CN108993342A - Photochemically reactive micro-hybrid system and method in a kind of tubular reactor - Google Patents
Photochemically reactive micro-hybrid system and method in a kind of tubular reactor Download PDFInfo
- Publication number
- CN108993342A CN108993342A CN201811038708.0A CN201811038708A CN108993342A CN 108993342 A CN108993342 A CN 108993342A CN 201811038708 A CN201811038708 A CN 201811038708A CN 108993342 A CN108993342 A CN 108993342A
- Authority
- CN
- China
- Prior art keywords
- tubular reactor
- liquid
- reaction solution
- reaction
- fluid column
- 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
Links
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 126
- 239000012530 fluid Substances 0.000 claims abstract description 91
- 238000006552 photochemical reaction Methods 0.000 claims abstract description 48
- 239000007788 liquid Substances 0.000 claims abstract description 47
- 230000008569 process Effects 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 79
- 239000012071 phase Substances 0.000 claims description 56
- 238000005286 illumination Methods 0.000 claims description 24
- 239000000203 mixture Substances 0.000 claims description 21
- 239000000463 material Substances 0.000 claims description 13
- 239000011521 glass Substances 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims description 8
- 229910052753 mercury Inorganic materials 0.000 claims description 8
- 229910052710 silicon Inorganic materials 0.000 claims description 8
- 239000010703 silicon Substances 0.000 claims description 8
- 238000004804 winding Methods 0.000 claims description 8
- 239000004812 Fluorinated ethylene propylene Substances 0.000 claims description 7
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 claims description 7
- 229920009441 perflouroethylene propylene Polymers 0.000 claims description 7
- 229920002545 silicone oil Polymers 0.000 claims description 7
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 6
- 239000005368 silicate glass Substances 0.000 claims description 6
- 229910052708 sodium Inorganic materials 0.000 claims description 6
- 239000011734 sodium Substances 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 5
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000007791 liquid phase Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- -1 polytetrafluoroethylene Polymers 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000008151 electrolyte solution Substances 0.000 claims description 3
- 239000004615 ingredient Substances 0.000 claims description 3
- 239000011541 reaction mixture Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 230000005540 biological transmission Effects 0.000 claims description 2
- 230000003760 hair shine Effects 0.000 claims description 2
- 239000012495 reaction gas Substances 0.000 claims description 2
- 230000005514 two-phase flow Effects 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims 1
- 238000003786 synthesis reaction Methods 0.000 abstract description 8
- 238000004519 manufacturing process Methods 0.000 abstract description 2
- 238000004886 process control Methods 0.000 abstract 1
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 29
- 229940012189 methyl orange Drugs 0.000 description 29
- 230000004087 circulation Effects 0.000 description 28
- 230000015572 biosynthetic process Effects 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 17
- 150000002500 ions Chemical class 0.000 description 11
- 238000003756 stirring Methods 0.000 description 11
- 239000007864 aqueous solution Substances 0.000 description 10
- 239000000843 powder Substances 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 238000005119 centrifugation Methods 0.000 description 6
- 230000003014 reinforcing effect Effects 0.000 description 6
- 238000000926 separation method Methods 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- 239000008247 solid mixture Substances 0.000 description 5
- 239000000975 dye Substances 0.000 description 4
- 239000000376 reactant Substances 0.000 description 4
- 230000003321 amplification Effects 0.000 description 3
- 238000004458 analytical method Methods 0.000 description 3
- 238000003491 array Methods 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 238000003199 nucleic acid amplification method Methods 0.000 description 3
- 229940058401 polytetrafluoroethylene Drugs 0.000 description 3
- 238000005070 sampling Methods 0.000 description 3
- 238000000889 atomisation Methods 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000007726 management method Methods 0.000 description 2
- 239000002609 medium Substances 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 1
- 229930003316 Vitamin D Natural products 0.000 description 1
- QYSXJUFSXHHAJI-XFEUOLMDSA-N Vitamin D3 Natural products C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C/C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-XFEUOLMDSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000005388 borosilicate glass Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000005112 continuous flow technique Methods 0.000 description 1
- 208000012839 conversion disease Diseases 0.000 description 1
- 230000002596 correlated effect Effects 0.000 description 1
- 230000000875 corresponding effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000010008 shearing Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000006163 transport media Substances 0.000 description 1
- 210000005239 tubule Anatomy 0.000 description 1
- 239000011710 vitamin D Substances 0.000 description 1
- 235000019166 vitamin D Nutrition 0.000 description 1
- 150000003710 vitamin D derivatives Chemical class 0.000 description 1
- 239000011647 vitamin D3 Substances 0.000 description 1
- QYSXJUFSXHHAJI-YRZJJWOYSA-N vitamin D3 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)CCCC(C)C)=C\C=C1\C[C@@H](O)CCC1=C QYSXJUFSXHHAJI-YRZJJWOYSA-N 0.000 description 1
- 229940046008 vitamin d Drugs 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J19/08—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor
- B01J19/12—Processes employing the direct application of electric or wave energy, or particle radiation; Apparatus therefor employing electromagnetic waves
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00889—Mixing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00891—Feeding or evacuation
- B01J2219/00894—More than two inlets
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
- B01J2219/00781—Aspects relating to microreactors
- B01J2219/00925—Irradiation
- B01J2219/0093—Electric or magnetic energy
Abstract
The present invention relates to photochemically reactive micro-hybrid system and methods in a kind of tubular reactor, it is characterized in that, the system is made of microring array unit and tubular type photochemical reaction device, microring array unit and tubular type photochemical reaction device are connected in series, in the microring array unit, reaction solution is mutually cut into fluid column by immiscible gas phase or liquid carrier with reaction solution, the present invention has continuous, stablize, the high advantage of the efficiency of light energy utilization, reaction solution may be implemented by the system and sufficiently receive light source irradiation, and effectively strengthen the disturbance inside reaction solution, strengthen photochemical syntheses process, its lower production costs, it is easy to operate, process control.There is huge prospect in photochemically reactive industrial applications.
Description
Technical field
It is the invention belongs to organic photochemistry synthesis field, in particular to photochemically reactive micro- mixed in a kind of tubular reactor
Close system and method.
Background technique
Photochemical reaction is because it causes chemical reaction using photon and promotes characteristic [Scholes, the G.D. of molecule conversion；
Fleming,G.R.；Olaya-Castro,A.；Van Grondelle, R., Nat.Chem.2011,3,763], have process green
The advantages such as color, low pollution, in the past few decades in be constantly subjected to extensive concern and the research of people.But by appointed condition
With the limitation of photon attenuation, there is the serious efficiencies of light energy utilization that low, equipment is difficult to the problems such as amplifying [Su, Y. for photochemistry production；
Straathof,N.J.W.；Hessel,V.；Noe··l,T.,Chem.-Eur.J.2014,20,10562].Specifically, due to
Photon causes difficulty to equipment amplification in a liquid with liquid layer thickness sharp-decay (Lang Bo-Beer law).Volume is used merely
The mode of amplification, on the one hand since the increase of liquid layer thickness causes photon utilization rate low, the reaction time is dramatically increased；On the other hand
Since product exists simultaneously among liquid phase, it is also easy to lead to the generation of by-product, or even the problem of excessive illumination occur.
