The content of the invention
It is existing for solving the embodiment of the invention discloses a kind of coal liquifaction RO concentrated waters processing system and its processing method
In coal liquifaction RO concentrated water processing systems, the problem of can not effectively reducing the COD value of RO concentrated waters.Technical scheme is as follows:
First, the invention provides a kind of coal liquifaction RO concentrated water processing systems, including successively by pipeline connection storage cistern,
Acid-base value regulating reservoir, ozone-ultraviolet integration catalysis oxidizing tower, oxidation discharge bay, hydrolysis-aerobic integratedization fluid bed, ozone
Oxidation pond and clear water reserviors;The ozone-ultraviolet integration catalysis oxidizing tower includes pre-mix zone, reaction zone successively by bottom to top
And the region of gas-liquid separation zone three;
Wherein, multiple catalysis buckets of layered arrangement are provided with the reaction zone, the catalysis bucket is filled including catalyst
Area and uviol lamp area, and the UV energy concentration in the uviol lamp area is 120~200mj/cm2;
Ozone nanometer aerator is installed in the pre-mix zone;
The gas-liquid separation zone is provided with first row gas port and discharge outlet.
In the preferred embodiment of the present invention, the pre-mix zone bottom is provided with slag-drip opening, the pre-mix zone
Side wall is additionally provided with air inlet, water inlet, acid inlet and second exhaust port;The air inlet passes through pipeline and the ozone nanometer
Aerator connects, and is provided with pressure gauge on the pipeline that is connected with the ozone nanometer aerator of the air inlet;It is described
The height of second exhaust port is higher than the ozone nanometer aerator, the air inlet, the water inlet and the acid inlet;Institute
State and valve is installed between pre-mix zone and the reaction zone.
In the preferred embodiment of the present invention, the bottom of the reaction zone is provided with ring-type supporting plate, the catalysis
Bucket is fixed by the ring-type supporting plate support;The catalysis bucket be cylindrical-shaped structure, and the external diameter of the catalysis bucket with it is described instead
The internal diameter in area is answered to be adapted;The catalysis bucket includes:Top plate, dividing plate and bottom plate, the top plate, dividing plate and bottom plate are hollow out net
Shape structure, the dividing plate are formed by two semi-circular plates are be hinged, and one of semi-circular plate is horizontally fixed on the side wall of the catalysis bucket
On, another semi-circular plate is articulated with the semi-circular plate being horizontally fixed in the side wall of the catalysis bucket by hinge;
Wherein, the top plate is connected with partition room by some support columns, the region formed between the top plate and dividing plate
For uviol lamp area, some uviol lamps are set in parallel in the uviol lamp area;Pass through hollow mesh between the dividing plate and bottom plate
Side wall connects, and forms hollow columnar structures, the region that the hollow columnar structures are formed is catalyst fill area.
In the preferred embodiment of the present invention, through the ozone-ultraviolet integration catalysis oxidizing tower with it is described
The corresponding side wall in the uviol lamp area of bucket is catalyzed, quartz ampoule is provided with, is be arranged in parallel between the quartz ampoule, and the quartz ampoule
Extend to inside the uviol lamp area;The uviol lamp is set in the quartz ampoule.
In the preferred embodiment of the present invention, the first row gas port is located at the top of the gas-liquid separation zone;
The gas-liquid separation zone is internally provided with hollow truncated cone round shape gas-liquid separation device, and the gas-liquid separation device is by being arranged at
Some support block supports in the gas-liquid separation zone side wall are fixed;The side wall of the gas-liquid separation zone is additionally provided with ring-type water outlet
Weir, the discharge outlet are arranged at ring-type effluent weir.
In the preferred embodiment of the present invention, the first row gas port is connected by pipeline and the ozone oxidation pond
It is logical.
In the preferred embodiment of the present invention, the oxidation discharge bay includes first area, second area and the
The bottom of three regions, the first area and second area is each provided with an agitator, and is provided with the second area
PH analyzers and centrifugal pump a, pH analyzers and centrifugal pump a linkage;Tank gage and centrifugation are installed in 3rd region
Pump b, tank gage and centrifugal pump the b linkages.
In the preferred embodiment of the present invention, the hydrolysis-aerobic integratedization fluid bed include one-stage hydrolysis area,
Aerobic zone and two level hydrolysis area, in the one-stage hydrolysis area suspension be provided with contact soft-filler;Contain in the aerobic zone
The activated sludge of mass fraction 10%~15% and the immobilized microbial inoculum of mass fraction 5%~20%, contain in immobilized microbial inoculum
There is high-efficiency aerobic bacterium;The top of the two level hydrolysis area is provided with soft contact filler, and the two level hydrolysis area is provided with two
The inclined baffle plate of block, the baffle plate are 15 °~25 ° with wall angle, and two pieces of baffle plates form an inverted triangle region, baffle bottom
There is interval;The upper surface of two pieces of baffle plates is equipped with contact soft-filler.
