CN105478118A - Cu-TiO2 nanorod catalyst and preparing method and application thereof in sewage wet oxidation - Google Patents
Cu-TiO2 nanorod catalyst and preparing method and application thereof in sewage wet oxidation Download PDFInfo
- Publication number
- CN105478118A CN105478118A CN201510989562.8A CN201510989562A CN105478118A CN 105478118 A CN105478118 A CN 105478118A CN 201510989562 A CN201510989562 A CN 201510989562A CN 105478118 A CN105478118 A CN 105478118A
- Authority
- CN
- China
- Prior art keywords
- catalyst
- tio
- preparation
- carrier
- application
- 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
- 239000003054 catalyst Substances 0.000 title claims abstract description 74
- 239000002073 nanorod Substances 0.000 title claims abstract description 17
- 238000000034 method Methods 0.000 title abstract description 21
- 238000009279 wet oxidation reaction Methods 0.000 title abstract description 10
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title abstract 6
- 239000010865 sewage Substances 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- 239000002245 particle Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 5
- 239000002184 metal Substances 0.000 claims abstract description 5
- 238000001556 precipitation Methods 0.000 claims abstract description 4
- 239000010949 copper Substances 0.000 claims description 53
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 23
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 15
- 229910052802 copper Inorganic materials 0.000 claims description 15
- 238000002360 preparation method Methods 0.000 claims description 15
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 230000003197 catalytic effect Effects 0.000 claims description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 8
- 235000010299 hexamethylene tetramine Nutrition 0.000 claims description 8
- 239000004312 hexamethylene tetramine Substances 0.000 claims description 8
- 238000007254 oxidation reaction Methods 0.000 claims description 8
- 239000001301 oxygen Substances 0.000 claims description 8
- 229910052760 oxygen Inorganic materials 0.000 claims description 8
- 238000005516 engineering process Methods 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 150000001879 copper Chemical class 0.000 claims description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 6
- 229910001220 stainless steel Inorganic materials 0.000 claims description 6
- 239000010935 stainless steel Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 230000015572 biosynthetic process Effects 0.000 claims description 3
- 239000010842 industrial wastewater Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 238000003786 synthesis reaction Methods 0.000 claims description 3
- 238000004065 wastewater treatment Methods 0.000 claims description 3
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 238000003672 processing method Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000005855 radiation Effects 0.000 claims 1
- 238000000967 suction filtration Methods 0.000 claims 1
- 238000010438 heat treatment Methods 0.000 abstract description 8
- 230000008901 benefit Effects 0.000 abstract description 4
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 230000035484 reaction time Effects 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract description 2
- 238000004904 shortening Methods 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 9
- 230000000694 effects Effects 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000002351 wastewater Substances 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000001914 filtration Methods 0.000 description 5
- 238000004062 sedimentation Methods 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- -1 hydroxyl radical free radical Chemical class 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000009849 deactivation Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000010815 organic waste Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000013112 stability test Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000009647 facial growth Effects 0.000 description 1
- 230000012010 growth Effects 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 238000003911 water pollution Methods 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/727—Treatment of water, waste water, or sewage by oxidation using pure oxygen or oxygen rich gas
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a Cu-TiO2 nanorod catalyst and a preparing method and application thereof in sewage wet oxidation. The catalyst takes Cu as an active component and TiO2 as a carrier; the content of the active component in the catalyst is 10-15wt%; the TiO2 carrier in the catalyst has a uniform nanorod morphology, has a diameter of 80-120nm and a length of 400-600nm; active metal Cu is uniformly dispersed at the surface of the carrier and a Cu particle size is 8-15nm. The catalyst is high in reactivity and stability and not easily deactivated. The catalyst is prepared by adopting a microwave auxiliary homogeneous precipitation method. The method is low in energy consumption, a microwave technique belongs to body heating, and has the advantages of uniform heating of a reaction system, promotion to collision probability among reacting molecules, shortening of reaction time, low reaction temperature and less consumed energy compared with a conventional heating method.
Description
Technical field
The present invention relates to a kind of Cu/TiO
2nanorods Catalyst and preparation method thereof and the application in waste water wet oxidation; Belong to catalytic chemistry and ambient water process field.
