CN104556465A - Liquid hydrocarbon alkali dreg wastewater treatment method - Google Patents

Liquid hydrocarbon alkali dreg wastewater treatment method Download PDF

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Publication number
CN104556465A
CN104556465A CN201310486496.3A CN201310486496A CN104556465A CN 104556465 A CN104556465 A CN 104556465A CN 201310486496 A CN201310486496 A CN 201310486496A CN 104556465 A CN104556465 A CN 104556465A
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alkali
waste liquid
acidification
sulfuric acid
acidifying
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CN104556465B (en
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赵磊
刘忠生
刘志禹
王新
王有华
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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China Petroleum and Chemical Corp
Sinopec Fushun Research Institute of Petroleum and Petrochemicals
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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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/08—Recovery of used refining agents
    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00—General aspects of water treatment
    • C02F2301/08—Multistage treatments, e.g. repetition of the same process step under different conditions

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Removal Of Specific Substances (AREA)

Abstract

The invention relates to a liquid hydrocarbon alkali dreg wastewater treatment method which comprises steps as follows: (1) acidifying liquid hydrocarbon alkali dreg wastewater with sulfuric acid, feeding nitrogen, and stopping acidification when the pH value is in a range of 3-7; (2) producing sulfuric acid with acidification tail gas produced by acidification, and reusing the sulfuric acid for acidifying treatment in step (1); (3) settling the acid wastewater after the acidifying treatment, and recovering an oil phase; (4) treating the wastewater with the oil phase recovered with sodium hydroxide, adding the sodium hydroxide until the final alkali concentration is in a range of 20wt%-50wt%, and reusing obtained alkali liquor in oil alkali washing and refining after precipitate is separated. With the adoption of the method, sulfides and naphthenic acid in the alkali dreg wastewater can be recovered efficiently, and the COD in the wastewater can be reduced; after alkali treatment, efficient desalination can be realized, the COD is further reduced, high-salt and high-COD wastewater cannot be produced, and the impact on a sewage treatment plant is avoided; meanwhile, the obtained alkali liquor can be reused for oil alkali washing and refining, and zero emission of the alkali dreg wastewater is realized.

