CN1421406A - Treating process of waste water containing binary acid - Google Patents

Treating process of waste water containing binary acid Download PDF

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Publication number
CN1421406A
CN1421406A CN02157884A CN02157884A CN1421406A CN 1421406 A CN1421406 A CN 1421406A CN 02157884 A CN02157884 A CN 02157884A CN 02157884 A CN02157884 A CN 02157884A CN 1421406 A CN1421406 A CN 1421406A
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China
Prior art keywords
water
biological fluidized
waste water
bed reactor
catalytic oxidation
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CN02157884A
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Chinese (zh)
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CN1161290C (en
Inventor
于永辉
刘守新
孙承林
肖羽堂
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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Priority to CNB021578842A priority Critical patent/CN1161290C/en
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    • Y—GENERAL 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

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  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Catalysts (AREA)

Abstract

In the treatment of waste water containing binary acid, biological fluidized bed technology and Ag/TiO2 photocatalytic oxidation technology are adopted. Stuffing is added into the biological fluidized bed to increase the microbe living space, increase biomass and raise organic load rate; and partial water is made to circulate to increase oxygen dissolved in waste water and eliminate organic matters in water effectively in constant aeration condition. The effluent from the biological fluidized bed is then treated in Ag/TiO2 photocatalytic oxidation equipment with certain amount of catalyst and air as oxidant; and under irradiation of ultraviolet ray the pollutant in water is photocatalytically oxidized. The present invention is suitable for treating waste water containing short-chain and long-chain binary acid, and has obvious treating effects including CODcr eliminating rate of 96.1% and chroma eliminating rate of 97.4%.

