CN110002629A - A kind of the oil removing dephenolize combination treatment method and system of high-concentration phenol ammonia waste water - Google Patents
A kind of the oil removing dephenolize combination treatment method and system of high-concentration phenol ammonia waste water Download PDFInfo
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- CN110002629A CN110002629A CN201910270837.0A CN201910270837A CN110002629A CN 110002629 A CN110002629 A CN 110002629A CN 201910270837 A CN201910270837 A CN 201910270837A CN 110002629 A CN110002629 A CN 110002629A
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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
- C02F1/24—Treatment of water, waste water, or sewage by flotation
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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
- C02F1/26—Treatment of water, waste water, or sewage by extraction
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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
- C02F1/40—Devices for separating or removing fatty or oily substances or similar floating material
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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
- C02F2001/007—Processes including a sedimentation step
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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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Abstract
The present invention relates to a kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water and system, processing method includes: (1) coke oven flue gas oil removal by air bubbling；(2) water-oil separating；(3) pressure extraction dephenolize；Processing system includes air flotation tank, oil water separator, extraction equipment, accumulator tank and flue gas surge tank；The present invention uses coke oven flue gas as foaming gas, improves oil removal efficiency using the apolar character of carbon dioxide in coke oven flue gas and the waste heat of coke oven flue gas, carries out saturated absorption to sour gas carbon dioxide while oil removing；PH by changing solution induces the phenolic substances of the free more molecular forms out of Phenol for Waste Water salt, improves distribution coefficient of the phenolic substances in extractant, improves extraction efficiency；Eventually by the synergistic effect of oil removal by air bubbling simultaneously acidifying and extraction process, waste water treatment efficiency greatly improved, realize killing three birds with one stone.
Description
Technical field
The present invention relates to phenol ammonia waste water oil removing dephenolize technical field more particularly to a kind of oil removing of high-concentration phenol ammonia waste water are de-
Phenol combination treatment method and system.
Background technique
High-concentration phenol ammonia waste water contains largely mainly from the industrial trades such as coal chemical industry, petrochemical industry, coking, this kind of waste water
The substances such as tar, phenol, ammonia, complicated component belongs to the toxic refractory organic industrial sewage of high concentration, and direct emission can be serious dirty
Environment or even polluted drinking water source are contaminated, significant damage is generated to human body.But phenolic substances contained in phenol ammonia waste water is weight again
The industrial chemicals wanted, resourcebility recycle, and therefore, efficient process phenol ammonia waste water reaches discharge standard and while recycling wherein
Phenolic substances not only has environment protection significance, it may have certain economic significance.
The presence of tar can seriously affect the subsequent handling of phenol ammonia waste water processing, so oil removing is phenol ammonia waste water treatment process
In committed step.Gravitational method is traditional deoiling method, and advantage is that structure is simple, operating cost is lower, but it the shortcomings that
It is obvious that such as staticly settling, the time is long, take up a large area, separating effect is undesirable.Therefore Coking Plant, Shijiazhuang (Ma Lirong,
1999) gravity oil-removing method is improved to sand filtration oil removal process.But can only to retain partial size biggish for coke or quartz sand filtration method
Dispersed oil, oil removal rate is lower, and filter is easy blocking, cannot regenerate, service life is short.Strong-hydrophobicity is industrially used at present
Inorganic ceramic membrane the more of oil removing is filtered to coking wastewater, have disclosed include Anyang steel coke-oven plant (Feng Haijun,
2007), the coke-oven plant Panzhihua Pan Gang (Xu Tingwan, 2016) etc..Ceramic membrane filter has higher oil removal efficiency and suspended matter
Removal rate, but that there is also fouling membranes is serious, not easy cleaning, the disadvantages of operating cost is high.Furthermore oil removal by air bubbling is also oil removing effect
A kind of relatively high method of rate, Shandong Huifeng petrochemical industry (South Korea's justice, 2010) use two-stage air-float technology in materialization section, effectively
Oily pollution is eliminated, but since coal tar cyclic organic materials content is high, fractions have surface-active containing groups such as carboxyls, difficult
With in conjunction with bubble, so oil removal by air bubbling water outlet oil content is still very high.