Description

A kind for the treatment of process of liquid hydrocarbon alkali residue waste liquid
Technical field
The present invention relates to a kind for the treatment of process of alkali residue waste liquid, the treatment process of the alkali residue waste liquid of particularly liquid hydrocarbon alkali cleaning treating process generation.
Background technology
In Refinery Oil alkali cleaning treating process, the alkaline waste liquor containing high density pollution thing can be produced, the quantity discharged of its COD, sulfide and phenol accounts for 40wt% ~ more than the 50%wt of this type of pollutant discharge amount of refinery, primarily of compositions such as ordinary pressure diesel alkaline residue, coker gasoline and diesel alkaline residue, liquid hydrocarbon alkali residue.These alkali residue waste liquid, if directly discharged, meeting serious environment pollution, if delivered to sewage farm, will have a strong impact on the normal running in sewage farm, make sewage be difficult to qualified discharge, and severe corrosion equipment.Alkaline residue problem is at refinery ubiquity.In the last few years, along with national environmental protection regulation, standard are increasingly complete and strict, and the cry of people to environmental protect quality was more and more higher, and the process of alkaline residue more and more comes into one's own.
In this several alkaline residue, what sulfide content was the highest is coker gasoline and diesel alkaline residue and liquid hydrocarbon alkali residue, generally use wet oxidation process at present, oxidation waste liquid sulfuric acid neutralizes, and reclaims phenol, petroleum acid, produces in alkaline residue and water, but COD is still very high, can 30000mg/L ~ 60000mg/L be reached, and create a large amount of salt in oxidation and N-process, impact very large to the sewage farm of Petrochemical Enterprises.Ordinary pressure diesel alkaline residue is mainly containing petroleum acid, and generally adopt in sulfuric acid and reclaim naphthenic acid process, produce in diesel alkaline residue and water, COD is relatively low, but salt concn is very high, just can enter sewage farm after needing Macrodilution.
Along with the development of oil refining process for refining, diesel oil and gasoline gradually adopt hydrofining technology, can avoid like this producing a large amount of alkali residue waste liquid.But liquid hydrocarbon is still based on alkali cleaning process for refining, the alkali residue waste liquid of corresponding high sulfur content height COD can be produced.For the process of alkali residue waste liquid, some patent proposes treatment technology, has hydrolysis method, oxidation style, biological process, extraction process, evaporation burning method etc.
CN201010244665.9 discloses a kind for the treatment of process of high-concentration sulfur-containing caustic sludge wastewater from oil refinery, and main process comprises precipitation-acidifying-electricity flocculation-Fenton reagent oxidizing process.The high-concentration sulfur-containing alkaline sewage that refinery is refined out, adds precipitation agent, first removes the stench class materials such as sulfide, thioether and the mercaptan in waste water, significantly weakens alkaline residue stink, cut down water body toxicity; Then, crude phenols and naphthenic acid are reclaimed in acidifying, then carry out oxide treatment by electricity flocculation-Fenton reagent, remove the organism of overwhelming majority pollution and bio-refractory in waste water.The method employs precipitation agent, Fenton reagent in a large number, can remove organic pollutant, but finally still can obtain the higher neutral water of salts contg.
CN02130781.4 discloses a kind for the treatment of process of refinery basic sewage, comprise: the refinery basic sewage of evaporation containing evaporation accelerators at 101 ~ 115 DEG C, the gaseous condensate evaporated recycles, and the alkaline residue after concentrated enters incinerator and burn at 750 ~ 950 DEG C generation sodium carbonate and sodium sulfate.But in alkaline residue, volatile organism and Stenchy sulfides can be able to send in a large number in the process of evaporation, cause gaseous condensate Pollutant levels very high, and evaporation and to burn energy consumption very large.
CN00110702.X discloses the treatment process of alkaline sewage of a kind of high COD content, high inorganic salt content, adopt Membrane Bioreactor for Wastewater Treatment alkaline sewage, waste water is through activated sludge biochemical process, and after process, water outlet is discharged through membrane filtration, and the film used is microfiltration membrane or ultra-filtration membrane.This patent is only applicable to influent COD <12000mg/L, the alkaline sewage of inorganic salt content <50mg/L.For the COD of most of alkali residue waste liquid all far above this index, fresh water is still needed to dilute.
