CN106186273A - A kind of method without metal catalyst system degraded dyeing waste water - Google Patents
A kind of method without metal catalyst system degraded dyeing waste water Download PDFInfo
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- CN106186273A CN106186273A CN201610641500.2A CN201610641500A CN106186273A CN 106186273 A CN106186273 A CN 106186273A CN 201610641500 A CN201610641500 A CN 201610641500A CN 106186273 A CN106186273 A CN 106186273A
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- metal catalyst
- waste water
- dyeing waste
- catalyst system
- system degraded
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- 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0235—Nitrogen containing compounds
- B01J31/0239—Quaternary ammonium compounds
-
- 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
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/30—Nature of the water, waste water, sewage or sludge to be treated from the textile industry
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of method without metal catalyst system degraded dyeing waste water, it is produced spike (hydroxyl radical free radical OH, hydroxyl radical free radical has higher oxidation-reduction potential 1.8 2.7V) by non-metal catalyst active oxidation agent at normal temperatures can efficient degradation dyeing waste water.The present invention not only overcomes the tradition deficiency such as Fenton (Fenton) method secondary pollution, low, the pH narrow application range of hydrogen peroxide utilization rate, and reaction condition is gentle, and removal effect is obvious, without metallic pollution, little to environmental hazard, catalyst amount is few, simple to operate, low cost.
Description
Technical field
The invention belongs to treatment method of printing and dying wastewater field, especially relate to a kind of useless without metal catalyst system degraded printing and dyeing
The method of water.
Background technology
China is weaving big country, and according to " whole nation environmental statistics publication " statistics display, China's textile waste discharge capacity reaches 20
Many hundred million tons, wherein dyeing waste water accounts for 80%, causes severe contamination to environment.Therefore, dyeing waste water is processed the most efficiently
It it is problem demanding prompt solution all the time.
At present, processing the more commonly used and effective method of dyeing waste water is Fenton method.Fenton method is advanced oxidation skill
The one of art, its reaction reagent is by ferrous ion and hydrogen peroxide (H2O2) composition, hydroxyl radical free radical (OH) tool that this reaction produces
Having the strongest oxidisability, its standard oxidationreduction potential is 1.8-2.7V, most organic pollutants of degrading to low toxicity, Yi Sheng
The little molecule of thing degraded even directly mineralising is inorganic matter.Although Fenton method have easily operated, without consume extraneous energy,
The advantages such as oxidation is thorough, but, the reaction of traditional F enton there is also some inherent shortcomings: (1) Fenton pH value in reaction is suitable for model
Enclose narrow, only carry out in the strong acid medium of 2-4；(2) present in reaction system, a large amount of iron ions are difficult to remove, and are easily formed
Mud, causes secondary pollution.
Along with the development of technology, new and effective water technology continues to bring out, have researcher use other oxidants or
Catalyst replaces hydrogen peroxide or ferrous ion to constitute Fenton-like system, achieves certain effect.(the Journal of such as Ling
Hazardous Materials, 2010,178:385-389.) use cobalt/permonosulphuric acid hydrogen salt (Co/PMS) system degradation of dye
Alkali blue, result shows, is under conditions of 0.13mM, PMS concentration is 0.4mM in Co ion concentration, and in 2min, alkali blue goes
Except rate is up to 100%.But there is cobalt ion overflow problem in this homogeneous system, and cobalt ion toxicity is very strong, can cause secondary pollution.
In known technology, " preparation method and the electricity class Fenton thereof of a kind of support type FeOOH catalyst give up Chinese patent CN 102218319
Water treatment system " disclose a kind of support type heterogeneous electricity preparation method of fenton catalyst FeOOH and catalytic effect, result
Finding, under the conditions of extra electric field, support type FeOOH catalyst constitutes out-phase electricity class Fenton oxidation system with hydrogen peroxide,
3.0gL-1Catalyst, 1.8gL-1Hydrogen peroxide, under the conditions of pH=6.8, in 1h, the amaranth azo dye of 200mg/L goes
Except rate is up to 100%.Chinese patent CN 102125848 " preparation of magnetic heterogeneous light Fenton and the side of degradable organic pollutant thereof
Method " disclose the preparation method of a kind of heterogeneous smooth fenton catalyst NiFe2O4, this catalyst has the catalysis activity of excellence,
Under 300W ultra violet lamp, catalyst system and catalyzing can remove the malachite green oxalate of more than 98%.Although above-mentioned catalyst system and catalyzing can efficiently drop
Solve dyeing waste water, but used catalyst all contains metal ion, the most inevitably exists a certain degree of
Metal loss problem, this greatly limits the actual application of catalyst system and catalyzing.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention provides a kind of utilization specifically can efficiently drop without metal catalyst system
Solve the method without metal catalyst system degraded dyeing waste water of dyeing waste water.
