CN107245749B - A kind of method and application preparing sulfur doping out-phase fenton catalyst in titanium alloy surface - Google Patents
A kind of method and application preparing sulfur doping out-phase fenton catalyst in titanium alloy surface Download PDFInfo
- Publication number
- CN107245749B CN107245749B CN201710436776.1A CN201710436776A CN107245749B CN 107245749 B CN107245749 B CN 107245749B CN 201710436776 A CN201710436776 A CN 201710436776A CN 107245749 B CN107245749 B CN 107245749B
- Authority
- CN
- China
- Prior art keywords
- titanium alloy
- fenton catalyst
- sulfur doping
- electrolyte
- phase fenton
- 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.)
- Active
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/026—Anodisation with spark discharge
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Electrochemistry (AREA)
- Metallurgy (AREA)
- Catalysts (AREA)
Abstract
A kind of method and application preparing sulfur doping out-phase fenton catalyst in titanium alloy surface, it is related to a kind of out-phase fenton catalyst and application.Long the invention aims to solve the existing homogeneous fenton catalyst reaction time, the applicable pH narrow range of Fenton's reaction system, catalyst can not recycle and the problem of the poor mechanical property of class fenton catalyst film layer.Summary of the invention: one, titanium alloy surface pre-processes；Two, electrolyte is prepared；Three, differential arc oxidation reacts, and obtains sulfur doping out-phase fenton catalyst.The mechanical property of sulfur doping out-phase fenton catalyst prepared by the present invention is also preferable, can be resistant to the ultrasound of 30min, and recycles convenient, directly takes out all right to make to wash with water, can be recycled；Sulfur doping out-phase fenton catalyst prepared by the present invention in neutral conditions, 60min can degrade 90% or more phenol.The present invention can get sulfur doping out-phase fenton catalyst.
Description
Technical field
The present invention relates to a kind of out-phase fenton catalyst and applications.
Background technique
Fenton oxidation Guttae Phacosylini uses homogeneous ferrous ion to be catalyzed under the conditions of certain pH as homogeneous catalyst
H2O2, H2O2It generates hydroxyl radical free radical and carrys out oxidative degradation organic pollutant.However, there are pH to be applicable in model for homogeneous Fenton oxidation method
Enclose that narrow i.e. degradation efficiency is high under the conditions of 3~4 pH, has what iron cement generation and catalyst can not recycle to lack in reaction
Point, thus have developed it and be widely used.The shortcomings that in order to overcome homogeneous Fenton to react, iron is further developed on this basis
Base type Fenton catalyst.These catalyst exist with powder, need to be centrifuged after embryonic stem-like cells or be separated by filtration,
The shortcomings that in the presence of recycling complexity, time-consuming, generally requires 2h~5h, and there are catalyst loss in removal process.Therefore, it prepares
It is returned with high catalytic activity, the immobilization film layer type Fenton catalyst being easily recycled for solving traditional type Fenton catalyst
Miscellaneous problem is recovered to have great importance.
Currently, differential arc oxidation law technology prepares ferriferous oxide film layer type Fenton catalyst, but its film on Q235 carbon steel
Layer bad mechanical property, ultrasound will appear film layer after five minutes and fall off；And although titanium alloy can obtain the film layer of good mechanical property,
But the correlative study of associated class fenton catalyst is less.
Summary of the invention
It is long the invention aims to solve the existing homogeneous fenton catalyst reaction time, the applicable pH of Fenton's reaction system
Narrow range, catalyst can not recycle and the problem of the poor mechanical properties of class fenton catalyst film layer, and provide one kind in titanium alloy
Surface prepares the method and application of sulfur doping out-phase fenton catalyst.
A method of sulfur doping out-phase fenton catalyst being prepared in titanium alloy surface, is specifically realized by the following steps
:
One, titanium alloy surface pre-processes:
Successively use 500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC
Sand paper carries out sanding and polishing to the surface of titanium alloy, until the surface of titanium alloy is mirror surface, obtains the titanium alloy of surface-brightening；First
It is cleaned 3 times~5 times using titanium alloy of the deionized water to surface-brightening, then using dehydrated alcohol to the titanium alloy of surface-brightening
Cleaning 3 times~5 times, is finally dried up using hair dryer, obtains pretreated titanium alloy；
Two, electrolyte is prepared:
By Na2SiO3·9H2O is add to deionized water, and is stirred for Na2SiO3·9H2O is completely dissolved, and is added secondary
Sodium phosphite is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
Na described in step 22SiO3·9H2The quality of O and the volume ratio of deionized water are (15g~25g): 1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are (0.5g~1.5g): 1L；
Three, electrolyte is added in stainless steel electrolytic cell, then pretreated titanium alloy obtained in step 1 is set
In electrolyte, pretreated titanium alloy is connected with positive pole, as anode；Stainless steel electrolytic cell is connected with power cathode
It connects, as cathode；It is powered using constant-current pulse mao power source, is 0.06A/cm in current density2~0.5A/cm2, power supply
The pH value of frequency 200Hz~2000Hz, 25 DEG C~35 DEG C of electrolyte temperature and electrolyte are 8~12 lower reaction 150s~300s,
Constant-current pulse mao power source is closed, the potassium ferricyanide and sodium thiosulfate are added into electrolyte, is stirred for the potassium ferricyanide
It is dissolved with sodium thiosulfate, then opens constant-current pulse mao power source, then in current density be 0.06A/cm2~0.50A/
cm2, supply frequency 200Hz~2000Hz, 25 DEG C~35 DEG C of electrolyte temperature and electrolyte pH value be 8~12 lower reactions
20min~40min, then pretreated titanium alloy is taken out, it reuses deionized water and rinses 3 times~5 times, finally using blowing
Machine drying, obtains sulfur doping out-phase fenton catalyst in titanium alloy surface, that is, completes one kind in titanium alloy surface and prepare sulfur doping
The method of out-phase fenton catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are (3g~8g): 1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are (1g~20g): 1L.
