CN1689696A - Visible photo-activated photochemical catalyst and lamp arraying type packed bed reaction apparatus - Google Patents
Visible photo-activated photochemical catalyst and lamp arraying type packed bed reaction apparatus Download PDFInfo
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- CN1689696A CN1689696A CN 200510063617 CN200510063617A CN1689696A CN 1689696 A CN1689696 A CN 1689696A CN 200510063617 CN200510063617 CN 200510063617 CN 200510063617 A CN200510063617 A CN 200510063617A CN 1689696 A CN1689696 A CN 1689696A
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Abstract
The present invention relates to the preparation process of nitrogen doped visible light sensitized TiO2 photocatalyst, and photocatalytic fluid treating method and apparatus with light array fixed bed. Through the thermal decomposition and ammonium bicarbonate to produce water and ammonia, homogeneous hydrolysis and ammonolysis of titanium tetrachloride to produce nitrogen doped titanic acid precursor, and low temperature treatment of the precursor in nitrogen atmosphere, visible light sensitized nanometer nitrogen doped TiO2 film or powder may be prepared. The light array reactor has homogeneously distributed ultraviolet lamp with loaded photocatalyst filled in the space between the lamp and sleeve. The preparation process has the advantages of mild reaction condition, low heat treatment temperature, etc. and the photocatalytic reactor has the advantages of continuous operation, high efficiency, etc. The present invention may be used in water treatment, air purification, etc.
Description
This case is for dividing an application, and the original bill applying date is on September 29th, 2003, and application number is 03151473.1, and denomination of invention is " visible light photoactivated photochemical catalyst and a lamp arraying type packed bed reaction unit ".
Technical field
The present invention relates to a kind of visible light photoactivated photochemical catalyst preparation method and lamp arraying type that is used for photocatalysis water treatment and air cleaning and fill the fixed bed photocatalytic reaction device.
Background technology
Photocatalysis water treatment and air purifying process are the environmental pollution treatment technologies that has DEVELOPMENT PROSPECT, and some practical applications have been arranged.Present broad research and think that the photochemical catalyst of tool using value is TiO
2Under the exciting of light, TiO
2The valence band electronics of photochemical catalyst is excited to its conduction band, produces photohole and electronics respectively in valence band and conduction band, and these photo-generated carriers migrate to TiO
2The surface of particle is also caught by surface species (as-OH, adsorbed water and oxygen etc.), generates the active oxygen species that oxidisability is extremely strong, reactivity is very high such as hydroxyl radical free radical, and by these active oxygen species pollutant (mainly being organic pollution) is oxidized to CO
2, H
2O and simple inorganic acid reach the purpose that purifies water and air.
TiO
2Generally believed it is the photochemical catalyst of most possible large-scale application, but TiO
2The optical wavelength that photochemical catalyst can absorb is shorter than 388 nanometers, is in ultraviolet region.Sunshine medium ultraviolet light proportion lower (about about 5%), the development that therefore makes full use of the photochemical catalyst of visible light is the key of photocatalysis practical technique exploitation.Famous " Science " magazine (Science, 2001,293 (5528): 269-271) delivered about at TiO
2In nitrating the scientific paper of good visible light photoactivated effect can be arranged, also disclosed a kind of among the JP200304621 A2 by (generally at 600-800 ℃) processing TiO under the high temperature in the atmosphere of the gaseous mixture of ammonia or ammonia and nitrogen
2Make the method for the visible light photoactivated photochemical catalyst of nitrating.
The photocatalytic applications technology can briefly be divided into two big classes, the one, suspension system, soon ultra-fine (nanometer) TiO
2Photochemical catalyst is distributed in the processed water body and forms suspended state.Though a lot of efficient that studies show that suspension system is higher, because light is at TiO
2Propagation distance is extremely limited in the suspension system, in addition with superfine Ti O
2It is extremely numerous and diverse to separate removal process water after handling or the air, it is generally acknowledged that the commercial Application of this system faces big difficulty.The 2nd, fixed system, soon ultra-fine (nanometer) TiO
2Photochemical catalyst immobilized on uviol lamp, wall of reactor and various carrier material (as glass fabric, quartz sand, silica gel particle, glass plate etc.) form fixed system.In order to reach higher photocatalysis efficiency, fixed system must be optimized with regard to following parameter or performance: the effectively maximization of illumination photocatalyst surface in (1) unit volume reactor; (2) processed material and photocatalyst surface excellent contact promptly eliminated the mass transport affects of pollutant in the pending fluid (air or water) as far as possible; (3) the reasonable distribution of light in reactor; (4) being easy to industry amplifies.