Secondly, the invention provides a kind of coal liquifaction RO concentrated water treatment methods, comprise the following steps:
Step A, after RO concentrated waters being stood into 1~2 hour in storage cistern, overflow to acidity adjustment pond, RO concentrated water saliferous matter
It is 1~2% to measure concentration;
Step B, the pH to 9~9.5 of the RO concentrated waters with sodium hydroxide solution regulation after standing, it is small that 1~2 is stood again
When;
Step C, the water inlet by the RO concentrated waters after acid-base value is adjusted from the ozone-ultraviolet integration catalysis oxidizing tower
The pre-mix zone of ozone-ultraviolet integration catalysis oxidizing tower is passed through, by ozone from the ozone-ultraviolet integration catalysis oxidizing tower
Air inlet is passed through the ozone nanometer aerator, ozone nanometer Air Exposure is carried out to the RO concentrated waters, in the pre-mix zone
Portion's pressure is 0.09~0.11MPa;
Step D, the RO concentrated waters after ozone nanometer Air Exposure are passed through the ozone-ultraviolet integration catalysis oxidizing tower
Reaction zone, RO concentrated waters pass sequentially through multiple catalysis buckets in reaction zone, obtain the waste water after catalytic oxidation treatment and waste gas;
Step E, the waste water that will be obtained through step D processing, the gas-liquid of the ozone-ultraviolet integration catalysis oxidizing tower is passed through
The discharge outlet discharge of Disengagement zone;The waste gas that will be obtained through step D processing, pass through the ozone-ultraviolet integration catalysis oxidizing tower
Gas-liquid separation zone first row gas port discharge;
Step F, the waste water discharged through step E is passed sequentially through to first area, the second area and the 3rd of oxidation discharge bay
Region, wherein, the residence time in first area is 0.5~1 hour, small for 0.3~0.5 in the residence time of second area
When, the residence time in the 3rd region is 0.3~0.5 hour;
Step G, the waste water obtained through step F processing is passed sequentially through to the one-level of the hydrolysis-aerobic integratedization fluid bed
Hydrolysis area and two level hydrolysis area, residence time of the waste water in the hydrolysis-aerobic integratedization fluid bed are 24~48 hours, are obtained
Waste water after to biodegradation;
Step H, the waste water after the biodegradation of step G processing gained is subjected to deep oxidation by ozone oxidation pond
Processing, 1~2 hour processing time;
Step I, the waste water after deep oxidation is handled are passed through clear water reserviors, after standing 1~2 hour, obtain the RO through processing
Concentrated water.
In the preferred embodiment of the present invention, when the pre-mix zone internal pressure is more than 0.12MPa, to described
Ozone nanometer aerator carries out pickling processes, and the pickling processes specifically include following steps:
Step 1, the valve and the water inlet of the pre-mix zone closed between the pre-mix zone and reaction zone, open described pre-
The second exhaust port and slag-drip opening of confounding, RO concentrated waters are discharged, are then shut off slag-drip opening;
Step 2, the watery hydrochloric acid that mass concentration is 5~10% is passed through pre-mix zone by the acid inlet of the pre-mix zone, directly
To being totally submerged nanometer aeration device;
Step 3, air is passed through nanometer aeration device by the air inlet of the pre-mix zone, carries out purge of gas processing,
Every half an hour processing once, 3~5 minutes time per treatment, after purge of gas is handled 2~3 hours, the pre-mix zone is discharged
In watery hydrochloric acid;
Step 4, repeat the above steps after 2 and each two to four times of step 3, pickling processes terminate.
Found by studying, a kind of coal liquifaction RO concentrated water processing systems provided by the invention, by ozone-ultraviolet one
Change the ozone nanometer aerator in the pre-mix zone of catalysis oxidizing tower, and the reaction of ozone-ultraviolet integration catalysis oxidizing tower
Multiple catalysis buckets in area, the organic matter in RO concentrated waters can be aoxidized by ozone and ultraviolet cooperating, reaching effectively reduces RO
The beneficial effect of COD value in concentrated water;By the catalysis bucket of multiple layered arrangements in reaction zone, RO concentrated waters can be made one by one to pass through
Each catalysis bucket, the time of contact of RO concentrated waters and catalyst is added, so as to improve the catalytic efficiency to RO concentrated waters.
Embodiment
Below in conjunction with the accompanying drawing in the embodiment of the present invention, the technical scheme in the embodiment of the present invention is carried out clear, complete
Site preparation describes, it is clear that described embodiment is only part of the embodiment of the present invention, rather than whole embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other under the premise of creative work is not made
Embodiment, belong to the scope of protection of the invention.
As shown in figure 1, the embodiments of the invention provide a kind of coal liquifaction RO concentrated water processing systems, including connected successively by pipeline
The storage cistern 20 that connects, acid-base value regulating reservoir 21, ozone-ultraviolet integration catalysis oxidizing tower 22, oxidation discharge bay 23, hydrolysis-good
Oxygen integration fluid bed 24, ozone oxidation pond 25 and clear water reserviors 26.
As shown in Fig. 2 ozone-ultraviolet integration catalysis oxidizing tower 20 is included pre-mix zone 1, reaction by bottom to top successively
Area 2 and the region of gas-liquid separation zone 3 three, wherein, valve 11 is installed between pre-mix zone 1 and reaction zone 2, can be to pre-mix zone 1
Passage between reaction zone 2 is opened and closed, and specifically, valve 11 can be flap valve;Due to bulky grain suspension in sewage
Seldom, therefore alternatively, larger ball valve can also be used as valve 11.In a kind of embodiment, pre-mix zone 1 accounts for tower body
High 1/10, reaction zone 2 account for the 4/5 of tower body height, and gas-liquid separation zone 3 accounts for the 1/10 of tower body height.
Ozone nanometer aerator 5 is installed in pre-mix zone 1.It should be noted that the ozone in the embodiment of the present invention is received
Rice aerator 5, is a kind of device that can produce nanoscale ozone bubbles, and the specific surface area of caused ozone bubbles is bigger,
Therefore the contact area of ozone bubbles and RO concentrated waters can be increased, so as to improve the oxidability to the dense Organic substance in water of RO.It is smelly
Oxygen nanometer aeration device can be obtained from the prior art in itself, and the present invention is no longer repeated its structure at this.
