulose base magnetic Nano material, it is characterised in that include the following steps：By fiber
Element is sent into supergravity reactor simultaneously with the mixed solution of metal salt and lye to react, after reaction Magneto separate reaction production
Object, deionized water and absolute ethyl alcohol are cleaned repeatedly to neutrality, and vacuum drying obtains cellulose base magnetic Nano material.
2. the hypergravity preparation method of cellulose base magnetic Nano material according to claim 1, it is characterised in that including
Following steps：
(1) cellulose and metal mixed salt solution are prepared：Cellulose is dissolved in water and is configured to the fibre that cellulose concentration is 0.1% ~ 2%
The aqueous solution of element is tieed up, metal M is then added thereto2+Salt and Fe3+It is 0.05 ~ 1.0 mol/L's that salt, which is configured to cation concn,
The mixed solution of cellulose and metal salt, wherein Fe3+Salt and metal M2+The molar ratio of salt is 2:1~3:2, the M2+For Mn2+、
Fe2+、Ni2+、Co2+、Zn2+、Mg2+In one kind；
(2) lye is prepared：Use sodium hydroxide or ammonium hydroxide for alkali source, by cation and OH-Molar ratio be 1:2.4~1:5 prepare
Concentration of lye is the aqueous solution of 0.12 ~ 5.0 mol/L；
(3) synthetic cellulose base magnetic nano material：The mixed solution of cellulose and metal salt, lye are placed in reservoir respectively
In, 25 ~ 80 DEG C are preheating to, two strands of isometric reaction masses are delivered in supergravity reactor by liquid distribution trough and are carried out instead
It answers, the mixed solution and lye of cellulose and metal salt are all according to isometric hybrid reaction at any time；Control two bursts of originals
The volume flow of feed liquid is 20 ~ 100 L/h, and the rotating speed of supergravity reactor is in 100 ~ 2500 rpm；
(4) after reaction, Magneto separate reaction product is cleaned repeatedly with deionized water and absolute ethyl alcohol to neutrality, vacuum drying
Obtain cellulose base magnetic Nano material.
3. the hypergravity preparation method of cellulose base magnetic Nano material according to claim 1, it is characterised in that：It is described
Magnetic Nano material include：Fe3O4、MnFe2O4、NiFe2O4、CoFe2O4、ZnFe2O4、MgFe2O4Any one of.
4. the hypergravity preparation method of cellulose base magnetic Nano material according to claim 1, it is characterised in that：It is described
Cellulose is any in cellulose derivative, including carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropyl methyl cellulose
Kind.
5. the hypergravity preparation method of cellulose base magnetic Nano material according to claim 1, it is characterised in that：It is described
M2+Salt is nitrate, sulfate and chlorate, M2+For Mn2+、Fe2+、Ni2+、Co2+、Zn2+、Mg2+Any one of.
6. a kind of hypergravity preparing cellulose base magnetic Nano material using claim 1 ~ 5 any one of them preparation method
Preparation facilities, it is characterised in that：Including supergravity reactor, cellulose and metal mixed salt solution storage tank, lye storage tank, fiber
Element is separately connected supergravity reactor with metal mixed salt solution storage tank, lye storage tank, and pump is respectively equipped on connecting line and is turned
Subflow gauge is equal with the flow of metal mixed salt solution and lye by pumping control fiber element；It is equipped in supergravity reactor
Liquid distribution trough, control fiber element are mixed with metal mixed salt solution and lye；Connection product below supergravity reactor
Storage tank.
7. the hypergravity preparation facilities of cellulose base magnetic Nano material according to claim 6, it is characterised in that：It is described
Supergravity reactor is any one of Impinging Stream-Rotating Packed Bed, rotary packed bed or rotating bed with helix channel.
8. the hypergravity preparation facilities of cellulose base magnetic Nano material according to claim 6, it is characterised in that：It is used
When supergravity reactor is Impinging Stream-Rotating Packed Bed, two strands of reaction masses are sprayed by the nozzle that two opposite on liquid distribution trough
Go out to form jet stream, and form the fan-shaped membrane cloudy surface perpendicular to jet direction after hitting, in the process two strands of reactants
Material realizes mixing for the first time, reaction；The weaker shock cloudy surface edge of mixing enters rotary packed bed inner cavity, in the work of centrifugal force
With lower along the outside edge flowing of filler hole, and liquid is repeatedly cut by filler during this period, coalescence and dispersion, completion mix for the second time
It closes, reaction；Finally, reaction product is thrown to from the outer rim of filler on shell under the influence of centrifugal force, is converged under gravity
Collect outlet discharge.
9. the hypergravity preparation facilities of cellulose base magnetic Nano material according to claim 6, it is characterised in that：It is used
Supergravity reactor is rotary packed bed, and two strands of reaction masses are sprayed onto by the nozzle of trepanning on liquid distribution trough on filler, liquid
It is flowed under the influence of centrifugal force from rotor inner edge to rotor periphery along filler hole；At this point, material liquid repeatedly cut by filler,
Coalescence and dispersion are mutually mixed reaction in packing layer；Finally, reaction product is got rid of from filler outer rim under the influence of centrifugal force
Onto shell, it is pooled to outlet discharge under the effect of gravity.
10. the hypergravity preparation facilities of cellulose base magnetic Nano material according to claim 6, it is characterised in that：Institute
It is rotating bed with helix channel with supergravity reactor, two strands of reaction masses are entered by liquid distribution trough in helical duct, liquid
It is flowed out from inside to outside along the rotor with spiral of Archimedes shape channel in the effect of centrifugal force；At this point, material liquid exists
It is mutually mixed, reacts in helical duct；Finally, reaction product is thrown to from rotor periphery on shell under the influence of centrifugal force,
Outlet discharge is pooled under the action of gravity.
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