CN107746160A - It is a kind of to be used for the processing of low temperature distillation waste water and reuse method in coal - Google Patents
It is a kind of to be used for the processing of low temperature distillation waste water and reuse method in coal Download PDFInfo
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- C02F1/44—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis
- C02F1/441—Treatment of water, waste water, or sewage by dialysis, osmosis or reverse osmosis by reverse osmosis
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
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Abstract
It is used for the processing of low temperature distillation waste water and reuse method in coal the invention discloses a kind of, this method includes pretreatment, biochemical treatment and advanced treating and reuse successively, by stripping depickling deamination after first waste water is carried out gravity oil removal, filtered, oil emulsion and suspension are removed by extracting and dephenolizing, flocculation-air floating again, electrochemical oxidation reduce COD after into biochemical treatment be Anaerobic Treatment, anoxic treatment and Aerobic Process for Treatment, eventually through advanced treating and reuse be coagulating treatment, catalytic ozonation processing, MBR is handled and reverse-osmosis treated, standard water discharge reuse；The present invention is combined by each unit reasonably optimizing and configured, and is realized the advanced treating to tar in waste water, ammonia, the high efficiente callback of phenol and middle low temperature distillation waste water, is eventually passed through desalination reuse, is realized pollution and is removed and the recycling of water resource.
Description
Technical field
The present invention relates to advanced treatment of industrial waste water field, more particularly to a kind of place for being used for low temperature distillation waste water in coal
Reason and reuse method.
Background technology
In coal low-temperature coal carbonization technology be using low-order coal as raw material, 600-800 DEG C of destructive distillation obtain semicoke, tar and
The coal sub-prime utilization technology of coal gas product, its caused waste water is similar with coking chemical waste water, but because coal used and technique have
Institute's difference, caused waste water are also had any different with coking chemical waste water, and pollutant concentration is 5-10 times of coking chemical waste water, its complicated component,
Colourity is high, and containing ammonia nitrogen in high density, volatile phenol and other organic pollutions, biodegradability is poor, is typical high-concentration hardly-degradable
Organic wastewater.The characteristics of middle low temperature distillation waste water, determines its complicated harmfulness, ammonia nitrogen, phenolic compound and virtue contained therein
There is grave danger in fragrant compounds of group, to ecological environment in addition, the industry byproduct such as tar, ammonia, phenol in waste water also has back
Receive the value utilized.
Patent CN104926029 discloses a kind of semi-coke wastewater processing method, and this method includes:Coarse filtration, acid adding are sunk
Shallow lake, phenol recovery, recovery ammonia, desulfurization, oxidation, Aerobic Process for Treatment, Anaerobic Treatment, secondary Aerobic Process for Treatment, electrolysis, MBR or aeration and biological
The processes such as filter tank, desalination, before phenol recovery is placed on recovery ammonia by the technique, extracting and dephenolizing efficiency is low, and desulfurization unit is placed on phenol ammonia
Behind recovery, sulphur ammonia Crystallization Plugging column plate and heat exchanger are easily generated in preceding segment unit, it is useless without improving before biochemical unit
Water biochemical measure, biochemical unit pollutants removal rate are low.
Patent CN105060628B discloses a kind of semi-coke wastewater processing method, and this method includes：Oil removal precipitation, coagulation gas
Process, the techniques such as floating, phenol extraction, ammonia aeration, Anaerobic Treatment, anoxic treatment, Aerobic Process for Treatment, BAF use stripping
Mode reclaims ammonia, and gas liquid ratio is high, deamination effect is poor, while ammonia aeration is placed on after phenol extraction, and extraction efficiency is low, in Aerobic Process for Treatment
BAF is followed by, BAF is substantially without removal effect, and the technique is without advanced treatment process, it is difficult to reaches discharge
Standard.
Patent CN104724886B discloses a kind of semi-coke wastewater decarburization removing total nitrogen technique, and pretreatment system is included in the system
System, biochemical system and advanced treatment system, pretreatment system include oil interceptor and two-stage air-floating apparatus, and the pretreatment system is without phenol
Recovery ammonia measure, advanced treating use photocatalytic ozonation, and investment and operating cost are high.
The content of the invention
For above-mentioned technical problem, it is used for the processing of low temperature distillation waste water and reuse side in coal the invention provides a kind of
Method, by effectively being reclaimed to tar, phenol and ammonia in waste water, biochemical system is reduced while improving wastewater treatment economy
Load, it is preferred to use ozone tail gas strengthens electrochemical oxidation and improves wastewater biodegradability, solves ozone tail gas emission problem, real
Existing effect utilizes, and combines and configures eventually through each unit reasonably optimizing, realizes the high efficiente callback to tar, ammonia and phenol in waste water
With the advanced treating of middle low temperature distillation waste water, desalination reuse is realized, pollution removes and the recycling of water resource.