Researchers use a variety of methods to strengthen photochemical reaction, increase the disturbance of internal fluid, improve reactant
The uniformity of concentration distribution.On the one hand it is the improvement of traditional equipment, is such as strengthened by way of gas sparging, reaction solution atomization molten
Liquid internal mix；On the other hand, in recent years combine continuous Flow Technique development (microchannel) tubular reactor also increasingly by
Pay attention to.For example, Chinese patent CN1445215A utilizes the nitrogen bubbling method reinforced solution internal mix of inner-immersed type, Chinese patent
CN202238034U improves vitamin D using the method for built-in atomizer3The intensity of illumination of synthesis process；Chinese patent
CN103553993A uses homogeneous miniflow tubular reactor photochemical syntheses vitamin D3, realize the company of photochemical syntheses process
Continuous operation.But the mode of gas sparging is limited for the strength of turbulence in solution, and atomization method is still unavoidable from far from light
At source the problem of light intensity attenuation, while it still relies on autoclave equipment, and reaction product can not remove system, however it remains excessive light
According to and the problem of side reaction.Although and tubular reactor can avoid volume from putting by the number amplification method of more covering devices in parallel
Big problem.However, tubular reactor still mostly uses homogeneous reaction solution to flow, can only be expanded by molecule in boundary layer at tube wall
Dissipate mass transfer, reactant is difficult to effectively migrate to that equipment wall surface receives illumination, product is difficult to be rapidly directed away from equipment wall surface prevents excessively
Illumination generates by-product [Knowles, J.P., Elliott, L.D., Booker-Milburn K.I., Beilstein
J.Org.Chem.2012,8,2025]；And the feature that height, surrounding are low among velocity flow profile is presented in homogeneous flow, will lead to reaction
The difference of object residence time in reactor, the problem of not being fully solved excessive illumination；In addition, the pipe of many microchannels rank
For formula reactor flow usually in a microlitre magnitude per minute, reaction efficiency is low.
In recent years, for the organic synthesis system in some microchannels, tubular reactor, people attempt by with reaction solution
Immiscible liquid or gas are as delivering phase, obtaining reaction solution fluid column stream by its effect separated, to guarantee every section of liquid
In column the residence time of reactant it is almost the same [Porta, R., Benaglia, M., Puglisi A.,
Org.Process.Res.Dev.2016,20,2].This method can effectively strengthen synthesis for general organic synthesis
Process improves the controllability of process, but for photochemical reaction, targetedly solves that uneven illumination is even to ask
It inscribes, the mixing intensity in simultaneous reactions liquid fluid column still needs to be further improved.For the structure of tubular reactor, core is asked
Topic is the position for having reaction solution to be in backlight always, can only be obtained across the energy of the later photon of liquid layer, existing pipe
Formula reactor is not directed to light source and changes its canoe.In addition, the radius of curvature of pipe winding is typically much deeper than tube inner diameter,
Cause fluid column flows excessively stable, internal disturbance degree is lower.
Summary of the invention
In this regard, the present invention proposes that strengthening mixed structure by the migration of reaction solution facing light sources position, binding reactor solves
The above problem.Specifically, the present invention provides photochemically reactive microring array in a kind of tubular reactor with inversion structures
System, which is characterized in that the system is made of microring array unit and tubular type photochemical reaction device, microring array unit and tubular type light
Chemical reaction equipment is connected in series, as shown in Figure 1.In the microring array unit, the delivery phase fluid immiscible with reaction solution
Reaction solution is cut into fluid column.
Further, it is characterised in that: the microring array unit is T-type, Y type, cross-flow shearing-type, hydraulics focus type
Or (diameter for the chamber that dispersant liquid drop is formed is greater than the diameter of tubular reactor, such as Fig. 2 institute for coaxial ring-pipe type and coaxial modified
Show) microchannel devices.
Preferably, coaxial cast and coaxial endless tube modified microchannel component；Further preferably coaxial endless tube and coaxial rings
The contact angle of the inner wall of inner tube and delivery phase fluid is greater than 150 ° in pipe modified；Further excellent preferably coaxial endless tube modified
Inner tube wall and delivery phase fluid contact angle be greater than 150 °, the chamber internal diameter of droplet formation is D, and dispersion inner tube diameter is Dd,
Meet with the internal diameter d of tubular reactor, 10Dd>D>2Dd, 2Dd>d>0；Further preferred 2Dd<D<3Dd, 2Dd>d>Dd。
Further, it is characterised in that: microring array unit material is polymer, stainless steel, unorganic glass or more
Mixture, channel size are 0.05~50 millimeter.
Further, it is characterised in that: tubular type photochemical reaction device includes tubular reactor and light source, and reactor can be with
For any tubular reactor of light transmission.The length of quantity of light source and tubular reactor light application time according to needed for photochemical reaction and
It is fixed.
Further, it is characterised in that: its tubular reactor material used is fluorinated ethylene propylene copolymer, polytetrafluoro
Ethylene, quartz glass, silicate glass, high-boron-silicon glass or the above mixture, internal diameter are 0.05~50 millimeter；The light source
For high-pressure sodium lamp, medium pressure mercury lamp, low pressure mercury lamp, light emitting diode (LED) lamp or its combination of the above, it is ultraviolet that light source, which shines,
Light, visible light, infrared light or its combination of the above；The cold-trap be material be quartz glass, silicate glass, high-boron-silicon glass or
The above mixture.
Further, tubular reactor including 1 and 1 or more reversion or strengthens mixed structure on canoe.
The structure of single reversion is as shown in Figure 3.By taking built-in light-source formula tubular reactor as an example, tubular reactor is with spiral wrap
In the process, the spiral wrap structure of the addition in stage and its axial angled (preferably 180 °).Due to the work of centrifugal force
With, it is screw type winding so that fluid column each section in pipe be subject to centrifugal forces it is in different size, there are it is interior circulation or
Person's Secondary Flow；The addition of this structure, can make the same angle of circulation rotating in the fluid column in tubular reactor, in this way can be with
Improve reaction solution in fluid column more evenly receive illumination, excessive illumination is further avoided, when lowering required for photochemical reaction
Between, and improve the selectivity of product and the utilization rate of light.
It is highly preferred that strengthen mixed structure, can be, but not limited to ring ear formula and column rib-type, as shown in Figure 4.It is this
Structure is that the Secondary Flow or interior circulation inside fluid column occur to turn to (preferably ± 90 °), strengthens the mixing inside fluid column, makes fluid column
Internal mixing more evenly, and then it is similar avoid excessive illumination, improve the selectivity of product and the utilization rate of light.Light source is external
The tubular reactor of formula, reinforcing mixed structure and original cloth office plane are angled, and preferred angle is 90 °.
It is special the invention also provides carrying out photochemically reactive method in a kind of tubular reactor with inversion structures
Sign is that this method comprises the following steps:
(1) in microring array unit, with the immiscible liquid of photochemical reaction liquid or gas as delivery phase fluid, pass through
Two phase flow is adjusted, reaction liquid phase fluid is cut into fluid column, obtains fluid column stream；
(2) the fluid column stream obtained enters tubular reactor and receives illumination, and illumination reaction occurs in the fluid column of reaction solution.?
In During Illumination, reaction solution remains that fluid column kenel flows.
(3) fluid column stream once passes through in tubular reactor or repeatedly recycles, and controls total residence time according to reaction process,
Reaction mixture is obtained after split-phase.
Further, which is characterized in that the reaction solution is the solution containing photochemical reaction ingredient.
Further, which is characterized in that the delivery is mutually 1:20~20:1 with the flow-rate ratio for reacting liquid phase；The delivery
It mutually include: the gases such as the liquid such as electrolyte solution, silicone oil, alkanes or nitrogen, argon gas, the i.e. liquid immiscible with reaction solution
Or gas, it can be used as delivery phase.
