CN100398456C - Process for degradation of organic waste water by fly ash - Google Patents

Process for degradation of organic waste water by fly ash Download PDF

Info

Publication number
CN100398456C
CN100398456C CNB200610054202XA CN200610054202A CN100398456C CN 100398456 C CN100398456 C CN 100398456C CN B200610054202X A CNB200610054202X A CN B200610054202XA CN 200610054202 A CN200610054202 A CN 200610054202A CN 100398456 C CN100398456 C CN 100398456C
Authority
CN
China
Prior art keywords
waste water
flyash
fly ash
mixed solution
wastewater
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
CNB200610054202XA
Other languages
Chinese (zh)
Other versions
CN1837076A (en
Inventor
刘作华
刘仁龙
杜军
孙大贵
陶长元
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Chongqing University
Original Assignee
Chongqing University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Chongqing University filed Critical Chongqing University
Priority to CNB200610054202XA priority Critical patent/CN100398456C/en
Publication of CN1837076A publication Critical patent/CN1837076A/en
Application granted granted Critical
Publication of CN100398456C publication Critical patent/CN100398456C/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02WCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00Technologies for wastewater treatment
    • Y02W10/30Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The present invention relates to a method for degrading organic wastewater by fly ash. The method has the steps: a. the fly ash and the wastewater are thoroughly mixed, and the mass ratio of the fly ash to the wastewater is from 0.8% to 1.5%; b. the pH value of wastewater mixed liquid is regulated to 1 to 4; c. hydrogen peroxide is added into the wastewater mixed liquid to cause the hydrogen peroxide and soluble metallic ions in the fly ash to form a Fenton type reagent; d. the wastewater mixed liquid passes through a glass or ceramic pipeline with a microwave field within 3 to 5 min; e. the fly ash with pollutants is filtered, precipitated, detected and collected, and treated water is discharge or recycled. The present invention artfully utilizes transition metal oxides containing ferric oxide, etc. in the fly ash to cause the transition metal oxide and the hydrogen peroxide to form the Fenton type reagent. The porous structure of the fly ash can be used for better absorbing microwave energy and can be used for adsorbing-catalyzing and oxidizing organic substances under the promote of microwaves, and the purpose of deep oxidizing treatment is achieved. The present invention has the advantages of high removing rate of COD, no biochemical tank and low wastewater treatment cost.

