CN100336735C - Method and apparatus for treating high concentrated organic wastewater by hydrothermal electrical catalytic oxidation - Google Patents
Method and apparatus for treating high concentrated organic wastewater by hydrothermal electrical catalytic oxidation Download PDFInfo
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- CN100336735C CN100336735C CNB200410022021XA CN200410022021A CN100336735C CN 100336735 C CN100336735 C CN 100336735C CN B200410022021X A CNB200410022021X A CN B200410022021XA CN 200410022021 A CN200410022021 A CN 200410022021A CN 100336735 C CN100336735 C CN 100336735C
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- 239000002351 wastewater Substances 0.000 title claims abstract description 39
- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000003647 oxidation Effects 0.000 title claims abstract description 14
- 238000007254 oxidation reaction Methods 0.000 title claims abstract description 14
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000005868 electrolysis reaction Methods 0.000 claims abstract description 19
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 19
- 239000001301 oxygen Substances 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001868 water Inorganic materials 0.000 claims abstract description 12
- 239000007789 gas Substances 0.000 claims abstract description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 8
- 150000002894 organic compounds Chemical class 0.000 claims abstract description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical class O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 4
- 150000003839 salts Chemical class 0.000 claims abstract description 4
- 239000010865 sewage Substances 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 14
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 238000011049 filling Methods 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 5
- 239000005909 Kieselgur Substances 0.000 claims description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 3
- 235000011089 carbon dioxide Nutrition 0.000 claims description 3
- 229910010272 inorganic material Inorganic materials 0.000 claims description 3
- 239000011147 inorganic material Substances 0.000 claims description 3
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 3
- 239000000395 magnesium oxide Substances 0.000 claims description 3
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- 239000011949 solid catalyst Substances 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000004575 stone Substances 0.000 claims description 3
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- DPDMMXDBJGCCQC-UHFFFAOYSA-N [Na].[Cl] Chemical compound [Na].[Cl] DPDMMXDBJGCCQC-UHFFFAOYSA-N 0.000 claims description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 2
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 claims description 2
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 claims description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 2
- -1 nitrogenous compound Chemical class 0.000 claims description 2
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 5
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 abstract 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 239000010936 titanium Substances 0.000 description 6
- 229910052719 titanium Inorganic materials 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Chemical compound O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229910001220 stainless steel Inorganic materials 0.000 description 4
- 239000010935 stainless steel Substances 0.000 description 4
- 238000009279 wet oxidation reaction Methods 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 238000007747 plating Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- 229910001925 ruthenium oxide Inorganic materials 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- HTUMBQDCCIXGCV-UHFFFAOYSA-N lead oxide Chemical compound [O-2].[Pb+2] HTUMBQDCCIXGCV-UHFFFAOYSA-N 0.000 description 2
- YEXPOXQUZXUXJW-UHFFFAOYSA-N lead(II) oxide Inorganic materials [Pb]=O YEXPOXQUZXUXJW-UHFFFAOYSA-N 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 2
- 241001253206 Andrias Species 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000011149 active material Substances 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- HIVLDXAAFGCOFU-UHFFFAOYSA-N ammonium hydrosulfide Chemical compound [NH4+].[SH-] HIVLDXAAFGCOFU-UHFFFAOYSA-N 0.000 description 1
- 230000003851 biochemical process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical group [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000005121 nitriding Methods 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910001404 rare earth metal oxide Inorganic materials 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 210000000952 spleen Anatomy 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 210000002784 stomach Anatomy 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- ZNRSXPDDVNZGEN-UHFFFAOYSA-K trisodium;chloride;sulfate Chemical compound [Na+].[Na+].[Na+].[Cl-].[O-]S([O-])(=O)=O ZNRSXPDDVNZGEN-UHFFFAOYSA-K 0.000 description 1
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- Water Treatment By Electricity Or Magnetism (AREA)
- Catalysts (AREA)
Abstract
The present invention relates to a method and an apparatus for treating high-concentration organic wastewater by hydrothermal electrical catalytic oxidation. The method is characterized in that high-concentration organic wastewater is treated by an electrolytic method, the temperature in an electrolytic reactor is from the room temperature to 250 DEG C, the pressure is from 0.5 to 7MPa, oxygen-containing gas is supplied to the electrolytic reactor, and then organic compounds and nitrogen-containing compounds in the wastewater are removed so that the wastewater is changed into the classes of carbon dioxide, nitrogen, water and inorganic salts. The electrolytic reactor is in an intermittent or continuous type. Compared with the traditional wet type catalytic oxidation, the method is characterized in that the wet type catalytic oxidation and high-temperature electrolysis are combined so that compared with a CWO method, the reaction pressure and temperature are greatly reduced, the reaction temperature can be reduced to the room temperature to 200 DEG C from the temperature of 200 DEG C to 300 DEG C, and due to the reduction of the reaction temperature, the pressure for keeping the liquid state of the water also correspondingly reduces along with the reaction temperature; therefore, the method greatly improves the treatment efficiency of the high-concentration organic wastewater and reduces the cost and the operation cost of the treating apparatus.