The present invention has the advantages that
By introducing with the immiscible fluid of reaction solution as delivery phase, pass through cross-flow, cocurrent etc. using microring array unit
Reaction solution is cut into fluid column by form, and enters the tubular reactor in tubular type photochemical reaction device jointly to receive illumination concurrent
Raw reaction.In During Illumination, reaction solution remains that fluid column kenel flows, can there are the flowing of stronger circulation inside fluid column
Reaction solution boundary layer thickness is greatly reduced, the reactant in fluid column everywhere is promoted all to receive illumination, is separated by delivery phase fluid
Method guarantee that the residence time of reaction solution is almost the same, and product accumulation is avoided to be generated pair by excessive illumination at wall surface
Product.Simultaneously by the reversion of tubular reactor and reinforcing mixed structure, promote far from reaction solution at light source to by close to sources one
Side migration, and strengthen reaction solution internal mix.It on the one hand ensure that the residence time of every section of reaction solution fluid column is consistent, effective in this way
Boundary layer thickness is reduced, photochemical reaction conversion ratio and yield are improved；It on the other hand can by interior circulation stronger in fluid column
Suitably to increase caliber and system flow, the treating capacity of reaction system is improved.
Detailed description of the invention
Fig. 1 is photochemically reactive micro-hybrid system structure chart in tubular reactor of the present invention；
Fig. 2 is various forms of microchannel devices in microring array unit, and wherein A is T-type；B is Y type；C is cross-flow shearing
Type；D is hydraulics focus type；E is coaxial ring-pipe type；F is to improve coaxial cast；
The reversion of Fig. 3 tubular reactor single and reinforcing mixed structure schematic diagram.
Fig. 4 tubular reactor and reinforcing mixed structure schematic diagram, wherein A is ring ear formula；B is rib-type.
Conventional tubular reactor schematic diagram of the Fig. 5 without inversion structures.
Specific embodiment
Feature of the invention and other correlated characteristics are described in further detail by embodiment below in conjunction with attached drawing, with
Convenient for the understanding of technical staff of the same trade:
Photochemically reactive micro-hybrid system includes microring array unit and tubular type photochemistry in tubular reactor of the invention
Reaction unit, wherein microring array unit and tubular type photochemical reaction device are connected in series, i.e. tubular reactor entrance and microring array
Unit outlet is connected, and product is collected in tubular reactor outlet, as shown in Figure 1.
Wherein, microring array unit includes microchannel devices, and the microchannel devices include reaction solution channel, delivery phase fluid
Channel, droplet formation chamber and output channel, wherein the one end in reaction solution channel and delivery phase fluid channel is reaction solution or delivery
The entrance of phase fluid, the other end are connected in droplet formation chamber, and reaction solution, which crosses with delivery phase fluid in droplet formation chamber, to be cut
Mixing is cut, forms fluid column stream, and output channel flows backward from droplet formation chamber.Output channel and tubular type photochemical reaction device
Connection.Preferably, the droplet formation chamber is identical with output channel internal diameter.Preferably, the delivery phase channel can have one
It is a, two or more.
Wherein；The microring array unit is microchannel devices, and form can be (but being not limited only to) T-type, Y type, mistake
Shearing-type, hydraulics focus type, coaxial ring-pipe type etc. are flowed, as shown in Figure 2.Preferably, microring array unit material is polymerization
Object, stainless steel, unorganic glass or the above mixture, channel size are 0.05~50 millimeter.It is furthermore preferred that in coaxial annular pipe
The contact angle of inside pipe wall and delivery phase fluid is greater than 150 °.
Wherein, T-type structure is that delivery phase channel and droplet formation chamber and output channel are linear structure, reaction solution channel
It is vertical with delivery phase channel.
Wherein y-type structure is, deliver phase channel and reaction solution channel respectively constitute Y-shaped top two sides, drop
Forming chamber and output channel is linear structure, constitutes the lower end of Y-shaped.
Wherein, cross-flow multi-layer Shear-type includes two delivery phase channels, and two delivery phase channel opposite directions are in 180 ° of settings, instead
Liquid channel is answered to be vertically arranged with delivery phase channel, droplet formation chamber delivers the intersection in phase channel and reaction solution channel at two,
Output channel and reaction solution channel are point-blank.
Wherein, hydraulics focus type structure and cross-flow multi-layer Shear-type the difference is that, droplet formation chamber with output
Also there is a diameter to reduce part between piping connection portion, to guarantee the formation of delivery phase drop.
Wherein coaxial rings cylinder structure includes two delivery phase channels, and two delivery phase channel opposite directions are in 180 ° of settings, liquid
Drop forms chamber and output channel is linear structure and is vertically arranged with two delivery phase channels.Reaction solution channel passes perpendicularly through two
Delivery phase channel extend into droplet formation chamber.
It is highly preferred that coaxial endless tube improved structure can be used in microchannel devices, phase channel and drop are delivered in the structure
It forms chamber to connect with one word of output channel, reaction solution channel is extended vertically into from droplet formation chamber side wall, and front end is towards fluid column stream
Dynamic direction turning.The internal diameter for wherein delivering phase channel is identical as output channel diameter, is d；The internal diameter of droplet formation chamber is
D；The internal diameter in reaction solution channel is Dd.Wherein, the intracavitary diameter D of droplet formation, reaction solution channel internal diameter DdAnd the internal diameter d of output channel
Meet: 10Dd>D>2Dd, 2Dd>d>0；Further preferred 2Dd<D<3Dd, 2Dd>d>Dd.Further preferably coaxial endless tube and coaxial rings
The contact angle of the inner wall and dispersion fluid of inner tube is greater than 150 ° in pipe modified；Further excellent preferably coaxial endless tube modified
Inner tube wall and dispersion fluid contact angle be greater than 150 °.This structure can guarantee that the blob length of transport medium is strictly controlled
System, is not influenced by reaction solution phase flow rate.
Wherein, tubular type photochemical reaction device includes tubular reactor, light source and cold-trap.Tubular reactor is in sprawl shape
When, light source single-side irradiance reactor；When tubular reactor is in winding, being coil-like, light source (such as fluorescent tube) is placed in pipe reaction
Among device.If light source heat release effectively causes temperature more than light reaction requirement temperature, it is also necessary to light source and tubular reactor it
Between place cold-trap, cold-trap material is depending on photochemical reaction requires wave-length coverage.
Wherein, tubular reactor material is fluorinated ethylene propylene copolymer, polytetrafluoroethylene (PTFE), quartz glass, glassy silicate
Glass, high-boron-silicon glass or the above mixture, internal diameter are 0.05~50 millimeter；The light source is high-pressure sodium lamp, medium pressure mercury lamp, low
Pressure mercury lamp, light emitting diode (LED) lamp or its combination of the above, light source shine for ultraviolet light, visible light, infrared light or its more than
Combination；The cold-trap is that material is quartz glass, silicate glass, high-boron-silicon glass or the above mixture.
Wherein, tubular reactor is on canoe, including 1 and 1 or more the turning knot different from winding direction
Structure, the turning structure are specially to be formed on component that tubular reactor is wrapped in except light source body, the light source body it
Outer component can be the branched structure stretched out in light source body, the component being also possible to except light source body.Specifically, described
Turning structure includes inversion structures or reinforcing mixed structure.
