CN204051661U - There is the board-like photocatalysis microreactor of the titanium dioxide of metal ion mixing - Google Patents
There is the board-like photocatalysis microreactor of the titanium dioxide of metal ion mixing Download PDFInfo
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- CN204051661U CN204051661U CN201420475678.0U CN201420475678U CN204051661U CN 204051661 U CN204051661 U CN 204051661U CN 201420475678 U CN201420475678 U CN 201420475678U CN 204051661 U CN204051661 U CN 204051661U
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Abstract
The utility model discloses the board-like photocatalysis microreactor of titanium dioxide of metal ion mixing, it comprises corrosion resistant plate substrate, described corrosion resistant plate substrate has a groove as single channel conversion zone, described corrosion resistant plate substrate has the entrance and exit be connected with the import and export of single channel conversion zone respectively, entrance is connected with suction line, outlet is connected with outlet line, in described corrosion resistant plate substrate reeded one side and transparent surface one side on equal load have the TiO of metal ion mixing
2catalyst film, on transparent surface, load has the one side of catalyst film be oppositely arranged with reeded one side in corrosion resistant plate substrate and be adhesively fixed at edge fluid sealant, is provided with incident light source above the transparent surface described in relative with groove.Adopt this device, the utilization ratio of light is higher, with plain TiO
2catalyst phase specific degradation rate brings up to original more than 2 times.
Description
Technical field
The utility model relates to photocatalysis technology field, particularly relates to microreaction technology.
Background technology
TiO
2catalysis material has the advantages such as photocatalytic activity is high, oxidability is strong, stability is high, pollution-free, is one of current most catalysis material applying potentiality.But, when being applied to light-catalyzed reaction, there is spectral response range narrow (below wavelength 387nm), photo-generate electron-hole to very easily compound, surperficial adsorption selectivity is poor wait not enough.Therefore, domestic and international researcher is to TiO
2photochemical catalyst has carried out study on the modification (Gu Hengda etc., application chemical industry, 2007,36 (2): 136-139; Ox new book etc., electronic component and material, 2004,23 (8): 39-44; Zhu Yuchan etc., Guangdong chemical industry, 2010,37 (12): 19-22), mainly comprise: semiconductors coupling, noble metal decorated, surface sensitization, metal ion mixing, nonmetallic ion-doped, codope, pattern modification etc.Modified catalyst or expanded spectral response range, makes it have catalytic activity at visible region, or stops the recombination process etc. in electronics and hole, makes photocatalysis effect and unmodified pure TiO
2catalyst is compared and is significantly improved.
Since the nineties in 20th century, microreactor came out, concern (the Lu et al. of researcher is caused with advantages such as its distinctive high-specific surface area, high mass transfer and heat transfer efficiency, the mixing of reactant energy Quick uniform, Lab on a Chip, 2001,1 (1): 22-28; Gole et al., Advanced Materials for Energy Conversion II Symposium, 2004,69-78; Takei et al., Catal.Commun., 2005,6 (5): 357-360; Teekateerawe et al., Adv.Mater.Res., 2006,11-12,303-306; Lindstrom et al., AIChE J., 2007,53 (3): 695-700; Daniel et al., Electr-ochem.Commun., 2007,9 (3): 522-528; Matsushita et al., Chem.Eng.J., 2008,135 (4): S303-S308; Meng et al., Nanoscale, 2013,5,4687-4690; Yin Xuefeng etc., analytical chemistry, 2003,31 (1): 116-119; Leaf the U.S. and Britain etc., Hangzhou Pedagogic University's journal (natural science edition), 2009,8 (2): 121-124; He Zhongyuan etc., Chinese Journal of Inorganic Chemistry, 2009,25 (11): 2021-2025; Leaf the U.S. and Britain etc., Hangzhou Pedagogic University's journal (natural science edition), 2012,11 (1): 1-6).The photo catalysis reactor catalytic efficiency of macro-scale is lower, and light attenuation is relatively serious, and catalyst powder particle is easily reunited, and catalyst such as need to reclaim at the shortcoming makes researcher attempt microreaction technology to be applied to photocatalysis field, and makes some progress.In photocatalysis microreactor, some organic pollutants just can be completely degraded within the time of staying of a few minutes, and catalytic efficiency improves greatly.But these photocatalysis microreactors are its basic structure (such as Chinese patent 200910197401.X) mainly with microchannel.This not only limit substrate flow, and effective illuminating area of single microchannel is very limited, very low to the overall utilization of luminous energy, and parallel amplification control system is complicated.Therefore, how to pass through technological invention, select suitable material and preparation technology, manufacture and design rational microreactor structure and size, microreactor is made both to have kept its Characteristics and advantages, have again larger effective illuminating area, the higher efficiency of light energy utilization, improving its room and time utilization ratio is urgent problem.
