CN102115283B - A treatment method for oil production wastewater - Google Patents
A treatment method for oil production wastewater Download PDFInfo
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Abstract
The invention discloses a method for treating oil extraction wastewater, which realizes effective treatment of pollutants in heavy oil, high-salt content and high-temperature oil extraction wastewater which are difficult to treat by a biological method by sequentially performing adsorption, coagulation, advanced oxidation, chemical alkaline precipitation, secondary oxidation and the like on the oil extraction wastewater. The method has obvious treatment effect and can reach or exceed the national oil extraction wastewater discharge standard. The whole process has the advantages of simple operation, short treatment period, good treatment effect, high efficiency and time saving, and thus has good industrialization prospect.
Description
Technical field
The invention belongs to the Environmental Science and Engineering field, relate to a kind of method of wastewater treatment, particularly relate to a kind of treatment process of oil extraction waste water.
Background technology
China normally all was recycled into the stratum with the sewage of extraction after treatment to the processing of oil extraction waste water in the past, or was used for displacement of reservoir oil by filling water, did not efflux basically.Along with the use of technology such as thermal recovery, polymer injection oil recovery, make the residue sewage quantity increasing the nineties in 20th century, and most of oil field faces the problem that oil extraction waste water effluxes.And along with the development of oil recovery technique, the composition of the oil extraction waste water that is discharged becomes increasingly complex, thereby the difficulty of the processing of oil extraction waste water is also increasing.The most of oil extraction waste waters of China directly discharging after the biological process main process is handled at present.Along with the raising of environmental protection requirement, the index of oil recovery waste discharge is also increasingly high.Existing waste water disposal facility and technology reach discharging standards after being difficult to make oil extraction waste water to be handled.
It is complicated that oil extraction waste water is formed; Only can just reach nearly 70 kinds by detected organism with the dichloromethane extraction technology; These organism can be divided into 7 types, are respectively phenols, hydrocarbon hydro carbons, ester class, alcohols, ketone, benzophenone class, acids, and are main with phenols and hydrocarbon hydro carbons mainly.Except that containing oil slick, oil in water emulsion and dissolving oil, also contain a large amount of suspended solidss in the oil extraction waste water, and the xylogen that adds of recovery process, whipping agent, tiff, clay etc., make the waste water composition very complicated.Also contain superpolymer in the oil production waste water in oil field, wherein in the majority with SEPIGEL 305.The COD of oil production waste water in oil field (COD) mainly is made up of waste oil and various chemicaladditives, and especially the latter belongs to the composition that is difficult to the biological process degraded.Waste water staple as on probation among the present invention has quaternary amine, sodium-chlor, and calcium chloride, guanidine that glue or hydroxypropyl guanidine that glue, borax, clay stabilizer, sodium hydroxide and diesel oil etc. are typical high saliferous, thick oil type oil extraction waste water.The oil field that viscosity of crude is big in addition or zero pour is low needs heating in production process, causes the recovered water temperature higher.
At present domesticly mainly handle oil extraction waste water as main technique, comprise aerobe method and anaerobic biological process with biological process.Anaerobic treatment is usually as the pre-treatment of aerobic treatment.Some is to belong to be difficult to biodegradable polycyclic aromatic hydrocarbons polymer substance for a organic pollutant in the oil production waste water in oil field; Utilize anaerobic treatment that some complicated organism in the waste water are hydrolyzed under anerobes effect and ferment; Be converted into and be easy to biodegradable simple organic; Thereby biodegradability is improved,, and remove a part of S for follow-up aerobic treatment provides condition
2-Biological process is particularly useful for the processing of solvability organic pollutant.But contain temporary toxic substance in the oil extraction waste water, mikrobe is played toxic action, the water quality characteristics of its high temperature and high salt makes microbial growth be suppressed simultaneously.At this moment, handle with general biological method, degradation rate is slower, and mikrobe needs one long period to adapt to.The multiple biochemical technology of Application and Development is handled the COD of oil field waste, but effect of field application is not ideal enough mostly.Particularly for thick-oil waste water and high slat-containing wastewater, it is poorer that biochemical technology is handled the effect of COD, and domestic still do not have ripe practical technology to the processing of this type waste water at present.
China application CN101481186 discloses a kind of oil gas field waste water technology and device, and this waste water treatment process comprises pre-treatment step and advanced treatment step, and pre-treatment step adopts electric floating processing+coagulating sedimentation facture; The advanced treatment step comprises oxide treatment, two-stage coagulation precipitation process, filtration, modifier treatment.This wastewater treatment equipment comprises the pretreatment unit and the advanced treatment apparatus that are disposed in order, and pretreatment unit comprises electric floating treatment unit and the one-level coagulating sedimentation device that is disposed in order.The water treatment effect of this method is better, and under the normal circumstances, effluent index can reach the GB8978-1996 primary standard after (gas) wastewater treatment of recovering the oil, and effluent index can reach the GB8978-1996 secondary standard after drilling and repairing well and the borehole operation wastewater treatment.But above-mentioned complex process, and when being used for the processing of viscous crude, the extraordinary oil extraction waste water of high saliferous, can't obtain above-mentioned effect.
In view of this, special proposition the present invention.
Summary of the invention
The object of the present invention is to provide a kind of treatment process of oil extraction waste water, be applicable to viscous crude, the extraordinary oil extraction waste water of high saliferous, be applicable to that also other viscous crude, high saliferous and pyritous are difficult to the processing of the oil extraction waste water of biological process processing.The combination process that the present invention adopts multistage physical chemistry treatment process to combine is handled oil extraction waste water, makes indissoluble separate material hard to manage and obtains separating, and the organism of difficult degradation obtains processing such as chemical oxidation.
