CN109928759A - A kind of SiC ceramic membrane electrochemical reaction electrode and preparation method thereof - Google Patents
A kind of SiC ceramic membrane electrochemical reaction electrode and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of SiC ceramic membrane electrochemical reaction electrode, from-inner-to-outer successively includes catalyst layer, carbon-coating and silicon carbide ceramic membrane matrix.Conductive carbon layer and catalyst in the electrode obtained of the present invention are adhere closely on silicon carbide ceramic membrane matrix, the feature that silicon carbide ceramic membrane matrix strength can be made full use of high, make conductive carbon layer and catalyst that there is higher intensity, to extend the service life of electrode, and catalyst and conductive carbon layer are combined closely, and have higher treatment effeciency；In addition, silicon carbide ceramic membrane, as matrix, voidage is greater than 35%, in wastewater treatment process, the effects of separating and filtering impurity can also be played；It is poor that graphite electrode intensity can effectively be solved, current density compared with it is high when export license is big, electrode efficiency is low, service life is short the problems such as.
Description
Technical field
The invention belongs to technical field of chemical engineering, and in particular to a kind of SiC ceramic membrane electrochemical reaction electrode and its system
Preparation Method.
Background technique
China is a water shortage big country, with the development of society, industrial and agricultural production and service trade demand of the expansion to water with
Day all increasings, while wastewater discharge is increasing, gets worse to the pollution of environment, and the water resource day in China is caused to be becoming tight；
Water pollution, exploitation water reuse (treatment utilization technology are controlled, has become and alleviates one of the important means of water resource anxiety.
Currently, processing organic wastewater method mainly includes physical-chemical process, bioanalysis and advanced oxidation processes etc., wherein electrification
Method (one kind of advanced oxidation processes) can be constantly be generated hydroxyl by the electrode effect with catalyst at normal temperatures and pressures
Free radical, oxidative degradation organic matter have treatment effeciency high, easy to operate good with environment compatibility etc. excellent until eliminating pollution
Point, application technology advantage is significant in organic wastewater punishment, becomes the developing direction of current Technologies for Organic Wastewater Treatment and becomes
Gesture.Electrode material in advanced oxidation processes generallys use graphite, aluminium sheet or iron plate as electrode；But graphite electrode intensity compared with
Difference, current density compared with it is high when export license it is big, electrode efficiency is low, and service life is short；And aluminium sheet or iron plate are soluble electricity
Pole, electrode consumption of materials itself is big, at high cost, generates the problems such as sludge quantity is big therewith.In addition, existing electrochemical process processing
During sewage, generally require to avoid particle contamination in front end setting filtering technique to remove the granule foreign object in sewage
Electrode, process are longer.
Therefore, a kind of electrode is invented, while having the characteristics that filtering, conduction, the long-life, efficient, is China's organic waste
The processing of water provides new material, is of great significance.
Summary of the invention
It is a primary object of the present invention in view of the deficienciess of the prior art, to provide a kind of SiC ceramic membrane electrochemical anti-
Electrode is answered, it is also excellent with long service life, treatment effeciency height and with separation impurity etc. on the basis of meeting conductive require
Point.
To achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of SiC ceramic membrane electrochemical reaction electrode, from-inner-to-outer successively include catalyst layer, carbon-coating and silicon carbide pottery
Porcelain film matrix, wherein the voidage of silicon carbide ceramic membrane matrix is greater than 35%, and aperture is 0.3-0.5 μm.
In above scheme, the catalyst layer is primary raw material through glue, coating and sintering using catalyst and cellulose ether
It forms；Wherein catalyst is TiO2With the mixture of activating oxide；Wherein TiO2Shared mass percent is 20% or more (excellent
It is selected as 20-65%), activating oxide RuO2、IrO2、SnO2、Ta2O5One or more of.
Preferably, the catalyst is RuO2、TiO2Mixture, RuO2、IrO2、SnO2、TiO2Mixture or IrO2、
Ta2O5、SnO2、TiO2Mixture.
In above scheme, the silicon carbide ceramic membrane matrix is in cylindrical tube；The length is 0.5-1m, outer diameter 20-
40mm, internal diameter 10-30mm.
In above scheme, the carbon-coating by by Polycarbosilane colloid be coated on silicon carbide ceramic membrane matrix inner wall, then
Drying, chlorine etch to be formed.