Description
Technical field
The present invention relates to technical field of sewage, specifically the hydro-thermal catalytic oxidation is handled the method and the device thereof of high concentrated organic wastewater.
Technical background
High concentrated organic wastewater is as a kind of pollutent, has that toxicity is big, the characteristics of bio-refractory, and current methods generally adopts and connects biochemical process after the dilution and handle.Also there are methods such as the distillation of employing, absorption, burning to be handled for special high concentrated organic wastewater.Handle waste water with existing electrolysis tech and be characterized in adding certain ionogen under normal pressure, the organifying compound decomposes, and its defective only is that at organic wastewater with medium-low concentration, longer 4-24 of time hour, power consumption was bigger.Also handled on the recent international in some advanced physical chemical processes of development, as the catalytic wet oxidation technology, the supercritical water oxidation technology.The needed temperature and pressure of catalytic wet oxidation technology (being called for short CWO) is still higher, and at 7-10MPa, temperature of reaction is at 200-350 ℃, and therefore, facility investment is higher, and working cost is also somewhat expensive.The reaction pair material requires height under supercritical oxidation technology supercritical water temperature, the pressure, and salt blocks, the process cost height.Other oxidation technology need consume chemical oxidizing agent, and the time is long, can not thoroughly handle.
Summary of the invention
The purpose of this invention is to provide a kind of hydro-thermal catalytic oxidation that can improve efficient, the cost that has reduced treatment facility and the running cost of handling high concentrated organic wastewater greatly and handle the method for high concentrated organic wastewater, and the device that uses this method.
Method of the present invention is: under certain temperature and pressure, oxygen in the feeding waste water is under electrolytic effect, with organic compound in the waste water in anode generation oxidizing reaction, generate carbonic acid gas, ammonia nitriding compound selective oxidation generates the nitrogen G﹠W, and other becomes stable inorganic salt as phosphorus, sulphur, heavy metal.Has active OH in the generation of negative electrode oxygen
-, H
2O
2, O
2Deng, the particle that oxidizing potential is higher, heavy metal ion is reduced to be removed.Simultaneously, present method also can be used solid catalyst, quickens organic compound and oxygen direct reaction, and two kinds of processes intercouple, and promotes mutually, reaches the purpose that organifying compound promote the oxidation is decomposed.
Concrete grammar is: directly add a certain amount of high concentrated organic wastewater in the electrolysis reactor, temperature is a room temperature to 250 ℃ in the electrolysis reactor, pressure is 0.5-7Mpa, feed oxygen-containing gas (air or oxygen-rich air or oxygen), stir 200～800r/min, regulating voltage 6～12V, 0.5～1.5 hour reaction times.Remove the organic compound in the decontaminated water, nitrogenous compound makes it to become carbonic acid gas, nitrogen, water and inorganic salts.When water inlet COD concentration during greater than 10000ppm, NH falls the rate of removing still greater than 85%, in COD
3-N concentration is during greater than 2000ppm, NH
3The clearance of-N is greater than 99%.
When the inorganic salt content in the waste water when 1g/L is following, can add inorganic salt on a small quantity in the sewage, as ionogen such as sodium sulfate, sodium-chlor, to increase the conductive capability of sewage, add-on is 0～5% of a sewage, and regulates pH value to 8～11; If the inorganic salt content in the waste water reaches more than the 1g/L, need not to add in addition other inorganic salt such as sodium-chlor, sodium sulfate.
