CN105668761B - A kind of method and apparatus removing organic matter and intermediate valence state metal ion in the high acid system of high temperature - Google Patents
A kind of method and apparatus removing organic matter and intermediate valence state metal ion in the high acid system of high temperature Download PDFInfo
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- CN105668761B CN105668761B CN201610021489.XA CN201610021489A CN105668761B CN 105668761 B CN105668761 B CN 105668761B CN 201610021489 A CN201610021489 A CN 201610021489A CN 105668761 B CN105668761 B CN 105668761B
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- 239000002253 acid Substances 0.000 title claims abstract description 25
- 239000005416 organic matter Substances 0.000 title claims abstract description 17
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims abstract description 10
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 94
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 47
- 230000003647 oxidation Effects 0.000 claims abstract description 39
- 238000006385 ozonation reaction Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 230000008676 import Effects 0.000 claims abstract description 10
- 239000007921 spray Substances 0.000 claims abstract description 5
- 239000002912 waste gas Substances 0.000 claims abstract description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 239000004033 plastic Substances 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000007789 gas Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 238000005273 aeration Methods 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 230000008859 change Effects 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims 1
- 150000004965 peroxy acids Chemical class 0.000 abstract description 8
- 239000007800 oxidant agent Substances 0.000 abstract description 6
- 230000001590 oxidative effect Effects 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 description 8
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- MWUXSHHQAYIFBG-UHFFFAOYSA-N nitrogen oxide Inorganic materials O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 3
- 230000001954 sterilising effect Effects 0.000 description 3
- 238000004659 sterilization and disinfection Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- BZSXEZOLBIJVQK-UHFFFAOYSA-N 2-methylsulfonylbenzoic acid Chemical compound CS(=O)(=O)C1=CC=CC=C1C(O)=O BZSXEZOLBIJVQK-UHFFFAOYSA-N 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000005708 Sodium hypochlorite Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000004332 deodorization Methods 0.000 description 1
- 239000000645 desinfectant Substances 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 239000000383 hazardous chemical Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000007130 inorganic reaction Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000000622 irritating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000001151 other effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- A—HUMAN NECESSITIES
- A62—LIFE-SAVING; FIRE-FIGHTING
- A62D—CHEMICAL MEANS FOR EXTINGUISHING FIRES OR FOR COMBATING OR PROTECTING AGAINST HARMFUL CHEMICAL AGENTS; CHEMICAL MATERIALS FOR USE IN BREATHING APPARATUS
- A62D3/00—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances
- A62D3/30—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents
- A62D3/38—Processes for making harmful chemical substances harmless or less harmful, by effecting a chemical change in the substances by reacting with chemical agents by oxidation; by combustion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Toxicology (AREA)
- General Chemical & Material Sciences (AREA)
- Business, Economics & Management (AREA)
- Emergency Management (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses the method and apparatus of organic matter and intermediate valence state metal ion in a kind of removal high acid system of high temperature.The device is retort, and feed inlet, foam-expelling spray port, waste gas outlet are opened up at the top of retort, and reaction pot bottom opens up discharge port；It is horizontally disposed with the netted aerated conduit of upper layer and lower layer in reacting tank body, is separately connected the ozonation aerated disk of the ozonation aerated disk in upper layer and lower layer thereon；Ozone is respectively enterd by the upper layer ozone import and lower layer's ozone import for being opened in reacting tank body side wall in the netted aerated conduit of upper layer and lower layer.Feed liquid enters retort from upper feed inlet 1, and ozone enters retort from lower part, and feed liquid forms reverse flow with ozone in retort；Feed liquid gets rid of organic matter and intermediate valence state metal ion in system after ozone oxidation, is flowed out by the discharge port of lower part.The present invention has broken the traditional concept that ozone should not be applied under the conditions of high temperature peracid, has widened application range and the field of ozone high-efficient oxidant.
Description
Technical field
The invention belongs to the ozonation technology fields of the high acid system of high temperature, the more particularly to a kind of high acid system of removal high temperature
The method and apparatus of middle organic matter and intermediate valence state metal ion.