Wherein anti-structure is as shown in figure 3, refer to that tubular reactor during with spiral wrap, is added one
Determine the steering of angle.It is described to turn to preferably greater than 30 °, more preferably it is greater than 90 °, most preferably 180 ° of steering structures.
Due to the effect of centrifugal force, it is screw type winding so that fluid column each section in pipe be subject to centrifugal forces it is not of uniform size
Sample, there are interior circulation or Secondary Flows；There are two the interior circulation formed in fluid column or drop is usual: being respectively in spiral
The interior circulation of the interior circulation of heart side and separate spiral center side.For the tubule wound on tubular reactor, liquid
The interior circulation formed inside column includes the interior circulation of a low beam pipe and the interior circulation of far lamp pipe, and the fluid column recycled in two is each
From interior circulation internal circulation flow, and it is substantially illogical with another inner recirculation flow.In the case where no inversion structures, the two
The position of interior circulation is relatively fixed-it is similar to the ground near the ground and remote of the moon, the interior circulation in low beam face receives always ultraviolet lamp
The direct irradiation of pipe, and to receive ultraviolet irradiation probability low for the interior circulation in far lamp face.As shown in figure 3, being arranged on the outside of light source body
Having support construction, (support construction can be a part for constituting light source body, and the structure being also possible to except light source can
To connect or be not connected to light source), tubular reactor is laid out from light source body winds on the support structure and returns light source master
Body is exchanged, i.e., the described support construction so that position occurs for the low beam tube portion of the fluid column in tubular reactor and far lamp tube portion
It joined 180 ° of steering to fluid column, so that the position recycled in the two is exchanged, the interior circulation of script far lamp pipe is close to fluorescent tube
Side receives ultraviolet lamp tube irradiation；And the fluorescent tube that the interior circulation of script low beam pipe is separate.It is that drop internal each section receives purple in this way
The probability of outer light irradiation more evenly, further avoids excessive illumination, lowers the time required for photochemical reaction, and improve product
Selectivity and light utilization rate.Wherein it is preferred to when steering angle is wound on the support structure by tubular reactor, around entering
Part and the angle control for laying out part.
Further, strengthen mixed structure as shown in figure 4, refer to tubular reactor during with spiral wrap,
The spiral wrap structure axially to form an angle with it being added, the angle absolute value are preferably greater than 30 degree, more preferably big
In 60 degree, most preferably 90 degree.By taking built-in light-source formula tubular reactor as an example, tubular reactor is with the process of spiral wrap
In, the addition in stage and its axial angled (preferably ± 90 °) branched structure (preferably, branch in light source body
The a part of structure as light source), tubular reactor spiral wrap on it, and winds multi-turn, such as more than three circles, excellent
It is selected as.According to foregoing description it is found that there are two the interior circulation formed in fluid column or drop is usual: being respectively close to spiral center
The interior circulation of the interior circulation of side and separate spiral center side；The addition of this branched structure of Fig. 4, can make tubular reactor
The same angle of circulation rotating in interior fluid column, in this way, after circulating in reinforced portion rotation in two in tubular reactor, two
It is a it is interior recycle some each group and be shaped to a new interior circulation, it is new interior that the another part recycled in two forms another
(when rotating angle is 90 degree, then for original, there are two interior circulations to be respectively divided into the two halves of equivalent, and is respectively combined and to form two for circulation
New interior circulation), the mixing inside fluid column can be strengthened in this way, make mixing inside fluid column more evenly, and then improved in fluid column
Reaction solution more evenly receive illumination, when tubular reactor returns to light source body from the reinforced structure, and primary rotation occurs
Turn, so that the interior circulation of fluid column further adjusts, so that the mixing inside fluid column is more uniform, further avoid excessive illumination,
Lower the time required for photochemical reaction, and improves the selectivity of product and the utilization rate of light.
It is described to strengthen mixed structure is preferably but not limited to ring ear formula and column rib-type, as shown in Figure 4, wherein ring
Ear formula is in the elongated circular or elongated generally elliptically cyclic annular or analogous shape component of light source appearance connection one, the oblong type or long oval
The long axis of type structure preferably with it is described axially vertical, the tubular reactor encounters annulus in along light source winding process
It is wound when part；Column rib-type structure be in the prominent a piece of or bar of light source appearance, the prominent angle preferably with
Light source be it is vertical, it is wound when tubular reactor passes through.Certainly strengthen mixed structure and be not limited to the above-mentioned knot enumerated
Structure, as long as with its axial angled spiral wrap structure.Similar, the pipe reaction of light source external
Device, reinforcing mixed structure and original cloth office plane are angled, and preferred angle is 90 °.The quantity for strengthening mixed structure
It can be to be more than one, two or three.
Photochemically reactive micro-hybrid system working method includes: in tubular reactor of the present invention
(1) reaction solution and delivery phase fluid are introduced in microring array unit, wherein delivery phase fluid is not mutual with reaction solution
Molten liquid or gas；It adjusts delivery phase and is cut reaction solution by forms such as cross-flow, cocurrents with flow quantity, delivery phase fluid is reacted
It is cut to fluid column, forms fluid column stream, i.e., is spaced apart between reaction solution fluid column by delivery phase fluid, reaction solution fluid column is avoided to melt
It closes, the flowing by delivering phase fluid drives the stream mass motion of two-phase fluid column；
(2) tubular reactor that fluid column stream enters in tubular type photochemical reaction device receives illumination, and reacts, and leads to
Cross the mixed intensified fluid column internal mix of pipe-line layout；In During Illumination, reaction solution remains that fluid column kenel flows；
(3) fluid column stream once passes through in tubular reactor or repeatedly recycles, and controls total residence time according to reaction process,
Reaction mixture is obtained after split-phase.
Wherein it is preferred to which the reaction solution is the solution containing photochemical reaction ingredient.
Wherein it is preferred to which the delivery mutually includes: the liquid such as electrolyte solution, silicone oil, alkanes or nitrogen, i.e., and instead
The gas or liquid that liquid is immiscible are answered, can be used as delivery phase.
Preferably, the delivery is mutually 1:20~20:1 with the flow-rate ratio for reacting liquid phase；
Embodiment 1:
Photochemically reactive micro-hybrid system in the tubular reactor with inversion structures of the embodiment of the present invention 1, by
Microring array unit and tubular type photochemical reaction device (including tubular reactor and light source) composition.
The microring array unit is T-type structure, main channel internal diameter 1mm, wing passage internal diameter 0.05mm；Light source is 50 watts
The light bar that LED lamp bead array is formed, wavelength 475nm；Tubular reactor is internal diameter 1mm, the perfluoroethylenepropylene of outer diameter 2mm is copolymerized
Property management, tubular reactor are wound in the way of Fig. 3；For illuminator band on the outside of tubular reactor, the two is coaxial, is also spiral
Canoe, control the distance between tube wall and LED light strip are that (the non-tubular reactor outside around axial portions is without LED by 1cm
Light bar winding).
Strengthen photochemically reactive micro-hybrid system in tubular reactor using above-mentioned fluid column stream and carries out photochemical reaction
Degrade Cr6+The step of ion are as follows:
1) Cr is prepared6+Ion initial concentration is the aqueous solution 10mL of 20ppm, adds TiO thereto2Powder 0.5g, stirring
Uniformly, as reaction solution.
2) silicone oil of flow 0.8mL/min is mixed for 0.5mL/min reaction solution in microring array unit and flow as delivery phase
Conjunction forms fluid column stream.