Advantages of the present invention:
One, electrolyte system prepared by the present invention is stablized, and alkaline system environmental pollution is small；Membrane aperture is widely distributed, both
Having protrusion again has many micro/nano levels aperture；
Two, sulfur doping out-phase fenton catalyst prepared by the present invention can expand the application range of fenton catalyst, Fenton
The application of reaction can be from highly acid to weakly acidic pH system；
Three, the mechanical property of sulfur doping out-phase fenton catalyst prepared by the present invention is also preferable, can be resistant to the super of 30min
Sound, and recycle convenient, it directly takes out all right to make to wash with water, can be recycled；
Four, sulfur doping out-phase fenton catalyst prepared by the present invention 60min can degrade 90% or more phenol.
The present invention can get sulfur doping out-phase fenton catalyst.
Detailed description of the invention
Fig. 1 is the SEM figure of sulfur doping out-phase fenton catalyst prepared by embodiment one；
Fig. 2 is the SEM figure of sulfur doping out-phase fenton catalyst prepared by embodiment two；
Fig. 3 is the SEM figure of sulfur doping out-phase fenton catalyst prepared by embodiment three；
Fig. 4 is macro morphology of the sulfur doping out-phase fenton catalyst of the preparation of embodiment three after ultrasonic 30min；
Fig. 5 is the ceramic film class fenton catalyst of comparative test preparation by the macro morphology of ultrasound 5min；
Fig. 6 is the degradation efficiency figure of the neutral phenolic waste water of degradation, 1 degradation to use titanium-based degradation of phenol waste water in Fig. 6
Efficiency curve, 2 be the degradation efficiency curve using iron-based degradation of phenol waste water, and 3 is different for the sulfur doping that is prepared using embodiment three
The degradation efficiency curve of phase fenton catalyst；
Fig. 7 is the efficiency chart of sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4, and 1 is real in Fig. 7
The efficiency curve of sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4 of the preparation of example one is applied, 2 be embodiment
The efficiency curve of sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4 of two preparations, 3 make for embodiment three
The efficiency curve of standby sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4；
Fig. 8 is the efficiency chart of sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions, and 1 is embodiment in Fig. 8
The efficiency curve of the sulfur doping out-phase fenton catalysts degradation of phenol in neutral conditions of three preparations, 2 for second of circulation realities
The efficiency curve of the sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions of the preparation of example three is applied, 3 recycle for third time
The efficiency curve of sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions for preparing of embodiment three.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of to prepare sulfur doping out-phase fenton catalyst in titanium alloy surface
What method was specifically realized by the following steps:
One, titanium alloy surface pre-processes:
Successively use 500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC
Sand paper carries out sanding and polishing to the surface of titanium alloy, until the surface of titanium alloy is mirror surface, obtains the titanium alloy of surface-brightening；First
It is cleaned 3 times~5 times using titanium alloy of the deionized water to surface-brightening, then using dehydrated alcohol to the titanium alloy of surface-brightening
Cleaning 3 times~5 times, is finally dried up using hair dryer, obtains pretreated titanium alloy；
Two, electrolyte is prepared:
By Na2SiO3·9H2O is add to deionized water, and is stirred for Na2SiO3·9H2O is completely dissolved, and is added secondary
Sodium phosphite is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
Na described in step 22SiO3·9H2The quality of O and the volume ratio of deionized water are (15g~25g): 1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are (0.5g~1.5g): 1L；
Three, electrolyte is added in stainless steel electrolytic cell, then pretreated titanium alloy obtained in step 1 is set
In electrolyte, pretreated titanium alloy is connected with positive pole, as anode；Stainless steel electrolytic cell is connected with power cathode
It connects, as cathode；It is powered using constant-current pulse mao power source, is 0.06A/cm in current density2~0.5A/cm2, power supply
The pH value of frequency 200Hz~2000Hz, 25 DEG C~35 DEG C of electrolyte temperature and electrolyte are 8~12 lower reaction 150s~300s,
Constant-current pulse mao power source is closed, the potassium ferricyanide and sodium thiosulfate are added into electrolyte, is stirred for the potassium ferricyanide
It is dissolved with sodium thiosulfate, then opens constant-current pulse mao power source, then in current density be 0.06A/cm2~0.50A/
cm2, supply frequency 200Hz~2000Hz, 25 DEG C~35 DEG C of electrolyte temperature and electrolyte pH value be 8~12 lower reactions
20min~40min, then pretreated titanium alloy is taken out, it reuses deionized water and rinses 3 times~5 times, finally using blowing
Machine drying, obtains sulfur doping out-phase fenton catalyst in titanium alloy surface, that is, completes one kind in titanium alloy surface and prepare sulfur doping
The method of out-phase fenton catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are (3g~8g): 1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are (1g~20g): 1L.
