CN108548859A - A kind of direct measurement device of solid pollutant COD and its assay method - Google Patents
A kind of direct measurement device of solid pollutant COD and its assay method Download PDFInfo
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- CN108548859A CN108548859A CN201810592733.7A CN201810592733A CN108548859A CN 108548859 A CN108548859 A CN 108548859A CN 201810592733 A CN201810592733 A CN 201810592733A CN 108548859 A CN108548859 A CN 108548859A
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- 239000003344 environmental pollutant Substances 0.000 title claims abstract description 38
- 231100000719 pollutant Toxicity 0.000 title claims abstract description 38
- 239000007787 solid Substances 0.000 title claims abstract description 33
- 238000005259 measurement Methods 0.000 title claims abstract description 21
- 238000003556 assay Methods 0.000 title claims abstract description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 59
- 239000001301 oxygen Substances 0.000 claims abstract description 59
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 59
- 239000007784 solid electrolyte Substances 0.000 claims abstract description 31
- 238000009284 supercritical water oxidation Methods 0.000 claims abstract description 20
- 230000003139 buffering effect Effects 0.000 claims abstract description 12
- 238000009413 insulation Methods 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 230000003647 oxidation Effects 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 8
- 239000000919 ceramic Substances 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 6
- 239000007800 oxidant agent Substances 0.000 claims description 5
- 230000001590 oxidative effect Effects 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
- 239000004020 conductor Substances 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
- 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
- 229910052759 nickel Inorganic materials 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
- 230000005611 electricity Effects 0.000 claims description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000012544 monitoring process Methods 0.000 description 4
- 230000007613 environmental effect Effects 0.000 description 3
- 238000005245 sintering Methods 0.000 description 3
- 239000010802 sludge Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000004519 manufacturing process 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
- 238000007789 sealing Methods 0.000 description 2
- 239000000126 substance Substances 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
- FGRBYDKOBBBPOI-UHFFFAOYSA-N 10,10-dioxo-2-[4-(N-phenylanilino)phenyl]thioxanthen-9-one Chemical compound O=C1c2ccccc2S(=O)(=O)c2ccc(cc12)-c1ccc(cc1)N(c1ccccc1)c1ccccc1 FGRBYDKOBBBPOI-UHFFFAOYSA-N 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
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009530 blood pressure measurement Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000000576 coating 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
- 238000011049 filling Methods 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000001755 magnetron sputter deposition Methods 0.000 description 1
- 229940074994 mercuric sulfate Drugs 0.000 description 1
- 229910000372 mercury(II) sulfate Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000003672 processing method Methods 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
- 238000010561 standard procedure Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Measuring Oxygen Concentration In Cells (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of direct measurement device of solid pollutant COD and its assay methods, including supercritical water oxidation system and oxygen sensor system, oxygen sensor system includes working electrode, solid electrolyte and reference electrode, working electrode includes electrode layer, electric current collection net and working electrode lead, electrode layer and electric current collection net are connected to solid electrolyte tube outside wall surface in turn, working electrode lead one end is connect with electric current collection net, and the other end is drawn outward；Reference electrode includes sealed insulation layer, oxygen buffering sintered body and reference electrode lead, oxygen buffering sintered body is filled in solid electrolyte tube, sealed insulation layer is mounted on solid electrolyte tube open end, and reference electrode lead one end is connect with oxygen buffering sintered body, and the other end is drawn outward；The exit of working electrode lead and reference electrode lead is connect with two terminals of same voltmeter respectively, and the present invention has many advantages, such as that determination efficiency and accuracy are high, does not easily cause secondary pollution.
Description
Technical field
The present invention relates to a kind of direct measurement device of solid pollutant COD and its assay methods, more particularly to solid
System oxygen content and its in-situ monitoring technology and device of variation, belong to environment during the direct supercritical water oxidation of body pollution object
Protection and environmental monitoring.
Background technology
COD is a particularly important parameter in environmental protection and environmental testing, is to weigh and evaluate dirt
Contaminate an important indicator of object pollution level.Meanwhile the height of pollutant chemistry oxygen demand also directly influences the pollutant ring
The selection of border processing method and technical process.Currently, the standard method that pollutant chemistry oxygen demand measures is potassium permanganate oxidation
Method and potassium dichromate oxidation.When measurement, pollutant is subjected to oxidation resolution under excessive oxidant existence condition, is then used
Chemistry titration or optical means carry out the determination of residual oxygen dosage, and then obtain the COD of pollutant.This method
There is apparent limitation：Determination efficiency is low；Manual operation is needed, human error is susceptible to；Be related to mercuric sulfate, silver sulfate,
The reagents such as the concentrated sulfuric acid, it is of high cost, it is also possible to cause secondary pollution.In addition, the applicable object of this method is limited only to liquid dirt
Dye system, and for many non-liquid Pollution Systems that modern society becomes increasingly complex（Solid-state, liquid mix admittedly）, then must be by it
The pollutant contained, which is transferred in fluid sample, to be measured, and not only brings difficulty to the determination of COD, and be easy
There is larger error, process is cumbersome, heavy workload.
