CN114560536B - Terbium-rhenium modified Ti/RuO 2 Dimensionally stable anode, preparation method and application - Google Patents
Terbium-rhenium modified Ti/RuO 2 Dimensionally stable anode, preparation method and application Download PDFInfo
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
The invention discloses a terbium-rhenium modified Ti/RuO 2 The dimensionally stable anode comprises a Ti substrate, wherein RuO is arranged on the surface of the Ti substrate 2 A coating, wherein RuO 2 The coating contains terbium oxide and rhenium oxide; ruO (Ruo) 2 In the coating, the molar ratio of the sum of terbium and rhenium to Ru is 0.12-0.24:1. and discloses a preparation method of the dimensionally stable anode and application of the dimensionally stable anode in electrochemical catalytic oxidation treatment of landfill leachate membrane filtration concentrate. The terbium-rhenium modified Ti/RuO adopts the invention 2 The dimensionally stable anode, the preparation method and the application thereof have the advantages of high catalytic activity and good stability, and can realize the environment-friendly and efficient treatment of wastewater.
Description
Technical Field
The invention relates to a terbium-rhenium modified Ti/RuO 2 A dimensionally stable anode, a preparation method and application thereof, belonging to the technical fields of electrode materials and wastewater treatment.
Background
Currently, the most common method of landfill leachate treatment is the combination of biochemical treatment with membrane group treatment. Compared with the landfill leachate, the concentration of organic pollutants, inorganic salts and nonmetallic ions in the landfill leachate concentrated solution after membrane interception is higher, and the biodegradability is poorer. The landfill leachate membrane filtration concentrate has the following characteristics: (1) The components are complex, the concentration of organic pollutants is high, the COD is usually 1000-5000 mg/L, and the highest concentration can reach more than 20000 mg/L. (2) The inorganic salt component is high, the conductivity is up to 20000-50000 mu S/cm, except for the conventional Na + 、K + In addition, contains trace Pb 2+ 、Cu 2+ And (3) an isoparaffinic metal ion. (3) problem of chloride ion corrosion after concentration. (4) The biodegradability is poor, BOD/COD is generally less than 0.1, and most of the substances are difficult to biodegrade. (5) The concentrated solution is brown-black, and the hardness is generally 1000-2500 mg/L.
At present, most of domestic landfill leachate membrane filtration concentrated solution adopts a landfill stack body, and the concentrated solution is repeatedly recharged and maliciously circulated for a long time, so that the concentration of salt-enriched and nondegradable organic matters in the leachate is increased, the activity of biological flora is reduced during biochemical treatment, the treatment capacity of the existing equipment is gradually reduced, the leachate is gradually accumulated, and new environmental potential safety hazards are formed. The main methods under trial in the domestic landfill leachate concentrated solution treatment field include evaporation or mechanical compression re-evaporation, submerged combustion, membrane group re-concentration decrement and the like. The methods have the common advantages of high energy consumption and low efficiency, and the operation of the process is interrupted due to blockage, and concentrated solution with higher concentration and higher treatment difficulty is also produced. How to keep the long-term stable operation of the percolate treatment facility, solve the contradiction that the generated amount of the garbage percolate is not suitable for the actual treatment capacity, and solve the problems that the treatment capacity is improved and the accumulated percolate is dissolved before each garbage disposal site.
The electrochemical advanced oxidation technology has the characteristics of high COD removal efficiency, no secondary pollution, environmental protection and the like. Anode materials are the core for electrochemical treatment of wastewater, and their main categories include metal electrodes, graphite electrodes, titanium-based oxide electrodes, boron-doped diamond electrodes (BDD), and the like. Noble metal oxide RuO 2 Is of a rutile structure and has excellent catalytic activity. Titanium-based RuO 2 The electrode has the advantages of high catalytic activity, long service life, good corrosion resistance and the like, and has wide application prospect in the wastewater treatment process.
