CN105060364B - A kind of organic wastewater in-situ treatment fixed bed and processing unit and processing method - Google Patents
A kind of organic wastewater in-situ treatment fixed bed and processing unit and processing method Download PDFInfo
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- CN105060364B CN105060364B CN201510468467.3A CN201510468467A CN105060364B CN 105060364 B CN105060364 B CN 105060364B CN 201510468467 A CN201510468467 A CN 201510468467A CN 105060364 B CN105060364 B CN 105060364B
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Abstract
The invention discloses a kind of organic wastewater in-situ treatment fixed bed and processing unit and processing method, fixed bed includes fixed bed ontology, and solid gallbladder is provided in fixed bed ontology, Gu iron-based sensitizer is filled in gallbladder.Processing unit includes device noumenon and the mobile device for being mounted on device noumenon lower end, device noumenon is internally provided with aerator, fixed bed, microwave cavity and microwave generating apparatus, wherein, the aerator is connected to the bottom end of fixed bed, the fixed bed is mounted in microwave cavity, microwave cavity is connect with microwave generating apparatus, and the fixed bed outside pipeline and device noumenon by being connected to.Organic wastewater enters after pre-acidified in the fixed bed of wastewater treatment equipment；Degradation and mineralising under the action of iron-based sensitizer and microwave in fixed bed.The iron-based sensitizer fixed bed of microwave of the invention realizes continuous, efficient, the quick processing of waste water；Iron-based sensitizer is environment-friendly material, will not lead to the problem of secondary pollution.
Description
Technical field
The invention belongs to technical field of waste water processing, and in particular to a kind of organic wastewater in-situ treatment fixed bed and processing dress
It sets and processing method.
Background technique
Organic wastewater with difficult degradation thereby can enter environment water by approach such as leakage, discharge of wastewater and Pesticide uses, be not easy
It decomposes or biodegradable, is easy to be enriched with accumulation in organism, water body and soil, to cause persistent pollution to environment.Institute
Important reality meaning is suffered to protection environment, maintenance ecology and guarantee health with being effectively treated for organic wastewater with difficult degradation thereby
Justice.
Organic wastewater with difficult degradation thereby is handled by biological method, generally requires longer hydraulic detention time, and handle effect
Rate is extremely low.In general, organic wastewater with difficult degradation thereby is mainly handled by high-level oxidation technology, needs to consume a large amount of oxidants, from
And generate higher cost.In addition, many organic wastewaters are shallow bid waste water when generating, row processing again, collects process after needing to collect
It needs to carry out pipe-line construction, not only land occupation, it is also possible to which leakage causes soil and groundwater to pollute.The present invention utilizes microwave
Form fixed bed with iron-based sensitizer, can with the processing organic wastewater with difficult degradation thereby of continuous high-efficient and other organic wastewaters, it can be achieved that
Organic wastewater convenient processing in situ, there is more wide application prospect.
Summary of the invention
In order to solve the technical problems existing in the prior art, the object of the present invention is to provide at a kind of organic wastewater original position
Manage fixed bed and processing unit and processing method.
In order to solve the above technical problems, technical scheme is as follows:
A kind of organic wastewater in-situ treatment fixed bed, including fixed bed ontology are provided with solid gallbladder in fixed bed ontology, Gu gallbladder
It is interior be filled with iron-based sensitizer, the iron-based sensitizer be Nanoscale Iron, active carbon and cobalt Raney nickel mixture, Nanoscale Iron and
The mass ratio of active carbon is 1:1-3:1, and cobalt Raney nickel is the 10%-20% of iron carbon gross mass.
Preferably, the fixed bed is additionally provided with mixing section, and the lower end of the solid gallbladder, the mixing section is arranged in mixing section
Bottom be provided with aerator, the upper end of aerator is provided with recycling waste water import.Waste water is abundant with oxygen in mixing section
It after mixing, degrades using solid gallbladder, the degradation and catalytic action of iron-based sensitizer can be given full play in this way, due to iron-based
Sensitizer participates in degradation reaction, so can be lossy, the part of loss can be supplemented.
It is further preferred that the upper end of the solid gallbladder is provided with heat exchange segment, it is respectively arranged with and follows above heat exchange segment
Ring wastewater outlet, treated water outlet and exhaust outlet, recycling waste water outlet and recycling waste water inlet communication.Heat exchange segment is for preheating
On the other hand water inlet and cooling water outlet mainly keep leaving water temperature not so high, avoid to work on the one hand for energy saving
Personnel generate harm.