Background technology
In industrial wastewater, some is the high concentrated organic wastewater of difficult degradation, and such waste component is complicated, poisonous and harmful hardly degraded organic substance content is high, is the Focal point and difficult point of water pollution control.High concentration hard-degraded organic waste water treatment technology processes mainly through chemical oxidization method at present, generally comprises the form such as coupling of ozone oxidation, photochemical catalytic oxidation, catalytic oxidation, wet oxidation, Fenton reagent oxidation, supercritical water oxidation and several method.Wherein CWO technology (CWAO) have that treatment effeciency is high, reaction speed is fast, plant area is little, applied widely, recyclable resource and the advantage such as secondary pollution is low, therefore CWAO is one of extremely promising technology of process high concentration hard-degraded organic waste water, both meet national related industry policy, also meet the demand of future market.
CWO process waste water catalyst used can be divided into noble metal and non-precious metal catalyst.Base metal copper-based catalysts, becomes domestic and international study hotspot with its high activity, low cost.But copper-based catalysts active component Cu under the hydrothermal reaction condition of harshness easily runs off, and causes rapid catalyst deactivation, it is the bottleneck problem suppressing its extensive use.Build design efficient stable copper-based catalysts, suppress the loss of Cu component and the generation of catalyst surface carbon distribution in course of reaction, have important promotion meaning to the exploitation of catalytic wet oxidation catalyst, the sciences problems wherein contained is worth us to further investigate.
Recent nanometer material science research proves that the catalytic performance of nanocatalyst not only affects by dimensional effect, and the pattern also with catalyst is closely related.The crystal face that the different nano-material surface of pattern preferentially exposes is different, can marked change be there is in the atom composition on surface, coordination mode, electronic structure, therefore the ability of absorption and activated reactant can difference to some extent, cause different catalytic perfomances, the pattern effect (being in fact the preferentially orienting effect of nanometer crystal face) namely in nano-catalytic.Based on mechanism of crystal growth in solution, can Effective Regulation crystal morphology from the different crystal face growth rate of dynamic (dynamical) angle modulation, the given activity crystal face of selective exposure nanocatalyst, Atomic Arrangement and the coordination environment of these exposure crystal faces have high level of homogeneity, not only be conducive to improving active site density and regulation and control catalytic reaction path, also contribute to setting up clear and definite catalyst structure-effect relationship.Catalysis material controlledly synthesis under nanoscale and be the key issue of nano-catalytic to the understanding of structure-effect relationship under its actual response atmosphere.Traditional hydro-thermal, solvent heat technology can by selecting presoma, and utilize ion slow release preparation and structure directing agent etc., accurate modulation preparation parameter, obtains the solid catalyst of morphology controllable to a certain extent.Utilize microwave technology to synthesize specific morphology catalyst compared with conventional heating techniques, heating using microwave speed is fast, homogeneous heating, efficient energy-saving, equipment are simple, be easy to control.
Research both at home and abroad for special appearance catalytic wet oxidation catalyst rarely has bibliographical information, and specific morphology copper-based catalysts is applied to Catalytic Wet Air Oxidation for Wastewater field and has no patent report.
Summary of the invention
The present invention adopts microwave thermal solution to synthesize the homogeneous Cu/TiO of pattern
2nanometer rods, by changing catalyst pattern quantitative design and preferential exposure high activity crystal face, and then improving the superficial density in activated centre, improving the ability that catalyst activation oxygen produces hydroxyl radical free radical; Strong interaction between Metal-Support is conducive to the loss suppressing copper component under hydrothermal reaction condition.This catalyst application is in the wet oxidation reaction system of model pollutant phenol simultaneously, shows high activity, high stability.
The invention provides a kind of Cu/TiO
2catalyst take copper as active component, TiO
2for carrier; In catalyst, active component content is 10 ~ 15wt%; TiO in catalyst
2carrier has homogeneous nanometer rods pattern, diameter 80 ~ 120nm, length 400 ~ 600nm; Active metal copper is dispersed in carrier surface, copper particle particle diameter 8 ~ 15nm.
