CN103979631B - A kind of absorption-catalytic oxidation degradation method of phenol in wastewater - Google Patents
A kind of absorption-catalytic oxidation degradation method of phenol in wastewater Download PDFInfo
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- CN103979631B CN103979631B CN201410228423.9A CN201410228423A CN103979631B CN 103979631 B CN103979631 B CN 103979631B CN 201410228423 A CN201410228423 A CN 201410228423A CN 103979631 B CN103979631 B CN 103979631B
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Abstract
A kind of absorption-catalytic oxidation degradation method of phenol in wastewater, belong to water-treatment technology field, fill in adsorption tower with the activated carbon fiber of load Z 250 for sorbent material, after adsorption treatment is carried out to the waste water containing phenol, added in adsorption tower by aqueous hydrogen peroxide solution, and blast air simultaneously, mixed system carried out oxide treatment after 1 ~ 3 hour, sorbent material is regenerated, then input is containing the waste water circulation adsorption treatment of phenol.The present invention solves degradation problem, the catalytic wet hydrogen peroxide oxidation technology problem that energy consumption is higher when processing a large amount of phenolic wastewater of phenol after the desorption and regeneration problem after carbon fiber adsorption and catalytic combustion phenol, desorption.The present invention has that technique is simple, processing ease, do not have the advantages such as secondary pollution to environment.
Description
Technical field
The invention belongs to water-treatment technology field, be specifically related to absorption and the catalytic oxidation treatment technology of phenolic wastewater.
Background technology
Phenolic wastewater extensively derives from the industries such as petrochemical complex, synthon, medicine, is that a class toxicity is high and be difficult to biodegradable organic waste water, and traditional biochemical process exists treatment time long, the shortcoming such as processing efficiency is low, is difficult to meet the demand that enterprise produces.In the treatment process of phenolic wastewater, the existing a large amount of report of the treatment processs such as absorption, heterogeneous catalytic oxidation.Absorption method is the porous character absorption Pollutants in Wastewater utilizing sorbent material, and as a kind of traditional wastewater processing technology, it can remove multiple pollutant in waste water effectively, and after process, effluent quality is good and more stable.Sorbent material generally has larger specific surface area and stronger adsorptive power, and common sorbent material has gac, activated carbon fiber, resin, molecular sieve etc.For the absorption of phenol in wastewater, activated carbon fiber is a kind of sorbent material of excellent property, has treatment condition gentleness, and the advantages such as adsorption rate is fast, loading capacity is large, activated carbon fiber can be reused after desorption and regeneration.Application number is adopt the method for current flow heats to regenerate activated carbon fiber in the technology of CN02133116.2, Xu Zhida etc. (look forward to by activated carbon fiber Refinery Wastewater, Treatment of Industrial Water 1998,18 (2)) 200 DEG C ~ 500 DEG C superheated vapours are adopted to carry out desorption and regeneration to activated carbon fiber, there is the higher shortcoming of energy consumption in aforesaid method, and solvent desorbing method can introduce new chemical substance, therefore the regeneration of activated carbon fiber is the subject matter of its application of puzzlement.In addition, the organic pollutant after desorption still needs process.
Adopt the existing a large amount of report of the research of the heterogeneous catalytic oxidation method Phenol-Containing Wastewater Treatment such as photochemical catalysis, O3 catalytic oxidation, catalytic wet air oxidation, catalytic wet hydrogen peroxide oxidation, wherein catalytic wet hydrogen peroxide oxidation method adopts hydrogen peroxide to be oxygenant, there is the features such as equipment is simple, operational condition is gentle, non-secondary pollution, but lot of documents reports that the optimum activity temperature of catalyzer in this method is many more than 50 DEG C, if whole waste water of factory are all heated to more than 50 DEG C reprocessing, energy consumption is also the subject matter affecting its application.As can be seen here, single treatment process is difficult to the effective degraded realizing phenol in wastewater, needs the phenol be coupled in the advantage process waste water of multiple method.Patent (application number 200710015182.X) adopts phenolic compound in active carbon fiber-ozone Synergistic degradation water, obtains good phenol clearance, but does not mention the COD clearance of phenolic wastewater in patent.Application number is disclose in CN201210142480.6 a kind ofly to mix cerium nano titanium oxide/activated carbon fiber composite photo-catalyst and preparation method thereof for purifying air, improve the photocatalytic activity of nano titanium oxide, but light-catalysed efficiency is also not high in the treatment of waste water.
