CN106219727A - A kind of technique of efficient catalytic ozonation advanced treating cephalo pharmacy waste water - Google Patents
A kind of technique of efficient catalytic ozonation advanced treating cephalo pharmacy waste water Download PDFInfo
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- CN106219727A CN106219727A CN201610676546.8A CN201610676546A CN106219727A CN 106219727 A CN106219727 A CN 106219727A CN 201610676546 A CN201610676546 A CN 201610676546A CN 106219727 A CN106219727 A CN 106219727A
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/064—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing iron group metals, noble metals or copper
- B01J29/072—Iron group metals or copper
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/18—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself
- B01J2229/186—After treatment, characterised by the effect to be obtained to introduce other elements into or onto the molecular sieve itself not in framework positions
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2103/00—Nature of the water, waste water, sewage or sludge to be treated
- C02F2103/34—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32
- C02F2103/343—Nature of the water, waste water, sewage or sludge to be treated from industrial activities not provided for in groups C02F2103/12 - C02F2103/32 from the pharmaceutical industry, e.g. containing antibiotics
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/782—Ozone generators
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2201/00—Apparatus for treatment of water, waste water or sewage
- C02F2201/78—Details relating to ozone treatment devices
- C02F2201/784—Diffusers or nozzles for ozonation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2209/00—Controlling or monitoring parameters in water treatment
- C02F2209/08—Chemical Oxygen Demand [COD]; Biological Oxygen Demand [BOD]
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Crystallography & Structural Chemistry (AREA)
- Materials Engineering (AREA)
- Treatment Of Water By Oxidation Or Reduction (AREA)
- Catalysts (AREA)
Abstract
The technique that the invention discloses a kind of efficient catalytic ozonation advanced treating cephalo pharmacy waste water, it is loaded into the ozone catalyst of independent development being catalyzed in oxidizing tower packing layer, cephalo pharmacy biochemical treatment water outlet and ozone are passed through submicron bubble generating means simultaneously, after being sufficiently mixed, enter catalysis oxidizing tower；Ozone is collected laggard enter submicron bubble generating means, mixed liquor catalysis oxidizing tower in reacted after, qualified discharge.Present invention process uses new catalyst, energy efficient hardening ozone oxidation ability, improve treatment effeciency, whole set process is stable, processing speed is fast, with low cost, can directly apply to cephalo pharmacy waste water advanced treating, both eliminate the pollutant that biochemical treatment is difficult to degrade, improve again treatment effeciency.
Description
Technical field
The present invention relates to Sewage advanced treatment technical field, specifically a kind of efficient catalytic ozonation advanced treating head
The technique of spore pharmacy waste water.
Background technology
In numerous industrial wastewaters, pharmacy waste water is big because of its quantity of wastewater effluent, contained organic pollutant category in sewage
Complexity, the features such as biodegradable is poor become the contaminated object that people are urgently to be resolved hurrily, relative to general industrial wastewater, pharmacy
The kind of waste water is more various, synthetic drug production waste water, bio-pharmaceuticals can be divided into produce fermentation and give up according to its main source
The washcoated water produced in water, Chinese patent medicine production wastewater and all kinds of formulation manufacturing processes and flushing water.Production technology because of medicine goods
Relatively more special and relative complex, pharmacy waste water has that water-quality constituents is complicated, impact load is big, Organic Pollutants in Wastewater content
The features such as height, poisonous and harmful substance is many, biodegradability is poor.
Cephalosporins is used mostly industrial chemicals in producing, and production process reactions steps is many, raw material availability is low, surplus
Remaining raw material is mostly with discharge of wastewater, and this is the main cause causing Pollutants in Wastewater matter high.Content of organics in cephalo waste water
High and toxic to microorganism, such as halogen compounds, nitro compound, organonitrogen compound, uncle press and season money salt chemical combination
Thing, the dispersant with bactericidal action or surfactant etc., the life to microorganism in biological treatment of these organic pollutions
Long have inhibitory action, more reduces the biodegradability of waste water, and the ratio shared by the composition of difficult for biological degradation is great, also becomes this kind of height
The intractable reason of the organic pharmacy waste water of concentration.