The technical solution adopted for the present invention to solve the technical problems is: a kind of without metal catalyst system degraded dyeing waste water
Method, dyeing waste water adds non-metal catalyst and oxidant, places and degrade, wherein non-metal catalyst is dense
Degree is 0.01-50mmol/L, and the concentration of oxidant is 0.01-100mmol/L, in this concentration range, and degradable dyeing waste water.
Further, described non-metal catalyst is surfactant or the inorganic matter of bromine ion-containing of bromine ion-containing.
Further, described non-metal catalyst is eight alkyl trimethyl ammonium bromides, Dodecyl trimethyl ammonium chloride
DTAB, Tetradecyl Trimethyl Ammonium Bromide TTAB, cetyl trimethylammonium bromide CTAB, Cetyltrimethylammonium bromide
One in OTAB or dodecyl triphenylphosphinebromide, in combination of two or more.
Further, described non-metal catalyst is cetyl trimethylammonium bromide CTAB or octadecyl trimethyl bromine
Change one or both combinations in ammonium OTAB.From the point of view of the effect of the degradation of dye waste water of the present invention, alkyl chain is the longest, degraded printing and dyeing
The effect of waste water is the best, and speed is the fastest.
Further, described non-metal catalyst is sodium bromide NaBr or ammonium bromide NH4Br.
Further, described oxidant is oxydol H2O2, one in persulfate PS or permonosulphuric acid hydrogen salt PMS, two
Plant or multiple combination.
Further, described oxidant is permonosulphuric acid hydrogen salt PMS.
Further, the concentration of described non-metal catalyst is 0.1-10mmol/L.Ensure that catalyst is in this concentration range
In, can efficient degradation dyeing waste water.
Further, the concentration of described oxidant is 0.1-5mmol/L.Ensure oxidant concentration in this range, can be high
Effect degraded dyeing waste water.
There is no particular restriction to the pH of the dyeing waste water of degraded for the method for the present invention, it is adaptable to the fall of wide scope dyeing waste water
Solve.
The invention has the beneficial effects as follows: produced spike (catalyst by non-metal catalyst active oxidation agent at normal temperatures
Activation PMS produces hydroxyl radical free radical OH, and hydroxyl radical free radical has higher oxidation-reduction potential 1.8-2.7V) can be useless to printing and dyeing
Water carries out efficient degradation, not only overcomes the method secondary pollution of traditional F enton, low, the pH narrow application range of hydrogen peroxide utilization rate etc. no
Foot, and reaction condition is gentle, and removal effect is obvious, and without metallic pollution, little to environmental hazard, catalyst amount is few, operation letter
Single, low cost.
Accompanying drawing explanation
Fig. 1 is the design sketch of Cetyltrimethylammonium bromide (OTAB) activation PMS degradation of dye acid orange (AO7).
Fig. 2 is the design sketch of cetyl trimethylammonium bromide (CTAB) activation PMS degraded different dyes.
Detailed description of the invention
In order to make those skilled in the art be better understood from the present invention program, below in conjunction with in the embodiment of the present invention
Accompanying drawing, carries out clear, complete description to the technical scheme in inventive embodiments, it is clear that described embodiment is only this
A part of embodiment of invention rather than whole embodiments.Based on the embodiment in the present invention, those of ordinary skill in the art
The every other embodiment obtained under not making creative work premise, all should belong to the scope of protection of the invention.
Embodiment one
Selection non-metal catalyst is Cetyltrimethylammonium bromide (OTAB), and oxidant is permonosulphuric acid hydrogen salt
(PMS).Reaction is carried out, by 0.92mM Cetyltrimethylammonium bromide (OTAB) and 0.25mM mistake in the reaction vessel of 40ml
One disulfate (PMS) is successively added to pH=7, concentration is in the acid orange (AO7) of 100 μMs, at normal temperatures after reaction 2min,
The clearance of dyestuff AO7 reaches more than 98%, and design sketch is as shown in Figure 1.
Embodiment two
Selection non-metal catalyst is cetyl trimethylammonium bromide (CTAB), and oxidant is permonosulphuric acid hydrogen salt
(PMS).Reaction is carried out, by 0.92mM cetyl trimethylammonium bromide (CTAB) and 0.25mM mistake in the reaction vessel of 40ml
One disulfate (PMS) is successively added to pH=7, concentration is in the acid orange (AO7) of 100 μMs, at normal temperatures after reaction 2min
The clearance of dyestuff AO7 reaches 81.2%；At normal temperatures after reaction 5min, the clearance of dyestuff AO7 is up to more than 99%, effect
Figure is as shown in Figure 2.