Multiple catalysis buckets of layered arrangement are provided with reaction zone 2, catalysis bucket includes catalyst fill area 12 and uviol lamp
Area 13.The mechanism that ozone and ultraviolet collaboration are handled RO concentrated waters is that ozone can decompose generation work under ultraviolet radiation
Bold and vigorous hydroxyl radical free radical, then by hydroxyl radical free radical oxidation of organic compounds.Thus it can aoxidize the organic matter that ozone is difficult to degrade, such as second
Aldehydic acid, malonic acid, acetic acid etc..Its middle-ultraviolet lamp plays the decomposition for promoting pollutant, accelerates the speed of ozone oxidation, shortens reaction
Time effect.In addition, the radiation of ultraviolet can also make the key of organic matter that fracture occur and directly decompose.Only in acid bar
During part, ozone is only main oxidant, and during neutral and alkalescence condition, oxidizing process is carried out by radical reaction pattern
, under ozone and ultraviolet collaboration process situation, phenol and TOC clearance are raised and raised with pH value, therefore, ozone and purple
Outside line collaboration processing is more effective compared to the processing of independent ozone.
Inventor through research it was unexpectedly observed that when by ozone and ultraviolet collaboration RO concentrated waters are handled when, if
The UV energy concentration in uviol lamp area 13 is less than 120mj/cm2, then the catalyzing cooperation oxidability of RO concentrated waters will be declined,
If the UV energy concentration in uviol lamp area 13 is higher than 200mj/cm2, then the catalyzing cooperation oxidability of RO concentrated waters is lifted
Unobvious, more or relatively high power uviol lamp is but needed, increase processing cost, therefore, a kind of embodiment of the present invention
In, the UV energy concentration in uviol lamp area 13 can be set as 120~200mj/cm2, so as to both have well
Ozone, ultraviolet synergistic oxidation ability, additionally it is possible to reduce unnecessary manufacturing cost.
It should be noted that the number of above-mentioned catalysis bucket can be determined by technical staff according to the process demand of reality,
The present invention does not limit herein.
Alternatively, be also equipped with backwashing mouth 17 in reaction zone 2, for carrying out backwash processing to reaction zone 2, it is specific and
Speech, backwash mouth 17 may be mounted on the outside of the tower wall of reaction zone 2, locate above valve 11.Reaction zone 2 is backwashed
When, it is alternatively possible to close valve 11, clear water is passed through in reaction zone 2 by backwashing mouth 17, reaction zone 2 is recoiled
Wash.
Gas-liquid separation zone 3 is provided with first row gas port 16 and discharge outlet 15, for the waste water after processing and waste gas separation.
As a kind of optional embodiment of the embodiment of the present invention, in the pre- of ozone-ultraviolet integration catalysis oxidizing tower 22
The bottom of confounding 1 can set at least one slag-drip opening 4, for discharging waste liquid or waste residue in pre-mix zone.Also, pre-mix zone
1 side-walls can also set air inlet 6, for being passed through gas to pre-mix zone 1;Water inlet 8 is set, for logical to pre-mix zone 1
Enter RO concentrated waters;Acid inlet 9 is set, for being passed through acid solution to pre-mix zone;Second exhaust port 10 is set, for discharging in pre-mix zone 1
Gas, it is to be understood that the height of second exhaust port 10 can be higher than ozone nanometer aerator 5, air inlet 6, water inlet
Mouth 8 and acid inlet 9, so as to the gas being effectively discharged out in pre-mix zone 1.Inside pre-mix zone 1, ozone nanometer aerator
5 are connected by pipeline with air inlet 6, and pressure gauge 7 can be installed between ozone nanometer aerator 5 and air inlet 6, for examining
Survey the pressure of ozone nanometer aerator 5.
In a kind of excellent optional embodiment of the embodiment of the present invention, the bottom of reaction zone 2 is provided with ring-type supporting plate 19, urges
Change bucket to fix by the support of ring-type supporting plate 19, the width of ring-type supporting plate 19 is 10~15cm;It can be cylindric to be catalyzed bucket
Structure., can be with it is easily understood that because the reaction zone 2 of ozone-ultraviolet integration catalysis oxidizing tower 20 is also cylindrical-shaped structure
Setting the external diameter of catalysis bucket can be adapted with the internal diameter of reaction zone 2, so that catalysis bucket is arranged on inside reaction zone 2.It is described
The adaptable external diameter that can be understood as being catalyzed bucket can be slightly less than the internal diameter of reaction zone 2, such as the external diameter of catalysis bucket can compare
Short 6~the 9cm of internal diameter of reaction zone 2.Also, each catalysis bucket can by be hollow mesh structure top plate, dividing plate and bottom
Plate forms, and so as to which catalysis bucket is divided into two regions, and hollow mesh structure can be such that the liquid in reaction zone smoothly enters to urge
Change bucket, meanwhile, the aperture of hollow mesh structure could be arranged to be less than catalyst particle size, so as to prevent catalyst from leaking outside.
In practical application, it can be spheric catalyst to be catalyzed the catalyst loaded in bucket, and its particle diameter is 4~6mm, and its is main
Active component can include TiO-MnO2-C。
In a kind of preferred embodiment of the embodiment of the present invention, the loading catalyst in bucket is catalyzed, is urged for convenience
The dividing plate for changing bucket could be arranged to the structure that can be switched and close.Such as it is specifically as follows:By the be hinged composition of two semi-circular plates
Dividing plate, it is hinged place at the diameter of dividing plate, one of semi-circular plate is horizontally fixed in the side wall of catalysis bucket, another semi-circular plate
It can be rotated by axle of hinged place.Alternatively, gag lever post can also be installed in the fixed semi-circular plate bottom with side wall, then can turns
Just it will not be rotated still further below after dynamic semi-circular plate contact gag lever post, so that the semi-circular plate can only rotate on horizontal plane.