For features such as the organic concentration height of pharmacy waste water, difficult for biological degradation, Chinese scholars has carried out substantial amounts of work
Making, present stage main processing method is materializing strategy, chemical treatment and biochemical treatment.Materializing strategy mainly includes absorption, gas
The methods such as floating, coagulating sedimentation and membrance separation.Chemical treatment mainly includes chemistry redox method, core-loss shape, Fenton reagent
Method, various advanced oxidation processes etc..Biochemical treatment process mainly includes that Aerobic biological process, anaerobic bio-treated, Aerobic-anaerobic are raw
Thing Combined Processing, it is processing method conventional in pharmacy waste water that biochemical treatment plus depth processes (advanced oxidation processes).
The reaction of ozone and target contaminant is broadly divided into two kinds, one be ozone directly and object direct reaction, separately
One is that ozone is broken down into and reacts with object through base free radical.It is light that advanced oxidation processes utilizes certain approach to produce exactly
Base free radical, light base free radical has extremely strong activity, the larger molecular organics in waste water can be aoxidized small organic molecule
Or carbon dioxide and water.
Individually ozonation technology strictly speaking and is not belonging to advanced oxidation processes, produces a lot light owing to it is main
Base free radical, and catalytic ozonation is owing to having added appropriate catalyst on the basis of independent ozone oxidation, excites
Produce light base free radical and belong to the category of advanced oxidation processes.There are some researches show, by independent ozone oxidation gas chromatography and catalysis
The effect of ozone oxidation gas chromatography compares discovery, and independent ozone oxidation Organic substance has selectivity, the most specific to some
Organism kinds there is good oxidation effectiveness, and the oxidation scope of catalytic ozonation is more extensive, this be due to
Ozone molecule oxidation of organic compounds has selectivity, does not then have selectivity through base free-radical oxidation Organic substance, and the latter's is anti-simultaneously
Answer speed faster much than the former.Ozonation technology is because its strong oxidizing property can be effectively by difficult for biological degradation in waste water
Larger molecular organics direct oxidation or oxidation become easier biodegradable small organic molecule so that improve waste water can
Biochemical.And add catalyst ozone oxidation and can produce that hydroxyl radical free radical is this most optionally to be aoxidized Organic substance
Agent, increases the range of application of ozonation technology.
Summary of the invention
It is an object of the invention to provide a kind of simple to operate, stable, catalytic ozonation degree of depth rapidly and efficiently
The technique processing cephalo pharmacy waste water, with the problem solving to propose in above-mentioned background technology.
For achieving the above object, the present invention provides following technical scheme:
This technical scheme is for passing through submicron bubble after cephalo pharmacy cephalo pharmacy biochemical treatment water outlet being mixed with ozone
Generating means enters in the catalysis oxidizing tower utilizing device equipped with cycle of ozone, fills novel ozone catalysis and fill out in catalysis oxidizing tower
Material, carries out catalyzing oxidizing degrading, after fast reaction, qualified discharge for the Organic substance in waste water.
The technique of a kind of efficient catalytic ozonation advanced treating cephalo pharmacy waste water, specifically comprises the following steps that
(1) by the TJS-2016001 type ozone catalyst that quality is M1, it is loaded into being catalyzed in oxidizing tower packing layer；TJS-
2016001 type ozone catalyst are with porous material as carrier, use infusion process by Metal Palladium, platinum, ruthenium, nickel and burning thereof
Thing loads to prepare on porous material, and porous material includes activated carbon and zeolite；
(2) be Q by cephalo pharmacy biochemical treatment water outlet that quality is M2 with flow, concentration be that the ozone of C1 is passed through super simultaneously
Micron bubble generating means, control pressure, at 0.09-0.10MPa, enters catalysis oxidizing tower, the grain of ozone bubbles after being sufficiently mixed
Footpath controls between 200nm-4 μm；
(3) open ozone reclaim circulating device, by unreacted ozone completely collect laggard enter submicron bubble fill
Put, it is achieved ozone recycle and reuse；
(4) mixed liquor is in catalysis oxidizing tower after reacted time 15-60min, qualified discharge.
