CN110092505A - A kind of method of Concave-convex clay rod processing wastewater containing phenol - Google Patents

A kind of method of Concave-convex clay rod processing wastewater containing phenol Download PDF

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Publication number
CN110092505A
CN110092505A CN201910443099.5A CN201910443099A CN110092505A CN 110092505 A CN110092505 A CN 110092505A CN 201910443099 A CN201910443099 A CN 201910443099A CN 110092505 A CN110092505 A CN 110092505A
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China
Prior art keywords
concave
clay rod
convex clay
wastewater containing
containing phenol
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Inventor
张法智
徐杰
雷晓东
孔祥贵
丁虹艺
运学海
杨晓彤
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Beijing University of Chemical Technology
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Beijing University of Chemical Technology
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/001Processes for the treatment of water whereby the filtration technique is of importance
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/722Oxidation by peroxides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • C02F2101/345Phenols
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/06Controlling or monitoring parameters in water treatment pH
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2209/00Controlling or monitoring parameters in water treatment
    • C02F2209/08Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/026Fenton's reagent

Abstract

The present invention provides a kind of methods of Concave-convex clay rod processing wastewater containing phenol.This method is first adjusted the pH value of wastewater containing phenol to 1-10 using acid or alkali, and Concave-convex clay rod is then added, continuously adds hydrogen peroxide, is stirred to react, filters, and is reused after obtained Concave-convex clay rod drying, filtrate is the waste water handled well.The efficient degradation of wastewater containing phenol can be realized using the high characteristic of ecosystem in Linze, Gansu, China Concave-convex clay rod iron-content using the method for Fenton reagent in the present invention in the unlimited system for being exposed to air.Fe in reaction process, in Concave-convex clay rod2+With Fe3+High activity OH is generated with hydrogen peroxide, OH and organic matter phenol, which react, generates CO2And H2O realizes degradation of phenol.Concave-convex clay rod used in entire reaction process needs not move through any processing.Handled wastewater containing phenol can reach national emission standard direct emission after dilution.