A kind of preparation method of above-mentioned SiC ceramic membrane electrochemical reaction electrode, it includes the following steps:
1) preparation of silicon carbide ceramic membrane matrix: based on silicon carbide powder, silicon powder, carbon black, plasticizer, lubricant and water
Raw material is wanted, is mixed, is aging, silicon carbide walk is obtained；Then extrusion molding, drying are carried out, silicon carbide green compact are obtained；Again by institute
It obtains silicon carbide green compact and carries out dumping, sintering, obtain silicon carbide ceramic membrane matrix；
2) it plates carbon: using Polycarbosilane, glucose, cellulose ether, polyethylene alcohol and water as primary raw material, mixing and stirred
Processing is mixed, Polycarbosilane colloid is obtained；Then gained Polycarbosilane colloid is coated on to silicon carbide ceramic membrane by the way of drenching glaze
The inner wall of matrix, drying (in 105-120 DEG C of baking oven, dry 2-4h)；Then chlorine etching is carried out, Polycarbosilane is changed into
Carbon, and it is plated on silicon carbide ceramic membrane matrix inner wall, obtain the silicon carbide ceramic membrane matrix for being coated with carbon-coating；
3) it the load of catalyst: using catalyst, cellulose ether and water as primary raw material, mixes and is stirred, obtain
Catalyst colloid；Then it is coated on to the inner wall for being coated with the silicon carbide ceramic membrane matrix of carbon-coating, (105- is successively dried
In 120 DEG C of baking ovens, dry 3-4.5h), sintering is to get the SiC ceramic membrane electrochemical reaction electrode.
In above scheme, silicon carbide powder average grain diameter described in step 1) is 20-40 μm, and purity is greater than 99wt%；Silicon
The average grain diameter of powder is 1-3 μm, and purity is greater than 95wt%；The partial size of carbon black is 0.1-0.3 μm, and carbon content is greater than 93wt%；Institute
The mixture that plasticizer is glycerol and polyethylene glycol is stated, purity is all larger than 98wt%；Lubricant is oleic acid, and purity is greater than
98wt%.
In above scheme, the silicon carbide powder, silicon powder, carbon black, plasticizer, lubricant and water mass ratio be 100:
(7-9):(2.5-4.5):(3-7):(3-7):(14-20)。
In above scheme, aging temperature described in step 1) is 18-25 DEG C, humidity 95-98%, time 24-48h.
In above scheme, drying temperature described in step 1) are as follows: predry 24-48h under the conditions of 30-35 DEG C first, then
Low temperature drying 12-24h under the conditions of 50-55 DEG C, finally high temperature drying 2-3h under the conditions of 115-120 DEG C, and naturally cool to room
Temperature.
In above scheme, binder removal described in step 1) includes: to be warming up in 50min first under protective atmosphere
250-280 DEG C, 30-35min is kept the temperature, then 360-380 DEG C of heat preservation 60-70min is warming up in 25min, finally in 80min
It is warming up to 650-680 DEG C of heat preservation 20-25min.
In above scheme, sintering process described in step 1) includes: under protective atmosphere, first with 10-12 DEG C/min's
Speed is warming up to 1600-1620 DEG C, keeps the temperature 2-2.5h, then with the speed of 5-8 DEG C/min, be warming up to 2100-2150 DEG C, heat preservation
1-1.5h。
In above scheme, the Polycarbosilane, glucose, cellulose ether, polyvinyl alcohol, water mass ratio be 100:(20
~25): (0.03~0.08): (3~5): (35~40).
In above scheme, the purity of the Polycarbosilane is greater than 97%, molecular weight 1000-2000；The polyvinyl alcohol
Molecular weight be 17000~20000.
In above scheme, the chlorine etching technics includes: first under protective atmosphere, with the speed of 10-12 DEG C/min
It is warming up to 1150-1200 DEG C of heat preservation 1-1.5h, then is cooled to 1000-1050 DEG C, and chlorine is passed through with the speed of 30-35mL/min
Gas reacts 1.5-2h.
In above scheme, the mass ratio of the catalyst, cellulose ether and water is 100:(0.05-0.1): (30-40).
In above scheme, the cellulose ether is hydroxymethyl cellulose ether or hydroxyethyl ether cellulose, and molecular weight is
20000-30000。
In above scheme, sintering process described in step 3) is under protective atmosphere, with the speed of 8-12 DEG C/min, heating
To 900-1050 DEG C, 1-2h is kept the temperature.