In order to solve the above problems, the present invention uses following technical scheme：
A kind of to be used for the processing of low temperature distillation waste water and reuse method in coal, methods described includes pretreatment, biochemical treatment successively
With advanced treating and reuse.
The pretreatment is first carries out the waste water after gravity oil removal, filtering by stripping depickling deamination, then passes through extraction
Dephenolize, flocculation-air floating is taken to remove oil emulsion and suspension, electrochemical oxidation enters biochemical treatment after reducing COD.
Water outlet enters biochemical treatment after pretreatment, and the biochemical treatment includes Anaerobic Treatment successively, anoxic treatment is become reconciled
Oxygen processing.
Biochemical treatment water outlet enters advanced treating and reuse, and the advanced treating and reuse include coagulating treatment, smelly successively
Oxygen catalytic oxidation treatment, MBR processing and reverse-osmosis treated.
The gravity oil removal, for removing most oil slick and heavy oil in waste water, tar is reclaimed, reduces the oil in waste water
Content, residence time are 3 ~ 5h, and oil extraction heating-up temperature is more than 70 DEG C；
The filtering, using ceramic membrane filter, for removing the oil and coal ash that are suspended in waste water；
The stripping depickling deamination, for removing CO in waste water2And H2S, reclaim the ammonia in waste water；
The extracting and dephenolizing, for reclaiming the crude phenols in waste water, the ratio between extractant and waste water are 1:5；
The flocculation-air floating, for further removing oil emulsion and suspension in water removal, to reach requirement of the biochemical system to oil,
Flocculant dosage is 50 ~ 300ppm；
The electrochemical oxidation is organic for the organic matter open loop chain rupture of difficult for biological degradation in waste water to be converted into easily biological-degradable
Thing, so as to improve wastewater biodegradability；The electrochemical oxidation residence time is 10 ~ 30min, and current density is 5 ~ 50mA.
The Anaerobic Treatment, for being the organic matter relatively easily degraded by hardly degraded organic substance generation anaerobic hydrolysis, together
When part hardly degraded organic substance Co metabolism anaerobic degradation occur be converted into relatively easy aerobic degradation organic matter, so as to further carry
High wastewater biodegradability, residence time are 10 ~ 20h；
The anoxic treatment, total nitrogen is removed by anti-nitration reaction and reinforcing removal part hardly degraded organic substance, residence time are
15~24h；
The Aerobic Process for Treatment, by adding methanol, further to the degradation capability of Recalcitrant chemicals, methanol adds COD ought for raising
It is 50 ~ 100h to measure as 20 ~ 100mg/L, residence time；
The reflux ratio of the Aerobic Process for Treatment nitrification liquid backflow anoxic treatment is 1:1~3:1.
The coagulating treatment, suspension in water removal is gone by coagulation；
The coagulant added is preferably the one or more in bodied ferric sulfate, polyaluminium sulfate or polyacrylamide；
The dosage of the coagulant is 3000-1000mg/L, and the coagulating time is 15min ~ 30min, the sedimentation time is 1 ~
3h；
The catalytic ozonation processing：Using the catalytic action of heterogeneous catalysis, the COD in depth degradation waste water, simultaneously
Refractory organic is converted into the organic matter of easily biological-degradable；
The catalytic ozonation processing, hydraulic detention time is 10 ~ 60min, and ozone dosage is 100 ~ 300mg/L；It is described
Catalyst is preferably KLCO-3 or KLCO-4；
The MBR processing：Easily biodegradable organicses caused by ozone oxidation are further degraded, while reduces out aqueous suspension and contains
Amount, the residence time is 5 ~ 15h, and operating pressure is -1 ~ -50kpa；
MBR processing uses hollow fiber ultrafiltration membrane or flat plate ultrafiltration membrane, membrane material be preferably Kynoar, polyether sulfone,
Polyvinyl chloride or the fine one kind of polypropylene；
The reverse-osmosis treated：For reducing salt content in waste water, so as to reach recycle water standard, the feed water by reverse osmosis pressure
For 0.5 ~ 2.0MPa, producing water ratio 70% ~ 80%；
The membrane module that counter-infiltration uses is preferably rolled membrane module, and membrane material is composite membrane, using two sections of arrangements.
Ozone tail gas caused by the ozone oxidation is delivered to electrochemical oxidation unit, further strengthens at electrochemical oxidation
Manage effect.
The extracting and dephenolizing includes extraction processing and extractant recycles, the phenol generalization obtained after extracting and dephenolizing is handled
The compound rate of recovery is up to more than 95%.
The stripping depickling deamination is deamination after single column tower top depickling survey line deamination or the depickling of two tower elder generations, is wherein adjusted before deamination
It is more than 10 to save wastewater pH.