The invention provides above-mentioned Cu/TiO
2the preparation method of catalyst, is dissolved in the glycol water of 10 ~ 20wt% by soluble copper salt, butyl titanate, hexamethylenetetramine under room temperature condition; Under inert atmosphere (nitrogen, helium, argon gas), in microwave reactor, power 200 ~ 300W reacts 10 ~ 15 minutes; Preferred 300W reacts 15 minutes; Be down to room temperature, sedimentation and filtration, with the deionized water washing of heat, at 80 ~ 120 DEG C dry 10 ~ 16 hours, at 400 ~ 600 DEG C in Muffle furnace roasting 4 ~ 8h, obtain Cu/TiO
2nanorods Catalyst.
Further, in technique scheme, preferably at 90 DEG C dry 12 hours, at 500 DEG C in Muffle furnace roasting 4h.
Further, in technique scheme, described soluble copper salt is selected from Cu (NO
3)
2, CuCl
2, CuSO
4deng.
Further, in technique scheme, the mass ratio of soluble copper salt, butyl titanate, hexamethylenetetramine is 0.1 ~ 0.6:11 ~ 15:5 ~ 15; Preferred 0.1:11:5.
The invention provides above-mentioned Cu/TiO
2the application of catalyst in Industrial Wastewater Treatment phenol.
Further, in above-mentioned application, processing method is catalytic wet air oxidation.
Further, in above-mentioned application, catalyst and the solution containing phenol are added in batch (-type) stainless steel autoclave, fills oxygen to 2 ~ 4MPa, under stirring, be heated to 170 ~ 250 DEG C, reaction 20 ~ 180min.
Further, in above-mentioned application, in the solution of phenol, COD content is less than 30000mg/L; Catalyst amount and phenol mass ratio are 0.1 ~ 0.5:5 ~ 30.Preferred 0.1:5.
Have particular application as Cu/TiO
2nanorods Catalyst is applied in the wet oxidation reaction of waste water model pollutant phenol.0.1 ~ 0.5 catalyst and 5 ~ 30mL phenol solution (COD:10000 ~ 30000mg/L) are added in stainless steel autoclave, after oxygen is repeatedly replaced, fill oxygen to 2 ~ 4MPa, 170 ~ 250 DEG C are heated to, reaction 20 ~ 180min under magnetic agitation (rotating speed 300 ~ 800r/min).
This catalyst preparing and be applied to tool in phenol wet oxidation reaction and have the following advantages:
(1) energy consumption is low: microwave technology belongs to body heating, has that reaction system is heated evenly, the advantage such as promote the collision probability between reaction molecular, Reaction time shorten, reaction temperature low consumption energy less compared with conventional heating methods.
(2) reactivity and stability high, unsuitable inactivation: TiO
2nanometer rods preferentially exposes high activity crystal face, improves surface-active bit density, is conducive to the generation of active specy hydroxyl radical free radical (OH); Strong interaction between Metal-Support is conducive to the loss suppressing Cu component in hydrothermal reaction process, strengthens catalyst stability.This catalyst stability test result as shown in Figure 3.Analyze known from Fig. 3: Cu/TiO
2after Nanorods Catalyst recycles five times, COD clearance does not obviously reduce.
By the Cu/TiO of preparation
2cu/TiO prepared by Nanorods Catalyst and ordinary precipitation process
2nano-particle catalyst contrasts.0.1g catalyst, 5mL phenol solution join in 50mL batch (-type) stainless steel cauldron as can be seen from Figure 2,3MPa oxygen pressure, and after 190 DEG C of reaction 100min, result is as follows: common Cu/TiO
2cOD clearance 75% under nano particle catalysis condition, and adopt Cu/TiO
2nanorods Catalyst COD clearance 99%.
Accompanying drawing explanation
Fig. 1 is Cu/TiO prepared by embodiment 1
2nanorods Catalyst TEM schemes.TiO can be found out in figure
2particle diameter about 100nm, about length 500nm.Active metal copper is dispersed in carrier surface, copper particle particle diameter 8 ~ 15nm.
Fig. 2 Cu/TiO
2nanorods Catalyst and common Cu/TiO
2phenol solution COD clearance contrast on nano-particle catalyst.
