CN105859034B - A kind of high COD, the organic salt acidic organic chemical waste water processing method of high concentration - Google Patents
A kind of high COD, the organic salt acidic organic chemical waste water processing method of high concentration Download PDFInfo
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Abstract
The invention discloses a kind of high COD, the organic salt acidic organic chemical waste water processing method of high concentration comprising hydrogen peroxide and ferrous sulfate, Ca (OH) successively S1, following steps: are added into waste water2And Na2CO3, stirring and adjusting pH value to 6.5-8.5 removes precipitating after static 1h, organic chemical waste water is discharged into sedimentation basin；Molecular sieve is added in S2, the waste water into S1, stirs, precipitating is removed after static 1h, supernatant is discharged into anaerobic reactor；Supernatant temperature is 15-35 DEG C in S3, maintenance S2, adds nitrogen phosphorus source according to the ratio that COD:N:P is 450:5:1, adjusting pH value is 7.5-8.5, and addition sulfate reduction flora carries out Anaerobic Treatment, and hydraulic retention is delivered in aerobic reactor afterwards for 24 hours；Supernatant temperature is 20-35 DEG C in S4, maintenance S3, nitrogen phosphorus source is added according to the ratio that COD:N:P is 250:5:1, adjusting pH value is 6.5-8, it adds Halophiles group and salt-tolerant cultures carries out one section of Aerobic Process for Treatment, aeration stirring, hydraulic retention is for 24 hours afterwards through two sections of Aerobic Process for Treatment, and aeration stirring, hydraulic retention is for 24 hours；S5, precipitating and supernatant water outlet.
Description
Technical field
The present invention relates to environmental projects and microorganisms technical field, more specifically, it relates to a kind of high COD, high concentration
Organic salt acidic organic chemical waste water processing method.
Background technique
Due to science and technology development and process of industrialization quickening, chemical industry, printing and dyeing, marine products processing, mineral mining,
The fields such as pesticide, papermaking and oil recovery can generate high COD and waste water with high salt, wherein not only containing high concentration it is inorganic from
Son, such as Cl-、Na+、SO4 2-、K+、Ca2+And Mg2+Deng, but also contain a large amount of organic pollutant, if being directly discharged to soil to it
In earth or water, the inorganic salts ion of high concentration, which penetrates into soil, causes the plant in soil dead due to dehydration, and high concentration
Inorganic salts ion also result in the plants mass propagation such as algae in water and eventually lead to eutrophication；Organic pollutant can be into
One step accelerates soil or water body to deteriorate.High-salt wastewater can not voluntarily be degraded by soil or water body, will lead to environmental pressure increase, and
The waste water drained into water can endanger aquatic animals and plants and the health of the mankind.Therefore, for high COD and organic wastewater with high salt and
Speech, processing technique is more crucial, and can just it be discharged by reaching national emission standard after processing.
The Chinese patent that application publication number is CN101618920A, data of publication of application is on May 30th, 2012 discloses one
The high COD of kind, high ammonia nitrogen, high salinity process for treating industrial waste water belong to wastewater treatment more particularly to a kind of chemical treatment, micro- life
The joint waste water treatment technology that object processing, membrane bioreactor advanced treating, reverse osmosis composite membrane desalination finishing are handled.
Provide before a kind of processing need not dilution, me.mbrane bioreactor processing it is high for COD, ammonia nitrogen removal frank, anti-pollution reverse osmosis membrane
Desalination, water quality that treated reach the ideal wastewater treatment method of medium-pressure boiler water technical standard.
In the prior art, by after internal mechanical admixture removal, during chemical treatment, antisludging agent, inhibition are added
After agent and dispersing agent, directly progress biochemical treatment.In the process, due in industrial wastewater there are a large amount of inorganic ions with
And the substances such as ammonia nitrogen, after adding chemical assistant, it may appear that the deposit that a large amount of dispersing agents can not disperse, to biochemical treatment
Membrane bioreactor employed in journey impacts, and will lead to the precipitated substance of membrane component and is blocked, Yi Yinqi membrane component
Treatment effect reduces, and since the price of membrane component is higher, to increase processing cost.
