CN101376549A - Method for comprehensively processing organic wastewater by ultrasonic field-inorganic membrane-photocatalysis oxidation - Google Patents
Method for comprehensively processing organic wastewater by ultrasonic field-inorganic membrane-photocatalysis oxidation Download PDFInfo
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- CN101376549A CN101376549A CNA2008101966165A CN200810196616A CN101376549A CN 101376549 A CN101376549 A CN 101376549A CN A2008101966165 A CNA2008101966165 A CN A2008101966165A CN 200810196616 A CN200810196616 A CN 200810196616A CN 101376549 A CN101376549 A CN 101376549A
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- organic wastewater
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- membrane
- ultrasonic field
- photocatalysis oxidation
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Abstract
The invention relates to an ultrasonic field-inorganic membrane-photocatalytic oxidation integrated method for organic wastewater treatment, which is characterized in that: the method comprises the following steps: the organic wastewater to be treated flows into a reaction kettle with a ultrasonic generator and is subjected to the ultrasonic photocatalytic oxidation reaction, to produce a photocatalytic oxidized organic wastewater degraded liquid; the organic wastewater degraded liquid is pumped to a separation system with a ultrasound-enhance membrane assembly for micro-filtration separation, and the dialysate liquid flows back to the reaction kettle after the micro-filtration separation in the ultrasound-enhance membrane assembly; and all the dialysate liquid is collected or flows back to the reaction kettle, or a part of the dialysate liquid is collected and the other flows back to the reaction kettle. The organic wastewater treatment method integrates the ultrasonic field, the inorganic membrane separation and the photocatalytic oxidation; can effectively solve the problems of low efficiency and slow reaction rate of photocatalytic degradation, difficulty in recycling photocatalysts, membrane pollution and concentration polarization in the prior art; and promotes the wide application of photocatalytic oxidation techniques.
Description
Technical field
The present invention relates to the treatment process of organic waste water, more specifically say so and carry out liquid-solid isolating method of wastewater treatment with photochemical catalytic oxidation bio-refractory organic waste water and to ultra-fine grain.
Background technology
Organism is a kind of novel water technology in the photochemical catalytic oxidation water, has suitable application potential.Up to now, catalyzer major part of photocatalysis technology research be ultra-fine micropowder, owing to the particulate super-refinement, utilizes to the Separation and Recovery of catalyzer again and to have brought very big difficulty, simultaneously, the low and speed of response of photocatalytic degradation efficient has all limited the large-scale application of photocatalysis oxidation technique slowly.
Characteristics such as the mineral membrane separation is acidproof because of having, alkaline-resisting, intensity is big have been applied on the photocatalysis oxidation technique, be expected to solve the recovery problem of ultrafine solids photocatalyst, but film pollutes and the concentration polarization phenomenon causes membrane flux decline that its practical application is restricted equally.
Summary of the invention
The present invention is directed to that photocatalytic oxidation degradation efficient is low, speed of reaction is slow, catalyst recovery is difficult, film pollutes and the problem of concentration polarization phenomenon, reach the mechanical effect that ultrasonic field shows at liquid and the characteristics of cavitation effect greatly in conjunction with mineral membrane separation efficiency height, intensity, provide a kind of ultrasonic field to strengthen the method for mineral membrane-Treatment by Photocatalysis Oxidation organic waste water, with the low and slow problem of speed of reaction of recovery, photocatalytic degradation efficient that solves catalyzer, advance the industrial applications of photocatalysis oxidation technique.
The technical scheme that technical solution problem of the present invention is adopted is:
The characteristics that ultrasonic field of the present invention is strengthened the method for mineral membrane-Treatment by Photocatalysis Oxidation organic waste water are to be undertaken by following technical process:
A, pending organic waste water enter the reactor that is provided with ultrasonic generator and carry out ultrasound light-catalyzed oxidizing reaction, obtain the organic wastewater degraded solution through photochemical catalytic oxidation;
B, organic wastewater degraded solution pump into the separation system with ultrasound-enhanced membrane module and carry out the micro-filtration separation, and after ultrasound-enhanced membrane module was finished the micro-filtration separation, trapped fluid was back to reactor; Penetrating fluid or all be collected, or all be back to reactor, or part is collected another part and is back to reactor.