3) fluid column stream enters tubular reactor, receives light source light and chemically reacts according to the concurrent third contact of a total solar or lunar eclipse, reaction solution is in pipe reaction
It is 30min that opportunity is stopped in device.Liquid-liquid split-phase is completed in receiving flask, passes through uv-spectrophotometric after sampling, addition color developing agent
Meter analysis, Cr6+The conversion ratio of ion is 43.4%.
Embodiment 2:
Photochemically reactive micro-hybrid system in the tubular reactor with inversion structures of the embodiment of the present invention 2, by
Microring array unit and tubular type photochemical reaction device composition, i.e. microring array unit and tubular type photochemical reaction device (including tubular type
Reactor and light source) composition.
The microring array unit is cross-flow multi-layer Shear-type, main channel internal diameter 0.5mm, two wing passage internal diameter 1mm；Light
Source is the light bar that 50 watts of LED lamp bead arrays are formed, wavelength 475nm；Tubular reactor is the perfluoroethylene of internal diameter 1mm, outer diameter 2mm
Propylene copolymer pipe, tubular reactor are wound in the way of Fig. 4 A；For illuminator band on the outside of tubular reactor, the two is coaxial,
It also is spiral wrap mode, control the distance between tube wall and LED light strip are 1cm (the non-pipe reaction around axial portions
It is wound on the outside of device without LED light strip).
Photochemistry is carried out using micro-hybrid system photochemically reactive in the above-mentioned tubular reactor with inversion structures
The step of reacting degradating organic dye methyl orange are as follows:
1) the aqueous solution 10mL that methyl orange initial concentration is 50ppm is prepared, adds TiO thereto2Powder 40mg, stirring are equal
It is even, as reaction solution.
2) flow 0.2mL/min air as delivery phase, in microring array unit with flow be 0.5mL/min reaction solution
It is mixed to form fluid column stream.
3) fluid column stream enters the tubular reactor with inversion structures, receives light source light and chemically reacts according to the concurrent third contact of a total solar or lunar eclipse, instead
Liquid is answered to stop opportunity in tubular reactor as 15min.The liquid-solid mixture after reaction is collected with receiving flask, is realized by centrifugation
It is separated by solid-liquid separation, the concentration of methyl orange in liquid is analyzed by ultraviolet specrophotometer, the conversion ratio that methyl orange is calculated is
77.5%.
Embodiment 3:
Photochemically reactive micro-hybrid system in the tubular reactor with inversion structures of the embodiment of the present invention 3, by
Microring array unit and 2 bushing type photochemical reaction devices (including 2 tubular reactors, 2 cold-traps and 2 light sources) composition.
The microring array unit is the coaxial endless tube structure of modified, and the intracavitary diameter of droplet formation is 2.5mm, reaction solution channel
Internal diameter is 1mm, and output channel internal diameter d is 1.5mm, and inner tube is that (contact angle with dispersion fluid is super-hydrophobic coat inner wall
151°)；First and second light source is 100 watts of high-pressure sodium lamps；First and second cold-trap is high-boron-silicon glass material, filter 300nm with
Under ultraviolet light, mercury lamp is placed among cold-trap；Tubular reactor is the fluorinated ethylene propylene copolymer pipe of internal diameter 1mm, outer diameter 2mm
For illuminator band on the outside of tubular reactor, the first and second tubular reactor is the quartz glass tube of internal diameter 2mm, outer diameter 3mm, pipe
Formula reactor is wrapped in outside cold-trap in the way of Fig. 4 B.
Photochemistry is carried out using micro-hybrid system photochemically reactive in the above-mentioned tubular reactor with inversion structures
The step of reacting degradating organic dye methyl orange are as follows:
1) the aqueous solution 10mL that methyl orange initial concentration is 50ppm is prepared, adds TiO thereto2Powder 20mg, stirring are equal
It is even, as reaction solution.
2) flow 0.4mL/min silicone oil as delivery phase, in microring array unit with flow be 0.2mL/min reaction solution
It is mixed to form fluid column stream.
3) fluid column stream enters the tubular reactor with inversion structures, receives light source light and chemically reacts according to the concurrent third contact of a total solar or lunar eclipse, instead
Liquid is answered to stop opportunity in tubular reactor as 16min.The liquid-solid mixture after reaction is collected with receiving flask, is realized by centrifugation
It is separated by solid-liquid separation, the concentration of methyl orange in liquid is analyzed by ultraviolet specrophotometer, the conversion ratio that methyl orange is calculated is
79.2%.
Comparative example 1 (compares) with embodiment 1:
Homogeneous flow photochemical reaction in the tubular reactor of comparative example 1 of the present invention is filled by single tubular type photochemical reaction
Set (including tubular reactor and light source) composition.The difference of comparative example 2 and embodiment 1 is the canoe of tubular reactor not
Together, and it is not introduced into delivery phase.
The tubular reactor is the fluorinated ethylene propylene copolymer pipe of internal diameter 1mm, outer diameter 2mm, and tubular reactor is equal
Around axle center spiral wrap；For illuminator band on the outside of tubular reactor, the two is coaxial, is also spiral wrap mode (such as Fig. 5
It is shown), control the distance between tube wall and LED light strip are 1cm, guarantee residence time and reality of the reaction solution in tubular reactor
It is identical to apply example 1, is 30min.
Photochemical reaction degradation Cr is carried out using homogeneous flow in above-mentioned carry out tubular reactor6+The step of ion are as follows:
1) Cr is prepared6+Ion initial concentration is the aqueous solution 10mL of 20ppm, adds TiO thereto2Powder 0.5g, stirring
Uniformly, as reaction solution.
2) flow is that the homogeneous flow reaction solution of 1.3mL/min enters tubular reactor, receives light source light according to the concurrent third contact of a total solar or lunar eclipse
Reaction is learned, reaction solution stops opportunity in tubular reactor as 30min.Liquid-liquid split-phase, sampling, addition are completed in receiving flask
It is analyzed after color developing agent by ultraviolet specrophotometer, Cr6+The conversion ratio of ion is 29.0%, compares embodiment 1, Cr6+Ion
Conversion ratio reduces by 33.1%.
Comparative example 2 (compares) with embodiment 1:
Photochemically reactive micro-hybrid system in the tubular reactor of the embodiment of the present invention 2, by microring array unit and pipe
Formula photochemical reaction device (including tubular reactor and light source) composition.The difference of comparative example 2 and embodiment 1 is pipe reaction
The canoe of device is different.
The microring array unit is T-type structure, main channel internal diameter 1mm, wing passage internal diameter 0.05mm；Light source is 50 watts
The light bar that LED lamp bead array is formed, wavelength 475nm；Tubular reactor is internal diameter 1mm, the perfluoroethylenepropylene of outer diameter 2mm is copolymerized
Property management, tubular reactor surround axle center spiral wrap, no structure (as shown in Figure 5) for stretching out axial portions；Illuminator band
On the outside of tubular reactor, the two is coaxial, is also spiral wrap mode, and control the distance between tube wall and LED light strip are
1cm guarantees that residence time and embodiment 1 of the reaction solution in tubular reactor are identical, is 30min.
Strengthen photochemically reactive micro-hybrid system in tubular reactor using above-mentioned fluid column stream and carries out photochemical reaction
Degrade Cr6+The step of ion are as follows:
1) Cr is prepared6+Ion initial concentration is the aqueous solution 10mL of 20ppm, adds TiO thereto2Powder 0.5g, stirring
Uniformly, as reaction solution.