The advantages of present embodiment:
One, the electrolyte system of present embodiment preparation is stablized, and alkaline system environmental pollution is small；Membrane aperture distribution is wide
General, existing protrusion has many micro/nano level apertures again；
Two, the sulfur doping out-phase fenton catalyst of present embodiment preparation can expand the application range of fenton catalyst,
The application of Fenton's reaction can be from highly acid to weakly acidic pH system；
Three, the mechanical property of the sulfur doping out-phase fenton catalyst of present embodiment preparation is also preferable, can be resistant to 30min
Ultrasound, and recycle convenient, directly take out all right to make to wash with water, can be recycled；
Four, for the sulfur doping out-phase fenton catalyst of present embodiment preparation under neutral system, 60min can degrade 90%
Above phenol.
Present embodiment can get sulfur doping out-phase fenton catalyst.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: described in step 2
Na2SiO3·9H2The quality of O and the volume ratio of deionized water are (18g~23g): 1L.Other steps and specific embodiment one
It is identical.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: institute in step 2
The quality for the sodium hypophosphite stated and the volume ratio of deionized water are (0.8g~1.2g): 1L.Other steps and specific embodiment party
Formula one or two is identical.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: institute in step 1
The titanium alloy stated is TC4.Other steps are identical as specific embodiment one to three.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: institute in step 3
The quality for the potassium ferricyanide stated and the volume ratio of electrolyte are (5g~8g): 1L.Other steps and specific embodiment one to four
It is identical.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: institute in step 3
The quality for the sodium thiosulfate stated and the volume ratio of electrolyte are (1g~5g): 1L.Other steps and specific embodiment one to
Five is identical.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: institute in step 3
The quality for the sodium thiosulfate stated and the volume ratio of electrolyte are (5g~10g): 1L.Other steps and specific embodiment one to
Six is identical.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: institute in step 3
The quality for the sodium thiosulfate stated and the volume ratio of electrolyte are (10g~15g): 1L.Other steps and specific embodiment one
It is identical to seven.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: will in step 3
Electrolyte is added in stainless steel electrolytic cell, then pretreated titanium alloy obtained in step 1 is placed in electrolyte, in advance
Treated, and titanium alloy is connected with positive pole, as anode；Stainless steel electrolytic cell is connected with power cathode, as cathode；
It is powered using constant-current pulse mao power source, is 0.06A/cm in current density2~0.1A/cm2, supply frequency 200Hz~
The pH value of 500Hz, 25 DEG C~30 DEG C of electrolyte temperature and electrolyte are 8~12 lower reaction 150s~200s, close constant-current pulse
The potassium ferricyanide and sodium thiosulfate are added into electrolyte, is stirred for the potassium ferricyanide and sodium thiosulfate for mao power source
Dissolution, then opens constant-current pulse mao power source, then in current density is 0.06A/cm2~0.1A/cm2, supply frequency
The pH value of 200Hz~500Hz, 25 DEG C~30 DEG C of electrolyte temperature and electrolyte are 8~12 lower reaction 20min~30min, then will
Pretreated titanium alloy takes out, and reuses deionized water and rinses 3 times~4 times, is finally dried up using hair dryer, in titanium alloy table
Face obtains sulfur doping out-phase fenton catalyst, that is, completes a kind of side that sulfur doping out-phase fenton catalyst is prepared in titanium alloy surface
Method；Other steps are identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: will in step 3
Electrolyte is added in stainless steel electrolytic cell, then pretreated titanium alloy obtained in step 1 is placed in electrolyte, in advance
Treated, and titanium alloy is connected with positive pole, as anode；Stainless steel electrolytic cell is connected with power cathode, as cathode；
It is powered using constant-current pulse mao power source, is 0.2A/cm in current density2~0.3A/cm2, supply frequency 1000Hz~
The pH value of 2000Hz, 30 DEG C~35 DEG C of electrolyte temperature and electrolyte are 8~12 lower reaction 200s~300s, close constant-current pulse
The potassium ferricyanide and sodium thiosulfate are added into electrolyte, is stirred for the potassium ferricyanide and sodium thiosulfate for mao power source
Dissolution, then opens constant-current pulse mao power source, then in current density is 0.2A/cm2~0.3A/cm2, supply frequency 200Hz
The pH value of~500Hz, 30 DEG C~35 DEG C of electrolyte temperature and electrolyte are 8~12 lower reaction 30min~40min, then will be located in advance
Titanium alloy after reason takes out, and reuses deionized water and rinses 4 times~5 times, is finally dried up using hair dryer, obtained in titanium alloy surface
To sulfur doping out-phase fenton catalyst, that is, complete a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface；
Other steps are identical as specific embodiment one to nine.
Specific embodiment 11: present embodiment is sulfur doping out-phase fenton catalyst for handling phenolic waste water.