Mainly there are 3 classes to the process flow of high-concentration phenol and ammonia removing phenol in waste water at present: 1. deamination technique after depickling extracting and dephenolizing；
2. extracting and dephenolizing technique after depickling deamination.3. the technique of extracting and dephenolizing depickling deamination again after acidification.
1. deamination technique after depickling extracting and dephenolizing: deamination technique is absorbed by SaiDing Engineering Co., Ltd after depickling extracting and dephenolizing
The German original process of Lucci corporation is redesigned, and is applied at present in many enterprises, including Harbin Gas Works original phenol recovery ammonia
Device (Zhou Zhiyuan etc., 2004), Yima gasification plant (Chen Li etc., 2007) etc..Typical process flow is that waste water temperature control is laggard
Enter extracting tower depickling, the wastewater heat exchange after depickling enters extraction tower after being cooled to about 50 DEG C and extracts.Extraction phase extracted enters
Solvent recovery tower, rectifying separate crude phenols and extractant；Raffinate phase enters solvent stripper, from the ammonium hydroxide vapour of side take-off through condensing
Part water and the laggard ammonia refining section of a small amount of ammonia, tower reactor waste water go to biochemical treatment workshop section.The technique is primarily present following problems: (1)
Extraction is before deamination, and for extraction water quality in alkalinity, dephenolization effect is bad, and waste water is by heating, cooling and heats up again, and energy consumption is high；
(2) eliminating efficiency of polyphenol is low, influences the progress of subsequent biochemical workshop section.
2. extracting and dephenolizing technique after depickling deamination.Chinese patent 200610033932.1, Chinese patent
200610036072.7, Chinese patent 200910036542.3 is preposition by deamination process, adopts ammonia by single column pressurization depickling side line
Method depickling deamination after extract phenol.Typical process flow is that waste water pressurizes caustic-soda aqueous solution while entering stripper depickling
It injects in stripper tower afterwards, converts ammonia for fixed ammonia, ammonia segregates to obtain high concentration ammonia through three-level from side take-off.Tower bottom
Produced Liquid pH is 6~7, and Produced Liquid is cooled to 60 DEG C or so and enters extraction tower counter-current extraction phenol, and extraction tower lower aqueous enters
Biochemical treatment is sent into water purification after solvent stripper stripping recycling extractant.The technology elder generation deamination, wastewater pH are 7 or so, and extraction is de-
Phenol carries out in acid condition, significantly improve extractant to can light current solution phenolic substances extraction distribution coefficient.But it should
Technique note alkali process increases salt content in waste water, is unfavorable for subsequent biochemical treatment；Additionally since depositing in high concentration phenols
In ammonia still process, gained ammonia contains the components such as volatile phenol.
3. the technique of extracting and dephenolizing depickling deamination again after acidification: depickling deamination technique is South Africa to extracting and dephenolizing again after acidification
SASOL company technique (Chen Qingjun, 2012), the technology combine existing phenol recovery ammonia process experience, and it is full to propose sour gas
Depickling deamination technology is stripped with combining single column to pressurize based on technique.Chinese patent 201210145173.7, Chinese patent
201710731727.0 etc. are all made of this technology, typical process flow be phenol ammonia waste water after pretreatment, CO is used in saturator2
Gas is saturated waste water and is acidified, and adjusts the pH to 6~7 of waste water；CO2Phenol ammonia waste water after saturation is discharged from tower bottom, is extracting
It is extracted in tower with solvent counter current；Oil mutually enters solvent recovery tower after extraction, recycles extractant；Water phase enters extracting tower and carries out depickling
Deamination, tower reactor purified water send biochemical treatment.The technique is the direction of high-concentration phenol and ammonia wastewater treatment development in recent years, but this work
Skill will be removed in advance suspended matter and tar processing to high-concentration phenol ammonia waste water, and sour gas is separately provided and was saturated
Journey not only reduces waste water treatment efficiency, and increases cost for wastewater treatment.