As the further scheme of the present invention: in described step (1), TJS-2016001 type ozone catalyst mass M 1 is
Process the 2-10% of waste water total amount, volume be 2.8-3.2L, TJS-2016001 type ozone catalyst be long 3-10mm, a diameter of
The cylindrical pellet of 2-5mm.
As the further scheme of the present invention: in described step (2), cephalo pharmacy biochemical treatment effluent characteristics M2 is 16-
18kg, COD value 100-300mg/L, ozone provides through ozonator, and flow Q is 0.45-0.55L/min, and concentration C 1 is 18-
22mg/L。
As the present invention further scheme: in described step (4), COD ＜ 50mg/L in the waste water after process.
Compared with prior art, the invention has the beneficial effects as follows:
1, TJS-2016001 type ozone catalyst, is that the one of independent research is with the porous material such as activated carbon, zeolite for carrying
Body, noble metal and the new and effective ozone catalyst of metal-oxide thereof such as supported palladium Pd, platinum pt, ruthenium Ru and nickel.There is spy
Different microstructure, hole prosperity, specific surface area huge (cellular), mechanical strength greatly, not cracky, acidproof alkali, high temperature resistant
Etc. advantage；On it, noble metal and the metal-oxide thereof of load can strengthen the catalytic capability to ozone, and promoting hydroxyl radical free radical has
Effect utilization rate, can remove the toxic organics in waste water more efficiently.
2, its principle of submicron bubble generating means is to make water mix with upward adverse flow of QI degree to mix, and ultrasonic cavitation disperse discharges
Submicron bubble highdensity, uniform, bubble diameter is between 200nm-4 μm, and bubble inclusion rate 84-90%, formation gas-liquid is mixed
Zoarium, makes waste water be sufficiently mixed with ozone, has both added ozone molecule and hydrone and the contact area of ozone catalyst, more hold
It is easily generated hydroxyl radical free radical, too increases the contact area of ozone molecule and hydroxyl radical free radical and Organic Pollutants in Wastewater matter,
Make degradation reaction more abundant.
3, catalytic ozonation and the micro-nano bubbler techniques of ozone have been carried out the combination of creativeness by this technical scheme, significantly
Improving ozone utilization rate, every mg COD that degrades consumes ozone and is less than 2mg, consumes ozone with the prior art every mg COD of degraded
It is the most notable that 4mg compares technological progress；
4, the cephalo pharmacy biochemical treatment water outlet processed through the technical program, COD, by 200-300mg/L, is down to 50mg/L,
Meet the requirement of pharmacy waste water discharge one-level A standard；Solve the technical barrier of puzzlement cephalo pharmacy corporation discharged wastewater met the national standard；
5, whole set process is stable, processing speed is fast, with low cost, can directly apply to cephalo pharmacy waste water depth
Reason, had both eliminated the pollutant that biochemical treatment is difficult to degrade, had improve again treatment effeciency.
Detailed description of the invention
Below in conjunction with the embodiment of the present invention, the technical scheme in the embodiment of the present invention is clearly and completely described,
Obviously, described embodiment is only a part of embodiment of the present invention rather than whole embodiments.Based in the present invention
Embodiment, the every other embodiment that those of ordinary skill in the art are obtained under not making creative work premise, all
Belong to the scope of protection of the invention.