Specific embodiment 12: the difference of present embodiment and specific embodiment 11 is: the sulfur doping
Out-phase fenton catalyst is completed by the following steps for handling phenolic waste water:
Sulfur doping out-phase fenton catalyst is immersed in phenolic waste water, then low whipping speed is 100r/min~500r/
The hydrogen peroxide that concentration is 6mmol/L is added under min, then the pH value of phenolic waste water is adjusted to 4, then low whipping speed is 100r/
It is stirred to react 60min~80min under min~500r/min, water after being handled；The sulfur doping out-phase fenton catalyst
Volume ratio (the 5cm of geometric area and phenolic waste water2~10cm2):50mL；The concentration of phenol is 20mg/ in the phenolic waste water
L~50mg/L；The geometric area and concentration of the sulfur doping out-phase fenton catalyst are the volume ratio of the hydrogen peroxide of 6mmol/L
For (5cm2~10cm2):50mL。
Other are identical as specific embodiment 11.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a method of sulfur doping out-phase fenton catalyst being prepared in titanium alloy surface, specifically by following
What step was completed:
One, titanium alloy surface pre-processes:
Successively use 500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC
Sand paper carries out sanding and polishing to the surface of titanium alloy, until the surface of titanium alloy is mirror surface, obtains the titanium alloy of surface-brightening；First
It is cleaned 4 times using titanium alloy of the deionized water to surface-brightening, then cleans 4 using titanium alloy of the dehydrated alcohol to surface-brightening
It is secondary, it is finally dried up using hair dryer, obtains pretreated titanium alloy；
Titanium alloy described in step 1 is TC4；
Two, electrolyte is prepared:
By Na2SiO3·9H2O is add to deionized water, and is stirred for Na2SiO3·9H2O is completely dissolved, and is added secondary
Sodium phosphite is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
Na described in step 22SiO3·9H2The quality of O and the volume ratio of deionized water are 20g:1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are 1.0g:1L；
Three, electrolyte is added in stainless steel electrolytic cell, then pretreated titanium alloy obtained in step 1 is set
In electrolyte, pretreated titanium alloy is connected with positive pole, as anode；Stainless steel electrolytic cell is connected with power cathode
It connects, as cathode；It is powered using constant-current pulse mao power source, is 0.06A/cm in current density2, supply frequency 500Hz,
The pH value of 30 DEG C of electrolyte temperature and electrolyte is 10 lower reaction 150s, constant-current pulse mao power source is closed, to electrolyte
The middle addition potassium ferricyanide and sodium thiosulfate are stirred for the potassium ferricyanide and sodium thiosulfate dissolving, then to open constant-current pulse micro-
Arc aoxidize power supply, then current density be 0.06A/cm2, supply frequency 200Hz, 30 DEG C of electrolyte temperature and electrolyte pH value
20min are reacted under being 10, then pretreated titanium alloy is taken out, and are reused deionized water and are rinsed 4 times, finally use hair dryer
Drying, obtains sulfur doping out-phase fenton catalyst in titanium alloy surface, that is, completing one kind, in titanium alloy surface to prepare sulfur doping different
The method of phase fenton catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are 5g:1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are 5g:1L.
Embodiment two: a method of sulfur doping out-phase fenton catalyst being prepared in titanium alloy surface, specifically by following
What step was completed:
One, titanium alloy surface pre-processes:
Successively use 500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC
Sand paper carries out sanding and polishing to the surface of titanium alloy, until the surface of titanium alloy is mirror surface, obtains the titanium alloy of surface-brightening；First
It is cleaned 4 times using titanium alloy of the deionized water to surface-brightening, then cleans 4 using titanium alloy of the dehydrated alcohol to surface-brightening
It is secondary, it is finally dried up using hair dryer, obtains pretreated titanium alloy；
Titanium alloy described in step 1 is TC4；
Two, electrolyte is prepared:
By Na2SiO3·9H2O is add to deionized water, and is stirred for Na2SiO3·9H2O is completely dissolved, and is added secondary
Sodium phosphite is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
Na described in step 22SiO3·9H2The quality of O and the volume ratio of deionized water are 20g:1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are 1.0g:1L；
Three, electrolyte is added in stainless steel electrolytic cell, then pretreated titanium alloy obtained in step 1 is set
In electrolyte, pretreated titanium alloy is connected with positive pole, as anode；Stainless steel electrolytic cell is connected with power cathode
It connects, as cathode；It is powered using constant-current pulse mao power source, is 0.06A/cm in current density2, supply frequency 500Hz,
The pH value of 30 DEG C of electrolyte temperature and electrolyte is 10 lower reaction 150s, constant-current pulse mao power source is closed, to electrolyte
The middle addition potassium ferricyanide and sodium thiosulfate are stirred for the potassium ferricyanide and sodium thiosulfate dissolving, then to open constant-current pulse micro-
Arc aoxidize power supply, then current density be 0.06A/cm2, supply frequency 200Hz, 30 DEG C of electrolyte temperature and electrolyte pH value
20min are reacted under being 10, then pretreated titanium alloy is taken out, and are reused deionized water and are rinsed 4 times, finally use hair dryer
Drying, obtains sulfur doping out-phase fenton catalyst in titanium alloy surface, that is, completing one kind, in titanium alloy surface to prepare sulfur doping different
The method of phase fenton catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are 5g:1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are 10g:1L.
Embodiment three: a method of sulfur doping out-phase fenton catalyst being prepared in titanium alloy surface, specifically by following
What step was completed:
One, titanium alloy surface pre-processes:
Successively use 500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC
Sand paper carries out sanding and polishing to the surface of titanium alloy, until the surface of titanium alloy is mirror surface, obtains the titanium alloy of surface-brightening；First
It is cleaned 4 times using titanium alloy of the deionized water to surface-brightening, then cleans 4 using titanium alloy of the dehydrated alcohol to surface-brightening
It is secondary, it is finally dried up using hair dryer, obtains pretreated titanium alloy；
Titanium alloy described in step 1 is TC4；
Two, electrolyte is prepared:
By Na2SiO3·9H2O is add to deionized water, and is stirred for Na2SiO3·9H2O is completely dissolved, and is added secondary
Sodium phosphite is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
Na described in step 22SiO3·9H2The quality of O and the volume ratio of deionized water are 20g:1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are 1.0g:1L；
Three, electrolyte is added in stainless steel electrolytic cell, then pretreated titanium alloy obtained in step 1 is set
In electrolyte, pretreated titanium alloy is connected with positive pole, as anode；Stainless steel electrolytic cell is connected with power cathode
It connects, as cathode；It is powered using constant-current pulse mao power source, is 0.06A/cm in current density2, supply frequency 500Hz,
The pH value of 30 DEG C of electrolyte temperature and electrolyte is 10 lower reaction 150s, constant-current pulse mao power source is closed, to electrolyte
The middle addition potassium ferricyanide and sodium thiosulfate are stirred for the potassium ferricyanide and sodium thiosulfate dissolving, then to open constant-current pulse micro-
Arc aoxidize power supply, then current density be 0.06A/cm2, supply frequency 200Hz, 30 DEG C of electrolyte temperature and electrolyte pH value
20min are reacted under being 10, then pretreated titanium alloy is taken out, and are reused deionized water and are rinsed 4 times, finally use hair dryer
Drying, obtains sulfur doping out-phase fenton catalyst in titanium alloy surface, that is, completing one kind, in titanium alloy surface to prepare sulfur doping different
The method of phase fenton catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are 5g:1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are 15g:1L.
