CN101560027A - Method for rapid degradation of triphenylmethane dye waste water - Google Patents
Method for rapid degradation of triphenylmethane dye waste water Download PDFInfo
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- CN101560027A CN101560027A CNA2009100294428A CN200910029442A CN101560027A CN 101560027 A CN101560027 A CN 101560027A CN A2009100294428 A CNA2009100294428 A CN A2009100294428A CN 200910029442 A CN200910029442 A CN 200910029442A CN 101560027 A CN101560027 A CN 101560027A
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- 238000000034 method Methods 0.000 title claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 28
- 239000010919 dye waste Substances 0.000 title claims abstract description 20
- AAAQKTZKLRYKHR-UHFFFAOYSA-N triphenylmethane Chemical compound C1=CC=CC=C1C(C=1C=CC=CC=1)C1=CC=CC=C1 AAAQKTZKLRYKHR-UHFFFAOYSA-N 0.000 title claims abstract description 19
- 230000015556 catabolic process Effects 0.000 title claims abstract description 18
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000002351 wastewater Substances 0.000 claims abstract description 22
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000203 mixture Substances 0.000 claims abstract description 6
- 239000012535 impurity Substances 0.000 claims abstract description 3
- 230000000694 effects Effects 0.000 claims description 15
- 101710134784 Agnoprotein Proteins 0.000 claims description 10
- 238000004065 wastewater treatment Methods 0.000 claims description 5
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 abstract description 8
- 229910001961 silver nitrate Inorganic materials 0.000 abstract description 4
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 abstract description 4
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract description 2
- 238000001556 precipitation Methods 0.000 abstract 1
- 239000000975 dye Substances 0.000 description 37
- 239000000243 solution Substances 0.000 description 16
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 7
- 230000003647 oxidation Effects 0.000 description 7
- 238000007254 oxidation reaction Methods 0.000 description 7
- 238000002360 preparation method Methods 0.000 description 7
- 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 description 7
- 229940043267 rhodamine b Drugs 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 5
- ZXJXZNDDNMQXFV-UHFFFAOYSA-M crystal violet Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1[C+](C=1C=CC(=CC=1)N(C)C)C1=CC=C(N(C)C)C=C1 ZXJXZNDDNMQXFV-UHFFFAOYSA-M 0.000 description 5
- 230000035484 reaction time Effects 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 238000004043 dyeing Methods 0.000 description 4
- 229940107698 malachite green Drugs 0.000 description 4
- FDZZZRQASAIRJF-UHFFFAOYSA-M malachite green Chemical compound [Cl-].C1=CC(N(C)C)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](C)C)C=C1 FDZZZRQASAIRJF-UHFFFAOYSA-M 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000009279 wet oxidation reaction Methods 0.000 description 4
- 238000004847 absorption spectroscopy Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- MECHNRXZTMCUDQ-RKHKHRCZSA-N vitamin D2 Chemical compound C1(/[C@@H]2CC[C@@H]([C@]2(CCC1)C)[C@H](C)/C=C/[C@H](C)C(C)C)=C\C=C1\C[C@@H](O)CCC1=C MECHNRXZTMCUDQ-RKHKHRCZSA-N 0.000 description 3
- 235000001892 vitamin D2 Nutrition 0.000 description 3
- 239000011653 vitamin D2 Substances 0.000 description 3
- 241000405217 Viola <butterfly> Species 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000004042 decolorization Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
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- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 238000009284 supercritical water oxidation Methods 0.000 description 2
- 208000028571 Occupational disease Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000002671 adjuvant Substances 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000001000 anthraquinone dye Substances 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000000593 degrading effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 239000002421 finishing Substances 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000010815 organic waste Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 201000007094 prostatitis Diseases 0.000 description 1
- 238000012797 qualification Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
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- Removal Of Specific Substances (AREA)
Abstract
The invention discloses a method for rapid degradation of triphenylmethane dye waste water. The method firstly removes impurities by a grill, stands for precipitation and regulates pH, wherein, the pH value of the triphenylmethane dye waste water is controlled to be about 7-10; the waste water is introduced into a simple reaction container, then a mixture consisting of sodium bismuthate and silver nitrate is added, the multi-phase uniform mixing reaction is kept under the action of stirring, the temperature of the dye waste water during the process is kept at room temperature, the pressure is normal pressure, and the waste water is discharged. The treatment method can high-efficiently degrade triphenylmethane dye which is typically difficult to biodegrade, the catalytic reaction can be realized without the use of any light source or other external energy, such as microwave and the like, and the treatment method has very low requirements on equipment, less energy consumption, low operation cost, convenient operation and no secondary pollution, thereby being the method which can realize the degradation at the room temperature.