2) silicone oil of flow 0.8mL/min is mixed for 0.5mL/min reaction solution in microring array unit and flow as delivery phase
Conjunction forms fluid column stream.
3) fluid column stream enters tubular reactor, receives light source light and chemically reacts according to the concurrent third contact of a total solar or lunar eclipse, reaction solution is in pipe reaction
It is 30min that opportunity is stopped in device.Liquid-liquid split-phase is completed in receiving flask, passes through uv-spectrophotometric after sampling, addition color developing agent
Meter analysis, Cr6+The conversion ratio of ion is 39.4%, compares embodiment 1, Cr6+The conversion ratio of ion reduces by 9.2%.
Comparative example 3 (compares) with embodiment 2:
Photochemically reactive micro-hybrid system in the tubular reactor of comparative example 3 of the present invention, by microring array unit and pipe
Formula photochemical reaction device (including tubular reactor and light source) composition.The difference of comparative example 3 and embodiment 2 is pipe reaction
The canoe of device is different.
The microring array unit is cross-flow multi-layer Shear-type, main channel internal diameter 0.5mm, two wing passage internal diameter 1mm；Light
Source is the light bar that 50 watts of LED lamp bead arrays are formed, wavelength 475nm；Tubular reactor is the perfluoroethylene of internal diameter 1mm, outer diameter 2mm
Propylene copolymer pipe, tubular reactor are wound in the way of Fig. 5；Tubular reactor is without the structure for stretching out axial portions, light source
For light bar on the outside of tubular reactor, the two is coaxial, is spiral wrap mode, and control the distance between tube wall and LED light strip are
1cm guarantees that residence time and embodiment 7 of the reaction solution in tubular reactor are identical, is 15min.
Carrying out photochemical reaction degradation using micro-hybrid system photochemically reactive in above-mentioned tubular reactor has engine dyeing
The step of expecting methyl orange are as follows:
1) the aqueous solution 10mL that methyl orange initial concentration is 50ppm is prepared, adds TiO thereto2Powder 40mg, stirring are equal
It is even, as reaction solution.
2) flow 0.2mL/min air as delivery phase, in microring array unit with flow be 0.5mL/min reaction solution
It is mixed to form fluid column stream.
3) fluid column stream enters tubular reactor, receives light source light and chemically reacts according to the concurrent third contact of a total solar or lunar eclipse, reaction solution is in pipe reaction
It is 15min that opportunity is stopped in device.The liquid-solid mixture after reaction is collected with receiving flask, is realized and is separated by solid-liquid separation by centrifugation, passed through
Ultraviolet specrophotometer analyzes the concentration of methyl orange in liquid, and the conversion ratio that methyl orange is calculated is 72.7%, compares implementation
The conversion ratio of example 2, methyl orange reduces by 6.2%.
Comparative example 4 (compares) with embodiment 2:
Photochemical reaction in the tubular reactor with inversion structures of comparative example 4 of the present invention, it is anti-by tubular type photochemistry
Device (including tubular reactor and light source) is answered to form.The difference of comparative example 4 and embodiment 2 is to be not introduced into delivery phase.
The light source is the light bar that 50 watts of LED lamp bead arrays are formed, wavelength 475nm；Tubular reactor be internal diameter 1mm,
The fluorinated ethylene propylene copolymer pipe of outer diameter 2mm, tubular reactor are wound in the way of Fig. 4 A；Illuminator band is in pipe reaction
On the outside of device, it is also spiral wrap mode that the two is coaxial, and control the distance between tube wall and LED light strip are 1cm (non-to surround axis
It is wound on the outside of the tubular reactor of center portion point without LED light strip).
Photochemical reaction drop is carried out using system photochemically reactive in the above-mentioned tubular reactor with inversion structures
The step of solving organic dyestuff methyl orange are as follows:
1) the aqueous solution 10mL that methyl orange initial concentration is 50ppm is prepared, adds TiO thereto2Powder 40mg, stirring are equal
It is even, as reaction solution.
2) aqueous solution of methyl orange enters tubular reactor with the speed injection of flow velocity 0.5mL/min, receives light source light photograph
Concurrent third contact of a total solar or lunar eclipse chemical reaction, reaction solution stop opportunity in tubular reactor as 15min.It is solid that the liquid after reaction is collected with receiving flask
Mixture is realized by centrifugation and is separated by solid-liquid separation, and the concentration of methyl orange in liquid is analyzed by ultraviolet specrophotometer, is calculated
The conversion ratio of methyl orange is 68.8%, compares embodiment 2, and the conversion ratio of methyl orange reduces by 11.2%.
Comparative example 5 (compares) with embodiment 3:
Photochemical reaction in the tubular reactor of comparative example 5 of the present invention, it is anti-by microring array unit and 2 bushing type photochemistry
Device (including 2 tubular reactors, 2 cold-traps and 2 light sources) are answered to form.The difference of comparative example 5 and embodiment 3 is tubular type
The canoe of reactor is different.
The microring array unit is the coaxial endless tube structure of modified, and the intracavitary diameter of droplet formation is 2.5mm, reaction solution channel
Internal diameter is 1mm, and output channel internal diameter d is 1.5mm, and inner tube is that (contact angle with dispersion fluid is super-hydrophobic coat inner wall
151°)；First and second light source is 100 watts of high-pressure sodium lamps；First and second cold-trap is high-boron-silicon glass material, filter 300nm with
Under ultraviolet light, mercury lamp is placed among cold-trap；Tubular reactor is the fluorinated ethylene propylene copolymer pipe of internal diameter 1mm, outer diameter 2mm
For illuminator band on the outside of tubular reactor, the first and second tubular reactor is the quartz glass tube of internal diameter 2mm, outer diameter 3mm, and two
A tubular reactor is wrapped in outside cold-trap in the way of Fig. 5.
Photochemical reaction drop is carried out using system photochemically reactive in the above-mentioned tubular reactor with inversion structures
The step of solving organic dyestuff methyl orange are as follows:
1) the aqueous solution 10mL that methyl orange initial concentration is 50ppm is prepared, adds TiO thereto2Powder 20mg, stirring are equal
It is even, as reaction solution.
2) flow 0.4mL/min silicone oil as delivery phase, in microring array unit with flow be 0.2mL/min reaction solution
It is mixed to form fluid column stream.
3) fluid column stream enters the tubular reactor with inversion structures, receives light source light and chemically reacts according to the concurrent third contact of a total solar or lunar eclipse, instead
Liquid is answered to stop opportunity in tubular reactor as 16min.The liquid-solid mixture after reaction is collected with receiving flask, is realized by centrifugation
It is separated by solid-liquid separation, the concentration of methyl orange in liquid is analyzed by ultraviolet specrophotometer, the conversion ratio that methyl orange is calculated is
73.2%, embodiment 3 is compared, the conversion ratio of methyl orange reduces by 7.5%.
Comparative example 6 (compares) with embodiment 3:
Comparative example 6 of the present invention uses 1 set of stirring-type photochemical reaction device, is made of light source and cold-trap, light source is put into cold
Among trap, cold-trap is placed in the stirring reactor of a 200mL volume.The difference of comparative example 6 and embodiment 3 is reactor
For stirring-type, and it is not introduced into delivery phase.
The light source is 1000 watts of high-pressure sodium lamps (power of guarantor unit's volumetric reaction liquid is consistent), cold-trap is high borosilicate
Glass material filters 300nm ultraviolet light below.
