CN107381770A - The method for treating water of activated hydrogen peroxide under a kind of neutrallty condition - Google Patents
The method for treating water of activated hydrogen peroxide under a kind of neutrallty condition Download PDFInfo
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- CN107381770A CN107381770A CN201710851329.2A CN201710851329A CN107381770A CN 107381770 A CN107381770 A CN 107381770A CN 201710851329 A CN201710851329 A CN 201710851329A CN 107381770 A CN107381770 A CN 107381770A
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- Prior art keywords
- clay mineral
- water
- ferruginous clay
- ferruginous
- deposition thing
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 58
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical class OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 29
- 239000002734 clay mineral Substances 0.000 claims abstract description 71
- 230000008021 deposition Effects 0.000 claims abstract description 48
- -1 Hydroxyl radical free radical Chemical class 0.000 claims abstract description 11
- 238000003911 water pollution Methods 0.000 claims abstract description 9
- 230000015556 catabolic process Effects 0.000 claims abstract description 8
- 238000006731 degradation reaction Methods 0.000 claims abstract description 8
- 239000000356 contaminant Substances 0.000 claims abstract description 5
- 230000008030 elimination Effects 0.000 claims abstract description 4
- 238000003379 elimination reaction Methods 0.000 claims abstract description 4
- 239000012535 impurity Substances 0.000 claims abstract description 4
- 230000009467 reduction Effects 0.000 claims abstract description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 35
- 239000004927 clay Substances 0.000 claims description 21
- 229910052742 iron Inorganic materials 0.000 claims description 16
- 239000007787 solid Substances 0.000 claims description 15
- 239000002253 acid Substances 0.000 claims description 11
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 8
- 229910052500 inorganic mineral Inorganic materials 0.000 claims description 8
- 239000011707 mineral Substances 0.000 claims description 8
- 239000011734 sodium Substances 0.000 claims description 8
- 229910052708 sodium Inorganic materials 0.000 claims description 8
- CLJTZNIHUYFUMR-UHFFFAOYSA-M sodium;hydrogen carbonate;2-hydroxypropane-1,2,3-tricarboxylic acid Chemical compound [Na+].OC([O-])=O.OC(=O)CC(O)(C(O)=O)CC(O)=O CLJTZNIHUYFUMR-UHFFFAOYSA-M 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 6
- 239000008236 heating water Substances 0.000 claims description 6
- 229910052604 silicate mineral Inorganic materials 0.000 claims description 6
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- 230000004913 activation Effects 0.000 claims description 4
- GUJOJGAPFQRJSV-UHFFFAOYSA-N dialuminum;dioxosilane;oxygen(2-);hydrate Chemical compound O.[O-2].[O-2].[O-2].[Al+3].[Al+3].O=[Si]=O.O=[Si]=O.O=[Si]=O.O=[Si]=O GUJOJGAPFQRJSV-UHFFFAOYSA-N 0.000 claims description 4
- 229910052901 montmorillonite Inorganic materials 0.000 claims description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 229910052626 biotite Inorganic materials 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 238000002203 pretreatment Methods 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 2
- 238000007789 sealing Methods 0.000 claims description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910001919 chlorite Inorganic materials 0.000 claims 1
- 229910052619 chlorite group Inorganic materials 0.000 claims 1
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 claims 1
- 239000010919 dye waste Substances 0.000 claims 1
- 239000003292 glue Substances 0.000 claims 1
- 229910052739 hydrogen Inorganic materials 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 claims 1
- 239000011780 sodium chloride Substances 0.000 claims 1
- 230000008901 benefit Effects 0.000 abstract description 8
- 230000007935 neutral effect Effects 0.000 abstract description 5
- 238000012545 processing Methods 0.000 abstract description 4
- 230000008439 repair process Effects 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 12
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 9
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical group ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 9
- 238000002474 experimental method Methods 0.000 description 9
- 230000000593 degrading effect Effects 0.000 description 7
- 229960002415 trichloroethylene Drugs 0.000 description 7
