CN1698950A - Photocatalyst and its preparing process - Google Patents
Photocatalyst and its preparing process Download PDFInfo
- Publication number
- CN1698950A CN1698950A CN200510042232.4A CN200510042232A CN1698950A CN 1698950 A CN1698950 A CN 1698950A CN 200510042232 A CN200510042232 A CN 200510042232A CN 1698950 A CN1698950 A CN 1698950A
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- CN
- China
- Prior art keywords
- glass spring
- obu
- sol
- ethanol
- photochemical catalyst
- 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.)
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 9
- 238000000034 method Methods 0.000 title abstract description 11
- 239000003054 catalyst Substances 0.000 claims abstract description 36
- 239000011521 glass Substances 0.000 claims abstract description 27
- 239000002245 particle Substances 0.000 claims abstract description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 26
- 239000010936 titanium Substances 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 16
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 10
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 9
- 238000010992 reflux Methods 0.000 claims description 8
- 239000002105 nanoparticle Substances 0.000 claims description 7
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- 238000002360 preparation method Methods 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 5
- 239000000725 suspension Substances 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 229940043237 diethanolamine Drugs 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- 238000007747 plating Methods 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000007654 immersion Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- 229910010413 TiO 2 Inorganic materials 0.000 claims 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 13
- 230000004907 flux Effects 0.000 abstract description 4
- 238000000576 coating method Methods 0.000 abstract description 3
- 239000002351 wastewater Substances 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 2
- 239000000499 gel Substances 0.000 description 10
- 239000000839 emulsion Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000000967 suction filtration Methods 0.000 description 6
- 238000009413 insulation Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000004140 cleaning Methods 0.000 description 3
- 239000012065 filter cake Substances 0.000 description 3
- 230000001699 photocatalysis Effects 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 239000011324 bead Substances 0.000 description 2
- 230000009514 concussion Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 239000000985 reactive dye Substances 0.000 description 2
- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 1
- 239000006004 Quartz sand Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal salt Chemical class 0.000 description 1
Landscapes
- Catalysts (AREA)
Abstract
This invention relates to a photocatalyst used for processing organic wastewater or pollution air, in addition to a preparing method. The catalyst uses the glass spring as the carrier, coating titania photocatalyst film in the glass spring surface, wherein the film is doped with titania particles. The surface after coating has a concave-convex shape because of particles, which can increase the specific surface area of the photocatalyst; the ultraviolet light passes through the gap of the glass spring, which can increase the flux and conveying distance, and shin more titania film surface, so to increase the efficiency of the photocatalyst.
Description
Affiliated technical field
The invention belongs to photochemical catalyst manufacturing technology field, specifically a kind ofly have many optical channels, specific area is big, is used to photochemical catalyst of handling organic wastewater or dusty gas and preparation method thereof.
Background technology
At present, the research of photochemical catalyst and use existing various kinds of document report, wherein particularly active to the research of fixing phase titanic oxide catalyst.The carrier of titanium deoxide catalyst is generally selected silicate materials such as quartz sand, bead for use.During these catalyst filling reactor practical applications, because of the catalyst buildup in the light degradation bed closely knit, overwhelming majority ultraviolet light suppressed by vector stops, thereby the propagation of ultraviolet light in reactor and evenly distribution have been hindered, only form effective catalytic domain of an aspect, reduced the utilization rate of ultraviolet luminous energy.
For the research of titanium dioxide film catalyst, focus mostly at present in to mixing of noble metal loading, transition metal salt and mixing of semi-conducting material, modify research seldom for the macroscopic view on surface.And do not appear in the newspapers for the research that increases ultraviolet light flux and propagation distance aspect thereof in the photocatalytic process.In addition, fixedly the intensity of load of phase catalyst also is one of the important indicator in photochemical catalyst service life, and coming off of photocatalyst film can produce secondary pollution.
Goal of the invention
The objective of the invention is to overcome deficiency of the prior art,, effectively increase the specific area of catalyst by embedding the nm-class catalyst particle on the photocatalyst film surface; By changing the carrier of catalyst, strengthen propagation, reflection, refraction, the scattering of ultraviolet light, increase its propagation distance and luminous flux, improve photocatalysis efficiency on the whole; By changing film plating process, increase the intensity of load of catalyst, reach the purpose that reduces secondary pollution.