Summary of the invention
The present invention provides a kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water and systems, use coke oven cigarette
Gas improves oil removal efficiency as foaming gas, using the apolar character of carbon dioxide in coke oven flue gas and the waste heat of coke oven flue gas,
Saturated absorption is carried out to sour gas carbon dioxide while oil removing；PH by changing solution induces Phenol for Waste Water salt free
The phenolic substances of more molecular forms out improves distribution coefficient of the phenolic substances in extractant, improves extraction efficiency；It is final logical
Waste water treatment efficiency greatly improved in the synergistic effect for crossing oil removal by air bubbling simultaneously acidifying and extraction process, realizes killing three birds with one stone.
In order to achieve the above object, the present invention is implemented with the following technical solutions:
A kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water, the index of the high-concentration phenol ammonia waste water are as follows:
COD=10000~30000mg/L, volatile phenol=2000~10000mg/L, oil=500~3000mg/L, ammonia nitrogen=2000~
8000mg/L；PH value=7~14；
The oil removing dephenolize combination treatment method the following steps are included:
(1) coke oven flue gas oil removal by air bubbling；
High-concentration phenol ammonia waste water from air flotation tank top enter, coke oven flue gas as foaming gas from air bearing pot bottom collection chamber into
Enter；Using carbon dioxide, nitrogen and the waste heat oil removing in coke oven flue gas, the water layer after oil removing is directly entered extraction equipment and is extracted
Dephenolize is taken, scum layer enters oil water separator and carries out water-oil separating；Coke oven flue gas returns to coke oven cigarette at the top of air flotation tank after discharge
Gas processing system；
(2) water-oil separating；
In oil water separator, oil reservoir of the scum layer after water-oil separating is discharged from oil water separator top, and water layer is under
Portion returns to air flotation tank；
(3) pressure extraction dephenolize；
High-concentration phenol ammonia waste water and extractant adverse current after step (1) oil removing enter extraction equipment, lead in extraction equipment
Enter coke oven flue gas pressurization, maintains extraction equipment air pressure inside in 0.2MPa or more, be dissolved in using the carbon dioxide in coke oven flue gas
The characteristic that carbonic acid is formed in water, changes the pH value of high-concentration phenol ammonia waste water；Mutually directly returning after pressure extraction containing phenol extraction is burnt
Oil processing centrifugal station, raffinate phase, which enters after accumulator tank stands 2h or more, to be layered, and residual extractant returns to tar production and separates work
Section, water phase then enter subsequent processing workshop section；
Waste water index after de-oiling dephenolize are as follows: COD≤3000mg/L, volatile phenol≤100mg/L, oil≤30mg/L.
The coke oven flue gas is the neat stress for reaching discharge standard after purified processing.
During the coke oven flue gas oil removal by air bubbling, the temperature in air flotation tank is 0~70 DEG C, and pressure is 0.2~0.5MPa,
Bubble diameter is 20~50 μm, and the oil removal by air bubbling time is 10~30min.
Water layer in the air flotation tank after oil removal by air bubbling is the aqueous solution of sour gas carbon dioxide saturation.
The extractant is the product light oil of tar production centrifugal station.
Extraction temperature in the extraction equipment is 0~80 DEG C, and the volume ratio of high-concentration phenol ammonia waste water and extractant is 0.5
~2:1, the air pressure in extraction equipment are 0.2~0.5MPa, and the pH value of high-concentration phenol ammonia waste water is 5~7 in extraction equipment, extraction
Series is 1~3.
The extraction equipment is packed extraction tower, perforated-plate extraction tower or centrifugal extractor.