The characteristics of the inventive method also are:
In ultrasonic generator in described reactor and the separation system and the ultrasound-enhanced membrane module ultrasonic transduction power all≤600W, frequency is 20-100KHz.
The photocatalyst that uses in described photocatalysis oxidation reaction is that concentration is 0.5g.L
-1-5.0g.L
-1TiO
2, ZnO, Cu
2O or ZnS; Used light source is that power is that ultraviolet lamp or the power of 8-100W is the mercury lamp of 100-500W; Described photocatalysis oxidation reaction temperature is 20-40 ℃, and the reaction times is 1-7 hour.
Described pending organic waste water adopted 0.1-2mol.L before entering reactor
-1Sulfuric acid and sodium hydroxide regulate its pH value for 2.0-6.0.
Pressure when described photocatalyst separates in separation system is set to 0.05-0.5MPa, temperature is 20-40 ℃.
In described separation system inorganic ceramic film is set, described inorganic ceramic film is Al
2O
3, ZrO
2, TiO
2Or SiO
2The porous ceramic film of inorganic materials preparation.
Described inorganic ceramic film is long to be 100-1000mm, and external diameter is 50-200mm, and internal diameter is 30-180mm, and the mean pore size of film pipe is 0.2 μ m, 0.5 μ m or 50nm.
Compared with the prior art, beneficial effect of the present invention is embodied in:
1, the inventive method is a kind of with ultrasonic field, mineral membrane separation and photocatelysis oxidation integrated method.Ultrasonic wave and liquid effects produce non-thermal effect, and it is fierce and mechanical movement fast and cavitation phenomenon can significantly improve photocatalytic degradation efficient to show as liquid, and can strengthen inorganic membrane separation efficiency.The present invention has the novel ultrasonic field of the continous way of pilot scale to strengthen photochemical catalysis-mineral membrane separation integrated reactor, and reactor design is simple, and is easy to operate, has industrial application value.The present invention has concentrated the characteristics of ultrasonic field, photocatalysis oxidation technique, mineral membrane isolation technique and gas backwash technology, it is isolating integrated to have realized that on the basis of photochemical catalysis-membrane sepn ultrasonic field is strengthened photochemical catalytic oxidation-mineral membrane, makes photochemical catalytic oxidation efficient and membrane sepn efficient all obtain improving largely.The present invention not only can carry out batch operation but also can carry out the continous way operation feed liquid, both can be used as and had independently operated system, can be used as an operating unit in the industrial production flow process again.
2, adopt inorganic ceramic film in the inventive method, because characteristics such as mineral membrane has anti-strong acid, anti-highly basic, chemical stability is good and machine capability is strong, so can either under high-risk conditions such as strong acid and strong base, work, also can bear ultrasonic strong mechanical effect and the cavitation effect that produces, effectively avoid the damage of face, be of value to the strengthening effect that realizes ultrasonic field.
3, two steps in the inventive method can be carried out under normal temperature 20-40 ℃, thereby can effectively reduce running cost.
4, used catalyzer both can be TiO in the inventive method
2Ultra-fine micropowder also can be other micro mists with photocatalytic activity, ultra-fine micropowder, nano powder, can realize the high-level efficiency and the high stability of catalyzing oxidizing degrading reaction.
5, the present invention both had been applicable to laboratory study, also was applicable to medium-sized engineering of water treatment of factory or superfine powder separation engineering.
Description of drawings
Fig. 1 is a process flow diagram of the present invention.
Number in the figure: 1 reactor, 2 ultrasonic transmitters, 3 cold-traps, 4 low pressure mercury lamps, 5 impeller pumps, 6 separation systems, 7 spinner-type flowmeter A, 8 spinner-type flowmeter B, 9 gas-holder, 10 air compressor, 11 back-purge systems.