Description

A kind of method of Concave-convex clay rod processing wastewater containing phenol
Technical field:
The invention belongs to technical field of waste water processing, in particular to a kind of side of Concave-convex clay rod processing wastewater containing phenol Method.
Background technique:
The pollution of water environment, especially organic contamination have become a global environmental problem, organic contamination Severity, pollution property and the harm to biology and the mankind are all continually changing with society and industrial expansion.Closely Nian Lai, the pollution and its improvement of hardly degraded organic substance become a hot spot of various countries researcher concern.Organic contamination difficult to degrade Object is that one kind is more toxic, is difficult to be degraded by microorganisms or be degraded by microorganisms speed slowly and decomposes halfway organic matter, than Such as halogenated organic matters, surfactant, nitro compound, heterocyclic compound, phenolic compound, polycyclic aromatic hydrocarbon type organic, Toxic action can all much wherein be generated to the mankind and biology, it is difficult to degrade organic such as three-induced effect (carcinogenic, teratogenesis and mutagenesis) The harm of object constitutes human health and the ecosystem and seriously threatens.Therefore, the dirt of hardly degraded organic substance how is administered Dye is always the important subject of field of environment protection.
Phenol wastewater source is very extensive, and many enterprises are the peculiar pollution sources of phenol, such as oil plant, chemical plant, resin processing plant And coke-oven plant etc..Processing for phenol wastewater, it is biochemical treatment process that enterprise, which uses at most, at present, however many phenol wastewater Biological degradability it is poor, some also have bio-toxicity, so that endobacillary enzyme is gone bad and lose activity, eventually lead to biological treatment Effect it is poor.And the costs of investment such as other methods such as extraction, absorption method are high, enterprise is difficult to bear.Therefore, research has wide The phenolic wastewater treatment method of general application value is the urgent task put in face of environmental worker.Wen Cheng et al. [Environmental Protection of Chemical Industry (2018) 38,282-287] is at Ca (OH)2System In use O3Degradation of phenol waste water, I.Polaert et al. [Chemical Engineering Science (2002) 57,1585- 1590) phenolic waste water, Tao Wang et al. [Chemosphere (2016)] are handled in the way of activated carbon adsorption and oxidation 155,94-99] phenolic waste water, Laura G.Cordova Villegas et al. are handled using film electricity bioreactor (MEBR) [Curr Pollution Rep (2016) 2,157-167] utilizes electrochemical treatments phenolic waste water.
Fenton reagent (i.e. H2O2+Fe2+) pass through H2O2And Fe2+Effect generates OH, makes it have extremely strong energy of oxidation Power, the oxidation processes of the organic wastewater hard to work especially suitable for bio-refractory or general chemical oxidation, thus Fenton The application of reagent in the treatment of waste water acquires a special sense.
Attapulgite is as " thousand with soil ", due to good adsorptivity, rheological characteristic, carrier-mediated, catalytic, plastic Property, the performances such as salt-resistance, water imbibition, be widely used in inorganic chemical industry, building materials industry, agricultural, edible oil processing, medicine and other fields Etc., the reserves of the attapulgite of coming from L inze County have reached 9.02 hundred million tons, account for the 63% of whole world proven reserve, surely It ranks first in the world.And by measurement, ecosystem in Linze, Gansu, China attapulgite iron-content is very high, and that give us to be combined with attapulgite The inspiration of Fenton reagent processing phenol organic wastewater.
Summary of the invention:
It is of the present invention the object of the present invention is to provide a kind of method of simple economy efficient degradation wastewater containing phenol Biodegrading process is Fenton reagent method.This method uses Concave-convex clay rod, preferably the Concave-convex clay rod raw ore of ecosystem in Linze, Gansu, China Powder utilizes H2O2With the Fe in Concave-convex clay rod2+Reaction generates the phenol in OH Heterogeneous oxidation waste water.
The method of Concave-convex clay rod processing wastewater containing phenol of the present invention are as follows: use acid or alkali by wastewater containing phenol PH value adjust to 1-10, Concave-convex clay rod is then added, continuously adds hydrogen peroxide, is stirred to react 5min-40min, filter, It is reused after obtained Concave-convex clay rod drying, filtrate is the waste water handled well.
The acid is sulfuric acid.
The alkali is sodium hydroxide.
The pH value of the wastewater containing phenol is adjusted to 3.
The wastewater containing phenol 100mL, the additive amount of phenol concentration 10-500ppm, Concave-convex clay rod are 0.01g-3g, the additive amount of hydrogen peroxide are 0.05-3mL.
The concentration of the hydrogen peroxide is 25-35wt%.
The temperature being stirred to react is 10-40 DEG C.
The drying temperature is 50-70 DEG C.
The filtrate sodium hydroxide or sulphur acid for adjusting pH is 10, is utilized respectively ultraviolet spectra absorption apparatus and COD measurement Instrument detection.
The present invention utilizes the high spy of ecosystem in Linze, Gansu, China Concave-convex clay rod iron-content using the method for Fenton reagent Property, the efficient degradation of wastewater containing phenol can be realized in the unlimited system for being exposed to air.In reaction process, attapulgite is viscous Fe in soil2+With Fe3+High activity OH is generated with hydrogen peroxide, OH and organic matter phenol, which react, generates CO2And H2O, Realize degradation of phenol.Concave-convex clay rod used in entire reaction process needs not move through any processing.Handled contains benzene Phenol waste water can reach national emission standard direct emission after dilution.This method is simple and easy to do, is expected to realize factory's industrialization.