The air flotation tank, extraction equipment pass through flue gas recirculation pipeline respectively and connect with coke oven flue gas processing system.
For realizing the oil removing dephenolize joint processing system of the high-concentration phenol ammonia waste water of the method, including air flotation tank, oil
Separator, extraction equipment, accumulator tank and flue gas surge tank；Coke oven flue gas entrance and coke oven flue gas are set on the flue gas surge tank
Outlet, coke oven flue gas entrance are connect with the neat stress pipeline of coke oven flue gas processing system, coke oven flue gas outlet connection air flotation tank bottom
The collection chamber in portion and the pressurizing device of extraction equipment bottom；The top of air flotation tank sets phenol ammonia waste water entrance and dross outlet, lower part
If separating water inlet and degreased wastewater outlet, dross outlet is connect with the material inlet at the top of oil water separator, oil water separator
The separation water out of bottom is connect with the separation water inlet on air flotation tank, and oil water separator top sets the oily outlet of separation；It is described
Degreased wastewater outlet on air flotation tank connects the waterwater entrance on extraction equipment top, and flue gas goes out after setting extraction at the top of extraction equipment
Mouthful, coke oven flue gas processing system is connected by flue gas recirculation pipeline；The top of extraction equipment sets extraction phase outlet, and lower part sets raffinate
It mutually exports, the material inlet on raffinate phase outlet connection accumulator tank, the top of accumulator tank sets residual extractant outlet, and lower part sets water
Mutually export.
Compared with prior art, the beneficial effects of the present invention are:
(1) be different from traditional gas floatation process and use air as foaming gas, the present invention use coke oven flue gas as foaming gas,
Using the apolar character and waste heat of coke-oven flue gas of carbon dioxide in coke oven flue gas, keep the more traditional gas floatation process of oil removal efficiency higher；
(2) high-concentration phenol ammonia waste water has also carried out saturated absorption to sour gas carbon dioxide while oil removing, and rear
Continuous extraction process forms synergistic effect, eliminates individual acidizing process, waste water treatment efficiency greatly improved；
(3) by changing the pH of solution, the phenolic substances of the free more molecular forms out of induction Phenol for Waste Water salt improves phenol
Distribution coefficient of the substance in extractant improves extraction efficiency；
(4) be different from traditional oil removing dephenolize technology and be first acidified the technique extracted again, the present invention by acidization with it is preposition
Process oil removing combines, and realizes oil removal by air bubbling simultaneously acidifying；It is pressurizeed in extraction equipment using coke oven flue gas simultaneously, utilizes coke oven cigarette
The carbon dioxide feature soluble in water for forming carbonic acid, realizes pressure extraction while changing pH value of waste water, improves extraction in gas
Efficiency.
Detailed description of the invention
Fig. 1 is a kind of oil removing dephenolize combined treatment process flow chart/system knot of high-concentration phenol ammonia waste water of the present invention
Composition.
Fig. 2 is phenol content detection spectrogram before and after middle and high concentration phenol ammonia waste water oil removing of embodiment of the present invention dephenolize.
Fig. 3 is the enlarged drawing of phenolic substances chromatographic peak (peak I) in Fig. 2.