Summary of the invention
It is organic salt acidic in view of the deficiencies of the prior art, the present invention intends to provide a kind of high COD, high concentration
Organic chemical waste water processing method.
To achieve the above object, the present invention provides the following technical scheme that
A kind of high COD, the organic salt acidic organic chemical waste water processing method of high concentration, include the following steps:
S1, hydrogen peroxide and ferrous sulfate, Ca (OH) are successively added into organic chemical waste water2And Na2CO3, sufficiently stir
It mixes and adjusts pH value to 6.5-8.5, precipitating is removed after static 1h, organic chemical waste water is discharged into sedimentation basin；
Molecular sieve is added in S2, the organic chemical waste water into step S1, is sufficiently stirred, precipitating is removed after static 1h, it will
Supernatant is discharged into anaerobic reactor；
Supernatant temperature is 15-35 DEG C in S3, maintenance step S2, adds nitrogen phosphorus according to the ratio that COD:N:P is 450:5:1
Source, adjusting pH value are 7.5-8.5, and sulfate reduction flora is added and carries out Anaerobic Treatment, hydraulic retention is delivered to aerobic anti-afterwards for 24 hours
It answers in device；
Supernatant temperature is 20-35 DEG C in S4, maintenance step S3, adds nitrogen phosphorus according to the ratio that COD:N:P is 250:5:1
Source, adjusting pH value are 6.5-8, add Halophiles group and salt-tolerant cultures carry out one section of Aerobic Process for Treatment, aeration stirring, hydraulic retention
For 24 hours afterwards through two sections of Aerobic Process for Treatment, aeration stirring again, hydraulic retention is for 24 hours；
S5, precipitating and supernatant water outlet.
In the application, hydrogen peroxide and ferrous sulfate are added first, after being sufficiently stirred, in acid organic wastewater, mistake
Hydrogen oxide and Fe2+Interaction forms the hydroxyl radical free radical with superpower oxidisability, and it is anti-that chain type occurs with the organic matter in waste water
It answers, so that organic matter is converted to mineral salt and carbon dioxide etc., facilitates next operation.Hydrogen peroxide simultaneously
It can be by Fe2+It is converted to Fe3+, to form ferric hydroxide precipitate, will not due to ferrous ion addition and make inorganic in waste water
Salt ion quantity increases.Add Ca (OH)2And Na2CO3, by stirring so that calcium ion and carbanion, hydroxyl with
The Fe of aluminium ion, hydroxyl and magnesium ion, hydroxyl and remaining not formed precipitating3+Between come into full contact with, formed precipitating, thus
By carbonate, calcium ion and the remaining Fe in organic wastewater3+Carry out precipitation process.Through Ca (OH)2And Na2CO3Treated
Still there is more suspended matter in organic wastewater, can not be precipitated since its quality is lower, molecular sieve itself has a large amount of holes,
Adsorbable suspended matter after separating deposit, further purifies waste water with suspended matter coprecipitation, also avoidable and waste water
In the excessive next further purified treatment of ion pair generate obstruction.
Ca(OH)2And Na2CO3In conjunction with the hydrogen ion in acidic organic wastewater, form water and carbon dioxide, reduce hydrogen from
Sub- concentration quickly improves its pH value to 6.5-8.5 to change the acid-base property of organic wastewater, reach suitable microorganism growth and
The pH value of breeding improves the efficiency of microbial cleaning waste water to make microorganism fast-growth and breeding in waste water.Using detesting
The processing mode of oxygen and two sections of aerobic combinations, flora using nitrogen phosphorus source as nutrient matrix, suitable pH and at a temperature of, fast fast-growing
Long breeding, by organic wastewater sodium ion and the inorganic ions such as sulfate ion convert, form hydrogen sulfide etc., thus
Substantially reduce the concentration of organic salt ion in waste water.After final separation precipitating, the COD in waste water is greater than from original
30000ml/L is down to 110mg/L or so, meets state three grade emissioning standard.