The step of carrying out photochemical reaction degradation methyl orange using above-mentioned stirring-type photochemical reaction device are as follows:
1) the aqueous solution 100mL that methyl orange initial concentration is 50ppm is prepared, adds TiO thereto2Powder 200mg, stirring
Uniformly, as reaction solution.
2) reaction solution is put into the corresponding stirring reactor of cold-trap, opens light source, causes photochemical reaction, mixing time
It is 16 minutes, collects the liquid-solid mixture after reaction with receiving flask, realized and be separated by solid-liquid separation by centrifugation, pass through uv-spectrophotometric
The concentration of methyl orange in meter analysis liquid, the conversion ratio that methyl orange is calculated is 58.0%, is compared
The conversion ratio of embodiment 3, methyl orange reduces by 26.7%.
Although above the present invention is described in detail with a general description of the specific embodiments,
On the basis of the present invention, those of ordinary skill in the art can be made some modifications or improvements it, this is to those skilled in the art
It is obvious for member.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to
The scope of protection of present invention.
Claims (10)
1. photochemically reactive micro-hybrid system in a kind of tubular reactor, which is characterized in that the system includes microring array unit
With tubular type photochemical reaction device, wherein liquid-liquid microring array unit and tubular type photochemical reaction device are connected in series, described
In liquid-liquid microring array unit, reaction solution is mutually cut into fluid column or drop by immiscible liquid carrier with reaction solution.
2. micro-hybrid system according to claim 1, it is characterised in that: the microring array unit is T-type, Y type, cross-flow
Shearing-type, hydraulics focus type, coaxial ring-pipe type or coaxial annular pipe modified microchannel devices.
3. micro-hybrid system according to claim 1, it is characterised in that: the tubular type photochemical reaction device can be used
Any tubular reactor of light transmission.The length of quantity of light source and tubular reactor light application time according to needed for photochemical reaction and
It is fixed.
4. micro-hybrid system according to claim 1-3, it is characterised in that: microring array unit material is poly-
Object, stainless steel, unorganic glass or the above mixture are closed, channel size is 0.05~50 millimeter.
5. micro-hybrid system according to claim 1-3, it is characterised in that: its tubular reactor material used
For fluorinated ethylene propylene copolymer, polytetrafluoroethylene (PTFE), quartz glass, silicate glass, high-boron-silicon glass or the above mixture,
Internal diameter is 0.05~50 millimeter.
6. micro-hybrid system according to claim 1, it is characterised in that: the light source in the tubular type photochemical reaction device
For high-pressure sodium lamp, medium pressure mercury lamp, low pressure mercury lamp, light emitting diode (LED) lamp or its combination of the above, it is ultraviolet that light source, which shines,
Light, visible light, infrared light or its combination of the above；The cold-trap be material be quartz glass, silicate glass, high-boron-silicon glass or
The above mixture.
7. micro-hybrid system according to claim 1-6, it is characterised in that: tubular reactor have it is different with
1 or 1 or more turning structure on the winding direction of light source.
8. a kind of photochemically reactive method in tubular reactor, it is characterised in that described in any item using claim 1-7
Micro-hybrid system realizes that this method comprises the following steps:
(1) in microring array unit, with the immiscible liquid of photochemical reaction liquid or gas as delivery phase fluid, pass through adjusting
Reaction liquid phase fluid is cut into fluid column, obtains fluid column stream by two phase flow；
(2) the fluid column stream obtained enters tubular reactor and receives illumination, and illumination reaction occurs in the fluid column of reaction solution.In illumination
In the process, reaction solution remains that fluid column kenel flows.
(3) fluid column stream once passes through in tubular reactor or repeatedly recycles, and controls total residence time, split-phase according to reaction process
After obtain reaction mixture.
9. according to the method described in claim 8, it is characterized in that, the reaction solution is to contain the molten of photochemical reaction ingredient
Liquid.
10. according to the method described in claim 8, it is characterized in that, the delivery is mutually 1:20 with the flow-rate ratio for reacting liquid phase
~20:1；The delivery mutually includes: the inert gases such as the liquid such as electrolyte solution, silicone oil, alkanes or nitrogen, argon gas, i.e., with
Reaction solution immiscible liquid or liquid, can be used as delivery phase.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811038708.0A CN108993342B (en) | 2018-09-06 | 2018-09-06 | Micro-mixing system and method for photochemical reaction in tubular reactor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811038708.0A CN108993342B (en) | 2018-09-06 | 2018-09-06 | Micro-mixing system and method for photochemical reaction in tubular reactor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108993342A true CN108993342A (en) | 2018-12-14 |
| CN108993342B CN108993342B (en) | 2024-01-23 |
Family
ID=64591202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811038708.0A Active CN108993342B (en) | 2018-09-06 | 2018-09-06 | Micro-mixing system and method for photochemical reaction in tubular reactor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108993342B (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109806823A (en) * | 2019-03-14 | 2019-05-28 | 凯莱英医药集团（天津）股份有限公司 | Continuous photochemical reaction unit and system |
| CN111434377A (en) * | 2019-01-11 | 2020-07-21 | 中国石油化工股份有限公司 | Coil microreactor and microreactor system |
| CN111790335A (en) * | 2019-04-08 | 2020-10-20 | 上海交通大学 | Ultraviolet photochemical reactor device based on continuous flow technology |
| CN113226533A (en) * | 2018-12-21 | 2021-08-06 | 制药流体股份有限公司 | Chemical reactor |
| CN113877494A (en) * | 2021-09-29 | 2022-01-04 | 国家纳米科学中心 | Multifunctional flowing microtube reaction device and operation method |
| CN113975227A (en) * | 2020-07-10 | 2022-01-28 | 天津大学 | Flow type synthesis device and synthesis method of nanogel |
| CN115318221A (en) * | 2022-10-13 | 2022-11-11 | 江苏富淼科技股份有限公司 | Solid polymerization multilayer initiation polymerization device and initiation polymerization method thereof |
Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4043886A (en) * | 1976-03-15 | 1977-08-23 | Pennwalt Corporation | Photochemical reactor and irradiation process |
| JPH08167734A (en) * | 1994-12-15 | 1996-06-25 | Matsushita Electric Ind Co Ltd | Method and device for manufacturing photoelectron material and light emitting element using the material |
| CN1657153A (en) * | 2004-12-06 | 2005-08-24 | 朱旻 | Differential photo chemical reactor and its application |
| CN101132854A (en) * | 2004-11-16 | 2008-02-27 | 万罗赛斯公司 | Multiphase reaction process using microchannel technology |
| CN201147688Y (en) * | 2007-12-17 | 2008-11-12 | 天津理工大学 | Actinic chemistry reactor using LED as light source |
| WO2010105365A1 (en) * | 2009-03-18 | 2010-09-23 | Exfo Photonic Solutions Inc. | Distributed light sources for photo-reactive curing |