Fig. 3 Cu/TiO
2nanorods Catalyst stability test result.After catalyst circulation uses five times, COD clearance does not obviously reduce.
Detailed description of the invention
Below in conjunction with drawings and the embodiments, the present invention is further detailed explanation:
The inventive method: by 0.1 ~ 0.6gCu (NO under room temperature condition
3)
2, 11 ~ 15g butyl titanate and 5 ~ 15g hexamethylenetetramine are dissolved in the glycol water of 10 ~ 20wt%.Under nitrogen atmosphere, in microwave reactor, power 200 ~ 300W reacts 10 ~ 15 minutes.Be down to room temperature, sedimentation and filtration, with the deionized water washing of heat, at 90 DEG C dry 12 hours, at 400 ~ 600 DEG C in Muffle furnace roasting 4h.Synthesis Cu/TiO
2nanorods Catalyst.
Art methods: by 0.1 ~ 0.6gCu (NO under room temperature condition
3)
2, 11 ~ 15g butyl titanate and 5 ~ 15g hexamethylenetetramine are dissolved in the glycol water of 10 ~ 20wt%.Under nitrogen atmosphere, 90 DEG C of magnetic agitation 1 ~ 3h, sedimentation and filtration, with the deionized water washing of heat, at 90 DEG C dry 12 hours, at 400 ~ 600 DEG C in Muffle furnace roasting 4 ~ 8h.Synthesize common Cu/TiO
2nano-particle catalyst.
Embodiment 1
Under magnetic agitation (mixing speed 600r/min), by 0.1gCu (NO
3)
2, 11g butyl titanate and 5g hexamethylenetetramine are dissolved in the glycol water of 10wt%.Under nitrogen atmosphere, in microwave reactor, power 300W reacts 10 minutes.Be down to room temperature, sedimentation and filtration, with the deionized water washing of heat, at 90 DEG C dry 12 hours, at 500 DEG C in Muffle furnace roasting 4h, obtained Cu/TiO
2nanorods Catalyst.By the Cu/TiO after preparation
2catalyst carries out TEM sign.As can be seen from Figure 1: carrier TiO
2particle diameter 80 ~ 120nm, length about 400 ~ 600nm.Active metal copper is dispersed in carrier surface, copper particle particle diameter 8 ~ 15nm.
Get 0.1g catalyst, 5mL phenol solution joins in 50mL batch (-type) stainless steel autoclave; 3MPa oxygen pressure, after 190 DEG C of reaction 100min, reactant liquor is centrifugal, COD clearance 99%.
Comparative example 1
Under magnetic agitation (mixing speed 600r/min), by 0.1gCu (NO under room temperature condition
3)
2, 11g butyl titanate and 5g hexamethylenetetramine are dissolved in the glycol water of 10wt%.Under nitrogen atmosphere, 90 DEG C of magnetic agitation 2h, sedimentation and filtration, with the deionized water washing of heat, at 90 DEG C dry 12 hours, at 500 DEG C in Muffle furnace roasting 4h, obtained common Cu/TiO
2nano-particle catalyst.
Get 0.1g catalyst, 5mL phenol solution joins in 50mL batch (-type) stainless steel autoclave; 3MPa oxygen pressure, after 190 DEG C of reaction 100min, reactant liquor is centrifugal, COD clearance 75%.
The common Cu/TiO of comparative example 1 preparation as can be seen from Figure 2
2cOD clearance 75% under nano particle catalysis condition, and adopt Cu/TiO prepared by embodiment 1
2nanorods Catalyst COD clearance 99%.
Catalyst stability is tested
The preparation of catalyst is with the catalyst in embodiment 1.Reaction terminates rear centrifugation, and gained catalyst is dry, rejoins secondary response in reactor.Circulation like this five times.The results are shown in Figure 3, COD clearance and keep constant, Cu/TiO
2nanorods Catalyst is without deactivation phenomenom.
Claims (10)
1. a Cu/TiO
2catalyst, is characterized in that: take copper as active component, TiO
2for carrier; In catalyst, active component content is 10 ~ 15wt%; TiO in catalyst
2carrier has homogeneous nanometer rods pattern, diameter 80 ~ 120nm, length 400 ~ 600nm; Active metal copper is dispersed in carrier surface, copper particle particle diameter 8 ~ 15nm.