Description

A kind of diprotic acid method of wastewater treatment
Technical field
The invention belongs to a kind of chemical wastewater treatment method, relate in particular to a kind of bio-oxidation and mix (C with the processing of photochemical catalytic oxidation coupling technique 4～C 6) method of diprotic acid organic waste water.
Background technology
At present, the chemical wastewater treatment method is a lot, and biological fluidized bed has higher adaptability because of it to water quality and quantity; Removal effect is good; The volumetric loading height; System is stable, reliable; Take up an area of few; Advantages such as investment, working cost is low and generally being promoted, new technology, novel process are also constantly used in engineering of water treatment.Photocatalysis oxidation technique is oxidation capacity strong (can remove most organic pollutants in the water body) aspect eliminating organic contamination, reaction conditions gentleness (normal temperature, normal pressure), product cleaning (H 2O, CO 2, salt), and thirst for utilizing ultraviolet portion in the sunlight, be a kind of environmental friendliness Pollution abatement technology that has development prospect.
Mix (C 4～C 6) diprotic acid waste water produces when being the industrial production hexanodioic acid.C in the waste water 6Diprotic acid accounts for organism 97%, and it has similar characteristic to long-chain biatomic acid, and BOD/COD is about 0.5, and good biodegradability is mainly dissolved organic matter, adopts biological treatment the most reasonable.But after the biological treatment, the colourity of waste water does not only solve, and slightly increases (Yang Jian, yellow big magnitude on the contrary.Environmental Pollution and Control, 1992,21 (1): 15～18).
Summary of the invention
The object of the present invention is to provide a kind of diprotic acid method of wastewater treatment, make waste water reach processing requirements, compare with additive method, not only organism is removed in a large number, and the colourity problem of waste water also solved, and the colourity of water outlet reaches national grade one discharge standard.
To achieve these goals, the present invention has adopted organism fluidization bed technique and Ag/TiO 2The photocatalysis oxidation technique coupling.Biological fluidized bed is interior filled, increases the living space of microorganism, increases biomass, has improved the organic loading rate greatly, makes the portion water circulation simultaneously, increases the dissolved oxygen in the waste water, can effectively remove the organism in the water like this under the condition of continuous aeration.The biological fluidized bed water outlet enters Ag/TiO again 2In the photocatalytic oxidation device, adding a certain amount of catalyzer in the device, is oxygenant with the air, the pollutent under the bar valency of ultraviolet radiation in the catalyzed oxidation water.
Ultimate principle of the present invention:
1, the ultimate principle of biological fluidized bed is to be power with the fluid, and air is an oxygen source, is carrier with cellular column filler, covering one deck microbial film above the carrier, in carrier and process that fluid fully contacts, organism enters microbial film, and the metabolism by microorganism makes organic matter degradation.The present invention adopts various types of microorganisms, mainly comprises the protozoon and the metazoan of bacterium and multiple kind, and the thread fungus of the stronger Sphaerotilus of oxidation etc. in addition grows.Because filling surface has certain roughness, it is slower to add the filling surface current, and abundant dissolved oxygen and organism are arranged, and microorganism perches reproduction at filling surface, and the cultivation domestication through after a while forms sophisticated microbial film at filling surface.
2, the ultimate principle of photochemical catalytic oxidation is that atomic Weak ultraviolet can induce reaction semiconductor light-catalyst TiO under＜387nm wavelength ultraviolet radiation 2The valence band electronics is excited and transits to conduction band, produces photohole (h on valence band +), produce light induced electron (e on the conduction band -), h +And e -Respectively at OH in the water -And O 2Effect, the OH free radical of generation strong oxidizing property, the OH free radical is that a kind of oxidation capacity is only second to F 2Superpower oxygenant, at OH and h +Direct effect under, organic pollutant is at reaction liquid phase and TiO 2The surface is by progressively oxidative degradation, and through series of intermediate products, last permineralization is H 2O, CO 2And inorganic salts.The present invention adopts Ag/TiO 2Catalyzer, wherein Ag plays and reduces light induced electron, hole-recombination probability, quickens light induced electron to the effect of dissolved oxygen transfer rate.
The concrete characteristics of the present invention are:
A, fluidized-bed process maturation adopt the dominant bacteria inoculation membrane formation, and biofilm is fast, and acclimation period is short, and treatment effect is good.
B, waste water PH regulate automatically, and equalizing tank is considered water inlet water quality and quantity malconformation, and water quality and quantity is had regulatory function preferably, helps subsequent biological treatment.This design technology has stronger economy, and is safe and reliable, practical.Mud has been realized total reflux, does not need sludge treatment, greatly reduces investment and working cost.