| EP2377609A1 (en) * | 2010-04-12 | 2011-10-19 | UV-Consulting Peschl e. K. | Modular photo tubular reactor |
| CN103553993A (en) * | 2013-11-12 | 2014-02-05 | 中国科学院理化技术研究所 | Method for synthesizing resinous vitamin D3 by using micro-flow photoreaction technology and micro-flow photochemical reactor |
| CN103849325A (en) * | 2012-11-29 | 2014-06-11 | 日东电工株式会社 | Production method of photoreaction product sheet and apparatus for the same |
| CN103848880A (en) * | 2014-03-10 | 2014-06-11 | 中国科学院理化技术研究所 | Method for preparing 9beta,10-alphat-dehydroprogesterone ketal by using dual-wavelength microflow technology and dual-wavelength microflow photochemistry reactor |
| CN105527233A (en) * | 2015-12-10 | 2016-04-27 | 中国计量学院 | Determination device of hexavalent chromium in water sample based on microfluidic reaction system and determination method thereof |
| CN106732223A (en) * | 2012-02-09 | 2017-05-31 | 加利福尼亚大学董事会 | The generation of high speed drop-on-demand and unicellular encapsulating driven by the cavitation for inducing |
| CN107297190A (en) * | 2017-05-27 | 2017-10-27 | 李贤章 | A kind of use LED as light source apparatus for photoreaction |
| CN108187598A (en) * | 2018-02-01 | 2018-06-22 | 福建工程学院 | Swirling eddy group structure solar heat chemical reactor device |
-
2018
- 2018-09-06 CN CN201811038708.0A patent/CN108993342B/en active Active
Patent Citations (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4043886A (en) * | 1976-03-15 | 1977-08-23 | Pennwalt Corporation | Photochemical reactor and irradiation process |
| JPH08167734A (en) * | 1994-12-15 | 1996-06-25 | Matsushita Electric Ind Co Ltd | Method and device for manufacturing photoelectron material and light emitting element using the material |
| CN101132854A (en) * | 2004-11-16 | 2008-02-27 | 万罗赛斯公司 | Multiphase reaction process using microchannel technology |
| CN1657153A (en) * | 2004-12-06 | 2005-08-24 | 朱旻 | Differential photo chemical reactor and its application |
| CN201147688Y (en) * | 2007-12-17 | 2008-11-12 | 天津理工大学 | Actinic chemistry reactor using LED as light source |
| WO2010105365A1 (en) * | 2009-03-18 | 2010-09-23 | Exfo Photonic Solutions Inc. | Distributed light sources for photo-reactive curing |
| EP2377609A1 (en) * | 2010-04-12 | 2011-10-19 | UV-Consulting Peschl e. K. | Modular photo tubular reactor |
| CN106732223A (en) * | 2012-02-09 | 2017-05-31 | 加利福尼亚大学董事会 | The generation of high speed drop-on-demand and unicellular encapsulating driven by the cavitation for inducing |
| CN103849325A (en) * | 2012-11-29 | 2014-06-11 | 日东电工株式会社 | Production method of photoreaction product sheet and apparatus for the same |
| CN103553993A (en) * | 2013-11-12 | 2014-02-05 | 中国科学院理化技术研究所 | Method for synthesizing resinous vitamin D3 by using micro-flow photoreaction technology and micro-flow photochemical reactor |
| CN103848880A (en) * | 2014-03-10 | 2014-06-11 | 中国科学院理化技术研究所 | Method for preparing 9beta,10-alphat-dehydroprogesterone ketal by using dual-wavelength microflow technology and dual-wavelength microflow photochemistry reactor |
| CN105527233A (en) * | 2015-12-10 | 2016-04-27 | 中国计量学院 | Determination device of hexavalent chromium in water sample based on microfluidic reaction system and determination method thereof |
| CN107297190A (en) * | 2017-05-27 | 2017-10-27 | 李贤章 | A kind of use LED as light source apparatus for photoreaction |
| CN108187598A (en) * | 2018-02-01 | 2018-06-22 | 福建工程学院 | Swirling eddy group structure solar heat chemical reactor device |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113226533A (en) * | 2018-12-21 | 2021-08-06 | 制药流体股份有限公司 | Chemical reactor |
| CN111434377A (en) * | 2019-01-11 | 2020-07-21 | 中国石油化工股份有限公司 | Coil microreactor and microreactor system |
| CN111434377B (en) * | 2019-01-11 | 2022-07-15 | 中国石油化工股份有限公司 | Coil microreactor and microreactor system |
| CN109806823A (en) * | 2019-03-14 | 2019-05-28 | 凯莱英医药集团（天津）股份有限公司 | Continuous photochemical reaction unit and system |
| CN111790335A (en) * | 2019-04-08 | 2020-10-20 | 上海交通大学 | Ultraviolet photochemical reactor device based on continuous flow technology |
| CN113975227A (en) * | 2020-07-10 | 2022-01-28 | 天津大学 | Flow type synthesis device and synthesis method of nanogel |
| CN113877494A (en) * | 2021-09-29 | 2022-01-04 | 国家纳米科学中心 | Multifunctional flowing microtube reaction device and operation method |
| CN115318221A (en) * | 2022-10-13 | 2022-11-11 | 江苏富淼科技股份有限公司 | Solid polymerization multilayer initiation polymerization device and initiation polymerization method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108993342B (en) | 2024-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108993342A (en) | Photochemically reactive micro-hybrid system and method in a kind of tubular reactor | |
| Zhao et al. | Scale-up of a luminescent solar concentrator-based photomicroreactor via numbering-up | |
| Yao et al. | Review of the applications of microreactors | |
| Naughton et al. | High temperature continuous flow synthesis of CdSe/CdS/ZnS, CdS/ZnS, and CdSeS/ZnS nanocrystals | |
| JP2002541788A (en) | Photobioreactor with improved light input through increased surface area, wavelength shifter or light transmission | |
| CN103848880B (en) | Dual wavelength microfluidic technology is utilized to prepare 9 β, the method for 10-α-dehydrogenation Progesterone ketal and dual wavelength miniflow photochemical reactor | |
| CN109081796B (en) | Photochemical synthesis of vitamin D in tubular reactor2、D3Method (2) | |
| CN103764660A (en) | Method and device for the synthesis of artemisinin | |
| CN106914203B (en) | Cyclobutanetetracarboxylic dianhydride continuous preparation device and method based on micro-mixer | |
| CN110878112B (en) | Gas separation flow system and method for photochemical synthesis of 9-beta, 10-alpha-dehydroprogesterone ketal | |
| CN104028188A (en) | Ultraviolet light micro-channel reactor | |
| CN107337194A (en) | A kind of preparation method of adjustable carbon point film of fluorescence and its application on LED | |
| CN107486115A (en) | The continuous preparation method of continuous photochemical reaction unit, system and propellane carbonylation | |
| CN209138596U (en) | Photochemically reactive micro-hybrid system in a kind of tubular reactor | |
| CN108525622A (en) | A kind of reaction of high order micro fluidic device and its prepare applications to nanostructures | |
| CN106076218A (en) | Micro-fluidic chip and the synthetic method of carbon quantum dot | |
| CN106237953B (en) | The small gas-liquid bubble column reactor of photocatalysis | |
| CN103553993B (en) | Method for synthesizing resinous vitamin D3 by using micro-flow photoreaction technology and micro-flow photochemical reactor | |
| CN108212046A (en) | A kind of honeycomb type channel microreactor | |
| Zhao et al. | Reactor optimization and process intensification of photocatalysis for capillary-based PMMA LSC-photomicroreactors | |
| CA3115258A1 (en) | Continuous flow reactor for viral inactivation | |
| Hermens et al. | Development of a modular photoreactor for the upscaling of continuous flow photochemistry | |
| CN208591820U (en) | A kind of honeycomb type channel microreactor | |
| Basso et al. | 3 Recent applications of photochemistry on large-scale synthesis (2015–2019) | |
| Niu et al. | Photochemical microfluidic synthesis of vitamin D3 by improved light sources with photoluminescent substrates |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |