CN104556465B - A kind of processing method of liquid hydrocarbon alkali residue waste liquid - Google Patents

A kind of processing method of liquid hydrocarbon alkali residue waste liquid Download PDF

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CN104556465B
CN104556465B CN201310486496.3A CN201310486496A CN104556465B CN 104556465 B CN104556465 B CN 104556465B CN 201310486496 A CN201310486496 A CN 201310486496A CN 104556465 B CN104556465 B CN 104556465B
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alkali
waste liquid
acidification
sulphuric acid
acidifying
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CN104556465A (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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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F9/00Multistage treatment of water, waste water or sewage
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G19/00Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
    • C10G19/08Recovery of used refining agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/40Devices for separating or removing fatty or oily substances or similar floating material
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/66Treatment of water, waste water, or sewage by neutralisation; pH adjustment
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/10Inorganic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2301/00General aspects of water treatment
    • C02F2301/08Multistage 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 present invention relates to the processing method of a kind of liquid hydrocarbon alkali residue waste liquid, including: (1) uses sulphuric acid to be acidified liquid hydrocarbon alkali residue waste liquid, and is passed through nitrogen, when pH value reaches 3~7, and stopping acidification;(2) the acidifying tail gas that acidifying produces is used for producing sulphuric acid, and sulphuric acid is back to the acidification of step (1);(3) after acidification, acid waste liquid settles, and reclaims oil phase;(4) the waste liquid sodium hydroxide after reclaiming oil phase processes, and adds according to the amount that final alkali concn is 20wt%~50wt%, and after isolating precipitate, the alkali liquor obtained is back to treating oil by alkali washing and refines.The inventive method with the sulfide in high efficiente callback alkali residue waste liquid and petroleum acids, can reduce the COD of waste liquid;Through alkali process after, can efficiently desalination, reduce COD further, high saliferous height COD waste liquid will not be produced, it is to avoid sewage farm is impacted;The alkali liquor simultaneously obtained can be back to treating oil by alkali washing and refine, it is achieved that the zero-emission of alkali residue waste liquid.