Alternatively, top plate can be connected with partition room by some support columns, so as to be formed between top plate and dividing plate
Region is set in parallel in uviol lamp area 13 as uviol lamp area 13, and by some uviol lamps;It can pass through between dividing plate and bottom plate
The side wall connection of hollow mesh, forms hollow columnar structures, so as to using the region that hollow columnar structures are formed as catalysis
Agent fill area 12.
In practical application, uviol lamp area 13 can be generally arranged to the top of catalyst fill area 12, so that uviol lamp
It is irradiated from top to down.
In a kind of preferable scheme of the embodiment of the present invention, for the ease of the handling of uviol lamp, while uviol lamp is protected,
The side wall corresponding with the uviol lamp area 13 of catalysis bucket of ozone-ultraviolet integration catalysis oxidizing tower 22 can be run through, and wherein
Quartz ampoule 14 is set, and uviol lamp just may be mounted at the inside of quartz ampoule 14.When laying uviol lamp, each uviol lamp can be put down
Row lay, so as to so that uviol lamp light distribution uniformly, without dead angle.
It is easily understood that quartz ampoule 14 can be sealed with tower wall contact position, it is specific close so as to prevent intravenous extravasation
Envelope mode can be determined by technical staff according to the process demand of reality, such as can use filling sealant sealing, or
Quartz ampoule 14 is fixed on tower wall using flange, the present invention does not limit herein.
As a kind of optional embodiment of the embodiment of the present invention, first row gas port 16 can be located at gas-liquid separation zone 3
Top, so that gas is more smoothly discharged;Hollow truncated cone round shape gas-liquid separation device can be provided with gas-liquid separation zone 3
18, bulk catalyst can be made to be stopped and be fallen after rise to reaction zone 2 by the side wall of truncated cone round shape gas-liquid separation device 18.Need to illustrate
, truncated cone round shape gas-liquid separation device 18 is not provided with upper bottom surface and bottom surface.
As a kind of optional embodiment of the embodiment of the present invention, gas-liquid separation device 18 can be by being arranged at gas-liquid point
Fixed from some support block supports in the side wall of area 3, the length of support block is generally 4~5cm.Still optionally further, support block
A netted supporting plate can also be placed between truncated cone round shape gas-liquid separation device 18, can be by truncated cone round shape gas-liquid separation device 18
It is placed directly on supporting plate.
Wherein, gas-liquid separation device 18 is gone to the bottom under the 0.3~0.5m of bottom of gas-liquid separation zone 3, gas-liquid separation device 18
The ratio between bottom radius radius of catalysis oxidizing tower 22 integrated with ozone-ultraviolet is 4:5~9:10, bottom distance on gas-liquid separation device 18
0.3~0.5m of the top of gas-liquid separation zone 3, radius catalysis oxidizing tower 22 integrated with ozone-ultraviolet in bottom on gas-liquid separation device 18
The ratio between radius is 1:5~2:5;The side wall of gas-liquid separation zone 3 is additionally provided with ring-type effluent weir, can use annular overflow water outlet, and
And discharge outlet 15 is arranged at ring-type effluent weir, effluent weir can stop fritter catalyst, prevent catalyst from being flowed from discharge outlet 15
Go out.
Contain ozone in the tail gas discharged due to ozone-ultraviolet integration catalysis oxidizing tower 22, it is preferable that can be by first
Exhaust outlet 16 is connected by pipeline with ozone oxidation pond 25, and tail gas is passed through into ozone oxidation pond 25.Or ozone can also be sent out
Part ozone gas and tail gas caused by raw device are together passed through ozone oxidation pond 25, in mixed gas ozone concentration be 15~
30mg/L.Alternatively, volcanic filling material can also be contained in ozone oxidation pond 25, the ozone bubbles that can make to be passed through are through volcanic rock
Minute bubbles are converted into after filler buffering, while reduce air bubble flow rate, improve ozone bubbles and connect with waste water in ozone oxidation pond 25
Contacting surface and time of contact.Under normal circumstances, the particle diameter of volcanic filling material can be 0.5~2cm, filling out in ozone oxidation pond 25
It is 1.5~2m to fill height.
As a kind of optional embodiment of the embodiment of the present invention, oxidation discharge bay 23 can include three regions, each area
It can be divided between domain by baffle, spout hole can be set on dividing plate, current can flow through oxidation discharge bay 23 by spout hole
Each region.Wherein, first area can set agitator, stir water body by agitator, reach the dissolubility in water removal
The purpose of ozone;Second area can be used for adjust waste water pH, can set in the second area agitator, pH analyzers and
Centrifugal pump, by the way that pH analyzers and centrifugal pump linkage are set, when pH analyzers detect pH changes, start or close centrifugation
Pump;3rd region can be used for water storage, and tank gage and centrifugal pump can be installed in the 3rd region, when tank gage detects
Also it is after change, starts or close centrifugal pump.
As another optional embodiment of the embodiment of the present invention, contain matter in hydrolysis-aerobic integratedization fluid bed 24
The activated sludge of fraction 10~15% and the immobilized microbial inoculum of mass fraction 5%~20% are measured, is contained in immobilized microbial inoculum
Oxygen bacterium, immobilized microbial inoculum main carriers be activated carbon, volcanic rock, zeolite, wheat bran, cereal, polyurethane, polyvinyl alcohol etc. it is a kind of or
Several, high-effect bacterial is the microbial inoculum specifically for ozone oxidation water outlet development, based on corynebacteria and coccus.