Description

A kind of method with the flyash degradation of organic waste water
Technical field
The present invention relates to the treatment process of a kind of organic waste water (sewage), relate in particular to the organic method in the flyash absorption degradation waste water of utilizing.
Background technology
Flyash is the aggregate of sphere or microballon, diameter 1 μ m~100 μ m, proportion between 2.02~2.56, CaO and Fe 2O 3Content increases, and proportion increases, and do not burn the charcoal amount when increasing proportion can reduce.The whiteness of flyash is 26~66, is limited by Fe 2O 3Content.The BET specific surface area fluctuates in 0.7m 2/ g~36.6m 2/ g is not burnt the influence of charcoal, and increases with the increase that does not burn the charcoal amount.The BET specific surface area of taking off the flyash of charcoal fully is 0.5m 2/ g~1.5m 2/ g.SiO in the flyash 2, Al 2O 3, Fe 2O 3Three kinds of compositions account for more than 70%, and the content of CaO and MgO changes with the composition of raw coal is different with the output epoch, generally change between 0.2%~10%.Flyash mainly is made of mutually amorphous glass, and crystalline mineral comprises quartz, mullite, rhombohedral iron ore, magnetite, lime and gypsum.Wherein, quartz is main crystallization phases, and the thermolysis of silicon, aluminium mineral (as kaolinite) is relevant in the formation of mullite and the raw coal.The component ratio of mineral state is controlled by carbonaceous and burning cooling conditions in the flyash, and its pH value can be from slightly acidic to the strongly-acid transition.
China is maximum in the world coal producer and consumption coal state, fire coal has accounted for 70% of China's energy structure, oneself reached 1.6 hundred million tons in 2000, occupied a large amount of soils and consumed a large amount of water for disposing the storage ash field that these flyash build, and China's utilization of coal ash rate has only 30% at present, and major part concentrates on the material of construction aspect.Therefore, the utilization ratio that how to dispose flyash, improves it is an important problem for China.Flyash is a kind of industrial solid wastes of China's quantity discharged maximum, and environment and human body have been caused very big harm, so the own decision of China is the breach of the comprehensive utilization of flyash as the solid waste utilization.The discharging of China's flyash at present with utilize feature to be: quantity discharged is big, make a low multiple use.The total utilization of PCA rate is 25%~30%, and exhausted major part concentrates on building and building material industry, and the utilization ratio of high added value is less.
For example, publication number is that the Chinese patent of CN1273944A stores up flyash as diafiltration bed and oxidation bed, makes black water receive the bio-oxidation decomposing, purifying of the diafiltration of flyash, absorption and sunlight, air.Publication number is that the Chinese patent of CN1064664A is first through biochemical treatment with the coking chemical waste water that contains pollutents such as prussiate, sulfide, oil, phenol of coke-oven plant, again with flyash as sorbent material, adopt the grey water slurry attitude bed absorption of canalization, after the solid-liquid separation, the flyash that contains pollutent is used to fire internal burned brick; Water after chemical treatment and cinder filtration, is utilized as the make up water of recirculated water again.These utilize flyash that organic pollutant is only carried out adsorption, organism is not carried out deep oxidation and handle, and the technical costs of processing waste water is than higher.
Summary of the invention
The objective of the invention is, at the deficiencies in the prior art, provide a kind of can with flyash as sorbent material and catalyzer, to the method for the organic waste water that organism carries out efficiently, deep oxidation is handled.
For reaching goal of the invention, provide a kind of like this method with the flyash degradation of organic waste water.This method also is to adopt flyash as organic sorbent material in the waste water.Compare as the method for sorbent material with the existing flyash that adopts, different steps are:
A, with flyash and waste water thorough mixing, the mass ratio of its flyash and waste water is 0.8%~1.5%;
B, the acidity of regulating the waste water mixed solution, it is between 1~4 that the pH value is controlled at;
C, add hydrogen peroxide in the waste water mixed solution, its add-on is 0.25%~0.4% of a waste water mixed solution quality, so that the soluble metal ion in itself and the flyash forms Fenton-like reagent;
D, allow glass or the earthenware duct of waste water mixed solution by microwave field is arranged, each particle in this waste water mixed solution is by the time 3~5min of pipeline; Microwave frequency is 2000~2800MHz, power 600~1000W;
E, last filters, precipitates, detects, and collects the flyash that contains pollutent, discharging or recycle treated water.
Superiority of the present invention is as follows:
Compare as the method for sorbent material with existing employing flyash.Because the present invention is ingenious and reasonably utilized the transition metal oxides such as ferric oxide that contain in the flyash.Under acidic conditions, these transition metal oxides are partly dissolved the generation transition metal ion.Transition metal ion can form Fenton-like reagent with hydrogen peroxide, has produced the extremely strong hydroxyl radical free radical of oxidisability.Under the promotion of microwave, the organism in more can deep oxidation waste water has improved the utilising efficiency of hydrogen peroxide.Compare as the method for sorbent material with existing employing flyash, the present invention not only handles, the processing power of degradation of organic waste water is strengthened greatly because of carrying out deep oxidation to organism, and makes processing efficiency be greatly improved owing to having reduced the biochemical treatment process; Also save the setting of biochemistry pool simultaneously, reduced the processing cost of waste water.
Further, in the present invention, flyash is utilized as a kind of catalyzer again.Compare with the method for other existing microwave catalysis degrade organic compounds, flyash is more extensive than other sources as the catalyzer of Chemicals such as ferric sulfate, and cost is cheaper.Because flyash not only can adsorb the organism in the waste water as porous structure material, also can absorb micro-wave energy, and organism can be focused on flyash; And use microwave heating, no thermograde, heat utilization ratio height, be swift in response.The present invention can greatly improve the efficient that absorbs micro-wave energy at inner form " focus " of flyash with after microwave heating, promoting, produces the efficient height of hydroxyl radical free radical, and mineralising, degradation of organic substances are thorough.