Embodiment 1
(1) by the TJS-2016001 type ozone catalyst of 0.51kg (processing the 3% of wastewater quality), it is packed into uniformly
In catalysis oxidizing tower packing layer；
(2) by cephalo pharmacy biochemical treatment water outlet (cephalo synthesis technique) that quality is 17kg (volume is about 17L), detection
COD value is 272mg/L, squeezes into submicron bubble generating means through pump；
(3) being provided by ozonator, flow is 1.0L/min, and concentration is that the ozone of 72mg/L is under pressure 0.095Map
Being passed through submicron bubble generating means, mixed liquor is squeezed into catalysis oxidizing tower through pump after being sufficiently mixed by ozone and waste water；
(4) ozone opening catalysis oxidizing tower top reclaims circulating device, when mixed liquor is reacted in being catalyzed oxidizing tower
Between after 1h, detection water outlet COD value is 33mg/L.
Embodiment 2
(1) by the TJS-2016001 type ozone catalyst of 0.85kg (processing the 5% of wastewater quality), it is packed into uniformly
In catalysis oxidizing tower packing layer；
(2) by cephalo pharmacy biochemical treatment water outlet (cephalo synthesis technique) that quality is 17kg (volume is about 17L), detection
COD value is 272mg/L, squeezes into submicron bubble generating means through pump；
(3) being provided by ozonator, flow is 1.0L/min, and concentration is that the ozone of 72mg/L is under pressure 0.095Map
Being passed through submicron bubble generating means, mixed liquor is squeezed into catalysis oxidizing tower through pump after being sufficiently mixed by ozone and waste water；
(4) ozone opening catalysis oxidizing tower top reclaims circulating device, when mixed liquor is reacted in being catalyzed oxidizing tower
Between after 1h, detection water outlet COD value is 33mg/L.
Embodiment 3
(1) by the TJS-2016001 type ozone catalyst of 0.85kg (processing the 5% of wastewater quality), it is packed into uniformly
In catalysis oxidizing tower packing layer；
(2) by cephalo pharmacy biochemical treatment water outlet (cephalo synthesis technique) that quality is 17kg (volume is about 17L), detection
COD value is 272mg/L, squeezes into submicron bubble generating means through pump；
(3) being provided by ozonator, flow is 1.0L/min, and concentration is that the ozone of 81mg/L is under pressure 0.095Map
Being passed through submicron bubble generating means, mixed liquor is squeezed into catalysis oxidizing tower through pump after being sufficiently mixed by ozone and waste water；
(4) ozone opening catalysis oxidizing tower top reclaims circulating device, when mixed liquor is reacted in being catalyzed oxidizing tower
Between after 1h, detection water outlet COD value is 26mg/L.
Embodiment 4
(1) by the TJS-2016001 type ozone catalyst of 0.51kg (processing the 3% of wastewater quality), it is packed into uniformly
In catalysis oxidizing tower packing layer；
(2) by cephalo pharmacy biochemical treatment water outlet (cephalo synthesis technique) that quality is 17kg (volume is about 17L), detection
COD value is 272mg/L, squeezes into submicron bubble generating means through pump；
(3) being provided by ozonator, flow is 1.0L/min, and concentration is that the ozone of 90mg/L is under pressure 0.095Map
Being passed through submicron bubble generating means, mixed liquor is squeezed into catalysis oxidizing tower through pump after being sufficiently mixed by ozone and waste water；
(4) ozone opening catalysis oxidizing tower top reclaims circulating device, when mixed liquor is reacted in being catalyzed oxidizing tower
Between after 1h, detection water outlet COD value is 35mg/L.
It is obvious to a person skilled in the art that the invention is not restricted to the details of above-mentioned one exemplary embodiment, Er Qie
In the case of the spirit or essential attributes of the present invention, it is possible to realize the present invention in other specific forms.Therefore, no matter
From the point of view of which point, all should regard embodiment as exemplary, and be nonrestrictive, the scope of the present invention is by appended power
Profit requires rather than described above limits, it is intended that all by fall in the implication of equivalency and scope of claim
Change is included in the present invention.