Description

A kind of processing method of liquid hydrocarbon alkali residue waste liquid
Technical field
The present invention relates to the processing method of the alkali residue waste liquid that the processing method of a kind of alkali residue waste liquid, particularly liquid hydrocarbon alkali cleaning subtractive process produce.
Background technology
In Refinery Oil alkali cleaning subtractive process, the alkaline waste liquor containing high density pollution thing can be produced, the discharge capacity of its COD, sulfide and phenol accounts for the 40wt%~more than 50%wt of this type of pollutant discharge amount of oil plant, is mainly made up of ordinary pressure diesel alkaline residue, coker gasoline and diesel alkaline residue, liquid hydrocarbon alkali residue etc..These alkali residue waste liquid, if directly discharged, meeting serious environment pollution, if being passed to sewage farm, it will have a strong impact on the normal operating in sewage farm, make sewage be difficult to qualified discharge, and severe corrosion equipment.Alkaline residue problem generally exists at oil plant.In the last few years, along with national environmental protection regulation, standard are the most complete and strict, and people were more and more higher to the cry improving environmental quality, and the process of alkaline residue increasingly comes into one's own.
In these several alkaline residues, what sulfide content was the highest is coker gasoline and diesel alkaline residue and liquid hydrocarbon alkali residue, commonly use wet oxidation at present to process, oxidation waste liquid sulphuric acid neutralizes, and reclaims phenol, petroleum acids, produces in alkaline residue and water, but COD is the highest, up to 30000mg/L~60000mg/L, and create substantial amounts of salt in oxidation and N-process, the sewage farm of Petrochemical Enterprises is impacted the biggest.Ordinary pressure diesel alkaline residue mainly contains petroleum acids, processes with recovery aphthenic acids, produce in diesel alkaline residue and water in commonly used sulphuric acid, and COD is relatively low, but salinity is the highest, 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, so can avoid producing a large amount of alkali residue waste liquid.But liquid hydrocarbon still based on alkali cleaning process for refining, can produce the alkali residue waste liquid of corresponding high sulfur content height COD.For the process of alkali residue waste liquid, some patent proposes treatment technology, has Hydrolyze method, oxidizing process, bioanalysis, extraction, evaporation burning method etc..
CN201010244665.9 discloses the processing method of a kind of high-concentration sulfur-containing caustic sludge wastewater from oil refinery, and main process includes precipitation-acidifying-electricity flocculation-Fenton reagent oxidation technology.The refined high-concentration sulfur-containing alkaline sewage out of oil plant, adds precipitant, first removes the stench class materials such as sulfide, thioether and mercaptan in waste water, significantly weakens alkaline residue stink, cut down water body toxicity;Then, crude phenols and aphthenic acids are reclaimed in acidifying, then carry out oxidation processes by electricity flocculation-Fenton reagent, remove the overwhelming majority in waste water and pollute and the Organic substance of bio-refractory.The method employs precipitant, Fenton reagent in a large number, can remove removal organic polluter, but the most still can obtain the neutral water that salt content is higher.
CN02130781.4 discloses the processing method of a kind of refinery basic sewage, including: the evaporation refinery basic sewage containing evaporation accelerators at 101~115 DEG C, the gaseous condensate that evaporates recycles, and the alkaline residue after concentration enters incinerator and burn at 750~950 DEG C and generate sodium carbonate and sodium sulfate.But, in alkaline residue, volatile Organic substance and Stenchy sulfides can be able to issue during evaporation in a large number, cause gaseous condensate pollutant levels the highest, and evaporation and burning energy consumption are the biggest.
CN00110702.X discloses the processing method of the alkaline sewage of a kind of high COD content, high inorganic salt content, use Membrane Bioreactor for Wastewater Treatment alkaline sewage, waste water processes through activated sludge biochemical, and after process, water outlet is discharged through membrane filtration, and the film used is micro-filtration membrane or ultrafilter membrane.This patent is only applicable to influent COD < 12000mg/L, the inorganic salt content < alkaline sewage of 50mg/L.COD for major part alkali residue waste liquid is far above this index, it is still necessary to fresh water dilutes.
CN200810239660.X discloses the processing method of a kind of spent lye or alkaline residue, fluidized catalytic cracker regenerated flue gas is utilized to process, including: the alkaline residue of alkaline residue (abbreviation liquefied gas alkaline mud) and other devices that the alkaline residue (abbreviation gasoline alkaline residue) gasoline refining produced and liquefied gas refine generation is in harmonious proportion;Alkaline residue after mediation is passed through fluidized catalytic cracker regenerated flue gas be neutralized;Isolate the oil in alkaline residue and phenol, aphthenic acids sulfide etc..But, the method processes alkaline residue, the most 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 present invention provides the processing method of a kind of liquid hydrocarbon alkali residue waste liquid.The inventive method with the sulfide in high efficiente callback alkali residue waste liquid and petroleum acids, can reduce the COD of waste liquid;Through alkali process after, can efficiently desalination, reduce COD further, high saliferous height COD waste liquid will not be produced, it is to avoid sewage farm is impacted;The alkali liquor simultaneously obtained can be back to treating oil by alkali washing and refine, it is achieved that the zero-emission of alkali residue waste liquid.
The processing method of liquid hydrocarbon alkali residue waste liquid of the present invention, including following content:
(1) use sulphuric acid that alkali residue waste liquid is carried out acidification, and be passed through nitrogen, when pH value reaches 3~7, stopping acidification;
(2) the acidifying tail gas that acidifying produces is used for producing sulphuric acid, and sulphuric acid is back to step (1) acidification;