Summary of the invention
In order to solve the desorption and regeneration problem after carbon fiber adsorption and catalytic combustion phenol, the object of the invention is the method proposing phenol in a kind of absorption-catalytic oxidation technologies degrading waste water.
Technical solution of the present invention is: fill in adsorption tower with the activated carbon fiber of load Z 250 for sorbent material, after adsorption treatment is carried out to the waste water containing phenol, aqueous hydrogen peroxide solution is added in adsorption tower, and blast air simultaneously, mixed system carried out oxide treatment after 1 ~ 3 hour, sorbent material is regenerated, then input is containing the waste water circulation adsorption treatment of phenol.
Principle of work of the present invention:
(1) at the upper load Z 250 (Fe of viscose-based active carbon fiber (ACF)
3o
4), the activated carbon fiber (Fe of Z 250 by load
3o
4/ ACF) layering fills in adsorption tower, for adsorbing the phenol in waste water.This waste water is that early stage is through pretreated waste water such as sedimentations.
(2) after Adsorption of Phenol is saturated, add the proper amount of hydrogen peroxide aqueous solution, and blast air simultaneously, utilize the Fe of load in activated carbon fiber
3o
4for catalyzer, hydrogen peroxide and air are oxygenant, and the result of oxidizing reaction is: be carbonic acid gas, water by the phenol degrading be adsorbed in activated carbon fiber, and activated carbon fiber is regenerated.In operation, air also serves the effect that bubbling stirs.
(3) in the present invention, with the Fe of load in activated carbon fiber
3o
4during for catalyzer, hydrogen peroxide and air have synergistic oxidation effect, with hydrogen peroxide be separately oxygenant or be separately oxygenant with air time phenol degrading effect all undesirable, hydrogen peroxide and air add the rate of oxidation substantially increasing phenol simultaneously.
The present invention is first adsorbed the phenol in industrial pretreated waste water by the sorbent material of metal active constituent modification, by phenol rich on sorbent material, carry out catalyzing oxidizing degrading with the metal active constituent on sorbent material for catalyzer adds oxygenant Pyrogentisinic Acid again, desorbing agent is regenerated.Owing to degrading after phenol rich again, not only play the advantage that catalytic wet hydrogen peroxide oxidation is effective, also do not needed the process of all waste water heating and oxidation.Therefore, the present invention solves the desorption and regeneration problem after carbon fiber adsorption and catalytic combustion phenol, solves the degradation problem of phenol after desorption, also solves the catalytic wet hydrogen peroxide oxidation technology problem that energy consumption is higher when processing a large amount of phenolic wastewater.The present invention has that technique is simple, processing ease, do not have the advantages such as secondary pollution to environment.
In addition, the empty tower gas velocity scope that the present invention blasts air is 0.02 ~ 0.06m/s, ensures that air through adsorbent bed, can ensure again the stable of bed.So-called empty tower gas velocity refers to the cross-sectional area of flow divided by adsorption tower of air.
H in the aqueous hydrogen peroxide solution that the present invention adds
2o
2be 14 ~ 28: 1 with the mol ratio of the phenol that sorbent material adsorbs, ensure the hydrogen peroxide use needed for oxidation of phenol in theory.
During oxide treatment, the temperature of mixed system is 30 DEG C ~ 70 DEG C, preferably 50 DEG C ~ 60 DEG C, Fe in this temperature range
3o
4better catalytic activity be conducive to the oxidation of phenol.
Accompanying drawing explanation
Fig. 1 is Fe
3o
4scanning electron microscopic picture.
Fig. 2 is the scanning electron microscopic picture of ACF.
Fig. 3 is Fe
3o
4the scanning electron microscopic picture of/ACF.
Fig. 4 is the structural representation of absorption-catalyzing oxidizing degrading device.
Fig. 5 is the liquid chromatogram of waste water before absorption.
Fig. 6 is the liquid chromatogram of waste water after absorption.
Embodiment
One, the activated carbon fiber (Fe of load Z 250
3o
4/ ACF) preparation:
1. activated carbon fiber (ACF): (specific surface area is greater than 1100m to adopt the viscose-based active carbon fiber felt that market is sold
2/ g).Its scanning electron microscopic picture is shown in Fig. 1.