CN200810239660.X discloses the treatment process of a kind of waste lye or alkaline residue, utilize fluidized catalytic cracker regenerated flue gas to process, comprising: the alkaline residue of alkaline residue (abbreviation liquefied gas alkaline mud) and other devices that the alkaline residue (abbreviation gasoline alkaline residue) produce gasoline refining and liquefied gas refine generation is in harmonious proportion; Pass in alkaline residue after mediation fluidized catalytic cracker regenerated flue gas carry out in and; Isolate the oil in alkaline residue and phenol, naphthenic acid sulfide etc.But the method process alkaline residue, finally also can be formed in the alkaline residue of high salt and water, still can impact sewage farm.
Summary of the invention
For the deficiencies in the prior art, the invention provides a kind for the treatment of process of liquid hydrocarbon alkali residue waste liquid.The inventive method can sulfide in high efficiente callback alkali residue waste liquid and petroleum acid, reduces the COD of waste liquid; After alkaline purification, can efficiently desalination, reduce COD further, high saliferous height COD waste liquid can not be produced, avoid impacting sewage farm; The alkali lye simultaneously obtained can be back to treating oil by alkali washing and refine, and achieves the zero release of alkali residue waste liquid.
The treatment process of liquid hydrocarbon alkali residue waste liquid of the present invention, comprises following content:
(1) use sulfuric acid to carry out acidification to alkali residue waste liquid, and pass into nitrogen, when pH value reaches 3 ~ 7, stopping acidification;
(2) the acidifying tail gas of acidifying generation is for the production of sulfuric acid, and sulfuric acid is back to step (1) acidification;
(3) acid waste liquid after acidification carries out sedimentation, reclaims oil phase;
(4) the waste liquid sodium hydroxide after reclaiming oil phase processes, and the amount being 20wt% ~ 50wt% according to final alkali concn adds, and after isolating precipitate, the alkali lye obtained is back to treating oil by alkali washing and refines.
In the inventive method, the volumetric concentration of the sulfuric acid added in step (1) is 60% ~ 80%.When the pH value of waste liquid preferably reaches 3 ~ 5, stopping acidification process.Pass into nitrogen in acidification as carrier gas, can stirring action be played on the one hand, be conducive to strengthening acidifying reaction gas liquid mass transfer process; On the other hand, constantly strengthen along with waste liquid is acid, sulfide exists with molecular form, mainly with mercaptan, H 2the forms such as S, methyl disulfide, thioether evaporate, and these sulfide can carry out by carrier gas, improve the removal effect of sulfide.In addition, carrier gas also contributes to oil phase and the aqueous phase layering of generation, plays certain air supporting effect.The acidification process of step (1), can remove more than 99.6% by the sulfide in alkali residue waste liquid.
In the inventive method, the acidifying tail gas of step (2) is mainly containing organic sulfide and H 2s, uses nitrogen as carrier gas, because sulfide concentration is wherein unstable, if sulfide concentration is lower, very uneconomical for production sulfuric acid, needs to obtain sulfide volume content and reaches more than 50% for the production of sulfuric acid.Therefore, pass into nitrogen when acidifying starts, the acidifying tail gas of generation carries out refluxing as carrier gas, control load volume and reflux ratio, make acidification reactor pressure at 0.05 ~ 0.3MPa, control acidifying tail gas medium sulphide content volume content and run up to more than 50%, for the production of sulfuric acid.Acidifying tail gas backflow acidification produced is used as carrier gas, can reduce the usage quantity of nitrogen; On the other hand, sulfide content runs up to acidifying tail gas to a certain degree for the preparation of sulfuric acid, can not increase the manufacturing cost of sulfuric acid; Especially for preparation volumetric concentration be 60% ~ 80% sulfuric acid, can production cost be reduced.The production of sulfuric acid can be produced by the mode of well known to a person skilled in the art, produces the acidification that the sulfuric acid obtained may be used for step (1), achieves effective utilization of resource.
In the inventive method, be mainly petroleum acid in the oil phase of step (3), petroleum acid can reclaim further; After reclaiming oil phase, COD clearance can reach more than 85%.
In the inventive method, the sodium hydroxide used in step (4) is technical grade caustic soda, and the amount being 30wt% ~ 45wt% according to final alkali concn adds sodium hydroxide.Along with the membership that adds of sodium hydroxide produces a large amount of precipitates, mainly sodium sulfate in precipitate.The present invention utilizes the alkali residue waste liquid after sodium-hydroxide treatment acidifying, and the sodium hydroxide added is excessive, is not merely neutralization, but makes sodium hydroxide excessive thus the salts such as sodium sulfate are separated out fast.After sodium-hydroxide treatment, can remove the sulfate radical of more than 90%, and COD reduces further, COD clearance can reach more than 93%, can not produce high saliferous height COD waste liquid, obtain the sodium hydroxide lye of 20wt% ~ 50wt% simultaneously.According to the requirement that treating oil by alkali washing is refining, the alkali lye obtained just can be used for treating oil by alkali washing and refines after being diluted to suitable concn, the alkali residue waste liquid that treating oil by alkali washing refines generation continues to enter present invention process process.After alkali lye reuse, a small amount of sodium sulfate remaining in alkali lye can accelerate the settlement separate speed of water-oil phase in treating oil by alkali washing treating process.
