CN102372355B - Method for processing organic waste water - Google Patents
Method for processing organic waste water Download PDFInfo
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- CN102372355B CN102372355B CN201110302520.4A CN201110302520A CN102372355B CN 102372355 B CN102372355 B CN 102372355B CN 201110302520 A CN201110302520 A CN 201110302520A CN 102372355 B CN102372355 B CN 102372355B
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- 238000000034 method Methods 0.000 title claims abstract description 46
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 36
- 239000010815 organic waste Substances 0.000 title claims abstract description 32
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 100
- 229910052742 iron Inorganic materials 0.000 claims abstract description 41
- 230000008569 process Effects 0.000 claims abstract description 22
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 15
- -1 polyethylene Polymers 0.000 claims abstract description 10
- 239000004033 plastic Substances 0.000 claims abstract description 8
- 229920003023 plastic Polymers 0.000 claims abstract description 8
- 239000004698 Polyethylene Substances 0.000 claims abstract description 5
- 229920000573 polyethylene Polymers 0.000 claims abstract description 5
- 239000004743 Polypropylene Substances 0.000 claims abstract description 4
- 229920001155 polypropylene Polymers 0.000 claims abstract description 4
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 42
- IZUPBVBPLAPZRR-UHFFFAOYSA-N pentachlorophenol Chemical compound OC1=C(Cl)C(Cl)=C(Cl)C(Cl)=C1Cl IZUPBVBPLAPZRR-UHFFFAOYSA-N 0.000 claims description 8
- ISPYQTSUDJAMAB-UHFFFAOYSA-N 2-chlorophenol Chemical compound OC1=CC=CC=C1Cl ISPYQTSUDJAMAB-UHFFFAOYSA-N 0.000 claims description 7
- 239000000975 dye Substances 0.000 claims description 7
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 claims description 6
- 239000002351 wastewater Substances 0.000 claims description 6
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims description 5
- 229940043267 rhodamine b Drugs 0.000 claims description 5
- POJOORKDYOPQLS-UHFFFAOYSA-L barium(2+) 5-chloro-2-[(2-hydroxynaphthalen-1-yl)diazenyl]-4-methylbenzenesulfonate Chemical compound [Ba+2].C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O.C1=C(Cl)C(C)=CC(N=NC=2C3=CC=CC=C3C=CC=2O)=C1S([O-])(=O)=O POJOORKDYOPQLS-UHFFFAOYSA-L 0.000 claims description 4
- 238000004064 recycling Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 3
- 239000002699 waste material Substances 0.000 claims description 3
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 2
- 239000011248 coating agent Substances 0.000 claims 1
- 238000000576 coating method Methods 0.000 claims 1
- 238000005516 engineering process Methods 0.000 abstract description 7
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 230000007613 environmental effect Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- VGVRPFIJEJYOFN-UHFFFAOYSA-N 2,3,4,6-tetrachlorophenol Chemical class OC1=C(Cl)C=C(Cl)C(Cl)=C1Cl VGVRPFIJEJYOFN-UHFFFAOYSA-N 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011946 reduction process Methods 0.000 description 3
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- 230000002779 inactivation Effects 0.000 description 2
- 150000007524 organic acids Chemical class 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000003044 adaptive effect Effects 0.000 description 1
- 239000000987 azo dye Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000031018 biological processes and functions Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000006298 dechlorination reaction Methods 0.000 description 1
- 238000004042 decolorization Methods 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 230000005662 electromechanics Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 229960005191 ferric oxide Drugs 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000001475 halogen functional group Chemical group 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 235000000396 iron Nutrition 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
- 238000009941 weaving Methods 0.000 description 1
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Abstract
The invention discloses a method for processing organic waste water, which comprises the following steps that: a cladding-typed iron-based material is prepared by utilizing organic plastic to incompletely wrap an iron-based material, and the cladding-typed iron-based material is arranged in organic waste water with the pH value of 3 to 7 to process; and the organic plastic is polyethylene, polypropylene or polyfluortetraethylene, and the iron-based material is zero-valent iron. The iron-based material has vast raw material source, low cost, simple production process, stable performance, environmental friendliness, high reaction efficiency, repeatability and long service life. The method can be used for processing water having different organic pollution, can be adjusted according to characteristics of typical organic pollutants in different industries and according to the local conditions, can overcome the weaknesses of the different traditional technologies, is convenient and easy to operate and has high efficiency.
Description
Technical field
The invention belongs to water pollution control and reparation field, be specifically related to a kind of method of processing organic waste water.