Comparative test: a kind of to prepare ceramic film class Fenton using plasma electrolytic oxidation method on Q235 carbon steel surface and urge
The method of agent, is completed by the following steps:
One, Q235 carbon steel pre-treatment: successively using 500# sand paper, 1500# sand paper and 2500# sand paper to the table of Q235 carbon steel
The surface that face carries out being polishing to Q235 carbon steel is mirror surface；Q235 carbon steel surface is rinsed 4 times using deionized water, reuses anhydrous second
Alcohol rinses Q235 carbon steel surface 4 times, is finally dried up using hair dryer, obtains bright Q235 carbon steel；
Two, Q235 carbon steel bright obtained in step 1 is placed in the electrolyte in stainless steel electrolytic cell, as sun
Pole；Stainless steel electrolytic cell is connected with power cathode, as cathode；
Three, it is powered using the pulse power, is 12A/cm in current density2, supply frequency 2000Hz, 30 DEG C of electrolyte temperature
Plasma electrolytic oxidation is carried out under conditions of being 14.0 with electrolyte ph and reacts 20min, is made pottery on Q235 carbon steel surface
Porcelain film layer class fenton catalyst is completed a kind of on Q235 carbon steel surface to prepare ceramic film using plasma electrolytic oxidation method
The method of class fenton catalyst；
Electrolyte described in step 3 is made of sodium metasilicate, sodium hypophosphite and water；Sodium metasilicate in the electrolyte
Concentration be 25g/L；The concentration of sodium hypophosphite is 1g/L in the electrolyte.
Fig. 1 is the SEM figure of sulfur doping out-phase fenton catalyst prepared by embodiment one；
From fig. 1, it can be seen that there are some protrusions and hole in the surface of sulfur doping out-phase fenton catalyst prepared by embodiment one, and
Also hole is distributed in protrusion.
Fig. 2 is the SEM figure of sulfur doping out-phase fenton catalyst prepared by embodiment two；
As can be seen from Figure 2, there are more protrusion and hole in the surface for the sulfur doping out-phase fenton catalyst that prepared by embodiment two,
And also hole is distributed in protrusion.
Fig. 3 is the SEM figure of sulfur doping out-phase fenton catalyst prepared by embodiment three；
As can be seen from Figure 3, there are a large amount of protrusion and hole in the surface for the sulfur doping out-phase fenton catalyst that prepared by embodiment three,
And in protrusion other than hole, there are also many particles.
Sulfur doping out-phase fenton catalyst prepared by embodiment three ultrasound in the distilled water that ultrasonic power is 60W
30min, the macro morphology of sulfur doping out-phase fenton catalyst prepared by embodiment three after ultrasonic 30min are as shown in Figure 4；
Fig. 4 is macro morphology of the sulfur doping out-phase fenton catalyst of the preparation of embodiment three after ultrasonic 30min；
As can be seen from Figure 4, the sulfur doping out-phase fenton catalyst that prepared by embodiment three still compares by ultrasound 30min rear surface
More complete, film layer engineering properties is stablized.
The ceramic film class fenton catalyst of comparative test preparation is ultrasonic in the distilled water that ultrasonic power is 60W
5min, macro smooth pattern of the ceramic film class fenton catalyst of comparative test preparation after ultrasonic 5min are as shown in Figure 5；
Fig. 5 is the ceramic film class fenton catalyst of comparative test preparation by the macro morphology of ultrasound 5min；
As can be seen from Figure 5, the ceramic film class fenton catalyst of comparative test preparation has gone out by ultrasound 5min rear surface
Show film layer to fall off.
Fig. 4 and Fig. 5 is the digital photograph shot using digital camera.
The Degrading experiment one of phenol:
By 6cm2Titanium alloy TC 4 be added in the neutral phenolic waste water of 50mL, then low whipping speed be 300r/min under
The hydrogen peroxide that 34 μ L concentration are 30% is added, then low whipping speed is to be stirred to react 0min~75min under 300r/min, is obtained everywhere
Water after reason；The concentration of phenol is 35mg/L in the neutral phenolic waste water, and situation of degrading is as shown in 1 in Fig. 6；
By 6cm2Q235 alloy be added in 50mL neutrality phenolic waste water, then low whipping speed be 300r/min under be added
The hydrogen peroxide that 34 μ L concentration are 30%, then low whipping speed are to be stirred to react 0min~75min under 300r/min, after obtaining processing
Water；The concentration of phenol is 35mg/L in the neutral phenolic waste water, and situation of degrading is as shown in 2 in Fig. 6；
By 6cm2Embodiment three prepare sulfur doping out-phase fenton catalyst be immersed in 50mL neutrality phenolic waste water, then
Low whipping speed is the hydrogen peroxide that 34 μ L concentration are 30% to be added under 300r/min, then low whipping speed is to stir under 300r/min
React 0min~75min, water after being handled；The concentration of phenol is 35mg/L in the neutral phenolic waste water, situation of degrading
As shown in 3 in Fig. 6；
Fig. 6 is the degradation efficiency figure of degradation of phenol waste water, 1 degradation efficiency to use titanium-based degradation of phenol waste water in Fig. 6
Curve, 2 be the degradation efficiency curve using iron-based degradation of phenol waste water, the 3 sulfur doping out-phase sweet smell to be prepared using embodiment three
The degradation efficiency curve of catalyst；
As can be seen from Figure 6, in neutral conditions, 60min's sulfur doping out-phase fenton catalyst that prepared by embodiment three can degrade
90% or more phenol, and the degradation of titanium alloy and iron Pyrogentisinic Acid has almost no change.
