CN105198048B - A kind of three-diemsnional electrode filler and preparation method thereof - Google Patents
A kind of three-diemsnional electrode filler and preparation method thereof Download PDFInfo
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- CN105198048B CN105198048B CN201510705791.2A CN201510705791A CN105198048B CN 105198048 B CN105198048 B CN 105198048B CN 201510705791 A CN201510705791 A CN 201510705791A CN 105198048 B CN105198048 B CN 105198048B
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- 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
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
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Abstract
The invention discloses a kind of three-diemsnional electrode filler and preparation method thereof, it is mainly included, and iron filings are carried out into activation process, copper plating treatment and the Nickel Plating Treatment including oil removing, derusting, obtain improveing iron filings；By the improvement iron filings Jing Guo Nickel Plating Treatment and a certain proportion of powdered active carbon, mix clay and uniformly mixed with certain proportion, 5~10mm of diameter granulated filler is made, dry, be calcined 2 hours at 600 DEG C under the conditions of starvation, cooling obtains three-diemsnional electrode filler.It has been mainly characterized by iron filings electroplating surface stable nickel coating, substantially prolongs the service life of iron carbon filler；Wastewater containing phenol is handled using the three-diemsnional electrode filler of the present invention, the degradation rate of phenol can be made to reach more than 80%, substantially increase the biodegradability of water sample.When the three-diemsnional electrode filler of recovery is repeatedly used, the degradation rate of phenol can also reach more than 60%, reduce the cost of wastewater treatment.
Description
Technical field
The present invention relates to electrode filler, more particularly to a kind of three-diemsnional electrode filler and preparation method thereof.
Background technology
Phenol is a kind of important industrial chemicals, has in chemical industry and has been widely used, but is caused because it has
Carcinous and mutability, priority pollutant is classified as by U.S. EPA and China.Therefore, the discharge of any wastewater containing phenol all should be by
To strict control.Wastewater containing phenol and by the minimizing technology of its polluted underground water include charcoal absorption, polymer resin adsorb, steam
Vapour, air are peeled off, biodegradable and heat damage etc..Although these method removal efficiency are higher, there is that energy resource consumption is big, cost
The problems such as height and organic efficiency are low.In the last few years, three-dimensional electrolysis technology due to high treating effect, technique is simple, applicability is extensive
The features such as and have become important industrial wastewater pollution control technology.
Three-dimensional electrolysis technology is one kind in electrochemistry sewage disposal technology, and in three-dimensional electrolysis technology, three-diemsnional electrode is filled out
Material is the core of the technology, the selection and preparation of filler material, is had to the removal effect and operation stability of pollutant
Critical influence.Three-diemsnional electrode filler is in the majority with iron carbon filler at present, but the experimental results show, the filler is in the application
Many defects be present, this electrolysis material is after a period of time is run, and material surface can form passivating film, while material is easily tied
Block, so as to hinder material to be contacted with the effective of waste water, cause electrolysis material utilization rate low, under making the treatment effect of waste water rapid
Drop, add the cost of wastewater treatment.It greatly limit the application of three-dimensional electrolysis technology.Therefore, develop it is high-effect, stably, can
The novel three-dimensional electrolysis material for repeating to recycle is significant for promoting three-dimensional electrolysis technology.
The content of the invention
The defects of in order to overcome in the presence of prior art, the present invention provide a kind of three-diemsnional electrode filler be used as it is a kind of new
The three-diemsnional electrode filler of type.It has stability is high, corrosion-resistant, intensity is big, activity is high, to water without it is secondary stain, service life
The characteristics of long, good side is provided to solve the problems such as filler is easily hardened, service life is short, perishable in three-dimensional electrolysis reaction
Case.By the copper facing zinc-plated processing to industrial waste iron filing, using its with activated carbon and clay as raw material, be prepared for one kind by roasting
New three-dimensional electrolysis filler, in the environment of using simulated wastewater containing phenols as subjects, not only effectively reduces sewage
In COD (COD), still have when improving the biodegradability of waste water, and being used repeatedly well degraded effect
Fruit.
A kind of three-diemsnional electrode filler of the present invention and preparation method thereof is achieved through the following technical solutions：
A kind of three-diemsnional electrode filler, the component and each component mass percent of the three-diemsnional electrode filler are as follows：Improve iron
Consider 10%-25%, activated carbon 35%-50% and mixing clay 30%-45% to be worth doing；And
The mixing clay is made up of the kaolin and 5%-15% bentonite that mass percent is 85%-95%.