Detailed description of the invention:
Fig. 1 is scanning electron microscope (SEM) characterization of Concave-convex clay rod in embodiment 1-5.
Fig. 2 is transmission electron microscope (TEM) characterization of Concave-convex clay rod in embodiment 1-5.
Fig. 3 is X-ray diffraction (XRD) characterization of Concave-convex clay rod in embodiment 1-5.
Fig. 4 is the infrared spectroscopy of Concave-convex clay rod in embodiment 1-5.
Fig. 5 is the Fe ion characterization in the X-ray photoelectron spectroscopic analysis (XPS) of Concave-convex clay rod in embodiment 1-5.
Fig. 6 is the removal rate experimental result of Concave-convex clay rod Pyrogentisinic Acid and COD at different pH in embodiment 1.
Fig. 7 is the removal rate experimental result of Concave-convex clay rod Pyrogentisinic Acid and COD in quality difference in embodiment 2.
Fig. 8 is that Concave-convex clay rod removal rate of Pyrogentisinic Acid and COD under the amount of different hydrogen peroxide is tested in embodiment 3 As a result.
Fig. 9 be in embodiment 4 Concave-convex clay rod in the removal rate experimental result of differential responses time Pyrogentisinic Acid and COD.
Figure 10 be in embodiment 5 Concave-convex clay rod in the removal rate experimental result of differential responses temperature Pyrogentisinic Acid and COD.
Specific embodiment:
Embodiment 1
A. 250ml (10) beaker and magneton (10) are cleaned and is dried with deionized water and dehydrated alcohol.It uses respectively Graduated cylinder, which accurately measures 100ml and prepared and be diluted to the simulation phenolic waste water of 100ppm, to be added in beaker.Magneton is added The moderate-speed mixer on magnetic stirring apparatus.
B. the pH value of solution in 10 beakers 1,2,3,4,5,6,7,8,9,10 are transferred to respectively with pH reagent (to utilize (as schemed) Sulfuric acid and sodium hydroxide finely tune pH).Totally 10 parts of Concave-convex clay rod 0.5g are weighed respectively, are added separately to step A and are being stirred Beaker in.10 parts of 0.5ml 30wt% hydrogenperoxide steam generators are accurately measured with liquid-transfering gun rapidly and are added separately to above-mentioned beaker In.Temperature is maintained at 20 DEG C.
C. after being stirred to react 15min, magnetic stirring apparatus, filtering, weight after 60 DEG C of obtained Concave-convex clay rod drying are closed Multiple to use, being adjusted to each filtrate pH with sodium hydroxide solution and sulfuric acid solution is 10, is measured using ultraviolet spectra absorption apparatus and COD Instrument measures respectively.
Through measuring, the removal rate of phenol and COD reach highest when pH is 3, and respectively 95% and 92%.
Embodiment 2
A. 250ml (7) beaker and magneton (7) are cleaned and is dried with deionized water and dehydrated alcohol.Dosage respectively Cylinder is accurate to measure 100ml and has prepared and be diluted to the simulation phenolic waste water of 100ppm and be added in beaker.Magneton is added to exist Moderate-speed mixer on magnetic stirring apparatus.
B. the pH value of solution in 7 beakers is adjusted to 3 (finely tuning pH using sulfuric acid and sodium hydroxide) with pH reagent.It weighs respectively Concave-convex clay rod 0.05,0.1,0.5,1,1.5,2, totally 7 parts of 3g (as schemed), are added in the beaker that step A is being stirred.It is fast Speed accurately measures 7 parts of 0.5ml 30wt% hydrogenperoxide steam generators with liquid-transfering gun and is added separately in above-mentioned beaker.Temperature is maintained at 20℃。
C.15min after, magnetic stirring apparatus is closed, filtering is reused after 60 DEG C of obtained Concave-convex clay rod drying, used It is 10 that sodium hydroxide solution, which adjusts each filtrate pH, is measured respectively using ultraviolet spectra absorption apparatus and COD measuring instrument.
Through measuring, phenol and COD removal rate reach highest, respectively 95% He when the quality of Concave-convex clay rod is 0.5g 92%.
Embodiment 3
A. 250ml (7) beaker and magneton (7) are cleaned and is dried with deionized water and dehydrated alcohol.Dosage respectively Cylinder is accurate to measure 100ml and has prepared and be diluted to the simulation phenolic waste water of 100ppm and be added in beaker.Magneton is added to exist Moderate-speed mixer on magnetic stirring apparatus.
B. the pH value of solution in 7 beakers is adjusted to 3 (finely tuning pH using sulfuric acid and sodium hydroxide) with pH reagent.It weighs respectively It totally 7 parts of Concave-convex clay rod 0.5g, is added in the beaker that step A is being stirred.Rapidly with liquid-transfering gun correct amount 0.05,0.5, 1,1.5,2,2.5, totally 7 parts of 3ml (as schemed) 30wt% hydrogenperoxide steam generator is added separately in above-mentioned beaker.Temperature is maintained at 20 ℃。
C.15min after, magnetic stirring apparatus is closed, filtering is reused after 60 DEG C of obtained Concave-convex clay rod drying, used It is 10 that sodium hydroxide solution, which adjusts each filtrate pH, is measured respectively using ultraviolet spectra absorption apparatus and COD measuring instrument.
Through measuring, the removal rate of phenol and hydrogen peroxide increases as the amount of hydrogen peroxide increases, and examines for economic factor Consider, recommending the volume of hydrogen peroxide is 0.5-1ml, and the removal rate of phenol and COD can reach 90% at this time.
Embodiment 4