Disclosure of Invention
The invention aims at: in order to solve the problems, a terbium-rhenium modified Ti/RuO is provided 2 Dimensionally stable anode, preparation method and application thereof, ti/RuO of the invention 2 The dimensionally stable anode has the advantages of high catalytic activity and good stability, and can realize the environment-friendly and efficient treatment of wastewater.
The technical scheme adopted by the invention is as follows:
terbium-rhenium modified Ti/RuO 2 The dimensionally stable anode comprises a Ti substrate, wherein RuO is arranged on the surface of the Ti substrate 2 A coating, wherein RuO 2 Terbium-containing oxygen in the coatingA compound and a rhenium oxide.
In the present invention, ruO 2 The main component in the coating is ruthenium dioxide, and the coating is modified by terbium and rhenium oxide, wherein terbium belongs to rare earth element and has a 4f electronic structure, rhenium belongs to transition metal element and has a d electronic structure and an f electronic structure, and the Ti/RuO can be improved 2 The catalytic activity and stability of the dimensionally stable anode.
Preferably, the RuO 2 In the coating, the molar ratio of the sum of terbium and rhenium to Ru is 0.12-0.24:1.
in the above scheme, terbium and rhenium act as a catalyst for RuO 2 The coating is modified, if the terbium and rhenium are added in excessive amount (the molar ratio is more than 0.24:1), the terbium and rhenium do not play a role in modification, and RuO 2 The performance of terbium and rhenium is more presented in the coating, and the effects of improving the catalytic activity and the like cannot be achieved; if the amount of terbium and rhenium added is too small (molar ratio is less than 0.12:1), the effect of modification is not achieved as well, and the effect of improving the catalytic activity and the like cannot be achieved.
Preferably, the molar ratio of terbium to rhenium is between 0.1 and 10:1.
preferably, the RuO 2 The thickness of the coating is 3-10 um.
In the scheme, the catalytic effect of the dimensionally stable anode is poor if the thickness of the coating is too thin; the cost is increased when the thickness of the coating is too thick, and the catalytic activity is not increased continuously until a certain thickness is reached; ruO (Ruo) 2 The thickness of the coating is 3-10 um, and the coating has higher catalytic activity.
Preferably, the RuO 2 In the coating, ruO 2 The terbium oxide and the rhenium oxide are uniformly distributed.
Preferably, the terbium oxide is Tb 2 O 3 And/or Tb 4 O 7 The oxide of rhenium is ReO 3 And/or Re 2 O 3 And/or ReO 2 And/or Re 2 O。
Preferably, the Ti substrate is a titanium sheet or a titanium mesh.
Preferably, the Ti substrate is polished and etched.
Terbium-rhenium modified Ti/RuO 2 The preparation method of the dimensionally stable anode comprises the following steps:
step a: mixing isopropanol with concentrated hydrochloric acid to form a mixed solution, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, stirring and ultrasonically forming a uniform coating solution, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.12-0.24:1, a step of;
step b: pre-treating a Ti substrate;
step c: coating the coating liquid on the surface of the Ti substrate, and then drying and calcining;
step d: repeating the step c for a plurality of times after cooling to enable the coating to reach the required thickness;
step e: sintering the anode obtained in the step d at 450-550 ℃ for 2-3 h to obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
Preferably, in the step a, the volume ratio of the isopropanol to the concentrated hydrochloric acid is 8-10:1.
preferably, in the step b, the pretreatment process of the Ti substrate is as follows: polishing the Ti substrate by sand paper until the Ti substrate presents uniform metallic luster; sequentially and respectively carrying out ultrasonic treatment on a Ti substrate in acetone, naOH solution and distilled water for 10-15 min; and (3) putting the Ti substrate into oxalic acid solution, and etching for 1-3 hours at the temperature of 80-90 ℃ to enable the Ti substrate to present gray pitted surfaces without metallic luster.