Fig. 2 is that the employed ultrasonic field of the inventive method is strengthened mineral membrane separation system synoptic diagram.
Number in the figure: 12 feed liquids inlet, 13 inorganic ceramic films, 14 membrane modules, 15 separation system ultrasonic transmitters, the outlet of 16 penetrating fluids, 17 joint flanges, the outlet of 18 trapped fluids.
Below pass through embodiment, and in conjunction with the accompanying drawings the present invention be further described:
Embodiment
Referring to Fig. 1, in reactor 1, be positioned at its central authorities cold-trap 3 is set, low pressure mercury lamp 4 is arranged in the cold-trap 3, and ultrasonic transmitter 2 is set below cold-trap 3.
Referring to Fig. 2, ultrasound-enhanced film separating system 6 is a tubular structure in concrete the enforcement, in membrane module 14, separation system ultrasonic transmitter 15 is positioned at cylindrical shell central authorities, in the periphery of separation system ultrasonic transmitter 15, the inboard that is positioned at membrane module 14 tubulose inorganic ceramic film 13 is set, feed liquid inlet 12 is positioned at the top of membrane module 14, and penetrating fluid outlet 16 is positioned at the below sidepiece of membrane module 14, trapped fluid outlet 18 is positioned at the bottom of membrane module 14, and joint flange 17 is set routinely.
Overall system by the technical process setting constitutes:
Pending organic waste water output channel is set to be communicated with the input channel of reactor 1 through control valve V0;
Organic wastewater degraded solution output channel in the reactor 1 is communicated with the input channel of separation system 6 by impeller pump 5; Separation system 6 has the liquid of damming output channel and the output of penetrating fluid output channel two-way, and wherein, the trapped fluid output channel is communicated with the input channel of reactor 1 by control valve V8, spinner-type flowmeter A7; The penetrating fluid output channel branches into two-way by after the control valve V6, and the spinner-type flowmeter B8 of leading up to is communicated with the input channel of reactor 1; Another road is by control valve V10 and permeate collection channel connection.
The pressurized air output channel of the back-purge system that is made of gas-holder 9 and air compressor 10 is set to the bypass input channel of penetrating fluid output channel.
Above system is provided with and can realizes continuous production.
Pending organic waste water enters the reactor 1 that is provided with ultrasonic generator 2 through control valve V0 and carries out ultrasound light-catalyzed oxidizing reaction, obtains the organic wastewater degraded solution through photochemical catalytic oxidation.
Organic wastewater degraded solution provides power to enter to have the separation system 6 of ultrasound-enhanced membrane module to carry out micro-filtration by pump 5 to separate, and after ultrasound-enhanced membrane module was finished micro-filtration and separated, trapped fluid was back to reactor 1 by spinner-type flowmeter A7 metering; Penetrating fluid can all flow out as product by control valve V10 and obtain collecting, or all is back to reactor 1 recycling by spinner-type flowmeter 8 meterings; Or the effect by control valve V10, control wherein part or all penetrating fluid is flowed out as product.This total reflux, partial reflux and do not have the different path combinations of backflow, can control the residence time of different concns organic waste water solution in reactor, both can satisfy the needs of the actual organic waste water of business processes engineering, also can satisfy the requirement of enterprise's pilot scale amplification or R﹠D institution's laboratory study.
Embodiment 1:
With the methyl orange solution is object, and the total reflux penetrating fluid is handled methyl orange solution
TiO
2The suspension vol that-methyl orange solution is formed is 15L, temperature 20-40 ℃, and TiO
2Consumption 2.0g.L
-1, the starting point concentration of tropeolin-D is 15mg.L
-1, the pH value is 4.0, is under the mercury lamp of the ultraviolet lamp of power 8-100W or power 100-500W at ultraviolet source; Ultrasonic power 0-600W; Frequency is to add reactor under the condition of 21KHz to carry out ultrasonic field and strengthen photocatalysis oxidation reaction, is delivered to ultrasonic field through impeller pump and strengthens the mineral membrane separator.At working pressure is 0.05-0.5MPa, and cross-flow velocity is 1.0m.s
-1, recoil pressure is 0.6MPa, and the recoil time is 3s, and the recoil cycle is 10min, ultrasonic power 180W, frequency is under the condition of 21KHz, photocatalyst TiO
2After the micro-filtration separation was finished, trapped fluid and penetrating fluid after the spinner-type flowmeter metering, all were back to reactor and continue circulation, 6 hours reaction times respectively.