Background technology
Oxidation technology is widely used in all trades and professions as a kind of processing method, as the organic matter of water treatment field is gone
Remove, the production and processing workshop section needed to be oxidized in chemical industry, field of smelting, health care, food-processing industry sterilizing etc..Mesh
Preceding common oxidation technology both at home and abroad is divided into liquid phase oxidation technology and gaseous oxidation technology.Liquid phase oxidation technology includes sodium hypochlorite
Oxidation, sodium chlorate oxidation, potassium permanganate oxidation etc. are also easy to produce irritative gas or waste water in reaction process, pollute environment, these
Oxidant belongs to hazardous chemical mostly, and storage traffic condition is more demanding and expensive, therefore the city of Oxygen in Liquid agent
Field competitiveness continuously decreases.Gaseous oxidizing agent has ozone, oxygen, nitrogen oxides etc., and wherein ozone is because its oxidability is strong, reaction
Mild condition, not generate the advantages such as secondary pollution of interest by people.
Ozone has extremely strong oxidability, and oxidation-reduction potential is only second to fluorine, both can with inorganic matter such as Fe, Cl,
The reactions such as Mn, cyanide can also react with organic matter, have very strong oxidation, sterilization, disinfection, deodorization and other effects.Cause
This ozone is widely used in frequently as oxidant and disinfectant in the fields such as water process, medicine, food sterilization.Ozone has oxygen
The advantages that change ability is strong, there is no secondary pollution, preparation facilities, makes its application range gradually widen.But ozone water solution is steady
Qualitative impurities in by water are affected, and in the presence of especially having metal ion, ozone can be decomposed into rapidly oxygen, in pure water
Middle decomposition is slower.Also, ozone molecule structure is unstable, it is in water than being easier voluntarily to decompose in air.Content
For 1% ozone below, half life of decomposition is 20-30 minutes or so in the air of room temperature normality normal pressure.With the liter of temperature
Height, decomposition rate is accelerated, and when temperature is more than 100 DEG C, decomposition is very violent, when reaching 270 DEG C of high temperature, can be immediately converts into oxygen
Gas.At the same time, PH is affected to the oxidability of ozone.In neutral and alkaline conditions, ozone can faster speed
It decomposes and generates the stronger hydroxyl radical free radical of oxidability, improve the oxidability of ozone, but in acid condition, ozone point
The ability that solution generates hydroxyl radical free radical significantly reduces, and reduces the oxidability of ozone significantly, reduces ozone utilization ratio.This
Outside, the solubility of ozone is also by pressure influence, and the solubility of the bigger ozone of ozone partial pressure in a liquid increases therewith, normal conditions
Lower reaction condition is normal pressure state, seldom considers influence of the pressure to solubility.
Due to above, ozone is hardly used in the high acid system of high temperature.Therefore, smelly in the high acid system of high temperature
The application study of peroxygen oxidising agent needs further deeply, to develop the ozone efficient oxidation technology under a kind of high acid system of high temperature
It is very necessary.
Invention content
The present invention provides solution for the application limitation of ozone oxidation agent, and that widens ozone oxidation agent applies model
It encloses, ozone oxidation agent is efficiently applied in the high acid system of high temperature.
Ozone efficient oxidation reaction unit under a kind of high acid system of high temperature, the device are retort 9, are opened up at the top of retort
Feed inlet 1, foam-expelling spray port 2, waste gas outlet 3, reaction pot bottom open up discharge port 8；It is horizontally disposed with up and down in reacting tank body
Two layers of netted aerated conduit is separately connected the ozonation aerated disk of the ozonation aerated disk 4 in upper layer and lower layer 7 thereon；Ozone is anti-by being opened in
The upper layer ozone import 5 and lower layer's ozone import 6 for answering tank wall respectively enter in the netted aerated conduit of upper layer and lower layer.
The ozonation aerated disk uses nanoporous structure, the exposure of the ozonation aerated disk of the ozonation aerated disk 4 in upper layer and lower layer 7
Tolerance ratio is 0.5:1-2:1.
The ozonation aerated disk uses the plastic material of resistance to ozone oxidation, reacting tank body to use the steel lining plastics of resistance to ozone oxidation
Material.
A method of organic matter and intermediate valence state metal ion in the removal high acid system of high temperature, using the high acid system of high temperature
Lower ozone efficient oxidation reaction unit, feed liquid enter retort from upper feed inlet 1, and ozone enters retort from lower part, anti-
Feed liquid in tank is answered to form reverse flow with ozone；Controlling reaction temperature is room temperature to 100 DEG C, preferably 80-100 DEG C, PH in retort<
1, pressure 0.1-0.3MPa, feed liquid get rid of organic matter and intermediate valence state metal ion in system after ozone oxidation, by
The discharge port of lower part flows out.