In a word, the present invention for the comprehensive utilization that realizes flyash and efficiently, the recycling of the waste water of degradation of organic waste water, and realization apace provides a kind of scheme that bright prospects are arranged.
Below in conjunction with accompanying drawing and enforcement embodiment, the present invention is further illustrated.
Description of drawings
The graph of a relation of Fig. 1---microwave power and percent of decolourization
The graph of a relation of the consumption of Fig. 2---hydrogen peroxide and COD clearance
Embodiment
A kind of method with the flyash degradation of organic waste water, this method adopts flyash as organic sorbent material in the waste water.This method may further comprise the steps:
A, with flyash and waste water thorough mixing, the mass ratio of flyash and waste water is 0.8%~1.5%;
B, the acidity of regulating the waste water mixed solution are controlled at the pH value between 1~4;
C, add hydrogen peroxide in the waste water mixed solution, its add-on is 0.25%~0.4% of a waste water mixed solution quality, so that the soluble metal ion in itself and the flyash forms Fenton-like reagent;
D, allow glass or the earthenware duct of waste water mixed solution by microwave field is arranged, each particle is by the time 3~5min of pipeline; Microwave frequency is 2000~2800MHz, power 600~1000W;
E, last filters, precipitates, detects, and collects the flyash that contains pollutent, discharging or recycle treated water.
Disclose so far, those skilled in the art can be clear that, the present invention compares as the degradation method of organic sorbent material in the waste water with existing employing flyash, its difference is, the present invention has added the hydrogen peroxide that did not add in the existing method in degradation process, and has adopted and do not adopted the exhausted step of microwave heating as the promotion means in the existing method.Though, do not have the step described in the distinguishing characteristics of the present invention for a long time in the prior art, still, consult, study the those skilled in the art of being of the present invention after all, therefore, device and the described ducted microwave heating installation that adds hydrogen peroxide just do not given unnecessary details; The all process steps of step e in the scheme also all can adopt existing any method and apparatus.
For guaranteeing (or saying further raising) degradation efficiency:, before the filtration operation of step e, all in mixing process and to mixed solution, stir with whipping appts from flyash is mixed with waste water.It is equally evident that to those skilled in the art, described whipping appts also needn't be given unnecessary details.
Obviously, the processing parameter during actually operating (or proportioning) value should be adjusted according to the source of flyash is different.According to the situation of most flyash, in following processing parameter (or proportioning) scope, choose usually better, that is:
In step a, the mass ratio of flyash and waste water is 1%~1.2%;
In step b, the pH value is 2~3;
In step c, the amount of hydrogen peroxide of adding is 0.25%~0.35% of a waste water mixed solution quality;
In steps d, each particle of waste water mixed solution is by the time 4~5min of pipeline, microwave power 600~800W.
, in laboratory oppose better processing parameter (or proportioning) value than test back, that draw of the present invention as checking is:
In step a, the mass ratio of flyash and waste water is 1%;
In step b, the pH value is 3;
In step c, the amount of hydrogen peroxide of adding is 0.3% of a waste water mixed solution quality;
In steps d, each particle of waste water mixed solution is by the time 5min of pipeline; Microwave frequency is 2450MHz, power 800W.
Wherein:
Flyash is the one-level bituminous coal that produce in Nan Tong colliery, Chongqing, collects after burning;
It is with sulfuric acid and sodium hydroxide that the pH value is regulated;
Concentration of hydrogen peroxide is 30%, and after the conversion, the ratio among the c adds set by step again;
Microwave heating installation is a microwave oven;
Detection reagent during checking is a methyl orange solution.
Detect content:
(a) percent of decolourization is measured---with the concentration of residue methyl orange solution after the spectrophotometer analyzing and processing.
Percent of decolourization α=(tropeolin-D starting point concentration-processing back tropeolin-D residual concentration)/tropeolin-D starting point concentration * 100%
(b) mensuration of COD clearance---measure the COD value that methyl orange solution is handled front and back with dichromate titration (GB11914-89).
COD clearance=(COD of the initial COD concentration of methyl orange solution-processing back solution)/initial COD concentration of methyl orange solution * 100%
Checking comparing result such as following table:
Numbering Flyash and tropeolin-D mass ratio Microwave power/W Hydrogen peroxide is used and the methyl orange solution volume ratio Initial tropeolin-D concentration/mg.L -1 Microwave irradiation time/min The pH value Percent of decolourization/% COD clearance/%
One ??10 ??1000 ??0.01 ??1000 ??4 ??3 ??99.9 ??78.0
Two ??10 ??800 ??0.01 ??1000 ??5 ??3 ??99.9 ??93.4
Three ??30 ??1000 ??0.01 ??900 ??3 ??4 ??99.8 ??55.7
Four ??10 ??1000 ??0.05 ??1000 ??4 ??1 ??99.9 ??65.1
The relation of microwave power and percent of decolourization of investigating is found (referring to Fig. 1): the increase of microwave power helps the decolouring of methyl orange solution.Because improve the power of microwave, the body temperature of solution increases, and the adsorptive power of flyash is strengthened, and has also quickened the process of hydroxyl radical free radical oxidation of organic compounds.But microwave power is after 600W, and the percent of decolourization of tropeolin-D is all near 99.9%.
The relation of hydrogen peroxide consumption and COD clearance of investigating is found (referring to Fig. 2): azo dye wastewater is one of organic waste water of difficult for biological degradation.Tropeolin-D has typical azo structure, this patent with tropeolin-D as the simulation azo dye wastewater.The hydrogen peroxide that adds is as oxygenant, and flyash is as the sorbent material and the catalysis H of absorption azo dye wastewater 2O 2Produce the extremely strong hydroxyl radical free radical of oxidisability, thus the absorption degradation azo dye wastewater.The consumption of hydrogen peroxide is 0.8% o'clock of tropeolin-D volume, and its COD clearance is the highest, can reach 71.4%.Excessive peroxidation Hydrogen Energy increases the COD value of handling in the solution of back.

