CN105668761A - Method for removing organic matter and metal ion with intermediate valence in high-temperature high-acid system and device thereof - Google Patents
Method for removing organic matter and metal ion with intermediate valence in high-temperature high-acid system and device thereof Download PDFInfo
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- CN105668761A CN105668761A CN201610021489.XA CN201610021489A CN105668761A CN 105668761 A CN105668761 A CN 105668761A CN 201610021489 A CN201610021489 A CN 201610021489A CN 105668761 A CN105668761 A CN 105668761A
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- 239000002253 acid Substances 0.000 title claims abstract description 26
- 229910021645 metal ion Inorganic materials 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title claims abstract description 9
- 239000005416 organic matter Substances 0.000 title abstract description 5
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 98
- 238000006385 ozonation reaction Methods 0.000 claims abstract description 23
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- 238000005273 aeration Methods 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims description 61
- 230000003647 oxidation Effects 0.000 claims description 50
- 230000008676 import Effects 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 6
- 239000002912 waste gas Substances 0.000 claims description 4
- 229910000831 Steel Inorganic materials 0.000 claims description 3
- 239000007921 spray Substances 0.000 claims description 3
- 239000010959 steel Substances 0.000 claims description 3
- 239000007800 oxidant agent Substances 0.000 abstract description 3
- 238000005276 aerator Methods 0.000 abstract 2
- 238000005507 spraying Methods 0.000 abstract 1
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 7
- 150000004965 peroxy acids Chemical class 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- 239000003795 chemical substances by application Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 230000007935 neutral effect Effects 0.000 description 4
- 238000004659 sterilization and disinfection Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000007791 liquid phase Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- -1 hydroxyl radical free radical Chemical class 0.000 description 2
- WQYVRQLZKVEZGA-UHFFFAOYSA-N hypochlorite Chemical compound Cl[O-] WQYVRQLZKVEZGA-UHFFFAOYSA-N 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 230000009466 transformation Effects 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
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001877 deodorizing effect Effects 0.000 description 1
- 239000004744 fabric 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
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000003206 sterilizing agent Substances 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 a method for removing organic matter and metal ion with intermediate valence in a high-temperature high-acid system and a device thereof. The device is a reaction tank, the top of which is provided with a feed inlet, a defoaming spraying port and an exhaust-gas outlet. The bottom of the reaction tank is provided with a discharge hole. Upper and lower two-layer net aerator pipes are horizontally arranged inside the reaction tank, and are respectively connected to an upper-layer ozone aeration disk and a lower-layer ozone aeration disk. Ozone respectively enters the upper and lower two-layer net aerator pipes through an upper-layer ozone inlet and a lower-layer ozone inlet arranged in the side wall of the reaction tank. A feed liquid enters the reaction tank through an upper feed inlet, and ozone enters the reaction tank through the lower part. In the reaction tank, the feed liquid and ozone form counter flow. The feed liquid undergoes ozonation to remove organic matter and metal ion with intermediate valence in the system, and the organic matter and metal ion with intermediate valence flow out of the discharge hole at the lower part. The traditional concept that ozone is not suitable to be applied under high-temperature high-acid conditions is broken down, and application range and field of an ozone efficient oxidizing agent are widened.
Description
Technical field
The invention belongs to the ozonation technology field of high temperature height acid system, in particular to a kind of method and the device of removing organism and intermediate price state metal ion in high temperature height acid system.
Background technology
Oxidation technology is widely used in all trades and professions as a kind for the treatment of process, such as the organic matter removal of water treatment field, needs the process for processing workshop section of oxidation, the sterilization and disinfection etc. of health care, food-processing industry in chemical industry, field of smelting. Oxidation technology conventional both at home and abroad at present is divided into liquid-phase oxidation technology and gas phase oxidation technology. Liquid-phase oxidation technology comprises hypochlorite oxidation, sodium chlorate oxidation, potassium permanganate oxidation etc., reaction process easily produces irritant gas or waste water, contaminate environment, these oxygenants belong to hazardous chemical mostly, storing transport condition requires higher, and expensive, therefore the market competitiveness of liquid-phase oxidation agent reduces gradually. Gaseous oxidizing agent has ozone, oxygen, oxynitride etc., and wherein ozone is paid close attention to by people because its oxidation capacity is strong, reaction conditions is gentle, do not produce the advantages such as secondary pollution.
