CN104128137A - Double fish-shaped reactor - Google Patents

Double fish-shaped reactor Download PDF

Info

Publication number
CN104128137A
CN104128137A CN201410380345.4A CN201410380345A CN104128137A CN 104128137 A CN104128137 A CN 104128137A CN 201410380345 A CN201410380345 A CN 201410380345A CN 104128137 A CN104128137 A CN 104128137A
Authority
CN
China
Prior art keywords
runner
branch flow
reaction
flow passage
angle
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201410380345.4A
Other languages
Chinese (zh)
Other versions
CN104128137B (en
Inventor
王东光
竺柏康
张仁坤
陶亨聪
李翠翠
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zhejiang Ocean University ZJOU
Original Assignee
Zhejiang Ocean University ZJOU
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Zhejiang Ocean University ZJOU filed Critical Zhejiang Ocean University ZJOU
Priority to CN201510817976.2A priority Critical patent/CN105396521B/en
Priority to CN201410380345.4A priority patent/CN104128137B/en
Publication of CN104128137A publication Critical patent/CN104128137A/en
Application granted granted Critical
Publication of CN104128137B publication Critical patent/CN104128137B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/02Making microcapsules or microballoons
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00274Sequential or parallel reactions; Apparatus and devices for combinatorial chemistry or for making arrays; Chemical library technology
    • B01J2219/00277Apparatus
    • B01J2219/00279Features relating to reactor vessels
    • B01J2219/00281Individual reactor vessels
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/24Stationary reactors without moving elements inside
    • B01J2219/2401Reactors comprising multiple separate flow channels
    • B01J2219/2402Monolithic-type reactors
    • B01J2219/2403Geometry of the channels

Abstract

The invention provides a double fish-shaped reactor comprising a reaction channel, two colliding channels, side channels and 24 branch channels, an inlet of the reaction channel is communicated with colliding ports of the two colliding channels, the reaction channel is communicated with outlets of the branch channels, inlets of the branch channels are communicated with the side channels, the side channels are located at both sides of the reaction channel, the 24 branch channels are successively arranged at both sides of the reaction channel at intervals; the double fish-shaped reactor is characterized in that the number of the side channels is four, two side channels of a first group are symmetrically arranged at both sides of the front part of the reaction channel, the two side channels of the first group are respectively communicated with 6 near branch channels at the same side; and two side channels of a second group are symmetrically arranged at both sides of the rear part of the reaction channel, the two side channels of the second group are respectively communicated with 6 near branch channels at the same side. The double fish-shaped reactor makes flow distribution regulation of the branch channels easier, the flow distribution of the branch channels is more stable, and operation parameters have flexible adjustable variable functions.