Background technology
Chemical industry, printing and dyeing, weaving, food, electromechanics, brewage, the industry industrial production such as pharmacy causes a large amount of waste water containing organic pollutant, threatens that ecological safety and the mankind's is healthy.The treatment process of organic waste water commonly used mainly is divided into Physical, chemical method and biological process three classes, as absorption, membrane sepn, burning, extraction, Wet Catalytic Oxidation Method, photochemical catalysis, electrochemistry and microbial degradation method etc., various technology all have benefit and limitation separately, to the organic waste water of complicated component, difficult for biological degradation, in the urgent need to the treatment process of the comparatively pervasive economy of development on the basis at comprehensive various factors.
The past Zero-valent Iron receives much concern with the environmental improvement containing the nitro organic pollutant for vattability heavy metal, halo organic pollutant.In recent years, it is found that Zero-valent Iron can produce active oxygen species-hydroxyl radical free radical that oxidation susceptibility is stronger (OH) having under the existence conditions such as oxygen, hydrogen peroxide, low molecular weight organic acid, this free radical degradable mineralising refractory organics organic pollutant is nontoxic inorganic molecules (CO
2, H
2o etc.).Be different from high-level oxidation technology, Zero-valent Iron is cheap and easy to get, so it may be one of important channel obtained high oxidation activity OH.Zero-valent Iron and hydrogen peroxide system form Fenton-like; While ferriferous oxide and the various materials, particularly magnetic iron oxide that contain the iron species, also can form heterogeneous Fenton-likes with hydrogen peroxide, organic acid etc., efficiently processes organic waste water.With respect to traditional homogeneous phase Fenton system (Fe
2+/ H
2o
2), heterogeneous Fenton-like has advantages of that the hydrogen peroxide consumption is few, catalytic material easily reclaims, but still has the problems such as the easy inactivation of pH narrow range, catalyzer of useful effect and difficult life, is difficult to that adaptive element is complicated, the harsh treatment of Organic Wastewater of envrionment conditions.
Document " development of iron-based-tetrafluoroethylene composite self-lubricating material " (lubricated and sealing, 02 phase in 1985,25 ~ 31) introduced the preparation technology of iron-based-tetrafluoroethylene composite self-lubricating material, the performance of mechanical property and frictional wear aspect, and its Mechanism of Friction Reduction has been made to Primary Study, it is applied as a kind of lubricant.
Summary of the invention
The object of the invention is to, according to the above-mentioned deficiency in existing Technologies for Organic Wastewater Treatment, provides a kind of new method for processing organic wastewater.
The present invention is achieved through the following technical solutions above-mentioned purpose:
A kind of method of processing organic waste water, be not exclusively to coat iron with organic plastics to be prepared into the cladded type iron, in the organic waste water that to insert the pH value be 3 ~ 7, processed; Described organic plastics is polyethylene, polypropylene or tetrafluoroethylene, and described iron is Zero-valent Iron, can select the various materials such as magnet, iron wire, iron plate, waste iron filing, iron shot, iron alloy as iron.
Adopt the cladded type iron of effective exposure as heterogeneous class Fenton's reaction catalyzer, sufficient chain carrier can be provided as far as possible, direct-reduction vattability organic pollutant is so that other techniques that are coupled reach innoxious purpose, avoid the quick corrosion of self big area or inactivation simultaneously, and have advantages of that the convenient regeneration of recovery utilizability is strong.
As a kind of preferred version, the method for above-mentioned processing organic waste water can also add a small amount of hydrogen peroxide in treating processes, preferably adds the final concentration of hydrogen peroxide lower than 10mM.The micro-hydrogen peroxide of arranging in pairs or groups can produce reactive oxygen species, thoroughly the various organic pollutants of mineralising.In general, the amount of hydrogen peroxide used with add treatment time after hydrogen peroxide significantly lower than the scheme that does not add hydrogen peroxide, the Pollutant levels of processing can exceed more than ten times.
In the method for above-mentioned processing organic waste water, described organic waste water is one or more the organic waste water contained in tropeolin-D, reactive brilliant red, Pentachlorophenol, ortho chloro phenol or rhodamine B.Described organic plastics and iron surface alternative arrangement expose, and are prepared into the cladded type iron.Treatment time is preferably 1 ~ 10 hour.The cladded type iron is inserted the mode processed in the organic waste water that the pH value is 3 ~ 7 for stirring, as can granulation, the shape such as bar-shaped, the devices such as collocation pump, stirrer carry out water treatment.
The method of above-mentioned processing organic waste water, suitable environment is when in organic waste water, pollutent is dyestuff, and dye strength is below 500mg/L, and when organic pollutant is organochlorine (as chlorophenol), organochlorine concentration is not higher than 100mg/L.
Cladded type iron after above-mentioned disposal methods, can reclaim by magnetic, net the modes such as receipts and carry out recycling.
Compared with prior art, the present invention has following beneficial effect:
Treatment process of the present invention can be suited measures to local conditions to be adjusted for different industries Typical Industrial organic pollutant characteristics for the water treatment of various organic contaminations, can overcome the deficiency of various technology in the past, facilitates easy to operate and efficiency is high.