In above scheme, nitrogen or argon gas etc. is can be selected in the protective atmosphere.
The principle of the present invention are as follows:
SiC ceramic membrane electrochemical reaction electrode of the present invention include from the outside to the core silicon carbide ceramic membrane matrix, carbon-coating and
Catalyst layer；Wherein silicon carbide ceramic membrane matrix strength reaches 25MPa or more, on the one hand can provide for electrode enough strong
Degree protects carbon-coating and catalyst layer, extends the service life of carbon-coating and catalyst layer, and one side silicon carbide ceramic membrane matrix is empty
Gap rate is greater than 35%, in wastewater treatment process, can also play the role of separating and filtering impurity；Carbon-coating is etched by chlorine
The pyroreaction object of Polycarbosilane obtains, and Polycarbosilane generates silicon carbide, this carbonization of formation during pyroreaction
Silicon product can with silicon carbide ceramic membrane base inner wall interface bonds well, and Polycarbosilane crack out silicon carbide activity
It is higher, can be generated derived carbon after chlorine cracking etching, on the one hand this derived carbon can in silicon carbide ceramic membrane base
Wall surface continues to keep good bonding, on the one hand also has preferable electric conductivity, thus on the basis for playing electric action
On, with silicon carbide ceramic membrane base bonds well, the high feature of silicon carbide ceramic membrane foundation base intension can be given full play to, it is made
There is good service life in use, existing easy loss, defeated and dispersed etc. lack when avoiding directlying adopt carbon as electrode
Point；Catalyst layer can adhere well to carbon-coating surface, the electricity in effective lifting waste water treatment process by the method for sintering
Chemical reaction efficiency and stability.
Compared with prior art, the invention has the benefit that
1) present invention constructs carbon-coating and catalyst with silicon carbide ceramic membrane matrix and inside it, and gained SiC ceramic film is electric
Chemically reacting electrode can express excellent electrochemical reaction effect and stability, and effectively solution graphite electrode intensity is poor,
Current density compared with it is high when export license is big, electrode efficiency is low, and service life is short the problems such as.
2) carbon-coating of the present invention is obtained by the pyroreaction object that chlorine etches Polycarbosilane, is made pottery being effectively ensured with silicon carbide
It on the basis of Ci Mo base inner wall adhesive property, can express excellent electric conductivity, take into account gained combination electrode can effectively
Good mechanical property and electric conductivity.
Detailed description of the invention
Fig. 1 is the structural schematic diagram of SiC ceramic membrane electrochemical reaction electrode described in embodiment 1.
In figure, 1 is silicon carbide ceramic membrane matrix, and 2 be carbon-coating, and 3 be catalyst layer.
Specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is furture elucidated, but it is of the invention
Content is not limited solely to the following examples.
In following embodiment, for the average grain diameter of the silicon carbide powder used for 20-40 μm, purity is greater than 99%；Silicon powder
Average grain diameter is 1-3 μm, and purity is greater than 95%；The partial size of carbon black is 0.1-0.3 μm, and carbon content is greater than 93%；
In following embodiment, the Polycarbosilane purity of use is greater than 98%；Glucose purity is greater than 98%；Cellulose ether is
For hydroxymethyl cellulose ether or hydroxyethyl ether cellulose, molecular weight 20000-30000；Polyvinyl alcohol molecule amount be 17000~
20000。
Embodiment 1
A kind of SiC ceramic membrane electrochemical reaction electrode, structural schematic diagram are shown in Fig. 1, and preparation method includes the following steps:
1) preparation of silicon carbide ceramic membrane matrix:
A1: the selection of raw material
By silicon carbide powder, silicon powder, carbon black, plasticizer (mixture that glycerol and polyethylene glycol press 1:1 mass ratio), lubrication
The mass ratio of agent (oleic acid) and solvent (deionized water) 100:7:3:3:3:14 weigh spare；
A2: the mixing of raw material with it is aging
Using pair roller type batch mixer, weighed each raw material is mixed, specific hybrid technique are as follows: first by carborundum powder