Can in electrolysis reactor, add solid filling material, as granulated active carbon, or granular diatomaceous earth, or molded molecular sieve, or titanium oxide, or aluminum oxide, or zirconium white, or violet cyanines stone, or water-fast inorganic materials such as magnesium oxide, its granular size is 2～6mm; The solid material that adds is solid catalyst also, makes the droop loss of reactor reduce to minimum.
The used device of aforesaid method is made up of three parts:
1, electrolysis reactor.Loading catalyst or two kinds of loading catalysts are not arranged, face shaping is a cylinder shape, the optional stainless steel composite material of material is as lining titanium stainless steel, withstand voltage common steel tube inside lining anti-corrosive material such as tetrafluoroethylene, the safe dragon of spraying fluorine etc., type of heating can adopt thermal oil to heat or steam-heated cal(l)andria, and packaged unit can adopt the resistance wire furnace heating.Electrolysis reactor middle-jiao yang, function of the spleen and stomach is titanium or conductive carbon very, cover plumbic oxide thereon, or antimonous oxide, or stannic oxide, or ruthenium oxide or their mixture, other helps to improve auxiliary composition rare earth oxide or the manganese oxide or the cobalt oxide of anodic oxidation efficient, auxiliary composition mass percent accounts for anodic 0～10%, consider the bonding force of activated coating and base material, do an intermediate layer between base material and activated coating, intermediate layer material preferably is gold or platinum or palladium.Negative electrode adopts stainless steel or other electro-conductive material, and the negative electrode in the electrolysis reactor can adopt electrolysis reactor itself.Electrolysis reactor adopts linear sealing or ball face sealing.Can adopt semi-permeable membranes as conductive diaphragm in the electrolysis reactor between negative electrode and the anode.Contain Cl in processing
-Waste water the time, electrolysis reactor liner tetrafluoroethylene, negative electrode adopt the titanium material.For no Cl
-Waste water directly make negative electrode with reactor.
Electrolysis reactor can be the cylinder shape flow-through appt, and promptly sewage and oxygen-containing gas enter from reactor bottom, and sewage is after treatment discharged after heat exchange, gas-liquid separation continuously, and sewage disposal can be carried out automatically continuously.It also can be step electrolysis reactor.
2, energy-recuperation system.Surpass 20,000 waste water for COD, must think over energy recovery, can realize like this in this covering device: cooling system is circulated by waste water, reach the target of pre-thermal wastewater, unnecessary heat produces steam or generating by Re Jiaore, reclaim heat energy, by turbine pressure recovery energy.
3, robot control system(RCS).Adopt computer, instrument control, each reactor is by pressure transmitter, temperature sensor, mass flowmeter, the control of electric current and voltage stabilizer.The native system height is integrated, after temperature, pressure operation set(ting)value reduce pressure automatically, lower the temperature, and treat that system recovery is normal, starts automatically.
As required, but native system end distribution body monitor is monitored gaseous emission in real time, and COD, NH
3-N on line analyzer grasp the physical and chemical index of handling waste water in real time, and according to these indexs, Automatic Optimal import tolerance, flooding quantity, pressure, temperature makes system be in the optimum process state.
Above-mentioned energy-recuperation system and robot control system(RCS) etc. all can directly adopt prior art.
Method of the present invention is compared with traditional catalytic wet oxidation, be characterized in catalytic wet oxidation and high-temperature electrolysis are combined, make the pressure of reaction, the temperature CWO method of comparing all has very big decline, can make temperature of reaction reduce to room temperature～200 ℃ from 200～300 ℃, because the reduction of temperature of reaction, the corresponding water that makes keeps liquid pressure also to decrease, reduce to 0.5-7MPa from 7～10MPa, as handle the phenolic waste water temperature and can drop to 150 ℃ from 270 ℃, pressure drops to 4MPa from 10MPa, and effect is identical, therefore, improve the efficient of handling high concentrated organic wastewater greatly, reduced the cost and the running cost of treatment facility.
Key of the present invention is that also electrolysis reactor is the core of equipment therefor of the present invention, and the efficient of this reactor has determined the efficient of whole plant.Adopt on anode base material and electroplate, the pyrolysated mode is coated with the last layer active material, and its effect is that oxygen is had higher overpotential, does not produce oxygen or produces oxygen less, helps the oxidation of organic compound.Negative electrode is for no Cl
-Waste water directly make negative electrode with reactor, help the protection of reactor.Negative electrode selects titanium material or cathode gas electrode, helps the reduction of oxygen, suppresses H
2Generation.