Compared with prior art, the invention has the advantages that：
1st, tar, phenol and ammonia in waste water are effectively reclaimed, wastewater treatment economy reduces biochemical system simultaneously and born in raising
Lotus：
（1）Classification removal is carried out to oil slick, heavy oil, suspended oil and oil emulsion in water, ensures that pretreatment final outflow water oil content reaches
To biochemical inflow requirement；
（2）Each pollutant oil, phenol, ammonia and coal ash in waste water targetedly reclaimed and removed, each pollutant of reasonable arrangement
Removal order, ensure the removal effect and stability of whole pretreatment system；
2nd, for wastewater biodegradability it is low the characteristics of, electrochemical oxidation is strengthened using ozone tail gas and improves wastewater biodegradability, it is real
Effective utilization of existing ozone tail gas, while methanol co-substrate is added in aerobic system, improve the metabolism environment of microorganism, improve it
To the degradation capability of Recalcitrant chemicals；
3rd, combined and configured by each unit reasonably optimizing, realized and tar, ammonia, the high efficiente callback of phenol and middle low temperature in waste water are done
The advanced treating of waste water is evaporated, eventually passes through desalination reuse, realizes pollution removal and the recycling of water resource.
Brief description of the drawings
Fig. 1 is a kind of process chart for being used for the preprocess method of low temperature distillation waste water in coal of the present invention.
Embodiment
Further illustrate technical scheme with reference to the accompanying drawings and examples:
As shown in figure 1, it is a kind of be used for coal in low temperature distillation waste water processing and reuse method, this method successively include pretreatment,
Biochemical treatment and advanced treating and reuse；
Wherein, pre-process will first to be taken off after the oil removal of waste water progress gravity, filtering by stripping depickling deamination, then by extracting
Phenol, flocculation-air floating remove oil emulsion and suspension, and electrochemical oxidation enters biochemical treatment after improving wastewater biodegradability.
Water outlet enters biochemical treatment after pretreatment, and the biochemical treatment includes Anaerobic Treatment successively, anoxic treatment is become reconciled
Oxygen processing.Biochemical treatment water outlet enters advanced treating and reuse, and the advanced treating and reuse include coagulating treatment, ozone successively
Catalytic oxidation treatment, MBR processing and reverse-osmosis treated.
Further, gravity oil removal, for removing most oil slick and heavy oil in waste water, tar is reclaimed, reduces waste water
In oil content, the residence time is 3 ~ 5h, and oil extraction heating-up temperature is more than 70 DEG C；Filtering, using ceramic membrane filter, for removing
The oil and coal ash to be suspended in waste water；Depickling deamination is stripped, for removing CO in waste water2And H2S, reclaim the ammonia in waste water；Extraction is de-
Phenol, for reclaiming the crude phenols in waste water, the ratio between extractant and waste water are 1:5；Flocculation-air floating, for further removing the breast in water removal
Carburetion and suspension, to reach requirement of the biochemical system to oil, flocculant dosage is 50 ~ 300ppm；Electrochemical oxidation is used for
The organic matter open loop chain rupture of difficult for biological degradation in waste water is converted into easily biological-degradable organic matter, it is biochemical so as to improve waste water
Property；The electrochemical oxidation residence time is 10 ~ 30min, and current density is 5 ~ 50mA.
Further, Anaerobic Treatment, it is organic relatively easily to degrade for hardly degraded organic substance into anaerobic hydrolysis to occur
Thing, while part hardly degraded organic substance occurs Co metabolism anaerobic degradation and is converted into relatively easy aerobic degradation organic matter, so as to enter
One step improves wastewater biodegradability, and the residence time is 10 ~ 20h；Anoxic treatment, remove total nitrogen by anti-nitration reaction and strengthen and go
Except part hardly degraded organic substance, the residence time is 15 ~ 24h；Aerobic Process for Treatment, further improved to difficult degradation dirt by adding methanol
The degradation capability of thing is contaminated, it is 20 ~ 100mg/L that methanol, which adds COD equivalents, and the residence time is 50 ~ 100h；Aerobic Process for Treatment nitrification liquid returns
The reflux ratio for flowing anoxic treatment is 1:1~3:1.