Further preferably are as follows: hydrogen peroxide and ferrous sulfate is first added in the step S1, stands 0.5h after being sufficiently stirred,
Removal precipitates and organic chemical waste water is discharged into the first sedimentation basin for the first time；Ca is added in first sedimentation basin
(OH)2, rear static 0.5h is sufficiently stirred, organic chemical waste water is discharged into the second sedimentation basin by second of removal precipitating；Described
Na is added in second sedimentation basin2CO3, it is sufficiently stirred and adjusts pH value to 7-8.5, static 0.5h, third time removal precipitating heel row
Enter in third sedimentation basin.
Add hydrogen peroxide and ferrous sulfate in organic salt acidic organic chemical waste water, ferrous ion be transformed into iron from
Son sufficiently after precipitating, remove ferric hydroxide precipitate when removal precipitating for the first time；It is added Ca (OH)2Afterwards, the magnesium in waste water
The ferric ion of ion, chloride ion and also some residual is formed together precipitating with hydroxide ion respectively, which can
By the iron ion removing in back；Na is added2CO3Afterwards, it is heavy to be formed together with calcium ion, the carbanion etc. in waste water
It forms sediment and removes, so that the calcium ion that back is added will not influence subsequent purification processing.Therefore, using first time, second
Secondary and third time removal precipitating, influencing each other for the chemical substance that can prevent substep from adding avoid the occurrence of the chemical substance of addition
Between generate the phenomenon that chemical action even forms precipitating, and the step of each step additive, is separated, so that phase in waste water
It is formed between the substance that the ion answered can be added with the step and is sufficiently reacted, play excellent precipitation.
Further preferably are as follows: the molecular sieve in step S2 passes through freezing processing.
In the application, it is placed in organic chemical waste water after the chilled processing of molecular sieve, since the temperature in waste water compares molecule
It sieves the temperature height of itself and transfers heat to molecular sieve, so that molecular sieve itself expanded by heating, so that its hole is increased, from
And the contact area adsorbed with suspended matter in waste water is increased, the adsorption capacity of molecular sieve can be improved.
Further preferably are as follows: Ca (OH) in the step S12: H+Molar ratio be 1-1.5:2.
Neutralization reaction is generated between hydroxyl and hydrogen ion in calcium hydroxide, it is dense can efficiently and quickly to reduce hydrogen ion
Degree, so that the pH value of organic wastewater be made to improve to required range.
Further preferably are as follows: the wet thallus weight ratio of Halophiles group and salt-tolerant cultures is 1:1 in the step S4.
Due to still containing the inorganic ions such as sodium ion, chloride ion in organic wastewater after processing, adopted simultaneously in the application
With Halophiles group and salt-tolerant cultures, and the weight that the two uses is identical, so that the amount of the two keeps putting down in organic wastewater
Weighing apparatus, collective effect simultaneously improve the decomposition to organic matter remaining in waste water by intracorporal enzyme, reduce the content of organic matter, thus
Prevent waste water eutrophication.
Further preferably are as follows: the Halophiles group includes single purulence flora and extra large bacillus group.
Sodium ion and single purulence flora and extra large bacillus group cell membrane component occur specific action and enhance the mechanical strength of film,
The construction for being conducive to maintain cell membrane, to preventing Halophiles bacteriolyze from playing an important role, therefore, single purulence flora and extra large bacillus group are right
Sodium ion in organic wastewater has interdependence, can rapidly adapt to, grow in the waste water containing sodium ion and breed, and improves salt discharge
Effect.
Further preferably are as follows: the salt-tolerant cultures include bacillus group, Candida flora and lemon coccus group.
Bacillus group, Candida flora and lemon coccus group have excellent salt resistant character, can be in organic wastewater
It adapts to and survives, and remaining organic matter in degrading waste water is played the role of by the enzyme inside Facultative Halophiles body.