Further, the three-diemsnional electrode filler is made up of the following component of mass percent：Improve iron filings 25%, activity
Charcoal 37.5% and mixing clay 37.5%；And
The mixing clay is made up of mass percent for 90% kaolin and 10% bentonite.
Further, the three-diemsnional electrode filler is made up of the following component of mass percent：Improve iron filings 15%, activity
Charcoal 45% and mixing clay 40%；And
The mixing clay is made up of mass percent for 89% kaolin and 11% bentonite.
Further, the three-diemsnional electrode filler is made up of the following component of mass percent：Improve iron filings 22%, activity
Charcoal 44% and mixing clay 34%；And
The mixing clay is made up of mass percent for 91% kaolin and 9% bentonite.
A kind of method for preparing three-diemsnional electrode filler, comprises the following steps：
Step 1：Improvement iron filings are prepared, its specific steps includes：
Oil removing, 0.5-2mm iron filings are put into 5%-15% sodium hydroxide solution, heated simultaneously at 50 DEG C -80 DEG C
Filtered after being ultrasonically treated 40min-100min；
Derusting, by through oil removal treatment and filter gained iron filings be placed in 5%-20% dilute sulfuric acid soak 10-30min after mistake
Filter；
Copper facing, by through processing of rust removing and filter gained iron filings be placed in 3%-7% copper-bath, at 40-60 DEG C
Heating response 60min, filter, dry, be calcined 4 hours under starvation at 500 DEG C；And
Nickel plating, it will be soaked in through iron filings obtained by copper plating treatment in nickel-plating liquid, 40~60 DEG C are heated under ultrasound condition
40min, filtering, with water washing is distilled 3 times, dry, air roasting 4 hours are completely cut off at 600 DEG C -800 DEG C, obtain improveing iron
Bits；
Step 2：By the improvement iron filings, activated carbon and mixing clay 10%-25%, 35%-50% and 30%-
45% mass percent uniformly mixes, and adds water in the mixture, is shaken the graininess that diameter 3-5mm is made；
Step 3：It is put into Muffle furnace, described 60 DEG C of vacuum dryings of granular iron carbon filler under conditions of isolating oxygen
Heating roasting 2-4 hours, it is 0.4-1.0m that specific surface area, which is made,2/ g three-diemsnional electrode filler.
Further, the preparation of the nickel-plating liquid comprises the following steps：
Step 1：500ml 3%-6% nickel sulfate solution is prepared, sequentially adds 25~40g of sodium citrate, three ethanol
15~20g of amine；
Step 2：30~50g sodium hypophosphite solids, stirring and dissolving are added under agitation；
Step 3：It is 8 to be adjusted under agitation with 10% sodium hydroxide solution to pH；And
Step 4：Filtering, obtains the nickel-plating liquid.
Due to using above technical scheme, the present invention has the following advantages that compared with prior art：
1. improvement iron filings surface uses copper-plating technique, the ductility of iron filings is substantially improved；
2. improvement iron filings surface uses nickel plating technology, stabilization, corrosion resistant nickel coating are formd on surface, substantially prolongs
Its service life；
3. mixing clay is mainly mixed by a certain percentage by kaolin and bentonite, bentonite has after bonding
Certain expansion, space not of uniform size is formed after calcining, adds the specific surface area of filler to a certain extent；
4. after the three-diemsnional electrode filler processing wastewater containing phenol 200min prepared using the method for the present invention, degradation rate is higher than
80%, far above the 50% of conventional iron carbon filler；
5. the three-diemsnional electrode filler of the present invention can be recycled, the three-diemsnional electrode filler of recycling containing phenol to giving up
The degradation rate of water is higher than 70%, and the degradation rate higher than 60% can be still realized after multiple Reusability, is effectively improved iron
The utilization rate of carbon filler.
Brief description of the drawings
Fig. 1 is with the time according to three-diemsnional electrode filler and conventional iron carbon filler of the invention to the degradation rate of wastewater containing phenol
The curve map of change.
Embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiment, to the present invention
It is further elaborated.It should be appreciated that specific embodiment described herein is not used to limit only to explain the present invention
The fixed present invention.