Body, silicon powder, carbon black mixing 10min add plasticizer, lubricant, solvent mixing 40min；The raw material mixed is taken out, is set
In the environment that humidity is 98%, temperature is 18 DEG C it is aging for 24 hours, obtain silicon carbide walk；
A3: molding and drying
Extrusion molding is carried out to gained silicon carbide walk using vacuum screw extruder, obtains single channel tubular type silicon carbide embryo
Body is subsequently placed in drying box, and first for 24 hours, then low temperature drying 12h under the conditions of 50 DEG C finally exists for predry under the conditions of 30 DEG C
High temperature drying 2h under the conditions of 115 DEG C, cooled to room temperature obtain silicon carbide raw embryo, carry out in air atmosphere in drying process；
A4: dumping and sintering
Gained silicon carbide raw embryo is placed in tube furnace and carries out dumping, specific binder removal are as follows: in a nitrogen atmosphere, first
It is warming up to 250 DEG C of heat preservation 30min in 50min, then is warming up to 360 DEG C of heat preservation 60min in 25min, finally in 80min
650 DEG C are warming up to, 20min is kept the temperature, cools to room temperature with the furnace and obtain silicon carbide element embryo；
Silicon carbide element embryo is placed in high temperature furnace and is sintered, specific sintering process are as follows: under an argon atmosphere, first with 10
DEG C/speed of min, and it is warming up to 1600 DEG C of heat preservation 2h, then with the speed of 5 DEG C/min, is warming up to 2100 DEG C of heat preservation 1h, it is cold with furnace
But to room temperature, silicon carbide ceramic membrane matrix is obtained；
2) the plating carbon of silicon carbide ceramic membrane matrix
B1: the preparation of Polycarbosilane colloid
Polycarbosilane, glucose, cellulose ether, polyethylene alcohol and water are claimed by the mass ratio of 100:20:0.03:3:35
Amount, is put into agitated kettle and is sufficiently stirred, obtain Polycarbosilane colloid；
B2: coating and drying
By gained Polycarbosilane colloid by the way of drenching glaze, the inner wall of coating to silicon carbide ceramic membrane matrix, after the completion
Dry 2h is placed in 105 DEG C of baking ovens；
B3: chlorine etching
Silicon carbide ceramic membrane matrix through B2 step process is placed in progress chlorine etching, specific steps in high temperature process furnances
Are as follows: under protection of argon gas, 1150 DEG C of heat preservation 1h are warming up to the speed of 10 DEG C/min, then be cooled to 1000 DEG C, and with 30mL/
The speed of min is passed through chlorine reaction 1.5h, and Polycarbosilane is made to be changed into carbon, and is plated on the table of silicon carbide ceramic membrane matrix inner wall
Face must be coated with the silicon carbide ceramic membrane matrix (carbon layers having thicknesses 1.5mm) of carbon-coating；
3) load of catalyst
C1: the preparation of catalyst colloid
Catalyst, cellulose ether, water are weighed by the mass ratio of 100:0.05:30, is put into agitated kettle and is sufficiently stirred, obtain
Catalyst colloid；
C2: coating and drying
By gained catalyst colloid by the way of drenching glaze, coating is to through step (2) silicon carbide obtained for being coated with carbon-coating
The inner wall of ceramic membrane matrix, completion are placed in 105 DEG C of baking ovens, dry 3h；
C3: sintering
Sample through C2 step process is placed in tube furnace, in a nitrogen atmosphere, with 8 DEG C of speed, is warming up to 900 DEG C
1h is kept the temperature, room temperature is cooled to the furnace after the completion, catalyst is made to be carried on inner wall (the catalyst thickness of silicon carbide ceramic membrane matrix
Degree is 0.5mm) to get the SiC ceramic membrane electrochemical reaction electrode.
In step 1), the average grain diameter of the silicon carbide powder is 25 μm, purity 99.5%；The average grain of the silicon powder
Diameter is 1.5 μm, purity 96%；The partial size of carbon black is 0.1 μm, carbon content 95%；The plasticizer is that glycerol and polyethylene glycol are pressed
According to the mixture of mass ratio 1:1, purity is 99%；Lubricant is oleic acid, purity 99%；Solvent is deionized water；Gained carbon
SiClx ceramic membrane matrix is cylindrical tube, length 0.5m, outer diameter 20mm, internal diameter 10mm, voidage 37%, 0.35 μ of average pore size
m。
In step 2), the Polycarbosilane purity 99%；Glucose purity 99%；Cellulose ether is hydroxymethyl cellulose
Ether, molecular weight 21000；Polyvinyl alcohol molecule amount is 17200；Water is deionized water；The purity 99.1% of chlorine.