In the inventive method, liquid hydrocarbon alkali residue waste liquid is the alkaline waste liquor that liquid hydrocarbon alkali cleaning treating process produces.
The treatment process tool of liquid hydrocarbon alkali residue waste liquid of the present invention has the following advantages:
1, the inventive method can sulfide in efficient recovery alkali residue waste liquid and petroleum acid, reduces the COD of waste liquid; Adopt after sodium-hydroxide treatment, can efficiently desalination, reduce COD further, avoid producing high saliferous height COD waste liquid, it is refining that the alkali lye simultaneously obtained can be back to treating oil by alkali washing.The present invention makes high-risk unmanageable alkali residue waste liquid be effectively addressed and reuse, achieves the zero release of waste liquid, avoids it on the impact of Sewage treatment systems, has good environmental benefit and economic benefit.
2, in acidification, pass into nitrogen as carrier gas, can stirring action be played on the one hand, be conducive to strengthening acidifying reaction gas liquid mass transfer process; On the other hand, constantly strengthen along with waste liquid is acid, sulfide exists with molecular form, mainly with mercaptan, H 2the forms such as S, methyl disulfide, thioether evaporate, and these sulfide can carry out by carrier gas in time, are conducive to the thorough removal of sulfide.If sulfide is removed not thorough, when using sodium hydroxide to process, not removed sulfide molecules, becomes again sodium sulphite or sodium mercaptides, affect the quality of the alkali lye that alkaline purification produces, be back to when treating oil by alkali washing is refined and oil quality is also had a certain impact.
3, the present invention utilizes the alkali residue waste liquid after sodium-hydroxide treatment acidifying, can remove the sulfate radical of more than 90%; And COD reduces further, COD clearance can reach more than 93%, can not produce high saliferous height COD waste liquid, avoid impacting sewage farm.The alkali lye simultaneously obtained is diluted to suitable concn just can directly be used as the refining alkali lye for the treatment of oil by alkali washing, and this alkali lye is in quality or quantitatively meet the requirement to alkali lye that treating oil by alkali washing refines all completely, on oil quality without any impact.
The steps such as the sulfuric acid acidation 4, related in the present invention, gas washing in SA production, sodium-hydroxide treatment are simple to operate, and without the need to large scale investment, operational condition is gentle, does not relate to high-temperature high-pressure apparatus, integral device investment and process cost all lower.
Accompanying drawing explanation
Fig. 1 is the process flow sheet of the inventive method.
Wherein: 101-acidification reactor, 102-sulphuric acid plant, 103-slurry tank, 104-alkaline purification equipment, 105-treating oil by alkali washing is refined; 201-alkali residue waste liquid, 202-acid waste liquid, 203-oil phase, 204-reclaims the waste liquid after oil phase, 205-sodium hydroxide, 206-precipitate, the alkali lye after 207-alkaline purification; 301-sulfuric acid, 302-nitrogen, the acidifying tail gas of 303-backflow, 304-height sulfur compound acidifying tail gas.
Embodiment
In the inventive method, as shown in Figure 1, sulfuric acid (301) liquid towards hydrocarbon alkali residue waste liquid (201) in acidification reactor (101) is used to carry out acidification, pass into nitrogen (302) as carrier gas simultaneously, constantly strengthen along with waste liquid is acid, the sulfide in waste liquid is with mercaptan, H 2s, methyl disulfide, thioether equimolecular form exist, carried out by carrier gas, form acidifying tail gas, the acidifying tail gas (303) of backflow can be used as carrier gas, when acidifying tail gas medium sulphide content volumetric concentration reaches more than 50%, be sent to sulphuric acid plant (102) for the production of sulfuric acid as high sulfur compound acidifying tail gas (304).When the pH value of alkali residue waste liquid reaches 3 ~ 7, stopping acidification process, sulfide clearance can reach more than 99.6%.Acid waste liquid (202) after acidification enters slurry tank (103) and carries out sedimentation, and reclaim oil phase (203), be mainly petroleum acid in this oil phase, petroleum acid can reclaim further.The waste liquid (204) reclaimed after oil phase enters alkaline purification equipment (104), add sodium hydroxide (205) to process, after isolating precipitate (206), obtain the alkali lye (207) of high density, the sulfate radical of more than 90% can be removed, and COD reduces further, COD clearance can reach more than 93%.Alkali lye (207) after alkaline purification can be diluted to suitable concentration as required, is back to treating oil by alkali washing refining (105), and the refining liquid hydrocarbon alkali residue waste liquid (201) produced continues to enter present invention process process.