Test result after permeate flow, the concentration stabilize shows: the degradation rate of methyl orange solution is 76.7% during no ultrasonic radiation, and the degradation rate of methyl orange solution can reach 90.3% when ultrasonic field was arranged, and ultrasonic field can improve the catalyzing oxidizing degrading rate about 14%.TiO
2The catalyzer rejection can reach 99.9%.
Embodiment 2:
With the phenol solution is object, and the partial reflux method is handled phenol solution
Reactor inner control TiO
2-phenol suspension cumulative volume stabilizes to 15L, and temperature of reaction 20-40 ℃, TiO
2Catalyst levels 2.0g.L
-1, phenol solution starting point concentration 200mg.L
-1, pH value 4.0.At ultraviolet source is the ultraviolet lamp of power 36W, ultrasonic power 0-600W, frequency is under the condition of 21KHz, phenol solution adds reactor continuously with 5 liters flow per hour and carries out ultrasonic field and strengthen photocatalysis oxidation reaction, be delivered to ultrasonic field through impeller pump and strengthen the mineral membrane separator, at working pressure 0.05-0.5MPa, cross-flow velocity 1.0m.s
-1, recoil pressure 0.6MPa, 3 seconds recoil time, the recoil cycle is 10 minutes, ultrasonic power 180W is under the condition of frequency 21KHz, to photocatalyst TiO
2Carrying out micro-filtration separates.After reaction-sepn process is finished, trapped fluid is back to reactor after the spinner-type flowmeter metering, penetrating fluid is after the synergy of control valve, spinner-type flowmeter, and a part flows out as product continuously with 5 liters flow per hour and obtains, and another part is back to reactor.
Test result after permeate flow, the concentration stabilize shows: TiO
2The catalyzer rejection can reach 99.9%, the degradation rate that no ultrasonic field is made the time spent phenol solution is about 35%, the degradation rate of phenol solution can reach about 51% when ultrasonic radiation was arranged, and when having realized that phenol solution is handled in serialization, ultrasonic field can improve about 16% with the catalyzing oxidizing degrading rate.
Claims (7)
1, the method for comprehensively processing organic wastewater by ultrasonic field-inorganic membrane-photocatalysis oxidation is characterized in that being undertaken by following technical process:
A, pending organic waste water enter the reactor (1) that is provided with ultrasonic generator (2) and carry out ultrasound light-catalyzed oxidizing reaction, obtain the organic wastewater degraded solution through photochemical catalytic oxidation;
B, organic wastewater degraded solution pump into the separation system (6) with ultrasound-enhanced membrane module and carry out the micro-filtration separation, and after ultrasound-enhanced membrane module was finished the micro-filtration separation, trapped fluid was back to reactor (1); Penetrating fluid or all be collected, or all be back to reactor (1), or part is collected another part and is back to reactor (1).
2, the method for comprehensively processing organic wastewater by ultrasonic field-inorganic membrane-photocatalysis oxidation according to claim 1, it is characterized in that in ultrasonic generator in described reactor (1) and the separation system (6) and the ultrasound-enhanced membrane module ultrasonic transduction power all≤600W, frequency is 20-100KHz.