Description
Technical field
The present invention relates to the treatment process of waste water from dyestuff, the treatment process of the triphenylmethane dye waste water of saying so more specifically.
Background technology
Along with the development of printing and dyeing with dyestuffs industries, factory effluent has become one of current main pollution source of water body.Dyestuff is as the important source of pollution of a kind of environment of a large amount of existence, and its world's annual production is about 80～900,000 tons.China's dyestuff annual production reaches 150,000 tons, occupies prostatitis, the world.There is 10%～15% dyestuff enter environment approximately with waste water in the production of dyestuff with in using.China's dyestuffs industries, textile printing and dyeing industry prosperity, waste water from dyestuff is even more serious to the pollution of environment.According to the data of environment communique in 1998, China's industrial wastewater treatment rate is about 87.4% at present, administers qualification rate and only handles 63% of total amount for existing device.And as many, the complex structure of dyestuff kind of environmental pollutant, the synthetic dyestuff that the whole world is used reach kind more than 30,000.Triphenylmethane dye is a kind of many benzene ring compounds as a kind of common dye discoloration, and the principal character of its structure is to be connected with three phenyl ring around central carbon atom, and one of them phenyl ring links to each other with two keys with carbon atom.Such dyestuff is the third-largest dyestuff of usage quantity after azoic dyestuff, anthraquinone dye, produces a large amount of waste water in its production, use.Wherein the middle degraded product of some dye well is in the news and has " three cause " effect (Wang Ziqi, Feng Yuting, the hazardness research of dye class chemical substance, [J] chemical industry labour protection: industrial hygiene and occupational illness fascicle-1998 year 1 phase).Even dye component concentration remaining in the waste water from dyestuff is very low, enters water body and also can cause the water body transmittance to reduce the destruction that causes water ecosystem.
The difficulty in treatment of triphenylmethane dye waste water is: (1) COD height, and biodegradability is poor; (2) colourity height, complicated component, decolouring difficulty are big.Along with the progress of the development of dyestuffs industries and back finishing technique, the organism of difficult for biological degradation such as New-type adjuvant, dyestuff, finishing composition is used in a large number at dyeing, causes that COD in the dyeing waste water increases, BOD/COD is lower.Usually physical method that adopts for the removal of dyestuff contaminant such as charcoal absorption, ultrafiltration, reverse osmosis, chemical flocculation, ion-exchange or the like.Yet these methods are not all degraded to dye molecule, and they are a kind of enrichment process to pollutent, therefore also can produce secondary pollution.The result also needs to expend the further reproducing adsorbent of substantial contribution and solid waste carries out subsequent disposal.In addition, in order to satisfy the painted requirement of the degree of depth, traditional bioremediation also is difficult to waste water from dyestuff to high density and decolours and degrade.
In more than ten years in the past, high-level oxidation technology has developed into the effective means of removing organic dye waste water, all obtained significant progress (Shao Bing such as wet oxidation, catalytic wet oxidation, supercritical water oxidation, photochemical catalytic oxidation, microwave-assisted photochemical catalysis and microwave induction catalytic etc., high-level oxidation technology is in Application of Sewage progress [J], economic and technical assistance information, 2008 26 phases).These methods all have characteristics and deficiency separately, and wet oxidation, catalytic wet oxidation, supercritical water oxidation technology all need be carried out under high temperature, high pressure, conversion unit is had relatively high expectations, and high temperature resistant, the high pressure of palpus, and corrosion-resistant.UV-light need be provided for photochemical catalytic oxidation and microwave-assisted photocatalysis technology and light utilization efficiency is low and the low problem of photo-quantum efficiency.The restriction that microwave induction catalytic is subjected to the place equipment is applied to the big difficulty of existence in the reality at present.In addition, these above-mentioned methods are all higher relatively to the demand of the energy, are not a kind of ideal degraded mode from energy-conservation angle.Therefore, research and development high-level oxidation technology low to energy demand, that reaction conditions is gentle comes that organic dye pollutant is of great practical significance in the degradation of dye waste water.
Summary of the invention:
1. invent the technical problem that will solve:
Technology at existing processing triphenylmethane dye waste water is all higher relatively to the demand of the energy, conversion unit requires complicated, the invention provides a kind of method of rapid degradation of triphenylmethane dye waste water, use degradation of triphenylmethane dye waste water under sodium bismuthate and the Silver Nitrate acting in conjunction, under condition of stirring, add the method for two kinds of chemical reagent degradation of triphenylmethane dye waste water, make that the degradation method equipment used is simple, energy consumption is little, easy to operate, need not illumination and non-secondary pollution, can reach decolouring at short notice, degraded, remove the target of dyestuff.