Description

Pisces shaped reaction device
Technical field
The technical field that the present invention relates to prepare the nano-complex particle of nucleocapsid structure, particularly, the present invention be more particularly directed to a kind of Pisces shaped reaction device.
Background technology
Core-shell type nano compound particle is that to take a size be core at the particle of micron to nano grade, a kind of compound heterogeneous structure forming at the coated several layers of even film in its surface.Between core and shell, by physics or the chemical action forming composite structure that is together with each other, by controlling nucleocapsid thickness, realize the regulation and control of composite performance.By cutting out nucleocapsid structure, size, can regulate and control their character such as magnetics, optics, mechanics, calorifics, electricity, catalysis, absorption, thereby there is the character that is different from monocomponent nanocomposite particle, at numerous areas such as materialogy (as: solid electrolyte, semiconductor, pottery, light-sensitive material), Chemical assembly, drug delivery, biochemistry diagnosis, photonic crystal, catalytic adsorption materials, be all widely used.
In recent years, design, synthetic single dispersion, controlled core-shell type nano compound particle have become the focus of the area researches such as numerous hybrid materials, nano material.The design of nucleocapsid structure is all to have very strong specific aim; as: adopt nuclear particle in the shell protection that character is comparatively stable that physics, chemical change do not occur, or distinctive electromagnetic property, optical characteristics, catalysis characteristics, characterization of adsorption are given and being integral etc. separately by outer shell particles and interior nuclear particle.
Realize industrialization low cost, on a large scale produce there is high-quality, high performance core-shell nano-composite material is the focus of Chemical Reaction Engineering technical field research.Along with going deep into of research, the preparation method of hud typed composite is more and more, mainly contain surface deposition method, ion-exchange, sonochemical method, self-assembly method (static assembling, vapour deposition, chemical plating) etc., but there are three obvious technological deficiencies in existing method: 1), in coated process, nano inner core particle is easily reunited; 2) coated precursor trends towards self nucleation, rather than is coated to the surface of interior nuclear particle; 3) coated film is inhomogeneous, imperfect.
Application number is that 201210394616.2 Chinese invention patent application discloses a kind of Road narrows formula impact flow reactor, its Road narrows are shaped heat dissipating fins layout, Road narrows comprise sprue, side runner and branch flow passage, outside feed liquid induction system is carried different feed liquid to Road narrows, each feed liquid bumps in Road narrows, finally generate the particle with nucleocapsid structure, but first this Road narrows formula shaped heat dissipating fins reactor cannot guarantee reaction and deposition process, only in sprue, carry out, also cannot produce in addition the overweight position of high frequency direction transformation and the effect that high frequency liquid-liquid film clashes into, therefore, cannot realize the effect of multiple dimensioned mixing, be an impediment to and prepare core-shell nano-composite material.
Application number is that 20130087052.2 Chinese invention patent application discloses a kind of fish shaped reaction device, first this reactor guarantees to react and deposition process is only carried out in reaction runner, disclose in addition the inner link between inside reactor structural parameters and operating parameter, and can realize that super gravity field, the high frequency liquid-liquid film that high frequency direction changes clashes into, equifrequency clashes into and the effect such as isoconcentration is coated.But still there is technological deficiency clearly in this fish shaped reaction device:
The first, in fish shaped reaction device, every side runner is connected with 12 Zhi Liuliang, because the branch flow passage number that side runner is communicated with is too many, cause flow design and adjusting to become very difficult, and the flow distribution of branch flow passage is very unstable.
The second, each main operating parameters is subject to the restriction of branch flow passage flow distribution very obvious, makes whole reactor lack the function of flexible modulation, causes fish shaped reaction device to lack necessary modulation function.
The 3rd, in fish shaped reaction device, because the projected angle of impact of high frequency liquid-liquid film knockout process is higher than 60 degree, formed Elastic Impact, Elastic Impact is unfavorable for reacting slurries and the rapid mixing between the two of the covering liquid in branch flow passage in runner.
Therefore, be necessary this fish shaped reaction device to carry out architecture advances and optimization.
Summary of the invention
The object of the present invention is to provide a kind of Pisces shaped reaction device, to solve operability and the not good problem of practicality of existing fish shaped reaction device.
In order to address the above problem, technical scheme provided by the invention is:
A kind of Pisces shaped reaction device, comprise a reaction runner, article two, runner clashes, side runner, article 24, branch flow passage, the import of described reaction runner is communicated with the shock mouth of two described head-on collision runners, described reaction runner is communicated with described branch flow passage outlet, the import of described branch flow passage is communicated with described side runner, described side runner is positioned at the both sides of described reaction runner, article 24, described branch flow passage is located at the both sides of described reaction runner in compartment of terrain successively, wherein, described side runner is four, wherein first group two described side runners are located at the both sides of the leading portion of described reaction runner symmetrically, and 6 described branch flow passages that two described side runners of first group close on homonymy are respectively communicated with, two described side runners of other second group are located at the both sides of the back segment of described reaction runner symmetrically, and 6 described branch flow passages that two described side runners of second group close on homonymy are respectively communicated with.
According to a kind of preferred embodiment of above-mentioned Pisces shaped reaction device, along the length direction of described reaction runner, described reaction runner comprises a plurality of semicircular segmental arcs that set gradually, and makes the whole undulate of described reaction runner.
According to a kind of preferred embodiment of above-mentioned Pisces shaped reaction device, the number of described segmental arc is more than or equal to the number of described branch flow passage.
According to a kind of preferred embodiment of above-mentioned Pisces shaped reaction device, the connectivity points of described reaction runner and branch flow passage residing angle in described segmental arc is called confluent angle, and described confluent angle equals the angle of converging between described reaction runner and described branch flow passage.