Further, coagulating treatment, suspension in water removal is gone by coagulation；The coagulant added is preferably polymerised sulphur
One or more in sour iron, polyaluminium sulfate or polyacrylamide；The dosage of coagulant is 3000-1000mg/L, coagulation
Reaction time is 15min ~ 30min, and the sedimentation time is 1 ~ 3h；Catalytic ozonation processing：Utilize the catalysis of heterogeneous catalysis
Act on, the COD in depth degradation waste water, while refractory organic is converted into the organic matter of easily biological-degradable；Ozone
Catalytic oxidation treatment, hydraulic detention time are 10 ~ 60min, and ozone dosage is 100 ~ 300mg/L；The catalyst is preferably
KLCO-3 or KLCO-4；MBR processing：Easily biodegradable organicses caused by ozone oxidation are further degraded, while reduces water outlet and hangs
Float content, residence time are 5 ~ 15h, and operating pressure is -1 ~ -50kpa；MBR processing uses hollow fiber ultrafiltration membrane or flat board
Milipore filter, membrane material are preferably Kynoar, polyether sulfone, polyvinyl chloride or the fine one kind of polypropylene；Reverse-osmosis treated：For
Salt content in waste water is reduced, so as to reach recycle water standard, the feed water by reverse osmosis pressure is 0.5 ~ 2.0MPa, producing water ratio 70% ~
80%；The membrane module that counter-infiltration uses is preferably rolled membrane module, and membrane material is composite membrane, using two sections of arrangements.
Further, ozone tail gas caused by ozone oxidation is delivered to electrochemical oxidation unit, further strengthens electrochemistry
Oxidation processes effect；Extracting and dephenolizing includes extraction processing and extractant recycles, the phenols obtained after extracting and dephenolizing is handled
The compound rate of recovery is up to more than 95%；It is deamination after single column tower top depickling survey line deamination or the depickling of two tower elder generations to strip depickling deamination, its
It is more than 10 that wastewater pH is adjusted before middle deamination.
Embodiment 1：
Certain coal medium temperature carbonization enterprise wastewater, water quality leading indicator are：COD：20000mg/L, total phenol：4000mg/L, oil：
1000mg/L, NH4-N：2000mg/L, CO2：1500mg/L, H2S：100mg/L, pH 8.1.
Wastewater treatment and reuse method is as follows：
Gravity oil removal unit：Most oil slick and heavy oil in waste water are removed, reclaims tar, the oil content in waste water is reduced, adopts
With flat flow grease removal tank, residence time 4h, heavy oil uses steam indirectly heat in oil pooling dipper, oil extraction heating-up temperature 70 DEG C with
On；
Ceramic membrane filter unit：The oil and coal ash to be suspended in waste water is removed, prevents from blocking column plate during depickling deamination is stripped
And heat exchanger；Ceramic membrane uses microfiltration membranes, using steam and water mix backwash is filtered out, through gravity oil removal unit and ceramic membrane
Waste water oil content is reduced to below 150mg/L after filtering；
Strip depickling deamination unit：For removing CO in waste water2And H2S, the ammonia in waste water is reclaimed, using single column top depickling side line
It is more than 10 that wastewater pH is adjusted before deamination technique, wherein ammonia still process ammonia, strips NH after depickling deamination4- N 200mg/L, CO2：30mg/
L, H2S 20mg/L；
Extracting and dephenolizing unit：For reclaiming the crude phenols in waste water；Extractant can be methyl iso-butyl ketone (MIBK), extractant and waste water ratio
For 1:5；Extracting and dephenolizing unit includes extraction cells and extractant recycles unit, and extractant recycles, waste water after dephenolize
Total phenol is 200mg/L, and COD is below 6000mg/L.
Flocculation-air floating unit：By flocculate and pneumatically supported mode further go water removal in oil emulsion and suspension, with up to
Requirement to biochemical system to oil, air supporting include dosing area and air flotation zone, and flocculant added by dosing area is bodied ferric sulfate, is added
Measure and use nitrogen air supporting for 300ppm, air supporting, to prevent Phenol for Waste Water to be oxidized to the quinones of difficult degradation, while use closed air supporting
Device, caused waste gas is handled.
Electrochemical oxidation unit：Strengthen electrochemicial oxidation effect using advanced treatment unit ozone tail gas, for dropping
Low a part of waste water COD, reduce biochemical system load, it is often more important that by the organic matter open loop chain rupture of difficult for biological degradation in waste water
Easily biological-degradable organic matter is converted, improves wastewater biodegradability.Electrochemical oxidation residence time 30min, current density 40mA.Go out
Water COD can be reduced to 4500mg/L, and wastewater biodegradability B/C ratios are improved to 0.38 from 0.24.
Anaerobic Treatment unit：In the case where anaerobic bacteria acts on, hardly degraded organic substance occurs anaerobic hydrolysis and relatively easily degraded
Organic matter, while part hardly degraded organic substance occurs Co metabolism anaerobic degradation and is converted into relatively easy aerobic degradation organic matter, enters
One step improves wastewater biodegradability, residence time 12h, and wastewater biodegradability is improved to 0.42 from 0.38.