The Degrading experiment two of phenol:
By 6cm2The sulfur doping out-phase fenton catalyst for preparing of embodiment one be immersed in 50mL phenolic waste water, then stirring
Mixing speed is that the hydrogen peroxide that 34 μ L concentration are 30% is added under 300r/min, and reusing concentration is 0.01mol/L dilute sulfuric acid by benzene
The pH value of phenol waste water is adjusted to 4.0, then low whipping speed is to be stirred to react 0min~75min under 300r/min, after obtaining processing
Water；The concentration of phenol is 35mg/L in the phenolic waste water, and situation of degrading is as shown in 1 in Fig. 7；
By 6cm2The sulfur doping out-phase fenton catalyst for preparing of embodiment two be immersed in 50mL phenolic waste water, then stirring
Mixing speed is that the hydrogen peroxide that 34 μ L concentration are 30% is added under 300r/min, and reusing concentration is 0.01mol/L dilute sulfuric acid by benzene
The pH value of phenol waste water is adjusted to 4.0, then low whipping speed is to be stirred to react 0min~75min under 300r/min, after obtaining processing
Water；The concentration of phenol is 35mg/L in the phenolic waste water, and situation of degrading is as shown in 2 in Fig. 7；
By 6cm2The sulfur doping out-phase fenton catalyst for preparing of embodiment three be immersed in 50mL phenolic waste water, then stirring
Mixing speed is that the hydrogen peroxide that 34 μ L concentration are 30% is added under 300r/min, and reusing concentration is 0.01mol/L dilute sulfuric acid by benzene
The pH value of phenol waste water is adjusted to 4.0, then low whipping speed is to be stirred to react 0min~75min under 300r/min, after obtaining processing
Water；The concentration of phenol is 35mg/L in the phenolic waste water, and situation of degrading is as shown in 3 in Fig. 7；
Fig. 7 is the efficiency chart of sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4, and 1 is real in Fig. 7
The efficiency curve of sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4 of the preparation of example one is applied, 2 be embodiment
The efficiency curve of sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4 of two preparations, 3 make for embodiment three
The efficiency curve of standby sulfur doping out-phase fenton catalyst degradation of phenol under conditions of pH value is 4；
As can be seen from Figure 7, with the increase of sulphur source content, the degradation rate of phenol is accelerated.
The Degrading experiment three of phenol: by 6cm2Embodiment three prepare sulfur doping out-phase fenton catalyst be immersed in 50mL
In neutral phenolic waste water, then low whipping speed is the hydrogen peroxide that 34 μ L concentration are 30% to be added under 300r/min, then stirring
Speed is to be stirred to react 0min~80min under 300r/min, water after being handled；Phenol in the neutral phenolic waste water
Concentration is 35mg/L, and situation of degrading is as shown in 1 in Fig. 8；
Cycle performance test one: the embodiment three after degradation of phenol 75min obtained in the Degrading experiment three by phenol is made
Standby sulfur doping out-phase fenton catalyst is taken out, and reuses distilled water and cleans 5 times, then is dried in vacuo 10h at being 60 DEG C in temperature,
Obtain sulfur doping out-phase fenton catalyst prepared by the embodiment three of second of circulation；It prepared by the embodiment three of second of circulation
Sulfur doping out-phase fenton catalyst be immersed in the phenolic waste water of 50mL neutrality, then low whipping speed be 300r/min under be added
The hydrogen peroxide that 34 μ L concentration are 30%, then low whipping speed are to be stirred to react 0min~90min under 300r/min, after obtaining processing
Water；The concentration of phenol is 35mg/L in the neutral phenolic waste water, and situation of degrading is as shown in 2 in Fig. 8；
Cycle performance test two: by second of circulation after degradation of phenol 90min obtained in cycle performance test one
Sulfur doping out-phase fenton catalyst prepared by embodiment three is taken out, and reuses distilled water and cleans 5 times, then temperature be at 60 DEG C it is true
The dry 10h of sky obtains sulfur doping out-phase fenton catalyst prepared by the embodiment three that third time recycles；By the reality of third time circulation
The sulfur doping out-phase fenton catalyst for applying the preparation of example three is immersed in the phenolic waste water of 50mL neutrality, then low whipping speed is
Be added under 300r/min 34 μ L concentration be 30% hydrogen peroxide, then low whipping speed be 300r/min under be stirred to react 0min~
90min, water after being handled；The concentration of phenol is 35mg/L in the described neutral phenolic waste water, 3 in situation of degrading such as Fig. 8
It is shown；
Fig. 8 is the efficiency chart of sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions, and 1 is embodiment in Fig. 8
The efficiency curve of the sulfur doping out-phase fenton catalysts degradation of phenol in neutral conditions of three preparations, 2 for second of circulation realities
The efficiency curve of the sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions of the preparation of example three is applied, 3 recycle for third time
The efficiency curve of sulfur doping out-phase fenton catalyst degradation of phenol in neutral conditions for preparing of embodiment three.