(3) acid waste liquid after acidification settles, and reclaims oil phase;
(4) the waste liquid sodium hydroxide after reclaiming oil phase processes, and adds according to the amount that final alkali concn is 20wt%~50wt%, and after isolating precipitate, the alkali liquor obtained is back to treating oil by alkali washing and refines.
In the inventive method, the volumetric concentration of the sulphuric acid added in step (1) is 60%~80%.When the pH value of waste liquid preferably reaches 3~5, stopping acidification processes.Acidification is passed through nitrogen and can play stirring action as carrier gas, one side, be conducive to strengthening acidifying reaction gas liquid mass transport process;On the other hand, constantly strengthening along with waste liquid is acid, sulfide exists with molecular forms, mainly with mercaptan, H2The forms such as S, methyl disulfide, thioether evaporate, and these sulfide can be carried out by carrier gas, improve the removal effect of sulfide.It addition, the oil phase that carrier gas additionally aids generation is layered with aqueous phase, play 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) mainly contains organic sulfur compound and H2S, use nitrogen is as carrier gas, owing to sulfide concentration therein is unstable, if sulfide concentration is relatively low, the most uneconomical for producing sulphuric acid, needs to obtain sulfide volume content and reaches more than 50% for producing sulphuric acid.Therefore, being passed through 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 0.05~0.3MPa, control sulfide volume content in acidifying tail gas and run up to more than 50%, be used for producing sulphuric acid.Acidifying tail gas backflow acidification produced is used as carrier gas, it is possible to reduce the usage amount of nitrogen;On the other hand, sulfide content runs up to a certain degree of acidifying tail gas for preparing sulphuric acid, will not increase the manufacturing cost of sulphuric acid;It is 60%~80% sulphuric acid especially for preparation volumetric concentration, production cost can be reduced.The production of sulphuric acid can produce in a manner known to those skilled in, produces the sulphuric acid obtained and may be used for the acidification of step (1), it is achieved that effective utilization of resource.
In the inventive method, being mainly petroleum acids in the oil phase of step (3), petroleum acids can reclaim further;After reclaiming oil phase, COD clearance is up to more than 85%.
In the inventive method, the sodium hydroxide used in step (4) is technical grade caustic soda, adds sodium hydroxide according to the amount that final alkali concn is 30wt%~45wt%.Along with the membership that adds of sodium hydroxide produces substantial amounts of precipitate, precipitate is mainly sodium sulfate.The present invention utilizes the alkali residue waste liquid after naoh treatment acidifying, and the sodium hydroxide of addition is excessive, is not merely to neutralize, but makes sodium hydroxide excess so that the salts such as sodium sulfate quickly separate out.After naoh treatment, can remove the sulfate radical of more than 90%, and COD reduces further, COD clearance, up to more than 93%, will 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 refined, the alkali liquor obtained just can be used for treating oil by alkali washing and refines after being diluted to suitable concn, and treating oil by alkali washing refines the alkali residue waste liquid of generation and goes successively to present invention process process.After alkali liquor reuse, in alkali liquor, a small amount of sodium sulfate of remaining can accelerate the settlement separate speed of water-oil phase in treating oil by alkali washing subtractive process.
In the inventive method, liquid hydrocarbon alkali residue waste liquid is the alkaline waste liquor that liquid hydrocarbon alkali cleaning subtractive process produces.
The processing method of liquid hydrocarbon alkali residue waste liquid of the present invention has the advantage that
1, the inventive method can sulfide in efficient recovery alkali residue waste liquid and petroleum acids, reduce the COD of waste liquid;Use after naoh treatment, can efficiently desalination, reduce COD further, it is to avoid produce high saliferous height COD waste liquid, it is refined that the alkali liquor simultaneously obtained can be back to treating oil by alkali washing.The present invention makes high-risk intractable alkali residue waste liquid be effectively addressed and reuse, it is achieved that the zero-emission of waste liquid, it is to avoid its impact on sewage disposal system, has good environmental benefit and economic benefit.
2, in acidification, it is passed through nitrogen can play stirring action as carrier gas, one side, be conducive to strengthening acidifying reaction gas liquid mass transport process;On the other hand, constantly strengthening along with waste liquid is acid, sulfide exists with molecular forms, mainly with mercaptan, H2The forms such as S, methyl disulfide, thioether evaporate, and these sulfide can be carried out by carrier gas in time, beneficially the thorough removal of sulfide.If sulfide is removed not thorough, when using sodium hydroxide to process, the most removed sulfide molecules, become again sodium sulfide or sodium mercaptides, affect alkali and process the quality of the alkali liquor produced, be back to when treating oil by alkali washing refines, oil quality also be had a certain impact.
3, the alkali residue waste liquid after the present invention utilizes naoh treatment acidifying, can remove the sulfate radical of more than 90%;And COD reduces further, COD clearance, up to more than 93%, will not produce high saliferous height COD waste liquid, it is to avoid impact sewage farm.The alkali liquor simultaneously obtained is diluted to suitable concn just can be directly used as the alkali liquor that treating oil by alkali washing is refined, and this alkali liquor all fully meets the requirement to alkali liquor that treating oil by alkali washing is refined in quality or quantity, does not has any impact to oil quality.
The step operation such as the sulphuric acid acidifying that 4, relates in the present invention, gas washing in SA production, naoh treatment are simple, it is not necessary to large scale investment, and operating condition is gentle, are not related to high-temperature high-pressure apparatus, and integral device investment and operating cost are the most relatively low.
Accompanying drawing explanation
Fig. 1 is the process chart of the inventive method.