Claims (4)

1. method with the flyash degradation of organic waste water, this method adopt flyash as organic sorbent material in the waste water, it is characterized in that this method may further comprise the steps:
A, with flyash and waste water thorough mixing, the mass ratio of flyash and waste water is 0.8%~1.5%;
B, the acidity of regulating the waste water mixed solution are controlled at the pH value between 1~4;
C, add hydrogen peroxide in the waste water mixed solution, its add-on is 0.25%~0.4% of a waste water mixed solution quality,
So that the soluble metal ion in itself and the flyash forms Fenton-like reagent;
D, allow glass or the earthenware duct of waste water mixed solution by microwave field is arranged, each particle is by the time 3~5min of pipeline; Microwave frequency is 2000~2800MHz, power 600~1000W;
E, last filters, precipitates, detects, and collects the flyash that contains pollutent, discharging or recycle treated water.
2. the method with the flyash degradation of organic waste water according to claim 1 is characterized in that:
In step a, the mass ratio of flyash and waste water is 1%~1.2%;
In step b, the pH value is 2~3;
In step c, the amount of hydrogen peroxide of adding is 0.25%~0.35% of a waste water mixed solution quality;
In steps d, each particle of waste water mixed solution is by the time 4~5min of pipeline, microwave power 600~800W.
3. the method with the flyash degradation of organic waste water according to claim 2 is characterized in that:
In step a, the mass ratio of flyash and waste water is 1%;
In step b, the pH value is 3;
In step c, the amount of hydrogen peroxide of adding is 0.3% of a waste water mixed solution quality;
In steps d, each particle of waste water mixed solution is by the time 5min of pipeline; Microwave frequency is 2450MHz, power 800W.
4. according to claim 1 or 3 described methods, it is characterized in that:, before the filtration operation of step e, all have whipping appts in mixing process and to mixed solution, to stir from flyash is mixed with waste water with the flyash degradation of organic waste water.
CNB200610054202XA 2006-04-07 2006-04-07 Process for degradation of organic waste water by fly ash Expired - Fee Related CN100398456C (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CNB200610054202XA CN100398456C (en) 2006-04-07 2006-04-07 Process for degradation of organic waste water by fly ash

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CNB200610054202XA CN100398456C (en) 2006-04-07 2006-04-07 Process for degradation of organic waste water by fly ash

Publications (2)

Publication Number Publication Date
CN1837076A CN1837076A (en) 2006-09-27
CN100398456C true CN100398456C (en) 2008-07-02

Family

ID=37014611

Family Applications (1)

Application Number Title Priority Date Filing Date
CNB200610054202XA Expired - Fee Related CN100398456C (en) 2006-04-07 2006-04-07 Process for degradation of organic waste water by fly ash

Country Status (1)

Country Link
CN (1) CN100398456C (en)