In the scheme, the RuO can be improved by polishing and etching 2 The adhesive force of the coating on the Ti substrate improves the shape stable anode performance.
Preferably, in the step c, the temperature of the drying process is controlled to be 60-90 ℃ and the drying time is 15-20 min; the temperature in the calcination process is controlled to be 450-550 ℃ and the calcination time is 10-15 min.
Above terbium rhenium modified Ti/RuO 2 The application of the dimensionally stable anode is used for treating landfill leachate membrane filtration concentrate by electrochemical catalytic oxidation.
Preferably, the conditions of the electrocatalytic oxidation treatment are such that the pH is between 5 and 7.
The terbium-rhenium modified Ti/RuO 2 A dimensionally stable anode, a preparation method and application.
In summary, due to the adoption of the technical scheme, the beneficial effects of the invention are as follows:
1. terbium-rhenium modified Ti/RuO 2 The dimensionally stable anode has high catalytic activity and good stability;
2. can realize the environment-friendly and efficient treatment of the wastewater, and is particularly suitable for the wastewater with high COD and high ammonia nitrogen content.
Detailed Description
All of the features disclosed in this specification, or all of the steps in a method or process disclosed, may be combined in any combination, except for mutually exclusive features and/or steps.
Any feature disclosed in this specification may be replaced by alternative features serving the same or equivalent purpose, unless expressly stated otherwise. That is, each feature is one example only of a generic series of equivalent or similar features, unless expressly stated otherwise.
Example 1
The terbium-rhenium modified Ti/RuO of the embodiment 2 The preparation method of the dimensionally stable anode comprises the following steps:
step a: mixing isopropanol and concentrated hydrochloric acid in a volume ratio of 8:1, mixing to form a mixed solution, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, stirring, and carrying out ultrasonic treatment for 30 minutes to form a uniform coating solution, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.12:1, terbium to rhenium molar ratio 10:1, a step of;
step b: the Ti substrate is a titanium sheet, and is pretreated by the following steps: polishing the Ti substrate by sand paper until the Ti substrate presents uniform metallic luster; sequentially and respectively carrying out ultrasonic treatment on a Ti substrate in acetone, a 20wt% NaOH solution and distilled water for 10min; placing the Ti substrate into oxalic acid solution, and etching for 1h at 80 ℃ to enable the Ti substrate to present gray pitted surfaces without metallic luster;
step c: uniformly brushing the coating liquid on two sides of a Ti substrate, drying for 20min in a baking oven at 60 ℃, and calcining for 15min in a muffle furnace at 450 ℃;
step d: repeating the step c for a plurality of times after cooling to make the thickness of the coating be 3um;
step e: sintering the anode obtained in the step d in a muffle furnace at 550 ℃ for 2 hours, cooling to room temperature, and taking out to obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
The terbium-rhenium modified Ti/RuO is prepared in the embodiment 2 The anode is stabilized in shape.
Example 2
The terbium-rhenium modified Ti/RuO of the embodiment 2 The preparation method of the dimensionally stable anode comprises the following steps:
step a: isopropanol and concentrated hydrochloric acid are mixed according to a volume ratio of 10:1, mixing to form a mixed solution, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, stirring, and carrying out ultrasonic treatment for 30 minutes to form a uniform coating solution, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.24:1, terbium to rhenium molar ratio of 0.1:1, a step of;
step b: the Ti substrate is a titanium sheet, and is pretreated by the following steps: polishing the Ti substrate by sand paper until the Ti substrate presents uniform metallic luster; sequentially carrying out ultrasonic treatment on a Ti substrate in acetone, a 20wt% NaOH solution and distilled water for 15min; putting the Ti substrate into oxalic acid solution, and etching for 3 hours at 90 ℃ to enable the Ti substrate to present gray pitted surfaces without metallic luster;
step c: uniformly brushing the coating liquid on two sides of a Ti substrate, drying for 15min in a 90 ℃ oven, and calcining for 10min in a 550 ℃ muffle furnace;
step d: repeating the step c for a plurality of times after cooling to make the thickness of the coating be 10um;
step e: sintering the anode obtained in the step d in a muffle furnace at 450 ℃ for 2 hours, cooling to room temperature, and taking out to obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
The terbium-rhenium modified Ti/RuO is prepared in the embodiment 2 The anode is stabilized in shape.