As it can be observed in the picture that sulfur doping out-phase fenton catalyst circulation prepared by embodiment three is three times, in neutral conditions still
There is degradation property.
Claims (8)
1. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface, it is characterised in that one kind is in titanium alloy table
Wheat flour is specifically realized by the following steps for the method for sulfur doping out-phase fenton catalyst:
One, titanium alloy surface pre-processes:
Successively use 500#SiC sand paper, 1000#SiC sand paper, 1500#SiC sand paper, 2000#SiC sand paper and 2500#SiC sand paper
Sanding and polishing is carried out to the surface of titanium alloy, until the surface of titanium alloy is mirror surface, obtains the titanium alloy of surface-brightening；It uses first
Deionized water cleans the titanium alloy of surface-brightening 3 times~5 times, is then cleaned using titanium alloy of the dehydrated alcohol to surface-brightening
It 3 times~5 times, is finally dried up using hair dryer, obtains pretreated titanium alloy；
Titanium alloy described in step 1 is TC4；
Two, electrolyte is prepared:
By Na2SiO3·9H2O is add to deionized water, and is stirred for Na2SiO3·9H2O is completely dissolved, and adds time phosphorous
Sour sodium is stirred for sodium hypophosphite being completely dissolved, obtains electrolyte；
Na described in step 22SiO3·9H2The quality of O and the volume ratio of deionized water are (15g~25g): 1L；
The quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are (0.5g~1.5g): 1L；
Three, electrolyte is added in stainless steel electrolytic cell, then pretreated titanium alloy obtained in step 1 is placed in electricity
It solves in liquid, pretreated titanium alloy is connected with positive pole, as anode；Stainless steel electrolytic cell is connected with power cathode,
As cathode；It is powered using constant-current pulse mao power source, is 0.06A/cm in current density2~0.5A/cm2, supply frequency
The pH value of 200Hz~2000Hz, 25 DEG C~35 DEG C of electrolyte temperature and electrolyte are 8~12 lower reaction 150s~300s, are closed
The potassium ferricyanide and sodium thiosulfate are added into electrolyte, is stirred for the potassium ferricyanide and sulphur for constant-current pulse mao power source
Sodium thiosulfate dissolution, then opens constant-current pulse mao power source, then in current density is 0.06A/cm2~0.50A/cm2, electricity
The pH value of source frequency 200Hz~2000Hz, 25 DEG C~35 DEG C of electrolyte temperature and electrolyte be 8~12 lower reaction 20min~
40min, then pretreated titanium alloy is taken out, it reuses deionized water and rinses 3 times~5 times, finally dried up using hair dryer,
Sulfur doping out-phase fenton catalyst is obtained in titanium alloy surface, that is, completes one kind in titanium alloy surface and prepares sulfur doping out-phase Fenton
The method of catalyst；
The quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are (3g~8g): 1L；
The quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are (1g~20g): 1L.
2. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, special
Sign is Na described in step 22SiO3·9H2The quality of O and the volume ratio of deionized water are (18g~23g): 1L.
3. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, special
Sign is that the quality of sodium hypophosphite described in step 2 and the volume ratio of deionized water are (0.8g~1.2g): 1L.
4. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, special
Sign is that the quality of the potassium ferricyanide described in step 3 and the volume ratio of electrolyte are (5g~8g): 1L.
5. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, special
Sign is that the quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are (1g~5g): 1L.
6. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, special
Sign is that the quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are (5g~10g): 1L.
7. a kind of method for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface according to claim 1, special
Sign is that the quality of sodium thiosulfate described in step 3 and the volume ratio of electrolyte are (10g~15g): 1L.