Hydrolysis-aerobic integratedization fluid bed 24 can include one-stage hydrolysis area, aerobic zone and two level hydrolysis area, hydrolysis-good
Oxygen integration fluid bed 24 is rectangular shape, and one-stage hydrolysis area can be located at one end of hydrolysis-aerobic integratedization fluid bed 24,
Two level hydrolysis area can be located at the other end of hydrolysis-aerobic integratedization fluid bed 24, and aerobic zone is located at one-stage hydrolysis area and two level
Between hydrolysis area.Wherein, suspension is provided with contact soft-filler in one-stage hydrolysis area, will be big in waste water by hydrolysis
Molecular organic is decomposed into the small-molecule substance easily degraded, and improves waste water B/C ratios;The top of two level hydrolysis area is provided with soft
Filler is contacted, macromolecular substances that can further in Decomposition Wastewater.Two level hydrolysis area is provided with two pieces of inclined baffle plates simultaneously,
Baffle plate is 15 °~25 ° with wall angle, and two pieces of baffle plates form an inverted triangle region, and inverted triangle sections bottom has gap, waste water
Flowed out from the gap in inverted triangle region, the upper surface of two pieces of baffle plates is equipped with contact soft-filler, can be by consolidating in waste water
Surely microbial inoculum and activated sludge retention are changed.
As another optional embodiment of the embodiment of the present invention, clear water reserviors 26 are used to deposit through ozone oxidation Chi25Chu
Waste water after reason.It is alternatively possible to COD testers, if water quality is below standard in detection cell, Ke Yitong are installed in clear water reserviors 26
Piping is passed through storage cistern 20 again, is handled again.Alternatively, the clear water in clear water reserviors 25 can also be led to by pipeline
Enter to backwash mouth 17, so as to be backwashed to reaction zone 2.
In summary, coal liquifaction RO concentrated water processing systems provided in an embodiment of the present invention, it is catalyzed in ozone-ultraviolet integration
In ozone nanometer aerator in the pre-mix zone of oxidizing tower, and the reaction zone of ozone-ultraviolet integration catalysis oxidizing tower
Multiple catalysis buckets, the organic matter in the synergistic oxidation RO concentrated waters of ozone and ultraviolet light can be carried out to RO concentrated waters, reaches effective drop
The beneficial effect of COD value in low RO concentrated waters.
Moreover, in coal liquifaction RO concentrated water processing systems provided in an embodiment of the present invention, multiple stratiform rows in reaction zone
It the catalysis bucket of row, can make RO concentrated waters one by one by each catalysis bucket, add the time of contact of RO concentrated waters and catalyst, from
And improve the catalytic efficiency to RO concentrated waters.
Using coal liquifaction RO concentrated water processing systems provided in an embodiment of the present invention, present invention also offers a kind of coal liquifaction RO
Concentrated water treatment method;The coal liquifaction RO concentrated water treatment methods of the present invention are illustrated below by specific embodiment.
Processing Example 1
The large-scale coal liquifaction chemical plant of Factory, Shenmu, Shanxi, coal liquifaction process section waste water enter back into counter-infiltration after biochemical treatment
System, reverse osmosis water outlet fresh water direct reuse, reverse osmosis concentrated water form the RO concentrated waters of coal liquifaction, and RO concentrated water salt content is
1.2%, COD 120mg/L, water 150m3/ h, wherein COD main providers are untreated during biochemical treatment early stage
Organic matter, and the organic matter such as bactericide added in reverse osmosis membrane cleaning process.
After RO concentrated waters are stood into 1 hour in storage cistern, overflow to acidity adjustment pond;Adjusted with sodium hydroxide solution through quiet
The pH to 9 of the RO concentrated waters postponed, stand 1 hour again;RO concentrated waters after acid-base value is adjusted are urged from ozone-ultraviolet integration
The water inlet for changing oxidizing tower is passed through the pre-mix zone of ozone-ultraviolet integration catalysis oxidizing tower, and ozone is integrated from ozone-ultraviolet
The air inlet of catalysis oxidizing tower is passed through ozone nanometer aerator, ozone nanometer Air Exposure is carried out to RO concentrated waters, in pre-mix zone
Portion's pressure is 0.09MPa;RO concentrated waters after ozone nanometer Air Exposure are passed through the ozone-ultraviolet integration catalysis oxidation
The reaction zone of tower, by two ozone-ultraviolet integration catalysis oxidizing tower paired runnings, every ozone-ultraviolet integration catalysis oxygen
Change tower and include 10 catalysis buckets, RO concentrated waters pass sequentially through 10 catalysis buckets in reaction zone, obtain useless after catalytic oxidation treatment
Water and waste gas;By through handling obtained waste water, pass through the draining of the gas-liquid separation zone of ozone-ultraviolet integration catalysis oxidizing tower
Mouth discharge, water outlet COD is 70mg/L;Obtained waste gas will be handled, pass through the gas-liquid point of ozone-ultraviolet integration catalysis oxidizing tower
First row gas port from area is discharged;The waste water of discharge is passed sequentially through to first area, the second area and the 3rd of oxidation discharge bay
Region, wherein, first area residence time be 1 hour, second area residence time be 0.5 hour, regulation pH to
7.5, the residence time in the 3rd region is 0.5 hour;The waste water that reason obtains is passed sequentially through into hydrolysis-aerobic integratedization fluid bed
One-stage hydrolysis area and two level hydrolysis area, the efficient immobilized microbial inoculum of addition 30%, waste water in hydrolysis-aerobic integratedization fluid bed
Residence time in hydrolysis-aerobic integratedization fluid bed is 36 hours, obtains the waste water after biodegradation, water outlet COD is
30mg/L;By the waste water after the biodegradation for handling gained by ozone oxidation pond, deep oxidation processing, processing time 1 are carried out
Hour;Waste water after deep oxidation is handled is passed through clear water reserviors, after standing 1 hour, obtains the RO concentrated waters through processing.
As an alternative embodiment, when the COD for the RO concentrated waters that processing obtains is more than 25mg/L, processing is obtained
RO concentrated waters be passed through storage cistern again, handled again.