2, technical scheme
The present invention proposes a kind of method of rapid degradation of triphenylmethane dye waste water, concrete technical scheme is as follows:
(A) grid removal of impurities, staticly settle and pH regulator, wherein the pH value of waste water will be controlled at about 7～10;
(B) waste water is introduced simple reaction vessel, adds the mixture that sodium bismuthate and Silver Nitrate are formed afterwards, keeps heterogeneous homogeneous hybrid reaction under the effect of stirring, and the temperature of waste water from dyestuff remains on room temperature in this process, and pressure is normal pressure, and waste water is discharged.
The above-mentioned step B residence time is about 5～15 minutes, and the time, long effect can not be significantly improved to be no less than 5 minutes for good.Only need during use these two kinds of compounds are pressed NaBiO
3: AgNO
3Be 1: the ratio of (0.5～4) adds in the pretreated waste water simultaneously.The total input amount of said mixture is 1g/L～5g/L, degrading waste water under intensively stirred situation.
Sodium bismuthate is yellow amorphous powder, and is water insoluble, and strong oxidizing property is arranged in acidic medium, can directly buy.Silver Nitrate is a kind of water white transparency rhomboidal crystal or white fine crystallization, is a kind of common chemical reagent equally.Black powder appears at once after two kinds of compounds drop in the water, this insolubles can be under the effect of stirring degradation of organic waste water.
3. beneficial effect:
Compared with the prior art, beneficial effect of the present invention is embodied in:
(1) the wastewater treatment mode of the present invention suitability that is used for dye wastewater treatment using is strong, can carry out under the normal temperature.The catalytic oxidant of being invented has very strong oxidation capacity, can the most of organic dye of oxidation.
(2) method of wastewater treatment of the present invention need not to adopt any external energy, only only needs waste liquid is stirred, and is not subjected to illumination effect.
(3) treatment process of invention energy efficient degradation organic dye, non-secondary pollution.
(4) oxygenant of being allocated among the present invention can repeatedly use continuously, need not regeneration, and is active high.In addition, the desired raw material preparation is simple, cheap.
(5) a whole set of system operating cost is very low, and equipment is simple, is that the methyl violet of 40mg/L is example with degraded 100mL concentration, and 5 minutes working times, the initial input of chemical agent is 0.014 yuan (this part can reuse repeatedly), 0.0017 yuan of power consumption.
Description of drawings
Fig. 1 is the percent of decolourization variation diagram of the inventive method degraded rhodamine B;
Fig. 2 is the uv-visible absorption spectroscopy figure of malachite green under the degraded system of the present invention;
Fig. 3 is the uv-visible absorption spectroscopy figure of methyl violet under the degraded system of the present invention;
Fig. 4 is the uv-visible absorption spectroscopy figure of Viola crystallina under the degraded system of the present invention;
Embodiment
Below further specify the present invention by specific examples.
Embodiment 1:
Preparation 20mg/L rhodamine B aqueous solution dye wastewater is measured the 100mL dye solution and is packed in the reaction flask.The mid-stirrer of bottle, stirred solution under the effect of agitator.Take by weighing 200mg NaBiO
3And 50mg AgNO
3Add into above-mentioned solution, under the effect of stirring, begin reaction.Measure rhodamine B concentration subsequently with the changing conditions in reaction times, experimental result shows, rhodamine B concentration reduces that TOC descends 54% after 99%, 15 minute in the 14min, specifically referring to Fig. 1.
Embodiment 2:
Preparation 20mg/L malachite green aqueous solution dye wastewater is measured the 50mL dye solution and is packed in the reaction flask.The mid-stirrer of bottle, stirred solution under the effect of agitator.Take by weighing 100mg NaBiO
3And 200mg AgNO
3Add into above-mentioned reaction solution.Mensuration malachite green concentration is with the changing conditions in reaction times after the reaction beginning, and experimental result shows that the malachite green percent of decolourization descends 21% above TOC after 95%, 15 minute in the 8min, specifically referring to Fig. 2.
Embodiment 3:
Preparation 40mg/L methyl violet aqueous solution dye wastewater is measured the 100mL dye solution and is packed in the reaction flask.The mid-stirrer of bottle, stirred solution under the effect of agitator.Take by weighing 300mg NaBiO
3And 100mg AgNO
3Add into above-mentioned solution, under the effect of stirring, begin reaction.Measure methyl violet concentration subsequently with the changing conditions in reaction times, experimental result shows, methyl violet concentration reduces that TOC descends 75% after 92%, 15 minute in the 4min, specifically referring to Fig. 3.
Embodiment 4:
Preparation 20mg/L Viola crystallina aqueous solution dye wastewater is measured the 50mL dye solution and is packed in the reaction flask.The mid-stirrer of bottle, stirred solution under the effect of agitator.Take by weighing 25mg NaBiO
3And 25mg AgNO
3Add into above-mentioned solution, under the effect of stirring, begin reaction.Measure Viola crystallina concentration subsequently with the changing conditions in reaction times, experimental result shows, the purple concentration of 3min post crystallization reduces that TOC descends 43% after 94%, 15 minute, specifically referring to Fig. 4.