The present invention devises ozone efficient oxidation reaction unit under a kind of high acid system of high temperature, and aeration plate uses in the device
Nanoporous structure makes the uniform gas distribution of ozone, improves mass-transfer efficiency, so that ozone is preferably come into full contact with feed liquid and react；Using
The double-deck ozonation aerated dish structure, improves oxidability and ozone utilization rate；Top is equipped with foam-expelling device, prevents ozone flux mistake
The bubble generated when big.The device can improve ozone partial pressure, increase ozone solubility, improve ozone utilization rate, be suitable for
The high acid system of high temperature compares the variation of the ozone oxidation ability under normal condition and under the high acid system of high temperature, obtains high temperature peracid
Under the conditions of ozone oxidation ability be normal condition under ozone oxidation ability 80-87%.The present invention has broken ozone should not be in height
The traditional concept applied under the conditions of warm peracid has widened application range and the field of ozone high-efficient oxidant.
Description of the drawings
Fig. 1 is ozone efficient oxidation reaction unit figure under the high acid system of high temperature, and feed inlet -1, gives up at foam-expelling spray port -2
Gas outlet -3, the ozonation aerated disk -4 in upper layer, upper layer ozone import -5, lower layer's ozone import -6, the ozonation aerated disk -7 of lower layer, discharging
Mouth -8, retort -9.
Fig. 2 is 1 ozone oxidation Fe of embodiment2+Changing effect comparison diagram.
Fig. 3 is the removal effect comparison diagram of 2 ozone oxidation organic matter of embodiment.
Specific implementation mode
Respectively with Fe2+Inorganic reaction object is represented, organic reactant is represented with certain industrial wastewater, uses Fe2+Conversion ratio and
The removal rate of COD investigates oxidability of the ozone to inorganic matter and organic matter.Respectively under normal conditions with high temperature peracid condition
Under compared.
Embodiment 1
Ozone efficient oxidation reaction unit under the high acid system of high temperature that the present invention designs, the device are retort 9, retort
Top opens up feed inlet 1, foam-expelling spray port 2, waste gas outlet 3, and reaction pot bottom opens up discharge port 8；It is horizontal in reacting tank body
The netted aerated conduit of upper layer and lower layer is set, is separately connected the ozonation aerated disk of the ozonation aerated disk 4 in upper layer and lower layer 7 thereon；Ozone by
The upper layer ozone import 5 and lower layer's ozone import 6 for being opened in reacting tank body side wall respectively enter the netted aerated conduit of upper layer and lower layer
It is interior；The ozonation aerated disk uses nanoporous structure, the aeration quantity of the ozonation aerated disk of the ozonation aerated disk 4 in upper layer and lower layer 7
Ratio is 1:1；The ozonation aerated disk uses the plastic material of resistance to ozone oxidation, and reacting tank body is using the resistance to ozone oxidation modeling of steel lining
Expect material.
Using ozone efficient oxidation reaction unit under the high acid system of above-mentioned high temperature, feed liquid enters from upper feed inlet 1 reacts
Tank, feed liquid are the FeCl of a concentration of 2.8g/L2PH is transferred to 0.5 by solution with HCl, and ozone enters retort from lower part, is reacting
Feed liquid forms reverse flow with ozone in tank；Controlling reaction temperature is 85 DEG C, pressure 0.15MPa in retort, ozone concentration
66g/m3, ferrous iron is measured in 12.5min, 16.5min, 21min, 26.25min, 42min sampling and measuring and total iron contains respectively
Amount calculates Fe2+Conversion ratio.
Above-mentioned experiment content is repeated under normal atmosphere temperature neutral.
As seen from Figure 2, under the conditions of high temperature peracid, ozone concentration Fe in 650mg/L2+All it is converted to Fe3 +, ozone oxidation Fe2+Oxidation rate be 1.35mg/Ls；Under normal atmosphere temperature neutral, ozone concentration Fe in 560mg/L2+
All it is converted to Fe3+, ozone oxidation Fe2+Oxidation rate be 1.56mg/Ls.Ozone oxidation under the conditions of high temperature peracid
Rate is 86.5% of oxidation rate under normal atmosphere temperature neutral.
Embodiment 2
Using ozone efficient oxidation reaction unit under the high acid system of the high temperature of embodiment 1, feed liquid enters from upper feed inlet 1
Retort, feed liquid are the industrial wastewater of a concentration of 110mg/L of COD, pH are transferred to 0.6 with HCl, ozone enters reaction from lower part
Tank, feed liquid forms reverse flow with ozone in retort；Controlling reaction temperature is 90 DEG C, pressure 0.2MPa in retort, smelly
Oxygen concentration 20g/m3, COD is measured in 10min, 20min, 30min, 40min, 60min, 100min sampling and measuring respectively, is calculated
COD degradation speed.