In conclusion the invention has the following advantages:
1, hydrogen peroxide and ferrous sulfate are added into organic chemical waste water, hydrogen peroxide, which is formed, has strong oxidation
Hydroxyl radical free radical makes organic matter transform into carbon dioxide, water and inorganic salts, and ferrous iron is oxidized to ferric iron, forms hydrogen
Fe 3 O has absorption and flocculation, to generate precipitating in water body；Ca is added after removal precipitating for the first time
(OH)2, second removal precipitating sufficiently after precipitating, by internal a large amount of sulfate radicals, magnesium ion, aluminium ion and a small amount of remaining
Iron ion removing；And add Na2CO3, sufficiently removal for the third time precipitates after precipitating, eliminates calcium ion, carbanion.It is logical
It crosses substep and successively adds hydrogen peroxide and ferrous sulfate, Ca (OH)2And Na2CO3, make substance respectively and in organic chemical waste water
Organic matter, inorganic ion are sufficiently acted on, and on the other hand, improve the combination effect between inorganic ion and generation is sunk
It forms sediment, is deposited a large amount of inorganic salts in organic chemical waste water.COD value is not only greatly reduced, inorganic ion is also reduced
Content.
2, after chemicals is handled, using the molecular sieve after freezing processing to remaining organic in organic chemical waste water
Object or suspended matter are adsorbed and are precipitated, and the effective area of absorption is improved, so that absorption and deposition efficiency are improved, to have
Effect prevents organic matter or suspended matter from hindering microorganism growth or breeding, removes obstacle for subsequent processing.
Specific embodiment
Below with reference to embodiment, the present invention will be described in detail.
The above is only a preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-mentioned implementation
Example, all technical solutions belonged under thinking of the present invention all belong to the scope of protection of the present invention.It should be pointed out that for the art
Those of ordinary skill for, several improvements and modifications without departing from the principles of the present invention, these improvements and modifications
It should be regarded as protection scope of the present invention.
Embodiment 1: a kind of high COD, the organic salt acidic organic chemical waste water processing method of high concentration
Test specimen: certain agricultural product producting factory is mainly engaged in agricultural product pickling, with the pickling obtained after factory pickling
Waste water is as test specimen, and wherein complicated component multiplicity, is in acidity, pH value 2.3-3.5, pollution level is more serious, COD value
For 30000mg/L, Na ion concentration 74023.8mg/L, chlorine ion concentration 74943.6mg/L.
Processing method includes the following steps:
S1, hydrogen peroxide and ferrous sulfate, Ca (OH) are successively added into pickling waste water2And Na2CO3, tune is sufficiently stirred
PH value is saved to 6.5-8.5, precipitating is removed after static 1h, organic chemical waste water is discharged into sedimentation basin；
Molecular sieve is added in S2, the pickling waste water into step S1, is sufficiently stirred, precipitating is removed after static 1h, by supernatant
Liquid is discharged into anaerobic reactor；
Supernatant temperature is 15 DEG C in S3, maintenance step S2, adds nitrogen phosphorus source according to the ratio that COD:N:P is 450:5:1,
Adjusting pH value is 7.5-8.5, and sulfate reduction flora is added and carries out Anaerobic Treatment, hydraulic retention is delivered to aerobic reaction afterwards for 24 hours
In device；
Supernatant temperature is 20 DEG C in S4, maintenance step S3, adds nitrogen phosphorus source according to the ratio that COD:N:P is 250:5:1,
Adjusting pH value is 6.5-8, adds Halophiles group and salt-tolerant cultures and carries out one section of Aerobic Process for Treatment, aeration stirring, hydraulic retention for 24 hours after
Through two sections of Aerobic Process for Treatment, aeration stirring again, hydraulic retention is for 24 hours；
S5, precipitating and supernatant water outlet.
Test result: the indices value before and after the pickling wastewater treatment of certain factory is shown in table 1.It follows that adopting
After the present embodiment, the pH value for being pickled waste water becomes faintly acid or alkalescent, and sodium ion, chloride ion and sulfate radical from highly acid
The concentration and COD of ion have significantly reduce.
Certain factory of table 1 is pickled the indices value before and after wastewater treatment
| pH | COD(mg/L) | Na+(mg/L) | Cl-(mg/L) | SO4 2-(mg/L) | |
| Before processing | 2.3-3.5 | 30000 | 74023.8 | 74943.6 | 87510.3 |
| After processing | 6.5-8 | 110 | 9084.2 | 10485.5 | 11034.9 |
Embodiment 2: a kind of high COD, the organic salt acidic organic chemical waste water processing method of high concentration
Test specimen is referring to the test specimen in embodiment 1.