Description of drawings
Fig. 1 is an intermittent mode synoptic diagram of the present invention;
Fig. 2 is a continuous mode synoptic diagram of the present invention.
Among the figure, the 1-stirring arm, 2-blowing air or oxygen, the 3-catalyzer, the 4-reactor, 5-waste water, the 6-preheating tube, the 7-reactor, the 8-catalyzer, the 9-air water separator, the 10-condenser, 11-handles gas, 12-treating water.
Embodiment
Can be divided into intermittent mode and continuous mode.
Embodiment 1: the enforcement on the intermittence device:
1, use batch reactor:
Reactor 316L body of stainless steel 500ml (one type of prior art syringe);
Anode: titanium net plating PbO
2, 2 * 7mm (or plating plumbic oxide, or antimonous oxide, or stannic oxide, or ruthenium oxide or their mixture);
Catalyzer: a kind of by titanium oxide 75%, cerium dioxide 20%, ruthenium 0.5%, the catalyzer (or other existing catalyzer) that bismuth oxide 4.5% is formed;
Negative electrode: reactor itself;
Voltage: 6V; Electric current: 5A;
Ionogen Na
2SO
45% (account for wastewater flow rate 5%);
COD concentration (initial) 18000ppm 150ml waste water (phenol);
NH
3-N concentration (initial) 3000ppm
O
2Dividing potential drop 1MPa (initial) PH is adjusted into 10
200 ℃ of 1 hour reaction times of temperature
COD clearance 90% NH
3-N 99%
Embodiment 2: the enforcement on continuous apparatus
Electrolysis reactor is the cylinder shape flow-through appt, and promptly sewage and oxygen-containing gas enter from reactor bottom, and sewage is after treatment discharged after heat exchange, gas-liquid separation continuously, and sewage disposal can be carried out automatically continuously.
Wherein:
Anode: conductive carbon coating one deck stannic oxide;
Catalyzer: Ru/Ce-ZrO
2
Voltage: 6V; Electric current: 5A;
Reactor volume 2L, NH
3-N concentration (initial) 3000ppm COD initial concentration 18000ppm (phenol and sulphur ammonium);
Negative electrode: reactor itself;
Result is as shown in the table:
Table 1, the relation (during air speed 2/) of temperature and waste water degradation rate
| T | 100℃ | 150℃ | 180℃ | 200℃ | 250℃ |
| COD Cr(clearance) NH 3-N (clearance) | 45.3％ 30.3％ | 75.5％ 80.7％ | 89.2％ 90.3％ | 95.4％ 99.1％ | 99.9％ 99.9％ |
Table 2, the relation (during air speed 1/) of temperature and waste water degradation rate
| T | 100℃ | 150℃ | 180℃ | 200℃ |
| COD Cr(clearance) NH 3-N (clearance) | 50.9％ 45.2％ | 85.7％ 85.6％ | 98.2％ 99.1％ | 99.7％ 99.5％ |
Embodiment 3: the enforcement on continuous apparatus:
Electrolysis reactor is the cylinder shape flow-through appt, and promptly sewage and oxygen-containing gas enter from reactor bottom, and sewage is after treatment discharged after heat exchange, gas-liquid separation continuously, and sewage disposal can be carried out automatically continuously.