Preferably, the lower end of the heat exchange segment is arranged in water intake.Waste water needs after heat exchange segment preheats,
It enters back into solid gallbladder and degrades, be greatly improved the treatment effeciency of waste water.
A kind of organic wastewater in-situ treatment device, including device noumenon and the mobile device for being mounted on device noumenon lower end,
Device noumenon is internally provided with aerator, fixed bed, microwave cavity and microwave generating apparatus, wherein the aerator
It is connected to the bottom end of fixed bed, the fixed bed is mounted in microwave cavity, and microwave cavity is connect with microwave generating apparatus, described
Fixed bed outside pipeline and device noumenon by being connected to.
Preferably, it is connected between microwave cavity and microwave generating apparatus by circulator.Circulator is recycled by water, to protect
Protect magnetron.
Preferably, microwave generating apparatus is industrial microwave oven, has magnetron protective device.It can prevent microwave device from connecting
Continuous work damages magnetron.
Preferably, the upper end of the fixed bed is provided with recycling waste water outlet, treated water outlet and exhaust outlet, fixed bed
Lower end be provided with the recycling waste water entrance with recycling waste water outlet, treated water outlet and exhaust outlet pass through the first pipe respectively
It is connected to outside road and second pipe and device noumenon.Be arranged recycling waste water export and import, be in order to make waste water preheat after carry out
Degradation, and may degrade for wastewater degradation one time and be not thorough, circulation degradation can be carried out at this time, until heel row up to standard of degrading
It puts.
It is further preferred that being provided with condenser in the first pipe.Condenser can carry out the moisture in tail gas
Tail gas moisture is recycled in condensation.
It is further preferred that being connected between the condenser and second pipe by third pipeline.The water of condenser condensation,
It is entered in second pipe by third pipeline and is recycled together with purified water, save pipeline.
A kind of organic wastewater in-situ treatment method, includes the following steps:
1) wastewater treatment equipment is drawn to appropriate position, organic wastewater is after pre-acidified into wastewater treatment equipment
The continuous aeration in fixed bed and into fixed bed；
2) after waste water is preheated, degradation and mineralising under the action of iron-based sensitizer and microwave in fixed bed；
3) purified water and exhaust gas are discharged.The temperature of purified water can be recycled at 70 DEG C or so.
Preferably, in step 1), the pre-acidified acid is hydrochloric acid or sulfuric acid.
It is further preferred that the pH value of the waste water after pre-acidified is less than 7.0 in step 1).
Preferably, the output power of the microwave is 400-1000W.Under the output power, the degradation effect of waste water compared with
It is good.
Preferably, in step 2), the iron-based sensitizer is the mixture of Nanoscale Iron, active carbon and cobalt Raney nickel, is received
The mass ratio of meter Tie and active carbon is 1:1-3:1, and cobalt Raney nickel is the 10%-20% of iron carbon gross mass.The iron-based sensitizer
Realize continuous, efficient, the quick processing of waste water；Iron-based sensitizer is environment-friendly material, will not lead to the problem of secondary pollution.
It is further preferred that the fixed bed includes mixing section, solid gallbladder and heat exchange segment from top to bottom in step 2), mix
Aerator is installed in the lower end for closing section, and recycling waste water entrance is arranged in the top of aerator, Gu filled with described iron-based quick in gallbladder
Agent is provided with recycling waste water outlet, treated water outlet and exhaust outlet, the lower section setting of heat exchange segment above heat exchange segment
Waste water inlet.Recycling waste water export and import is set, is to degrade after preheating waste water, and wastewater degradation one time can
It can degrade and be not thorough, circulation degradation can be carried out at this time, until rear discharge up to standard of degrading.
It is further preferred that the treatment process of waste water includes the following steps: that waste water enters fixed bed by waste water inlet
Heat exchange segment preheated, be then recycled into mixing section and oxygen mix, enter back into solid gallbladder and degraded and purified, will give up
Water circulation degradation, after purification is up to standard, discharge.
It is further preferred that residence time of the waste water in solid gallbladder is 3-5 minutes.Under the residence time, it is ensured that
Reach best clean-up effect within the shortest time.