According to a kind of preferred embodiment of above-mentioned Pisces shaped reaction device, described confluent angle, converge angle between 0 to 60 degree.
According to a kind of preferred embodiment of above-mentioned Pisces shaped reaction device, described confluent angle, converge angle between 30 degree to 60 degree.
According to a kind of preferred embodiment of above-mentioned Pisces shaped reaction device, described confluent angle, to converge angle be 45 degree.
According to a kind of preferred embodiment of above-mentioned Pisces shaped reaction device, between the import and outlet of described reaction runner, along the length direction of described reaction runner, the diameter of described segmental arc increases gradually.
Analyze known, the present invention carries out architecture advances and optimization by the fish shaped reaction device to prior art, the adjusting of branch flow passage flow distribution is become to be more prone to, prop up flow distribution more stable, each operating parameter has the function of certain flexible modulation, can be widely used in the nano-complex particle of the various nucleocapsid structures of preparation.Further, the present invention can also make the shock between slurries and covering liquid reach non-resilient shock, promotes the two rapid mixing on molecular scale
Accompanying drawing explanation
Structure drawing of device when Fig. 1 is embodiment of the present invention application;
Fig. 2 is the internal structure Parameter Map of the embodiment of the present invention;
The schematic diagram that variation and the branch flow passage that Fig. 3 is super gravity field direction in the reaction runner of the reaction embodiment of the present invention connects;
Fig. 4 is the TEM electromicroscopic photograph of the nano-complex particle with nucleocapsid structure prepared of the embodiment of the present invention;
Fig. 5 be in the embodiment of the present invention super gravity field direction change frequency with the variation diagram that clashes into number of times.
Fig. 6 is the sample prepared of the present embodiment and pure nanometer Fe 3o 4the XRD spectra of particle.
The specific embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in further details.
Structure when Fig. 1 shows one embodiment of the invention application, the Pisces shaped reaction device that the embodiment of the present invention provides is connected with feed liquid supply and storage system, and this feed liquid supply and storage system comprise six storage tanks, can produce stable and the high-pressure air source (as: air compressor or cyclinder gas) of continuous nitrogen N 2 and many connecting lines, pipe fitting, a plurality of flowmeter 17 (comprising fluid flowmeter and gas flowmeter), Pressure gauge (not shown), triple valve 18 etc.Six storage tanks are respectively storage tank 11, storage tank 12, storage tank 13, storage tank 14, storage tank 15, storage tank 16, and because of institute's material stock liquid quantity, character difference to some extent, the size of each storage tank, material etc. are also different, and to this, those skilled in the art are to be understood that.
As shown in Figure 1, Figure 2, Figure 3 shows, the Pisces shaped reaction device that the embodiment of the present invention provides comprises: 15,2 head-on collision 2,4 side runner of runner of reaction runner and 24 branch flow passages 6, wherein, side runner comprise be positioned at reaction runner 5 leading portion both sides two side runners 4, be positioned at reaction runner 5 back segment both sides two side runners 3.The import of reaction runner 5 is communicated with the shock mouth of two head-on collision runners 2, reaction runner 5 is communicated with branch flow passage 6 outlets, the import of branch flow passage 6 is communicated with side runner 3,4, and 24 branch flow passages 6 are located at the both sides of reacting runner 5 in compartment of terrain successively, also in the both sides of reaction runner 5, respectively have 12 branch flow passages.Article two, side runner 4 is located at the leading portion both sides of reaction runner 5 symmetrically, and 6 branch flow passages 6 that each side runner 4 closes on homonymy are respectively communicated with.Article two, side runner 3 is located at the back segment both sides of reaction runner 5 symmetrically, and 6 branch flow passages 6 that each side runner 3 closes on homonymy are respectively communicated with.
24 branch flow passages 6 are divided into four groups, and every group of 6 branch flow passages 6 are communicated with a side runner 3 or side runner 4, are convenient to control the flow of 24 branch flow passages 6.Overall View it, therefore the present embodiment exactly likes two fishes that move about from the appearance, is referred to as Pisces shaped reaction device.
As shown in Figure 2, on reaction runner 5, the import of reaction runner 5 and the length length parameter a between adjacent branch flow passage 6 0length between the import of expression, each adjacent branch flow passage 6 is used respectively 23 length parameter a 1~a 23represent; Article 24, the length of branch flow passage 6 is used respectively other 24 length parameter l 1~l 24represent; On side runner 3,4, the length between the import of adjacent branch flow passage 6 is used respectively other 22 length parameter L 1~L 16represent.
Preferably, the width of all runners is 1.1mm, and the degree of depth is 5.0mm.Reaction runner 5 with the coupling part of branch flow passage 6 by being more than or equal to a plurality of of branch flow passage 6 numbers, for example 24, and segmental arc 31 (half round runner) docking that radius changes from small to big forms, and makes to react runner 5 and is the waveform that integral width increases gradually.Article 24, branch flow passage 6 is arranged in the both sides of reaction runner 5 symmetrically.As Fig. 3, joint residing angle in segmental arc 31 between reaction runner 5 and branch flow passage 6 is called confluent angle, confluent angle equals to react the angle of converging between runner 5 and branch flow passage 6, confluent angle, converge angle preferably between 0 to 60 °, more preferably, between 30 to 60 °, for example, in Fig. 3, confluent angle, converge angle size and be 30 °, still, confluent angle, converge angle and preferably equal 45 °.Again as shown in Figure 3, the stainless steel lag screws 8 that has inserted a 1mm in each branch flow passage 6 exit makes to export flow area reduced width to 0.1mm.
Below in conjunction with the application of the present embodiment, the parameter of each runner in the present embodiment is described in detail, so that those skilled in the art understand the present invention.
Before preparing nano-complex particle, first need to regulate the flow of each runner to reach designing requirement by the experiment that repeats of several times.Repeat the device of experiment all as shown in Figure 1 at every turn, use a gas flowmeter to control the total flow of feed liquid in two head-on collision runners 2, the flow of adjustments of gas flowmeter not in walking material process, only use two fluid flowmeters accurately to control the total flow of each 12 branch flow passages 6 of both sides, front and back, and the volume of the interior feed liquid of mensuration outlet feed liquid unit interval section (volume of the feed liquid that storage tank 16 receives), then calculate the total flow of two head-on collision runners 2, according to result of calculation adjusting gas flow meter, carry out again experiment next time, until this flow reaches setting requirement.
