CN108548859B - Direct determination device and determination method for chemical oxygen demand of solid pollutants - Google Patents
Direct determination device and determination method for chemical oxygen demand of solid pollutants Download PDFInfo
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- 239000001301 oxygen Substances 0.000 title claims abstract description 88
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 88
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 85
- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 39
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 39
- 239000007787 solid Substances 0.000 title claims abstract description 33
- 239000000126 substance Substances 0.000 title claims abstract description 29
- 238000000034 method Methods 0.000 title claims description 24
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 31
- 238000009284 supercritical water oxidation Methods 0.000 claims abstract description 21
- 238000007789 sealing Methods 0.000 claims abstract description 13
- 238000006243 chemical reaction Methods 0.000 claims description 35
- 230000001590 oxidative effect Effects 0.000 claims description 11
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003566 sealing material Substances 0.000 claims description 7
- 239000007800 oxidant agent Substances 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 239000010931 gold Substances 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- -1 oxygen ion Chemical class 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 238000005259 measurement Methods 0.000 abstract description 14
- 238000000691 measurement method Methods 0.000 abstract description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 230000007613 environmental effect Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000010802 sludge Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000010525 oxidative degradation reaction Methods 0.000 description 2
- KMUONIBRACKNSN-UHFFFAOYSA-N potassium dichromate Chemical compound [K+].[K+].[O-][Cr](=O)(=O)O[Cr]([O-])(=O)=O KMUONIBRACKNSN-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- DOBUSJIVSSJEDA-UHFFFAOYSA-L 1,3-dioxa-2$l^{6}-thia-4-mercuracyclobutane 2,2-dioxide Chemical compound [Hg+2].[O-]S([O-])(=O)=O DOBUSJIVSSJEDA-UHFFFAOYSA-L 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000012625 in-situ measurement Methods 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910000370 mercury sulfate Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- YPNVIBVEFVRZPJ-UHFFFAOYSA-L silver sulfate Chemical compound [Ag+].[Ag+].[O-]S([O-])(=O)=O YPNVIBVEFVRZPJ-UHFFFAOYSA-L 0.000 description 1
- 229910000367 silver sulfate Inorganic materials 0.000 description 1
- 239000008247 solid mixture Substances 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/403—Cells and electrode assemblies
- G01N27/406—Cells and probes with solid electrolytes
- G01N27/407—Cells and probes with solid electrolytes for investigating or analysing gases
- G01N27/409—Oxygen concentration cells
Abstract
The invention discloses a direct measurement device of chemical oxygen demand of solid pollutants and a measurement method thereof, comprising a supercritical water oxidation system and an oxygen sensor system, wherein the oxygen sensor system comprises a working electrode, a solid electrolyte and a reference electrode, the working electrode comprises an electrode layer, a current collecting net and a working electrode lead, the electrode layer and the current collecting net are sequentially connected to the outer wall surface of a solid electrolyte tube, one end of the working electrode lead is connected with the current collecting net, and the other end of the working electrode lead is led out outwards; the reference electrode comprises a sealing insulating layer, an oxygen buffer sintered body and a reference electrode lead, wherein the oxygen buffer sintered body is filled in the solid electrolyte tube, the sealing insulating layer is arranged at the opening end of the solid electrolyte tube, one end of the reference electrode lead is connected with the oxygen buffer sintered body, and the other end of the reference electrode lead is led out outwards; the working electrode lead and the leading-out end of the reference electrode lead are respectively connected with the two wiring ends of the same voltmeter, and the invention has the advantages of high measurement efficiency and accuracy, difficult secondary pollution and the like.
Description
Technical Field
The invention relates to a direct measurement device and a measurement method of chemical oxygen demand of solid pollutants, in particular to an in-situ monitoring technology and device for oxygen content and change of the oxygen content in a system in a direct supercritical water oxidation process of the solid pollutants, and belongs to the fields of environmental protection and environmental monitoring.