Anoxic treatment unit：Denitrifying bacterium is anti-using the nitrite nitrogen in phegma and nitrate nitrogen progress denitrification
Should, nitrite nitrogen and nitrate nitrogen become nitrogen and removed by anti-nitration reaction, while organic matter supplies as electronics
Body is removed, and particularly some organic matters for being difficult to aerobic degradation can be strengthened by denitrification removes.Residence time 18h.
Aerobic treatment unit：Reacted using microorganism aerobic by contaminant degradations such as organic matter, ammonia nitrogens.Aerobic unit adds
Methanol improves the metabolism environment of microorganism, improves its degradation capability to Recalcitrant chemicals, methanol adds as co-substrate
COD equivalents are 60mg/L, and the residence time is 60h, and the reflux ratio of aerobic nitrification liquid backflow anoxic unit is 3:1.Aerobic Process for Treatment
Water outlet COD can be reduced to 200mg/L afterwards, and ammonia nitrogen is reduced to below 5mg/L.
Coagulation unit：Suspension in water removal is gone by coagulation, coagulant polymeric ferric sulfate, dosage 600mg/L, mixed
In solidifying reaction time 15min, sedimentation time 1h, water outlet COD are reduced to 120mg/L；
Ozone catalytic oxidation unit：Under the catalysis of heterogeneous catalysis, the organic matter in waste water further reduces waste water COD,
Refractory organic is converted into the organic matter of easily biological-degradable simultaneously, caused ozone tail gas is delivered to electrochemical oxidation
Unit.Catalytic ozonation reaction hydraulic detention time is 30min, ozone dosage 150mg/L；The ozone Oxidation Treatment
Middle addition catalyst is KLCO-3, and KLCO-4, ozone water outlet COD can be reduced to below 60mg/L.
MBR unit：Easily biodegradable organicses caused by ozone oxidation are further degraded, while reduces out aqueous suspension and contains
Amount, MBR unit use flat plate ultrafiltration membrane, and membrane material is Kynoar, and residence time 5h, operating pressure is -25kpa, is gone out
Water COD can be reduced to below 40mg/L.
Reverse osmosis units：Salt content in waste water is reduced, membrane module is rolled membrane module, and membrane material is composite membrane, is used
Two sections of arrangements, intake pressure 0.8-1.51MPa, producing water ratio 75%, reverse osmosis water outlet reach industrial reuse water quality standard.
Embodiment 2：
Certain coal medium temperature carbonization enterprise wastewater, water quality leading indicator are：COD 32000mg/L, total phenol：7000mg/L, oil：
1500mg/L, NH4-N：2500mg/L, CO2：2500mg/L, H2S：120mg/L, pH 8.3.
Wastewater treatment and reuse method is as follows：
Gravity oil removal unit：Most oil slick and heavy oil in waste water are removed, reclaims tar, the oil content in waste water is reduced, adopts
With flat flow grease removal tank, residence time 3h, heavy oil uses steam indirectly heat in oil pooling dipper, oil extraction heating-up temperature 70 DEG C with
On；
Ceramic membrane filter unit：The oil and coal ash to be suspended in waste water is removed, prevents from blocking column plate during depickling deamination is stripped
And heat exchanger；Ceramic membrane uses microfiltration membranes, using steam and water mix backwash is filtered out, through gravity oil removal unit and ceramic membrane
Waste water oil content is reduced to below 200mg/L after filtering；
Strip depickling deamination unit：For removing CO in waste water2And H2S, the ammonia in waste water is reclaimed, using single column top depickling side line
It is more than 10 that wastewater pH is adjusted before deamination technique, wherein ammonia still process ammonia, strips NH4-N 200mg/L, CO after depickling deamination2 30mg/
L, H2S 20mg/L；
Extracting and dephenolizing unit：For reclaiming the crude phenols in waste water；Extractant can be methyl iso-butyl ketone (MIBK), extractant and waste water ratio
For 1:5；Extracting and dephenolizing unit includes extraction cells and extractant recycles unit, and extractant recycles, waste water after dephenolize
Total phenol is 300mg/L, and COD is below 7000mg/L.
Flocculation-air floating unit：By flocculate and pneumatically supported mode further go water removal in oil emulsion and suspension, with up to
Requirement to biochemical system to oil, air supporting include dosing area and air flotation zone, and flocculant added by dosing area is bodied ferric sulfate, is added
Measure and use nitrogen air supporting for 200ppm, air supporting, to prevent Phenol for Waste Water to be oxidized to the quinones of difficult degradation, while use closed air supporting
Device, caused waste gas is handled.
Electrochemical oxidation unit：Strengthen electrochemicial oxidation effect using advanced treatment unit ozone tail gas, for dropping
Low a part of waste water COD, reduce biochemical system load, it is often more important that by the organic matter open loop chain rupture of difficult for biological degradation in waste water
Easily biological-degradable organic matter is converted, improves wastewater biodegradability.Electrochemical oxidation residence time 30min, current density 40mA.Go out
Water COD can be reduced to 6000mg/L, and wastewater biodegradability B/C ratios are improved to 0.36 from 0.23.