Article two, in head-on collision runner 2, the control method of assignment of traffic is to insert stainless steel lag screws in the large head-on collision runner 2 of flow, by regulating the flow area of stainless steel lag screws to control the distribution of flow, until the feed liquid in two head-on collision runners 2 has flowed simultaneously.
Article 4, the indicator that the flow of side runner 3,4 and the flow of 24 branch flow passages 6 are exported by storage tank 12 is observed the size of flow.In experimentation, open triple valve 18, indicator is flowed to respectively in the side runner 3,4 and branch flow passage 6 of both sides, front and back, if two import of side runner 3 variable color simultaneously, the flow that 2 side runners 3 are described equates, if the outlet of corresponding 12 branch flow passages 6 variable color simultaneously, illustrates that the flow of these 12 branch flow passages 6 has reached designing requirement.If above-mentioned flow does not reach requirement, the stainless steel lag screws 8 that is 1mm by the assigned address insertion diameter in branch flow passage 6 and side runner 3 regulates the flow of these runners.In a word, the adjusting of the present embodiment flow is needed to certain adjusting number of times and test repeatedly.
In indicator inflow side runner 3,4 and branch flow passage 6, if two import of side runner 3 or side runner 4 variable color simultaneously, and the outlet of corresponding 12 branch flow passages 6 is also during simultaneously variable color, between the internal structure parameter (as shown in Figure 2) of the present embodiment and flow, collision frequency, exit precursor CONCENTRATION DISTRIBUTION parameter, just there is inherent contacting, as follows:
There is following relational expression in the total flow of covering liquid storage tank 13,15 outputs and the flow in two pairs of side runners 3,4 and the flow in 24 branch flow passages 6:
F 1-24=F 1-12+F 13-24 (1)
F 1-12=F 1-11+F 2-12 (2)
F 13-24=F 13-23+F 14-24 (3)
F 1-11=F 1+F 3+F 5+F 7+F 9+F 11 (4)
F 2-12=F 2+F 4+F 6+F 8+F 10+F 12 (5)
(1) F in formula 1-12and F 13-24(Fig. 1, Fig. 2 mark these two parameters, and each F all represents flow) is two covering liquid storage tanks 13,15 total flows separately, F 1-24represent covering liquid flow sum; (2) F in formula and (3) formula 1-11, F 2-12, F 13-23and F 14-24(Fig. 1, Fig. 2 mark these four parameters) is four side runners 3,4 total flows separately; (4), (5) formula has provided the relation between six branch flow passage 6 flows that the total flow of side runner 3 is connected with it.For the discharge relation between side runner 4 and corresponding branch flow passage, can analogize according to (4), (5) formula.In (4), (5) formula, article 6, the flow distribution principle of 6 of branch flow passages is equal to the Distribution Principle of 12 branch flow passages in the fish shaped reaction device of prior art, be that branch flow passage 6 flow distribution are associated with the drawingdimension of side runner 3 and branch flow passage 6, correlation is as follows:
l 1 F 1 = L 1 F 1 - 11 - F 1 + l 3 F 3 = · · · = L 1 F 1 - 11 - F 1 + · · · + L 7 F 1 - 11 - F 1 - · · · - F 7 + l 9 F 9 ( or l 11 F 11 ) - - - ( 6 )
l 2 F 2 = L 2 F 2 - 12 - F 2 + l 4 F 4 = · · · = L 2 F 2 - 12 - F 2 + · · · + L 8 F 2 - 12 - F 2 - · · · - F 8 + l 10 F 10 ( or l 12 F 12 ) - - - ( 7 )
For the flow distribution of side runner 4 and branch flow passage 6 and the relation between runner design size, can analogize according to (6), (7) formula.
Owing to having inserted some nails in branch flow passage 6 and side runner 3,4, the volume of nail does not calculate in the middle of formula above, so there is certain systematic error, why be referred to as systematic error, be owing to can inserting several nails in design during the present embodiment and in not knowing each runner, caused existing between design discharge and actual flow certain deviation.In addition, in observing each runner change color process, also there is certain accidental error.
In addition, co-exist in 25 times and clash into and 24 collision time intervals in reaction runner 5, therefore, also just exist 24 collision frequencies to distribute, these 24 collision frequency f distribute and the initial flow F that reacts runner 5 0, there is following relation between 24 Zhi Liuliang and reaction runner 5 sizes:
f 0 = F 0 a 0 s = 1 t 0 ; f 1 = F 0 + F 1 a 1 s ; · · · ; f n = F 0 + F 1 + · · · + F n a n s ; t = 1 f 1 + · · · + 1 f n ( n = 1,2 , · · · , 23 ) - - - ( 8 )
The frequency distribution that hypergravity direction changes and collision frequency distribute basic identical, at this, do not elaborate.
There is following relational expression in the distribution of flow velocity u in reaction runner 5:
u 0 = F 0 s , u n = F 0 + F 1 + · · · + F n s ; ( n = 1,2 , · · · , 24 ) - - - ( 9 )
According to the distribution of flow velocity, can calculate the distribution of the horizontal g' of super gravity field in reaction runner 5, relational expression is as follows:
g 1 ′ = u 1 2 r 1 g ; g n ′ = u n 2 r n g ; ( n = 1,2 , · · · , 24 ) - - - ( 10 )
According to the concentration of covering in the distribution of flow in each branch flow passage 6 flow distribution, reaction runner 5 and storage tank, when mixing very uniformly, microcosmic can calculate coated precursor concentration c distribution under condition, and relational expression is as follows:
c 1 = F 1 c F 0 + F 1 ; c 2 = F 2 c F 0 + F 1 + F 2 ; · · · ; c n = F n c F 0 + F 1 + · · · + F n ( n = 1,2 , · · · , 24 ) - - - ( 11 )
From above relational expression, can find out, for the present embodiment, the distribution of Zhi Liuliang is basis, need to be designed, observes, regulates and check, and it plays important influence to the distribution of other important response parameter.And suspension initial flow F 0with respect to a flow distribution, it is an independently variable
Next be the preparation process of the nano-complex particle of nucleocapsid structure: first open high pressure gas valve, make the N of certain pressure 2gas (5atm) enters in other storage tanks outside storage tank 16, under the pressure-acting of gases at high pressure, the feed liquid of oppressing in each storage tank flows in the Pisces shaped reaction device of the present embodiment, first in two head-on collision runner 2 exits, there are the strong slurries that generate nano inner core particle that clash into the feed liquid from storage tank 14 in the feed liquid from storage tank 11, these slurries have formed the super gravity field of high-frequency direction transformation (as Fig. 5 in crooked reaction runner 5 flow at high speed processes, wherein, ordinate represents super gravity field, abscissa represents to clash into number of times), and in 24 branch flow passage 6 exits, there is strong shock with the feed liquid from storage tank 13 and storage tank 15 under this super gravity field effect, this strong shock has greatly been strengthened branch flow passage 6 feed liquids and has been seen and micro mixing with Jie between the slurries that react in runner 5, make coated precursor that reaction the generates dispersion rate in slurries surpass homogeneous nucleation rate, the Determining Micromixing Characteristic Time of coated precursor is shorter than nucleation induction period, and then the out-phase that has realized coated precursor is evenly overmolding to nuclear process.Clash into end rear slurry and be expelled to storage tank 16 from reaction runner 5 exits, obtain the slurries of core-shell type nano compound particle, then obtain final products through a series of last handling process.Before connecting material or after connecting material, if desired observe branch flow passage flow distribution situation, can open triple valve 18, indicator in storage tank 12 is observed in each 12 branch flow passages 6 before and after flowing into respectively, in the process of connecting material, triple valve 18 is all the time in closed condition.