Example 3
The terbium-rhenium modified Ti/RuO of the embodiment 2 The preparation method of the dimensionally stable anode comprises the following steps:
step a: isopropanol and concentrated hydrochloric acid are mixed according to the volume ratio of 9:1, mixing to form a mixed solution, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, stirring, and carrying out ultrasonic treatment for 30 minutes to form a uniform coating solution, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.18:1, terbium to rhenium molar ratio is 1:1, a step of;
step b: the Ti substrate is a titanium sheet, and is pretreated by the following steps: polishing the Ti substrate by sand paper until the Ti substrate presents uniform metallic luster; sequentially carrying out ultrasonic treatment on a Ti substrate in acetone, a 20wt% NaOH solution and distilled water for 12min; putting the Ti substrate into oxalic acid solution, and etching for 2 hours at 85 ℃ to enable the Ti substrate to present gray pitted surfaces without metallic luster;
step c: uniformly brushing the coating liquid on two sides of a Ti substrate, drying the Ti substrate in an oven at 75 ℃ for 18min, and calcining the Ti substrate in a muffle furnace at 500 ℃ for 12min;
step d: after cooling, repeating the step c for a plurality of times to enable the thickness of the coating to be 6um;
step e: sintering the anode obtained in the step d in a muffle furnace at 500 ℃ for 2.5h, cooling to room temperature, and taking out to obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
The terbium-rhenium modified Ti/RuO is prepared in the embodiment 2 The anode is stabilized in shape.
Example 4
The terbium-rhenium modified Ti/RuO of the embodiment 2 The preparation method of the dimensionally stable anode comprises the following steps:
step a: isopropanol and concentrated hydrochloric acid are mixed according to the volume ratio of 9:1, mixing to form a mixed solution, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, stirring, and carrying out ultrasonic treatment for 30 minutes to form a uniform coating solution, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.24:1, terbium to rhenium molar ratio of 0.5:1, a step of;
step b: the Ti substrate is a titanium sheet, and is pretreated by the following steps: polishing the Ti substrate by sand paper until the Ti substrate presents uniform metallic luster; sequentially carrying out ultrasonic treatment on a Ti substrate in acetone, a 20wt% NaOH solution and distilled water for 12min; putting the Ti substrate into oxalic acid solution, and etching for 2 hours at 90 ℃ to enable the Ti substrate to present gray pitted surfaces without metallic luster;
step c: uniformly brushing the coating liquid on two sides of a Ti substrate, drying for 15min in a 70 ℃ oven, and calcining for 15min in a 500 ℃ muffle furnace;
step d: after cooling, repeating the step c for a plurality of times to enable the thickness of the coating to be 8um;
step e: sintering the anode obtained in the step d in a muffle furnace at 550 ℃ for 2 hours, cooling to room temperature, and taking out to obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
The terbium-rhenium modified Ti/RuO is prepared in the embodiment 2 The anode is stabilized in shape.
Example 5
The difference between this embodiment and embodiment 4 is that the Ti substrate in this embodiment is a titanium mesh.
Examples 6 to 9
Examples 6-9 differ from example 4 in that the molar ratio of the sum of terbium and rhenium to Ru in step a of examples 6-9 is 0.12, respectively: 1. 0.15: 1. 0.18: 1. 0.21:1.
comparative example 1
The difference between this comparative example and example 4 is that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.09:1, obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
Comparative example 2
The difference between this comparative example and example 4 is that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.06:1, obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
Comparative example 3
The difference between this comparative example and example 4 is that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.03:1, obtain terbium-rhenium modified Ti/RuO 2 Dimensionally stable anode
Comparative example 4
The difference between this comparative example and example 4 is that only ruthenium trichloride was added in step a, yielding unmodified Ti/RuO 2 The anode is stabilized in shape.
