CN105439368B - A kind of deep treatment method of ethylene waste lye - Google Patents
A kind of deep treatment method of ethylene waste lye Download PDFInfo
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Abstract
The invention discloses a kind of methods of independent processing ethylene waste lye.Fenton oxidation technique is catalyzed using ozone oxidation biological aerated filter, the pretreated ethylene waste lye of wet oxidation is handled, the process runs well, treatment effeciency is high, and effluent quality is good, is discharged colorless and odorless, as clear as crystal, COD<150mg/L, and dilution water is not needed, the consumption of water resource can be reduced, independent processing and the advanced treating of ethylene waste lye are realized.
Description
Technical field
The present invention relates to the deep treatment methods of a kind of strong basicity, high salinity, high COD petrochemical wastewaters more specifically to relate to
And a kind of deep treatment method through the pretreated ethylene waste lye of wet oxidation.
Background technology
Ethylene waste lye is the waste liquid that the sour gas generated in ethylene production is formed after alkali cleaning is handled, wherein removing
Outside containing remaining NaOH, also contain the Na generated in alkaline cleaning procedure2S、Na2CO3Equal inorganic salts, simultaneously as in cracking gas
The polymerization of the condensation and diene hydrocarbons of heavy constituent makes a large amount of organic matter also enter in spent lye, therefore, ethylene waste lye
Be a kind of typical strong basicity, high salinity, high COD petrochemical wastewater.
For the processing of ethylene waste lye, generally adopt the technology that at present：Wet type oxygen is carried out to ethylene waste lye first
Change, desulfuration-deodorization, then, with other waste water mixed dilutings, is discharged into composite wastewater treatment plant and carries out aerobic treatment.Aerobic life
Chemical industry skill generally use activated sludge process and contact oxidation method.There are the following problems for this treatment process：(1) in ethylene waste lye
Salt content is very high, it is suppressed that the normal growth of microorganism causes aerobic sludge slow-growing, and activity reduces, and settleability is poor, sludge
It is lost in serious.(2) it needs to consume a large amount of dilution water.In order to reduce influence of the salinity to microorganism in ethylene waste lye, need
It is diluted with a large amount of hyposaline waste water, extension rate is usually several times or even dozens of times, considerably increases the water consumption of enterprise.
(3) machine object biodegradability contained in ethylene waste lye is poor, these hardly degraded organic substances accumulate for a long time in biochemical system,
The efficiency for having seriously affected biochemical system causes Biochemical Treatment bad, and water outlet is difficult to qualified discharge.In order to avoid ethylene is useless
Impact of the lye to biochemical system mitigates treatment pressure of sewage, improve it is outer drain compliance rate, many enterprises, which take, " to remove contamination point
Stream, dirty dirt are divided and ruled " measure, it is quasi- that ethylene waste lye is individually handled.
In the prior art, Chinese patent CN101693579A discloses a kind of processing method of high-concentration wastewater containing alkaline mud,
Method is discharged to passing through the pretreated refinery basic sewage of mild wet air oxidation process, aerobic using light electrolysis-coagulation-acidification hydrolization-
Biochemistry-precipitation-sterilization process is handled, and water outlet can be directly discharged to urban sewage pipe, receiving water body or be incorporated to other
System processing, can also meet reuse standard.
Chinese patent CN102690017A discloses a kind of the treatment for reuse system and treatment for reuse method of sewage in ethylene plant：
Ethylene waste lye mixes after wet oxidation is handled with recirculated cooling water sewerage, then in turn through biological aerated filter, height
After grade oxidation and biological aerated filter processing, with acidic and alkaline waste water dual disposal.
Chinese patent CN103359880A discloses a kind of biochemical treatment process method of ethylene waste lye, and the technique is by two
A activated Sludge System and a biological aerated filter Cascade System are constituted, and are added in first activated sludge aeration reaction tank
Intermediate thiobacilli Thiomonas intermedia BCRC17547 are added false single in second activated sludge aeration reaction tank
Born of the same parents bacterium Pseudomonas sp.XQ3m-2CCTCCM2010162, are added pseudomonad in biological aerated filter
Pseudomonas sp.XQ3e CCTCCM209182, three cascade reaction ponds give full play to the addition respective speciality of strain, real
Now have complementary functions.The technique has the advantages that high treating effect, impact resistance strong, stable effluent quality, processing cost are low etc..