A. 250ml (7) beaker and magneton (7) are cleaned and is dried with deionized water and dehydrated alcohol.Dosage respectively Cylinder is accurate to measure 100ml and has prepared and be diluted to the simulation phenolic waste water of 100ppm and be added in beaker.Magneton is added to exist Moderate-speed mixer on magnetic stirring apparatus.
B. the pH value of solution in 7 beakers is adjusted to 3 (finely tuning pH using sulfuric acid and sodium hydroxide) with pH reagent.It weighs respectively It totally 7 parts of Concave-convex clay rod 0.5g, is added in the beaker that step A is being stirred.7 parts are accurately measured with liquid-transfering gun rapidly 0.5ml 30wt% hydrogenperoxide steam generator is added separately in above-mentioned beaker.Temperature is maintained at 20 DEG C.
C. the reaction time be 0,5,10,15,20,30,40min totally 7 periods (as schemed), close magnetic stirring apparatus, mistake Filter is reused after 60 DEG C of obtained Concave-convex clay rod drying, and being adjusted to each filtrate pH with sodium hydroxide solution is 10, is utilized Ultraviolet spectra absorption apparatus and COD measuring instrument measure respectively.
Through measuring, the removal rate of phenol and COD increase as time increases, it is contemplated that industrial production, each reaction Time is advisable for 15min, and the removal rate of phenol and COD are respectively 95% and 92% at this time.
Embodiment 5
A. 250ml (8) beaker and magneton (8) are cleaned and is dried with deionized water and dehydrated alcohol.Dosage respectively Cylinder is accurate to measure 100ml and has prepared and be diluted to the simulation phenolic waste water of 100ppm and be added in beaker.Magneton is added to exist Moderate-speed mixer on magnetic stirring apparatus.
B. the pH value of solution in 10 beakers is transferred to 3 (as schemed) with pH reagent (sulfuric acid and sodium hydroxide finely tune pH).Respectively Totally 10 parts of Concave-convex clay rod 0.5g are weighed, is added in the beaker that step A is being stirred.10 are accurately measured with liquid-transfering gun rapidly Part 0.5ml 30wt% hydrogenperoxide steam generator is added separately in above-mentioned beaker.Temperature is transferred to 10 respectively, 15,20,25,30,35, 40,45 DEG C of totally 8 temperature (as schemed).
C.15min after, magnetic stirring apparatus is closed, filtering is reused after 60 DEG C of obtained Concave-convex clay rod drying, used It is 10 that sodium hydroxide solution and sulfuric acid solution, which are adjusted to each filtrate pH, is surveyed respectively using ultraviolet spectra absorption apparatus and COD measuring instrument Amount.
Through measuring, phenol and COD removal rate reach highest when temperature is 20 DEG C, and respectively 95% and 92%.
The characterization of appearance structure is carried out to above-mentioned Concave-convex clay rod and handles the performance characterization result of phenolic waste water:
As seen from Figure 1, attapulgite is in rodlike, is attached to above some impurity, width only has several nanometers, and length is about several Hundred nanometers are differed to several microns.
Little particle of black is Fe in Fig. 22O3
X-ray diffraction (XRD) characterization of ecosystem in Linze, Gansu, China attapulgite, diffraction maximum and attapulgite standard x RD in Fig. 3 Card (JCPDF02-0018) is consistent, but due to being that concave convex rod stone ore soil is impure, there is apparent impurity diffraction maximum.
In Fig. 4 3618 be-OH stretching vibration peak, 3436 be Coordinated Water (in conjunction with water), and 1633 are Zeolitic Water (zeolite water) 1029 be Si-O-Si asymmetry stretching vibration, 797 and 471 be Si-O midplane extrusion and Bending vibration, micro- peak between 528-797 are the Fe above ATP2O3Fe-O vibration peak.
It is simulated by XPS, as can be seen from Figure 5 ferro element is stored in attapulgite in the form of divalent and trivalent.
Fig. 6 is addition 100ml 100ppm phenol solution, attapulgite 0.5g, pH 1-10, hydrogen peroxide in beaker Amount be 0.5ml, temperature be 20 DEG C, magnetic agitation mixing time be 15min, probe into size Pyrogentisinic Acid's waste water removal rate of pH It influences, when pH is 3, removal rate reaches maximum value.
Fig. 7 is addition 100ml 100ppm phenol solution, attapulgite 0.05-3g, pH 3, hydrogen peroxide in beaker Amount be 0.5ml, temperature be 20 DEG C, the magnetic agitation time be 15min, probe into amount Pyrogentisinic Acid's waste water removal rate of attapulgite It influences, when the quality of attapulgite is 0.5g, removal rate reaches maximum value.
Fig. 8 is addition 100ml 100ppm phenol solution, attapulgite 0.5g, pH 3, the amount of hydrogen peroxide in beaker 0.1-3.5ml, temperature are 20 DEG C, and the magnetic agitation time is 15min, probes into the shadow of amount Pyrogentisinic Acid's waste water removal rate of hydrogen peroxide It rings, with the increase of the amount of hydrogen peroxide, removal rate is gradually increased, but considers economic factor, it is recommended to use 0.5-1ml peroxidating Hydrogen.
Fig. 9 is addition 100ml 100ppm phenol solution, attapulgite 0.5g, pH 3, the amount of hydrogen peroxide in beaker For 0.5ml, temperature is 20 DEG C, and the magnetic agitation time is 15min, probes into the shadow of differential responses time Pyrogentisinic Acid's waste water removal rate It rings, as time increases, removal rate is gradually increased, it is contemplated that industrial production, time control in 15min.
Figure 10 is that 100ml 100ppm phenol solution is added in beaker, attapulgite 0.5g, pH 3, hydrogen peroxide 0.5ml is measured, temperature is 10 DEG C -45 DEG C, and the magnetic agitation time is 15min, probes into differential responses temperature Pyrogentisinic Acid's waste water removal rate Influence, temperature be 20 DEG C when, removal rate reaches maximum value.Also it is suitble to industrial temperature.