Summary of the invention
The present invention is achieved in that this photochemical catalyst is carrier with the glass spring, contains the photocatalyst film of Nano titanium dioxide particulate in the plating of glass spring surface.During plated film, mix prefabricated nanoscale titanium hydroxide particle in sol-gel solution, the glass spring surface behind the plated film is owing to the embedding that nanoparticle is arranged has formed male and fomale(M﹠F).The existence of male and fomale(M﹠F) can effectively increase the specific area of photochemical catalyst; Coating process adopts czochralski method, and repeated multiple times is invaded, slowly pulled out, dries, the catalyst cupport intensity height that this explained hereafter goes out, difficult drop-off.This catalyst adds uncoated glass spring in use more by a certain percentage, the internal voids during in order to increase catalytic bed glazing catalyst buildup.Ultraviolet light is by the space of glass spring, can effectively improve the ultraviolet light flux and transmit distance, makes more titanium dioxide film surface in the photocatalytic degradation bed be subjected to the irradiation of light, improves the efficient of photocatalytic degradation pollutant.
Photochemical catalyst preparation method step provided by the present invention is as follows:
(1) gets a certain amount of Ti (OBu)
4(butyl titanate) joins in 4 times of volume of ethanol and stirs, and adds Ti (OBu)
425%～35% diethanol amine of volume adds low amounts of water after stirring 2h, stir 15min after, add Ti (OBu) again
45%～10% dimethyl formamide of volume stirs evenly, and it is standby to leave standstill 24h.A certain amount of polyethylene glycol is joined in the ethanol of about 25 times (mass/volume) and be dissolved into colloidal sol, join above-mentioned leaving standstill in the solution again, stirring becomes sol-gel.(2) in the container of reflux is arranged with a certain amount of Ti (OBu)
4Mix wiring solution-forming with 2～5 times of volume of ethanol, under the powerful stirring of agitator, slowly add deionized water, add suitable Ti (OBu) again
435～45 times of n-butanols of volume are heated to about 117 ℃, move into porcelain dish behind the backflow 5min, 80～90 ℃ of oven dry, grind to form nanoscale Ti (OH)
4Powder is standby.
(3) glass spring is cleaned with ultrasonic cleaner after, again with deionized water, ethanol clean up repeatedly, dry for standby.
(4) with nanoscale Ti (OH)
4Powder and sol-gel are in 0.4～3.2: 1 (grams per liter) ratio is mixed, and the powerful 30min that stirs makes the sol-gel suspension that contains nano particle.
(5) the glass spring immersion is contained in the sol-gel suspension of nano particle,, adopt czochralski method that glass spring is pulled out with the speed of 0.5～2mm/s, 75～95 ℃ of oven dry, immerse again, lift, dry and repeat repeatedly, be warming up to 450～550 ℃, insulation 2～3h with 3～5 ℃/min speed.
Effective effect:
(1) with the glass spring being carrier, can effectively improving the irradiated area of ultraviolet light in catalytic bed, is that carrier institute controlling catalyst is compared with bead, can improve more than 4 times.
(2) photochemical catalyst that adds nano particle is compared with the photochemical catalyst that does not add nano particle, and photocatalysis efficiency improves 9.7%.
(3) when catalyst be 400g, handling pH is 3.0, reactive dye concentration is the wastewater flow rate 3L of 20mg/L, when about 50 ℃ of temperature, flow velocity 5ml/s, the photocatalytic degradation rate of 3 hours reactive dye can reach 94.7%, the COD clearance can reach 80.7%.
(4) czochralski method is fired titanium dioxide film and is made film intensity of load height than infusion process, and the wear rate of 24 hours catalyst is 0.01%～1.37% in ebullated bed.
Embodiment
Embodiment 1
1. a 800ml beaker is placed on the magnetic stirring apparatus, add 400mL ethanol, stir adding 100mL Ti (OBu) down
4And the 28.8mL diethanol amine, behind the stirring 2h, in the mixed liquor adding reaction system with 10.5mL deionized water and 80mL ethanol, continue to stir after 15 minutes, add 7mL N again, dinethylformamide is made intermediate solution, leaves standstill 24 hours.With the 1.8g molecular weight is that 1500 poly-7 glycol join in the intermediate solution, makes sol-gel solution.
2. a 500mL beaker is placed on the magnetic stirring apparatus, stir adding 100mL ethanol and 20mL Ti (OBu) down
4After 5 minutes, under stirring, brute force slowly adds the 200mL deionized water.Form white emulsion.With this emulsion suction filtration, the gained filter cake changes in the 1000mL round-bottomed flask that reflux is housed, and adds the 400mL n-butanol, be heated to about 117 ℃ refluxed 5 minutes after, take out product, the suction filtration product is at 80 ℃ of baking 24h, grind, make the Ti that diameter is 20～40 nanometers (OH)
4Powder is standby.