Advantageous effects of the invention are as follows:
1, the iron-based sensitizer fixed bed of microwave of the invention realizes continuous, efficient, the quick processing of waste water；It is iron-based quick
Agent is environment-friendly material, will not lead to the problem of secondary pollution；
2, the present invention can be used for the pretreatment of high concentrated organic wastewater, it can also be used to the depth of low concentration used water difficult to degradate
Reason, application range are wider；
4, the method for the present invention can adapt to a variety of different organic wastewater solution, can adapt to organic wastewater change of water quality
Impact；
5, wastewater treatment equipment of the invention can be used for difficult to degrade and common organic wastewater continuous processing, can 5 minutes it
Inside obtain 90% or more removal efficiency；In addition, the wastewater treatment equipment can also move, by traction, waste water may be implemented
In-situ treatment.
6, since the water flowed out after wastewater treatment is hot water, it is possible to utilize Recovery of the hot water, save the energy.
Detailed description of the invention
Fig. 1 is processing technological flow structural schematic diagram of the invention；
Fig. 2 is the structural schematic diagram of fixed bed of the invention；
Fig. 3 is the curve graph that 1 Malachite Green degradation efficiency of embodiment changes with water velocity；
Fig. 4 is schematic diagram of the iron-based sensitizer of unit to malachite green degradation capacity with water velocity；
Fig. 5 is the curve graph that aeration mode influences malachite green degradation efficiency；
Fig. 6 is influence curve figure of the pre-acidified to malachite green degradation efficiency and TOC removal efficiency；
Fig. 7 is influence curve figure of the microwave power to malachite green degradation efficiency and TOC removal efficiency；
Fig. 8 is the anti-load impact performance chart of wastewater treatment equipment；
Fig. 9 is the main component chromatogram of wastewater treatment equipment exhaust.
Wherein, 1, pre-acidified tank, 2, solidification bed, 3, circulator, 4, microwave control device, 5, drier, 6, condenser, 7,
Microwave generating apparatus, 8, microwave cavity, 9, aerator, 10, mixing section, 11, solid gallbladder, 12, heat exchange segment.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention will be further described, but not limited to this.
As shown in Figure 1, a kind of organic wastewater in-situ treatment device, including device noumenon and is mounted on device noumenon lower end
Mobile device, the mobile device are generally configured to wheel, also may be designed to other transportable structures, such as crawler belt
Deng；Device noumenon is internally provided with aerator 9, fixed bed 2, microwave cavity and microwave generating apparatus, wherein the aeration
Device 9 is connected to the bottom end of fixed bed 2, and fixed bed 2 is mounted in microwave cavity 8, and microwave cavity 8 and microwave generating apparatus 8 connect
It connecing, microwave generating apparatus 8 is connect with microwave control device 4, and microwave control device 4 controls the output power of microwave generating apparatus 8,
Fixed bed 2 outside pipeline and device noumenon by being connected to.
It is connected between microwave cavity 8 and microwave control device 4 by circulator 3.
As shown in Fig. 2, fixed bed 2, including fixed bed ontology, be provided in fixed bed ontology solid gallbladder 11, mixing section 10 with
And heat exchange segment 12, Gu iron-based sensitizer is filled in gallbladder 11；The lower end of solid gallbladder 11, the bottom of mixing section 10 is arranged in mixing section 10
Portion is provided with aerator 9, and the upper end of aerator 9 is provided with recycling waste water import.The upper of solid gallbladder is arranged in heat exchange segment 12
End, the top of heat exchange segment 12 are respectively arranged with recycling waste water outlet, treated water outlet and exhaust outlet, and recycling waste water is exported and followed
The connection of ring waste water inlet.The lower end of heat exchange segment 12 is arranged in water intake.
Condenser 6 is provided in the first pipe, which can be used to condense the moisture in tail gas, tail gas warp
It is discharged into atmosphere after crossing the drying of drier 5 at 6 rear of condenser.
A kind of organic wastewater in-situ treatment method, includes the following steps:
1) wastewater treatment equipment is drawn to appropriate position, is entered at waste water after organic wastewater hydrochloric acid or sulfuric acid pre-acidified
Manage device fixed bed in and the continuous aeration into fixed bed；
2) after waste water is preheated, degradation and mineralising under the action of iron-based sensitizer and microwave in fixed bed；
3) purified water and exhaust gas are discharged.
The iron-based sensitizer is the mixture of Nanoscale Iron, active carbon and cobalt Raney nickel, the matter of Nanoscale Iron and active carbon
For amount than being 2:1, cobalt Raney nickel is the 15% of iron carbon gross mass.