In step 3), the catalyst is RuO2、TiO2Mixture, wherein TiO2Shared mass percent is 50%；
Cellulose ether is hydroxymethyl cellulose ether, molecular weight 21000；Water is deionized water.
Embodiment 2
A kind of SiC ceramic membrane electrochemical reaction electrode, preparation method include the following steps:
1) preparation of silicon carbide ceramic membrane matrix:
A1: the selection of raw material
By silicon carbide powder, silicon powder, carbon black, plasticizer (mixture that glycerol and polyethylene glycol press 1:1 mass ratio), lubrication
The mass ratio of agent (oleic acid) and solvent (deionized water) 100:8:3.5:5:5:17 weigh spare；
A2: the mixing of raw material with it is aging
Using pair roller type batch mixer, weighed each raw material is mixed, specific hybrid technique are as follows: first by carborundum powder
Body, silicon powder, carbon black mixing 13min add plasticizer, lubricant, solvent mixing 45min；The raw material mixed is taken out, is set
The aging 36h in the environment that humidity is 98%, temperature is 20 DEG C, obtains silicon carbide walk；
A3: molding and drying
Extrusion molding is carried out to gained silicon carbide walk using vacuum screw extruder, obtains single channel tubular type silicon carbide embryo
Body is subsequently placed in drying box, and first for 24 hours, then low temperature drying 12h under the conditions of 53 DEG C finally exists for predry under the conditions of 33 DEG C
High temperature drying 2h under the conditions of 117 DEG C, cooled to room temperature obtain silicon carbide raw embryo, carry out in air atmosphere in drying process；
A4: dumping and sintering
Gained silicon carbide raw embryo is placed in tube furnace and carries out dumping, specific binder removal are as follows: in a nitrogen atmosphere, first
It is warming up to 270 DEG C of heat preservation 33min in 50min, then is warming up to 370 DEG C of heat preservation 65min in 25min, finally in 80min
670 DEG C are warming up to, 23min is kept the temperature, cools to room temperature with the furnace and obtain silicon carbide element embryo；
Silicon carbide element embryo is placed in high temperature furnace and is sintered, specific sintering process are as follows: under an argon atmosphere, first with 11
DEG C/speed of min, 1610 DEG C of heat preservation 2.3h are warming up to, then with the speed of 7 DEG C/min, be warming up to 2125 DEG C of heat preservation 1.3h, with
Furnace is cooled to room temperature, and obtains silicon carbide ceramic membrane matrix；
2) the plating carbon of silicon carbide ceramic membrane matrix
B1: the preparation of Polycarbosilane colloid
Polycarbosilane, glucose, cellulose ether, polyethylene alcohol and water are claimed by the mass ratio of 100:23:0.06:4:38
Amount, is put into agitated kettle and is sufficiently stirred, obtain Polycarbosilane colloid；
B2: coating and drying
By gained Polycarbosilane colloid by the way of drenching glaze, the inner wall of coating to silicon carbide ceramic membrane matrix, after the completion
Dry 3h is placed in 113 DEG C of baking ovens；
B3: chlorine etching
Silicon carbide ceramic membrane matrix through B2 step process is placed in progress chlorine etching, specific steps in high temperature process furnances
Are as follows: under protection of argon gas, 1175 DEG C of heat preservation 1.3h are warming up to the speed of 11 DEG C/min, then be cooled to 1025 DEG C, and with
The speed of 33mL/min is passed through chlorine reaction 1.7h, and Polycarbosilane is made to be changed into carbon, and is plated on silicon carbide ceramic membrane matrix inner wall
Surface, the silicon carbide ceramic membrane matrix (carbon layers having thicknesses 2mm) of carbon-coating must be coated with；
3) load of catalyst
C1: the preparation of catalyst colloid
Catalyst, cellulose ether, water are weighed by the mass ratio of 100:0.07:35, is put into agitated kettle and is sufficiently stirred, obtain
Catalyst colloid；
C2: coating and drying
By gained catalyst colloid by the way of drenching glaze, coating is to through step (2) silicon carbide obtained for being coated with carbon-coating
The inner wall of ceramic membrane matrix, completion are placed in 113 DEG C of baking ovens, dry 4h；
C3: sintering
Sample through C2 step process is placed in tube furnace, in a nitrogen atmosphere, with 10 DEG C of speed, is warming up to 980
DEG C heat preservation 1.5h, cool to room temperature with the furnace after the completion, catalyst made to be carried on the inner wall (catalyst of silicon carbide ceramic membrane matrix
Layer is with a thickness of 1mm)；Up to the SiC ceramic membrane electrochemical reaction electrode.