Claims (9)

1. a kind of method of Concave-convex clay rod processing wastewater containing phenol, which is characterized in that the method are as follows: will using acid or alkali The pH value of wastewater containing phenol is adjusted to 1-10, and Concave-convex clay rod is then added, continuously adds hydrogen peroxide, is stirred to react 5min- 40min, filtering are reused after obtained Concave-convex clay rod drying, and filtrate is the waste water handled well.
2. the method for Concave-convex clay rod processing wastewater containing phenol according to claim 1, which is characterized in that the acid For sulfuric acid.
3. the method for Concave-convex clay rod processing wastewater containing phenol according to claim 1, which is characterized in that the alkali For sodium hydroxide.
4. the method for Concave-convex clay rod processing wastewater containing phenol according to claim 1, which is characterized in that described contains The pH value of phenolic waste water is adjusted to 3.
5. the method for Concave-convex clay rod processing wastewater containing phenol according to claim 1, which is characterized in that described contains Phenolic waste water 100mL, phenol concentration 10-500ppm, the additive amount of Concave-convex clay rod are 0.01g-3g, the addition of hydrogen peroxide Amount is 0.05-3mL.
6. the method for Concave-convex clay rod processing wastewater containing phenol according to claim 1, which is characterized in that described is double The concentration of oxygen water is 25-35wt%.
7. the method for Concave-convex clay rod processing wastewater containing phenol according to claim 1, which is characterized in that described stirs The temperature for mixing reaction is 10-40 DEG C.
8. the method for Concave-convex clay rod processing wastewater containing phenol according to claim 1, which is characterized in that the baking Dry temperature is 50-70 DEG C.
9. the method for Concave-convex clay rod processing wastewater containing phenol according to claim 1, which is characterized in that the filter Liquid sodium hydroxide or sulphur acid for adjusting pH are 10, are utilized respectively ultraviolet spectra absorption apparatus and the detection of COD measuring instrument.
CN201910443099.5A 2019-05-26 2019-05-26 A kind of method of Concave-convex clay rod processing wastewater containing phenol Pending CN110092505A (en)

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Application publication date: 20190806