Background
Chemical oxygen demand is an extremely important parameter in the fields of environmental protection and environmental detection, and is an important index for measuring and evaluating the pollution degree of pollutants. Meanwhile, the chemical oxygen demand of the pollutants also directly influences the selection of the environmental treatment method and the technological process of the pollutants. Currently, standard methods for determining the chemical oxygen demand of pollutants are the potassium permanganate oxidation method and the potassium dichromate oxidation method. During measurement, the pollutant is oxidized and digested in the presence of excessive oxidant, and then the residual oxidant amount is determined by adopting a chemical titration or optical method, so that the chemical oxygen demand of the pollutant is obtained. This approach has significant limitations: the measurement efficiency is low; manual operation is needed, and human errors are easy to occur; the method relates to reagents such as mercury sulfate, silver sulfate, concentrated sulfuric acid and the like, has high cost and can cause secondary pollution. In addition, the method is applicable to liquid pollution systems, and for a plurality of non-liquid pollution systems (solid state and liquid-solid mixture) which are more and more complicated in modern society, pollutants contained in the non-liquid pollution systems are required to be transferred into a liquid sample for measurement, so that not only is the difficulty brought to the determination of the chemical oxygen demand, but also larger errors are easy to occur, the process is complicated, and the workload is large.
Disclosure of Invention
The invention aims to solve the technical problems that: the device and the method for directly measuring the chemical oxygen demand of the solid pollutants are provided, so that the problems of poor automation degree, low measurement efficiency, low accuracy, easiness in causing secondary pollution and the like in the process of measuring the chemical oxygen demand of the solid pollutants in the prior art are solved.
The technical scheme of the invention is as follows: a direct measurement device for the chemical oxygen demand of solid pollutants comprises a supercritical water oxidation system with a reaction kettle body, wherein an oxygen sensor system is arranged in the reaction kettle body and comprises a working electrode, a solid electrolyte and a reference electrode,
the solid electrolyte is a solid electrolyte tube with oxygen ion conductivity;
the working electrode comprises an electrode layer, a current collecting net and a working electrode lead, wherein the electrode layer and the current collecting net are sequentially connected to the outer wall surface of the bottom of the sealed end of the solid electrolyte tube, one end of the working electrode lead is connected with the current collecting net, and the other end of the working electrode lead penetrates through the reaction kettle body to extend outwards;
the reference electrode comprises a sealing insulating layer, an oxygen buffer sintered body and a reference electrode lead, wherein the oxygen buffer sintered body is filled in the solid electrolyte tube, the sealing insulating layer is arranged at the opening end of the solid electrolyte tube and is configured to seal the oxygen buffer sintered body in the solid electrolyte tube, one end of the reference electrode lead is connected with the oxygen buffer sintered body, and the other end of the reference electrode lead penetrates through the sealing insulating layer and the reaction kettle body to extend outwards;
and the leading-out ends of the working electrode lead and the reference electrode lead are respectively connected with two wiring ends of the same voltmeter.
The outer surface of a working electrode lead in the reaction kettle body is coated with a glassy inorganic sealing material layer, and the outer surface of a reference electrode lead in the reaction kettle body is coated with a glassy inorganic sealing material layer.
An alumina ceramic film is surrounded outside the working electrode.
The working electrode lead and the reference electrode lead are platinum, gold, palladium, silver, stainless steel, nickel, cobalt, tungsten or copper, and the diameter is 0.3-1.0 mm.
The wall thickness of the solid electrolyte tube is 2-5mm, the length is 10-15mm, and the electronic conductivity is less than 0.1% of the total conductivity.
The invention also provides a determination method of the direct determination device for the chemical oxygen demand of the solid pollutant, which comprises the following steps:
firstly, adding solid pollutants to be detected, water and excessive oxidant into a reaction kettle body;
secondly, after the whole device is synchronously heated and boosted to a set value, maintaining the state until the reaction is completed;
and thirdly, measuring the electromotive force of the oxygen sensor system, converting the residual oxygen amount in the reaction kettle body, and combining the initial given oxygen amount to obtain the oxygen amount consumed by thoroughly oxidizing the solid pollutants.