The Patents of current photocatalysis microreactor has: Chinese patent 200910197401.X, it is characterized in that with quartz capillary (internal diameter 530-550 μm, length 100-200mm) as photocatalytic region microchannel, adopt the liquid chemical method making ZnO coating of surperficial prefabricated nanosized seeds, with the single semiconductor of the ZnO of vertical-growth on the inner surface of microchannel, TiO
2the ZnO couple semiconductor that nano particle is coated or Pt metal-ZnO semiconductor composite nano rod array as photochemical catalyst, to the degradation rate of organic matter methylene blue solution more than 80%.
Chinese patent 201010148412.1, it is characterized in that on silicon wafer, etching forms specific silicon micro-flow groove pattern, place appropriate high temperature bubble release agent at its two ends or ad-hoc location local, make silicon micro-flow groove form glass micro-channel seal chamber at air or vacuum Anodic bonding above-mentioned silicon wafer and glass wafer.By the nano-TiO buied
2powder is first dissolved into suspension, then this immersion is entered glass micro-channel, dries afterwards and high-temperature heat treatment fluid channel, repeatedly, by photocatalyst coating on fluid channel inwall, forms thermoforming glass photocatalytic microreactor.
Chinese patent 201210051512.1, it is characterized in that in reactor, optical fiber lower end is supported on cellular glass sand dividing plate through micropore glass sheet, and upper end and light transmission piece are fixed, reactor bottom is provided with admission line, and light source incidence mode penetrates formula in being changed into by traditional out-shoot type.Adopt cathode sputtering at optical fiber surface plating titanium, then obtain TiO by anodic oxidation
2nanotube light reaction catalyst.
Said method all has some limitations, industrialization difficulty.Organic sewage process is that a treating capacity is large, and energy consumption is high, nothing very economic interests, but can reduce the engineering of environmental pollution.Photocatalysis microreactor technology is applied to organic sewage process should towards raising single microchannel treating capacity, efficiency utilization sunshine as future developments such as light source, reduction energy consumptions.Using circular microchannel as conversion zone, not only there is light-receiving area little in Chinese patent 200910197401.X and 201010148412.1, single microchannel treating capacity is low, and parallel amplification difficulty, and engineering issues is difficult to solve.Chinese patent 201210051512.1 provides a kind of mode of parallel amplification, but there is the restriction (AIChEJ.2006 of effective propagation distance of light as the passage of light using optical fiber, 52 (6): 2271-2280), the direction of propagation of light and the problem such as need the catalyst surface by illumination inconsistent, simultaneous reactions device is intermittently operated.
Summary of the invention
The purpose of this utility model is the shortcoming overcoming prior art, there is provided a kind of significantly improve microreactor effective illuminating area and feed processing capacity, to significantly improve light-catalysed effect, technical maturity simply ripe, with low cost has the board-like photocatalysis microreactor of the titanium dioxide of metal ion mixing.
Of the present utility model have the board-like photocatalysis microreactor of the titanium dioxide of metal ion mixing, it comprises corrosion resistant plate substrate, described corrosion resistant plate substrate has a groove as single channel conversion zone, described recess width is 15-50mm, the degree of depth is 250-500 μm, described corrosion resistant plate substrate has the entrance and exit be connected with the import and export of single channel conversion zone respectively, entrance is connected with suction line, outlet is connected with outlet line, in described corrosion resistant plate substrate reeded one side and transparent surface one side on all load have the TiO of metal ion mixing
2catalyst film, on transparent surface, load has the one side of catalyst film be oppositely arranged with reeded one side in corrosion resistant plate substrate and be adhesively fixed at edge fluid sealant, is provided with incident light source above the transparent surface described in relative with groove.