Embodiment 1
A diameter of 0.5-2mm iron filings 200g is put into 15% sodium hydroxide solution, heating and ultrasound at 60 DEG C
Filtered after processing 40min, so as to oil removing.Gained solid after 10% dilute sulfuric acid immersion 30min with filtering, to derust.It is above-mentioned
Oil removing and processing of rust removing are referred to as carrying out activation process to iron filings.Iron filings after activation are placed in 5% copper-bath,
Heating response 60min at 60 DEG C, filter, dry, be then calcined 4 hours under 500 DEG C of starvations.Cooled iron filings are soaked
Steep in the 1000mL nickel-plating liquids configured, 50 DEG C heated under ultrasound condition) nickel plating 40min, filtering, with distillation water washing 3
It is secondary, dry, air roasting 4 hours are completely cut off at 800 DEG C, obtain improveing iron filings.The step of wherein configuring nickel-plating liquid includes：Prepare
500ml 3% nickel sulfate solution, sodium citrate 20g, triethanolamine 11g are sequentially added, adds hypophosphorous acid under agitation
Sodium solid 26g, stirring and dissolving, it is 8 then to be adjusted under agitation with 10% sodium hydroxide to pH, filtering, obtains nickel-plating liquid.
By the improvement iron filings for handling to obtain by activation process and plating copper and nickel, active powdered carbon, mixing clay by 2：3：3
Ratio --- i.e. mass percent improvement iron filings 25%, activated carbon 37.5% and mixing clay 37.5% --- it is uniformly mixed
Close, wherein, mixing clay is made up of 90% kaolin and 10% bentonite.A small amount of water is added in said mixture,
The graininess that diameter 3-5mm is made is shaken, 60 DEG C of vacuum dryings, is put into Muffle furnace, heating roasting 4 is small under conditions of isolating oxygen
When, cooling obtains three-diemsnional electrode filler.
In order to examine the ability of three-diemsnional electrode filler processing wastewater containing phenol, with graphite cake (surface area 50cm2) it is negative electrode
Plate, DSA electrodes (surface area 50cm2) it is anode material, 1000mg/L sodium sulphate is electrolyte, electrode spacing 7cm, is electrolysed
Time is 60~120min minutes, current density：60mA cm-2, at a temperature of 40 DEG C, use three-dimensional electricity obtained by the present embodiment
The oxybenzene compound aqueous solution that tassement polaire degraded concentration is 2500mg/L, under conditions of pH=8, electrolysis time 100min,
Phenol degrading rate is 84%.By reacting liquid filtering, washing recovery three-diemsnional electrode filler, again with above-mentioned electrolytic condition cell reaction
100min, phenol degrading rate are 80%.When third time repeats this step, the degradation rate of phenol is 79%.
Embodiment 2
A diameter of 0.5-2mm iron filings 200g is put into 10% sodium hydroxide solution, heating and ultrasound at 60 DEG C
Filtered after processing 40min, so as to oil removing.Gained solid after 10% dilute sulfuric acid immersion 30min with filtering, to derust.It is above-mentioned
Oil removing and processing of rust removing are referred to as carrying out activation process to iron filings.Iron filings after activation are placed in 5% copper-bath,
Heating response 60min at 60 DEG C, filter, dry, be then calcined 4 hours under 500 DEG C of starvations.Cooled iron filings are soaked
Steep in the 1000mL nickel-plating liquids configured, 50 DEG C of nickel plating 40min, filtering, with distillation water washing 3 are heated under ultrasound condition
It is secondary, dry, air roasting 4 hours are completely cut off at 800 DEG C, obtain improveing iron filings.The step of wherein configuring nickel-plating liquid includes：Wherein
The step of configuring nickel-plating liquid includes：500ml 5% nickel sulfate solution is prepared, sequentially adds sodium citrate 30g, triethanolamine
18g；Under agitation add 42g sodium hypophosphite solids, stirring and dissolving, then under agitation with 10% sodium hydroxide adjust to
PH is 8, filtering, obtains nickel-plating liquid.
By the improvement iron filings for handling to obtain by activation process and plating copper and nickel, active powdered carbon, mixing clay by 1：3：
2.5 ratio --- i.e. mass percent improvement iron filings 15%, activated carbon 45% and mixing clay 40% --- uniformly mixing,
Wherein, mixing clay is made up of 89% kaolin and 11% bentonite.A small amount of water is added in said mixture, the system of shaking
Into diameter 3-5mm graininess, 60 DEG C of vacuum dryings, it is put into Muffle furnace, heating roasting 4 hours, cold under conditions of isolating oxygen
But three-diemsnional electrode filler is obtained.