Embodiment 5:
Preparation 20mg/L rhodamine B aqueous solution dye wastewater is measured the 100mL dye solution and is packed in the reaction flask.The mid-stirrer of bottle, stirred solution under the effect of agitator.Take by weighing 100mg NaBiO
3And 50mg AgNO
3Add into above-mentioned solution, under the effect of stirring, begin reaction.Centrifugation goes out catalyzer after rhodamine B almost is degraded entirely, adds use after the drying once more, keeps the system of secondary response in full accord with reaction system before again.This process has repeated 7 times, and the real reaction time is 114min, and the rhodamine B solution of the 7th preparation is decolouring fully still.
The present invention is not limited to above specific embodiment.
Claims (5)
1. the method for a rapid degradation of triphenylmethane dye waste water, its step is
(A), be adjusted to 7～10 with the pH value with the removal of impurities of triphenylmethane dye waste water grid with staticly settle;
(B) waste water is introduced reaction vessel, adds NaBiO
3And AgNO
3Mixture, under the effect of stirring, keep heterogeneous homogeneous hybrid reaction, temperature remains on room temperature, pressure is normal pressure, discharges after the wastewater treatment.
2. the method for rapid degradation of triphenylmethane dye waste water according to claim 1 is characterized in that the residence time is 5～15 minutes in the step (B).
3. the method for rapid degradation of triphenylmethane dye waste water according to claim 2 is characterized in that NaBiO in the step (B)
3And AgNO
3The mixture input amount be 1g/L～5g/L.
4. according to the method for each described rapid degradation of triphenylmethane dye waste water in the claim 1～3, it is characterized in that in the step (B) with weight ratio NaBiO
3: AgNO
3Be 1: the ratio of (0.5～4) adds in the waste water simultaneously.
5. the method for rapid degradation of triphenylmethane dye waste water according to claim 1 is characterized in that the recyclable NaBiO in reaction back
3And AgNO
3, continue to use.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2009100294428A CN101560027B (en) | 2009-04-10 | 2009-04-10 | Method for rapid degradation of triphenylmethane dye waste water |
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|---|---|---|---|
| CN2009100294428A CN101560027B (en) | 2009-04-10 | 2009-04-10 | Method for rapid degradation of triphenylmethane dye waste water |
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|---|---|
| CN101560027A true CN101560027A (en) | 2009-10-21 |
| CN101560027B CN101560027B (en) | 2011-07-20 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491450A (en) * | 2011-12-15 | 2012-06-13 | 南京大学 | Method for treating dye waste water by using ultraviolet-acetylacetone oxidation treatment process |
| CN101759269B (en) * | 2009-12-31 | 2013-01-02 | 南京大学 | Preparation method of Bi/Cu composite oxide and method for degrading triphenylmethane dye wastewater by Bi/Cu composite oxide |
| CN105417620A (en) * | 2015-12-18 | 2016-03-23 | 南京大学 | Method for degrading dye wastewater by using sunlight |
| CN108285412A (en) * | 2017-01-09 | 2018-07-17 | 中国地质大学（北京） | A kind of method of solid catalysis oxidation polycyclic aromatic hydrocarbon |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103626278B (en) * | 2013-05-28 | 2017-11-21 | 上海市环境科学研究院 | A kind of method of inexpensive fast deep degrading organic dye waste water |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1214864C (en) * | 2003-09-19 | 2005-08-17 | 南京大学 | Visible light responding photocatalyst of alkali metal and Ag-Bi oxide and its application |
-
2009
- 2009-04-10 CN CN2009100294428A patent/CN101560027B/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101759269B (en) * | 2009-12-31 | 2013-01-02 | 南京大学 | Preparation method of Bi/Cu composite oxide and method for degrading triphenylmethane dye wastewater by Bi/Cu composite oxide |
| CN102491450A (en) * | 2011-12-15 | 2012-06-13 | 南京大学 | Method for treating dye waste water by using ultraviolet-acetylacetone oxidation treatment process |
| CN105417620A (en) * | 2015-12-18 | 2016-03-23 | 南京大学 | Method for degrading dye wastewater by using sunlight |
| CN105417620B (en) * | 2015-12-18 | 2018-09-25 | 南京大学 | A method of utilizing sunlight degradation of dye waste water |
| CN108285412A (en) * | 2017-01-09 | 2018-07-17 | 中国地质大学（北京） | A kind of method of solid catalysis oxidation polycyclic aromatic hydrocarbon |
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