Invention content
The technical problem to be solved by the present invention is to：There is provided a kind of direct measurement device of solid pollutant COD and its
Assay method, it is poor to solve the prior art existing the degree of automation when measuring solid pollutant COD, measure effect
Rate is low, and accuracy is not high, easily causes secondary pollution problems.
The technical scheme is that：A kind of direct measurement device of solid pollutant COD, including there is reaction
The supercritical water oxidation system of autoclave body is equipped with oxygen sensor system in reaction kettle body, and the oxygen sensor system includes work
Electrode, solid electrolyte and reference electrode, wherein
Solid electrolyte, for the solid electrolyte tube with oxygen conduction；
Working electrode, including electrode layer, electric current collection net and working electrode lead, electrode layer and electric current collection net are connected in turn
Solid electrolyte tube blind end bottom outer wall face, working electrode lead one end are connect with electric current collection net, and the other end passes through reaction
Autoclave body extends outwardly；
Reference electrode, including sealed insulation layer, oxygen buffering sintered body and reference electrode lead, wherein oxygen buffers sintered body filling
In solid electrolyte tube, sealed insulation layer is mounted on solid electrolyte tube open end, is configured to oxygen buffering sintered body sealing
In in solid electrolyte tube, reference electrode lead one end is connect with oxygen buffering sintered body, and the other end is across sealed insulation layer and instead
Autoclave body is answered to extend outwardly；
The exit of the working electrode lead and reference electrode lead is connect with two terminals of same voltmeter respectively.
Working electrode lead appearance in reaction kettle body is coated with glassy state inorganic sealing material layer, is located at reaction kettle
Reference electrode lead appearance in body is coated with glassy state inorganic sealing material layer.
Aluminium oxide ceramics film is surrounded by outside working electrode.
The working electrode lead and reference electrode lead are platinum, gold, palladium, silver, stainless steel, nickel, cobalt, tungsten or copper, diameter
For 0.3-1.0 mm.
The wall thickness of the solid electrolyte tube is 2-5mm, and length 10-15mm, electronic conductivity is less than total conductivity
0.1%。
The present invention also provides a kind of assay methods of the direct measurement device of solid pollutant COD, including with
Lower step：
Solid pollutant to be measured, water and excessive oxidant are added in reaction kettle body the first step；
Second step, whole device synchronize increasing temperature and pressure to setting value after, hold mode to react complete；
Third walks, and measures the electromotive force of oxygen sensor system, converses remaining oxygen amount in reaction kettle body, in conjunction with initial given oxygen
Amount, you can obtain the oxygen amount spent by solid pollutant exhaustive oxidation.
The beneficial effects of the invention are as follows：Compared with the prior art, the advantages of the present invention are as follows：
（1）The present invention provides a kind of direct measurement devices of solid pollutant COD.The device utilizes lambda sensor system
System carries out in-situ monitoring to system institute oxygen content during solid pollutant supercritical water oxidation, and then can directly obtain solid dirt
Contaminate the COD of object.
（2）The direct measurement device of solid pollutant COD includes supercritical water oxidation system and lambda sensor system
System, lambda sensor are integrally placed in supercritical water oxidation system, and working electrode is by erosion-resisting alumina porous ceramic film
It surrounds and protects, avoid the pollution of organic substance and salt to electrode in system to be measured.
（3）By using method and apparatus provided by the invention, solid pollution system can directly carry out its chemical oxygen demand
It is fixed to measure, and is greatly improved it is not necessary that pollutant is transferred in liquid row measurement, efficiency again.
Description of the drawings
Fig. 1 is the structural schematic diagram of the present invention；
Reference sign：1 reaction kettle body, 2 solid electrolyte tubes, 3 sealed insulation layers, 4 oxygen buffering sintered body, 5 electrode layers, 6
Electric current collection net, 7 aluminium oxide ceramics films, 8 reference electrode leads, 9 working electrode leads, 10 glassy state inorganic sealing materials
Layer.
Specific implementation mode
Below in conjunction with the accompanying drawings and invention is described further in specific embodiment：
With reference to figure 1, according to a kind of direct measurement device of solid pollutant COD of the present invention, including supercritical water oxidation system
System and sensing system.
Supercritical water oxidation system is made of high-temperature high-pressure reaction kettle body 1 and appurtenances, have heating, sample introduction, thermometric,
The functions such as pressure measurement carry out supercritical water oxidation for solid pollutant and provide required place and condition, can be rapid
Oxidation resolution.