Coal liquifaction RO concentrated water treatment methods provided in an embodiment of the present invention, ozone and ultraviolet light, synergistic oxidation can be passed through
Organic matter in RO concentrated waters, reach the beneficial effect for effectively reducing COD value in RO concentrated waters.
Processing Example 2
Erdos coal liquifaction chemical plant, coal liquifaction process section waste water enter back into counter-infiltration system after biochemical treatment
System, reverse osmosis water outlet fresh water direct reuse, reverse osmosis concentrated water form the RO concentrated waters of coal liquifaction, and RO concentrated waters salt content is 1.5%,
COD is 180mg/L, water 100m3/ h, wherein COD main providers are untreated organic during biochemical treatment early stage
The organic matters such as the bactericide added in thing, and reverse osmosis membrane cleaning process.
After RO concentrated waters are stood into 1 hour in storage cistern, overflow to acidity adjustment pond;Adjusted with sodium hydroxide solution through quiet
The pH to 9.5 of the RO concentrated waters postponed, stand 1 hour again;RO concentrated waters after acid-base value is adjusted is integrated from ozone-ultraviolet
The water inlet of catalysis oxidizing tower is passed through the pre-mix zone of ozone-ultraviolet integration catalysis oxidizing tower, and ozone is integral from ozone-ultraviolet
The air inlet for changing catalysis oxidizing tower is passed through ozone nanometer aerator, and ozone nanometer Air Exposure, pre-mix zone are carried out to RO concentrated waters
Internal pressure is 0.09MPa;Run by two groups of ozone-ultraviolet integration catalysis oxidizing tower array parallels, every group of ozone from ozone-
Ultraviolet integrated catalysis oxidizing tower array includes three ozone from ozone-ultraviolet integration catalysis oxidizing tower, and every ozone is from smelly
There are 4 catalysis buckets in oxygen-ultraviolet integrated catalysis oxidizing tower, the RO concentrated waters after ozone nanometer Air Exposure are passed through each smelly
The reaction zone of oxygen-ultraviolet integrated catalysis oxidizing tower, RO concentrated waters pass sequentially through 4 catalysis buckets in reaction zone, obtain being catalyzed oxygen
Waste water and waste gas after change processing;By through handling obtained waste water, pass through the gas-liquid of ozone-ultraviolet integration catalysis oxidizing tower
The discharge outlet discharge of Disengagement zone, water outlet COD is 80mg/L;Obtained waste gas will be handled, pass through ozone-ultraviolet integration catalysis oxygen
Change the first row gas port discharge of the gas-liquid separation zone of tower;By the waste water of discharge pass sequentially through oxidation discharge bay first area, the
Two regions and the 3rd region, wherein, the residence time in first area is 1 hour, small for 0.5 in the residence time of second area
When, pH to 7.5 is adjusted, the residence time in the 3rd region is 0.5 hour;Obtained waste water will be managed and pass sequentially through hydrolysis-aerobic
The one-stage hydrolysis area and two level hydrolysis area of integrated fluid bed, addition 30% is efficiently solid in hydrolysis-aerobic integratedization fluid bed
Surely microbial inoculum is changed, residence time of the waste water in hydrolysis-aerobic integratedization fluid bed is 48 hours, is obtained useless after biodegradation
Water, water outlet COD are 32mg/L;By the waste water after the biodegradation for handling gained by ozone oxidation pond, carry out at deep oxidation
Reason, 1 hour processing time;Waste water after deep oxidation is handled is passed through clear water reserviors, after standing 1 hour, obtains the RO through processing
Concentrated water.
As an alternative embodiment, when the COD for the RO concentrated waters that processing obtains is more than 28mg/L, processing is obtained
RO concentrated waters be passed through storage cistern again, handled again.
Processing Example 3
The large-scale coal liquifaction chemical plant in Xinjiang, coal liquifaction process section waste water enter back into counter-infiltration system after biochemical treatment
System, reverse osmosis water outlet fresh water direct reuse, reverse osmosis concentrated water form the RO concentrated waters of coal liquifaction, and RO concentrated waters salt content is 2%,
COD is 180mg/L, water 200m3/ h, wherein COD main providers are untreated organic during biochemical treatment early stage
The organic matters such as the bactericide added in thing, and reverse osmosis membrane cleaning process.
After RO concentrated waters are stood into 1 hour in storage cistern, overflow to acidity adjustment pond;Adjusted with sodium hydroxide solution through quiet
The pH to 9.5 of the RO concentrated waters postponed, stand 1 hour again;RO concentrated waters after acid-base value is adjusted is integrated from ozone-ultraviolet
The water inlet of catalysis oxidizing tower is passed through the pre-mix zone of ozone-ultraviolet integration catalysis oxidizing tower, and ozone is integral from ozone-ultraviolet
The air inlet for changing catalysis oxidizing tower is passed through ozone nanometer aerator, and ozone nanometer Air Exposure, pre-mix zone are carried out to RO concentrated waters
Internal pressure is 0.09MPa;By three ozone-ultraviolet integration catalysis oxidizing tower paired runnings, every ozone is from ozone-ultraviolet
There are 8 catalysis buckets in integrated catalysis oxidizing tower, the RO concentrated waters after ozone nanometer Air Exposure are passed through each ozone-ultraviolet one
The reaction zone of body catalysis oxidizing tower, RO concentrated waters pass sequentially through 8 catalysis buckets in reaction zone, after obtaining catalytic oxidation treatment
Waste water and waste gas;By through handling obtained waste water, pass through the row of the gas-liquid separation zone of ozone-ultraviolet integration catalysis oxidizing tower
The mouth of a river is discharged, and water outlet COD is 90mg/L;Obtained waste gas will be handled, pass through the gas-liquid of ozone-ultraviolet integration catalysis oxidizing tower
The first row gas port discharge of Disengagement zone;The waste water of discharge is passed sequentially through into the oxidation first area of discharge bay, second area and the
Three regions, wherein, the residence time in first area is 0.5 hour, is 0.3 hour in the residence time of second area, regulation
PH to 7.5, the residence time in the 3rd region are 0.3 hour;The waste water that reason obtains is passed sequentially through into hydrolysis-aerobic integratedization stream
Change the one-stage hydrolysis area and two level hydrolysis area of bed, 30% efficient immobilized microbial inoculum added in hydrolysis-aerobic integratedization fluid bed,
Residence time of the waste water in hydrolysis-aerobic integratedization fluid bed is 48 hours, obtains the waste water after biodegradation, water outlet COD
For 35mg/L;By the waste water after the biodegradation for handling gained by ozone oxidation pond, deep oxidation processing, processing time are carried out
1 hour;Waste water after deep oxidation is handled is passed through clear water reserviors, after standing 1 hour, obtains the RO concentrated waters through processing.