The beneficial effects of the invention are as follows: compared with the prior art, the invention has the advantages that:
(1) The invention provides a direct measurement device for chemical oxygen demand of solid pollutants. The device utilizes an oxygen sensor system to monitor the oxygen content of the system in situ in the supercritical water oxidation process of the solid pollutants, so that the chemical oxygen demand of the solid pollutants can be directly obtained.
(2) The device for directly measuring the chemical oxygen demand of the solid pollutant comprises a supercritical water oxidation system and an oxygen sensor system, wherein the oxygen sensor is integrally arranged in the supercritical water oxidation system, and a working electrode of the oxygen sensor is surrounded and protected by an anti-corrosion alumina porous ceramic membrane, so that the pollution of organic substances and salts in the system to be measured to the electrode is avoided.
(3) By utilizing the method and the device provided by the invention, the chemical oxygen demand of the solid pollution system can be directly measured, and the pollutant is not required to be transferred into liquid for measurement, so that the efficiency is greatly improved.
Drawings
FIG. 1 is a schematic diagram of the structure of the present invention;
reference numerals illustrate: 1 reaction kettle body, 2 solid electrolyte tube, 3 sealing insulating layer, 4 oxygen buffer sintered body, 5 electrode layer, 6 current collecting net, 7 alumina ceramic film, 8 reference electrode lead, 9 working electrode lead and 10 vitreous inorganic sealing material layer.
Detailed Description
The invention will be further described with reference to the accompanying drawings and specific examples:
referring to fig. 1, a direct measurement apparatus for chemical oxygen demand of solid contaminants according to the present invention includes a supercritical water oxidation system and a sensor system.
The supercritical water oxidation system consists of a high-temperature high-pressure reaction kettle body 1 and accessory components, has the functions of heating, sample injection, temperature measurement, pressure measurement and the like, and provides required places and conditions for supercritical water oxidation reaction of solid pollutants, so that the solid pollutants can be rapidly oxidized and digested.
The oxygen sensor system comprises a working electrode, a solid electrolyte and a reference electrode, and the connection mode can be expressed as: working electrode |solid electrolyte|reference electrode. The method is used for in-situ monitoring of the oxygen content of the system when the solid pollutants are subjected to oxidative degradation in the supercritical water oxidation system.
Specifically, the solid electrolyte is a solid electrolyte tube 2 having oxygen ion conductivity, the tube wall thickness is preferably 2 to 5mm, the length is preferably 10 to 15mm, and the electron conductivity is preferably less than 0.1% of the total conductivity.
The working electrode mainly comprises an electrode layer 5, a current collecting net 6 and a working electrode lead 9, wherein the electrode layer 5 and the current collecting net 6 are sequentially connected to the outer wall surface of the bottom of the closed end of the solid electrolyte tube 2, the thickness of the electrode layer 5 is preferably 10-50 mu m and is tightly combined with the solid electrolyte tube 2; the current collecting net 6 is one or more of noble metals such as platinum, gold, silver, palladium and the like, the density of the net is 500-800 meshes, and the current collecting net 6 is used for connecting a working electrode and an electrode lead of the sensor. One end of the working electrode lead 9 is connected with the current collecting net 6, and the other end of the working electrode lead passes through the reaction kettle body 1 to extend outwards.