With the present embodiment, prepare Fe 3o 4/ MnOOH nano-complex particle is example, and storage tank 11 is ferric sulfate, ferrous sulfate and the manganese sulfate mixed solution of amount seldom, and storage tank 14 is sodium hydroxide solutions, storage tank the 13, the 15th, and the mixed solution of manganese sulfate and hydrogen peroxide, storage tank 12 is red indicator storage tanks.In experimentation, first there is the strong nanometer Fe that generates black of clashing in head-on collision runner 2 exit positions in the feed liquid of storage tank 11 and storage tank 14 3o 4kernel gel particles and the seldom Mn (OH) of amount 2milky colloidal sol, this colloidal sol is very easily generated MnOOH by hydrogen peroxide oxidation, therefore can protect nanometer Fe 3o 4fe in kernel 2+, prevent that it is by hydrogen peroxide oxidation.(these slurries show strong basicity to the black slurries that generate, wherein contain NaOH) in rapid flow process forward, with the mixed solution of manganese sulfate from storage tank 13,15 and hydrogen peroxide, strong shock occurs, NaOH reacts with manganese sulfate and first generates Mn (OH) 2, then react the MnOOH that generates black with hydrogen peroxide and be coated to Fe 3o 4core surface, obtains Fe 3o 4/ MnOOH nano-complex particle.Branch flow passage 6 is 30 degree with the confluent angle reacting between runner 5, as shown in Figure 3.
Want by experiment to prepare clad ratio and be 0.125 nano-complex particle.Clad ratio refers to the Mn/Fe mol ratio in product.When this product of preparation, branch flow passage flow distribution is: F 1-12=6.67ml/s, F 13-24=8.33ml/s, as shown in Figure 4; Reaction runner 5 initial flows are F 0=10.0ml/s.Can be by regulating the concentration of storage tank 14,13,15 to realize different clad ratios.
Gained sample has been carried out to TEM/EDS (high-resolution projection Electronic Speculum/energy spectrum analysis), XRD (analysis of X ray crystal diffraction), VSM (specific saturation magnetization) and BET (specific area) to be analyzed.Figure 4 shows that the TEM electromicroscopic photograph of the sample of acquisition, from the TEM electromicroscopic photograph of low multiple, can find out, Nano composite granules is the particle of almost spherical, and particle surface is very totally smooth, and particle performance goes out good dispersiveness.From high power TEM electromicroscopic photograph, can see the sub-box of the class quasi-lattice of surface coating layer, lip-deep these sub-boxes and nanometer Fe 3o 4the lattice of kernel is diverse.Reach a conclusion thus, why the latter's particle surface is very totally smooth, is because partially-crystallized phenomenon has appearred in surface coating layer.Fig. 6 is this sample (open tubular column represents) and pure nanometer Fe 3o 4the XRD spectra of particle (solid post represents).From XRD spectra, can find out this sample and pure nanometer Fe 3o 4spectrogram is basically identical, do not find other crystalline phase, illustrate that MnOOH only has heterogeneous nucleation there is no homogeneous nucleation, do not generate amorphous phase precipitation yet, because if occur that amorphous phase precipitation can observe some clouds or detritus from TEM electromicroscopic photograph, and reunion is very serious between particle.The BET specific area measuring value of this sample is 90.53m 2/ g and VSM specific saturation magnetization result are 61.1emu/g.In a word, this nano-complex particle has good magnetic intensity and paramagnetism and very high specific area.
Specifically, the fish shaped reaction device or the Pisces shaped reaction device provided by the invention that are prior art have all comprised 24 branch flow passages, the function that these two reactors all should have the multiple dimensioned mixing of remarkable strengthening from engineering philosophy just can prepare the nano-complex particle with nucleocapsid structure, and so-called multiple dimensioned mixing refers to and comprised micromixing, is situated between to see and mixes and the mixing of the three kind different scales of microcosmic in being blended in.In these two reactors, multiple dimensioned mixing to as if nano suspending liquid and covering liquid between multiple dimensioned mixing.Strengthening micromixing is that the macroscopic view by 24 branch flow passages distributes and suspension is formed to 24 high-frequency shocks realizes.Knockout process between each covering liquid and suspension comprises four steps: (1) covering liquid bangs in suspension; (2) react and generate coated presoma with suspension; (3) coated presoma is dispersed into quickly and evenly very low concentration in suspension; (4) the coated presoma of low concentration all deposits to nanometer nuclear particle surface by heterogeneous nucleation process and completes once coated process.
If be less than the time interval (inverse in the time interval is collision frequency) of adjacent twice shock the total time of above-mentioned four steps, just can guarantee that the CONCENTRATION DISTRIBUTION of covering liquid in suspension reaches floor level, otherwise the CONCENTRATION DISTRIBUTION of covering liquid in suspension will raise and cause the appearance of homogeneous nucleation.
In addition, it is not only the basis of strengthening micromixing that the macroscopic view of Zhi Liuliang distributes, because the distribution of other important parameter comprises: precursor concentration distribution in collision frequency, knockout process, impact strength, super gravity field level etc. all with the macroscopic view of these 24 Zhi Liuliang distribute have associated closely, and above-mentioned these parameters some to be situated between to see mixing, play a decisive role, some mixes and plays a decisive role microcosmic, therefore, the distribution of the macroscopic view of Zhi Liuliang is also that strengthening Jie sees the basis that mixing mixes with microcosmic.Reach a conclusion thus, what the macroscopic view distribution of Zhi Liuliang was played for reactor is basic effect.