8. according to a kind of method preparation for preparing sulfur doping out-phase fenton catalyst in titanium alloy surface as described in claim 1
Sulfur doping out-phase fenton catalyst application, it is characterised in that sulfur doping out-phase fenton catalyst is for handling phenolic waste water；
The sulfur doping out-phase fenton catalyst is completed by the following steps for handling phenolic waste water:
Sulfur doping out-phase fenton catalyst is immersed in phenolic waste water, then low whipping speed is under 100r/min~500r/min
The hydrogen peroxide that concentration is 6mmol/L is added, then the pH value of phenolic waste water is adjusted to 4, then low whipping speed be 100r/min~
It is stirred to react 60min~80min under 500r/min, water after being handled；The geometry of the sulfur doping out-phase fenton catalyst
Volume ratio (the 5cm of area and phenolic waste water2~10cm2):50mL；In the phenolic waste water concentration of phenol be 20mg/L~
50mg/L；The volume ratio for the hydrogen peroxide that the geometric area of the sulfur doping out-phase fenton catalyst is 6mmol/L with concentration is
(5cm2~10cm2):50mL。
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710436776.1A CN107245749B (en) | 2017-06-09 | 2017-06-09 | A kind of method and application preparing sulfur doping out-phase fenton catalyst in titanium alloy surface |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710436776.1A CN107245749B (en) | 2017-06-09 | 2017-06-09 | A kind of method and application preparing sulfur doping out-phase fenton catalyst in titanium alloy surface |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107245749A CN107245749A (en) | 2017-10-13 |
| CN107245749B true CN107245749B (en) | 2019-03-12 |
Family
ID=60017942
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710436776.1A Active CN107245749B (en) | 2017-06-09 | 2017-06-09 | A kind of method and application preparing sulfur doping out-phase fenton catalyst in titanium alloy surface |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107245749B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111690972A (en) * | 2019-03-06 | 2020-09-22 | 苏州鱼得水电气科技有限公司 | Processing technology of high-temperature-resistant ceramic oxide film |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE112015005466A5 (en) * | 2014-12-04 | 2017-08-31 | Meotec GmbH & Co. KG | Component of a turbo device, internal combustion engine with a turbo device and method for producing a turbo device component |
| CN105195150B (en) * | 2015-10-16 | 2017-11-03 | 哈尔滨工业大学 | One kind prepares efficient Fe3O4/FeAl2O4The methods and applications of composite film class fenton catalyst |
| CN105297108B (en) * | 2015-11-16 | 2017-08-25 | 哈尔滨工业大学 | A kind of utilization plasma electrolytic oxidation method prepares the methods and applications of ceramic film class fenton catalyst on Q235 carbon steels surface |
| CN105568343B (en) * | 2015-12-29 | 2017-11-03 | 哈尔滨工业大学 | The methods and applications of ferriferous oxide ceramic film class fenton catalyst are prepared in titanium alloy surface using plasma electrolytic oxidation method |
| CN106345472A (en) * | 2016-08-05 | 2017-01-25 | 哈尔滨工业大学 | Method for preparing high-efficient Fenton-like catalyst of sulphur modified iron-based composite material solid acid ceramic film layer and application |
-
2017
- 2017-06-09 CN CN201710436776.1A patent/CN107245749B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN107245749A (en) | 2017-10-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106145102B (en) | A method of preparing expanded graphite or graphene | |
| CN104843770A (en) | Method of resource utilization of tin sludge | |
| CN107245749B (en) | A kind of method and application preparing sulfur doping out-phase fenton catalyst in titanium alloy surface | |
| CN106702425B (en) | A method of preparing molybdenum disulfide/copper/cobalt catalytic hydrogen evolution layer in foam iron surface | |
| CN104711654A (en) | Graphene oxide/electrophoretic paint composite coating and method for preparing composite coating through electrophoretic deposition | |
| CN105925807B (en) | A kind of recovery process of waste battery lead | |
| CN111653846B (en) | Treatment method of waste lithium iron phosphate battery | |
| CN109126685A (en) | A method of photocatalysis adsorbent material is prepared using high-titanium blast furnace slag | |
| CN109103442A (en) | A kind of preparation method of graphene-coated lithium iron phosphate positive electrode | |
| CN109225325A (en) | Fe-PANI/ zeolite catalyst and preparation method thereof | |
| CN106744902B (en) | A kind of preparation method of Ni-coated graphite alkene | |
| CN106159286B (en) | A kind of modified electrode and preparation method thereof applied to zinc-bromine flow battery | |
| CN106299436B (en) | Full vanadium cell carbon fiber felt and its method of modifying and full vanadium battery electrode | |
| CN102002738B (en) | Plating method for plating black chrome on oxygen-free copper matrix | |
| CN109742363A (en) | One kind may be implemented graphene and closely coats SiO negative materials and preparation method thereof | |
| CN108706689A (en) | A kind of method of the preparation method and wastewater treatment of electrode material | |
| CN109103436A (en) | A kind of lithium sulfur battery anode material and preparation method thereof | |
| CN105951133A (en) | Alkaline electrolyte and nickel electroplating method in alkaline system | |
| CN107154496B (en) | A kind of method for preparing graphene/sodium manganate fexible film method and preparing water system sodium zinc composite battery using it | |
| CN105297108B (en) | A kind of utilization plasma electrolytic oxidation method prepares the methods and applications of ceramic film class fenton catalyst on Q235 carbon steels surface | |
| CN106345472A (en) | Method for preparing high-efficient Fenton-like catalyst of sulphur modified iron-based composite material solid acid ceramic film layer and application | |
| CN108383208B (en) | Method for treating organic wastewater by virtue of micro-battery-Fenton-like system | |
| CN110115993A (en) | A kind of method of high-level oxidation technology processing adsorption saturation powdered activated carbon | |
| CN105908223A (en) | Alkaline electrolyte and method for preparing bright nickel by means of electrolysis in alkaline electrolyte | |
| CN106362781B (en) | It is a kind of to prepare Fe3O4/t-ZrO2/FePO4The method and application of the efficient class fenton catalyst of solid acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20210118 Address after: Building 9, accelerator, 14955 Zhongyuan Avenue, Songbei District, Harbin City, Heilongjiang Province Patentee after: INDUSTRIAL TECHNOLOGY Research Institute OF HEILONGJIANG PROVINCE Address before: 150001 No. 92 West straight street, Nangang District, Heilongjiang, Harbin Patentee before: HARBIN INSTITUTE OF TECHNOLOGY |
|
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20230411 Address after: 150027 Room 412, Unit 1, No. 14955, Zhongyuan Avenue, Building 9, Innovation and Entrepreneurship Plaza, Science and Technology Innovation City, Harbin Hi tech Industrial Development Zone, Heilongjiang Province Patentee after: Heilongjiang Industrial Technology Research Institute Asset Management Co.,Ltd. Address before: Building 9, accelerator, 14955 Zhongyuan Avenue, Songbei District, Harbin City, Heilongjiang Province Patentee before: INDUSTRIAL TECHNOLOGY Research Institute OF HEILONGJIANG PROVINCE |
|
| TR01 | Transfer of patent right |