As an alternative embodiment, when the COD for the RO concentrated waters that processing obtains is more than 30mg/L, processing is obtained
RO concentrated waters be passed through storage cistern again, handled again.
Processing Example 4
The large-scale coal liquifaction chemical plant in Datong, coal liquifaction process section waste water enter back into counter-infiltration after biochemical treatment
System, reverse osmosis water outlet fresh water direct reuse, reverse osmosis concentrated water form the RO concentrated waters of coal liquifaction, and RO concentrated waters salt content is 1%,
COD is 100mg/L, water 100m3/ h, wherein COD main providers are untreated organic during biochemical treatment early stage
The organic matters such as the bactericide added in thing, and reverse osmosis membrane cleaning process.
After RO concentrated waters are stood into 2 hours in storage cistern, overflow to acidity adjustment pond;Adjusted with sodium hydroxide solution through quiet
The pH to 9 of the RO concentrated waters postponed, stand 2 hours again;RO concentrated waters after acid-base value is adjusted are urged from ozone-ultraviolet integration
The water inlet for changing oxidizing tower is passed through the pre-mix zone of ozone-ultraviolet integration catalysis oxidizing tower, and ozone is integrated from ozone-ultraviolet
The air inlet of catalysis oxidizing tower is passed through ozone nanometer aerator, ozone nanometer Air Exposure is carried out to RO concentrated waters, in pre-mix zone
Portion's pressure is 0.10MPa;By two ozone-ultraviolet integration catalysis oxidizing tower paired runnings, every ozone is from ozone-ultraviolet one
There are 10 catalysis buckets in body catalysis oxidizing tower, the RO concentrated waters after ozone nanometer Air Exposure are passed through each ozone-ultraviolet one
The reaction zone of body catalysis oxidizing tower, RO concentrated waters pass sequentially through 10 catalysis buckets in reaction zone, after obtaining catalytic oxidation treatment
Waste water and waste gas;The gas-liquid separation zone of ozone-ultraviolet integration catalysis oxidizing tower will be passed through through handling obtained waste water
Discharge outlet is discharged, and water outlet COD is 60mg/L;Obtained waste gas will be handled, pass through the gas of ozone-ultraviolet integration catalysis oxidizing tower
The first row gas port discharge of liquid Disengagement zone;By the waste water of discharge pass sequentially through the oxidation first area of discharge bay, second area and
3rd region, wherein, the residence time in first area is 0.8 hour, is 0.4 hour in the residence time of second area, adjusts
PH to 7.5 is saved, the residence time in the 3rd region is 0.4 hour;The waste water that reason obtains is passed sequentially through into hydrolysis-aerobic integratedization
The one-stage hydrolysis area and two level hydrolysis area of fluid bed, the efficient immobilized bacterium of addition 30% in hydrolysis-aerobic integratedization fluid bed
Agent, residence time of the waste water in hydrolysis-aerobic integratedization fluid bed are 32 hours, obtain the waste water after biodegradation, water outlet
COD is 30mg/L;By the waste water after the biodegradation for handling gained by ozone oxidation pond, deep oxidation processing, processing are carried out
1.5 hours time;Waste water after deep oxidation is handled is passed through clear water reserviors, and after standing 1.5 hours, it is dense to obtain the RO through processing
Water.
As an alternative embodiment, when the COD for the RO concentrated waters that processing obtains is more than 28mg/L, processing is obtained
RO concentrated waters be passed through storage cistern again, handled again.
Processing Example 5
The large-scale coal liquifaction chemical plant in Yulin, coal liquifaction process section waste water enter back into counter-infiltration after biochemical treatment
System, reverse osmosis water outlet fresh water direct reuse, reverse osmosis concentrated water form the RO concentrated waters of coal liquifaction, and RO concentrated water salt content is
1.5%, COD 120mg/L, water 80m3/ h, wherein COD main providers are untreated during biochemical treatment early stage
The organic matters such as the bactericide added in organic matter, and reverse osmosis membrane cleaning process.