Claims (4)
1. the technique of an efficient catalytic ozonation advanced treating cephalo pharmacy waste water, it is characterised in that concrete steps are such as
Under:
(1) by the TJS-2016001 type ozone catalyst that quality is M1, it is loaded into being catalyzed in oxidizing tower packing layer；TJS-
2016001 type ozone catalyst are with porous material as carrier, use infusion process by Metal Palladium, platinum, ruthenium, nickel and burning thereof
Thing loads to prepare on porous material, and porous material includes activated carbon and zeolite；
(2) be Q by cephalo pharmacy biochemical treatment water outlet that quality is M2 with flow, concentration be that the ozone of C1 is passed through ultra micro rice simultaneously
Bubble generator, control pressure, at 0.09-0.10MPa, enters catalysis oxidizing tower, the particle diameter control of ozone bubbles after being sufficiently mixed
System is between 200nm-4 μm；
(3) open ozone and reclaim circulating device, unreacted ozone completely is collected laggard enter submicron bubble generating means, real
Existing ozone recycle and reuse；
(4) mixed liquor is in catalysis oxidizing tower after reacted time 15-60min, qualified discharge.
The technique of efficient catalytic ozonation advanced treating cephalo pharmacy waste water the most according to claim 1, its feature
Being, in described step (1), TJS-2016001 type ozone catalyst mass M 1 is to process the 2-10% of waste water total amount, and volume is
2.8-3.2L, TJS-2016001 type ozone catalyst is long 3-10mm, the cylindrical pellet of a diameter of 2-5mm.
The technique of efficient catalytic ozonation advanced treating cephalo pharmacy waste water the most according to claim 1, its feature
Being, in described step (2), cephalo pharmacy biochemical treatment effluent characteristics M2 is 16-18kg, COD value 100-300mg/L, ozone
Thering is provided through ozonator, flow Q is 0.45-0.55L/min, and concentration C 1 is 18-22mg/L.
The technique of efficient catalytic ozonation advanced treating cephalo pharmacy waste water the most according to claim 1, its feature
It is, in described step (4), COD ＜ 50mg/L in the waste water after process.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109205760A (en) * | 2018-10-12 | 2019-01-15 | 辽宁科技学院 | A kind of pretreated system of pharmacy waste water, method and catalyst |
| CN110773160A (en) * | 2019-11-08 | 2020-02-11 | 河北科技大学 | Ozone oxidation catalyst and preparation method and application thereof |
| WO2024138432A1 (en) * | 2022-12-28 | 2024-07-04 | 清华大学 | Method and device for treating wastewater containing organic pollutants |
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| CN104891713A (en) * | 2015-06-23 | 2015-09-09 | 杭州大地环保工程有限公司 | Catalytic ozonation process for treatment of organic wastewater |
| CN105502630A (en) * | 2016-02-02 | 2016-04-20 | 博天环境集团股份有限公司 | Treatment method of antibiotic production wastewater |
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| WO2001046074A1 (en) * | 1999-12-22 | 2001-06-28 | K-V Associates, Inc. | Springbox for water remediation |
| CN102115253A (en) * | 2011-01-14 | 2011-07-06 | 中国环境科学研究院 | Novel multi-technology synergetic catalysis advanced micro-bubble ozone oxidation tower |
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|---|---|---|---|---|
| CN109205760A (en) * | 2018-10-12 | 2019-01-15 | 辽宁科技学院 | A kind of pretreated system of pharmacy waste water, method and catalyst |
| CN109205760B (en) * | 2018-10-12 | 2021-06-04 | 辽宁科技学院 | System and method for pretreatment of pharmaceutical wastewater and catalyst |
| CN110773160A (en) * | 2019-11-08 | 2020-02-11 | 河北科技大学 | Ozone oxidation catalyst and preparation method and application thereof |
| WO2024138432A1 (en) * | 2022-12-28 | 2024-07-04 | 清华大学 | Method and device for treating wastewater containing organic pollutants |
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Application publication date: 20161214 |