Illustrate the inventive method and effect further below in conjunction with example, wherein wt% is massfraction.
Embodiment 1
The liquid hydrocarbon alkali residue waste liquid of certain enterprise, wherein COD is 1.36 × 10 5mg/L, sulfide is 2.62 × 10 4mg/L, volatile phenol is 1.45 × 10 4mg/L.Adopt the method process shown in Fig. 1 of the present invention, first use volumetric concentration be 75% sulfuric acid acidification is carried out to alkali residue waste liquid, pass into nitrogen as carrier gas, until the pH of waste liquid is down to 3.5.The acidified process of alkali residue waste liquid, removes sulfide more than 99.9%.
Nitrogen is passed into when acidifying starts, the acidifying tail gas produced carries out refluxing as carrier gas, control load volume and reflux ratio, make acidification reactor pressure at 0.05 ~ 0.3MPa, control acidifying tail gas medium sulphide content volume content and run up to more than 50%, for the production of sulfuric acid, the sulfuric acid of production is back to acidification step.
After acid waste liquid sedimentation after acidifying, be separated upper oil phase, reclaim petroleum acid.After reclaiming oil phase, COD clearance can reach more than 85%.
Use sodium hydroxide to process the waste liquid after recovery oil phase, sodium hydroxide is technical grade caustic soda, and the amount being 40wt% according to final alkali concn adds sodium hydroxide, and produce a large amount of precipitate, precipitate is sodium sulfate mainly, and sulfate radical clearance can reach more than 95%; And COD reduces further, COD clearance can reach more than 93%.
Through the alkali lye that the inventive method process obtains, adopt service water to be diluted to the alkali lye of 15wt%, return liquid hydrocarbon alkali cleaning treating process.Liquid hydrocarbon medium sulphide content content is greater than 2000mg/m 3, after alkali cleaning is refining, total sulfur is down to 10mg/m 3below, mercaptan is less than 10ppm, meets treating oil by alkali washing and refines requirement, on oil product without any impact.
Embodiment 2
The liquid hydrocarbon alkali residue waste liquid of certain enterprise, wherein COD is 1.05 × 10 5mg/L, sulfide is 1.63 × 10 4mg/L, volatile phenol is 1.03 × 10 4mg/L.Adopt the method process shown in Fig. 1 of the present invention, first use volumetric concentration be 65% sulfuric acid acidification is carried out to alkali residue waste liquid, pass into nitrogen as carrier gas, until the pH of alkali residue waste liquid is down to 5.The acidified process of alkali residue waste liquid, removes sulfide more than 99.9%.
Nitrogen is passed into when acidifying starts, the acidifying tail gas produced carries out refluxing as carrier gas, control load volume and reflux ratio, make acidification reactor pressure at 0.05 ~ 0.3MPa, control acidifying tail gas medium sulphide content volume content and run up to more than 50%, for the production of sulfuric acid, the sulfuric acid of production is back to acidification step.
After acid waste liquid sedimentation after acidifying, be separated upper oil phase, reclaim petroleum acid.After reclaiming oil phase, COD clearance can reach more than 85%.
Use sodium hydroxide to process the waste liquid after recovery oil phase, sodium hydroxide is technical grade caustic soda, and the amount being 30wt% according to final alkali concn adds sodium hydroxide, and produce a large amount of precipitate, precipitate is sodium sulfate mainly, and sulfate radical clearance can reach more than 95%; And COD reduces further, COD clearance can reach more than 93%.
Through the alkali lye that the inventive method process obtains, adopt service water to be diluted to the alkali lye of 15wt%, return liquid hydrocarbon alkali cleaning treating process.Liquid hydrocarbon medium sulphide content content is greater than 1800mg/m 3, after alkali cleaning is refining, total sulfur is down to 10mg/m 3below, mercaptan is less than 10ppm, meets treating oil by alkali washing and refines requirement, on oil product without any impact.
Comparative example 1
Process with the identical alkali residue waste liquid of embodiment 1, COD is 1.36 × 10 5mg/L, sulfide is 2.62 × 10 4mg/L.First use volumetric concentration be 75% sulfuric acid acidification is carried out to alkali residue waste liquid, obstructed nitrogen just stirs back-mixing, until the pH of waste liquid is down to 3.5.The acidified process of alkali residue waste liquid, sulfide clearance only has 81wt%, means in the acid waste liquid after also having the sulfide of 5000mg/L to be nearly present in acidifying.Sedimentation after acidifying, is separated upper oil phase, reclaims petroleum acid.After reclaiming oil phase, COD clearance is 83%, re-uses sodium hydroxide and processes, and not removed sulfide molecules, becomes again sodium sulphite or sodium mercaptides, affects the quality of reuse alkali lye.