The reference electrode comprises a sealing insulating layer 3, an oxygen buffer sintered body 4 and a reference electrode lead 8, wherein the oxygen buffer sintered body 4 is filled in the solid electrolyte tube 2, and the sealing insulating layer 3 is arranged at the open end of the solid electrolyte tube 2 so as to seal the oxygen buffer sintered body 4 in the solid electrolyte tube 2. The specific manufacturing method is as follows: filling oxygen reference buffer into the inside of the solid electrolyte ceramic tube, forming an oxygen buffer sintered body 4 in an inert atmosphere furnace higher than the sensor operating temperature; the sealing insulating layer 3 is formed by sintering an oxide, aluminosilicate, and a binder to the upper surface of the oxygen buffer sintered body under the condition that the sintering temperature of the oxygen buffer is not more than the operating temperature of the sensor. One end of the reference electrode lead 8 is connected with the oxygen buffer sintered body 4, and the other end of the reference electrode lead passes through the sealing insulating layer 3 and the reaction kettle body 1 to extend outwards.
The material of the working electrode lead 9 and the reference electrode lead 8 is one or more of platinum, gold, palladium, silver, stainless steel, nickel, cobalt, tungsten or copper, and the diameter is 0.3-1.0 mm. The outer surface of a working electrode lead 9 positioned in the reaction kettle body 1 is coated with a glassy inorganic sealing material layer 10, and the outer surface of a reference electrode lead 8 positioned in the reaction kettle body 1 is coated with the glassy inorganic sealing material layer 10. The wrapping layer has the function of isolating the electrode lead from an external system until the electrode lead enters the air with normal temperature and pressure, so that the measurement accuracy is ensured.
The leading-out ends of the working electrode lead 9 and the reference electrode lead 8 are respectively connected with two wiring ends of the same voltmeter in the air with normal temperature and pressure, and the high-precision digital voltmeter is preferred. During measurement, the potential difference between the working electrode and the reference electrode is measured through the voltmeter, so that in-situ measurement of the oxygen content of the system in the supercritical water oxidation process of the solid pollutants is realized, and the chemical oxygen demand of the solid pollutants is determined according to the oxygen content initially given by the supercritical water oxidation system.
The working electrode is surrounded by an alumina ceramic film 7, the density of which is controlled to be 1000-2000 meshes, preferably 1500 meshes. It can block out some organic pollutant or salt which pollutes the working electrode of oxygen sensor to protect the working electrode. Meanwhile, the accurate measurement of the oxygen content in the supercritical water oxidation system of the pollutant should not be influenced.
The invention relates to a method for measuring the chemical oxygen demand of solid pollutants by a direct measuring device, which comprises the following steps:
firstly, adding solid pollutants to be detected, water and excessive oxidant into a reaction kettle body 1;
secondly, after the whole device is synchronously heated and boosted to a set value, maintaining the state until the reaction is completed;
and thirdly, measuring the electromotive force of the oxygen sensor system, converting the residual oxygen amount in the reaction kettle body 1, and combining the initial given oxygen amount to obtain the oxygen amount consumed by thoroughly oxidizing the solid pollutants.
In the following examples, the supercritical water oxidation reaction system for contaminants was fabricated using nickel-based alloys with an effective volume of 50mL, an oxidative degradation temperature set point of 500 ℃, a pressure set point of 25MPa, a reaction time of 10 minutes, and an oxidant of hydrogen peroxide.
Example 1
Adding 5 g of dried sludge sample, water and excessive hydrogen peroxide into a supercritical water oxidation reaction system, ensuring that the material filling amount is lower than 40%, then starting heating and boosting, keeping the state for 10 minutes after the temperature and pressure reach set values, measuring the electromotive force of an oxygen sensor arranged in the supercritical water oxidation reaction device, obtaining the residual oxygen amount in the supercritical water oxidation reaction device to be 0.284 g, and obtaining the oxygen amount consumed by thoroughly oxidizing 5 g of dried sludge to be 0.428 g by combining the initial given oxygen amount to be 0.712 g, wherein the chemical oxygen demand is 85.6 mg/g.