2. Cu/TiO according to claim 1
2catalyst, is characterized in that: described catalyst adopts the preparation of microwave radiation technology sluggish precipitation.
3. Cu/TiO as claimed in claim 1 or 2
2the preparation method of catalyst, is characterized in that: be dissolved in the glycol water of 10 ~ 20wt% by soluble copper salt, butyl titanate, hexamethylenetetramine under room temperature condition; Under inert atmosphere, in microwave reactor, power 200 ~ 300W reacts 10 ~ 15 minutes; Be down to room temperature, precipitation suction filtration, washing, drying, roasting, synthesis Cu/TiO
2nanorods Catalyst.
4. Cu/TiO according to claim 1 or 2
2the preparation method of catalyst, is characterized in that: described inert atmosphere is nitrogen, helium, argon gas; Described drying is at 80 ~ 120 DEG C dry 10 ~ 16 hours.
5. Cu/TiO according to claim 1 or 2
2the preparation method of catalyst, is characterized in that: described roasting is at 400 ~ 600 DEG C of not kiln roasting 4 ~ 8h that get down from horse.
6. Cu/TiO according to claim 1 or 2
2the preparation method of catalyst, is characterized in that: described soluble copper salt is selected from Cu (NO
3)
2, CuCl
2, CuSO
4.
7. Cu/TiO according to claim 1 or 2
2the preparation method of catalyst, is characterized in that: the mass ratio of soluble copper salt, butyl titanate, hexamethylenetetramine is 0.1 ~ 0.6:11 ~ 15:5 ~ 15.
8. Cu/TiO described in claim 1 or 2
2the application of catalyst in Industrial Wastewater Treatment phenol.
9. application according to claim 8, is characterized in that: processing method is catalytic wet air oxidation.
10. application according to claim 9, is characterized in that: catalyst and the solution containing phenol are added in batch (-type) stainless steel autoclave, fill oxygen to 2 ~ 4MPa, be heated to 170 ~ 250 DEG C under stirring, reaction 20 ~ 180min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510989562.8A CN105478118B (en) | 2015-12-24 | 2015-12-24 | A kind of Cu/TiO2Nanorods Catalyst and preparation method thereof and the application in waste water wet oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510989562.8A CN105478118B (en) | 2015-12-24 | 2015-12-24 | A kind of Cu/TiO2Nanorods Catalyst and preparation method thereof and the application in waste water wet oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105478118A true CN105478118A (en) | 2016-04-13 |
| CN105478118B CN105478118B (en) | 2017-12-29 |
Family
ID=55665600
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510989562.8A Active CN105478118B (en) | 2015-12-24 | 2015-12-24 | A kind of Cu/TiO2Nanorods Catalyst and preparation method thereof and the application in waste water wet oxidation |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105478118B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105923854A (en) * | 2016-06-08 | 2016-09-07 | 浙江奇彩环境科技股份有限公司 | Treatment method of high-strength organic wastewater |
| CN105921149A (en) * | 2016-05-12 | 2016-09-07 | 岭南师范学院 | Method for solvothermal preparation of copper modified titanium dioxide nanorod |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003251195A (en) * | 2002-03-01 | 2003-09-09 | Tayca Corp | Titanium oxide photocatalyst having excellent nitrogen oxide removing capacity |
| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
| CN103272592A (en) * | 2013-05-08 | 2013-09-04 | 陕西科技大学 | Preparation method of one-dimensional silver-loaded titanium dioxide nanorod photocatalyst |
| CN104923216A (en) * | 2015-06-25 | 2015-09-23 | 青岛科技大学 | Precious metal loaded TiO2 nanorod photocatalyst preparation method |
-
2015
- 2015-12-24 CN CN201510989562.8A patent/CN105478118B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2003251195A (en) * | 2002-03-01 | 2003-09-09 | Tayca Corp | Titanium oxide photocatalyst having excellent nitrogen oxide removing capacity |
| CN101219371A (en) * | 2007-01-08 | 2008-07-16 | 北京化工大学 | Photocatalysis oxidation treated high concentration organic trade waste |
| CN103272592A (en) * | 2013-05-08 | 2013-09-04 | 陕西科技大学 | Preparation method of one-dimensional silver-loaded titanium dioxide nanorod photocatalyst |