Anaerobic Treatment unit：In the case where anaerobic bacteria acts on, hardly degraded organic substance occurs anaerobic hydrolysis and relatively easily degraded
Organic matter, while part hardly degraded organic substance occurs Co metabolism anaerobic degradation and is converted into relatively easy aerobic degradation organic matter, enters
One step improves wastewater biodegradability, residence time 12h, and wastewater biodegradability is improved to 0.40 from 0.36.
Anoxic treatment unit：Denitrifying bacterium is anti-using the nitrite nitrogen in phegma and nitrate nitrogen progress denitrification
Should, nitrite nitrogen and nitrate nitrogen become nitrogen and removed by anti-nitration reaction, while organic matter supplies as electronics
Body is removed, and particularly some organic matters for being difficult to aerobic degradation can be strengthened by denitrification removes.Residence time 20h.
Aerobic treatment unit：Reacted using microorganism aerobic by contaminant degradations such as organic matter, ammonia nitrogens.Aerobic unit adds
Methanol improves the metabolism environment of microorganism, improves its degradation capability to Recalcitrant chemicals, methanol adds as co-substrate
COD equivalents are 80mg/L, and the residence time is 80h, and the reflux ratio of aerobic nitrification liquid backflow anoxic unit is 3:1.Aerobic Process for Treatment
Water outlet COD can be reduced to 250mg/L afterwards, and ammonia nitrogen is reduced to below 5mg/L.
Coagulation unit：Suspension in water removal is gone by coagulation, coagulant polymeric ferric sulfate, dosage 800mg/L, mixed
In solidifying reaction time 15min, sedimentation time 1h, water outlet COD are reduced to 150mg/L；
Ozone catalytic oxidation unit：Under the catalysis of heterogeneous catalysis, the organic matter in waste water further reduces waste water COD,
Refractory organic is converted into the organic matter of easily biological-degradable simultaneously, caused ozone tail gas is delivered to electrochemical oxidation
Unit.Catalytic ozonation reaction hydraulic detention time is 30min, ozone dosage 200mg/L；The ozone Oxidation Treatment
Middle addition catalyst is KLCO-3, and KLCO-4, ozone water outlet COD can be reduced to below 80mg/L.
MBR unit：Easily biodegradable organicses caused by ozone oxidation are further degraded, while reduces out aqueous suspension and contains
Amount, MBR unit use flat plate ultrafiltration membrane, and membrane material is Kynoar, and residence time 7h, operating pressure is -35kpa, is gone out
Water COD can be reduced to below 50mg/L.
Reverse osmosis units：Salt content in waste water is reduced, membrane module is rolled membrane module, and membrane material is composite membrane, is used
Two sections of arrangements, intake pressure 0.8-1.5MPa, producing water ratio 75%, reverse osmosis water outlet reach industrial reuse water quality standard.
Embodiment 3：
Certain coal low temperature distillation enterprise wastewater, water quality leading indicator are：COD：52000mg/L, total phenol：12000mg/L, oil：
1800mg/L, NH4-N：3000mg/L, CO2：3500mg/L, H2S：150mg/L, pH 8.5.
Wastewater treatment and reuse method is as follows：
Gravity oil removal unit：Most oil slick and heavy oil in waste water are removed, reclaims tar, the oil content in waste water is reduced, adopts
With flat flow grease removal tank, residence time 5h, heavy oil uses steam indirectly heat in oil pooling dipper, oil extraction heating-up temperature 70 DEG C with
On；
Ceramic membrane filter unit：The oil and coal ash to be suspended in waste water is removed, prevents from blocking column plate during depickling deamination is stripped
And heat exchanger；Ceramic membrane uses microfiltration membranes, using steam and water mix backwash is filtered out, through gravity oil removal unit and ceramic membrane
Waste water oil content is reduced to below 200mg/L after filtering；
Strip depickling deamination unit：For removing CO in waste water2And H2S, the ammonia in waste water is reclaimed, using single column top depickling side line
It is more than 10 that wastewater pH is adjusted before deamination technique, wherein ammonia still process ammonia, strips NH after depickling deamination4- N 200mg/L, CO2：30mg/
L, H2S：20mg/L；
Extracting and dephenolizing unit：For reclaiming the crude phenols in waste water；Extractant can be methyl iso-butyl ketone (MIBK), extractant and waste water ratio
For 1:5；Extracting and dephenolizing unit includes extraction cells and extractant recycles unit, and extractant recycles, waste water after dephenolize
Total phenol is 400mg/L, and COD is below 8000mg/L.