- UBOXGVDOUJQMTN-UHFFFAOYSA-N trichloroethylene Natural products ClCC(Cl)Cl UBOXGVDOUJQMTN-UHFFFAOYSA-N 0.000 description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- 229910000273 nontronite Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000002585 base Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 238000011161 development Methods 0.000 description 3
- 239000003344 environmental pollutant Substances 0.000 description 3
- 230000001590 oxidative effect Effects 0.000 description 3
- 231100000719 pollutant Toxicity 0.000 description 3
- 230000004308 accommodation Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000010842 industrial wastewater Substances 0.000 description 2
- 150000002505 iron Chemical class 0.000 description 2
- 238000011017 operating method Methods 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 239000012028 Fenton's reagent Substances 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003295 industrial effluent Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- QXADHXQCAQTNGW-UHFFFAOYSA-M sodium;boric acid;hydroxide Chemical compound [OH-].[Na+].OB(O)O QXADHXQCAQTNGW-UHFFFAOYSA-M 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002352 surface water Substances 0.000 description 1
- 239000002699 waste material Substances 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
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
-
- 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
- C02F2305/026—Fenton's reagent
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of method for treating water of activated hydrogen peroxide under neutrallty condition, by the actual deposition thing or ferruginous clay mineral reduction of ferruginous clay mineral, impurity elimination, the actual deposition thing or ferruginous clay mineral of reduction-state are obtained, and H is activated in neutral conditions using it2O2Hydroxyl radical free radical is produced, and then degradation of contaminant carries out water pollution reparation.Processing speed of the present invention is fast, efficiency high, cost are low, environment-friendly, can repair field in wastewater treatment, contaminated site water and produce great economic benefit and social benefit.
Description
Technical field
The present invention relates to a kind of method for treating water of activated hydrogen peroxide under method for treating water, more particularly to neutrallty condition.
Background technology
Water is Source of life, is the valuable source that the mankind depend on for existence and development.It is more next with the fast development of industrial or agricultural
More discarded objects is discharged into environment during industrial production, agricultural development and family life and causes water pollution.Mesh
Before, China's water resource pollution is very serious.National 195 city monitoring results show that 97% urban groundwater is by difference
Degree pollutes, wherein 40% Urban Underground water pollution has aggravates trend year by year.The most river surface water of China by
Different degrees of pollution, wherein the Changjiang river, the Zhujiang River, Song Hua River, the Yellow River, Huaihe River, the Liaohe River and seven big river pollution of Haihe River are the most serious.
Industrial wastewater is not equally optimism, and national discharged volume of industrial waste water in 2014 is 205.3 hundred million tons, and is in increase trend year by year.In
State is the country that a water resource lacks, and serious water pollution not only influences industrial and agricultural production, but also the serious threat mankind, life
The health and destruction ecological environment of thing.Therefore, it is extremely urgent to develop quick, efficient and economic and environment-friendly water pollution recovery technique.
In order to solve water pollution problems, Conservation Scientist continually develop efficient, environmentally friendly and economic water technology.Closely
Nian Lai, high-level oxidation technology overcome common because it can produce the hydroxyl radical free radical efficient degradation pollutant of strong oxidizing property
Ozone (the O used in oxidizing process3), chlorine (Cl2), hydrogen peroxide (H2O2) etc. it is oxidizing indifferent the deficiencies of, it is wide
It is general to be applied in water process.According to activation H2O2Medicament and mode divide, typical efficient oxidation technology mainly has O3/H2O2、
UV/H2O2、H2O2/Fe2+(Fenton reagent).Comparatively speaking, O3H is activated with ultraviolet light (UV)2O2Need O3With UV generators etc.