In above-mentioned three patented technologies, patent CN101693579A is proposed for refinery basic sewage waste water, especially suitable
In the advanced treating through the pretreated refinery basic sewage waste water of wet oxidation.Patent CN102690017A be by ethylene waste lye with
After other waste water mixed processings of ethylene plant, through rushing dilute discharge, need to consume Macrodilution water.Patent CN103359880A is adopted
The efficient process to ethylene waste lye is realized with special microorganism fungus kind, still, which also needs to use hyposaline
Waste water is diluted the ethylene waste lye after wet oxidation, and extension rate is 4~13 times.
It can be seen that for the independent processing of the pretreated ethylene waste lye of wet oxidation, not yet formed at present effective
Technique.
Invention content
The invention discloses a kind of methods of independent processing ethylene waste lye, it is intended to solve existing ethylene waste lye processing skill
The problem that water consumption is big, biochemical treatment efficiency is low, effluent quality is poor is diluted in art.It is urged using ozone oxidation-biological aerated filter-
Change Fenton oxidation technique, the pretreated ethylene waste lye of wet oxidation is handled, fortune can be realized to provide one kind
Row stabilization, effluent quality are good, COD removal rates are high, can individually handle the method with advanced treating ethylene waste lye.
What the method for the present invention was realized in：
Heretofore described ethylene waste lye is through the pretreated ethylene waste lye of wet oxidation, main water quality characteristic
Parameter is as follows：PH >=12, COD concentration are between 5000~7000mg/L, Na+Concentration between 10000~20000mg/L,
SO4 2-、SO3 2-And S2O3 2-Total concentration between 7000~25000mg/L, conductivity between 40000~70000us/cm,
Coloration is between 50~200.
A kind of deep treatment method of ethylene waste lye, this method include the following steps successively：
(1) ozone oxidation：Ethylene waste lye enters ozone oxidation reaction device and carries out oxidation processes.
(2) pH value is adjusted：Ethylene waste lye after ozone oxidation enters pH value regulating reservoir, and it is useless to adjust ethylene with the concentrated sulfuric acid
The pH value of lye is between 7.0~9.0.
(3) biological aerated filter：The ethylene waste lye for regulating pH value enters biological aerated filter, carries out at aerobic biochemical
Reason.
(4) pH value is adjusted：The water outlet of biological aerated filter enters pH value regulating reservoir, and sulfuric acid is added in regulating reservoir, adjusts
PH value is between 3.0~5.0.
(5) it is catalyzed Fenton oxidation：The bio-chemical effluent for regulating pH value enters catalysis Fenton oxidation reactor, catalysis
Activated-carbon catalyst is loaded in Fenton oxidation reactor, sequentially adds ferrous sulfate and hydrogen peroxide (H2O2), and it is aided with machinery
Stirring, carries out catalysis Fenton oxidation.
(6) it precipitates：Through being catalyzed Fenton oxidation, treated that ethylene waste lye enters sedimentation basin, is added into sedimentation basin
Alkali adjusts pH value between 8.5~9.0, carries out precipitation process, realizes and be separated by solid-liquid separation.
When it is implemented, in step (1), ozone oxidation reaction device bottom is laid with aeration tube.Ethylene waste lye enters smelly
Oxygen oxidation reactor, logical ozone are aerated.Ozone generator outlet ozone flow is adjusted between 50~100L/h, when aeration
Between be 60~90min.Ozone is prepared by ozone generator.
When it is implemented, in step (1), into the ethylene waste lye of ozone oxidation reaction device, pH value >=12.