The treatment process of waste water includes the following steps: that waste water enters the heat exchange segment 12 of fixed bed 2 by waste water inlet
It is preheated, is then recycled into mixing section 10 and oxygen mix, entered back into solid gallbladder 11 and degraded and purified, waste water is recycled
Degradation, after purification is up to standard, after the cooling of heat exchange segment 12, discharge.
The parameters of malachite green wastewater treatment are optimized:
Main reagent to be used is purchased from Tianjin chemical reagent research institute in the embodiment of the present invention, is that analysis is pure, packet
Include:, sodium chloride, sodium bicarbonate, concentrated hydrochloric acid, sodium hydroxide, malachite green.
Using the malachite green aqueous solution of different amounts of pure water dilution 2000mg/L to different working concentrations, as mould
Quasi- waste water.By simulated wastewater after the iron-based sensitizer fixed bed processing of portable microwave, the aqueous solution that obtains that treated uses purple
Outer visible spectrophotometer analysis malachite green concentration utilizes gas chromatographic analysis using the TOC of total organic carbon instrument analytical solution
Gas-phase product.The preferred method of condition is as follows:
(1) influence of waste water residence time in solid gallbladder
100mg/L malachite green solution is entered into water flow velocity (Q in differencei=4-24mL/min) it is passed through in fixed bed, it is fixed
Bed fillers be the iron-based sensitizer of 10g, waste water acidification after pH be 7.0, microwave power 600W, aeration rate be 20mL (air)/
The degradation versus time curve of min malachite green is shown in Fig. 3.
From the figure 3, it may be seen that the degradation of malachite green is divided into three phases, respectively rise period (< 30min), the stage of stable development (30-
140min), degradation period (140-170min).The degradation efficiency of malachite green gradually rises with the reduction for entering water flow velocity,
The average treatment efficiency of the stage of stable development is respectively 98.2% (Qi=4mL/min), 95.5% (Qi=8mL/min), 83.6% (Qi=
12mL/min), 75.0% (Qi=16mL/min), 63.5% (Qi=20mL/min), 37.5% (Qi=24mL/min).Unit
Iron-based sensitizer is shown in Fig. 4 with the variation for entering water flow velocity to the degradation capacity of malachite green.As shown in Figure 4, the iron-based sensitizer of unit
Q is appeared in the degradation maximum capacity of malachite greeniAt=16mL/min, so, when the iron-based sensitizer of portable microwave is fixed
When bed is used for pre-treating high concentration organic waste water, Q can be usedi=16mL/min, and be used for meet the depth of discharge standard
When processing, can be used it is lower enter water flow velocity until wastewater to reach standard.
(2) influence of the aeration process to reaction
Air, O is respectively adopted2、N2Aeration, and the feasibility of preaeration is had studied, as shown in Figure 5.As shown in Figure 5, peacock
Malachite green degradation has with oxygen content in aeration compared with Important Relations, but uses pure oxygen aeration, be easy to cause the aging of iron-based sensitizer with
Failure.So situation should be required according to waste water quality and water outlet, suitable aeration mode is selected.
(3) pre-acidified is to the degradation of malachite green and the influence of mineralising efficiency
By 100mg/L malachite green solution to enter water flow velocity (Qi=4mL/min) it is passed through in fixed bed, fixed bed fillers are
The iron-based sensitizer of 10g, it is pH 7.0 that waste water is gradually acidified by pH 9.0, is 600W, aeration rate 20mL in microwave power
(air) under conditions of/min, the degradation efficiency and TOC removal efficiency versus time curve of malachite green are shown in Fig. 6.
It will be appreciated from fig. 6 that pre-acidified can be improved the degradation efficiency and TOC removal efficiency of malachite green, it is therefore necessary to
Pre-acidified link is added between fixed bed.
(4) influence of microwave power
By 100mg/L malachite green solution to enter water flow velocity (Qi=4mL/min) it is passed through in fixed bed, fixed bed fillers are
The iron-based sensitizer of 10g, microwave power is gradually increased by 0 as 1000W, and in pH7.0, aeration rate is the item of 20mL (air)/min
Under part, the degradation efficiency and TOC removal efficiency versus time curve of malachite green are shown in Fig. 7.
As shown in Figure 7, the introducing of microwave greatly improves malachite green degradation efficiency and TOC removal efficiency, but with micro-
The raising of wave power, removal efficiency increase trend and gradually slow down, so may be selected lower under the premise of meeting water outlet requirement
Microwave output power, it is energy saving to achieve the purpose that.