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100431688C (en) * 2006-12-13 2008-11-12 大连理工大学 Modified fly ash absorbent and method for processing nitrophenol polymerization inhibitor production waste water
CN101580288B (en) * 2009-07-07 2011-07-20 哈尔滨工业大学 Organic wastewater treating method adopting combined zeolite-microwave-hydrogen peroxide
CN102408178A (en) * 2010-09-21 2012-04-11 上海市政工程设计研究总院 Deep dewatering method for sludge
CN102001780A (en) * 2010-11-29 2011-04-06 沈阳工业大学 Method for pre-treating high-concentration organic waste water
CN103058294A (en) * 2011-10-18 2013-04-24 成都快典科技有限公司 Sewage treatment process by microwave
CN102424451A (en) * 2011-10-21 2012-04-25 沈阳建筑大学 Processing method for Fenton-Like oxidation of high density heavy oil wastewater through inducing fly ash source by microwaves
CN102874915A (en) * 2012-10-24 2013-01-16 西南大学 Method for treating dye wastewater by microwave coordinating with magnetic type Fenton catalyst
CN103623853B (en) * 2013-10-23 2015-06-24 大连理工大学 Method for preparing catalyst from coal ash and biomasses and application of catalyst
CN103935963B (en) * 2014-04-30 2016-06-08 贵州大学 The method of purifying industrial aqueous hydrogen peroxide solution
CN103936134B (en) * 2014-05-06 2015-12-09 南京大学 A kind of method utilizing synthetic ammonia gasification Slag treatment phenolic wastewater
CN106746075A (en) * 2016-12-09 2017-05-31 苏州纳贝通环境科技有限公司 A kind of processing method of high-concentration phosphorus-containing wastewater

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1121702A (en) * 1993-04-27 1996-05-01 沃尔特克斯公司 Water purification unit
CN1374260A (en) * 2002-04-23 2002-10-16 大连理工大学 MIcrowave catalytic oxidation process and apparatus for treating waste water containing hard-to-degrade organic matters

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1121702A (en) * 1993-04-27 1996-05-01 沃尔特克斯公司 Water purification unit
CN1374260A (en) * 2002-04-23 2002-10-16 大连理工大学 MIcrowave catalytic oxidation process and apparatus for treating waste water containing hard-to-degrade organic matters

Also Published As

Publication number Publication date
CN1837076A (en) 2006-09-27

Similar Documents

Publication Publication Date Title
CN100398456C (en) Process for degradation of organic waste water by fly ash
CN105859105B (en) A kind of Treatment of Sludge and method of resource
CN101745197B (en) Method of treating refractory pollutants through catalyzing H2O2 oxidation by pyrite cinder
CN102151546B (en) Modified zeolite as well as preparation method and application thereof
CN105214625B (en) A kind for the treatment of process of activation lignite and the coking wastewater using the activation lignite
CN101514112A (en) Ceramic aggregate biological filler and preparation method thereof
CN101700524B (en) Fixing agent and method for safely disposing heavy metal polluted soil repairing plant
CN102303918B (en) Method for treating acidic high-iron and high-manganese mine water and method for modifying fly ash
Nachiappan et al. Treatment of pharmaceutical effluent using novel heterogeneous fly ash activated persulfate system
CN101962590A (en) Regenerative coal produced by multiple kinds of oily sludge in oil refinery and preparation method thereof
CN108212164B (en) Fenton-like catalyst and preparation method thereof
CN106116000B (en) It is a kind of it is main using biomass material by the method for industrial wastes taste removal, turning sludge into fuel and recycling
CN103013613B (en) Clean fuelization system and fuelization method for urban sludge
CN101830537A (en) Method for degrading organic components in ore-dressing wastewater of sulphide ores by catalysis under visible light
CN101580288B (en) Organic wastewater treating method adopting combined zeolite-microwave-hydrogen peroxide
CN103086457A (en) Method for treating acid pickling citric acid wastewater of power plant boiler by using fly ash
CN104787956B (en) The processing method and its device of a kind of percolate
CN101700947B (en) Method for treatment of citric acid cleaning wastewater from power plant boiler
CN104073312A (en) Composite sludge coal and preparation method thereof as well as fuel
CN103691448B (en) The preparation method of magnetic sludge base ozone catalyst and application
CN102092755B (en) Preparation method of Ca(OH)2 for desulfuration
JP6825456B2 (en) Treatment method for organic sludge and sulfur-containing waste
CN208898834U (en) It is a kind of using house refuse preparation biomass can charcoal system
CN108793650B (en) Treatment method of steel rolling oily sludge
CN213527924U (en) High-efficient desulfurization dust collector of retort tail gas

Legal Events

Date Code Title Description
PB01 Publication
C06 Publication
SE01 Entry into force of request for substantive examination
C10 Entry into substantive examination
GR01 Patent grant
C14 Grant of patent or utility model
CF01 Termination of patent right due to non-payment of annual fee

Granted publication date: 20080702

C17 Cessation of patent right