Above-mentioned experiment content is repeated under normal conditions.
As seen from Figure 3, under the conditions of high temperature peracid, when ozone dosage reaches 500mg/L, COD removal rates are
29.1%, the oxidation rate of ozone oxidation organic matter is 0.334mg/Lmin；Under the conditions of routinely, ozone dosage reaches
When 500mg/L, COD removal rates are 36.9%, and the oxidation rate of ozone oxidation organic matter is 0.397mg/Lmin.High temperature peracid
Under the conditions of ozone oxidation rate be normal condition under oxidation rate 84.1%.
Claims (3)
1. a kind of method of organic matter and intermediate valence state metal ion in removal high acid system of high temperature, which is characterized in that this method
Using ozone efficient oxidation reaction unit under the high acid system of high temperature, ozone efficient oxidation reacts dress under the high acid system of the high temperature
It is set to retort（9）, retort top opens up feed inlet（1）, foam-expelling spray port（2）, waste gas outlet（3）, react pot bottom
Open up discharge port（8）；It is horizontally disposed with the netted aerated conduit of upper layer and lower layer in reacting tank body, it is ozonation aerated to be separately connected upper layer thereon
Disk（4）With the ozonation aerated disk of lower layer（7）；Ozone is by being opened in the upper layer ozone import of reacting tank body side wall（5）With lower layer's ozone
Import（6）It respectively enters in the netted aerated conduit of upper layer and lower layer；Feed liquid is from upper feed inlet（1）Into retort, ozone is under
Portion enters retort, and feed liquid forms reverse flow with ozone in retort；Controlling reaction temperature is room temperature to 100 in retort
DEG C, pH<1, pressure 0.1-0.3MPa, feed liquid got rid of after ozone oxidation organic matter in system and intermediate valence state metal from
Son is flowed out by the discharge port of lower part.
2. the side of organic matter and intermediate valence state metal ion in a kind of removal high acid system of high temperature according to claim 1
Method, which is characterized in that the ozonation aerated disk uses nanoporous structure, the ozonation aerated disk in upper layer（4）It is exposed with lower layer's ozone
Gas disk（7）Aeration quantity ratio be 0.5:1-2:1.
3. the side of organic matter and intermediate valence state metal ion in a kind of removal high acid system of high temperature according to claim 1
Method, which is characterized in that the ozonation aerated disk uses the plastic material of resistance to ozone oxidation, reacting tank body to use the steel lining oxygen of resistance to ozone
Change plastic material.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610021489.XA CN105668761B (en) | 2016-01-13 | 2016-01-13 | A kind of method and apparatus removing organic matter and intermediate valence state metal ion in the high acid system of high temperature |
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| CN201610021489.XA CN105668761B (en) | 2016-01-13 | 2016-01-13 | A kind of method and apparatus removing organic matter and intermediate valence state metal ion in the high acid system of high temperature |
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| CN115738953A (en) * | 2022-11-27 | 2023-03-07 | 昆明理工大学 | Device and method for enhancing quality improvement effect of ozone on flue gas desulfurization product |
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| CN205472871U (en) * | 2016-01-13 | 2016-08-17 | 宋英豪 | Get rid of in high temperature high acid system organic matter and middle valence state metal ion's device |
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Effective date of registration: 20181218 Address after: 100029 Beijing Chaoyang District Cherry Blossom Street cherry garden 23, Hua Chang business building 205. Patentee after: HEROS (BEIJING) ENVIRONMENT TECHNOLOGY Co.,Ltd. Address before: 100029, No. 15 East Third Ring Road, Chaoyang District, Beijing Co-patentee before: Wang Min Patentee before: Song Yinghao Co-patentee before: Su Xianghong Co-patentee before: Wang Huansheng Co-patentee before: Cui Zhifeng Co-patentee before: Xu Jing |
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Denomination of invention: A method and device for removing organic matter and intermediate metal ions in high-temperature and high acid system Effective date of registration: 20221026 Granted publication date: 20180914 Pledgee: Zhongguancun Beijing technology financing Company limited by guarantee Pledgor: HEROS (BEIJING) ENVIRONMENT TECHNOLOGY Co.,Ltd. Registration number: Y2022990000741 |
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Granted publication date: 20180914 Pledgee: Zhongguancun Beijing technology financing Company limited by guarantee Pledgor: HEROS (BEIJING) ENVIRONMENT TECHNOLOGY Co.,Ltd. Registration number: Y2022990000741 |