Ozone has extremely strong oxidation capacity, and its redox potential is only second to fluorine, both can with inorganics as Fe, Cl, Mn, prussiate etc. had reacted, it is also possible to react with organism, have the effects such as very strong oxidation, sterilization, sterilization, deodorizing. Therefore ozone Chang Zuowei oxygenant and sterilizing agent are widely used in the fields such as water treatment, medical science, foodstuffs sterilisation. Ozone has oxidation capacity and by force, there is not the advantage such as secondary pollution, preparation facility so that it is range of application is widened gradually. But the stability of ozone water solution is relatively big by the impact of impurities in water, and when particularly having metal ion to exist, ozone can rapid decomposition be oxygen, decomposes slower in pure water. Further, ozone molecule structure is unstable, it in water than easier disintegrate in atmosphere. Content is the ozone of less than 1%, and in the air of normal temperature normality normal pressure, half life of decomposition is about 20-30 minute.Along with the rising of temperature, decomposition rate is accelerated, and when temperature is more than 100 DEG C, decomposes very violent, when reaching 270 DEG C of high temperature, can be converted into oxygen immediately. Meanwhile, PH is bigger on the oxidation capacity impact of ozone. In neutral and alkaline conditions, ozone can produce the stronger hydroxyl radical free radical of oxidation capacity by resolution of velocity faster, improve the oxidation capacity of ozone, but in acid condition, ozone decomposes the ability producing hydroxyl radical free radical significantly to be reduced, greatly reduce the oxidation capacity of ozone, reduce ozone utilising efficiency. In addition, the solubleness of ozone is also stressed impact, and the more big ozone of ozone dividing potential drop solubleness in a liquid increases thereupon, and reaction conditions is atmospheric pressure state under normal circumstances, seldom considers that pressure is on the impact of solubleness.
Due to above reason, ozone is not almost used in high temperature height acid system. Therefore, in high temperature height acid system, the applied research of ozone oxidation agent needs further deeply, and the ozone efficient oxidation technology developed under a kind of high temperature height acid system is very necessary.
Summary of the invention
The present invention is directed to the application limitation of ozone oxidation agent and terms of settlement is provided, widen the range of application of ozone oxidation agent, ozone oxidation agent is effectively applied in high temperature height acid system.
Ozone efficient oxidation reaction unit under a kind of high temperature height acid system, this device is retort 9, and opening for feed 1, foam-expelling mouth spray 2, waste gas outlet 3 are offered in retort top, offer discharge port 8 bottom retort; Reacting tank body is horizontally disposed with upper and lower two layers of mesh shape aerated conduit, it connects the ozonation aerated dish in upper strata 4 and lower floor ozonation aerated dish 7 respectively; Ozone is entered in upper and lower two layers of mesh shape aerated conduit respectively by the upper strata ozone import 5 and lower floor's ozone import 6 being opened in reacting tank body sidewall.
Described ozonation aerated dish adopts nanoporous structure, and the aeration rate ratio of the ozonation aerated dish 7 of the ozonation aerated dish in upper strata 4 and lower floor is 0.5:1-2:1.
Described ozonation aerated dish adopts the plastic material of resistance to ozone oxidation, and reacting tank body adopts the steel lining plastic material of resistance to ozone oxidation.
A kind of method removing organism and intermediate price state metal ion in high temperature height acid system, ozone efficient oxidation reaction unit under employing high temperature height acid system, feed liquid enters retort from upper feed inlet 1, and ozone enters retort from bottom, and in retort, feed liquid and ozone form reverse flow; Retort inner control temperature of reaction is that normal temperature is to 100 DEG C, it is preferable that 80-100 DEG C, PH < 1, and pressure is 0.1-0.3MPa, and feed liquid gets rid of the organism in system and intermediate price state metal ion after ozone oxidation, flows out by the discharge port of bottom.
