CN106396185B - A kind of processing method of sulphide-containing waste water - Google Patents
A kind of processing method of sulphide-containing waste water Download PDFInfo
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- CN106396185B CN106396185B CN201611014537.9A CN201611014537A CN106396185B CN 106396185 B CN106396185 B CN 106396185B CN 201611014537 A CN201611014537 A CN 201611014537A CN 106396185 B CN106396185 B CN 106396185B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F9/00—Multistage treatment of water, waste water or sewage
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/001—Processes for the treatment of water whereby the filtration technique is of importance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/78—Treatment of water, waste water, or sewage by oxidation with ozone
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/101—Sulfur compounds
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/40—Organic compounds containing sulfur
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- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
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- Treatment Of Water By Oxidation Or Reduction (AREA)
Abstract
The invention discloses a kind of processing methods of sulphide-containing waste water, this method uses oxidation-precipitation method, after acid solution adjusting pH value is added in the sulphide-containing waste water into conditioning tank, into oxidation pond, it is stirred with the oxidant of addition, sulfide content is reduced by oxidation reaction, if sulfide content is less than or equal to 1mg/L, waste water is passed through in filter and is filtered；If sulfide content is greater than 1mg/L, waste water is introduced into reaction tank, is stirred with the precipitating reagent of addition, water outlet enters sedimentation basin, stands；The present invention solves sulfide leakage problem in sulphide-containing waste water treatment process, and whole processing technology process is short, investment is small, and high treating effect, is widely portable to sulphide-containing waste water processing.
Description
Technical field
The present invention relates to field of waste water treatment, and in particular to a kind of processing method of sulphide-containing waste water.
Background technique
Sulphide-containing waste water is from a wealth of sources, including the industries such as oil refining, coking, pharmacy, process hides, the component of every profession and trade waste water with
And sulfide concentration is all very different, the harm of sulfide mainly has following 3 aspects:
(1) to the corrosion of equipment
Hydrogen sulfide can react with the ferrous ion in water, generate FeS and Fe (OH)2, this causes iron pipe to corrode
Main cause.Simultaneously under humid conditions, the hydrogen sulfide evaporated into air can be by bacterial oxidation at sulfuric acid, so that corrosion is mixed
The reinforcing bar and calcium carbonate being exposed in solidifying soil；
(2) to the influence of ecological environment
Sulfide mainly shows the pollution of environment in the form of hydrogen sulfide, when content is hydrogen sulfide in air
When 0.05mg/L, people will be poisoned, and when being greater than 1mg/L, it will lead to people's death；
(3) to the influence of wastewater biochemical processing
When waste water sulfide concentration is excessively high, microorganism will be suppressed and poison, and be mainly manifested in the normal configuration of cell
It is destroyed and endobacillary enzyme is rotten, and lost activity.
Therefore, take suitable method to sulfur-containing waste water be effectively treated very it is necessary to.
Currently, the processing method of sulphide-containing waste water mainly has: acidization, vaporizing extract process, oxidizing process, the precipitation method and biology
Method.
Acidization makes sulfide generate the vulcanization of highly volatile in acid condition by the acid adding into sulphide-containing waste water
Hydrogen, then hydrogen sulfide gas is absorbed with lye, generate akali sulphide reuse.This method require hydrogen sulfide absorption system be in negative pressure with
Air-tight state, to ensure that hydrogen sulfide gas does not leak outside.
Vaporizing extract process utilizes H2S and H2The difference of O relative volatility is separated them with vapor, and vaporizing extract process is suitable for sewage
Measure big, sulfide concentration higher (generally in 2000~20000mg/L) sulfur compound sewage treatment.Patent CN102844275A
Using vaporizing extract process to refinery's Wastewater Pretreatment sulphur removal containing ammonia and hydrogen sulfide, waste water is passed through stripper, pressure is 800~
The shortcomings that 2000kPa, temperature are 120~200 DEG C, at least 30 separating steps of progress, this method is that process flow is long, plant investment
Greatly, operating cost is high.
Bioanalysis makes to vulcanize by the way that the microorganisms such as colorless sulfur bacteria, Filamentous sulfur bacteria, photosynthetic sulfur bacteria are added into waste water
Object is oxidized and recycles, and product is sulphur simple substance or sulfate, which is not suitable for the sulphide-containing waste water of processing high concentration, stability
It is poor.
The above several method has that sulfide is easily revealed, plant investment is big, operating cost is high and narrow application range.