C, Ag/TiO 2Photocatalytic reaction conditions gentleness (normal temperature, normal pressure), product cleaning (H 2O, CO 2, salt).
D, system process advanced person, stable, be easy to the management, operate very simple, anti impulsion load, stable water outlet.
Description of drawings
Fig. 1 is a device synoptic diagram of the present invention.
Embodiment
Please, be device synoptic diagram of the present invention in conjunction with Fig. 1.In pH adjustment tank 1, add pulverulent lime,, waste water ph is transferred to 6～7 by original 1～2, squeeze into biological fluidized-bed reactor 4 by recycle pump 3 by magnetic stirrer.Biological fluidized-bed reactor is 4 to be the jar shape reactor that material is done by ABS, and reactor lower part is established a sieve plate 2, and filler is filled on top; The bottom is by adorning an aeration head 5.A is a bypass outlet, and it is in order to improve the dissolved oxygen in the biological fluidized bed; B is a water-in; C, d, e are water outlet, and according to water outlet position different adjustment aquifer yield, the bed useful volume is 1 liter, and packing volume is 0.3 liter.Through aerator 6 aerations, the dissolved oxygen in the waste water is controlled at more than the 8mg/l, simultaneously by the metabolic degradation of organic substances of microorganism.Water after fluidized-bed 4 is handled is squeezed into photocatalytic oxidation device by recycle pump 7 again.This device mainly is made up of reactor (8), ultra-violet lamp (10) and magnetic stirring apparatus (9), and reactor 8 is a Glass Containers, and f is a water-in; G is an inlet mouth; H is a water outlet.In reactor, add a certain amount of (0.1～5g/L) Ag/TiO 2Catalyzer, bubbling air under UV-irradiation, by magnetic stirrer, carries out oxidative decoloration.
The present invention is an example with the water quality shown in the table 1, specifically describes.
Table 1: mix (C 4～C 6) diprotic acid waste water quality situation
BOD 5
Project COD Cr(mg/l) PH colourity (doubly)
(mg/l)
Content 3000～4,200 1200～1,600 1～2 300～500
Embodiment 1: the preparation of bio-carrier
The employing polypropylene is a raw material, and compressed shaper is compressed into the cellular pipe of Φ 30mm, and being cut into length is 15mm column filler, and density is 0.94 * 10 3Kilograms per cubic meter.
Embodiment 2: Preparation of catalysts
With 100g TiO 2It is 0.3mol/L AgNO that carrier joins 500mL concentration 3In the solution, 60 ℃ of constant temperature stirred dipping 5 hours.Then reaction mixture was shone 8 hours under the 365nm UV-light.With deionized water wash catalyzer 3～4 times.With the reaction product standing sedimentation, adopt the supernatant tipping is carried out catalyst separating, under 120 ℃ of temperature dry 2 hours then, dried solid abrasive to the 100-200 order, is obtained catalyst A.
Embodiment 3: the bio-carrier of utilization embodiment 1, active sludge is fetched by company limited from bay, Dalian wet tank harbour, inoculates domestication, treat system stable operation after, with mixed dibasic acid (C 4～C 6) waste water does continuous experiment, waste water PH is transferred to 6～7, and the bio-oxidation experiment condition sees Table 2 under the normal temperature and pressure.
Table 2
The worker inferior 12345 Flow (l/d) 0.4 0.6 0.8 0.9 1.0 Water inlet ??HR ??T ??(h) ??24 ??16 ??12 ??10 ??8 Water outlet ??COD crClearance (%) 96.6 95.6 94.2 93.8 92.0
?COD cr(mg/l) ?3737 ?3766 ?3766 ?3686 ?3686 ?PH ?6.0 ?6.3 ?6.0 ?6.0 ?6.0 Colourity (doubly) 582 593 586 586 580 ?COD cr?(mg/l) ?127 ?167 ?217 ?228 ?296 ?pH ?8.5 ?8.5 ?8.5 ?8.4 ?8.4 Colourity (doubly) 629 620 632 617 596
By the experimental result of table 2 as can be seen, adopt the organism fluidization bed technique can effectively remove organism in the waste water, but colourity obviously increase.Experimental data shows that it is 10 hours that waste water stops Best Times.
Embodiment 4
Get the former water of worker inferior 4 water outlet as photocatalysis oxidation reaction, with the catalyst A of embodiment 2, catalyst consumption 2.0g/L, air consumption 8L/h, radiating light source wavelength 253.7nm, the photochemical catalytic oxidation experiment condition sees Table 3 under the normal temperature and pressure.
Table 3
The worker inferior 1234 Flow (l/h) 6666 Water inlet ??HR ??T ??(mi ??n) ??15 ??30 ??45 ??60 Water outlet Chroma removal rate (%) 89.1 96.9＞97.6＞97.6
???COD cr??(mg/l) ??228 ??228 ??228 ??228 ??PH ??8.4 ??8.4 ??8.4 ??8.4 Colourity (doubly) 617 617 617 617 ??COD cr??(mg/l) ??206 ??154 ??143 ??138 ??PH ??7.9 ??7.9 ??7.9 ??7.9 Colourity (doubly) 67 19＜15＜15
By table 3 experimental result as can be seen, adopt Ag/TiO 2Photocatalysis oxidation technique is handled and is mixed (C 4～C 6) diprotic acid waste water, the colourity of waste water reduces greatly, simultaneously the COD of waste water CrAlso be minimized.
Adopt biological fluidized bed+Ag/TiO 2The photochemical catalytic oxidation combination process, its COD CrSee Table 4 with the treatment effect of colourity.
Table 4
?????????????COD cr Colourity
(mg/l) (%) 3,686 143 96.1 of water removal rate (mg/l) of intaking out The water removal rate (doubly) (doubly) (%) 586＜15＞97.4 of intaking out
Find out COD by table 4 experimental result CrClearance 96.1%, chroma removal rate are greater than 97.4, and water outlet reaches national secondary discharge standard.