3, the method for comprehensively processing organic wastewater by ultrasonic field-inorganic membrane-photocatalysis oxidation according to claim 1 is characterized in that the photocatalyst that uses is that concentration is 0.5g.L in described photocatalysis oxidation reaction
-1-5.0g.L
-1TiO
2, ZnO, Cu
2O or ZnS; Used light source is that power is that ultraviolet lamp or the power of 8-100W is the mercury lamp of 100-500W; Described photocatalysis oxidation reaction temperature is 20-40 ℃, and the reaction times is 1-7 hour.
4, the method for comprehensively processing organic wastewater by ultrasonic field-inorganic membrane-photocatalysis oxidation according to claim 1 is characterized in that described pending organic waste water is entering reactor (1) before, adopts 0.1-2mol.L
-1Sulfuric acid and sodium hydroxide regulate its pH value for 2.0-6.0.
5, the method for comprehensively processing organic wastewater by ultrasonic field-inorganic membrane-photocatalysis oxidation according to claim 3 is characterized in that the pressure when photocatalyst separates is set to 0.05-0.5MPa, temperature is 20-40 ℃ in separation system (6).
6, ultrasonic field according to claim 1 is strengthened the method for mineral membrane-Treatment by Photocatalysis Oxidation organic waste water, it is characterized in that inorganic ceramic film (13) is set in described separation system (6), and described inorganic ceramic film is Al
2O
3, ZrO
2, TiO
2Or SiO
2The porous ceramic film of inorganic materials preparation.
7, the method for comprehensively processing organic wastewater by ultrasonic field-inorganic membrane-photocatalysis oxidation according to claim 6, it is characterized in that the long 100-1000mm of being of described inorganic ceramic film (13), external diameter is 50-200mm, and internal diameter is 30-180mm, and the mean pore size of film pipe is 0.2 μ m, 0.5 μ m or 50nm.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101966165A CN101376549A (en) | 2008-09-12 | 2008-09-12 | Method for comprehensively processing organic wastewater by ultrasonic field-inorganic membrane-photocatalysis oxidation |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNA2008101966165A CN101376549A (en) | 2008-09-12 | 2008-09-12 | Method for comprehensively processing organic wastewater by ultrasonic field-inorganic membrane-photocatalysis oxidation |
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ID=40420294
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101704600B (en) * | 2009-11-19 | 2011-05-25 | 同济大学 | Segmented treatment method of high-concentration high-chromaticity dye wastewater |
| CN101596409B (en) * | 2009-06-12 | 2011-07-27 | 南京中医药大学 | Ceramic membrane separation on-line coupling ultrasonic method of traditional Chinese medicine liquid preparation |
| CN103241881A (en) * | 2013-04-12 | 2013-08-14 | 宁波大学 | Method for expanding capacity of reactor capable of actively detecting agglomeration incentives and used for photocatalytic wastewater degradation |
| CN112390324A (en) * | 2020-12-07 | 2021-02-23 | 福州大学 | Novel acousto-optic catalytic water purifying device and working method thereof |
-
2008
- 2008-09-12 CN CNA2008101966165A patent/CN101376549A/en active Pending
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101596409B (en) * | 2009-06-12 | 2011-07-27 | 南京中医药大学 | Ceramic membrane separation on-line coupling ultrasonic method of traditional Chinese medicine liquid preparation |
| CN101704600B (en) * | 2009-11-19 | 2011-05-25 | 同济大学 | Segmented treatment method of high-concentration high-chromaticity dye wastewater |
| CN103241881A (en) * | 2013-04-12 | 2013-08-14 | 宁波大学 | Method for expanding capacity of reactor capable of actively detecting agglomeration incentives and used for photocatalytic wastewater degradation |
| CN103241881B (en) * | 2013-04-12 | 2015-11-25 | 宁波大学 | The photocatalytic waste water degradation reactor expansion method initiatively can detected reunion inducement |
| CN112390324A (en) * | 2020-12-07 | 2021-02-23 | 福州大学 | Novel acousto-optic catalytic water purifying device and working method thereof |
| CN112390324B (en) * | 2020-12-07 | 2023-10-31 | 福州大学 | Novel acousto-optic catalytic water purifying device and working method thereof |
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Open date: 20090304 |