In order to examine the ability of three-diemsnional electrode filler processing wastewater containing phenol, with graphite cake (surface area 50cm2) it is negative electrode
Plate, DSA electrodes (surface area 50cm2) it is anode material, 1000mg/L sodium sulphate is electrolyte, electrode spacing 7cm, is electrolysed
Time is 60~120min minutes, current density：60mA cm-2, at a temperature of 40 DEG C, use three-dimensional electricity obtained by the present embodiment
The oxybenzene compound aqueous solution that tassement polaire degraded concentration is 2500mg/L, under conditions of pH=8, electrolysis time 100min,
Phenol degrading rate is 78%.By reacting liquid filtering, washing recovery three-diemsnional electrode filler, again with above-mentioned electrolytic condition cell reaction
100min, phenol degrading rate are 76%.When third time repeats this step, the degradation rate of phenol is 72%.
Embodiment 3
A diameter of 0.5-2mm iron filings 200g is put into 10% sodium hydroxide solution, heating and ultrasound at 60 DEG C
Filtered after processing 40min, so as to oil removing.Gained solid after 10% dilute sulfuric acid immersion 30min with filtering, to derust.It is above-mentioned
Oil removing and processing of rust removing are referred to as carrying out activation process to iron filings.Iron filings after activation are placed in 5% copper-bath,
Heating response 60min at 60 DEG C, filter, dry, be then calcined 4 hours under 500 DEG C of starvations.Cooled iron filings are soaked
Steep in the 1000mL nickel-plating liquids configured, 40 DEG C of nickel plating 40min, filtering, with distillation water washing 3 are heated under ultrasound condition
It is secondary, dry, air roasting 4 hours are completely cut off at 700 DEG C, obtain improveing iron filings.The step of wherein configuring nickel-plating liquid includes：Prepare
500ml 5% nickel sulfate solution, sequentially add sodium citrate 30g, triethanolamine 18g；Add 42g times under agitation
Sodium phosphate solid, stirring and dissolving, it is 8 then to be adjusted under agitation with 10% sodium hydroxide to pH, filtering, obtains nickel-plating liquid.
By the improvement iron filings for handling to obtain by activation process and plating copper and nickel, active powdered carbon, mixing clay by 2：4：3
Ratio --- i.e. mass percent improvement iron filings 22%, activated carbon 44% and mixing clay 34% --- uniformly mixing, its
In, mixing clay is made up of 91% kaolin and 9% bentonite.A small amount of water is added in said mixture, shakes and is made
Diameter 3-5mm graininess, 60 DEG C of vacuum dryings, is put into Muffle furnace, heating roasting 4 hours, cooling under conditions of isolating oxygen
Obtain three-diemsnional electrode filler.
In order to examine the ability of three-diemsnional electrode filler processing wastewater containing phenol, with graphite cake (surface area 50cm2) it is negative electrode
Plate, DSA electrodes (surface area 50cm2) it is anode material, 1000mg/L sodium sulphate is electrolyte, electrode spacing 7cm, is electrolysed
Time is 60~120min minutes, current density：60mA cm-2, at a temperature of 40 DEG C, use three-dimensional electricity obtained by the present embodiment
The oxybenzene compound aqueous solution that tassement polaire degraded concentration is 2500mg/L, under conditions of pH=8, electrolysis time 100min,
Phenol degrading rate is 85%.By reacting liquid filtering, washing recovery three-diemsnional electrode filler, again with above-mentioned electrolytic condition cell reaction
100min, phenol degrading rate are 85%.When third time repeats this step, the degradation rate of phenol is 81%.
For the present invention by stable nickel coating on iron filings electroplating surface, substantially prolongs iron carbon filler uses the longevity
Life.Fig. 1 is that the degradation rate of wastewater containing phenol is changed over time with conventional iron carbon filler according to three-diemsnional electrode filler of the invention
Curve map.As illustrated, after using the three-diemsnional electrode filler processing wastewater containing phenol 200min of the present invention, phenol can be made
Degradation rate reaches more than 80%, far above the 50% of conventional iron carbon filler.The three-diemsnional electrode filler of recycling is to containing phenol
The degradation rate of waste water is higher than 70%, and the degradation rate higher than 60% can be still realized after multiple Reusability, is effectively improved
The utilization rate of iron carbon filler, reduce the cost of wastewater treatment.