Claims (11)

1, a kind of diprotic acid method of wastewater treatment, waste water enters biological fluidized-bed reactor, and the while aeration is by the microbiological deterioration organism;
Water after biological fluidized-bed reactor is handled is through Ag/TiO 2Photocatalyst, photocatalyst concentration 0.1～5g/L, bubbling air under the UV-irradiation, carries out the photochemical catalytic oxidation decolouring.
2, the method for claim 1 is characterized in that, described waste water its pH value before entering biological fluidized-bed reactor is adjusted into 6～7.
3, the method for claim 1 is characterized in that, described aeration is that the dissolved oxygen in the waste water is controlled at more than the 8mg/l.
4, the method for claim 1 is characterized in that, hydraulic detention time is 8～24 hours on the described biological fluidized-bed reactor.
5, the method for claim 1 is characterized in that, hydraulic detention time is 15～60 minutes during described photochemical catalytic oxidation decoloring reaction.
As claim 1 or 4 described methods, it is characterized in that 6, hydraulic detention time is 10～14 hours on the described biological fluidized-bed reactor.
As claim 1 or 5 described methods, it is characterized in that 7, hydraulic detention time is 30～45 minutes during described photochemical catalytic oxidation decoloring reaction.
8, the method for claim 1 is characterized in that, described ultraviolet lamp predominant wavelength is 253.7nm.
9, a kind of device of realizing aforesaid method, it mainly comprises:
One biological fluidized bed reactor is a jar shape, the inner filler of filling, and a sieve plate is established in the lower end, and the sieve plate below is provided with an aeration head; Reactor top one side is provided with a bypass outlet, to improve the dissolved oxygen in the biological fluidized-bed reactor, is provided with a water-in with side lower part; Corresponding another side is provided with an above water outlet;
One photocatalysis oxidation reaction device is container-like, and ultra-violet lamp is installed in inside, has dosed catalyzer between this lamp and the photocatalysis oxidation reaction device inwall; Top one side of photocatalysis oxidation reaction device device is provided with a water-in, is provided with an inlet mouth with side lower part; Corresponding another side is provided with water outlet;
The water outlet of biological fluidized-bed reactor is connected by the water-in of a water pump with the photochemical catalytic oxidation device;
Aeration head in the biological fluidized-bed reactor is connected an aerator with the inlet mouth of photochemical catalytic oxidation device, in order to each reactor bubbling air.
10, device as claimed in claim 8 is characterized in that, the water-in of described biological fluidized-bed reactor is connected by water pump with a waste water ph regulating tank.
11, device as claimed in claim 8 is characterized in that, described photochemical catalytic oxidation device is connected with a magnetic stirring apparatus magnetic force, enters waste water in the photocatalysis oxidation reaction device in order to stirring, to strengthen the effect of catalyzer.
CNB021578842A 2002-12-20 2002-12-20 Treating process of waste water containing binary acid Expired - Fee Related CN1161290C (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102417241A (en) * 2011-10-24 2012-04-18 沈阳建筑大学 Optical fluidized bed reactor for organic wastewater treatment
CN102701544A (en) * 2012-06-29 2012-10-03 河海大学 External-mounting photocatalytic - biological fluidized bed reactor
CN103145272A (en) * 2013-04-02 2013-06-12 河海大学 Sewage deep treatment device and application thereof
CN108557947A (en) * 2018-06-26 2018-09-21 唐山中科格润环境技术有限公司 A kind of wastewater from chemical industry catalytic reactor
CN114906976A (en) * 2022-03-14 2022-08-16 安徽工业大学 Device and method for treating heavy metal sewage by using plastic fragments of biological membrane

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102417241A (en) * 2011-10-24 2012-04-18 沈阳建筑大学 Optical fluidized bed reactor for organic wastewater treatment
CN102417241B (en) * 2011-10-24 2014-05-21 沈阳建筑大学 Optical fluidized bed reactor for organic wastewater treatment
CN102701544A (en) * 2012-06-29 2012-10-03 河海大学 External-mounting photocatalytic - biological fluidized bed reactor
CN102701544B (en) * 2012-06-29 2013-10-30 河海大学 External-mounting photocatalytic - biological fluidized bed reactor
CN103145272A (en) * 2013-04-02 2013-06-12 河海大学 Sewage deep treatment device and application thereof
CN108557947A (en) * 2018-06-26 2018-09-21 唐山中科格润环境技术有限公司 A kind of wastewater from chemical industry catalytic reactor
CN114906976A (en) * 2022-03-14 2022-08-16 安徽工业大学 Device and method for treating heavy metal sewage by using plastic fragments of biological membrane

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