Japan Patent JP 2002166176A2 loads on photochemical catalyst on the carriers such as bead that granularity is 0.3～5mm, be configured to the ring-like packed bed reactor of concentric circles that uviol lamp places interior tube hub then, the annular space narrower in width that this reactor allows is difficult to provide the scheme of amplifying application.Japan Patent JP 2001239257A2 with photocatalyst coating at the glass tube inwall, then these glass tubes are formed shell and tube reactor, in pending fluid (waste gas or the waste water) flowing pipe, the shortcoming of this class reactor is that the photochemical catalyst specific area is very low, fluid and catalyst surface to contact effect (being mass transfer) relatively poor, evenly the light source of irradiation is supplied with also existing problems.In order to solve problems such as mass transfer, Japan Patent JP 2000176469A2 and U.S. Pat 5069885A have proposed the outer wall of inner tube of ring-like reactor is designed to corrugated or helical form, perhaps in annular space, settle monoblock type helical form object to increase the turbulence of fluid, and photochemical catalyst can be loaded on the object of this class one-piece auger structure.Add one group of baffle plate that is arranged in zig-zag type in the annular space of Japan Patent JP2001029946A2 employing in ring-like reactor, be coated with photochemical catalyst on the baffle plate, to increase mass transfer and photochemical catalyst specific area.U.S. Pat 5683589A has designed a kind of comparatively complicated ring-like photo catalysis reactor of concentric tube, in annular space, settled the pyramid type rim of some inclinations, and the glass fabric that each rim is scribbled photochemical catalyst again covers, to reach bigger photochemical catalyst specific area and mass transfer effect preferably.
Summary of the invention
The objective of the invention is for overcoming the deficiency of prior art, the novel loaded photocatalyst that the patented technology (ZL 00 1 19439.9) of utilizing the main inventor of the present invention to authorize is disclosed with helical spring structure, propose to prepare visible light photoactivated photochemical catalyst, and a kind of " lamp arraying type " fills the method and apparatus of fixed bed photocatalysis water treatment and air cleaning with the method for nitrating.
The technical scheme that realizes the object of the invention comprises the steps:
The visible light photoactivated titanium dioxide optical catalyst preparation method of nitrating that the present invention proposes, utilize carbonic hydroammonium to decompose produced simultaneously water and ammonia down be heated (being preferably in 50-90 ℃), make titanium material under the controlled condition of gentleness, metatitanic acid colloidal sol, gel or precipitation that uniform hydrolysis and ammonolysis reaction generate nitrating take place simultaneously, after filming or directly filtering, be (to be preferably in 250-450 ℃) under 150-600 ℃ in nitrogen atmosphere heat treatment obtains nanometer nitrating titanium dioxide film or powder in temperature.
The method and the reactor assembly of " lamp arraying type " packed bed light-catalyzed reaction bodies for purifying fluids that the present invention proposes, adopt " row lamp " formula uviol lamp arrangement method, the uviol lamp of in reaction tube, evenly arranging, the material filling type loaded photocatalyst is filled in the mode that huddles in the gap between the tubulation of being made up of ultraviolet lamp sleeve, constitutes filling fixed-bed reactor.Maximum lamp between uviol lamp is apart from being determined by ultraviolet light permeable distance in the photochemical catalyst packed bed, uviol lamp places in the glass bushing, separate with pending fluid and photochemical catalyst, uviol lamp is built in the reactor, and ultraviolet light can both effectively be absorbed by catalyst.Uviol lamp can be formed the uviol lamp assembly by the series/parallel method at axial direction and be placed in the sleeve pipe, and reactor not only can amplify in radial direction but also can axially carry out the height amplification.Can adopt the mode of operation of multistage reactor series connection.
The present invention compared with prior art has following beneficial effect:
1. the decomposition reaction by carbonic hydroammonium is proposed, carbonic hydroammonium can be to disperse solid-state preferably or the molecular level dissolved state is distributed in whole reaction system, thereby make the hydrolysis of titanium material and ammonolysis reaction in whole system gentleness, controlled and carry out equably, and carbonic hydroammonium decompose the speed that discharges water and ammonia can be by methods such as the adding mode control of reaction temperature and temperature program(me) and carbonic hydroammonium.
2. when TiO 2 precursor such as metatitanic acid synthetic, in metatitanic acid, introduced the nitrogen element by ammonolysis reaction simultaneously, thereby required temperature when having reduced subsequent heat treatment significantly and generating nitrogenous titanium dioxide, can be under lower heat treatment temperature, obtain the mixed product titanium dioxide of Detitanium-ore-type of the nitrating of certain rutile content.