Embodiment described above only expresses embodiments of the present invention, and its description is more specific and detailed, but can not
Therefore it is interpreted as the limitation to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art,
Without departing from the inventive concept of the premise, various modifications and improvements can be made, these belong to the protection model of the present invention
Enclose.Therefore, the protection domain of patent of the present invention should be determined by the appended claims.
Claims (6)
1. a kind of three-diemsnional electrode filler, it is characterised in that the component and each component mass percent of the three-diemsnional electrode filler are such as
Under：Improve iron filings 10%-25%, activated carbon 35%-50% and mixing clay 30%-45%；And
The mixing clay is made up of the kaolin and 5%-15% bentonite that mass percent is 85%-95%；
The preparation of the improvement iron filings comprises the steps of：
Oil removing, 0.5-2mm iron filings are put into 5%-15% sodium hydroxide solution, heating and ultrasound at 50 DEG C -80 DEG C
Filtered after processing 40min-100min；
Derusting, by through oil removal treatment and filter gained iron filings be placed in 5%-20% dilute sulfuric acid soak 10-30min after filter；
Copper facing, by through processing of rust removing and filter gained iron filings be placed in 3%-7% copper-bath, heated at 40-60 DEG C
60min is reacted, is filtered, dries, is calcined 4 hours under starvation at 500 DEG C；And
Nickel plating, will be soaked in nickel-plating liquid through iron filings obtained by copper plating treatment, and 40~60 DEG C of processing are heated under ultrasound condition
40min, filtering, with water washing is distilled 3 times, dry, air roasting 4 hours are completely cut off at 600 DEG C -800 DEG C, obtain improveing iron
Bits.
2. three-diemsnional electrode filler according to claim 1, it is characterised in that the three-diemsnional electrode filler is by mass percent
Following component composition：Improve iron filings 25%, activated carbon 37.5% and mixing clay 37.5%；And
The mixing clay is made up of mass percent for 90% kaolin and 10% bentonite.
3. three-diemsnional electrode filler according to claim 1, it is characterised in that the three-diemsnional electrode filler is by mass percent
Following component composition：Improve iron filings 15%, activated carbon 45% and mixing clay 40%；And
The mixing clay is made up of mass percent for 89% kaolin and 11% bentonite.
4. three-diemsnional electrode filler according to claim 1, it is characterised in that the three-diemsnional electrode filler is by mass percent
Following component composition：Improve iron filings 22%, activated carbon 44% and mixing clay 34%；And
The mixing clay is made up of mass percent for 91% kaolin and 9% bentonite.
A kind of 5. method for preparing three-diemsnional electrode filler, it is characterised in that comprise the following steps：
Step 1：Improvement iron filings are prepared, its specific steps includes：
Oil removing, 0.5-2mm iron filings are put into 5%-15% sodium hydroxide solution, heating and ultrasound at 50 DEG C -80 DEG C
Filtered after processing 40min-100min；
Derusting, by through oil removal treatment and filter gained iron filings be placed in 5%-20% dilute sulfuric acid soak 10-30min after filter；
Copper facing, by through processing of rust removing and filter gained iron filings be placed in 3%-7% copper-bath, heated at 40-60 DEG C
60min is reacted, is filtered, dries, is calcined 4 hours under starvation at 500 DEG C；And
Nickel plating, will be soaked in nickel-plating liquid through iron filings obtained by copper plating treatment, and 40~60 DEG C of processing are heated under ultrasound condition
40min, filtering, with water washing is distilled 3 times, dry, air roasting 4 hours are completely cut off at 600 DEG C -800 DEG C, obtain improveing iron
Bits；
Step 2：The improvement iron filings, activated carbon and mixing clay are pressed into 10%-25%, 35%-50% and 30%-
45% mass percent uniformly mixes, and adds water in the mixture, is shaken the graininess that diameter 3-5mm is made；
Step 3：Described 60 DEG C of vacuum dryings of granulated filler are put into Muffle furnace, roasting is heated under conditions of isolating oxygen
2-4 hours, it is 0.4-1.0m that specific surface area, which is made,2/ g three-diemsnional electrode filler.