Wherein:
Anode: plate ruthenium oxide on the titanium rod earlier, and then plating one deck plumbous oxide;
Negative electrode: titanium net;
Solid filling material: grain active carbon (or granular diatomaceous earth, or molded molecular sieve, or titanium oxide, or aluminum oxide, or zirconium white, or violet cyanines stone, or water-fast inorganic materials such as magnesium oxide);
Voltage: 6V, PO
2Dividing potential drop is 2MPa; Electric current: 10A;
Waste water is coking chemical waste water, and COD is 19950PPm, NH
3-N is 1300PPm;
Transfer pH ≈ 11, add the Na of wastewater flow rate 5%
2SO
4Make to support ionogen;
Result is as shown in the table::
Table 1, the relation (during air speed 2/) of temperature and waste water degradation rate
| T | 100℃ | 150℃ | 180℃ | 200℃ |
| COD Cr(clearance) NH 3-N (clearance) | 55.3％ 30.3％ | 80.2％ 85.3％ | 95.3％ 95.4％ | 98.9％ 99.3％ |
Table 2, the relation (during air speed 1/) of temperature and waste water degradation rate
| T | 100℃ | 150℃ | 180℃ | 200℃ |
| COD Cr(clearance) NH 3-N (clearance) | 70.2％ 65.4％ | 90.5％ 89.1％ | 99.0％ 98.3％ | 99.9％ 99.9％ |
Claims (3)
1, a kind of hydro-thermal catalytic oxidation is handled the method for high concentrated organic wastewater, it is characterized in that adopting electrolytic method to handle high concentrated organic wastewater, add solid filling material in electrolysis reactor, temperature is 200～250 ℃, and oxygen partial pressure is 1～7Mpa, feed oxygen-containing gas, stir 200～800r/min, regulating voltage 6～12V, 0.5～1.5 hour reaction times, remove organic compound, nitrogenous compound in the decontaminated water, make it to become carbonic acid gas, nitrogen, water and inorganic salts; Described solid filling material is water-fast inorganic materials; be selected from granulated active carbon or granular diatomaceous earth or molded molecular sieve or titanium oxide or aluminum oxide or zirconium white or violet cyanines stone or magnesium oxide; its granular size is 2～6mm; perhaps described solid filling material is a solid catalyst, i.e. catalyzer or the Ru/Ce-ZrO that is made up of titanium oxide 75%, cerium dioxide 20%, ruthenium 0.5%, bismuth oxide 4.5%
2Catalyzer.
2, method according to claim 1 is characterized in that described oxygen-containing gas is air or oxygen-rich air or oxygen.
3, method according to claim 1 is characterized in that adding in the sewage inorganic salt sodium sulfate or sodium-chlor as ionogen, and to increase the conductive capability of sewage, add-on is 0～5% of a sewage.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410022021XA CN100336735C (en) | 2004-03-12 | 2004-03-12 | Method and apparatus for treating high concentrated organic wastewater by hydrothermal electrical catalytic oxidation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB200410022021XA CN100336735C (en) | 2004-03-12 | 2004-03-12 | Method and apparatus for treating high concentrated organic wastewater by hydrothermal electrical catalytic oxidation |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1654344A CN1654344A (en) | 2005-08-17 |
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| CN101020590B (en) * | 2006-02-14 | 2010-08-11 | 北京国力源高分子科技研发中心 | Process of treating refractory organic effluent with free radical |
| CN101973623B (en) * | 2010-11-11 | 2012-07-18 | 利尔化学股份有限公司 | Wet-type electrocatalytic oxidation method and device |
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| CN102502924A (en) * | 2011-10-27 | 2012-06-20 | 浙江理工大学 | Method for deeply treating alpha-naphthylamine wastewater |
| CN103288254A (en) * | 2012-02-29 | 2013-09-11 | 张太亮 | Process and device for electric cracking catalytic oxidation for petroleum drilling wastewater |
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| CN105174389B (en) * | 2015-09-23 | 2017-12-22 | 深圳清华大学研究院 | Strengthen electrochemical oxidation wastewater treatment equipment and processing method |
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| CN106630297A (en) * | 2017-01-18 | 2017-05-10 | 上海应用技术大学 | Wet-method catalytic oxidation treatment method of vanillin production wastewater |
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| CN108059281A (en) * | 2017-12-25 | 2018-05-22 | 南京工业大学 | Membrane-process zero-discharge treatment technology for coal chemical industry wastewater |
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| CN110713249A (en) * | 2019-11-01 | 2020-01-21 | 云南大学 | Method for treating hardly biodegradable organic wastewater |
| CN112079675A (en) * | 2020-08-21 | 2020-12-15 | 上海耀嵘环保科技有限公司 | Process for deeply treating eutrophic algae such as blue algae and preparing methane |
| CN116573731B (en) * | 2023-06-09 | 2024-02-09 | 中国标准化研究院 | Method and system for simultaneously removing total cyanogen and polycyclic aromatic hydrocarbons from coking biochemical effluent |
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