Embodiment three
Selection non-metal catalyst is Tetradecyl Trimethyl Ammonium Bromide (TTAB), and oxidant is permonosulphuric acid hydrogen salt
(PMS).Reaction is carried out, by 0.92mM Tetradecyl Trimethyl Ammonium Bromide (TTAB) and 0.25mM mistake in the reaction vessel of 40ml
One disulfate (PMS) is successively added to pH=7, concentration is in the acid orange (AO7) of 100 μMs, reacts 40min at normal temperatures
After, the clearance of dyestuff AO7 reaches 95%.
Embodiment four
Selection non-metal catalyst is Dodecyl trimethyl ammonium chloride (DTAB), and oxidant is permonosulphuric acid hydrogen salt
(PMS).Reaction is carried out, by 0.92mM Dodecyl trimethyl ammonium chloride (DTAB) and 0.25mM mistake in the reaction vessel of 40ml
One disulfate (PMS) is successively added to pH=7, concentration is in the acid orange (AO7) of 100 μMs, reacts 70min at normal temperatures
After, the clearance of dyestuff AO7 reaches 95%.
Embodiment five
Selecting non-metal catalyst is eight alkyl trimethyl ammonium bromides, and oxidant is permonosulphuric acid hydrogen salt (PMS).React
The reaction vessel of 40ml is carried out, by 0.92mM eight alkyl trimethyl ammonium bromide and 0.25mM permonosulphuric acid hydrogen salt (PMS) successively
Be added to pH=7, concentration is in the acid orange (AO7) of 100 μMs, and at normal temperatures after reaction 70min, the clearance of dyestuff AO7 reaches
To 88.8%.
Embodiment six
Selection non-metal catalyst is cetyl trimethylammonium bromide (CTAB), and oxidant is permonosulphuric acid hydrogen salt
(PMS).Reaction is carried out, by 0.92mM cetyl trimethylammonium bromide (CTAB) and 0.25mM mistake in the reaction vessel of 40ml
One disulfate (PMS) is successively added to pH=7, concentration is in the Viride Nitens 1 (BG1) of 50 μMs, at normal temperatures after reaction 2min,
The clearance of dyestuff BG1 reaches 100%, and design sketch is as shown in Figure 2.
Embodiment seven
Selection non-metal catalyst is cetyl trimethylammonium bromide (CTAB), and oxidant is permonosulphuric acid hydrogen salt
(PMS).Reaction is carried out, by 0.92mM cetyl trimethylammonium bromide (CTAB) and 0.25mM mistake in the reaction vessel of 40ml
One disulfate (PMS) is successively added to pH=5, concentration is in the reactive brilliant red 3BF of 50 μMs, at normal temperatures after reaction 15min,
The clearance of dyestuff 3BF reaches 93%, and design sketch is as shown in Figure 2.
Embodiment eight
Selection non-metal catalyst is Cetyltrimethylammonium bromide (OTAB), and oxidant is permonosulphuric acid hydrogen salt
(PMS).Reaction is carried out, by 0.92mM Cetyltrimethylammonium bromide (OTAB) and 0.25mM mistake in the reaction vessel of 40ml
One disulfate (PMS) is successively added to pH=3, concentration is in the reactive brilliant red x-3b of 50 μMs, reacts 25min at normal temperatures
After, the clearance of dyestuff X-3B reaches more than 94%.
Embodiment nine
Selection non-metal catalyst is cetyl trimethylammonium bromide (CTAB), and oxidant is permonosulphuric acid hydrogen salt
(PMS).Reaction is carried out, by 0.92mM cetyl trimethylammonium bromide (CTAB) and 0.5mM mono-in the reaction vessel of 40ml
Disulfate (PMS) is successively added to pH=10, concentration is in the methyl blue (MB) of 50 μMs, at normal temperatures after reaction 25min, and dye
The clearance of material 3BF reaches 95%, and design sketch is as shown in Figure 2.
Embodiment ten
Selection non-metal catalyst is Cetyltrimethylammonium bromide (OTAB), and oxidant is permonosulphuric acid hydrogen salt
(PMS).Reaction is carried out, by 0.92mM Cetyltrimethylammonium bromide (OTAB) and 0.25mM mistake in the reaction vessel of 40ml
One disulfate (PMS) is successively added to pH=11, concentration is in the azophloxine of 50 μMs, reacts 8min at normal temperatures
After, the clearance of dyestuff azophloxine reaches 100%.