3. the titanium dioxide optical catalyst that makes is because the nitrogen event of having mixed can make full use of visible light, because heat treatment temperature is low, be easier to obtain the crystal grain of nanometer scale, and crystal grain is the duplex grain structure that contains controlled rutile content, thereby has good photocatalytic activity.
4. the present invention adopts the photocatalytic reaction device of " lamp arraying type " filling fixed bed water (gas) processing method to have following effect:
(1) adopt the loaded photocatalyst with good carrier performance, decline to a great extent for eliminating the required air capacity of mass transport affects, promptly required vapor/liquid ratio is low when water treatment.
(2) compare with pellet type catalyst, bed pressure drop reduces an order of magnitude approximately, thereby air supply and the processed required power of fluid significantly descends, and reaches the saving energy consumption, the purpose that reduces cost.
(3) because uviol lamp adopts built-in mode, all be that loaded photocatalyst is filled bed around the uviol lamp, thereby whole effective utilizations of ultraviolet luminous energy, can prevent the light pollution that ultraviolet ray leaks and causes simultaneously.
(4) owing to avoided ultraviolet ray to leak, thereby reduced enclosure material requirement, can adopt cheap materials such as common plastics, reduced the cost of device reactor assembly.
Description of drawings
Fig. 1 is the side view that lamp arraying type is filled fixed-bed reactor
Fig. 2 is the A-A profile that lamp arraying type is filled fixed-bed reactor
Fig. 3 is the Fixing shrink ring schematic diagram
The specific embodiment
Below in conjunction with embodiment the present invention is further described.The cited case does not limit protection domain of the present invention.
Embodiment 1
Carbonic hydroammonium is fully ground, with TiCl
4Be mete-wand, get 1 part of (mole) TiCl
4Under ice bath, add 6 parts of 4 parts in carbonic hydroammonium and isopropyl alcohols, dispersed with stirring is warming up to 85 ℃, constant temperature 2 hours with the speed of 2 ℃ of per minutes, then in 150 ℃ of oven dry down, after dry powder grinds, use deionized water washing by soaking 3 times, filtering drying, under nitrogen atmosphere,, grind after the cooling and obtain Powdered nitrating TiO 2-base optical catalyst 300 ℃ of heat treatments 2 hours.
Embodiment 2
Carbonic hydroammonium is fully ground, with TiCl
4Be mete-wand, get 1 part of (mole) TiCl
4Under ice bath, add 4 parts of 3 parts in carbonic hydroammonium and isopropyl alcohols, dispersed with stirring is warming up to 50 ℃, constant temperature 1.5 hours with the speed of 1 ℃ of per minute, then in 120 ℃ of oven dry down, after dry powder grinds, use deionized water washing by soaking 2 times, filtering drying, under nitrogen atmosphere,, grind after the cooling and obtain Powdered nitrating TiO 2-base optical catalyst 550 ℃ of heat treatments 1 hour.
Embodiment 3
Carbonic hydroammonium is fully ground, with TiCl
4Be mete-wand, get 1 part of (mole) TiCl
4Under ice bath, add 9 parts of 6.5 parts in carbonic hydroammonium and isopropyl alcohols, dispersed with stirring, speed with 3 ℃ of per minutes is warming up to 92 ℃, constant temperature 2 hours, in 150 ℃ of oven dry down, under nitrogen atmosphere,, grind after the cooling and obtain Powdered nitrating TiO 2-base optical catalyst then 250 ℃ of heat treatments 3 hours.
Embodiment 4
Carbonic hydroammonium is fully ground, with TiCl
4Be mete-wand, get 1 part of (mole) TiCl
4Under ice bath, add 4 parts and 6 parts isopropyl alcohols of carbonic hydroammonium, dispersed with stirring, speed with 2 ℃ of per minutes is warming up to 85 ℃, constant temperature 3 hours, obtain the colloidal sol of certain viscosity, after the cooling glass spring carrier is dropped into this colloidal sol, make fully submergence carrier of colloidal sol, the good carrier of filtration load after the dip-coating is in 150 ℃ of oven dry, after the dip-coating drying course repeats 3 times, with the carrier 3 times of load of deionized water washing by soaking and oven dry, the oven dry back 300 ℃ of heat treatments 2 hours, obtains support type nitrating TiO 2-base optical catalyst under nitrogen atmosphere.