In fish shaped reaction device, the flow of each 12 branch flow passages of every side is mutually closely associated, and Pisces shaped reaction device each side 12 branch flow passages be divided into before and after each 6 branch flow passages, this branch flow passage number that just makes to be mutually related is reduced to 6 by 12.From formula (4), (5), can find out that structural limitations parameter that Pisces shaped reaction device props up flow distribution subtracts is a half manyly, has strengthened conversely the adjustability of a flow distribution.The adjustability of propping up flow distribution strengthens, and the adjustability that other important parameter distributes is also strengthened thereupon.Moreover, because the flow distribution of branch flow passage is that the mutual restriction between flow distribution, must cause the mutual restriction between pressure distribution by regulating the pressure distribution of branch flow passage to realize.Therefore, between Zhi Liuliang, restriction is stronger mutually, and the mutual restriction between pressure is also stronger, for adjust flux, distributes, can be more difficult and more unstable.So Pisces shaped reaction device has not only strengthened the adjustability of flow distribution, also strengthened the adjustability of pressure distribution.Experiment is found, a Flow-rate adjustment of fish shaped reaction device is difficulty very, almost be difficult to realize, comparatively speaking, a Flow-rate adjustment of Pisces shaped reaction device is very easy to realize, and the antijamming capability that the flow distribution regulating is subject to other independent parameter to change (mainly referring to the variation of suspension initial flow F0) obviously strengthens.From macroscopic view, analyze, because 24 branch flow passages need both sides and the Zhi Liuliang of shock suspension thread continuously, it is continually varying, be divided into each 12 of left and right two halves, although solved symmetry problem, continually varying yardstick is too large, is more further divided into each 6 all around, substantially solved continually varying scale problem, this also meets the metaphysics of " raw everything in all one's life two, two raw four, four ".
In addition, in Pisces shaped reaction device, when suspension is when half round runner high speed flows, flowing of a secondary stack be can on the vertical plane of main flow direction, form, Secondary Flow or dien vertex in engineering, are referred to as.Half round runner more easily forms dien vertex with respect to waveform runner.In addition, because 24 outlet flow areas that prop up threads are less than 0.1 millimeter, therefore, the collision of propping up between thread and suspension belongs to high speed thin liquid film shock, for the shock between high speed thin liquid film, from the 1950's, just there is large quantity research report, when the projected angle of impact of thin liquid film is greater than 60 while spending, this shock belongs to elastic collision, and collision angle belongs to inelastic collision between 0 to 60 degree.Inelastic collision can greatly be strengthened the mixing on molecular scale between two stock material liquid.Therefore, the collision in Pisces shaped reaction device between a thread and suspension thread belongs to non-resilient shock, and in fish shaped reaction device, the shock between the two belongs to Elastic Impact.
Because the width of fish shaped reaction device, Pisces shaped reaction device internal-response runner is all 1.1 millimeters, suspension carries out in the reaction runner of 1.1 mm wides with covering liquid mixes that belonging to is situated between and sees and mix.The step that Liang Ge reactor intermediary see to be mixed comprises first three step in described four steps above.In order to prevent that covering liquid from generating precipitation from homogeneous solution (precipitation from homogeneous solution comprises two kinds of modes: generate nucleus or amorphous sediment) with suspension in the moment reaction contacting and also needing to meet two preconditions: first, the concentration of covering liquid can be diluted in extremely short moment below the required critical concentration of homogeneous nucleation, prevents from forming nucleus shape precipitation; The second, continue on this basis rapid dilution and prevent from generating amorphous phase precipitation.In order to meet first precondition, the mode that 24 high speed thin liquid films clash into suspension must be non-Elastic Impact, props up thread and reacts converging angle and must being less than 60 degree of runner; In order to meet second precondition, in reaction runner, mobile suspension must form the dien vertex Forced Dispersion of High Rotation Speed, needs to form continual super gravity field.Therefore, Pisces shaped reaction device can clash into and continuous semicircle reaction flow passage forms high-intensity dien vertex and strengthens to be situated between and see mixing by 24 stiff thin liquid films, but fish shaped reaction device is not owing to forming, stiff thin liquid film clashes into and the intensity of dien vertex is also lower, therefore the successful that, in fish shaped reaction device, Jie's sight mixes is poor.
The micro mixing of coated presoma is mainly reflected in two aspects for the impact of the coated process of heterogeneous nucleation: the first, and microcosmic mixability is higher, and coating is finer and close; The second, when microcosmic mixability reaches equally distributed state, nucleation process is only subject to the assertive evidence dynamics Controlling of heterogeneous nucleation, the interference that not mixed by microcosmic.
Pisces shaped reaction device is in the main distinction of reacting on runner design with fish shaped reaction device: the reaction runner of fish shaped reaction device is that linear pattern or wave are linear, linear pattern can not produce super gravity field (being centrifugal force field), the structure of wave line style is also concrete not and clear and definite, and the super gravity field of generation is continually varying often.The reaction runner of Pisces shaped reaction device is that continuous semi-circular runner docking forms, and the structure of this runner is concrete with clear and definite, and super gravity field existence all the time and forward and oppositely super gravity field are non-continually varying (as shown by the arrows in Figure 3).In Pisces shaped reaction device, because the nanocrystal in suspension is subject to the super gravity field effect that high frequency direction is put upside down, and there is high-frequency strong vibration, this high-frequency strong oscillation energy is significantly strengthened feed liquid flowing and mixing in micro-scale, and then realize micro mixing fast, than fish shaped reaction device, be more conducive to form the coated process of out-phase homogeneous nucleation.
In sum, the present invention can realize following advantage and effect:
1, more easily regulate a flow distribution, and the flow distribution regulating has very high stability, therefore, the operation and prepare the nano-complex particle of nucleocapsid structure of being more convenient for.
2, can be with the distribution of other important parameter of time modulation, fish shaped reaction device modulation is in this respect very poor, lacks necessary flexibility.
3, can be for the preparation of the nano-complex particle of core-shell-shell structure, and fish shaped reaction device can only be prepared the nano-complex particle of core-shell type structure.
4, can produce the super gravity field of the discontinuous variation that both forward and reverse directions puts upside down.
5, the collision between interior thread and suspension thread belongs to inelastic collision, and this collision can make two stock material liquid mix on molecular scale.
6, there is the multiple dimensioned mixed function of strengthening, realize even heterogeneous nucleation process.
As known by the technical knowledge, the present invention can realize by other the embodiment that does not depart from its Spirit Essence or essential feature.Therefore, above-mentioned disclosed embodiment, with regard to each side, all just illustrates, and is not only.Change within the scope of the present invention all or within being equal to scope of the present invention is all included in the invention.