Complex device and expensive, and Fe2+Activate H2O2Then it is easier to realize industrialization because equipment is simple and low-cost.Therefore,
Fe2+Activate H2O2Fenton oxidation method turned into most wide one kind of application surface in high-level oxidation technology.But in Fenton oxygen
In change method, Fe2+Activate H2O2Need to maintain the progress of pH 2~3 so as to avoid Fe (OH)3Precipitation generation and terminating reaction, it is necessary to
It is unfriendly using substantial amounts of acid for adjusting pH, environment；On the other hand, because the water outlet after being disposed need to maintain pH neutral, therefore
The alkali for needing to add respective amount neutralizes the acid above added, and this can produce substantial amounts of iron-contained waste material, adds follow-up extra
Safe disposal problem.
The content of the invention
In view of this, the embodiment provides a kind of processing speed is fast, efficiency high, cost are low and environment-friendly
The method for treating water of activated hydrogen peroxide under neutrallty condition.
Embodiments of the invention provide a kind of method for treating water of activated hydrogen peroxide under neutrallty condition, by ferruginous clay ore deposit
The actual deposition thing of thing or ferruginous clay mineral reduction, impurity elimination, the actual deposition thing or ferruginous clay mineral of reduction-state are obtained, and
H is activated in neutral conditions using it2O2Hydroxyl radical free radical is produced, and then degradation of contaminant carries out water pollution reparation.
Further, the actual deposition thing of the ferruginous clay mineral comes from the shallow underground ambient deposition of field acquisition
Thing, the ferruginous clay mineral are rich iron layer silicate mineral, and the rich iron layer silicate mineral is montmorillonite, green mud
Stone, biotite, the actual deposition things of ferruginous clay mineral are loam mould or silty clay type, the actual deposition of ferruginous clay mineral
Iron content ＞ 2% in thing, and content of organic matter ＜ 3%, ferruginous clay iron in minerals content ＞ 2%.
Further, following steps are specifically included：
S1. the actual deposition thing or ferruginous clay mineral of ferruginous clay mineral are pre-processed；
S2. add successively into the actual deposition thing or ferruginous clay mineral of the ferruginous clay mineral by step S1 pretreatments
Insure powder, sodium acid carbonate-sodium citrate cocktail buffer and water, sealing, 2~4h of heating water bath, stands cooling, that is, is gone back
The actual deposition thing or ferruginous clay mineral of ortho states；
S3. the actual deposition thing of the obtained reduction-states of step S2 or ferruginous clay mineral are first cleaned with 1mol/LNaCl,
Cleaned more than 5 times with deionized water again, collect solid portion, and preserve under anaerobic stand-by；
S4. H is added into organic polluting water2O2, stir while adding the solid portion activation of step S3 collections
H2O2Carry out water process；
S5. the suspension obtained after step S4 water process is subjected to separation of solid and liquid, and collects solid portion, then successively
Recycled according to step S1~S3.
Further, in the step S1, the actual deposition thing or ferruginous clay mineral of ferruginous clay mineral are located in advance
Reason is specially：The actual deposition thing of ferruginous clay mineral or ferruginous clay mineral are air-dried or dried, crosses 200 mesh sieves, collection is
Can.
Further, in the step S2, the actual deposition things of sodium hydrosulfite and ferruginous clay mineral or ferruginous clay mineral
Ratio is 1:10~2:The actual deposition thing of 10g/g, sodium acid carbonate-sodium citrate cocktail buffer and ferruginous clay mineral contains
The ratio of clunch mineral is 1.5:1~40:The actual deposition thing or ferruginous clay mineral of 1mL/g, water and ferruginous clay mineral
Ratio be 2:1~50:1mL/g, the body of sodium acid carbonate and sodium citrate in the sodium acid carbonate-sodium citrate cocktail buffer
Product is than being 10：1~30：1, the sodium acid carbonate is 0.5~2.0mol/L, and the sodium citrate is 0.5~2.0mol/L.
Further, in the step S2, the temperature of heating water bath is 30~100 DEG C.
Further, in the step S2, it is sealed in glass container, the volume and ferruginous clay mineral of the glass container
Actual deposition thing or ferruginous clay mineral ratio be 20:1~300:1mL/g.