When it is implemented, in step (3), the ethylene waste lye to regulating pH value carries out aerobic treatment.It is aerobic
Biochemical reactor uses biological aerated filter.Filler in biological aerated filter can select inorganic filler such as：Biological shale pottery
Grain, volcanic rock biological filter material, zeolite, expansion alumino-silicate etc., can also select organic polymer filler such as：Polystyrene gathers
Vinyl chloride, polypropylene, polyurethane material etc..In biological aerated filter, a certain amount of nutritive salt is added, wherein nitrogen source is selected from
Ammonium chloride, phosphate are selected from potassium dihydrogen phosphate or sodium dihydrogen phosphate, and the ammonium chloride and phosphatic addition are：Biochemistry water inlet
COD：N：The mass ratio of P is 100：5：1.Meanwhile suitable trace element is added, including：10~30mg/L of iron chloride, magnesium sulfate
10~50mg/L, 10~20mg/L of calcium chloride, 1~3mg/L of zinc sulfate, 0.1~0.5mg/L of cobalt chloride, manganese chloride 0.1~
0.1~0.2mg/L of 0.3mg/L and potassium iodide.
When it is implemented, in step (3), the condition of aerobic treatment is：48~72h of hydraulic detention time, sludge
5~7g/L of concentration, 4~6mg/L of dissolved oxygen concentration, pH value 7.0~9.0.
When it is implemented, in step (4), the water outlet of biological aerated filter enters pH value regulating reservoir, is adjusted with the concentrated sulfuric acid
The pH value of waste water is between 3.0~5.0.
When it is implemented, in step (5), it is catalyzed in Fenton oxidation reactor and loads activated-carbon catalyst filler, fill out
Charge is the 5~10% of reactor volume.Activated-carbon catalyst selects commercial product, is by activated carbon supported transiting metal oxidation
Made of object.Its appearance is cylindric, appearance and size：3~5 × 10mm of φ, moisture<5%, mechanical strength>90, year breakage rate<
5%.
When it is implemented, in step (5), in being catalyzed Fenton oxidation reactor, ferrous sulfate and mistake are sequentially added
Hydrogen oxide, 2~3h of mechanic whirl-nett reaction.Wherein, H2O2/Fe2+Molar ratio between 8~12, H2O2The mass ratio of/COD exists
Between 2.0~3.0.
When it is implemented, in step (6), the alkali is sodium hydroxide.
The processing method of the present invention, using ozone oxidation-biological aerated filter-catalysis Fenton oxidation process wet type
Ethylene waste lye after oxidation pre-treatment：
1, ozone oxidation
Ethylene waste lye is typical highly salt containing organic waste water.On the one hand, through the pretreated ethylene salkali waste of wet oxidation
In liquid, Na+Concentration is between 10000~20000mg/L, SO4 2-、SO3 2-And S2O3 2-Total concentration 7000~25000mg/L it
Between, conductivity is between 40000~70000us/cm.So high salinity generates inhibition to the growth and breeding of microorganism, leads
Microbial activity is caused to reduce, treatment effect declines, and is mainly manifested in：Excessively high salinity is easy that microbial cell dehydration is made to cause
Cellular plasm detaches, meanwhile, salting out can be such that the activity of dehydrogenase in microbial body reduces again.On the other hand, ethylene is useless
Hardly degraded organic substance content is high in lye, the poor (B/C of biodegradability<0.1), direct biochemical treatment efficiency is very low, for this purpose, right first
Ethylene waste lye carries out chemical oxidation treatment.
Ozonation technology is a kind of advanced oxidation technology to grow up in recent ten years, is usually used in difficult to degrade
The processing of organic wastewater.Studies have shown that under alkaline condition, ozone can decompose in water body generates hydroxyl radical free radical (OH), oxygen
Change degradation gas chromatography.Therefore, ozone oxidation can either significantly reduce the COD in waste water, and can make giving birth to for waste water
The property changed is improved, in addition, also very strong decoloring ability, can significantly improve the apparent effect of water outlet.
The pretreated ethylene waste lye alkalinity of wet oxidation is very strong, usual pH value >=12, can directly carry out ozone oxygen
Change, without carrying out acid-base accommodation, to simplify technological operation.