Wherein: 101-acidification reactor, 102-sulphuric acid plant, 103-settling tank, 104-alkali processing equipment, 105-treating oil by alkali washing refines;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 liquor after the process of 207-alkali;301-sulphuric acid, 302-nitrogen, the acidifying tail gas of 303-backflow, 304-height sulfur compound acidifying tail gas.
Detailed description of the invention
In the inventive method, as shown in Figure 1, use sulphuric acid (301), in acidification reactor (101), liquid hydrocarbon alkali residue waste liquid (201) is carried out acidification, it is passed through nitrogen (302) as carrier gas simultaneously, constantly strengthening along with waste liquid is acid, the sulfide in waste liquid is with mercaptan, H2S, methyl disulfide, thioether equimolecular form exist, it is carried out by carrier gas, form acidifying tail gas, the acidifying tail gas (303) of backflow can serve as carrier gas, when sulfide volumetric concentration reaches more than 50% in acidifying tail gas, it is sent to sulphuric acid plant (102) as high sulfur compound acidifying tail gas (304) and is used for producing sulphuric acid.When the pH value of alkali residue waste liquid reaches 3~7, stopping acidification processes, and sulfide clearance can reach more than 99.6%.Acid waste liquid (202) after acidification enters settling tank (103) and settles, and reclaims oil phase (203), is mainly petroleum acids in this oil phase, and petroleum acids can reclaim further.Reclaim the waste liquid (204) after oil phase and enter alkali processing equipment (104), add sodium hydroxide (205) to process, after isolating precipitate (206), obtain the alkali liquor (207) of high concentration, the sulfate radical of more than 90% can be removed, and COD reduces further, COD clearance is up to more than 93%.Alkali liquor (207) after alkali processes can be diluted to suitable concentration as required, is back to treating oil by alkali washing refined (105), and the refined liquid hydrocarbon alkali residue waste liquid (201) produced goes successively to present invention process and processes.
Being further elucidated with the inventive method and effect below in conjunction with example, wherein wt% is mass fraction.
Embodiment 1
The liquid hydrocarbon alkali residue waste liquid of certain enterprise, wherein COD is 1.36 × 105Mg/L, sulfide is 2.62 × 104Mg/L, volatile phenol is 1.45 × 104mg/L.Use the method shown in Fig. 1 of the present invention to process, first by the sulphuric acid that volumetric concentration is 75%, alkali residue waste liquid is carried out acidification, be passed through nitrogen as carrier gas, until the pH of waste liquid is down to 3.5.The acidified process of alkali residue waste liquid, removes sulphide removal more than 99.9%.
It is passed through 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 0.05~0.3MPa, control sulfide volume content in acidifying tail gas and run up to more than 50%, for producing sulphuric acid, the sulphuric acid of production is back to acidification step.
After acid waste liquid sedimentation after acidifying, separate upper oil phase, reclaim petroleum acids.After reclaiming oil phase, COD clearance is up to more than 85%.
Using sodium hydroxide to process the waste liquid after reclaiming oil phase, sodium hydroxide is technical grade caustic soda, adds sodium hydroxide according to the amount that final alkali concn is 40wt%, produces a large amount of precipitate, and precipitate is mainly sodium sulfate, and sulfate radical clearance is up to more than 95%;And COD reduces further, COD clearance is up to more than 93%.
Process the alkali liquor obtained through the inventive method, use industry water to be diluted to the alkali liquor of 15wt%, return liquid hydrocarbon alkali cleaning subtractive process.In liquid hydrocarbon, sulfide content is more than 2000mg/m3, after alkali cleaning is refined, total sulfur is down to 10mg/m3Hereinafter, mercaptan is less than 10ppm, meets treating oil by alkali washing and refines requirement, does not has any impact on oil product.
Embodiment 2
The liquid hydrocarbon alkali residue waste liquid of certain enterprise, wherein COD is 1.05 × 105Mg/L, sulfide is 1.63 × 104Mg/L, volatile phenol is 1.03 × 104mg/L.Use the method shown in Fig. 1 of the present invention to process, first by the sulphuric acid that volumetric concentration is 65%, alkali residue waste liquid is carried out acidification, be passed through 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 sulphide removal more than 99.9%.
It is passed through 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 0.05~0.3MPa, control sulfide volume content in acidifying tail gas and run up to more than 50%, for producing sulphuric acid, the sulphuric acid of production is back to acidification step.
After acid waste liquid sedimentation after acidifying, separate upper oil phase, reclaim petroleum acids.After reclaiming oil phase, COD clearance is up to more than 85%.
Using sodium hydroxide to process the waste liquid after reclaiming oil phase, sodium hydroxide is technical grade caustic soda, adds sodium hydroxide according to the amount that final alkali concn is 30wt%, produces a large amount of precipitate, and precipitate is mainly sodium sulfate, and sulfate radical clearance is up to more than 95%;And COD reduces further, COD clearance is up to more than 93%.
Process the alkali liquor obtained through the inventive method, use industry water to be diluted to the alkali liquor of 15wt%, return liquid hydrocarbon alkali cleaning subtractive process.In liquid hydrocarbon, sulfide content is more than 1800mg/m3, after alkali cleaning is refined, total sulfur is down to 10mg/m3Hereinafter, mercaptan is less than 10ppm, meets treating oil by alkali washing and refines requirement, does not has any impact on oil product.
Comparative example 1
Processing the alkali residue waste liquid identical with embodiment 1, COD is 1.36 × 105Mg/L, sulfide is 2.62 × 104mg/L.First by the sulphuric acid that volumetric concentration is 75%, alkali residue waste liquid being carried out acidification, obstructed nitrogen simply 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%, it is meant that in the acid waste liquid after also having the sulfide of nearly 5000mg/L to be present in acidifying.Settle after acidifying, separate upper oil phase, reclaim petroleum acids.After reclaiming oil phase, COD clearance is 83%, re-uses sodium hydroxide and processes, and the most removed sulfide molecules becomes again sodium sulfide or sodium mercaptides, affects the quality of reuse alkali liquor.