Oxygen sensor system includes working electrode, solid electrolyte, reference electrode, and connection type is represented by：Work
Electrode ︱ solid electrolyte ︱ reference electrodes.Body when for carrying out oxidative degradation in supercritical water oxidation system to solid pollutant
It is the in-situ monitoring of institute's oxygen content.
Specifically, solid electrolyte is the solid electrolyte tube 2 with oxygen conduction, and tube body wall thickness is preferably 2-
5mm, length are preferably 10-15mm, and electronic conductivity is preferably smaller than the 0.1% of total conductivity.
Working electrode is mainly made of electrode layer 5, electric current collection net 6 and working electrode lead 9, and electrode layer 5 and electric current are received
Collection net 6 is connected to 2 blind end bottom outer wall face of solid electrolyte tube, wherein preferred 10-50 μm of 5 thickness of electrode layer in turn, and with
Solid electrolyte tube 2 is combined closely, and specific production method is to clean and dry solid electrolyte tube 2, using magnetron sputtering or very
Oxygen-sensitive material is formed one layer of electrode layer 5 combined closely with it by empty coating method in ceramic tube outer surface；Electric current collection net 6 is
One or more in the noble metals such as platinum, gold, silver, palladium, the consistency of the net is 500-800 mesh, which carries
Connect the task of working sensor electrode and contact conductor.9 one end of working electrode lead is connect with electric current collection net 6, the other end
Extend outwardly across reaction kettle body 1.
Reference electrode includes sealed insulation layer 3, oxygen buffering sintered body 4 and reference electrode lead 8, wherein oxygen buffering sintering
Body 4 is filled in solid electrolyte tube 2, and sealed insulation layer 3 is mounted on 2 open end of solid electrolyte tube, and oxygen is buffered and is sintered
Body 4 is sealed in solid electrolyte tube 2.Specifically production method is：Oxygen reference buffer agent is filled into solid electrolyte ceramic pipe
Inside forms oxygen buffering sintered body 4 in the inert atmosphere stove higher than senor operating temperature；By oxide, aluminosilicate, glue
Agent is tied in the sintering temperature no more than oxygen buffer, higher than sintering to oxygen buffer sintered body under conditions of senor operating temperature
Upper surface form sealed insulation layer 3.8 one end of reference electrode lead is connect with oxygen buffering sintered body 4, and the other end passes through sealing exhausted
Edge layer 3 and reaction kettle body 1 extend outwardly.
In working electrode lead 9 and 8 material of reference electrode lead selection platinum, gold, palladium, silver, stainless steel, nickel, cobalt, tungsten or copper
One or more, a diameter of 0.3-1.0 mm.It is coated with glass in 9 appearance of working electrode lead in reaction kettle body 1
State inorganic sealing material layer 10 is coated with the inorganic sealing material of glassy state in 8 appearance of reference electrode lead in reaction kettle body 1
The bed of material 10.The effect of the wrapping layer is contact conductor with extraneous system being isolated, until contact conductor enters room temperature pressure
Air in, ensure measure accuracy.
The exit of working electrode lead 9 and reference electrode lead 8 respectively with the same electricity in the air of room temperature pressure
Press the two terminals connection of table, preferred high accuracy digital voltmeter.When measurement, by voltmeter to working electrode and reference electrode
Between potential difference be measured, to realize, the in situ of system institute oxygen content is surveyed during solid pollutant supercritical water oxidation
Amount, and the oxygen amount initially given according to supercritical water oxidation system, determine the COD of solid pollutant.
Aluminium oxide ceramics film 7 is surrounded by outside working electrode, the consistency of the alumina porous ceramic film, which should control, is
1000-2000 mesh, preferably 1500 mesh.Its certain organic pollution or salt that lambda sensor working electrode will can be polluted
Class protects working electrode outside being blocked in.At the same time, it should not influence to oxygen amount in pollutant supercritical water oxidation system
Accurate Determining.
The assay method of the direct measurement device of solid pollutant COD of the present invention, includes the following steps：
Solid pollutant to be measured, water and excessive oxidant are added in reaction kettle body 1 first step；
Second step, whole device synchronize increasing temperature and pressure to setting value after, hold mode to react complete；
Third walks, and measures the electromotive force of oxygen sensor system, converses remaining oxygen amount in reaction kettle body 1, in conjunction with initial given oxygen
Amount, you can obtain the oxygen amount spent by solid pollutant exhaustive oxidation.
In the following embodiments, pollutant supercritical water oxidation system is made of nickel-base alloy, and dischargeable capacity is
50mL, oxidative degradation temperatures setting value are 500 DEG C, pressure set points 25MPa, and the reaction time is 10 minutes, and oxidant uses
Hydrogen peroxide.