(5) the anti-load impact performance of system
Malachite green is entered into water concentration, 200mg/L is increased to by 100mg/L suddenly, the stability of system water outlet is shown in Fig. 8.
As shown in Figure 8, system has preferable anti-load impact performance, after waste strength is increased to 200mg/L suddenly, system still have compared with
High treatment effeciency and preferable outlet effect, sensitizer fails after 120min, and treatment effeciency declines to a great extent, aqueous concentration liter
It is high.
(2) main component being vented
O is respectively adopted2、N2Aeration collects its main component of exhaust gas analysis, sees Fig. 9.As shown in Figure 9, master is vented outside system
Wanting ingredient is CO2, illustrate that malachite green realizes complete mineralising under systemic effect, and the gas generated can direct outlet.
Above-mentioned, although the foregoing specific embodiments of the present invention is described with reference to the accompanying drawings, not to invention protection scope
Limitation, those skilled in the art should understand that, based on the technical solutions of the present invention, those skilled in the art are not required to
It is still within the scope of the present invention to make the creative labor the various modifications or changes that can be made.
Claims (7)
1. a kind of organic wastewater in-situ treatment device, it is characterised in that: including device noumenon and be mounted on device noumenon lower end
Mobile device, device noumenon are internally provided with aerator, fixed bed, microwave cavity and microwave generating apparatus, wherein described
Aerator is connected to the bottom end of fixed bed, and the fixed bed is mounted in microwave cavity, microwave cavity and microwave generating apparatus
Connection, the fixed bed outside pipeline and device noumenon by being connected to；
The upper end of the fixed bed is provided with recycling waste water outlet, treated water outlet and exhaust outlet, the lower end setting of fixed bed
There is the recycling waste water entrance with recycling waste water outlet, treated water outlet and exhaust outlet pass through first pipe and the second pipe respectively
It is connected to outside road and device noumenon；
The fixed bed includes fixed bed ontology, is filled with iron-based sensitizer, the iron-based sensitization in the solid gallbladder of fixed bed ontology
Agent is the mixture of Nanoscale Iron, active carbon and cobalt Raney nickel, and the mass ratio of Nanoscale Iron and active carbon is 1:1-3:1, and cobalt nickel is urged
Agent is the 10%-20% of iron carbon gross mass；
The fixed bed is additionally provided with mixing section, and the lower end of the solid gallbladder, the bottom setting of the mixing section is arranged in mixing section
There is aerator, the upper end of aerator is provided with recycling waste water import；
The upper end of the solid gallbladder is provided with heat exchange segment, and recycling waste water outlet, purified water are respectively arranged with above heat exchange segment
Outlet and exhaust outlet, recycling waste water outlet and recycling waste water inlet communication.
2. the organic wastewater in-situ treatment method carried out using organic wastewater in-situ treatment device described in claim 1, special
Sign is: including the following steps:
1) wastewater treatment equipment is drawn to appropriate position, organic wastewater enters the fixation of wastewater treatment equipment after pre-acidified
Bed in and the continuous aeration into fixed bed；
2) after waste water is preheated, degradation and mineralising under the action of iron-based sensitizer and microwave in fixed bed；
3) purified water and exhaust gas are discharged.
3. processing method according to claim 2, it is characterised in that: in step 1), the pH value of the waste water after pre-acidified is small
In 7.
4. processing method according to claim 2, it is characterised in that: the output power of the microwave is 400-1000W.
5. processing method according to claim 2, it is characterised in that: in step 2), the fixed bed includes from top to bottom
Aerator is installed in mixing section, solid gallbladder and heat exchange segment, the lower end of mixing section, and the top setting recycling waste water of aerator enters
Mouthful, it is solid that the iron-based sensitizer is filled in gallbladder, be provided with above heat exchange segment recycling waste water export, treated water outlet and
Waste water inlet is arranged in the lower section of exhaust outlet, heat exchange segment.
6. processing method according to claim 5, it is characterised in that: the treatment process of waste water includes the following steps: waste water
It is preheated by the heat exchange segment that waste water inlet enters fixed bed, is then recycled into mixing section and oxygen mix, then into
Enter solid gallbladder to be degraded and purified, waste water is recycled and is degraded, after purification is up to standard, discharge.
7. processing method according to claim 6, it is characterised in that: residence time of the waste water in solid gallbladder is 3-5 minutes.
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| CN102992444B (en) * | 2012-12-25 | 2014-07-16 | 湘潭大学 | Method for degrading organic wastewater by adopting active carbon-based microwave catalyst |
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