3. be that 2mm, d are 0.5mm, H with D
0For the glass spring 400g of 10mm puts into after the ultrasonic concussion of the ultrasonic cleaner that the 1000mL deionized water is housed cleans 3 minutes, respectively wash 3 times with deionized water, ethanol again.85 ℃ of dry for standby.
4. with 0.8g nanoscale Ti (OH)
4Powder joins in the 500mL sol-gel solution, and powerful the stirring 30 minutes made mixed liquor.
5. the glass spring after will cleaning is worn bunchiness and is immersed in the mixed liquor, with pulling machine is that the czochralski method of 0.5mm/s is pulled out glass spring with speed, 75 ℃ of baking 30min, repeat 4 times, in muffle furnace, be warming up to 450 ℃ with 3 ℃/minute, obtaining photochemical catalyst behind the insulation 2.5h, is 0.132mg/g through testing its load capacity, and wear rate is 0.02%.
Embodiment 2
With embodiment 1 in the identical step of the first step prepare sol-gel.
2. a 500mL beaker is placed on the magnetic stirring apparatus, stir adding 100mL ethanol and 20mL Ti (OBu) down
4After 5 minutes, under stirring, brute force slowly adds the 200mL deionized water.Form white emulsion.With this emulsion suction filtration, the gained filter cake changes in the 1000mL round-bottomed flask that reflux is housed, and adds the 400mL n-butanol, adds hot reflux after 5 minutes, takes out product, and the suction filtration product grinds at 80 ℃ of baking 24h, makes the Ti that length is 40～60 nanometers (OH)
4Powder is standby.
3. in 500 milliliters of sol-gels, add 0.4g nanoscale Ti (OH)
4Powder, the powerful stirring 30 minutes made mixed liquor.
4. be that 4mm, d are that 1mm, H0 are that the glass spring 400g of 20mm puts into the ultrasonic cleaner that the 1000ml deionized water is housed with D, ultrasonic oscillation cleaned after 3 minutes, respectively washed 2 times with deionized water, ethanol again.85 ± 2 ℃ of dry for standby.
5. the glass spring after will cleaning immerses in the mixed liquor, glass spring is pulled out with the czochralski method of speed 1mm/s with pulling machine, dries 30 minutes for 85 ± 2 ℃, repeats 4 times, is warming up to about 500 ℃ insulation 3h in muffle furnace with 5 ℃/min.Obtain catalyst I I, its load capacity is 0.107mg/g, and wear rate is 0.1%.
Embodiment 3
With embodiment 1 in the first step. the sol-gel of identical preparation method preparation.
2. a 500mL beaker is placed on the magnetic stirring apparatus, stir adding 100mL ethanol and 20mL Ti (OBu) down
4After 5 minutes, under stirring, brute force slowly adds the 200mL deionized water.Form white emulsion.With this emulsion suction filtration, the gained filter cake changes in the 1000mL round-bottomed flask that reflux is housed, and adds the 400mL n-butanol, adds hot reflux after 5 minutes, takes out product, and the suction filtration product grinds at 85 ℃ of baking 24h, makes the Ti that length is 60～80 nanometers (OH)
4Powder is standby.
3.500 in the milliliter, add 1.6g nanoscale Ti (OH)
4Powder, the powerful stirring 30 minutes made mixed liquor.
4. be that 10mm, d are that 2mm, H0 are that the glass spring 400g of 30mm puts into the ultrasonic cleaner that the 1000ml deionized water is housed with D, ultrasonic concussion was cleaned after 3 minutes, respectively washed 3 times with deionized water, ethanol again.85+2 ℃ of dry for standby.
5. the glass spring after will cleaning immerses mixed liquor I IIA, glass spring is pulled out with the czochralski method of speed 2mm/s with pulling machine, and oven dry is 30 minutes about 90 ± 2 ℃, repeats 4 times, is warming up to about 550 ℃ insulation 2h in muffle furnace with 3 ℃/min.Obtain catalyst I II, its load capacity 0.323mg/g, wear rate are 1.37%.
Claims (5)
1. fixing phase TiO
2Photochemical catalyst is characterized in that this catalyst is carrier with the glass spring, at glass spring surface plating TiO
2Photocatalyst film is doped with the Nano titanium dioxide particulate in the plated film, film surface concave-convex surface under microstate.
2. photochemical catalyst according to claim 1, the glass spring material diameter d that carrier uses is 0.5～2mm, mean diameter of coil D is 2～10mm, spring free height H
0Be 10～30mm.
3. photochemical catalyst according to claim 1, contained TiO 2 particles is 20～80nm in the plated film.
4. photochemical catalyst according to claim 1, contained TiO 2 particles is 40～70nm in the plated film.