2. Fe
3o
4preparation:
Get 6.0 g FeCl respectively
36H
2o, 3.0 g polyvinylpyrrolidones (PVP) and 6.0 g anhydrous Na Ac, then add 120 mL ethylene glycol, at room temperature stir 2.0 h, guarantee that all solids material is all dissolved in ethylene glycol.Above-mentioned mixed solution is transferred in the stainless steel cauldron of inner liner polytetrafluoroethylene, by said mixture at 200 DEG C of reaction 6.0h.Reaction terminate after, naturally cool to room temperature, with distilled water wash repeatedly, vacuum 60 DEG C of drying 24 h.
The Fe of preparation
3o
4scanning electron microscopic picture see Fig. 2.
3. Fe
3o
4the preparation of/ACF:
Other condition is with 2, and difference is after stainless steel cauldron mixed solution being transferred to inner liner polytetrafluoroethylene, adds 3.0gACF, 200 DEG C of reactions 6 hours in mixed solution.After reaction terminates, naturally cool to room temperature, the activated carbon fiber in reactor taken out, with distilled water wash repeatedly, vacuum 60 DEG C of drying 24 h, obtained Fe
3o
4/ ACF, wherein Fe
3o
4content is 3.2%(w%).
Other condition is identical, adds the ACF of Different Weight in mixed solution, can obtain Fe respectively
3o
4activated carbon fiber (the Fe of the load Z 250 of content (i.e. charge capacity)
3o
4/ ACF).
The Fe obtained
3o
4the scanning electron microscopic picture of/ACF is shown in Fig. 3.
Two, containing the absorption-catalytic oxidation cycle method of the waste water of phenol:
As shown in Figure 4, absorption-catalytic oxidizing equipment is assembled into.
Operation instructions:
(1) by Fe
3o
4/ ACF segmentation fills in adsorption tower;
(2), during absorption, shut-off valve 2,3,4,5,6, opens valve 1,7;
(3) start waste water pump, carry out adsorption operations;
(4) after absorption terminates, shut-off valve 1,7, opens valve 2,3,4,5, input aqueous hydrogen peroxide solution, after conveying terminates, and shut-off valve 3,4,5;
(5) open valve 6, after process certain hour, shut-off valve 6, opens valve 7.
During process, waste water has liquid spraying device in tower top ingress, and there is distribution device in gas-fluid air ingress at the bottom of tower, has heating jacket controlled oxidization temperature outside adsorption column.
Concrete operations example: get 3.0g Fe
3o
4/ ACF, wherein Fe
3o
4content is 3.2%(w%), dividing three sections to fill in internal diameter is in the glass device of 2cm.Certain industrial phenolic wastewater phenol concentration is 102.0mg/L, COD is 786.0mg/L, and waste water sends into adsorbing-oxidising device by peristaltic pump, wastewater flow 30mL/min.After conveying 1.8L waste water, reach adsorption equilibrium, water outlet COD is 138.0mg/L, and in water outlet, phenol content is 3.8mg/L, calculates to obtain the equilibrium adsorption capacity q of ACF thus
e=58.9 (mg/g).Adsorption unit is discharged in time by leakage fluid dram by the liquid after adsorption treatment.
The liquid chromatography of adsorbing forward and backward waste water is shown in shown in Fig. 5,6, comparison diagram 5,6 visible: through Fe
3o
4after/ACF absorption, in liquid, phenol content reduces greatly, and visible phenol in wastewater is adsorbed on Fe
3o
4on/ACF.
After absorption terminates, by fluid inlet and leakage fluid dram sealing, in glass device, then input the H of 40mL
2o
2the aqueous solution [H
2o
2/ phenol (mol ratio)=28:1], the empty tower gas velocity controlling air is 0.03m/s, and the temperature controlling mixed system is 50 DEG C and carries out oxide treatment, and the treatment time is about 3.0h.After testing, the simultaneous oxidation phenol desorption rate through hydrogen peroxide and air reaches 100.0%, phenol do not detected after oxidation in water outlet.
The sorbent material obtaining after oxidation the regenerating adsorption treatment for the waste water containing phenol capable of circulation.
Contrast scheme: after absorption terminates, other condition is constant, as added hydrogen peroxide separately in glass device, then after oxidation, phenol desorption rate is 27.0%; As separately to input air in glass device, then after oxidation, phenol desorption rate is 15.3%.Hydrogen peroxide and air can be adopted to be oxidized, and the raising of Pyrogentisinic Acid's desorption rate has significant effect simultaneously.