Summary of the invention
Containing Sulfur good, at low cost, applied widely that in order to solve the above-mentioned technical problems, the present invention provides a kind of effects
Object wastewater treatment method, this method are combined using oxidation-precipitated phase, are also solved and are easy to appear sulfide leakage in treatment process
The problem of, safety is good, and no gas pollutant generates.
In order to achieve the above object, the present invention adopts the following technical scheme:
A kind of processing method of sulphide-containing waste water, using oxidation-precipitation method, the method specifically includes the following steps:
(1) waste water enters conditioning tank, and the pH value that acid solution adjusts waste water is added；
(2) waste water obtained by step (1) is introduced into oxidation pond, oxidant is added, stirring carries out oxidation reaction；
(3) waste water is passed through in filter and carries out if sulfur content is less than or equal to 1mg/L by the concentration for measuring sulfide
Filtering；If sulfur content is greater than 1mg/L, waste water is introduced into reaction tank, is stirred with the precipitating reagent of addition；
(4) waste water obtained by step (3) is passed through sedimentation basin, stood.
Sulfide includes inorganic sulphide and organic sulfur compound in the sulphide-containing waste water.
Sulfide mass concentration is 50~20000mg/L in the sulphide-containing waste water；
Preferably, sulfide mass concentration is 500~5000mg/L.
Acid solution is added into waste water for the step (1), and pH is adjusted to≤11；
Preferably, pH is adjusted to≤9.
The acid solution can be one of hydrochloric acid, sulfuric acid, nitric acid or organic acid soln or a variety of mixing.
The middle oxidant and sulfide molar ratio of the step (2) are 0.5~5, and the reaction time is 5min~5h；
Preferably, oxidant and sulfide molar ratio are 0.5~3, and the reaction time is 5min~2h.
The oxidant can be one of chlorine, ozone, potassium permanganate or hydrogen peroxide or a variety of mixing.
The molar ratio of precipitating reagent and remaining sulfide in the step (3) is 1~5, and stirring rate is 30~600r/
Min, reaction time are 5min~5h；
Preferably, the molar ratio of precipitating reagent and remaining sulfide is 1~2.
The precipitating reagent can be one of mantoquita, lead salt, molysite, zinc salt or manganese salt or a variety of mixing.
The time of repose of the step (4) is 1~9h；
Preferably, time of repose is 1~5h.
Compared with prior art, the present invention having the following beneficial effects:
(1) the present invention provides a kind of sulphide-containing waste water processing methods that oxidation-precipitation method combine；
(2) this method combines oxidizing process with the precipitation method, solves sulfide leakage problem, has safety good, nothing
The characteristics of gas pollutant generates；
(3) this method can carry out at normal temperatures and pressures, and of less demanding to reactor, energy consumption is small；
(4) process, not only process flow is short, easy to operate, and expense is low, and high treating effect, the scope of application
Extensively.
Detailed description of the invention
Fig. 1 is process flow chart of the invention.
Specific embodiment
Embodiment 1
Certain factory provides a kind of sulphide-containing waste water, sulfide content 50mg/L, pH=12.Waste water enters conditioning tank, adds
Enter salt acid for adjusting pH=8, into oxidation pond, uses chlorine as oxidant, oxidization time 5min, during which the flow of chlorine is certain, always
Chlorine and sulfide molar ratio be 1, sulfide concentration is down to 0.86mg/L, and waste water is passed through in filter and is filtered.
Embodiment 2
Certain factory provides a kind of sulphide-containing waste water, sulfide content 500mg/L, pH=12.Waste water enters conditioning tank,
Sulphur acid for adjusting pH=11 are added, into oxidation pond, use hydrogen peroxide as oxidant, hydrogen peroxide and sulfide molar ratio are 3, oxygen
The change time is 1h, and sulfide concentration is down to 55mg/L, into reaction tank, CuSO is added into the waste water after oxidation4, CuSO4With oxygen
The molar ratio for changing after cure object is 1, and waste water is passed through in sedimentation basin by stirring rate 30r/min, reaction time 5min, quiet
1h is set, sulfide concentration is down to 0.45mg/L.
Embodiment 3
Certain factory provides a kind of sulphide-containing waste water, sulfide content 500mg/L, pH=12.Waste water enters conditioning tank,
Sulphur acid for adjusting pH=9 are added, into oxidation pond, use hydrogen peroxide as oxidant, hydrogen peroxide and sulfide molar ratio are 3, oxidation
Time is 1h, and sulfide concentration is down to 35mg/L, and into reaction tank, CuSO is added into the waste water after oxidation4, CuSO4With oxidation
The molar ratio of after cure object is 1, and waste water is passed through in sedimentation basin by stirring rate 30r/min, reaction time 5min, is stood
1h, sulfide concentration are down to 0.32mg/L.