The pretreated ethylene waste lye coloration of wet oxidation is in light yellow between 50~200, after ozone oxidation,
Coloration<1, water outlet is as clear as crystal, meanwhile, COD concentration substantially reduces, and biodegradability improves, and is conducive to subsequent biochemical processing.This
Outside, during ozone oxidation, secondary pollution is not generated, sludge is not generated, operated and manage and is very convenient.
2, biological aerated filter
Ethylene waste lye is after ozone Oxidation Treatment, and major part organic matter therein is completely removed, and biodegradability obtains
Improve, suitable for carrying out biochemical treatment.In order to further increase effluent quality, optimization processing efficiency, the present invention uses aeration and biological
Filter tank is as aerobic biochemical reactor.This is because：Biological aerated filter is to be incorporated in bio-contact oxidation and in-depth filtration
A kind of novel biochemical reactor together can synchronize and play biological oxidation and Physical entrapment effect, oxygen transfer and utilization ratio
Height, sludge concentration is high and not easily runs off, and treatment effeciency is high, and effluent quality is good.
In biological aerated filter, the filtrate as biofilm carrier is the core of the technique.Filtrate affects microorganism
Growth, breed, fall off and form, absorption and crown_interception are played to the suspended matter in sewage, while also acting as retention sludge, cut
It cuts, stop bubble, increase residence time and gas liquid interfacial area of the bubble in water body, improve a variety of effects such as mass-transfer efficiency.
The filler of biological aerated filter can select inorganic filler such as：Biological haydites of book structure, zeolite, active volcanic rock etc., can also select
Such as with organic filler：The tubulose made by fiberglass, polyvinyl chloride, polypropylene, polyurethane, vinylon etc., pencil, netted, bee
Nest shape filler etc..
In the pretreated ethylene waste lye of wet oxidation, the content of nitrogen and phosphorus element is insufficient, and therefore, it is necessary to be given birth in aeration
A certain amount of nutritive salt is added in object filter tank, wherein nitrogen source is selected from ammonium chloride, and phosphate is selected from potassium dihydrogen phosphate or biphosphate
Sodium, the ammonium chloride and phosphatic addition are：Biochemical influent COD：N：The mass ratio of P is 100：5：1.In order to promote micro- life
Its treatment effeciency is strengthened in the growth of object, it is also necessary to a small amount of iron, magnesium, calcium, zinc, cobalt, manganese and potassium trace element are added, this is because：
Many biological enzyme of degradation of contaminant are to complete their exclusive catalytic decomposition function, metal by the presence of various metals
It is the activated centre of prothetic group enzyme, if lacking these metal ions in water body, the bioactivity of microorganism will be greatly reduced, even
It loses activity, directly results in water treatment effect decline.
3, it is catalyzed Fenton oxidation
Ethylene waste lye is after aerobic treatment, only remaining a small amount of hardly degraded organic substance.In order to further increase processing
Depth, improves effluent quality, and the present invention is handled using catalysis Fenton oxidation.Fenton oxidation is with ferrous ion (Fe2 +) it is catalyst, with hydrogen peroxide (H2O2) carry out chemical oxidation wastewater treatment method.It is mainly characterized by hydrogen peroxide in Asia
Under the catalytic action of iron ion generate the very strong hydroxyl radical free radical of oxidability (OH), using hydroxyl radical free radical as oxidant with have
Machine object reacts, and organic matter is finally decomposed to carbon dioxide and water, to achieve the purpose that oxidative degradation organic matter, especially
It is suitable for the oxidation processes of bio-refractory or general chemical oxidation organic wastewater hard to work.
Fenton oxidation technique is catalyzed to be added that is, in the Fenton oxidation system that hydrogen peroxide and ferrous ion form
Compound activated-carbon catalyst.Compound activated-carbon catalyst be activated carbon supported transition metal oxide and made of,
Feature is as follows：(1) there is huge specific surface area and loose porous structure feature, this adds increased the contacts of oxidation reaction
Face.(2) there is activated-carbon catalyst excellent Electronic Performance, surface to contain a large amount of acid or basic group, such as：Carboxyl,
Phenolic hydroxyl group, quinoid carbonyl, positive lactone group and epoxy formula peroxy etc., in foring many activity on the surface of catalyst
The presence of the heart, these groups can promote H2O2It is decomposed on its surface and releases atomic oxygen or generation OH, to improve H2O2
Utilization rate, strengthen Fenton oxidation effect.(3) activated-carbon catalyst also has certain reproducibility, is decomposing hydrogen peroxide
In the process, own face can be oxidized to the oxygen-containing group with oxidation susceptibility, these oxygen-containing groups can be with having in waste water
Machine object reacts, and is conducive to the decomposition of organic pollution.