Embodiment 1
Supercritical water oxidation system is added in mud sample, water, the excessive hydrogen peroxide that 5 grams are dried, and ensures that material is filled out
Charge is less than 40%, then starts to warm up boosting, after temperature, pressure reaches setting value, keeps the state 10 minutes, then measure
The lambda sensor electromotive force being placed in supercritical water oxidation device, and thus obtain in supercritical water oxidation device
Remaining oxygen amount is 0.284 gram, in conjunction with initial given 0.712 gram of oxygen amount, you can is obtained spent by 5 grams of drying sludge exhaustive oxidations
Oxygen amount is 0.428 gram, and COD is 85.6 milligrams per grams.
Embodiment 2
Sludge, water, excessive hydrogen peroxide are dried by 5 grams, supercritical water oxidation device is added, ensure that material loading is low
In 40%, boosting is then started to warm up, after temperature, pressure reaches setting value, keeps the state 10 minutes, then measurement is placed in super
Lambda sensor electromotive force in critical oxidation reaction apparatus, and thus obtain the residual oxygen in supercritical water oxidation device
Amount is 0.454 gram, in conjunction with initial given 0.903 gram of oxygen amount, you can obtaining the oxygen amount spent by 5 grams of drying sludge exhaustive oxidations is
0.449 gram, COD is 89.8 milligrams per grams.
The above content is a further detailed description of the present invention in conjunction with specific preferred embodiments, and it cannot be said that
The specific implementation of the present invention is confined to these explanations.For those of ordinary skill in the art to which the present invention belongs, exist
Under the premise of not departing from present inventive concept, a number of simple deductions or replacements can also be made, all shall be regarded as belonging to the present invention's
Protection domain.
Claims (6)
1. a kind of direct measurement device of solid pollutant COD, including with reaction kettle body（1）Supercritical water oxidation
System, it is characterised in that：In reaction kettle body（1）In be equipped with oxygen sensor system, the oxygen sensor system include working electrode,
Solid electrolyte and reference electrode, wherein
Solid electrolyte, for the solid electrolyte tube with oxygen conduction（2）；
Working electrode, including electrode layer（5）, electric current collection net（6）With working electrode lead（9）, electrode layer（5）And electric current collection
Net（6）It is connected to solid electrolyte tube in turn（2）Blind end bottom outer wall face, working electrode lead（9）One end and electric current collection
Net（6）Connection, the other end pass through reaction kettle body（1）Extend outwardly；
Reference electrode, including sealed insulation layer（3）, oxygen buffer sintered body（4）With reference electrode lead（8）, wherein oxygen buffering is burnt
Knot body（4）It is filled in solid electrolyte tube（2）It is interior, sealed insulation layer（3）Mounted on solid electrolyte tube（2）Open end, configuration
For oxygen is buffered sintered body（4）It is sealed in solid electrolyte tube（2）It is interior, reference electrode lead（8）One end buffers sintered body with oxygen
（4）Connection, the other end pass through sealed insulation layer（3）And reaction kettle body（1）Extend outwardly；
The working electrode lead（9）With reference electrode lead（8）Exit respectively with two terminals of same voltmeter connect
It connects.
2. the direct measurement device of solid pollutant COD according to claim 1, it is characterised in that：Positioned at reaction
Autoclave body（1）In working electrode lead（9）Appearance is coated with glassy state inorganic sealing material layer（10）, it is located at reaction kettle body（1）
In reference electrode lead（8）Appearance is coated with glassy state inorganic sealing material layer（10）.
3. the direct measurement device of solid pollutant COD according to claim 1, it is characterised in that：In work electricity
It is extremely outer to be surrounded by aluminium oxide ceramics film（7）.
4. the direct measurement device of solid pollutant COD according to claim 1, it is characterised in that：The work
Contact conductor（9）With reference electrode lead（8）For platinum, gold, palladium, silver, stainless steel, nickel, cobalt, tungsten or copper, a diameter of 0.3-1.0
mm。
5. the direct measurement device of solid pollutant COD according to claim 1, it is characterised in that：The solid
Electrolytic tube（2）Wall thickness be 2-5mm, length 10-15mm, electronic conductivity be less than total conductivity 0.1%.
6. the assay method of the direct measurement device of solid pollutant COD, feature as described in claim 1 to 5 is any
It is, includes the following steps：
Reaction kettle body is added in solid pollutant to be measured, water and excessive oxidant by the first step（1）In；
Second step, whole device synchronize increasing temperature and pressure to setting value after, hold mode to react complete；
Third walks, and measures the electromotive force of oxygen sensor system, converses reaction kettle body（1）Interior remnants oxygen amount, in conjunction with initial given
Oxygen amount, you can obtain the oxygen amount spent by solid pollutant exhaustive oxidation.
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