6. according to the method for claim 5, it is characterised in that the preparation of the nickel-plating liquid comprises the following steps：
Step 1：500ml 3%-6% nickel sulfate solution is prepared, sequentially adds 20~35g of sodium citrate, triethanolamine 10
~15g；
Step 2：25~45g sodium hypophosphite solids, stirring and dissolving are added under agitation；
Step 3：It is 8 to be adjusted under agitation with 10% sodium hydroxide solution to pH；And
Step 4：Filtering, obtains the nickel-plating liquid.
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| CN201510705791.2A CN105198048B (en) | 2015-10-27 | 2015-10-27 | A kind of three-diemsnional electrode filler and preparation method thereof |
| PCT/CN2016/103269 WO2017071564A1 (en) | 2015-10-27 | 2016-10-25 | Three-dimensional electrode filler and manufacturing method thereof |
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| CN201510705791.2A CN105198048B (en) | 2015-10-27 | 2015-10-27 | A kind of three-diemsnional electrode filler and preparation method thereof |
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| CN105198048B (en) * | 2015-10-27 | 2018-01-02 | 雅本化学股份有限公司 | A kind of three-diemsnional electrode filler and preparation method thereof |
| CN106809921B (en) * | 2017-01-17 | 2020-04-17 | 广西大学 | Preparation method of kaolin-based three-dimensional particle electrode |
| CN106809922B (en) * | 2017-01-23 | 2019-04-19 | 五邑大学 | A kind of preparation method of multi-element metal micro-electrolysis stuffing |
| CN106757174B (en) * | 2017-02-23 | 2020-08-21 | 黄芃 | Method for preparing metal powder by electrodeposition |
| CN106882885A (en) * | 2017-03-07 | 2017-06-23 | 南昌大学 | A kind of three-diemsnional electrode couples iron-carbon micro-electrolysis sewage treatment process |
| CN107032457A (en) * | 2017-04-13 | 2017-08-11 | 齐鲁工业大学 | Application, pulping wastewater treatment method and granule electrode preparation method of the alta-mud loaded nano Zero-valent Iron in three-diemsnional electrode technology |
| CN110282704B (en) * | 2019-05-07 | 2022-03-04 | 广东省测试分析研究所（中国广州分析测试中心） | Electrochemical modified filler for water treatment |
| CN111039421A (en) * | 2019-12-12 | 2020-04-21 | 江苏京源环保股份有限公司 | Circulating water online descaling device and method based on electrochemistry |
| CN111892175B (en) * | 2020-07-31 | 2022-07-19 | 江苏省农业科学院 | Preparation method and application of porous carbon reinforced microorganism biofilm carrier material |
| CN112794409A (en) * | 2020-12-28 | 2021-05-14 | 赵培棉 | Three-dimensional electrode biofilm reactor |
| CN112723798B (en) * | 2020-12-30 | 2023-09-22 | 黑晶科技(嘉兴)有限公司 | Preparation method of geopolymer particle three-dimensional electrode |
| CN113087109A (en) * | 2021-03-25 | 2021-07-09 | 渤瑞环保股份有限公司 | Iron-carbon material recycled by refinery hydrogenation catalyst, preparation method and application |
| CN113104939B (en) * | 2021-04-15 | 2022-07-05 | 北京科技大学 | Method for preparing micro-electrolysis active coke filler by using metallurgical dust and mud |
| CN113582297A (en) * | 2021-07-29 | 2021-11-02 | 北京林业大学 | Preparation method and application of nickel-iron double-element loaded particle electrode |
| CN113716655B (en) * | 2021-09-10 | 2022-11-22 | 吉林建筑大学 | Ferronickel bimetal three-dimensional electrode particle filler and preparation method and application thereof |
| CN114409028B (en) * | 2022-02-11 | 2024-04-16 | 中海油天津化工研究设计院有限公司 | Three-dimensional particle electrode for wastewater treatment and preparation method thereof |
| CN115231712A (en) * | 2022-08-05 | 2022-10-25 | 盛世生态环境股份有限公司 | Preparation method and application of constructed wetland plant carbon-based iron-carbon micro-electrolysis filler |
| CN115893594A (en) * | 2022-12-08 | 2023-04-04 | 辽宁大学 | Preparation method and application of modified activated carbon particle electrode loaded with tin and antimony |
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2016
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| Publication number | Publication date |
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| CN105198048A (en) | 2015-12-30 |
| WO2017071564A1 (en) | 2017-05-04 |
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