In step 1), the average grain diameter of the silicon carbide powder is 40 μm, purity 99.5%；The average grain of the silicon powder
Diameter is 3 μm, purity 98%；The partial size of carbon black is 0.3 μm, carbon content 94%；The plasticizer is that glycerol and polyethylene glycol are pressed
According to the mixture of mass ratio 1:1, purity is 99%；Lubricant is oleic acid, purity 99%；Solvent is deionized water；Silicon carbide
Ceramic membrane matrix be cylindrical tube, length 1m, outer diameter 40mm, internal diameter 30mm, voidage 39%, 0.5 μm of average pore size.
In step 2), the Polycarbosilane purity 99.1%；Glucose purity 99%；Cellulose ether is hydroxyethyl cellulose
Ether, molecular weight 30000；Polyvinyl alcohol molecule amount is 20000；Water is deionized water；The purity 99.3% of chlorine.
Step 3): the catalyst is RuO2、IrO2、SnO2、TiO2The mixture (waiting mass ratioes) of composition, wherein TiO2Institute
Accounting for mass percent is 25%；Cellulose ether is hydroxyethyl ether cellulose, molecular weight 30000；Water is deionized water.
Embodiment 3
A kind of SiC ceramic membrane electrochemical reaction electrode, preparation method include the following steps:
1) preparation of silicon carbide ceramic membrane matrix:
A1: the selection of raw material
By silicon carbide powder, silicon powder, carbon black, plasticizer (mixture that glycerol and polyethylene glycol press 1:1 mass ratio), lubrication
The mass ratio of agent (oleic acid) and solvent (deionized water) 100:9:3.9:7:7:20 weigh spare；
A2: the mixing of raw material with it is aging
Using pair roller type batch mixer, weighed each raw material is mixed, specific hybrid technique are as follows: first by carborundum powder
Body, silicon powder, carbon black mixing 15min add plasticizer, lubricant, solvent mixing 50min；The raw material mixed is taken out, is set
The aging 48h in the environment that humidity is 98%, temperature is 22 DEG C, obtains silicon carbide walk；
A3: molding and drying
Extrusion molding is carried out to gained silicon carbide walk using vacuum screw extruder, obtains single channel tubular type silicon carbide embryo
Body is subsequently placed in drying box, and first for 24 hours, then low temperature drying 12h under the conditions of 55 DEG C finally exists for predry under the conditions of 35 DEG C
High temperature drying 2h under the conditions of 120 DEG C, cooled to room temperature obtain silicon carbide raw embryo, carry out in air atmosphere in drying process；
A4: dumping and sintering
Gained silicon carbide raw embryo is placed in tube furnace and carries out dumping, specific binder removal are as follows: in a nitrogen atmosphere, first
It is warming up to 280 DEG C of heat preservation 35min in 50min, then is warming up to 380 DEG C of heat preservation 70min in 25min, finally in 80min
680 DEG C are warming up to, 25min is kept the temperature, cools to room temperature with the furnace and obtain silicon carbide element embryo；
Silicon carbide element embryo is placed in high temperature furnace and is sintered, specific sintering process are as follows: under an argon atmosphere, first with 12
DEG C/speed of min, 1620 DEG C of heat preservation 2.5h are warming up to, then with the speed of 8 DEG C/min, be warming up to 2150 DEG C of heat preservation 1.5h, with
Furnace is cooled to room temperature, and obtains silicon carbide ceramic membrane matrix；
2) the plating carbon of silicon carbide ceramic membrane matrix
B1: the preparation of Polycarbosilane colloid
Polycarbosilane, glucose, cellulose ether, polyethylene alcohol and water are claimed by the mass ratio of 100:25:0.08:5:40
Amount, is put into agitated kettle and is sufficiently stirred, obtain Polycarbosilane colloid；
B2: coating and drying
By gained Polycarbosilane colloid by the way of drenching glaze, the inner wall of coating to silicon carbide ceramic membrane matrix, after the completion
Dry 4h is placed in 120 DEG C of baking ovens；
B3: chlorine etching
Silicon carbide ceramic membrane matrix through B2 step process is placed in progress chlorine etching, specific steps in high temperature process furnances