Claims (8)

1. a Pisces shaped reaction device, comprise a reaction runner, article two, runner clashes, side runner, article 24, branch flow passage, the import of described reaction runner is communicated with the shock mouth of two described head-on collision runners, described reaction runner is communicated with described branch flow passage outlet, the import of described branch flow passage is communicated with described side runner, described side runner is positioned at the both sides of described reaction runner, article 24, described branch flow passage is located at the both sides of described reaction runner in compartment of terrain successively, it is characterized in that, described side runner is four, wherein first group two described side runners are located at the both sides of the leading portion of described reaction runner symmetrically, and 6 described branch flow passages that two described side runners of first group close on homonymy are respectively communicated with,
Two described side runners of other second group are located at the both sides of the back segment of described reaction runner symmetrically, and 6 described branch flow passages that two described side runners of second group close on homonymy are respectively communicated with.
2. Pisces shaped reaction device according to claim 1, is characterized in that, along the length direction of described reaction runner, described reaction runner comprises a plurality of semicircular segmental arcs that set gradually, and makes the whole undulate of described reaction runner.
3. Pisces shaped reaction device according to claim 2, is characterized in that, the number of described segmental arc is more than or equal to the number of described branch flow passage.
4. Pisces shaped reaction device according to claim 3, it is characterized in that, the connectivity points of described reaction runner and branch flow passage residing angle in described segmental arc is called confluent angle, and described confluent angle equals the angle of converging between described reaction runner and described branch flow passage.
5. Pisces shaped reaction device according to claim 4, is characterized in that, described confluent angle, converges angle between 0 to 60 degree.
6. Pisces shaped reaction device according to claim 5, is characterized in that, described confluent angle, converges angle between 30 degree to 60 degree.
7. Pisces shaped reaction device according to claim 6, is characterized in that, described confluent angle, to converge angle be 45 degree.
8. Pisces shaped reaction device according to claim 2, is characterized in that, between the import and outlet of described reaction runner, along the length direction of described reaction runner, the diameter of described segmental arc increases gradually.
CN201410380345.4A 2014-08-04 2014-08-04 Pisces shaped reaction device Active CN104128137B (en)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201510817976.2A CN105396521B (en) 2014-08-04 2014-08-04 Pisces shaped reaction device
CN201410380345.4A CN104128137B (en) 2014-08-04 2014-08-04 Pisces shaped reaction device