Further, in the step S4, the pH of organic polluting water is 3~7.5, the COD of organic polluting water
Concentration is less than 200mg/L, according to the difference of COD concentration in organic polluting water, H2O2Concentration control 0.1~
Between 100mmol/L, according to the H added in organic polluting water2O2Concentration controls the concentration of the step S3 solid portions collected
Between 1~50g/L, according to COD concentration differential responses time control between 1~60min.
Compared with prior art, the invention has the advantages that：
(1) processing speed is fast, efficiency high, cost are low, environment-friendly, can repair field in wastewater treatment, contaminated site water
Produce great economic benefit and social benefit；
(2) reduction-state deposit or ferruginous clay ore deposit containing ferruginous clay ore deposit are used, activates H2O2Can be in neutrallty condition
Lower progress, without acid-base accommodation；
(3) that utilize is the structure state Fe (II) in clay mineral, H2O2Utilization rate is high, pollution good degrading effect；
(4) ferrous iron in actual deposition thing or ferruginous clay ore deposit will not or be seldom discharged into water, and recyclable repetition makes
With avoiding the continuous the problem of adding demand and producing iron containing sludge of tradition to divalent iron salt；
(5) deposit containing ferruginous clay ore deposit is widely present in underground environment, and ferruginous clay ore deposit is cheap and easy
It is low in acquisition, operating cost.
Brief description of the drawings
Fig. 1 is a flow chart of the method for treating water of activated hydrogen peroxide under a kind of neutrallty condition of the present invention.
Fig. 2 is the effect for the shallow underground ambient deposition thing activated hydrogen peroxide degradation of phenol that reduction-state contains ferruginous clay ore deposit
Fruit is schemed.
Fig. 3 is the design sketch of reduction-state nontronite activated hydrogen peroxide degraded trichloro ethylene.
Embodiment
To make the object, technical solutions and advantages of the present invention clearer, below in conjunction with accompanying drawing to embodiment party of the present invention
Formula is further described.
Fig. 1 is refer to, the embodiment provides a kind of method for treating water of activated hydrogen peroxide under neutrallty condition,
By the actual deposition thing of ferruginous clay mineral or ferruginous clay mineral reduction, impurity elimination, obtain the actual deposition thing of reduction-state or contain
Clunch mineral, and H is activated in neutral conditions using it2O2Hydroxyl radical free radical is produced, and then degradation of contaminant carries out water pollution
Repair.
In one embodiment, the actual deposition thing of the ferruginous clay mineral comes from the shallow underground environment of field acquisition
Deposit, the ferruginous clay mineral are rich iron layer silicate mineral, and the rich iron layer silicate mineral is montmorillonite, green
Mudstone, biotite, the actual deposition thing of ferruginous clay mineral is loam mould or silty clay type, and the reality of ferruginous clay mineral is sunk
Iron content ＞ 2% in product thing, and content of organic matter ＜ 3%, ferruginous clay iron in minerals content ＞ 2%.