Employing the beneficial effects of the utility model are:
(1) the microchannel grooves conversion zone of the utility model employing, add reaction volume and the feed processing capacity of reactor, breach the restriction of general microreactor, add the light-receiving area of reactor simultaneously, carry out continuously large-scale organic sewage process for utilizing sunshine and provide possibility, parallel amplification is simple.
(2) using this light tight and material that reflective function is good of corrosion resistant plate as substrate, light is from injecting catalyst film and all can excitation electron transition when stainless steel surfaces reflects again irradiate, with quartz and the light such as glass directly through material compare, the utilization ratio of light is higher.
(3) TiO of metal ion mixing is being had
2in catalyst, metal ion can catch the electronics by illumination excite transitions, stops the compound of electron-hole pair, significantly improves light-catalysed effect, with plain TiO
2catalyst phase specific degradation rate brings up to original more than 2 times.
Accompanying drawing explanation
Fig. 1 is the structural representation having the board-like photocatalysis microreactor of the titanium dioxide of metal ion mixing of the present utility model;
Fig. 2 is the reaction unit schematic diagram of the reactor shown in the utility model Fig. 1;
Fig. 3-1 is the single channel groove conversion zone top view in the microreactor shown in the utility model Fig. 1;
Fig. 3-2 and Fig. 3-3 is existing multichannel groove conversion zone top view;
Fig. 4 is doped with Cu
2+the degradation rate that molar concentration rate is 0.05% board-like photocatalysis microreactor when being 20mg/L methylene blue solution for photocatalytic degradation initial concentration 30 DEG C time and the graph of a relation of the time of staying of solution in reactor;
Fig. 5 is doped with Cu
2+the degradation rate that molar concentration rate is 0.05% board-like photocatalysis microreactor when being 10mg/L methyl orange solution for photocatalytic degradation initial concentration 30 DEG C time and the graph of a relation of the time of staying of solution in reactor.
Detailed description of the invention
Below in conjunction with the drawings and specific embodiments, the utility model is described in detail.
As shown in Figure 1 of the present utility model has the board-like photocatalysis microreactor of the titanium dioxide of metal ion mixing, it comprises corrosion resistant plate substrate 3, described corrosion resistant plate substrate has a groove as single channel conversion zone 4, described recess width is 15-50mm, the degree of depth is 250-500 μm, described corrosion resistant plate substrate has the entrance 1 that is connected with the import and export of single channel conversion zone respectively and exports 2, entrance is connected with suction line, outlet is connected with outlet line, in described corrosion resistant plate substrate reeded one side and transparent surface one side on all load have the TiO of metal ion mixing
2catalyst film 5, on transparent surface 6, load has the one side of catalyst film be oppositely arranged with reeded one side in corrosion resistant plate substrate and be adhesively fixed at edge fluid sealant.Incident light source 7 is provided with above transparent surface described in relative with groove.The horizontal cross sectional geometry of single channel groove is generally flat or rectangle.The formation method of passage comprises the methods such as chemical attack, machining and galvano-cautery.
Preferred described transparent surface 6 be Pyrex glass or quartz, the thickness≤1mm of described Pyrex glass or quartz, and advantage to ensure that reactor has certain mechanical strength, can make again light particularly UV light permeability time decay less.
The TiO2 catalyst film 5 of metal ion mixing is had at Thin Solid Films in the utility model, 2006, open in 496:273-280, there is the preparation method of the TiO2 catalyst film of metal ion mixing can adopt the method such as sol-gel, liquid deposition, method disclosed in Chinese patent CN102553813A.
As preferred embodiment of the present utility model, TiO
2catalyst film thickness is 300-350nm, thickness is neither too thick, neither be too thin, bind metal ion catches effect to light induced electron, and advantage is the catalyst for transparent surface side, because light is injected from the catalyst back side, not too thick film can ensure there is absorption to a certain degree to ultraviolet light, produce the light induced electron of q.s, also can make light induced electron in shorter distance, migrate to the interface reaction of reactant and catalyst, reduce and hole-recombination probability; Simultaneously, when the light of coming from transparent surface transmission is irradiated to corrosion resistant plate suprabasil catalyst, not too thick film makes light be unlikely to be absorbed completely by film, light is from injecting catalyst film and all can excitation electron transition when stainless steel surfaces reflects again irradiate, and migration distance is short, low with hole-recombination probability, with quartz and the light such as glass directly through material compare, the utilization ratio of light is higher.