Embodiment 4
Certain Tungsten smelting factory provides a kind of high-concentration ammonia nitrogenous wastewater of sulfur compound, sulfide content 5000mg/L, pH=9,
It needs to carry out pretreatment sulphur removal before rectifying deamination.Waste water enters conditioning tank, sulphur acid for adjusting pH=3 is added, into oxidation pond, with height
Potassium manganate is as oxidant, and potassium permanganate and sulfide molar ratio are 3, and oxidization time 1h, sulfide concentration is down to 45mg/L,
Into reaction tank, Pb (NO is added into the waste water after oxidation3)2, Pb (NO3)2Molar ratio with oxidation after cure object is 2, stirring
Rate is 100r/min, and waste water is passed through in sedimentation basin by reaction time 1h, stands 5h, and sulfide concentration is down to 0.35mg/L,
Supernatant is passed through rectifying column, sulfide content is less than 0.5mg/L in obtained ammonium hydroxide, can reuse.
Embodiment 5
Certain Tungsten smelting factory provides a kind of high-concentration ammonia nitrogenous wastewater of sulfur compound, sulfide content 5000mg/L, pH=9,
It needs to carry out pretreatment sulphur removal before rectifying deamination.Waste water enters conditioning tank, sulphur acid for adjusting pH=3 is added, into oxidation pond, with height
Potassium manganate is as oxidant, and potassium permanganate and sulfide molar ratio are 5, and oxidization time 5h, sulfide concentration is down to 42mg/L,
Into reaction tank, FeSO is added into the waste water after oxidation4·7H2O, FeSO4·7H2O and the molar ratio for aoxidizing after cure object are
Waste water is passed through in sedimentation basin by 2, stirring rate 100r/min, reaction time 1h, stands 5h, and sulfide concentration is down to
Supernatant is passed through rectifying column by 0.32mg/L, and sulfide content is less than 0.5mg/L in obtained ammonium hydroxide, can be reused.
Embodiment 6
Certain oil plant provides the acid waste water of a kind of sulfide hydrogen and ammonia, and sulfide content 1500mg/L, pH=6 are being adopted
It needs to pre-process sulphur removal before removing ammonia with bioanalysis.Waste water enters oxidation pond, uses ozone as oxidant, oxidization time 1h, phase
Between ozone flow it is certain, the molar ratio of total ozone and sulfide is 0.5, and sulfide concentration is down to 25mg/L, can be further
Biochemical treatment.
Embodiment 7
Certain factory provides a kind of sulphide-containing waste water, sulfide content 20000mg/L, pH=12.Waste water enters adjusting
Nitre acid for adjusting pH=8 are added in pond, into oxidation pond, use ozone as oxidant, oxidization time 5h, during which the flow one of ozone
Fixed, total ozone and sulfide molar ratio is 2, and sulfide concentration is down to 300mg/L, into reaction tank, to the waste water after oxidation
Middle addition Zn (NO3)2·6H2O, Zn (NO3)2·6H2The molar ratio of O and oxidation after cure object is 2, stirring rate 600r/
Min, reaction time 5h, waste water is passed through in sedimentation basin, stands 5h, and sulfide concentration is down to 0.52mg/L.
Embodiment 8
Certain factory provides a kind of sulphide-containing waste water, sulfide content 20000mg/L, pH=12.Waste water enters adjusting
Organic acid for adjusting pH=7 are added in pond, into oxidation pond, use hydrogen peroxide as oxidant, hydrogen peroxide is with sulfide molar ratio
5, oxidization time 5h, sulfide concentration is down to 200mg/L, and into reaction tank, MnSO is added into the waste water after oxidation4,
MnSO4Molar ratio with oxidation after cure object is 5, stirring rate 600r/min, reaction time 5h, and waste water is passed through precipitating
Chi Zhong, stands 9h, and sulfide concentration is down to 0.36mg/L.
Finally it should be noted that the above examples are only used to illustrate the technical scheme of the present invention and are not limiting, although reference
Invention is explained in detail for preferred embodiment, those skilled in the art should understand that, it can be to the present invention
Technical solution modify or equivalent replacement should all cover without departing from the spirit and scope of the technical solution of the present invention
In scope of protection of the claims of the invention.