Above-mentioned detailed description of the invention is used for illustrating the present invention rather than limiting the invention, the present invention's
In spirit and scope of the claims, any modifications and changes that the present invention is made, both fall within the protection model of the present invention
Enclose.
Claims (9)
1. the method without metal catalyst system degraded dyeing waste water, it is characterised in that: add without metal in dyeing waste water
Catalyst and oxidant, place and degrade, and wherein the concentration of non-metal catalyst is 0.01-50mmol/L, oxidant dense
Degree is 0.01-100mmol/L, in this concentration range, degradable dyeing waste water.
Method without metal catalyst system degraded dyeing waste water the most according to claim 1, it is characterised in that: described without gold
Metal catalyst is surfactant or the inorganic matter of bromine ion-containing of bromine ion-containing.
Method without metal catalyst system degraded dyeing waste water the most according to claim 1, it is characterised in that: described without gold
Metal catalyst is eight alkyl trimethyl ammonium bromides, Dodecyl trimethyl ammonium chloride DTAB, Tetradecyl Trimethyl Ammonium Bromide
TTAB, cetyl trimethylammonium bromide CTAB, Cetyltrimethylammonium bromide OTAB or dodecyl triphenylphosphinebromide
In one, in combination of two or more.
Method without metal catalyst system degraded dyeing waste water the most according to claim 1, it is characterised in that: described without gold
Metal catalyst is cetyl trimethylammonium bromide CTAB or one or both combinations in Cetyltrimethylammonium bromide OTAB.
Method without metal catalyst system degraded dyeing waste water the most according to claim 1, it is characterised in that: described without gold
Metal catalyst is sodium bromide NaBr or ammonium bromide NH4Br。
Method without metal catalyst system degraded dyeing waste water the most according to claim 1, it is characterised in that: described oxidation
Agent is oxydol H2O2, the one in persulfate PS or permonosulphuric acid hydrogen salt PMS, in combination of two or more.
Method without metal catalyst system degraded dyeing waste water the most according to claim 1, it is characterised in that: described oxidation
Agent is permonosulphuric acid hydrogen salt PMS.
Method without metal catalyst system degraded dyeing waste water the most according to claim 1, it is characterised in that: described without gold
The concentration of metal catalyst is 0.1-10mmol/L.
Method without metal catalyst system degraded dyeing waste water the most according to claim 1, it is characterised in that: described oxidation
The concentration of agent is 0.1-5mmol/L.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107670691A (en) * | 2017-09-21 | 2018-02-09 | 广州大学 | One kind is without heterogeneous class Fenton type catalyst of metal and preparation method and application |
| CN109912002A (en) * | 2019-01-23 | 2019-06-21 | 浙江理工大学 | A kind of method of organic pollutant in processing waste water from dyestuff |
| CN110124671A (en) * | 2019-04-16 | 2019-08-16 | 中山大学 | A kind of Cu1-XCoXFe2O4Class fenton catalyst and its preparation method and application |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104743633A (en) * | 2015-04-16 | 2015-07-01 | 安徽工业大学 | Method for degrading organic waste water by photo-assisted activation of potassium hydrogen persulfate through bismuth ferrite |
| CN104785266A (en) * | 2015-03-23 | 2015-07-22 | 上海电力学院 | Preparation method of nanometer cobalt oxide/graphene composite material |
-
2016
- 2016-08-08 CN CN201610641500.2A patent/CN106186273B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104785266A (en) * | 2015-03-23 | 2015-07-22 | 上海电力学院 | Preparation method of nanometer cobalt oxide/graphene composite material |
| CN104743633A (en) * | 2015-04-16 | 2015-07-01 | 安徽工业大学 | Method for degrading organic waste water by photo-assisted activation of potassium hydrogen persulfate through bismuth ferrite |
Non-Patent Citations (1)
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| 肖华花: ""磺胺二甲嘧啶在水环境中的光化学行为及光催化降解研究"", 《中国博士学位论文全文数据库 工程科技I辑》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107670691A (en) * | 2017-09-21 | 2018-02-09 | 广州大学 | One kind is without heterogeneous class Fenton type catalyst of metal and preparation method and application |
| CN107670691B (en) * | 2017-09-21 | 2020-04-14 | 广州大学 | Metal-free heterogeneous Fenton-like catalyst and preparation method and application thereof |
| CN109912002A (en) * | 2019-01-23 | 2019-06-21 | 浙江理工大学 | A kind of method of organic pollutant in processing waste water from dyestuff |
| CN110124671A (en) * | 2019-04-16 | 2019-08-16 | 中山大学 | A kind of Cu1-XCoXFe2O4Class fenton catalyst and its preparation method and application |
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