In Fig. 1: 1. flue gas surge tank, 2. air flotation tank, 3. oil water separator, 4. extraction equipment, 5. accumulator tank, 6. high-concentration phenol and ammonia
13. residual extractant of waste water 7. coke oven flue gas, 8. scum layer, 9. oil reservoir, 10. water layer, 11. water layer, 12. raffinate phase, 14. water phase 15. extraction
Take 16. flue gas recirculation pipeline of phase
In Fig. 2, Fig. 3: the I, phenols of waste water in the untreated high-concentration phenol ammonia waste water B. embodiment 1 of A. after oil removing dephenolize
Substance
Specific embodiment
Specific embodiments of the present invention will be further explained with reference to the accompanying drawing:
A kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water of the present invention, the high-concentration phenol ammonia waste water
Index are as follows: COD=10000~30000mg/L, volatile phenol=2000~10000mg/L, oil=500~3000mg/L, ammonia nitrogen
=2000~8000mg/L；PH value=7~14；
As shown in Figure 1, the oil removing dephenolize combination treatment method the following steps are included:
(1) coke oven flue gas oil removal by air bubbling；
High-concentration phenol ammonia waste water 6 enters from 2 top of air flotation tank, and coke oven flue gas 7 is used as foaming gas from 2 bottom gas collection of air flotation tank
Room enters；Using carbon dioxide, nitrogen and the waste heat oil removing in coke oven flue gas, the water layer 11 after oil removing is directly entered extraction equipment
4 carry out extracting and dephenolizing, and scum layer 8 enters oil water separator 3 and carries out water-oil separating；After coke oven flue gas 7 is discharged at the top of air flotation tank 2
Return to coke oven flue gas processing system；
(2) water-oil separating；
In oil water separator 3, oil reservoir 9 of the scum layer 8 after water-oil separating is discharged from 3 top of oil water separator, water layer
10 return to air flotation tank 2 from lower part；
(3) pressure extraction dephenolize；
High-concentration phenol ammonia waste water 6 after step (1) oil removing and extractant adverse current enter extraction equipment 4, in extraction equipment 4
It is passed through the pressurization of coke oven flue gas 7, maintains 4 air pressure inside of extraction equipment in 0.2MPa or more, utilizes the carbon dioxide in coke oven flue gas 7
The characteristic soluble in water for forming carbonic acid, changes the pH value of high-concentration phenol ammonia waste water 6；Phase containing phenol extraction 15 after pressure extraction is direct
Tar production centrifugal station is returned to, raffinate phase 12, which enters after accumulator tank 5 stands 2h or more, to be layered, and residual extractant 13 returns to tar
Centrifugal station is processed, water phase 14 then enters subsequent processing workshop section；
Waste water index after de-oiling dephenolize are as follows: COD≤3000mg/L, volatile phenol≤100mg/L, oil≤30mg/L.
The coke oven flue gas 7 is the neat stress for reaching discharge standard after purified processing.
During the coke oven flue gas oil removal by air bubbling, temperature in air flotation tank 2 is 0~70 DEG C, pressure is 0.2~
0.5MPa, bubble diameter are 20~50 μm, and the oil removal by air bubbling time is 10~30min.
Water layer 11 in the air flotation tank 2 after oil removal by air bubbling is the aqueous solution of sour gas carbon dioxide saturation.
The extractant is the product light oil of tar production centrifugal station.
Extraction temperature in the extraction equipment 4 is 0~80 DEG C, and high-concentration phenol ammonia waste water 6 and the volume ratio of extractant are
0.5~2:1, the air pressure in extraction equipment 4 are 0.2~0.5MPa, in extraction equipment 4 pH value of high-concentration phenol ammonia waste water 6 be 5~
7, extraction series is 1~3.
The extraction equipment 4 is packed extraction tower, perforated-plate extraction tower or centrifugal extractor.
The air flotation tank 2, extraction equipment 4 are connect by flue gas recirculation pipeline 16 with coke oven flue gas processing system respectively.