Reference examples 1
It is 5% water slurry that the P25 titanium dioxide optical catalyst powder of German Degussa company is mixed with solid content through ultrasonic dispersion, the glass spring carrier is dropped into this slurry, make fully submergence carrier of slurry, the good carrier of filtration load after the dip-coating, in 150 ℃ of oven dry, after the dip-coating drying course repeated 3 times, the oven dry back 300 ℃ of heat treatments 2 hours, obtained the P25 loaded photocatalyst under nitrogen atmosphere.
Characterize the photocatalytic activity of sample with the conversion ratio (degradation rate) of toluene gas-phase photocatalysis reaction.Reaction tube is the Pyrex glass tube, and bore is 6 millimeters, is parallel to reaction tube and settles two 8 watts blue-black lamp (dominant wavelength 365 nanometers) or fluorescent lamp (dominant wavelength is 450 nanometers), and reaction gas is toluene and Air mixing gas, and toluene concentration is 100ppm.When the photocatalyst activity of test powders sample, loading height is 20 millimeters, and when test load type photochemical catalyst sample, loading height is 100 millimeters.Table 1 is a test result.
The test result of table 1 sample
| Sample | Particle diameter 1?(nm) | Specific area (m 2/g) | Rutile contains 2Amount (%) | Toluene degradation rate (%) | |
| The blue-black lamp | Fluorescent lamp | ||||
| Embodiment 1 | ??11 | ??138 | ?12.4 | ??86.2 | ???47.8 |
| Embodiment 2 | ??23 | ??86 | ?38.2 | ??72.6 | ???36.5 |
| Embodiment 3 | ??8 | ??186 | ?1.1 | ??75.3 | ???12.8 |
| P25 3 | ??28 | ??48 | ?18.9 | ??85.6 | ???2.3 |
| Embodiment 4 | ??/ | ??/ | ?/ | ??96.4 | ???78.2 |
| Reference examples 1 | ??/ | ??/ | ?/ | ??92.1 | ???4.5 |
1, measures with X-ray diffraction peak width broadening method.2, measure with X-ray diffraction method.3, the P25 titania powder of German Degussa company.
The relevant lamp arraying type of the present invention is filled the embodiment of fixed bed photocatalysis fluid treatment method and device, is described in detail as follows in conjunction with Fig. 1:
Present embodiment is that lamp arraying type is filled the fixed bed photocatalytic water treatment device, its structure comprises shell of reactor 1 as shown in Figure 1, and air imports and distributor pipe 2, the importing of pending water and distributor pipe 3, the photochemical catalyst packed bed supports and solution-air secondary uniform board 4, ultraviolet lamp tube 5, ultraviolet lamp sleeve 6, huddle formula loaded photocatalyst filler 7, handle back water outlet 8, exhaust outlet 9, basic composition unit such as uviol lamp power line outlet 10.
Among Fig. 1, shell of reactor body 1 is an open circles tubular structure, and its axis normal is in horizontal plane, and material can be stainless steel and plastics class.Along B-B and C-C cross section is demountable structure (as flange).Lower flange at hat covers, and air leading-in conduit and distributor pipe 2 are arranged at the bottom, and the side is provided with liquid (waste water or running water) inlet tube and distributor pipe 3.Cover (B-B section) at lower flange and settle the gripper shoe and the solution-air uniform board 4 of photochemical catalyst bed, have the location shallow slot of ultraviolet lamp sleeve on the gripper shoe.Loaded photocatalyst is filled in the mode that huddles in the space that forms between ultraviolet lamp sleeve, and the flow through filling fixed bed 7 of loaded photocatalyst of uniform solution-air fluid-mixing carries out the photocatalysis treatment process.
The sleeve pipe 6 of ultraviolet lamp tube 5 and uviol lamp is by the uniform arrangement formation of axis parallel " row lamp " structure that is in the shell of reactor cylinder shown in Figure 2.Distance between ultraviolet lamp sleeve can be determined the thickness of bed layer of the penetrable mistake of corresponding ultraviolet light according to the character (power and optical wavelength) and the loaded photocatalyst of uviol lamp.The more excellent cover tube pitch of general 2 times of conducts selecting single uviol lamp to decay to zero distance (d) substantially through ultraviolet ray behind a certain photochemical catalyst thickness of bed layer from.And can make ultraviolet ray can not be radiated shell wall substantially slightly greater than d from the distance of shell near the ultraviolet lamp sleeve of shell cylinder.The lower end of ultraviolet lamp sleeve is the state of sealing.