After being catalyzed Fenton oxidation, it will a certain amount of molysite residue is generated, after precipitation, water outlet is as clear as crystal,
Colorless and odorless.
For ethylene waste lye after above-mentioned process, effluent quality is good, and COD removal rates are high, realize ethylene waste lye
Individually processing and advanced treating, and the process runs well.
Beneficial effects of the present invention：(1) it is pre-processed using ozone oxidation, has both reduced the COD in ethylene waste lye,
Biodegradability is improved again, is laid a good foundation for follow-up aerobic treatment.(2) ozone oxidation-biological aerated filter-catalysis
Fenton oxidation technique can individually be handled ethylene waste lye, not need dilution water, reduce the consumption of water resource.
(3) use ozone oxidation-biological aerated filter-catalysis Fenton oxidation technique to the pretreated ethylene waste lye of wet oxidation
It is handled, the process runs well, treatment effeciency is high, and effluent quality is good, is discharged colorless and odorless, as clear as crystal, COD<
150mg/L realizes the advanced treating of ethylene waste lye.
Description of the drawings
Fig. 1 is the process flow chart of the pretreated ethylene waste lye advanced treating of wet oxidation.
Specific implementation mode
In the following, with reference to the drawings and specific embodiments, the technical solution that the present invention is further explained.
Ethylene waste lye in embodiment is derived from certain Ethylene in Petrochemical Enterprises spent lye wet oxidation workshop, pre- through wet oxidation
Treated ethylene waste lye.Its main water quality characteristic parameter is as follows：PH >=12, COD concentration between 5000~7000mg/L,
Na+Concentration is between 10000~20000mg/L, SO4 2-、SO3 2-And S2O3 2-Total concentration between 7000~25000mg/L, electricity
Conductance is between 40000~70000us/cm, and coloration is between 50~200.
Embodiment 1
Ethylene waste lye is derived from certain ethylene waste lye wet oxidation workshop, and main water quality characteristic parameter is as follows：COD：
6936mg/L, coloration：200, pH value：13.21 conductance：40700us/cm, Na+：17082.2mg/L SO4 2-、S2O3 2-And SO3 2-
Total amount：22207.7mg/L.
Specific processing step is as follows：
(1) the pretreated ethylene waste lye of wet oxidation enters ozone oxidation reaction device, adjusts ozone generator outlet
Ozone flow is between 90~100L/h, continuous aeration time 60min.
(2) ethylene waste lye after ozone oxidation enters pH value regulating reservoir, its pH value is adjusted to 7.0 with the concentrated sulfuric acid.
(3) water outlet of step (2) enters biological aerated filter progress aerobic biochemical.Aerobic sludge in biological aerated filter
By being obtained after oil refining sewerage factory secondary settling tank sludge for agricultural use.Filler in biological aerated filter selects the shale pottery of different gradation
Grain biofilter material, particle size range is between 5~30mm.A certain amount of nutritive salt is added in biological aerated filter, wherein nitrogen source
For ammonium chloride, phosphate is potassium dihydrogen phosphate, and the addition of the ammonium chloride and potassium dihydrogen phosphate is：Biochemical influent COD：N：P
Mass ratio be 100：5：1.Trace element includes：Iron chloride 10mg/L, magnesium sulfate 20mg/L, calcium chloride 10mg/L, zinc sulfate
2mg/L, cobalt chloride 0.2mg/L, manganese chloride 0.1mg/L and potassium iodide 0.1mg/L.The treatment conditions of biological aerated filter are：Water
Power residence time 72h, 6~7g/L of sludge concentration, 4~6mg/L of dissolved oxygen concentration, pH value 7.0~7.5.