Flocculation-air floating unit：By flocculate and pneumatically supported mode further go water removal in oil emulsion and suspension, with up to
Requirement to biochemical system to oil, air supporting include dosing area and air flotation zone, and flocculant added by dosing area is bodied ferric sulfate, is added
Measure and use nitrogen air supporting for 300ppm, air supporting, to prevent Phenol for Waste Water to be oxidized to the quinones of difficult degradation, while use closed air supporting
Device, caused waste gas is handled.Air supporting water outlet oil content is reduced to below 30mg/L.
Electrochemical oxidation unit：Strengthen electrochemicial oxidation effect using advanced treatment unit ozone tail gas, for dropping
Low a part of waste water COD, reduce biochemical system load, it is often more important that by the organic matter open loop chain rupture of difficult for biological degradation in waste water
Easily biological-degradable organic matter is converted, improves wastewater biodegradability.Electrochemical oxidation residence time 30min, current density 50mA.Go out
Water COD can be reduced to 6500mg/L, and wastewater biodegradability B/C ratios are improved to 0.34 from 0.21.
Anaerobic Treatment unit：In the case where anaerobic bacteria acts on, hardly degraded organic substance occurs anaerobic hydrolysis and relatively easily degraded
Organic matter, while part hardly degraded organic substance occurs Co metabolism anaerobic degradation and is converted into relatively easy aerobic degradation organic matter, enters
One step improves wastewater biodegradability, residence time 12h, and wastewater biodegradability is improved to 0.38 from 0.34.
Anoxic treatment unit：Denitrifying bacterium is anti-using the nitrite nitrogen in phegma and nitrate nitrogen progress denitrification
Should, nitrite nitrogen and nitrate nitrogen become nitrogen and removed by anti-nitration reaction, while organic matter supplies as electronics
Body is removed, and particularly some organic matters for being difficult to aerobic degradation can be strengthened by denitrification removes.Residence time 20h.
Aerobic treatment unit：Reacted using microorganism aerobic by contaminant degradations such as organic matter, ammonia nitrogens.Aerobic unit adds
Methanol improves the metabolism environment of microorganism, improves its degradation capability to Recalcitrant chemicals, methanol adds as co-substrate
COD equivalents are 80mg/L, and the residence time is 80h, and the reflux ratio of aerobic nitrification liquid backflow anoxic unit is 3:1.Aerobic Process for Treatment
Water outlet COD can be reduced to 300mg/L afterwards, and ammonia nitrogen is reduced to below 5mg/L.
Coagulation unit：By coagulation go water removal in suspension, coagulant polymeric ferric sulfate, dosage 1000mg/L,
Coagulating time 15min, sedimentation time 1h, water outlet COD are reduced to 180mg/L；
Ozone catalytic oxidation unit：Under the catalysis of heterogeneous catalysis, the organic matter in waste water further reduces waste water COD,
Refractory organic is converted into the organic matter of easily biological-degradable simultaneously, caused ozone tail gas is delivered to electrochemical oxidation
Unit.Catalytic ozonation reaction hydraulic detention time is 30min, ozone dosage 300mg/L；The ozone Oxidation Treatment
Middle addition catalyst is KLCO-3, and KLCO-4, ozone water outlet COD can be reduced to below 100mg/L.
MBR unit：Easily biodegradable organicses caused by ozone oxidation are further degraded, while reduces out aqueous suspension and contains
Amount, MBR unit use flat plate ultrafiltration membrane, and membrane material is Kynoar, and residence time 10h, operating pressure is -35kpa, is gone out
Water COD can be reduced to below 50mg/L.
Reverse osmosis units：Salt content in waste water is reduced, membrane module is rolled membrane module, and membrane material is composite membrane, is used
Two sections of arrangements, intake pressure 0.8-1.5MPa, producing water ratio 75%, reverse osmosis water outlet reach industrial reuse water quality standard.
Finally it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention and it is unrestricted, although reference
The present invention is described in detail for preferred embodiment, it will be understood by those within the art that, can be to the present invention
Technical scheme modify or equivalent substitution, without departing from the spirit and scope of technical solution of the present invention, it all should cover
Among the scope of the claims of the present invention.
Claims (10)
1. a kind of be used for the processing of low temperature distillation waste water and reuse method in coal, it is characterised in that methods described includes pre- successively
Processing, biochemical treatment and advanced treating and reuse.
2. the method as described in claim 1, it is characterised in that the pretreatment for first by the waste water carry out gravity oil removal,
By stripping depickling deamination after filtering, then pass through extracting and dephenolizing, flocculation-air floating removes oil emulsion and suspension, electrochemical oxidation drop
Enter biochemical treatment after low COD.