Processing method includes the following steps:
S1, hydrogen peroxide and ferrous sulfate is first added into pickling waste water, 0.5h is stood after being sufficiently stirred, is removed for the first time
It precipitates and pickling waste water is discharged into the first sedimentation basin；
Ca (OH) is added in S2, pickling waste water in step sl2, rear static 0.5h is sufficiently stirred, second of removal
Pickling waste water is discharged into the second sedimentation basin by precipitating；
Na is added in S3, pickling waste water in step s 22CO3, it is sufficiently stirred and adjusts pH value to 7-8.5, it is static
0.5h, third time removal are discharged into third sedimentation basin after precipitating.
Molecular sieve is added in S4, the pickling waste water into step S3, is sufficiently stirred, precipitating is removed after static 1h, by supernatant
Liquid is discharged into anaerobic reactor；
Supernatant temperature is 35 DEG C in S3, maintenance step S2, adds nitrogen phosphorus source according to the ratio that COD:N:P is 450:5:1,
Adjusting pH value is 7.5-8.5, and sulfate reduction flora is added and carries out Anaerobic Treatment, hydraulic retention is delivered to aerobic reaction afterwards for 24 hours
In device；
Supernatant temperature is 35 DEG C in S4, maintenance step S3, adds nitrogen phosphorus source according to the ratio that COD:N:P is 250:5:1,
Adjusting pH value is 6.5-8, adds Halophiles group and salt-tolerant cultures and carries out one section of Aerobic Process for Treatment, aeration stirring, hydraulic retention for 24 hours after
Through two sections of Aerobic Process for Treatment, aeration stirring again, hydraulic retention is for 24 hours；
S5, precipitating and supernatant water outlet.
Test result: the indices value before and after the pickling wastewater treatment of certain factory is shown in table 2.It follows that adopting
After the present embodiment, the pH value for being pickled waste water becomes faintly acid or alkalescent from highly acid, and compared with Example 1, sodium ion,
The concentration and COD of chloride ion and sulfate ion tool are further reduced.
Certain factory of table 2 is pickled the indices value before and after wastewater treatment
| pH | COD(mg/L) | Na+(mg/L) | Cl-(mg/L) | SO4 2-(mg/L) | |
| Before processing | 2.3-3.5 | 30000 | 74023.8 | 74943.6 | 87510.3 |
| After processing | 6.5-8 | 92 | 8204.9 | 9843.1 | 9754.7 |
Embodiment 3: a kind of high COD, the organic salt acidic organic chemical waste water processing method of high concentration
Test specimen is referring to the test specimen in embodiment 1.
Processing method is referring to the processing method in embodiment 2, wherein the molecular sieve in step S4 is pickled waste water in merging
Pass through freezing processing 2h before.
Test result: the indices value before and after the pickling wastewater treatment of certain factory is shown in table 3.It follows that adopting
After the present embodiment, the pH value for being pickled waste water becomes faintly acid or alkalescent from highly acid, and compared with Example 2, sodium ion,
The concentration and COD of chloride ion and sulfate ion have largely reduce.
Certain factory of table 3 is pickled the indices value before and after wastewater treatment
| pH | COD(mg/L) | Na+(mg/L) | Cl-(mg/L) | SO4 2-(mg/L) | |
| Before processing | 2.3-3.5 | 30000 | 74023.8 | 74943.6 | 87510.3 |
| After processing | 6.5-8 | 75 | 6318.1 | 7819.5 | 7117.8 |
Claims (5)
1. the organic salt acidic organic chemical waste water processing method of a kind of high COD, high concentration, which comprises the steps of:
S1, hydrogen peroxide and ferrous sulfate is first added, 0.5h is stood after being sufficiently stirred, for the first time removal precipitating and by organic chemical industry
Waste water is discharged into the first sedimentation basin；Ca (OH) is added in first sedimentation basin2, it is sufficiently stirred rear static 0.5h, second
Secondary removal precipitating, organic chemical waste water is discharged into the second sedimentation basin；Na is added in second sedimentation basin2CO3, sufficiently
It stirs and adjusts pH value to 7-8.5, static 0.5h, third time removal is discharged into third sedimentation basin after precipitating；
Molecular sieve is added in S2, the organic chemical waste water into step S1, is sufficiently stirred, precipitating is removed after static 1h, by supernatant
Liquid is discharged into anaerobic reactor；
Supernatant temperature is 15-35 DEG C in S3, maintenance step S2, adds nitrogen phosphorus source according to the ratio that COD:N:P is 450:5:1,
Adjusting pH value is 7.5-8.5, and sulfate reduction flora is added and carries out Anaerobic Treatment, hydraulic retention is delivered to aerobic reaction afterwards for 24 hours
In device；
Supernatant temperature is 20-35 DEG C in S4, maintenance step S3, adds nitrogen phosphorus source according to the ratio that COD:N:P is 250:5:1,
Adjusting pH value is 6.5-8, adds Halophiles group and salt-tolerant cultures and carries out one section of Aerobic Process for Treatment, aeration stirring, hydraulic retention for 24 hours after
Through two sections of Aerobic Process for Treatment, aeration stirring again, hydraulic retention is for 24 hours；
S5, precipitating and supernatant water outlet；
Molecular sieve in step S2 passes through freezing processing.