(4) water outlet of biological aerated filter enters pH value regulating reservoir, and pH value is adjusted to 3.0 with the concentrated sulfuric acid.
(5) water outlet of step (4) enters catalysis Fenton oxidation reactor.It is catalyzed to load in Fenton oxidation reactor and live
Property Pd/carbon catalyst, packing volume 10%, activated-carbon catalyst appearance and size：3~5 × 10mm of φ.Sequentially add ferrous sulfate and
Hydrogen peroxide, wherein H2O2/Fe2+Molar ratio be 12, H2O2The mass ratio of/COD is 3.0.Mechanical agitation, reaction time is
3h。
(6) NaOH solution is added into catalysis Fenton oxidation treated ethylene waste lye, adjusts pH value to 8.5, sinks
It forms sediment, realizes and be separated by solid-liquid separation.
After above-mentioned process, effluent quality situation is as shown in table 1.
The situation of change of ethylene waste lye after 1 wet oxidation of table COD before and after the processing
Embodiment 2
Ethylene waste lye is derived from certain ethylene waste lye wet oxidation workshop, and main water quality characteristic parameter is as follows：COD：
5932mg/L, coloration：100, pH value：13.0 conductance：66900us/cm, Na+：17123.3mg/L SO4 2-、S2O3 2-And SO3 2-Always
Amount：18167.2mg/L.
Specific processing step is as follows：
(1) the pretreated ethylene waste lye of wet oxidation enters ozone oxidation reaction device, adjusts ozone generator outlet
Ozone flow is between 70~80L/h, continuous aeration time 75min.
(2) ethylene waste lye after ozone Oxidation Treatment enters pH value regulating reservoir, with the concentrated sulfuric acid adjust its pH value to
8.0。
(3) water outlet of step (2) enters biological aerated filter progress aerobic treatment.It is aerobic in biological aerated filter
Sludge after oil refining sewerage factory secondary settling tank sludge for agricultural use by obtaining.Filler in biological aerated filter selects the page of different gradation
Rock ceramic granule biofilter material, particle size range is between 5~30mm.A certain amount of nutritive salt is added in biological aerated filter, wherein
Nitrogen source is ammonium chloride, and phosphate is sodium dihydrogen phosphate, and the addition of the ammonium chloride and sodium dihydrogen phosphate is：Biochemical influent COD：
N：The mass ratio of P is 100：5：1.Trace element includes：Iron chloride 15mg/L, magnesium sulfate 10mg/L, calcium chloride 15mg/L, sulfuric acid
Zinc 1mg/L, cobalt chloride 0.1mg/L, manganese chloride 0.2mg/L and potassium iodide 0.1mg/L.The treatment conditions of biological aerated filter are：
Hydraulic detention time 60h, 5~6g/L of sludge concentration, 4~6mg/L of dissolved oxygen concentration, pH value 7.5~8.0.
(4) water outlet of biological aerated filter enters pH value regulating reservoir, its pH value is adjusted to 4.0 with the concentrated sulfuric acid.
(5) water outlet of step (4) enters catalysis Fenton oxidation reactor.It is catalyzed to load in Fenton oxidation reactor and live
Property Pd/carbon catalyst, packing volume 8%, activated-carbon catalyst appearance and size：3~5 × 10mm of φ.Sequentially add ferrous sulfate and mistake
Hydrogen oxide, wherein H2O2/Fe2+Molar ratio be 10, H2O2The mass ratio of/COD is 2.5.Mechanical agitation, reaction time is
2.5h。
(6) NaOH solution is added into catalysis Fenton oxidation treated ethylene waste lye, adjusts pH value to 9.0, sinks
It forms sediment, realizes and be separated by solid-liquid separation.
After above-mentioned process, effluent quality situation is as shown in table 2.