5. the preparation method of a photochemical catalyst:
(1) gets a certain amount of Ti (OBu)
4(butyl titanate) joins in 4 times of volume of ethanol and stirs, and adds Ti (OBu)
425%～35% diethanol amine of volume stirs and adds low amounts of water after 2 hours, stirs 15 minutes, adds Ti (OBu) again
45%～10% dimethyl formamide of volume stirs evenly, leave standstill 24 hours standby.Again a certain amount of polyethylene glycol is joined and be dissolved into colloidal sol in the ethanol, join above-mentioned leaving standstill in the solution, stir into sol-gel.
(2) in the container of reflux is arranged with a certain amount of Ti (OBu)
4Mix wiring solution-forming with 1～5 times of volume of ethanol, under the powerful stirring of agitator, slowly add deionized water, add suitable Ti (OBu) again
435～45 times n-butanol of volume is heated to 117 ℃, refluxes and moves into porcelain dish after 5 minutes, 80～90 ℃ of oven dry, grinds to form nanoscale Ti (OH)
4Powder is standby.
(3) glass spring is cleaned with ultrasonic cleaner after, again with deionized water, ethanol clean up, dry for standby.
(4) with nanoscale Ti (OH)
4Powder and sol-gel are in 0.4～3.2: 1 (grams per liter) ratio is mixed, and the powerful 30min that stirs makes the sol-gel suspension that contains nano particle.
(5) the glass spring immersion is contained in the sol-gel suspension of nano particle, speed with 0.5～2mm/s, slowly glass spring is pulled out, under 75～95 ℃ of temperature, dry, immerse again, lift, dry and repeat repeatedly, be warming up to about 450～550 ℃ with 3～7 ℃/min speed, be incubated 2～[3 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100422324A CN100342964C (en) | 2005-04-01 | 2005-04-01 | Photocatalyst and its preparing process |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005100422324A CN100342964C (en) | 2005-04-01 | 2005-04-01 | Photocatalyst and its preparing process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1698950A true CN1698950A (en) | 2005-11-23 |
| CN100342964C CN100342964C (en) | 2007-10-17 |
Family
ID=35475298
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005100422324A Expired - Fee Related CN100342964C (en) | 2005-04-01 | 2005-04-01 | Photocatalyst and its preparing process |
Country Status (1)
| Country | Link |
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| CN (1) | CN100342964C (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106940047A (en) * | 2015-12-29 | 2017-07-11 | 青岛道空优科技有限公司 | A kind of gas purification reforming unit |
| CN107008241A (en) * | 2017-04-28 | 2017-08-04 | 杨林 | A kind of preparation method of high-strength light catalytic film |
| CN113562803A (en) * | 2021-08-06 | 2021-10-29 | 河海大学 | Organic sewage treatment device and treatment method thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5069885A (en) * | 1990-04-23 | 1991-12-03 | Ritchie David G | Photocatalytic fluid purification apparatus having helical nontransparent substrate |
| CN1112237C (en) * | 2000-07-11 | 2003-06-25 | 上海维来现代科技发展有限公司 | Supported optical catalyst |
| KR200314844Y1 (en) * | 2003-02-21 | 2003-05-27 | 심종섭 | The air sterilization and purification system with the ozone and photocatalyst combination decomposer |
| CN1214863C (en) * | 2003-09-29 | 2005-08-17 | 华东理工大学 | Visible photoactivating photo catalyst and light-column type packed bed reaction unit |
-
2005
- 2005-04-01 CN CNB2005100422324A patent/CN100342964C/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106940047A (en) * | 2015-12-29 | 2017-07-11 | 青岛道空优科技有限公司 | A kind of gas purification reforming unit |
| CN107008241A (en) * | 2017-04-28 | 2017-08-04 | 杨林 | A kind of preparation method of high-strength light catalytic film |
| CN113562803A (en) * | 2021-08-06 | 2021-10-29 | 河海大学 | Organic sewage treatment device and treatment method thereof |
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| Publication number | Publication date |
|---|---|
| CN100342964C (en) | 2007-10-17 |
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Assignee: Shandong Qilu Petrochemical Engineering Co. Ltd. Assignor: Qingdao University of Science & Technology Contract fulfillment period: 2008.11.17 to 2018.11.16 contract change Contract record no.: 2008370000213 Denomination of invention: Photocatalyst and its preparing process Granted publication date: 20071017 License type: Exclusive license Record date: 20081222 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.11.17 TO 2018.11.16; CHANGE OF CONTRACT Name of requester: SHANDONG QILU PETROCHEMICAL ENGINEERING CO., LTD. Effective date: 20081222 |
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