Specifically include following steps：
S1. the actual deposition thing or ferruginous clay mineral of ferruginous clay mineral are pre-processed, by ferruginous clay mineral
Actual deposition thing or ferruginous clay mineral air-dry or drying, cross (0.074 μm) of 200 mesh sieve, collect；
S2. add successively into the actual deposition thing or ferruginous clay mineral of the ferruginous clay mineral by step S1 pretreatments
Insure powder, sodium acid carbonate-sodium citrate cocktail buffer and water, the actual deposition thing of sodium hydrosulfite and ferruginous clay mineral or contains
The ratio of clunch mineral is 1:10~2:The reality of 10g/g, sodium acid carbonate-sodium citrate cocktail buffer and ferruginous clay mineral
The ratio of border deposit or ferruginous clay mineral is 1.5:1~40:The actual deposition thing of 1mL/g, water and ferruginous clay mineral or
The ratio of ferruginous clay mineral is 2:1~50:1mL/g, in the sodium acid carbonate-sodium citrate cocktail buffer sodium acid carbonate and
The volume ratio of sodium citrate is 10：1~30：1, the sodium acid carbonate is 0.5~2.0mol/L, the sodium citrate is 0.5~
2.0mol/L, it is sealed in glass container, the volume of the glass container and the actual deposition thing or iron content of ferruginous clay mineral
The ratio of clay mineral is 20:1~300：1mL/g, 2~4h of heating water bath, the temperature of heating water bath is 30~100 DEG C, is stood
Cooling, that is, obtain the actual deposition thing or ferruginous clay mineral of reduction-state；
S3. the actual deposition thing of the obtained reduction-states of step S2 or ferruginous clay mineral are first cleaned with 1mol/LNaCl,
Cleaned more than 5 times with deionized water again, collect solid portion, and preserve under anaerobic stand-by；
S4. H is added into organic polluting water2O2, the pH of organic polluting water is 3~7.5, the change of organic polluting water
Learn oxygen demand (COD) concentration and be less than 200mg/L, stir while adding the solid portion activation H of step S3 collections2O2Carry out
Water process, according to the difference of COD concentration in organic polluting water, H2O2Concentration is controlled between 0.1~100mmol/L, according to having
The H added in machine pollutant effluents2O2Concentration controls the concentration of the step S3 solid portions collected between 1~50g/L, according to
COD concentration differential responses time controls are between 1~60min；
S5. the suspension obtained after step S4 water process is subjected to separation of solid and liquid, and collects solid portion, then successively
Recycled according to step S1~S3.
Application examples 1
Phenol is a kind of typical organic pollution, is widely present in underground water, ground water and industrial effluents.Due to it
High toxicity, high risks be present to the mankind and biological health and safety, it is therefore necessary to find a kind of side of efficient process phenolic waste water
Method.To investigate degradation effect of the deposit activated hydrogen peroxide containing ferruginous clay ore deposit of reduction-state to organic pollution, with
Phenol is that target contaminant carries out experiment.
Degrading experiment is carried out in 15mL vials, and 2mg/L phenol adds 15g/L reduction-state deposit, is used
H2SO4By pH value of solution control in 6 or so, reaction volume 10mL, 220rpm is placed in, in 25 DEG C of shaking table, it is eventually adding 2~
10mmol/L H2O2Start to react, terminate reaction after reacting 5min, while do isopropanol check experiment, specially add
200mmol/L isopropanols, other operating procedures are same as above, and the degradation effect of reduction-state deposit activated hydrogen peroxide Pyrogentisinic Acid is as schemed
Shown in 2, with the increase of concentration of hydrogen peroxide, the clearance of 2mg/L phenol gradually steps up, when concentration of hydrogen peroxide increase
During 10mmol/L, the clearance of 2mg/L phenol is almost close to 100%, good degrading effect.Pass through isopropanol check experiment simultaneously
It was found that after adding hydroxyl radical free radical quencher isopropanol, phenol hardly removes, and the degraded for illustrating phenol is reduction-state deposit
Activated hydrogen peroxide produces hydroxyl radical free radical contribution.
Application examples 2
Trichloro ethylene is a kind of organo-chlorine pollutant being widely present in underground water.To exclude the volatilization of trichloro ethylene
Effect, Degrading experiment are carried out under anaerobic, and this example is represented using nontronite as montmorillonite ferruginous clay ore deposit carries out
Experiment.
Degrading experiment is carried out in 11.5mL vial, sequentially adds 2mg/L trichloro ethylenes, 0.6g/L nontronite,
The reducing degree of nontronite about 40%, it is 7.5 with boric acid-sodium hydroxide regulation pH, vial is covered tightly containing polytetrafluoroethylene (PTFE)
The aluminium lid of pad, and it is rapidly added 0.5mmol/L H2O2, it is placed in 220rpm, 25 DEG C of shaking table and starts to react, reaction volume is
10mL.The trichloro ethylene change in concentration situation in different time (0~30min) samples the detection aqueous solution.Do isopropanol pair simultaneously
According to experiment, 100mmol/L isopropanols are specially added, other operating procedures are same as above.As a result as shown in figure 3, with the reaction time
Extension, the clearance of 2mg/L trichloro ethylenes gradually steps up, when reacted between when being 30min, 2mg/L trichloro ethylene is gone
Except rate reaches more than 90%, good degrading effect.Found simultaneously by isopropanol check experiment, it is different to add hydroxyl radical free radical quencher
After propyl alcohol, trichloro ethylene is almost non-degradable, and the degraded for illustrating trichloro ethylene is that reduction-state nontronite activated hydrogen peroxide produces hydroxyl
The contribution of base free radical.