Claims (10)

1. the processing method of a liquid hydrocarbon alkali residue waste liquid, it is characterised in that include following content:
(1) use sulphuric acid that alkali residue waste liquid is carried out acidification, and be passed through nitrogen, when pH value reaches 3~7, stopping acidification;
(2) the acidifying tail gas that acidifying produces is used for producing sulphuric acid, and sulphuric acid is back to step (1) acidification;
(3) acid waste liquid after acidification settles, and reclaims oil phase;
(4) the waste liquid sodium hydroxide after reclaiming oil phase processes, and adds according to the amount that final alkali concn is 20wt%~50wt%, and after isolating precipitate, the alkali liquor obtained is back to treating oil by alkali washing and refines.
The most in accordance with the method for claim 1, it is characterised in that: the volumetric concentration of the sulphuric acid added in step (1) is 60%~80%.
3. according to the method described in claim 1 or 2, it is characterised in that: in step (1), pH value reaches stopping acidification process when 3~5.
The most in accordance with the method for claim 1, it is characterized in that: step (2) is passed through 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 0.05~0.3MPa, control sulfide volume content in acidifying tail gas and run up to more than 50%, be used for producing sulphuric acid.
The most in accordance with the method for claim 1, it is characterised in that: being mainly petroleum acids in the oil phase of step (3), petroleum acids reclaims further;After reclaiming oil phase, COD clearance is up to more than 85%.
The most in accordance with the method for claim 1, it is characterised in that: step (4) adds sodium hydroxide according to the amount that final alkali concn is 30wt%~45wt%.
7. according to the method described in claim 1 or 6, it is characterised in that: the precipitate of step (4) is mainly sodium sulfate.
The most in accordance with the method for claim 1, it is characterised in that: step (4) can remove the sulfate radical of more than 90%, and COD reduces further, and COD clearance, up to more than 93%, obtains the sodium hydroxide lye of 20wt%~50wt% simultaneously.
The most in accordance with the method for claim 1, it is characterised in that: according to the requirement that treating oil by alkali washing is refined in step (4), the alkali liquor obtained can be used for treating oil by alkali washing and refines after being diluted to suitable concn, and the refined alkali residue waste liquid produced goes successively to step (1) and processes.
The most in accordance with the method for claim 1, it is characterised in that: liquid hydrocarbon alkali residue waste liquid is the alkaline waste liquor that liquid hydrocarbon alkali cleaning subtractive process produces.
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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

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US6824687B2 (en) * 2002-11-20 2004-11-30 Abb Lummus Global Inc. Extraction of phenol from wastewater

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Publication number Priority date Publication date Assignee Title
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

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