Are as follows: under protection of argon gas, 1200 DEG C of heat preservation 1.5h are warming up to the speed of 12 DEG C/min, then be cooled to 1050 DEG C, and with
The speed of 35mL/min is passed through chlorine reaction 2h, and Polycarbosilane is made to be changed into carbon, and is plated on silicon carbide ceramic membrane matrix inner wall
Surface must be coated with the silicon carbide ceramic membrane matrix (carbon layers having thicknesses 1-2mm) of carbon-coating；
3) load of catalyst
C1: the preparation of catalyst colloid
Catalyst, cellulose ether, water are weighed by the mass ratio of 100:0.1:40, is put into agitated kettle and is sufficiently stirred, obtain
Catalyst colloid；
C2: coating and drying
By gained catalyst colloid by the way of drenching glaze, coating is to through step (2) silicon carbide obtained for being coated with carbon-coating
The inner wall of ceramic membrane matrix, completion are placed in 120 DEG C of baking ovens, dry 4.5h；
C3: sintering
Sample through C2 step process is placed in tube furnace, in a nitrogen atmosphere, with 12 DEG C of speed, is warming up to 1050
DEG C heat preservation 2h, cool to room temperature with the furnace after the completion, catalyst made to be carried on the inner wall (catalyst layer of silicon carbide ceramic membrane matrix
With a thickness of 0.5-1mm)；Up to the SiC ceramic membrane electrochemical reaction electrode.
In step 1), the average grain diameter of the silicon carbide powder is 30 μm, purity 99.5%；The average grain of the silicon powder
Diameter is 2.5 μm, purity 97%；The partial size of carbon black is 0.18 μm, carbon content 96%；The plasticizer is glycerol and polyethylene glycol
According to the mixture of mass ratio 1:1, purity is 99%；Lubricant is oleic acid, purity 99%；Solvent is deionized water；Carbonization
Silicon ceramic membrane matrix be cylindrical tube, length 0.75m, outer diameter 35mm, internal diameter 15mm, voidage 39%, 0.4 μm of average pore size.
In step 2), the Polycarbosilane purity 99%；Glucose purity 99%；Cellulose ether is hydroxymethyl cellulose
Ether, molecular weight 25000；Polyvinyl alcohol molecule amount is 19000；Water is deionized water；The purity 99.4% of chlorine.
Step 3): the catalyst is IrO2、Ta2O5、SnO2、TiO2The mixture (waiting mass ratioes) of composition, wherein TiO2
Shared mass percent is 25%；Cellulose ether is hydroxymethyl cellulose ether, molecular weight 25000；Water is deionized water.
Comparative example 1
A kind of traditional graphite electrode is mixed with adhesive by natural graphite, molding, is fired, and then will
TiO2Catalyst is fixed on graphite electrode using sol-gal process film.
By 1 gained SiC ceramic membrane electrochemical reaction electrode of embodiment and traditional graphite electrode (graphite electrode+catalyst
Layer, wherein catalyst layer passes through the RuO that will wait mass ratioes2And TiO2Compound and use sol-gal process film is fixed on graphite electricity
Pole surface, with a thickness of 0.5mm) be respectively applied to carry out phenolic wastewater treatment, waste water temperature be 25~35 DEG C, voltage be 3.5~
4.0V, under the conditions of electric current is 8A, the treatment effect of different times is shown in Table 1.
Comparative example 2
A kind of electrode coating carbon-coating and catalyst layer on porous SiC ceramics, successively uses graphite and catalyst
Sol-gal process film is fixed on SiC ceramic pipe, forms electrode, wherein the preparation method and embodiment of porous SiC ceramics
1 step 1) is identical, catalyst layer selection is same as Example 1, graphite linings thickness and the catalyst layer thickness difference of coating
For 1.5mm and 0.5mm；The electrode obtained is applied to carry out phenolic wastewater treatment, wherein waste water temperature is 25~35 DEG C, voltage
For 3.5~4.0V, under the conditions of electric current is 8A, the treatment effect of different times is shown in Table 1.
1 embodiment of the present invention 1 of table and comparative example 1, the wastewater treatment result of 2 the electrode obtaineds
It is anti-that the above results show that gained SiC ceramic membrane electrochemical reaction electrode of the invention can express excellent electrochemistry
Answer effect and stability.