The situation of change of ethylene waste lye after 2 wet oxidation of table COD before and after the processing
| Project | Water inlet | Ozone oxidation | Biological aerated filter | It is catalyzed Fenton oxidation |
| Conductance (us/cm) | 66900 | |||
| COD(mg/L) | 5932 | 1631 | 730 | 101 |
| Coloration | 100 | <1 | ||
| COD accumulative removals | 72.5 | 87.7 | 98.3 |
| Rate (%) |
Embodiment 3
Ethylene waste lye is derived from certain ethylene waste lye wet oxidation workshop, and main water quality characteristic parameter is as follows：COD：
5012mg/L, coloration：50, pH value：12.0 conductance：49000us/cm, Na+：12467.6mg/L SO4 2-、S2O3 2-And SO3 2-Always
Amount：7109.4mg/L.
Specific processing step is as follows：
(1) the pretreated ethylene waste lye of wet oxidation enters ozone oxidation reaction device, adjusts ozone generator outlet
Ozone flow is between 50-60L/h, continuous aeration time 90min.
(2) ethylene waste lye after ozone Oxidation Treatment enters pH value regulating reservoir, with the concentrated sulfuric acid adjust its pH value to
9.0。
(3) water outlet of step (2) enters biological aerated filter progress aerobic biochemical.Aerobic sludge in biological aerated filter
By being obtained after oil refining sewerage factory secondary settling tank sludge for agricultural use.It is the poly- of 3-5cm that filler in biological aerated filter, which selects the length of side,
Urethane sponge block.A certain amount of nutritive salt is added in biological aerated filter, wherein nitrogen source is ammonium chloride, and phosphate is phosphoric acid
The addition of potassium dihydrogen, the ammonium chloride and potassium dihydrogen phosphate is：Biochemical influent COD：N：The mass ratio of P is 100：5：1.It is micro
Element includes：Iron chloride 30mg/L, magnesium sulfate 50mg/L, calcium chloride 20mg/L, zinc sulfate 3mg/L, cobalt chloride 0.5mg/L, chlorine
Change manganese 0.3mg/L and potassium iodide 0.2mg/L.The treatment conditions of biological aerated filter are：Hydraulic detention time 48h, sludge concentration
5-6g/L, 4~6mg/L of dissolved oxygen concentration, pH value 8.0~9.0.
(4) water outlet of biological aerated filter enters pH value regulating reservoir, its pH value is adjusted to 5.0 with the concentrated sulfuric acid.
(5) water outlet of step (4) enters catalysis Fenton oxidation reactor.It is catalyzed to load in Fenton oxidation reactor and live
Property Pd/carbon catalyst, packing volume 5%, activated-carbon catalyst appearance and size：3~5 × 10mm of φ.Sequentially add ferrous sulfate and mistake
Hydrogen oxide, wherein H2O2/Fe2+Molar ratio be 8, H2O2The mass ratio of/COD is 2.0.Mechanical agitation, reaction time 2h.
(6) NaOH solution is added into catalysis Fenton oxidation treated ethylene waste lye, adjusts pH value to 8.7, sinks
It forms sediment, realizes and be separated by solid-liquid separation.
After above-mentioned process, effluent quality situation is as shown in table 3.
The situation of change of ethylene waste lye after 3 wet oxidation of table COD before and after the processing
The foregoing is merely the preferable possible embodiments of the present invention, not thereby limit to the scope of the claims of the present invention, therefore all
It is to be both contained in protection scope of the present invention with equivalence changes made by description of the invention and accompanying drawing content.