2. the organic salt acidic organic chemical waste water processing method of a kind of high COD according to claim 1, high concentration, special
Sign is, Ca (OH) in the step S12: H+Molar ratio be 1-1.5:2.
3. the organic salt acidic organic chemical waste water processing method of a kind of high COD according to claim 1, high concentration, special
Sign is that the wet thallus weight ratio of Halophiles group and salt-tolerant cultures is 1:1 in the step S4.
4. the organic salt acidic organic chemical waste water processing method of a kind of high COD according to claim 1, high concentration, special
Sign is that the Halophiles group includes single purulence flora and extra large bacillus group.
5. the organic salt acidic organic chemical waste water processing method of a kind of high COD according to claim 1, high concentration, special
Sign is that the salt-tolerant cultures include bacillus group, Candida flora and lemon coccus group.
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| CN106746198B (en) * | 2016-12-13 | 2019-12-20 | 浙江省环境保护科学设计研究院 | Integrated treatment method for high-salt high-concentration degradation-resistant organic wastewater for producing cellulose ether |
| CN110563124A (en) * | 2018-06-06 | 2019-12-13 | 东莞市台腾环保材料科技有限公司 | Method for treating biochemical sewage by using enzyme |
| CN110156174B (en) * | 2019-05-30 | 2022-01-25 | 杭州秀川科技有限公司 | Mixed strain fermentation biological pretreatment method for high-concentration high-salt pharmaceutical wastewater |
| CN111606513A (en) * | 2020-05-29 | 2020-09-01 | 安庆丰源化工有限公司 | Method for treating high-COD high-concentration sulfate radical acidic organic chemical wastewater |
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| CN102190411A (en) * | 2010-05-17 | 2011-09-21 | 浙江大学 | Treatment method for acidic organic chemical wastewater with high COD (chemical oxygen demand) and high sulfate radical concentration |
| CN103183450A (en) * | 2011-12-31 | 2013-07-03 | 上海轻工业研究所有限公司 | Treatment method and treatment apparatus for wastewater of daily chemicals |
| CN103304017A (en) * | 2013-06-28 | 2013-09-18 | 华南理工大学 | Treatment method for synchronously removing COD (Chemical Oxygen Demand) and rigidity of waste water |
| CN103693804A (en) * | 2013-11-29 | 2014-04-02 | 西安近代化学研究所 | Method for treating energetic material synthetic wastewater |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102190411A (en) * | 2010-05-17 | 2011-09-21 | 浙江大学 | Treatment method for acidic organic chemical wastewater with high COD (chemical oxygen demand) and high sulfate radical concentration |
| CN103183450A (en) * | 2011-12-31 | 2013-07-03 | 上海轻工业研究所有限公司 | Treatment method and treatment apparatus for wastewater of daily chemicals |
| CN103304017A (en) * | 2013-06-28 | 2013-09-18 | 华南理工大学 | Treatment method for synchronously removing COD (Chemical Oxygen Demand) and rigidity of waste water |
| CN103693804A (en) * | 2013-11-29 | 2014-04-02 | 西安近代化学研究所 | Method for treating energetic material synthetic wastewater |
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