| CN104923216A (en) * | 2015-06-25 | 2015-09-23 | 青岛科技大学 | Precious metal loaded TiO2 nanorod photocatalyst preparation method |
Non-Patent Citations (2)
| Title |
|---|
| A. KATHALINGAM ET AL: "Synthesis of multi-linked ZnO rods by microwave heating", 《CRYST. RES. TECHNOL.》 * |
| LI-FEN CHIANG ET AL: "Cu–TiO2 nanorods with enhanced ultraviolet- and visible-light photoactivity for bisphenol A degradation", 《 JOURNAL OF HAZARDOUS MATERIALS》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105921149A (en) * | 2016-05-12 | 2016-09-07 | 岭南师范学院 | Method for solvothermal preparation of copper modified titanium dioxide nanorod |
| CN105921149B (en) * | 2016-05-12 | 2018-03-02 | 岭南师范学院 | A kind of method of solvent hot preparation copper modified titanic oxide nanometer rods |
| CN105923854A (en) * | 2016-06-08 | 2016-09-07 | 浙江奇彩环境科技股份有限公司 | Treatment method of high-strength organic wastewater |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105478118B (en) | 2017-12-29 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104028272B (en) | Graphene-supported copper-nickel compound nanometer photocatalyst, preparation method and application | |
| CN105664979B (en) | A kind of mesoporous nano microspheroidal Ln-Bi5O7I photochemical catalysts and preparation method thereof | |
| CN107008326A (en) | A kind of carbon quantum dot loads the preparation method of the efficient out-phase class fenton catalyst of iron-based material | |
| CN107252685A (en) | A kind of hydroxyl aminated compounds functional magnetic graphene oxide catalysis material and its preparation method and application | |
| CN107029786A (en) | A kind of magnetic composite photocatalyst Ppy@CdS/ZnFe2O4And its production and use | |
| Liu et al. | Nitrogen doped Cu/Fe@ PC derived from metal organic frameworks for activating peroxymonosulfate to degrade Rhodamine B | |
| CN113877599A (en) | Cobalt-manganese spinel material and preparation method and application thereof | |
| CN106694044A (en) | Preparation method of carbon nitride/silver/Cu-BTC optical catalyst | |
| CN103084195B (en) | Preparation method of (BiO)2CO3 nanosheet photocatalyst | |
| CN105478118A (en) | Cu-TiO2 nanorod catalyst and preparing method and application thereof in sewage wet oxidation | |
| CN115445620B (en) | Preparation method and application of leaf-based biochar supported cobalt-nickel binary metal catalyst | |
| CN105498780A (en) | Cu/ZnO catalyst, preparation method thereof and application thereof to CO2 chemical conversion | |
| CN104549269B (en) | Ultrasonic wave added photoreduction met hod deposits Ag particles to prepare hollow shell structure Ag/Bi2WO6The method of photocatalyst | |
| CN110064396B (en) | Reductive ionic liquid-based iron trioxide nitrogen fixation catalyst rich in oxygen vacancies, preparation method and electrocatalytic nitrogen fixation application thereof | |
| CN107051480A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107096542A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008380A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107020110A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN116726929A (en) | Preparation method of Co-CuO (Ov) single-atom catalyst for treating water pollution | |
| CN107020122A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008379A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008377A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107008376A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107159193A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst | |
| CN107051487A (en) | The preparation method of ozone Heterogeneous oxidation solid catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20201119 Address after: 610000 North Section of Hubin Road, Tianfu New District, Chengdu City, Sichuan Province, 366, 1 Building, 3 Floors, 1 Patentee after: SICHUAN LONGMEN ZHICHUANG ENVIRONMENTAL PROTECTION NEW MATERIAL TECHNOLOGY Co.,Ltd. Address before: 116034 Ganjingzi Light Industry Zone, Liaoning, No. 1, No. Patentee before: DALIAN POLYTECHNIC University |
|
| TR01 | Transfer of patent right |