3. method as claimed in claim 1 or 2, it is characterised in that water outlet enters biochemical treatment, the biochemistry after pretreatment
Processing includes Anaerobic Treatment, anoxic treatment and Aerobic Process for Treatment successively.
4. method as claimed in claim 3, it is characterised in that biochemical treatment water outlet enters advanced treating and reuse, the depth
Degree processing and reuse include coagulating treatment, catalytic ozonation processing, MBR processing and reverse-osmosis treated successively.
5. method as claimed in claim 2, it is characterised in that the gravity oil removal, it is most floating in waste water for removing
Oil and heavy oil, tar is reclaimed, reduce the oil content in waste water, the residence time is 3 ~ 5h, and oil extraction heating-up temperature is more than 70 DEG C；
The filtering, using ceramic membrane filter, for removing the oil and coal ash that are suspended in waste water；
The stripping depickling deamination, for removing CO in waste water2And H2S, reclaim the ammonia in waste water；
The extracting and dephenolizing, for reclaiming the crude phenols in waste water, the ratio between extractant and waste water are 1:5；
The flocculation-air floating, for further removing oil emulsion and suspension in water removal, to reach requirement of the biochemical system to oil,
Flocculant dosage is 50 ~ 300ppm；
The electrochemical oxidation is organic for the organic matter open loop chain rupture of difficult for biological degradation in waste water to be converted into easily biological-degradable
Thing, so as to improve wastewater biodegradability；The electrochemical oxidation residence time is 10 ~ 30min, and current density is 5 ~ 50mA.
6. method as claimed in claim 3, it is characterised in that the Anaerobic Treatment, for hardly degraded organic substance to be detested
Oxygen hydrolysis are the organic matter relatively easily degraded, while part hardly degraded organic substance occurs Co metabolism anaerobic degradation and is converted into relatively
Easy aerobic degradation organic matter, so as to further improve wastewater biodegradability, the residence time is 10 ~ 20h；
The anoxic treatment, total nitrogen is removed by anti-nitration reaction and reinforcing removal part hardly degraded organic substance, residence time are
15~24h；
The Aerobic Process for Treatment, by adding methanol, further to the degradation capability of Recalcitrant chemicals, methanol adds COD ought for raising
It is 50 ~ 100h to measure as 20 ~ 100mg/L, residence time；
The reflux ratio of the Aerobic Process for Treatment nitrification liquid backflow anoxic treatment is 1:1~3:1.
7. method as claimed in claim 4, it is characterised in that the coagulating treatment, go in water removal to suspend by coagulation
Thing；
The coagulant added is preferably the one or more in bodied ferric sulfate, polyaluminium sulfate or polyacrylamide；
The dosage of the coagulant is 3000-1000mg/L, and the coagulating time is 15min ~ 30min, the sedimentation time is 1 ~
3h；
The catalytic ozonation processing：Using the catalytic action of heterogeneous catalysis, the COD in depth degradation waste water, simultaneously
Refractory organic is converted into the organic matter of easily biological-degradable；
The catalytic ozonation processing, hydraulic detention time is 10 ~ 60min, and ozone dosage is 100 ~ 300mg/L；It is described
Catalyst is preferably KLCO-3 or KLCO-4；
The MBR processing：Easily biodegradable organicses caused by ozone oxidation are further degraded, while reduces out aqueous suspension and contains
Amount, the residence time is 5 ~ 15h, and operating pressure is -1 ~ -50kpa；
MBR processing uses hollow fiber ultrafiltration membrane or flat plate ultrafiltration membrane, membrane material be preferably Kynoar, polyether sulfone,
Polyvinyl chloride or the fine one kind of polypropylene；
The reverse-osmosis treated：For reducing salt content in waste water, so as to reach recycle water standard, the feed water by reverse osmosis pressure
For 0.5 ~ 2.0MPa, producing water ratio 70% ~ 80%；
The membrane module that counter-infiltration uses is preferably rolled membrane module, and membrane material is composite membrane, using two sections of arrangements.
8. method as claimed in claim 7, it is characterised in that ozone tail gas caused by the ozone oxidation is delivered to electrochemistry
Oxidation unit, further strengthen electrochemicial oxidation effect.
9. method as claimed in claim 5, it is characterised in that the extracting and dephenolizing includes extraction processing and extractant recovery profit
With, the phenolic compound rate of recovery obtained after extracting and dephenolizing is handled up to more than 95%.
10. method as claimed in claim 5, it is characterised in that the stripping depickling deamination is that single column tower top depickling survey line takes off
Deamination after ammonia or the depickling of two tower elder generations, it is more than 10 that wastewater pH is adjusted wherein before deamination.
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| CN111115977A (en) * | 2020-01-17 | 2020-05-08 | 岳阳林纸股份有限公司 | Method and system for treating quinacridone production wastewater |
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Application publication date: 20180302 |