Water and air is flowed through behind the photochemical catalyst packed bed bed from bottom to top, and the water after the processing is discharged from leakage fluid dram 8, and leakage fluid dram 8 should be higher than the height of uviol lamp, but is lower than the height of ultraviolet lamp sleeve, guarantees that water can overflow not enter ultraviolet lamp sleeve.Air is filled water in bed and the bed with the form of bubble (bubbling) photochemical catalyst of flowing through, huddled the effect of formula loaded photocatalyst filler, make air with the micro-bubble form of the cutting apart liquid water of flowing through, play the effect of stirring water, guaranteed the mass transfer conditions that gas-liquid-solid three-phase is good.The air that overflows water body is discharged from the exhaust outlet 9 that upper flange covers, and the power supply lead wire of uviol lamp is concentrated after soft sealing in upper shed place of ultraviolet lamp sleeve and drawn from upper flange caping end 10.
On photochemical catalyst is filled fixed bed, be pressed with a plate shape fixing ring set of uviol lamp pipe box as shown in Figure 3, also can play brokenly the bubble effect and prevent may moving of photochemical catalyst bed simultaneously.
According to the concentration of pending water pollutant with to the quality requirement of discharge water, the method for two kinds of basic water treatments is arranged.First method is the flow velocity (flow) of control water, and in this method, minimum discharge (Vs) is calculated according to hydromechanical back-mixing and determined.If under minimum discharge Vs, still can not reach the quality index of discharge water, then to solve by second method, it is the method for multistage photo catalysis reactor series connection, water with the outflow of first order reactor, pump into the water inlet of second level reactor again, form the plural serial stage structure, until reaching the displacement mass requirement.
Claims (4)
1, a kind of lamp arraying type is filled the fixed bed photocatalytic reaction device, it is characterized in that adopting " row lamp " formula uviol lamp arrangement method, the uviol lamp of in reaction tube, evenly arranging, the material filling type loaded photocatalyst is filled in the mode that huddles in the gap between the tubulation of being made up of ultraviolet lamp sleeve, constitutes filling fixed-bed reactor.
2, device as claimed in claim 5, it is characterized in that the maximum lamp distance between uviol lamp is determined by ultraviolet light permeable distance in the photochemical catalyst packed bed, uviol lamp places in the glass bushing, separate with pending fluid and photochemical catalyst, uviol lamp is built in the reactor, and ultraviolet light can both effectively be absorbed by catalyst.
3, device as claimed in claim 5 is characterized in that uviol lamp can be placed in the sleeve pipe by series/parallel method composition uviol lamp assembly at axial direction, and reactor not only can amplify in radial direction but also can axially carry out the height amplification.
4, device as claimed in claim 5 is characterized in that the mode of operation that can adopt multistage reactor to connect.
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| CN 200510063617 CN1689696A (en) | 2003-09-29 | 2003-09-29 | Visible photo-activated photochemical catalyst and lamp arraying type packed bed reaction apparatus |
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| CN 200510063617 CN1689696A (en) | 2003-09-29 | 2003-09-29 | Visible photo-activated photochemical catalyst and lamp arraying type packed bed reaction apparatus |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443156C (en) * | 2006-11-24 | 2008-12-17 | 哈尔滨工业大学 | Three-phase circulating fluidized bed photochemical reactor with a plurality of light sources and Fe/inorganic carrier catalyst preparation and method for processing waste water thereby |
| CN108211784A (en) * | 2018-03-19 | 2018-06-29 | 西安建筑科技大学 | A kind of purifier of high penetration support type axial direction photocatalysis treatment pernicious gas |
| CN108698020A (en) * | 2016-01-15 | 2018-10-23 | 株式会社光触媒研究所 | Solid photocatalysts material, its manufacturing method and the processing unit formed by the solids being only made of the titanium dioxide with photo-catalysis function |
-
2003
- 2003-09-29 CN CN 200510063617 patent/CN1689696A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100443156C (en) * | 2006-11-24 | 2008-12-17 | 哈尔滨工业大学 | Three-phase circulating fluidized bed photochemical reactor with a plurality of light sources and Fe/inorganic carrier catalyst preparation and method for processing waste water thereby |
| CN108698020A (en) * | 2016-01-15 | 2018-10-23 | 株式会社光触媒研究所 | Solid photocatalysts material, its manufacturing method and the processing unit formed by the solids being only made of the titanium dioxide with photo-catalysis function |
| CN108698020B (en) * | 2016-01-15 | 2020-04-03 | 株式会社光触媒研究所 | Solid photocatalytic material comprising solid matter composed only of titanium dioxide having photocatalytic function, method for producing same, and processing apparatus |
| CN108211784A (en) * | 2018-03-19 | 2018-06-29 | 西安建筑科技大学 | A kind of purifier of high penetration support type axial direction photocatalysis treatment pernicious gas |
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