As shown in Figure 1, the oil removing dephenolize joint processing system of the high-concentration phenol ammonia waste water for realizing the method, including
Air flotation tank 2, oil water separator 3, extraction equipment 4, accumulator tank 5 and flue gas surge tank 1；Coke oven cigarette is set on the flue gas surge tank 1
Gas entrance and coke oven flue gas outlet, coke oven flue gas entrance are connect with the neat stress pipeline of coke oven flue gas processing system, coke oven flue gas
The pressurizing device of 4 bottom of collection chamber and extraction equipment of outlet connection 2 bottom of air flotation tank；The top of air flotation tank 2 sets phenol ammonia waste water
Entrance and dross outlet, lower part set separation water inlet and degreased wastewater outlet, the material of dross outlet and 3 top of oil water separator
Entrance connection, the separation water out of 3 bottom of oil water separator is connect with the separation water inlet on air flotation tank 2, on oil water separator 3
Portion sets the oily outlet of separation；The waterwater entrance on 2 degreased wastewater outlet connection 4 top of extraction equipment, extraction on the air flotation tank
The top of device 4 sets exhanst gas outlet after extraction, connects coke oven flue gas processing system by flue gas recirculation pipeline 16；Extraction equipment 4
Top set extraction phase outlet, lower part set raffinate phase outlet, raffinate phase outlet connection accumulator tank 5 on material inlet, accumulator tank 5
Top set residual extractant outlet, lower part set water phase outlet.
Following embodiment is implemented under the premise of the technical scheme of the present invention, gives detailed embodiment and tool
The operating process of body, but protection scope of the present invention is not limited to following embodiments.Method therefor is such as without spy in following embodiments
Not mentionleting alone bright is conventional method.
[embodiment]
In the present embodiment, oil content is 850mg/mL, volatile phenol content 3800mg/mL, pH in high-concentration phenol ammonia waste water 6
Value is 8.25, and temperature is 50 DEG C.
High-concentration phenol ammonia waste water 6 enters from 2 top of air flotation tank, and coke oven flue gas 7 passes through flue gas surge tank 1 from 2 bottom of air flotation tank
Portion enters, and adjusting 7 flow of coke oven flue gas makes pressure 0.5MPa in air flotation tank 2, and adjusting aeration head makes 20 μm of microbubble diameter,
The air bearing time is 30min.Oil content is 10mg/mL in high-concentration phenol ammonia waste water 6 after oil removal by air bubbling.
Upper layer scum layer 8 after dissolved air flotation, which enters in oil water separator 3, carries out water-oil separating, and lower aqueous layer 10 returns
Air flotation tank 2, the oil reservoir 9 after water-oil separating are discharged from oil water separator 3, and water layer 11 enters extraction equipment 4.
It is uninterruptedly passed through coke oven flue gas 7 in extraction equipment 4, and maintains air pressure in 0.2MPa or more.Height after oil removal by air bubbling
Concentration phenol ammonia waste water enters extraction equipment 4；In extraction equipment 4, the pH value of high-concentration phenol ammonia waste water 6 is 6, and extractant is coke
The volume ratio of the product light oil of oil processing centrifugal station, high-concentration phenol ammonia waste water 6 and extractant is 1:1, carries out continuous flow upstream extraction
It takes；Extraction phase 15 extracted directly returns to tar production centrifugal station, after raffinate phase 12 enters the standing 4h layering of accumulator tank 5,
Residual extractant 13 returns to tar production centrifugal station, and water phase 14 then enters subsequent processing workshop section.Air flotation tank 2 and extraction equipment 4
The coke oven flue gas 7 of discharge returns to coke oven flue gas processing system by flue gas recirculation pipeline 16.
The raffinate phase liquid chromatographic detection phenol residual quantity being discharged from extraction equipment 4, result 50mg/L.Detect spectrogram such as
Shown in Fig. 2.Fig. 3 is the partial enlarged view in Fig. 2, is phenolic substances chromatographic peak (peak 1) enlarged drawing, removes through the method for the invention
In waste water after oily dephenolize, phenol peak (B) peak area significantly reduces compared with untreated waste water phenol peak (A), illustrates this hair
Bright dephenolization effect is more significant, and specially high-concentration phenol and ammonia Phenol for Waste Water substance peak area is before untreated
20822.67, the phenolic substances peak area after oil removing dephenolize of the present invention in waste water is 74.18, and phenol removal rate is greater than 99%.