Cladded type iron of the present invention and using method thereof can not cause secondary pollution to surrounding environment, surface water, underground water etc., ensure ecological safety and HUMAN HEALTH.
Iron raw material sources of the present invention are extensive, cost is low, making processes is simple, stable performance, environmental friendliness, and reaction efficiency is high, reusable, the rear recoverable that reaches capacity, long service life.
The waste water report of the organic pollutants such as Zero-valent Iron processing dyestuff is more, some nano zero valence irons of using, what have is these iron wire iron plates etc., but existing problems are to corrode very soon that to reclaim recycling property poor, and Zero-valent Iron is more for the reduction field, the this patent core is the use of incomplete cladded type iron, another outstanding main points are to coordinate micro-hydrogen peroxide can reach the purpose of thorough mineralising, there is bibliographical information zeroth order iron powder collocation hydrogen peroxide to process the good result of organic pollutant, exist equally Zero-valent Iron to reclaim the also comparatively serious situation of corrosion of difficulty, therefore adopt incomplete cladded type iron can process very efficiently organic waste water, avoid the corrosion of iron big area simultaneously, be easy to recycling.
The accompanying drawing explanation
Fig. 1 is that different systems are processed the halfhour effect comparison of rhodamine B (pH=5), wherein 1 means simple zeroth order iron powder (dosage 1g/L) treatment group, 2 mean simple hydrogen peroxide (dosage 2mM) treatment group, 3 mean zeroth order iron powder (1g/L)+hydrogen peroxide (2mM) treatment group, and 4 mean magnetic core+hydrogen peroxide (0.5mM) treatment group that tetrafluoroethylene coats.
Embodiment
5 millimeters of the waste iron wire diameters that polyethylene coats, long 20 centimetres expose circumference every two centimetres, paddle as stirrer, can efficiently reduce the processing azo dyes in pH3 to the pH7 scope, in half an hour, the dyestuffs such as 100mg/L tropeolin-D, reactive brilliant red in 200mL solution can be decoloured fully, significantly improve its biodegradability (pH more the reduction process time shorter, as pH be 3 o'clock the reaction less than 10 minutes, just the dyestuffs such as 100mg/L tropeolin-D, reactive brilliant red in 200mL solution can be decoloured fully).This lower cost for material, making processes are simple, repeat 30 its decrease in efficiency less than 5%, and it is easy to operate simultaneously, the efficient dye wastewater treatment using of different device of can arranging in pairs or groups.
5 millimeters of the iron wire diameters that polypropylene coats, long 20 centimetres expose circumference every two centimetres, paddle as stirrer, can efficiently reduce in pH3 to the pH7 scope and process chlorophenols organic pollutant (pH more reduction process time shorter), the chlorophenols organic pollutant dechlorination rates such as 10mg/L Pentachlorophenol, ortho chloro phenol in 200mL solution, up to more than 75%, can be significantly improved to its biodegradability in one hour.This lower cost for material, making processes are simple, repeat ten its decrease in efficiency less than 10%, and it is easy to operate simultaneously, and the different device of can arranging in pairs or groups is efficiently processed chlorophenols organic waste water.
Polyethylene coats iron plate (2m * 2m * 0.5cm) and exposes one side, paddle as stirrer, but in pH3 to efficient oxidation degrading chlorophenol class organic pollutant in the pH7 scope (pH more reduction process time shorter), can the chlorophenols organic pollutants such as 50mg/L Pentachlorophenol, ortho chloro phenol in 200mL solution are degradable in one hour.This lower cost for material, making processes are simple, repeat 30 its decrease in efficiency less than 10%, and it is easy to operate simultaneously, the different device efficient oxidation degrading chlorophenol class of can arranging in pairs or groups organic waste water.
embodiment 4
(different systems are processed the halfhour effect comparison of rhodamine B (pH=5) as shown in Figure 1, wherein 1 means simple zeroth order iron powder (dosage 1g/L) treatment group, 2 mean simple hydrogen peroxide (dosage 2mM) treatment group, 3 mean zeroth order iron powder (1g/L)+hydrogen peroxide (2mM) treatment group, 4 mean magnetic core+hydrogen peroxide (0.5mM) treatment group that tetrafluoroethylene coats), be compared to simple Zero-valent Iron, simple hydrogen peroxide and zeroth order iron powder add hydrogen peroxide system, 5 millimeters of the magnetic core diameters that tetrafluoroethylene coats, long 10 centimetres expose two ends, stirrer as agitator, but be in pH5.0 efficient oxidation rhodamine B degradation (RhB) under 0.5 mM hydrogen peroxide acting in conjunction at final concentration, can reach 98% percent of decolourization half an hour, can 50mg/L RhB in 200mL solution is degradable in one hour, zeroth order iron powder seriously corroded is difficult to recycle and reuse.Magnetic core lower cost for material, making processes that this tetrafluoroethylene coats are simple, repeat up to a hundred its decrease in efficiency less than 5%, and it is easy to operate simultaneously, the different device efficient oxidation degradation of dye organic waste water of can arranging in pairs or groups.