Processing speed of the present invention is fast, efficiency high, cost are low, environment-friendly, can be led in wastewater treatment, the reparation of contaminated site water
Domain produces great economic benefit and social benefit；Using reduction-state deposit or ferruginous clay ore deposit containing ferruginous clay ore deposit,
Activate H2O2It can carry out in neutral conditions, without acid-base accommodation；That utilize is the structure state Fe (II) in clay mineral,
H2O2Utilization rate is high, pollution good degrading effect；Ferrous iron in actual deposition thing or ferruginous clay ore deposit will not or be seldom discharged into
In water, it is recycled and reuses, avoids tradition and the problem of demand is with iron containing sludge is produced is added to the continuous of divalent iron salt；Contain
The deposit for having ferruginous clay ore deposit is widely present in underground environment, and ferruginous clay ore deposit is cheap and is easily obtained, and runs into
This is low.
In the case where not conflicting, the feature in embodiment and embodiment herein-above set forth can be combined with each other.
The foregoing is only presently preferred embodiments of the present invention, be not intended to limit the invention, it is all the present invention spirit and
Within principle, any modification, equivalent substitution and improvements made etc., it should be included in the scope of the protection.
Claims (8)
1. the method for treating water of activated hydrogen peroxide under a kind of neutrallty condition, it is characterised in that by the reality of ferruginous clay mineral
Deposit or ferruginous clay mineral reduction, impurity elimination, obtain the actual deposition thing or ferruginous clay mineral of reduction-state, and using its
H is activated under neutrallty condition2O2Hydroxyl radical free radical is produced, and then degradation of contaminant carries out water pollution reparation.
2. the method for treating water of activated hydrogen peroxide under neutrallty condition according to claim 1, it is characterised in that described to contain
The actual deposition thing of clunch mineral comes from the shallow underground ambient deposition thing of field acquisition, and the ferruginous clay mineral are richness
Iron layer silicate mineral, the rich iron layer silicate mineral is montmorillonite, chlorite, biotite, ferruginous clay mineral
Actual deposition thing is loam mould or silty clay type, iron content ＞ 2% in the actual deposition thing of ferruginous clay mineral, and organic matter
Content ＜ 3%, ferruginous clay iron in minerals content ＞ 2%.
3. the method for treating water of activated hydrogen peroxide under neutrallty condition according to claim 1 or 2, it is characterised in that tool
Body comprises the following steps：
S1. the actual deposition thing or ferruginous clay mineral of ferruginous clay mineral are pre-processed；
S2. guarantor is sequentially added into the actual deposition thing or ferruginous clay mineral of the ferruginous clay mineral by step S1 pretreatments
Dangerous powder, sodium acid carbonate-sodium citrate cocktail buffer and water, sealing, 2~4h of heating water bath, cooling is stood, that is, obtains reduction-state
Actual deposition thing or ferruginous clay mineral；
S3. the actual deposition thing of the obtained reduction-states of step S2 or ferruginous clay mineral are first cleaned with 1mol/L NaCl, then used
Deionized water is cleaned more than 5 times, collects solid portion, and preserve under anaerobic stand-by；
S4. H is added into organic polluting water2O2, stir while adding the solid portion activation H of step S3 collections2O2Enter
Water-filling is handled；
S5. the suspension obtained after step S4 water process is subjected to separation of solid and liquid, and collects solid portion, then successively according to
Step S1~S3 is recycled.