The foregoing is only a preferred embodiment of the present invention, but scope of protection of the present invention is not limited thereto,
Anyone skilled in the art in the technical scope disclosed by the present invention, according to the technique and scheme of the present invention and its
Inventive concept is subject to equivalent substitution or change, should be covered by the protection scope of the present invention.
Claims (9)
1. a kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water, which is characterized in that the high-concentration phenol ammonia waste water
Index are as follows: COD=10000~30000mg/L, volatile phenol=2000~10000mg/L, oil=500~3000mg/L, ammonia nitrogen
=2000~8000mg/L；PH value=7~14；
The oil removing dephenolize combination treatment method the following steps are included:
(1) coke oven flue gas oil removal by air bubbling；
High-concentration phenol ammonia waste water enters from air flotation tank top, and coke oven flue gas enters as foaming gas from air bearing pot bottom collection chamber；
Using carbon dioxide, nitrogen and the waste heat oil removing in coke oven flue gas, the water layer after oil removing is directly entered extraction equipment and is extracted
Dephenolize, scum layer enter oil water separator and carry out water-oil separating；Coke oven flue gas returns to coke oven flue gas after discharge at the top of air flotation tank
Processing system；
(2) water-oil separating；
In oil water separator, oil reservoir of the scum layer after water-oil separating is discharged from oil water separator top, and water layer is returned from lower part
Return-air buoyant tank；
(3) pressure extraction dephenolize；
High-concentration phenol ammonia waste water and extractant adverse current after step (1) oil removing enter extraction equipment, are passed through coke in extraction equipment
Kiln gas pressurization, maintains extraction equipment air pressure inside in 0.2MPa or more, soluble in water using the carbon dioxide in coke oven flue gas
The characteristic of carbonic acid is formed, the pH value of high-concentration phenol ammonia waste water is changed；The tar that mutually directly returns containing phenol extraction after pressure extraction adds
Work centrifugal station, raffinate phase, which enters after accumulator tank stands 2h or more, to be layered, and residual extractant returns to tar production centrifugal station, water
Phase then enters subsequent processing workshop section；
Waste water index after de-oiling dephenolize are as follows: COD≤3000mg/L, volatile phenol≤100mg/L, oil≤30mg/L.
2. a kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water according to claim 1, which is characterized in that
The coke oven flue gas is the neat stress for reaching discharge standard after purified processing.
3. a kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water according to claim 1, which is characterized in that
During the coke oven flue gas oil removal by air bubbling, the temperature in air flotation tank is 0~70 DEG C, and pressure is 0.2~0.5MPa, bubble diameter
It is 20~50 μm, the oil removal by air bubbling time is 10~30min.
4. a kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water according to claim 1, which is characterized in that
Water layer in the air flotation tank after oil removal by air bubbling is the aqueous solution of sour gas carbon dioxide saturation.
5. a kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water according to claim 1, which is characterized in that
The extractant is the product light oil of tar production centrifugal station.
6. a kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water according to claim 1, which is characterized in that
Extraction temperature in the extraction equipment is 0~80 DEG C, and the volume ratio of high-concentration phenol ammonia waste water and extractant is 0.5~2:1, extraction
Taking the air pressure in device is 0.2~0.5MPa, and the pH value of high-concentration phenol ammonia waste water is 5~7 in extraction equipment, and extraction series is 1
~3.
7. a kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water according to claim 1 or 6, feature exist
In the extraction equipment is packed extraction tower, perforated-plate extraction tower or centrifugal extractor.
8. a kind of oil removing dephenolize combination treatment method of high-concentration phenol ammonia waste water according to claim 1, which is characterized in that
The air flotation tank, extraction equipment pass through flue gas recirculation pipeline respectively and connect with coke oven flue gas processing system.