The measuring method of phenol desorption rate: be adsorbed onto Fe before oxide treatment
3o
4phenol quality on/ACF (is designated as m
1); Fe after oxide treatment will be carried out
3o
4/ ACF takes out, and with 10% quantitative NaOH solution wash-out, the quality measuring phenol in elutriant (is designated as m
2).
Desorption rate=.
By changing H
2o
2with the mol ratio of adsorbing phenol on sorbent material, air by the empty tower gas velocity of adsorption column, be oxidized time mixed system temperature, oxidization time, record the content of phenol in water outlet after the desorption rate of phenol and oxidation respectively, the results are shown in following table.
Claims (4)
1. absorption-the catalytic oxidation degradation method of a phenol in wastewater, it is characterized in that filling in adsorption tower with the activated carbon fiber of load Z 250 for sorbent material, after adsorption treatment is carried out to the waste water containing phenol, aqueous hydrogen peroxide solution is added in adsorption tower, and blast air simultaneously, mixed system carried out oxide treatment after 1 ~ 3 hour, and sorbent material is regenerated, and the sorbent circulation of regeneration was used for the adsorption treatment of the waste water containing phenol; During oxide treatment, the temperature of mixed system is 30 ~ 70 DEG C.
2. degradation method according to claim 1, the empty tower gas velocity that it is characterized in that blasting air is 0.02 ~ 0.06m/s.
3. degradation method according to claim 1, is characterized in that the H in the aqueous hydrogen peroxide solution added
2o
2be 14 ~ 28: 1 with the mol ratio of the phenol that sorbent material adsorbs.
4. degradation method according to claim 1, when it is characterized in that oxide treatment, the temperature of mixed system is 50 ~ 60 DEG C.
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| CN105347561A (en) * | 2015-11-26 | 2016-02-24 | 常州大学 | Integrated device for purifying phenol-containing geothermal water |
| CN105903460A (en) * | 2016-05-09 | 2016-08-31 | 东华大学 | Powdered activated carbon ectopic self generation and regeneration method for hard-degradation organic wastewater treatment |
| CN105905972A (en) * | 2016-05-09 | 2016-08-31 | 东华大学 | High-efficiency reducing treatment method and device for degradation-resistant organic substances in industrial wastewater |
| CN105800723A (en) * | 2016-05-09 | 2016-07-27 | 东华大学 | Hardly-degradable organic wastewater treatment method and device |
| CN106492785A (en) * | 2016-08-31 | 2017-03-15 | 浙江奇彩环境科技股份有限公司 | A kind of catalyst and its method of wastewater treatment for dye wastewater treatment |
| CN107398277A (en) * | 2016-10-24 | 2017-11-28 | 西南石油大学 | Application of the cupro-nickel molten iron talcs catalyst in wastewater containing phenol of degrading |
| CN107570213A (en) * | 2017-10-12 | 2018-01-12 | 湖北工业大学 | A kind of preparation method of ferroso-ferric oxide paper substrate heterogeneous catalysis material |
| CN108218146A (en) * | 2018-03-19 | 2018-06-29 | 苏州依斯倍环保装备科技有限公司 | A kind for the treatment of process and processing system of rubber chemicals class high concentrated organic wastewater |
| CN111320318A (en) * | 2020-03-19 | 2020-06-23 | 烟台金正环保科技有限公司 | Zero-emission advanced treatment process for RO (reverse osmosis) concentrated water |
| CN114853199B (en) * | 2021-02-03 | 2023-10-13 | 中国石油化工股份有限公司 | Treatment system and method for benzopyrene-containing wastewater |
| CN113209970B (en) * | 2021-05-13 | 2023-05-05 | 哈尔滨工业大学 | Preparation method and application of carbon-based catalyst prepared from excess sludge |
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| JP2013111553A (en) * | 2011-11-30 | 2013-06-10 | Toyobo Co Ltd | Water treatment system |
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| CN1792441A (en) * | 2005-12-21 | 2006-06-28 | 中国科学院山西煤炭化学研究所 | Adsorption-catalyst for treating phenol containing waste-water, prepn. method and application thereof |
| CN1919452A (en) * | 2006-09-13 | 2007-02-28 | 北京交通大学 | Ferric oxide catalyst carried by active carbon and method for preparation thereof |
| JP2013111553A (en) * | 2011-11-30 | 2013-06-10 | Toyobo Co Ltd | Water treatment system |
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