4. the method for treating water of activated hydrogen peroxide under neutrallty condition according to claim 3, it is characterised in that the step
In rapid S1, the actual deposition thing or ferruginous clay mineral of ferruginous clay mineral are pre-processed specially：By ferruginous clay ore deposit
The actual deposition thing or ferruginous clay mineral of thing air-dry or drying, crosses 200 mesh sieves, collection.
5. the method for treating water of activated hydrogen peroxide under neutrallty condition according to claim 3, it is characterised in that the step
In rapid S2, the actual deposition thing of sodium hydrosulfite and ferruginous clay mineral or the ratio of ferruginous clay mineral are 1:10~2:10g/g, carbon
The ratio of the actual deposition thing or ferruginous clay mineral of sour hydrogen sodium-sodium citrate cocktail buffer and ferruginous clay mineral is 1.5:
1~40:The actual deposition thing of 1mL/g, water and ferruginous clay mineral or the ratio of ferruginous clay mineral are 2:1~50:1mL/g,
The volume ratio of sodium acid carbonate and sodium citrate is 10 in the sodium acid carbonate-sodium citrate cocktail buffer：1~30：1, it is described
Sodium acid carbonate is 0.5~2.0mol/L, and the sodium citrate is 0.5~2.0mol/L.
6. the method for treating water of activated hydrogen peroxide under neutrallty condition according to claim 3, it is characterised in that the step
In rapid S2, the temperature of heating water bath is 30~100 DEG C.
7. the method for treating water of activated hydrogen peroxide under neutrallty condition according to claim 3, it is characterised in that the step
In rapid S2, it is sealed in glass container, the volume of the glass container and the actual deposition thing or iron content of ferruginous clay mineral glue
The ratio of native mineral is 20:1~300:1mL/g.
8. the method for treating water of activated hydrogen peroxide under neutrallty condition according to claim 3, it is characterised in that the step
In rapid S4, the pH of organic polluting water is 3~7.5, and the COD concentration of organic polluting water is less than 200mg/L, according to
The difference of COD concentration, H in organic polluting water2O2Concentration is controlled between 0.1~100mmol/L, according to organic dirt
The H added in dye waste water2O2Concentration controls the concentration of the step S3 solid portions collected between 1~50g/L, according to chemistry
Oxygen demand concentration differential responses time control is between 1~60min.
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| CN108314135A (en) * | 2018-02-05 | 2018-07-24 | 南昌大学 | A kind of quenching method of UV-Fenton systems hydroxyl radical free radical |
| CN111908585A (en) * | 2020-07-24 | 2020-11-10 | 南京工程学院 | Fenton-like water treatment method based on generation of hydroxyl free radicals by iron-containing clay minerals |
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| US20060076299A1 (en) * | 2004-10-08 | 2006-04-13 | The Hong Kong University Of Science And Technology | Synthesis of bentonite clay-based iron nanocomposite and its use as a heterogeneous photo fenton catalyst |
| CN105084507A (en) * | 2014-12-23 | 2015-11-25 | 郑州大学 | High-iron bauxite-hydrogen peroxide combined water treatment method |
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| US20060076299A1 (en) * | 2004-10-08 | 2006-04-13 | The Hong Kong University Of Science And Technology | Synthesis of bentonite clay-based iron nanocomposite and its use as a heterogeneous photo fenton catalyst |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108314135A (en) * | 2018-02-05 | 2018-07-24 | 南昌大学 | A kind of quenching method of UV-Fenton systems hydroxyl radical free radical |
| CN111908585A (en) * | 2020-07-24 | 2020-11-10 | 南京工程学院 | Fenton-like water treatment method based on generation of hydroxyl free radicals by iron-containing clay minerals |
| CN111908585B (en) * | 2020-07-24 | 2022-08-09 | 南京工程学院 | Fenton-like water treatment method based on generation of hydroxyl free radicals by iron-containing clay minerals |
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