Example 2
Adding 5 g of dried sludge, water and excessive hydrogen peroxide into a supercritical water oxidation reaction device, ensuring that the filling amount of materials is lower than 40%, then starting heating and boosting, keeping the state for 10 minutes after the temperature and the pressure reach set values, measuring the electromotive force of an oxygen sensor arranged in the supercritical water oxidation reaction device, obtaining 0.454 g of residual oxygen in the supercritical water oxidation reaction device, and obtaining 0.449 g of oxygen consumed by thoroughly oxidizing 5 g of dried sludge by combining with 0.903 g of initial given oxygen, wherein the chemical oxygen demand is 89.8 mg/g.
The foregoing is a further detailed description of the invention in connection with the preferred embodiments, and it is not intended that the invention be limited to the specific embodiments described. It will be apparent to those skilled in the art that several simple deductions or substitutions may be made without departing from the spirit of the invention, and these should be considered to be within the scope of the invention.
Claims (4)
1. The measuring method of the direct measuring device of the chemical oxygen demand of the solid pollutant, the device comprises a supercritical water oxidation system with a reaction kettle body (1), and is characterized in that: an oxygen sensor system is arranged in the reaction kettle body (1), the oxygen sensor system comprises a working electrode, a solid electrolyte and a reference electrode, wherein,
the solid electrolyte is a solid electrolyte tube (2) having oxygen ion conductivity;
the working electrode comprises an electrode layer (5), a current collecting net (6) and a working electrode lead (9), wherein the electrode layer (5) and the current collecting net (6) are sequentially connected to the outer wall surface of the bottom of the closed end of the solid electrolyte tube (2), one end of the working electrode lead (9) is connected with the current collecting net (6), the other end of the working electrode lead passes through the reaction kettle body (1) to extend outwards, and an alumina ceramic film (7) is surrounded outside the working electrode;
the reference electrode comprises a sealing insulating layer (3), an oxygen buffer sintered body (4) and a reference electrode lead (8), wherein the oxygen buffer sintered body (4) is filled in the solid electrolyte tube (2), the sealing insulating layer (3) is arranged at the opening end of the solid electrolyte tube (2) and is configured to seal the oxygen buffer sintered body (4) in the solid electrolyte tube (2), one end of the reference electrode lead (8) is connected with the oxygen buffer sintered body (4), and the other end of the reference electrode lead passes through the sealing insulating layer (3) and the reaction kettle body (1) to extend outwards;
the leading-out ends of the working electrode lead (9) and the reference electrode lead (8) are respectively connected with two wiring ends of the same voltmeter;
the method for measuring the chemical oxygen demand of the solid pollutant is characterized by comprising the following steps of:
firstly, adding solid pollutants to be detected, water and excessive oxidant into a reaction kettle body (1);
secondly, after the whole device is synchronously heated and boosted to a set value, maintaining the state until the reaction is completed;
and thirdly, measuring the electromotive force of the oxygen sensor system, converting the residual oxygen amount in the reaction kettle body (1), and combining the initial given oxygen amount to obtain the oxygen amount consumed by thoroughly oxidizing the solid pollutants.
2. The method for directly measuring the chemical oxygen demand of the solid pollutant according to claim 1, wherein: the outer surface of a working electrode lead (9) positioned in the reaction kettle body (1) is coated with a glassy inorganic sealing material layer (10), and the outer surface of a reference electrode lead (8) positioned in the reaction kettle body (1) is coated with the glassy inorganic sealing material layer (10).
3. The method for directly measuring the chemical oxygen demand of the solid pollutant according to claim 1, wherein: the working electrode lead (9) and the reference electrode lead (8) are platinum, gold, palladium, silver, stainless steel, nickel, cobalt, tungsten or copper, and the diameter is 0.3-1.0 mm.
4. The method for directly measuring the chemical oxygen demand of the solid pollutant according to claim 1, wherein: the wall thickness of the solid electrolyte tube (2) is 2-5mm, the length is 10-15mm, and the electronic conductivity is less than 0.1% of the total conductivity.
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