Comparative example 5
The difference between this comparative example and example 4 is that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.3:1, obtain terbium-rhenium modified Ti/RuO 2 Dimensionally stable anode。
Comparative example 6
The difference between this comparative example and example 4 is that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.4:1, obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
Comparative example 7
The difference between this comparative example and example 4 is that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.5:1, obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
Comparative example 8
The difference between this comparative example and example 4 is that the molar ratio of the sum of terbium and rhenium to Ru in step a is 0.6:1, obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
Comparative example 9
The difference between this comparative example and example 4 is that the molar ratio of the sum of terbium and rhenium to Ru in step a is 1:1, obtain terbium-rhenium modified Ti/RuO 2 The anode is stabilized in shape.
Comparative example 10
The difference between this comparative example and example 4 is that terbium trichloride is not added in step a, the molar ratio of rhenium to Ru being 0.24:1, obtaining a rhenium modified Ti/RuO 2 The anode is stabilized in shape.
Comparative example 11
The difference between this comparative example and example 4 is that rhenium trichloride is not added in step a, the molar ratio of terbium to Ru being 0.24:1, obtain terbium modified Ti/RuO 2 The anode is stabilized in shape.
The dimensionally stable anode obtained in the above examples and comparative examples is subjected to electrochemical catalytic oxidation treatment on a landfill leachate membrane filtration concentrate at a current density of 30mAcm -2 The initial COD of the percolate membrane filtration concentrate is 10547mg/L and the initial ammonia nitrogen content is 886mg/L after the treatment for 2.5 hours at the pH value of 6 and the temperature of 25 ℃, and the results are shown in the following table:
by passing throughAs can be seen from the above examples and comparative examples, terbium-rhenium modified Ti/RuO of the invention 2 The dimensionally stable anode has good catalytic activity, the COD removal rate can reach more than 99%, and the ammonia nitrogen removal rate can reach more than 94%; when the molar ratio of the sum of terbium and rhenium to Ru is less than 0.12 compared to example 6 by comparative examples 1-3: 1, the catalytic performance of the dimensionally stable anode is reduced rapidly; from examples 4, 6-9, it can be seen that when the molar ratio of the sum of terbium and rhenium to Ru is between 0.12 and 0.24:1, as the total content of terbium and rhenium increases, the catalytic performance of the dimensionally stable anode increases, but when a certain point (0.18:1) is reached, the catalytic performance of the total content of terbium and rhenium continues to increase and begins to decrease; by comparison of comparative examples 5-9 with example 4, continued increase in the total terbium and rhenium content, the catalytic performance of the dimensionally stable anode began to decline dramatically because too much terbium and rhenium addition adversely affected RuO 2 Is used for the catalytic performance of the catalyst. By comparing comparative examples 10-11 with example 4, it can be seen that terbium-rhenium modified Ti/RuO 2 Compared with a dimensionally stable anode, terbium alone or rhenium modified Ti/RuO 2 The catalysis performance of the dimensionally stable anode is worse, which shows that the terbium-rhenium two elements are modified by one element than Ti/RuO 2 The effect of the dimensionally stable anode is better; by comparison of comparative example 4 with the examples, it can be seen that the modified Ti/RuO is compared with that of unmodified Ti/RuO 2 Compared with a dimensionally stable anode, terbium-rhenium modified Ti/RuO 2 The catalytic performance of the dimensionally stable anode is greatly improved; by comparison of examples 4-5, the Ti substrate was slightly better in catalytic performance for the titanium mesh than for the titanium plate due to the larger contact area of the mesh anode and better catalytic effect.