Ozone efficient oxidation reaction unit under a kind of high temperature height acid system of inventive design, in this device, aeration plate adopts nanoporous structure to make the even cloth gas of ozone, it is to increase mass-transfer efficiency, make the ozone abundant contact reacts with feed liquid better; Adopt double-deck ozonation aerated dish structure, it is to increase oxidation capacity and ozone utilization rate; Top is provided with foam-expelling device, the bubble produced when preventing ozone flux excessive. This device can improve ozone dividing potential drop, increase ozone solution degree, improve ozone utilization rate, high temperature height acid system can be adapted to, the change of the ozone oxidation ability under contrast normal condition and under high temperature height acid system, when drawing high temperature peracid, ozone oxidation ability is the 80-87% of ozone oxidation ability under normal condition. The present invention has broken the traditional concept that ozone should not be applied when high temperature peracid, has widened range of application and the field of ozone high-efficient oxidant.
Accompanying drawing explanation
Fig. 1 is ozone efficient oxidation reaction unit figure under high temperature height acid system, opening for feed-1, foam-expelling mouth spray-2, waste gas outlet-3, the ozonation aerated dish-4 in upper strata, upper strata ozone import-5, lower floor's ozone import-6, the ozonation aerated dish-7 of lower floor, discharge port-8, retort-9.
Fig. 2 is embodiment 1 ozone oxidation Fe2+Changing effect comparison diagram.
Fig. 3 is the removal effect comparison diagram of embodiment 2 ozone oxidation organism.
Embodiment
Respectively with Fe2+Represent inorganic reaction thing, represent organic reactant with certain trade effluent, use Fe2+Transformation efficiency and COD clearance investigate ozone to the oxidation capacity of inorganics and organism. Contrast with when high temperature peracid under normal conditions respectively.
Embodiment 1
Ozone efficient oxidation reaction unit under the high temperature height acid system of inventive design, this device is retort 9, and opening for feed 1, foam-expelling mouth spray 2, waste gas outlet 3 are offered in retort top, offer discharge port 8 bottom retort; Reacting tank body is horizontally disposed with upper and lower two layers of mesh shape aerated conduit, it connects the ozonation aerated dish in upper strata 4 and lower floor ozonation aerated dish 7 respectively; Ozone enters in upper and lower two layers of mesh shape aerated conduit by the upper strata ozone import 5 and lower floor's ozone import 6 that are opened in reacting tank body sidewall respectively; Described ozonation aerated dish adopts nanoporous structure, and the aeration rate ratio of the ozonation aerated dish 7 of the ozonation aerated dish in upper strata 4 and lower floor is 1:1; Described ozonation aerated dish adopts the plastic material of resistance to ozone oxidation, and reacting tank body adopts the steel lining plastic material of resistance to ozone oxidation.
Adopting ozone efficient oxidation reaction unit under above-mentioned high temperature height acid system, feed liquid enters retort from upper feed inlet 1, and feed liquid is concentration is the FeCl of 2.8g/L2Solution, is transferred to 0.5 with HCl by pH, and ozone enters retort from bottom, and in retort, feed liquid and ozone form reverse flow; Retort inner control temperature of reaction is 85 DEG C, and pressure is 0.15MPa, ozone concn 66g/m3, measure ferrous iron and total iron content respectively at 12.5min, 16.5min, 21min, 26.25min, 42min sampling and measuring, calculate Fe2+Transformation efficiency.
Above-mentioned experiment content is repeated under normal atmosphere temperature neutral.
As seen from Figure 2, when high temperature peracid, ozone concn is Fe when 650mg/L2+All it is converted to Fe3+, ozone oxidation Fe2+Rate of oxidation be 1.35mg/L s; Under normal atmosphere temperature neutral, ozone concn is Fe when 560mg/L2+All it is converted to Fe3+, ozone oxidation Fe2+Rate of oxidation be 1.56mg/L s. Ozone oxidation speed when high temperature peracid is 86.5% of rate of oxidation under normal atmosphere temperature neutral.