Each raw material cited by the present invention can realize that the bound value of the present invention and each raw material, interval value can
Realize the present invention；Embodiment numerous to list herein.The bound value of technological parameter of the invention, interval value can be realized
The present invention, embodiment numerous to list herein.
Claims (10)
1. a kind of SiC ceramic membrane electrochemical reaction electrode, which is characterized in that its from-inner-to-outer successively includes catalyst layer, carbon-coating
With silicon carbide ceramic membrane matrix, wherein the voidage of silicon carbide ceramic membrane matrix is greater than 35%, and aperture is 0.3-0.5 μm.
2. SiC ceramic membrane electrochemical reaction electrode according to claim 1, which is characterized in that the catalyst layer is to urge
Agent and cellulose ether are that primary raw material through glue, coating and is sintered；Wherein catalyst is TiO2With activating oxide
Mixture, TiO2Shared mass percent is 20% or more, activating oxide RuO2、IrO2、SnO2、Ta2O5One of or
It is several.
3. SiC ceramic membrane electrochemical reaction electrode according to claim 1, which is characterized in that the silicon carbide ceramic membrane
Matrix is in cylindrical tube.
4. the preparation method of any one of claims 1 to 3 SiC ceramic membrane electrochemical reaction electrode, which is characterized in that including
Following steps:
1) preparation of silicon carbide ceramic membrane matrix: being main former with silicon carbide powder, silicon powder, carbon black, plasticizer, lubricant and water
Material, is mixed, is aging, obtaining silicon carbide walk；Then extrusion molding, drying are carried out, silicon carbide green compact are obtained；Gained is carbonized again
Silicon green compact carry out dumping, sintering, obtain silicon carbide ceramic membrane matrix；
2) it plates carbon: using Polycarbosilane, glucose, cellulose ether, polyethylene alcohol and water as primary raw material, mixing and be stirred place
Reason, obtains Polycarbosilane colloid；Then gained Polycarbosilane colloid is coated on to silicon carbide ceramic membrane matrix by the way of drenching glaze
Inner wall, drying；Then chlorine etching is carried out, so that Polycarbosilane is changed into carbon, and be plated on silicon carbide ceramic membrane matrix inner wall, obtains
To the silicon carbide ceramic membrane matrix for being coated with carbon-coating；
3) it the load of catalyst: using catalyst, cellulose ether and water as primary raw material, mixes and is stirred, must be catalyzed
Agent colloid；Then by its be coated on be coated with carbon-coating silicon carbide ceramic membrane matrix inner wall, be successively dried, be sintered to get
The SiC ceramic membrane electrochemical reaction electrode.
5. the preparation method according to claim 4, which is characterized in that the silicon carbide powder, silicon powder, carbon black, plasticizer,
The mass ratio of lubricant and water is 100:(7-9): (2.5-4.5): (3-7): (3-7): (14-20).
6. the preparation method according to claim 4, which is characterized in that sintering process described in step 1) includes: to protect
Under atmosphere, first with the speed of 10-12 DEG C/min, it is warming up to 1600-1620 DEG C, keeps the temperature 2-2.5h, then with the speed of 5-8 DEG C/min
Degree is warming up to 2100-2150 DEG C, keeps the temperature 1-1.5h.
7. the preparation method according to claim 4, which is characterized in that the Polycarbosilane, cellulose ether, gathers glucose
Vinyl alcohol, water mass ratio be 100:(20~25): (0.03~0.08): (3~5): (35~40).
8. the preparation method according to claim 4, which is characterized in that the chlorine etching technics includes: to protect first
Atmosphere system is warming up to 1150-1200 DEG C of heat preservation 1-1.5h with the speed of 10-12 DEG C/min, then is cooled to 1000-1050 DEG C, and
It is passed through chlorine with the speed of 30-35mL/min, reacts 1.5-2h.
9. the preparation method according to claim 4, which is characterized in that the mass ratio of the catalyst, cellulose ether and water
For 100:(0.05-0.1): (30-40).
10. the preparation method according to claim 4, which is characterized in that sintering process described in step 3) be with 8-12 DEG C/
The speed of min is warming up to 900-1050 DEG C, keeps the temperature 1-2h.
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| JP2020147845A (en) | 2020-09-17 |
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