Claims (12)
1. a kind of processing method of sulphide-containing waste water, which is characterized in that use oxidation-precipitation method, the method specifically includes
Following steps:
(1) waste water enters conditioning tank, and the pH value that acid solution adjusts waste water is added；
(2) waste water obtained by step (1) is introduced into oxidation pond, oxidant is added, stirring carries out oxidation reaction；
(3) waste water is passed through in filter and is filtered if sulfur content is less than or equal to 1mg/L by the concentration for measuring sulfide；
If sulfur content is greater than 1mg/L, waste water is introduced into reaction tank, is stirred with the precipitating reagent of addition；
(4) waste water obtained by step (3) is passed through sedimentation basin, stood；
Sulfide includes inorganic sulphide and organic sulfur compound in the sulphide-containing waste water；
Sulfide mass concentration is 50~20000mg/L in the sulphide-containing waste water；
The oxidant and sulfide molar ratio of the step (2) are 0.5~5, and the reaction time is 5min~5h.
2. processing method according to claim 1, which is characterized in that in the sulphide-containing waste water, it is preferable that sulfide
Mass concentration is 500~5000mg/L.
3. processing method according to claim 1, which is characterized in that acid solution is added into waste water for the step (1), will
PH is adjusted to≤11.
4. processing method according to claim 3, which is characterized in that preferably, pH is adjusted to≤9.
5. processing method according to claim 3, which is characterized in that the acid solution is hydrochloric acid, sulfuric acid, nitric acid or organic
One of acid solution or a variety of mixing.
6. processing method according to claim 1, which is characterized in that preferably, oxidant and sulfide molar ratio are 0.5
~3, the reaction time is 5min~2h.
7. processing method according to claim 6, which is characterized in that the oxidant be chlorine, ozone, potassium permanganate or
One of hydrogen peroxide or a variety of mixing.
8. processing method according to claim 1, which is characterized in that precipitating reagent and remaining vulcanization in the step (3)
The molar ratio of object is 1~5, and stirring rate is 30~600r/min, and the reaction time is 5min~5h.
9. processing method according to claim 8, which is characterized in that preferably, mole of precipitating reagent and remaining sulfide
Than being 1~2.
10. processing method according to claim 8, which is characterized in that the precipitating reagent is mantoquita, lead salt, molysite, zinc salt
Or one of manganese salt or a variety of mixing.
11. processing method according to claim 1, which is characterized in that the time of repose of the step (4) is 1~9h.
12. processing method according to claim 11, which is characterized in that preferably, time of repose is 1~5h.
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| CN108698867B (en) * | 2016-02-15 | 2021-11-23 | 威立雅水务技术支持公司 | Process for sulfide reduction from water and wastewater |
| CN110902802B (en) * | 2018-09-17 | 2022-11-15 | 保定加合精细化工有限公司 | Pretreatment method of diethylaminoethanethiol production wastewater |
| CN109205798B (en) * | 2018-10-08 | 2021-07-06 | 沈阳工业大学 | Method for producing mycoprotein by treating fatty acid wastewater with photosynthetic bacteria |
| CN109354264A (en) * | 2018-12-17 | 2019-02-19 | 浙江奇彩环境科技股份有限公司 | A kind of minimizing technology of sulfur-bearing organic wastewater foul odour |
| CN112707493A (en) * | 2019-10-24 | 2021-04-27 | 重庆川维科技有限公司 | Use of persulfates for treating thioethers and/or thiols |
| CN112707491B (en) * | 2019-10-24 | 2023-08-22 | 中国石油化工股份有限公司 | Method for treating thioethers and thiols |
| CN111675303A (en) * | 2020-04-28 | 2020-09-18 | 西北矿冶研究院 | Method for degrading sulfide in industrial wastewater by using hydrogen peroxide-bleaching powder combined oxidation |
| CN111573934A (en) * | 2020-05-29 | 2020-08-25 | 赛恩斯环保股份有限公司 | Method and device for removing sulfide in liquid after sulfuration of smelting waste acid |
| CN115385484B (en) * | 2022-09-16 | 2024-04-05 | 陕西佰昕源油气技术服务有限公司 | Sulfur-containing sewage treatment device for oil-gas field extraction |
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| CN102976474A (en) * | 2012-12-24 | 2013-03-20 | 天津工业大学 | Method for removing sulfur and organic matters in industrial sewage |
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