Embodiment 2
Ozone efficient oxidation reaction unit under the high temperature height acid system of employing embodiment 1, feed liquid enters retort from upper feed inlet 1, and feed liquid is COD concentration is the trade effluent of 110mg/L, with HCl, pH is transferred to 0.6, ozone enters retort from bottom, and in retort, feed liquid and ozone form reverse flow; Retort inner control temperature of reaction is 90 DEG C, and pressure is 0.2MPa, ozone concn 20g/m3, measure COD at 10min, 20min, 30min, 40min, 60min, 100min sampling and measuring respectively, calculate COD degradation speed.
Repeat above-mentioned experiment content under normal conditions.
As seen from Figure 3, when high temperature peracid, when ozone dosage reaches 500mg/L, COD clearance is 29.1%, and the rate of oxidation of ozone oxidation organism is 0.334mg/L min; Under condition routinely, when ozone dosage reaches 500mg/L, COD clearance is 36.9%, and the rate of oxidation of ozone oxidation organism is 0.397mg/L min. Ozone oxidation speed when high temperature peracid is 84.1% of rate of oxidation under normal condition.
Claims (4)
1. ozone efficient oxidation reaction unit under a high temperature height acid system, this device is retort (9), it is characterized in that, opening for feed (1), foam-expelling mouth spray (2), waste gas outlet (3) are offered in retort top, offer discharge port (8) bottom retort;It is horizontally disposed with upper and lower two layers of mesh shape aerated conduit in reacting tank body, it connects the ozonation aerated dish in upper strata (4) and lower floor ozonation aerated dish (7) respectively; Ozone is entered in upper and lower two layers of mesh shape aerated conduit respectively by upper strata ozone import (5) and lower floor's ozone import (6) being opened in reacting tank body sidewall.
2. ozone efficient oxidation reaction unit under a kind of high temperature height acid system according to claim 1, it is characterized in that, described ozonation aerated dish adopts nanoporous structure, and the aeration rate ratio on the ozonation aerated dish in upper strata (4) and lower floor ozonation aerated dish (7) is 0.5:1-2:1.
3. ozone efficient oxidation reaction unit under a kind of high temperature height acid system according to claim 1, it is characterised in that, described ozonation aerated dish adopts the plastic material of resistance to ozone oxidation, and reacting tank body adopts the steel lining plastic material of resistance to ozone oxidation.
4. remove the method for organism and intermediate price state metal ion in high temperature height acid system for one kind, it is characterized in that, ozone efficient oxidation reaction unit under the method employing high temperature height acid system, feed liquid enters retort from upper feed inlet (1), ozone enters retort from bottom, and in retort, feed liquid and ozone form reverse flow; Retort inner control temperature of reaction is that normal temperature is to 100 DEG C, it is preferable that 80-100 DEG C, PH < 1, and pressure is 0.1-0.3MPa, and feed liquid gets rid of the organism in system and intermediate price state metal ion after ozone oxidation, flows out by the discharge port of bottom.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| 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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| 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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| Publication Number | Publication Date |
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| CN105668761A true CN105668761A (en) | 2016-06-15 |
| CN105668761B CN105668761B (en) | 2018-09-14 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574197A (en) * | 2018-12-25 | 2019-04-05 | 广州市广深环保科技有限公司 | A kind of device and method handling aniline waste water |
| 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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| CN102701495A (en) * | 2012-06-25 | 2012-10-03 | 杨德敏 | Treatment device and treatment method for organic wastewater difficult to degrade |
| CN104150578A (en) * | 2014-07-10 | 2014-11-19 | 唐国民 | Catalytic ozonation water treatment device |
| 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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2016
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109574197A (en) * | 2018-12-25 | 2019-04-05 | 广州市广深环保科技有限公司 | A kind of device and method handling aniline waste water |
| 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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| CN105668761B (en) | 2018-09-14 |
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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 |