Claims (2)
1. a kind of deep treatment method of ethylene waste lye, includes the following steps：
(1) ozone oxidation：Ethylene waste lye enters ozone oxidation reaction device and carries out oxidation processes；
(2) pH value is adjusted：Ethylene waste lye after ozone oxidation enters pH value regulating reservoir, and ethylene waste lye is adjusted with the concentrated sulfuric acid
PH value between 7.0~9.0；
(3) biological aerated filter：The ethylene waste lye for regulating pH value enters biological aerated filter, carries out aerobic treatment；
(4) pH value is adjusted：The water outlet of biological aerated filter enters pH value regulating reservoir, and sulfuric acid is added in regulating reservoir, adjusts pH value
Between 3.0~5.0；
(5) it is catalyzed Fenton oxidation：The bio-chemical effluent for regulating pH value enters catalysis Fenton oxidation reactor, is catalyzed Fenton
Activated-carbon catalyst is loaded in oxidation reactor, sequentially adds ferrous sulfate and hydrogen peroxide (H2O2), and it is aided with mechanical agitation,
Carry out catalysis Fenton oxidation；
(6) it precipitates：Through being catalyzed Fenton oxidation, treated that ethylene waste lye enters sedimentation basin, and alkali is added into sedimentation basin, adjusts
PH value is saved between 8.5~9.0, precipitation is realized and is separated by solid-liquid separation；
In the ethylene waste lye：COD concentration 5000~7000mg/L, Na+Concentration is in 10000~20000mg/L, SO4 2-、
SO3 2-And S2O3 2-Total concentration in 7000~25000mg/L, conductivity is in 40000~70000us/cm, and coloration is 50~200；
In step (1), ozone oxidation reaction device bottom is laid with aeration tube；Ethylene waste lye enters ozone oxidation reaction device,
Logical ozone is aerated；Adjust ozone generator outlet ozone flow between 50~100L/h, aeration time be 60~
90min；
In step (1), into the ethylene waste lye of ozone oxidation reaction device, pH value >=12；
In step (3), the filler in biological aerated filter selects inorganic filler or organic polymer filler；It is filtered in aeration and biological
Chi Zhong adds a certain amount of nutritive salt, wherein and nitrogen source is selected from ammonium chloride, and phosphate is selected from potassium dihydrogen phosphate or sodium dihydrogen phosphate,
The ammonium chloride and phosphatic addition are：Biochemical influent COD：N：The mass ratio of P is 100：5：1；Meanwhile addition is suitable
Trace element includes：10~30mg/L of iron chloride, 10~50mg/L of magnesium sulfate, 10~20mg/L of calcium chloride, 1~3mg/ of zinc sulfate
L, 0.1~0.2mg/L of 0.1~0.5mg/L of cobalt chloride, 0.1~0.3mg/L of manganese chloride and potassium iodide；
In step (3), the condition of aerobic treatment is：48~72h of hydraulic detention time, 5~7g/L of sludge concentration, dissolving
4~6mg/L of oxygen concentration, pH value 7.0~9.0；
In step (5), activated-carbon catalyst filler loading is the 5~10% of reactor volume；
In step (5), in being catalyzed Fenton oxidation reactor, ferrous sulfate and hydrogen peroxide, mechanical agitation are sequentially added
React 2~3h；Wherein, H2O2/Fe2+Molar ratio 8~12, H2O2The mass ratio 2.0~3.0 of/COD；
It is discharged COD<150mg/L.
2. the deep treatment method of ethylene waste lye according to claim 1, which is characterized in that in step (6), the alkali
For sodium hydroxide.
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| CN201410373395.XA CN105439368B (en) | 2014-07-31 | 2014-07-31 | A kind of deep treatment method of ethylene waste lye |
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| CN108516634A (en) * | 2018-05-15 | 2018-09-11 | 济南云水腾跃环保科技有限公司 | A kind of catalytic ozonation processing method of alkalinity organic wastewater containing stink |
| CN109052850A (en) * | 2018-09-03 | 2018-12-21 | 河南省众和环保科技有限公司 | A kind of standard processing method of petroleum and the high sulfur-containing waste lye of coal chemical industry |
| CN110357369A (en) * | 2019-08-20 | 2019-10-22 | 陕西科技大学 | A kind of method of aerobic biodegradation and Fenton oxidation Combined Treatment cationic quaternary ammonium salt form polyvinyl waste water |
| CN112678984A (en) * | 2019-10-17 | 2021-04-20 | 中国石油化工股份有限公司 | Treatment method of cleaning wastewater of butylbenzene emulsion device |
| CN112850944B (en) * | 2020-12-23 | 2023-05-16 | 苏州清然环保科技有限公司 | Treatment method of ethylene waste caustic sludge wastewater |
| CN115594320B (en) * | 2021-06-28 | 2024-06-04 | 中国石油化工股份有限公司 | Treatment method of oil refining waste alkali liquor |
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