After RO concentrated waters are stood into 1 hour in storage cistern, overflow to acidity adjustment pond;Adjusted with sodium hydroxide solution through quiet
The pH to 9.5 of the RO concentrated waters postponed, stand 1.5 hours again;RO concentrated waters after acid-base value is adjusted is integral from ozone-ultraviolet
The water inlet for changing catalysis oxidizing tower is passed through the pre-mix zone of ozone-ultraviolet integration catalysis oxidizing tower, by ozone from ozone-ultraviolet one
The air inlet of body catalysis oxidizing tower is passed through ozone nanometer aerator, and ozone nanometer Air Exposure, premix are carried out to RO concentrated waters
Area's internal pressure is 0.11MPa;By two ozone-ultraviolet integration catalysis oxidizing tower paired runnings, every ozone is from ozone-purple
There are 8 catalysis buckets in outer integrated catalysis oxidizing tower, the RO concentrated waters after ozone nanometer Air Exposure are passed through each ozone-ultraviolet
The reaction zone of integrated catalysis oxidizing tower, RO concentrated waters pass sequentially through 8 catalysis buckets in reaction zone, after obtaining catalytic oxidation treatment
Waste water and waste gas;The gas-liquid separation zone of ozone-ultraviolet integration catalysis oxidizing tower will be passed through through handling obtained waste water
Discharge outlet is discharged, and water outlet COD is 70mg/L;Obtained waste gas will be handled, pass through the gas of ozone-ultraviolet integration catalysis oxidizing tower
The first row gas port discharge of liquid Disengagement zone;By the waste water of discharge pass sequentially through the oxidation first area of discharge bay, second area and
3rd region, wherein, the residence time in first area is 1 hour, is 0.5 hour in the residence time of second area, regulation
PH to 7.5, the residence time in the 3rd region are 0.5 hour;The waste water that reason obtains is passed sequentially through into hydrolysis-aerobic integratedization stream
Change the one-stage hydrolysis area and two level hydrolysis area of bed, 30% efficient immobilized microbial inoculum added in hydrolysis-aerobic integratedization fluid bed,
Residence time of the waste water in hydrolysis-aerobic integratedization fluid bed is 48 hours, obtains the waste water after biodegradation, water outlet COD
For 25mg/L;By the waste water after the biodegradation for handling gained by ozone oxidation pond, deep oxidation processing, processing time are carried out
2 hours;Waste water after deep oxidation is handled is passed through clear water reserviors, after standing 2 hours, obtains the RO concentrated waters through processing.
As an alternative embodiment, when the COD for the RO concentrated waters that processing obtains is more than 22mg/L, processing is obtained
RO concentrated waters be passed through storage cistern again, handled again.
In a kind of embodiment of the coal liquifaction RO concentrated water treatment methods of the present invention, such as in embodiment 1 to reality
Apply in example 5, when pre-mix zone internal pressure is more than 0.12MPa, pickling processes, pickling processes are carried out to ozone nanometer aerator
Specifically it may comprise steps of:
Step 1, the valve and the water inlet of pre-mix zone closed between pre-mix zone and reaction zone, the second row of pre-mix zone is opened
Gas port and slag-drip opening, RO concentrated waters are discharged, are then shut off slag-drip opening;
Step 2, the watery hydrochloric acid that mass concentration is 5% is passed through pre-mix zone by the acid inlet of pre-mix zone, until leaching completely
Do not have nanometer aeration device;
Step 3, air is passed through nanometer aeration device by the air inlet of pre-mix zone, carries out purge of gas processing, every
Half an hour is handled once, the 3 minutes time per treatment, after purge of gas is handled 2 hours, discharges the watery hydrochloric acid in pre-mix zone;
Step 4, repeat the above steps 2 and step 3 it is each it is secondary after, pickling processes terminate.
Coal liquifaction RO concentrated water treatment methods provided in an embodiment of the present invention, when ozone nanometer aerator is because of fouling and clogging
When, ozone nanometer aerator can be cleaned, so as to ensure the normal fortune of ozone-ultraviolet integration catalysis oxidizing tower
OK.
In a kind of embodiment of the coal liquifaction RO concentrated water treatment methods of the present invention, such as in embodiment 1 to reality
Apply in example 5, pickling processes, acid can also be carried out to ozone nanometer aerator when pre-mix zone internal pressure is more than 0.12MPa
Processing is washed specifically to may comprise steps of:
Step 1, the valve and the water inlet of pre-mix zone closed between pre-mix zone and reaction zone, the second row of pre-mix zone is opened
Gas port and slag-drip opening, RO concentrated waters are discharged, are then shut off slag-drip opening;
Step 2, the watery hydrochloric acid that mass concentration is 10% is passed through pre-mix zone by the acid inlet of pre-mix zone, until leaching completely
Do not have nanometer aeration device;
Step 3, air is passed through nanometer aeration device by the air inlet of pre-mix zone, carries out purge of gas processing, every
Half an hour is handled once, the 5 minutes time per treatment, after purge of gas is handled 3 hours, discharges the watery hydrochloric acid in pre-mix zone;
Step 4, repeat the above steps after 2 and each four times of step 3, pickling processes terminate.
Detailed Jie has been carried out to a kind of coal liquifaction RO concentrated waters processing system provided by the present invention and its processing method above
Continue.Specific embodiment used herein is set forth to the principle and embodiment of the present invention, the explanation of above example
It is only intended to help the method and its central idea for understanding the present invention.It should be pointed out that come for one of ordinary skill in the art
Say, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, these are improved and modification
Also fall into the protection of the claims in the present invention.
It should be noted that herein, such as first and second or the like relational terms are used merely to a reality
Body or operation make a distinction with another entity or operation, and not necessarily require or imply and deposited between these entities or operation
In any this actual relation or order.Moreover, term " comprising ", "comprising" or its any other variant are intended to
Nonexcludability includes, so that process, method, article or equipment including a series of elements not only will including those
Element, but also the other element including being not expressly set out, or it is this process, method, article or equipment also to include
Intrinsic key element.In the absence of more restrictions, the key element limited by sentence "including a ...", it is not excluded that
Other identical element also be present in process, method, article or equipment including the key element.
Each embodiment in this specification is described by the way of related, identical similar portion between each embodiment
Divide mutually referring to what each embodiment stressed is the difference with other embodiment.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the scope of the present invention.It is all
Any modification, equivalent substitution and improvements made within the spirit and principles in the present invention etc., are all contained in protection scope of the present invention
It is interior.