Claims (8)
1. a method of processing organic waste water, it is characterized in that not exclusively coating iron with organic plastics is prepared into the cladded type iron, in the organic waste water that to insert the pH value be 3 ~ 7, processed; Described organic plastics is polyethylene, polypropylene or tetrafluoroethylene, and described iron is magnet, iron wire, iron plate, waste iron filing, iron shot or iron alloy;
Described organic plastics and iron surface alternative arrangement expose, and are prepared into the cladded type iron.
2. process according to claim 1 the method for organic waste water, it is characterized in that adding hydrogen peroxide in treating processes.
3. process according to claim 1 the method for organic waste water, it is characterized in that described organic waste water is the waste water that contains one or more materials in tropeolin-D, reactive brilliant red, Pentachlorophenol, ortho chloro phenol or rhodamine B.
4. process according to claim 1 the method for organic waste water, it is characterized in that the treatment time is 1 ~ 10 hour.
5. process according to claim 1 the method for organic waste water, it is characterized in that it is stirring that the cladded type iron is inserted the mode of being processed in the organic waste water that the pH value is 3 ~ 7.
6. process according to claim 5 the method for organic waste water, it is characterized in that stirring velocity is 200 ~ 500 rev/mins.
7. process according to claim 1 the method for organic waste water, while it is characterized in that Organic Pollutants in Wastewater is dyestuff, dye strength is below 500mg/L, and when organic pollutant is organochlorine, organochlorine concentration is not higher than 100mg/L.
8. process according to claim 1 the method for organic waste water, after it is characterized in that being disposed, by magnetic or net, take in capable recycling.
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|---|---|---|---|
| CN201110302520.4A CN102372355B (en) | 2011-10-09 | 2011-10-09 | Method for processing organic waste water |
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|---|---|---|---|
| CN201110302520.4A CN102372355B (en) | 2011-10-09 | 2011-10-09 | Method for processing organic waste water |
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| CN102372355A CN102372355A (en) | 2012-03-14 |
| CN102372355B true CN102372355B (en) | 2014-01-08 |
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Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103318988B (en) * | 2013-06-19 | 2014-12-17 | 环境保护部华南环境科学研究所 | Novel method for treating rhodamine B by visible light reinforcement fenton-like reaction, and its application |
| CN103464160B (en) * | 2013-09-25 | 2016-05-04 | 南开大学 | A kind of iron C catalyst preparation method who is applied to heterogeneous Fenton system |
| CN103803695B (en) * | 2014-02-25 | 2015-04-15 | 天津城建大学 | Method for Fenton-like light-catalyzed reaction system for zero-valent iron and TiO2 photocatalytic coupling |
| CN104962584A (en) * | 2015-06-30 | 2015-10-07 | 王敏 | Microorganism synthesis method of Fe-containing active matter and application of Fe-containing active matter in methyl orange degradation and catalyzing field |
| CN114522726B (en) * | 2022-03-03 | 2023-08-25 | 武汉理工大学 | Reduced iron powder composite polytetrafluoroethylene material and preparation method and application thereof |
Citations (3)
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|---|---|---|---|---|
| WO2008119063A1 (en) * | 2007-03-28 | 2008-10-02 | Worcester Polytechnic Institute | Simultaneous reduction/oxidation process for destroying an organic solvent |
| CN102000608A (en) * | 2010-11-04 | 2011-04-06 | 哈尔滨工业大学 | Method for preparing polymer heterogeneous Fenton-like catalyst-polyvinylidene fluoride (PVDF) catalytic membrane |
| CN102173500A (en) * | 2011-02-25 | 2011-09-07 | 华中师范大学 | Method for treating water by Fenton oxidization of activated molecular oxygen |
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2011
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2008119063A1 (en) * | 2007-03-28 | 2008-10-02 | Worcester Polytechnic Institute | Simultaneous reduction/oxidation process for destroying an organic solvent |
| CN102000608A (en) * | 2010-11-04 | 2011-04-06 | 哈尔滨工业大学 | Method for preparing polymer heterogeneous Fenton-like catalyst-polyvinylidene fluoride (PVDF) catalytic membrane |
| CN102173500A (en) * | 2011-02-25 | 2011-09-07 | 华中师范大学 | Method for treating water by Fenton oxidization of activated molecular oxygen |
Non-Patent Citations (2)
| Title |
|---|
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