Claims (10)

1. a treatment process for liquid hydrocarbon alkali residue waste liquid, is characterized in that comprising following content:
(1) use sulfuric acid to carry out acidification to alkali residue waste liquid, and pass into nitrogen, when pH value reaches 3 ~ 7, stopping acidification;
(2) the acidifying tail gas of acidifying generation is for the production of sulfuric acid, and sulfuric acid is back to step (1) acidification;
(3) acid waste liquid after acidification carries out sedimentation, reclaims oil phase;
(4) the waste liquid sodium hydroxide after reclaiming oil phase processes, and the amount being 20wt% ~ 50wt% according to final alkali concn adds, and after isolating precipitate, the alkali lye obtained is back to treating oil by alkali washing and refines.
2. in accordance with the method for claim 1, it is characterized in that: the volumetric concentration of the sulfuric acid added in step (1) is 60% ~ 80%.
3. according to the method described in claim 1 or 2, it is characterized in that: stopping acidification process when pH value reaches 3 ~ 5 in step (1).
4. in accordance with the method for claim 1, it is characterized in that: step (2) passes into nitrogen when acidifying starts, the acidifying tail gas produced carries out refluxing as carrier gas, control load volume and reflux ratio, make acidification reactor pressure at 0.05 ~ 0.3MPa, control acidifying tail gas medium sulphide content volume content and run up to more than 50%, for the production of sulfuric acid.
5. in accordance with the method for claim 1, it is characterized in that: be mainly petroleum acid in the oil phase of step (3), petroleum acid can reclaim further; After reclaiming oil phase, COD clearance can reach more than 85%.
6. in accordance with the method for claim 1, it is characterized in that: the amount being 30wt% ~ 45wt% according to final alkali concn in step (4) adds sodium hydroxide.
7. according to the method described in claim 1 or 6, it is characterized in that: mainly sodium sulfate in the precipitate of step (4).
8. according to the method described in claim 1 or 6, it is characterized in that: step (4) can remove the sulfate radical of more than 90%, and COD reduces further, and COD clearance can reach more than 93%, obtains the sodium hydroxide lye of 20wt% ~ 50wt% simultaneously.
9. in accordance with the method for claim 1, it is characterized in that: according to the requirement that treating oil by alkali washing is refining in step (4), the alkali lye obtained can be used for treating oil by alkali washing after being diluted to suitable concn and refines, the refining alkali residue waste liquid produced continues to enter present invention process process.
10. in accordance with the method for claim 1, it is characterized in that: liquid hydrocarbon alkali residue waste liquid is the alkaline waste liquor that liquid hydrocarbon alkali cleaning treating process produces.
CN201310486496.3A 2013-10-17 2013-10-17 A kind of processing method of liquid hydrocarbon alkali residue waste liquid Active CN104556465B (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111778061A (en) * 2020-08-05 2020-10-16 伯尔菲特沧州科技中心 Method and system for regenerating light hydrocarbon desulfurization alcohol alkali liquor

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CN1683475A (en) * 2005-03-09 2005-10-19 中国石油化工股份有限公司 Complex extracting and dephenolizing method for alkaline slag of smeltery
CN103045288A (en) * 2011-10-17 2013-04-17 中国石油化工股份有限公司 Comprehensive treatment method of high-sulphur high-COD (Chemical Oxygen Demand) caustic sludge waste liquid

Patent Citations (3)

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Publication number Priority date Publication date Assignee Title
US20040094476A1 (en) * 2002-11-20 2004-05-20 Panditrao Sunil S. Extraction of phenol from wastewater
CN1683475A (en) * 2005-03-09 2005-10-19 中国石油化工股份有限公司 Complex extracting and dephenolizing method for alkaline slag of smeltery
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111778061A (en) * 2020-08-05 2020-10-16 伯尔菲特沧州科技中心 Method and system for regenerating light hydrocarbon desulfurization alcohol alkali liquor

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