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410380345.4A CN104128137B (en) 2014-08-04 2014-08-04 Pisces shaped reaction device

Related Child Applications (1)

Application Number Title Priority Date Filing Date
CN201510817976.2A Division CN105396521B (en) 2014-08-04 2014-08-04 Pisces shaped reaction device

Publications (2)

Publication Number Publication Date
CN104128137A true CN104128137A (en) 2014-11-05
CN104128137B CN104128137B (en) 2016-01-13

Family

ID=51801142

Family Applications (2)

Application Number Title Priority Date Filing Date
CN201510817976.2A Expired - Fee Related CN105396521B (en) 2014-08-04 2014-08-04 Pisces shaped reaction device
CN201410380345.4A Active CN104128137B (en) 2014-08-04 2014-08-04 Pisces shaped reaction device

Family Applications Before (1)

Application Number Title Priority Date Filing Date
CN201510817976.2A Expired - Fee Related CN105396521B (en) 2014-08-04 2014-08-04 Pisces shaped reaction device

Country Status (1)

Country Link
CN (2) CN105396521B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005048201A1 (en) * 2004-10-11 2006-04-20 Penth, Bernd, Dr. Method and device, for continuous precipitation of nanoscalic product, comprises preparing primary particles by chemical reaction precipitating and optionally modifying the particle surface by chemical precipitating or co-precipitating
EP1894619A2 (en) * 2006-09-01 2008-03-05 Tosoh Corporation Microchannel structure and fine-particle production method using the same
CN102872791A (en) * 2012-10-17 2013-01-16 浙江海洋学院 Magnetic nanometer lithium ion sieve adsorbent and preparation method thereof
CN103127888A (en) * 2013-03-18 2013-06-05 浙江海洋学院 Fish-shaped reactor
CN204034676U (en) * 2014-08-04 2014-12-24 浙江海洋学院 Pisces shaped reaction device

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5076742B2 (en) * 2006-09-01 2012-11-21 東ソー株式会社 Microchannel structure and microparticle manufacturing method using the same
CN102151533B (en) * 2011-01-26 2015-01-07 深圳航天科技创新研究院 Preparation method of micro-nanometer powder, reinforced micro-reaction device and micro-reaction system

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE102005048201A1 (en) * 2004-10-11 2006-04-20 Penth, Bernd, Dr. Method and device, for continuous precipitation of nanoscalic product, comprises preparing primary particles by chemical reaction precipitating and optionally modifying the particle surface by chemical precipitating or co-precipitating
EP1894619A2 (en) * 2006-09-01 2008-03-05 Tosoh Corporation Microchannel structure and fine-particle production method using the same
CN102872791A (en) * 2012-10-17 2013-01-16 浙江海洋学院 Magnetic nanometer lithium ion sieve adsorbent and preparation method thereof
CN103127888A (en) * 2013-03-18 2013-06-05 浙江海洋学院 Fish-shaped reactor
CN204034676U (en) * 2014-08-04 2014-12-24 浙江海洋学院 Pisces shaped reaction device

Also Published As

Publication number Publication date
CN105396521A (en) 2016-03-16
CN104128137B (en) 2016-01-13
CN105396521B (en) 2017-10-27

Similar Documents

Publication Publication Date Title
US8550120B2 (en) Apparatus and method for oscillating fluid jets
TWI499552B (en) Droplet-generating method and device
Liu et al. Experimental and CFD studies on the intensified micromixing performance of micro-impinging stream reactors built from commercial T-junctions
US10722860B2 (en) Mixing reactor and related process
CN106140038A (en) The method and apparatus preparing polymer particles
Song et al. Controlled growth of Cu nanoparticles by a tubular microfluidic reactor
Li et al. Numerical and experimental investigations of micromixing performance and efficiency in a pore-array intensified tube-in-tube microchannel reactor
KR101758813B1 (en) Toxic substances mixing apaaratus with multiple mixing chamber for environmental risk assessment
Abiev et al. Synthesis of cobalt ferrite nanoparticles by means of confined impinging-jets reactors
Zhou et al. Impact of mixing for the production of CuO nanoparticles in supercritical hydrothermal synthesis
Wakashima et al. Development of a new swirling micro mixer for continuous hydrothermal synthesis of nano-size particles
CN106109440A (en) A kind of micro-fluidic chip and the preparation method of alginate magnetic microsphere
CN204034676U (en) Pisces shaped reaction device
Sattari et al. Controlled preparation of compound droplets in a double rectangular co-flowing microfluidic device
CN104128137B (en) Pisces shaped reaction device
CN104437334B (en) A kind of hypergravity-continuous micro-impact flow reactor based on Eight-Diagram principle
Mu et al. Experimental and numerical investigations on characteristics of coaxial liquid cone in coflow focusing
CN208878529U (en) Micropore is vortexed casing mixing reactor
Yang et al. A high‐throughput chaotic advection microreactor for preparation of uniform and aggregated barium sulfate nanoparticles
CN106000707B (en) A kind of rain controller
CN103127888B (en) Fish-shaped reactor
Rahimi et al. On the mixing characteristics of a poorly water soluble drug through microfluidic‐assisted nanoprecipitation: Experimental and numerical study
Yang et al. Generation and evolution of double emulsions in a circular microchannel
JP4932718B2 (en) Method for producing metal powder
Aleksandrova et al. Development of flow reactor for the synthesis of semiconductor and metal nanoparticles

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C14 Grant of patent or utility model
GR01 Patent grant