The invention is not limited to the specific embodiments described above. The invention extends to any novel one, or any novel combination, of the features disclosed in this specification, as well as to any novel one, or any novel combination, of the steps of the method or process disclosed.
Claims (6)
1. A terbium-rhenium modified Ti/RuO2 stable anode is characterized in that: the titanium alloy comprises a Ti substrate, wherein a RuO2 coating is arranged on the surface of the Ti substrate, and the RuO2 coating contains terbium oxide and rhenium oxide;
in the RuO2 coating, the mol ratio of the sum of terbium and rhenium to Ru is 0.12-0.24:1, a step of;
the molar ratio of terbium to rhenium is 0.1-10:1, a step of;
the thickness of the RuO2 coating is 3-10 um;
in the RuO2 coating, ruO2, terbium oxide and rhenium oxide are uniformly distributed.
2. The terbium-rhenium modified Ti/RuO2 stable anode of claim 1, wherein: the Ti substrate is a titanium sheet or a titanium net.
3. A preparation method of a terbium-rhenium modified Ti/RuO2 stable anode is characterized by comprising the following steps: the method comprises the following steps:
step a: mixing isopropanol with concentrated hydrochloric acid to form a mixed solution, adding ruthenium trichloride, terbium trichloride and rhenium trichloride into the mixed solution, stirring and ultrasonically forming a uniform coating solution, wherein the molar ratio of the sum of terbium and rhenium to Ru is 0.12-0.24:1, a step of;
step b: pre-treating a Ti substrate;
step c: coating the coating liquid on the surface of the Ti substrate, and then drying and calcining;
step d: repeating the step c for a plurality of times after cooling to enable the coating to reach the required thickness;
step e: and d, sintering the anode obtained in the step at 450-550 ℃ for 2-3 hours to obtain the terbium-rhenium modified Ti/RuO2 stable anode.
4. The method for preparing the terbium-rhenium modified Ti/RuO2 stable anode according to claim 3, wherein the method comprises the following steps: in the step a, the volume ratio of the isopropanol to the concentrated hydrochloric acid is 8-10:1.
5. the method for preparing the terbium-rhenium modified Ti/RuO2 stable anode according to claim 3, wherein the method comprises the following steps: in the step b, the pretreatment process of the Ti substrate is as follows: polishing the Ti substrate by sand paper until the Ti substrate presents uniform metallic luster; sequentially and respectively carrying out ultrasonic treatment on a Ti substrate in acetone, naOH solution and distilled water for 10-15 min; and (3) putting the Ti substrate into oxalic acid solution, and etching for 1-3 hours at the temperature of 80-90 ℃ to enable the Ti substrate to present gray pitted surfaces without metallic luster.
6. Use of a terbium-rhenium modified Ti/RuO2 dimensionally stable anode according to any one of claims 1-2, characterized in that: the method is used for treating the landfill leachate membrane filtration concentrate by electrochemical catalytic oxidation.
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| JP2019179592A (en) * | 2018-03-30 | 2019-10-17 | Fdk株式会社 | Manufacturing method of catalyst for air secondary battery, manufacturing method of air secondary battery, catalyst for air secondary battery, and air secondary battery |
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| KR100407710B1 (en) * | 2001-11-08 | 2003-12-01 | (주) 테크윈 | Catalytic oxide anode manufacturing method by high temperature sintering |
| DE102010043085A1 (en) * | 2010-10-28 | 2012-05-03 | Bayer Materialscience Aktiengesellschaft | Electrode for electrolytic chlorine production |
| CN110129821A (en) * | 2019-05-10 | 2019-08-16 | 上海氯碱化工股份有限公司 | Tin, Sb doped titanium-based ruthenic oxide coated electrode preparation method |
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| CN102477565A (en) * | 2010-11-29 | 2012-05-30 | 淮南师范学院 | Ti-based electrode with high catalytic activity, Ti/nano TiO2-RE2O3;Ti/nanoTiO2-ZrO2Preparation of |
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