In the utility model, incident light source can adopt mercury lamp, xenon lamp or sunshine.
The metal ion of preferred doping is La
3+, Cu
2+, Mn
2+, Fe
3+, Zn
2+or Ni
2+in one.
As shown in Figure 2, board-like photocatalysis microreactor shown in Fig. 1 is in running, entrance is connected with constant flow syringe pump 8 by suction line, methylene blue or methyl orange solution 9 enter groove 4 by suction line, xenon lamp (can also be mercury lamp or sunshine) 7 is had to irradiate above the Pyrex glass relative with groove or quartz 6, the power of the light sources such as xenon lamp is 250W, and outlet is connected with outlet line, and board-like microreactor is placed in water-bath 10 and kept constant temperature 30 DEG C.
Doped with Cu
2+concentration be 0.05% the degradation rate of board-like photocatalysis microreactor when being respectively 20mg/L and 10mg/L methylene blue solution or methyl orange solution 9 two kinds of solution for photocatalytic degradation initial concentration under the same conditions and the relation of the time of staying of solution in reactor as shown in Figure 4, Figure 5, show very high photocatalytic activity when xenon lamp medium ultraviolet light content is so low.When solution flow rate is 0.1mL/min (time of staying is 90s), corresponding methylene blue and the degradation rate of methyl orange are respectively more than 75% and 55%.And non-doped with Cu
2+pure TiO
2board-like photocatalysis microreactor degradation rate is under the same conditions only 40% and about 26%.After the doping of metal ion as can be seen here, metal ion enters TiO
2lattice, causes Lacking oxygen defect, forms light induced electron adsorption site, stops the compound in electronics and hole, significantly improves photocatalytic activity.
Claims (4)
1. there is the board-like photocatalysis microreactor of the titanium dioxide of metal ion mixing, it is characterized in that: it comprises corrosion resistant plate substrate, described corrosion resistant plate substrate has a groove as single channel conversion zone, described recess width is 15-50mm, the degree of depth is 250-500 μm, described corrosion resistant plate substrate has the entrance and exit be connected with the import and export of single channel conversion zone respectively, entrance is connected with suction line, outlet is connected with outlet line, in described corrosion resistant plate substrate reeded one side and transparent surface one side on all load have the TiO of metal ion mixing
2catalyst film, on transparent surface, load has the one side of catalyst film be oppositely arranged with reeded one side in corrosion resistant plate substrate and be adhesively fixed at edge fluid sealant, is provided with incident light source above the transparent surface described in relative with groove.
2. according to claim 1 have the board-like photocatalysis microreactor of the titanium dioxide of metal ion mixing, it is characterized in that: described transparent surface is Pyrex glass or quartz, the thickness≤1mm of described Pyrex glass or quartz.
3. according to claim 1 and 2 have the board-like photocatalysis microreactor of the titanium dioxide of metal ion mixing, it is characterized in that: TiO
2catalyst film thickness is 300-350nm.
4. according to claim 3 have the board-like photocatalysis microreactor of the titanium dioxide of metal ion mixing, it is characterized in that: the metal ion of doping is La
3+, Cu
2+, Mn
2+, Fe
3+, Zn
2+or Ni
2+in one.
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| EP3450419A4 (en) * | 2016-04-29 | 2019-12-04 | Dalian Institute Of Chemical Physics, Chinese Academy Of Sciences | Catalytic reactor configuration and preparation, and method for directly synthesizing ethylene by catalyzing methane under oxygen-free condition |
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| CN106731879A (en) * | 2016-12-20 | 2017-05-31 | 济南大学 | Based on metal-doped nTiO2Visible light catalytic hollow fiber ultrafiltration membrane and preparation method |
| CN109289728A (en) * | 2018-10-08 | 2019-02-01 | 上海应用技术大学 | Photocatalysis successive reaction detection device and method |
| CN111298737A (en) * | 2020-03-12 | 2020-06-19 | 大连理工大学 | Multifunctional continuous flow synthesizer |
| CN111298737B (en) * | 2020-03-12 | 2021-08-17 | 大连理工大学 | Multifunctional continuous flow synthesizer |
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