9. the oil removing dephenolize Combined Treatment system of the high-concentration phenol ammonia waste water for realizing any one method described in claim 1-8
System, which is characterized in that including air flotation tank, oil water separator, extraction equipment, accumulator tank and flue gas surge tank；The flue gas buffering
Coke oven flue gas entrance and coke oven flue gas outlet, the neat stress pipeline company of coke oven flue gas entrance and coke oven flue gas processing system are set on tank
It connects, the collection chamber of coke oven flue gas outlet connection air bearing pot bottom and the pressurizing device of extraction equipment bottom；The top of air flotation tank is set
Phenol ammonia waste water entrance and dross outlet, lower part set separation water inlet and degreased wastewater outlet, dross outlet and oil water separator top
The material inlet in portion connects, and the separation water out of oil water separator bottom is connect with the separation water inlet on air flotation tank, grease point
The oily outlet of separation is set from device top；The waterwater entrance on the degreased wastewater outlet connection extraction equipment top on the air flotation tank,
Exhanst gas outlet after extracting is set at the top of extraction equipment, is passed through flue gas recirculation pipeline and is connected coke oven flue gas processing system；Extraction equipment
Top set extraction phase outlet, lower part set raffinate phase outlet, raffinate phase outlet connection accumulator tank on material inlet, accumulator tank
Top sets residual extractant outlet, and lower part sets water phase outlet.
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| CN201910270837.0A CN110002629B (en) | 2019-04-04 | 2019-04-04 | Oil and phenol removal combined treatment method and system for high-concentration phenol-ammonia wastewater |
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| CN201910270837.0A CN110002629B (en) | 2019-04-04 | 2019-04-04 | Oil and phenol removal combined treatment method and system for high-concentration phenol-ammonia wastewater |
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| CN110615553A (en) * | 2019-09-18 | 2019-12-27 | 兰州正丰石油化工技术装备有限责任公司 | Method for deeply treating thick oil produced water by using flue gas |
| CN111115966A (en) * | 2020-01-09 | 2020-05-08 | 北京宝沃石油技术有限责任公司 | Extraction technology-based underground water pumping treatment system and method |
| CN112591993A (en) * | 2020-12-09 | 2021-04-02 | 江苏鲲鹏环保工程技术有限公司 | Semi-coke wastewater zero-discharge treatment equipment and method |
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| CN115196806A (en) * | 2022-07-21 | 2022-10-18 | 中国科学院山西煤炭化学研究所 | Method for deoiling and dedusting low-rank coal pyrolysis wastewater |
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| CN110615553A (en) * | 2019-09-18 | 2019-12-27 | 兰州正丰石油化工技术装备有限责任公司 | Method for deeply treating thick oil produced water by using flue gas |
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| CN111115966A (en) * | 2020-01-09 | 2020-05-08 | 北京宝沃石油技术有限责任公司 | Extraction technology-based underground water pumping treatment system and method |
| CN112678911A (en) * | 2020-12-08 | 2021-04-20 | 北京星枫先控科技有限公司 | Control method for wastewater discharge index of phenol ammonia recovery device |
| CN112591993A (en) * | 2020-12-09 | 2021-04-02 | 江苏鲲鹏环保工程技术有限公司 | Semi-coke wastewater zero-discharge treatment equipment and method |
| CN112591993B (en) * | 2020-12-09 | 2022-08-30 | 江苏鲲鹏环保工程技术有限公司 | Semi-coke wastewater zero-discharge treatment equipment and method |
| CN115196806A (en) * | 2022-07-21 | 2022-10-18 | 中国科学院山西煤炭化学研究所 | Method for deoiling and dedusting low-rank coal pyrolysis wastewater |
| CN115196806B (en) * | 2022-07-21 | 2024-01-12 | 中国科学院山西煤炭化学研究所 | Deoiling and dedusting method for low-rank coal pyrolysis wastewater |
| CN115215482A (en) * | 2022-07-27 | 2022-10-21 | 伊吾疆纳新材料有限公司 | Novel coking wastewater oil removing process |
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