A kind of treatment process of oil extraction waste water, described method comprises the steps:
1) absorption: oil extraction waste water is carried out adsorption treatment, and the solution after absorption is flowed out removes to contain admittedly thing, gets treatment solution I;
2) coagulation: in filtrating I, add coagulating agent, removal gets treatment solution II after containing thing admittedly;
3) advanced oxidation: with Fenton reagent solution II is carried out oxidative degradation, removal gets treatment solution III after containing thing admittedly;
4) chemical bases is analysed deposition: in handling III, add precipitation agent, removal gets treatment solution IV after containing thing admittedly;
5) secondary oxidation: treatment solution IV is carried out secondary oxidation with Fenton reagent.
Described step 1 is: oil extraction waste water is poured in the adsorption unit that sulphonated coal and/or boiler ash sediment and/or gac are housed carried out adsorption treatment; The particle diameter of sulphonated coal is 3-6mm, and the particle diameter of boiler ash sediment is 2-8mm, and the particle diameter of gac is after 0.5-3mm will adsorb solution left standstill 1-3 hour after flowing out or filters; Get treatment solution I; The particle diameter of preferred sulphonated coal is 4-5mm, and the particle diameter of boiler ash sediment is 4-6mm, and the particle diameter of gac is that 1-2mm will adsorb the solution left standstill 2 hours after the outflow; Removal contains thing admittedly, gets treatment solution I.
Described step 2 is: coagulating agent is added among the above-mentioned treatment solution I; Stirred 2-8 minute earlier fast, stir about 15-25 minute at interval at a slow speed again leaves standstill or filters the back and removes and contain thing admittedly; Get treatment solution II; Preferred stirred 5 minutes fast earlier, stir about 20 minutes at interval at a slow speed again, remove contain admittedly behind the thing treatment solution II.
Described coagulating agent be quality than the compound ferro-aluminum suspension-s of 5-15% of concentration or for concentration be polymeric aluminum chlorides solution or the quality of 5-20g/L 1.5-2.5% polyacrylamide solution than concentration.9% compound ferro-aluminum suspension-s of preferred mass specific concentration, add-on are that to make the volume by volume concentration in its waste water after adding be 0.8%; Or concentration is the polymeric aluminum chlorides solution of 10g/L, and add-on is that to make the volume by volume concentration in its waste water after adding be 3%.
Described step 3 is: with the pH to 3.0-3.5 of hydrochloric acid adjusting treatment solution II, adding quality is the ydrogen peroxide 50 of 20-30% than concentration, presses Fe again
2+: H
2O
2Be 1: 2-1: it is the FeSO of 0.5-1.5mol/L that 3 volume proportion adds concentration
47H
2O solution, FeSO
47H
2The add-on of O solution is 25-35mmol/L; Preferably regulate the pH to 3.2 of treatment solution II with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.5 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 30mmol/L.
Described step 3 was carried out under the normal daylighting condition stirring reaction 35-45 minute on room temperature, daytime, and preferred 40 minutes, removal got treatment solution III after containing thing admittedly.
Precipitation agent is precipitation agent sodium hydroxide or the yellow soda ash of order number greater than 260 purpose fine powdered in the described step 4; It is 0.5-1.5% than concentration that their add-on makes its quality respectively, 1%-1.5%, and it is 1%, 1.3% than concentration that the add-on of preferred sodium hydroxide, yellow soda ash makes its quality; After precipitation agent adds; After stirring reaction 1-3 minute, removal contains thing admittedly, gets treatment solution IV.
Described step 5 is: with the pH to 3.0-3.5 of hydrochloric acid adjusting treatment solution IV, adding quality is the ydrogen peroxide 50 of 20-30% than concentration, presses Fe again
2+: H
2O
2Be 1: 2.5-1: it is the FeSO of 0.5-1.5mol/L that 3 volume proportion adds concentration
47H
2O solution, FeSO
47H
2The add-on of O solution is 2-8mmol/L; Preferably regulate the pH to 3.2 of treatment solution II with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.8 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 5mmol/L; Carried out stirring reaction 25-35 minute preferred 30 minutes under the normal daylighting condition on room temperature, daytime.
The COD that also comprises water sample among the described method steps 1-5, the mensuration of BOD, pH and turbidity.
Described oil extraction waste water staple comprises quaternary amine, sodium-chlor, calcium chloride, other composition of guanidine that glue, borax, clay stabilizer, sodium hydroxide, diesel oil and crude oil.
Below in conjunction with treatment scheme of the present invention the present invention is done further to introduce in detail.
The present invention adopts physico-chemical process to handle oil extraction waste water.Waste water staple on probation among the present invention has quaternary amine, sodium-chlor, and calcium chloride, guanidine that glue or hydroxypropyl guanidine that glue, borax, clay stabilizer, other one-tenth of sodium hydroxide, diesel oil and crude oil grades, and is typical high saliferous, thick oil type oil extraction waste water.
In addition, in each step of the present invention, can adopt the mode of getting supernatant or crossing leaching filtrating that leaves standstill, adopt to leave standstill and get supernatant, be advisable, preferably leave standstill after 2 hours and get supernatant to leave standstill 1-3 hour admittedly contain the removal of thing.
Combination process flow process of the present invention is following:
" absorption---leave standstill or filter removal and contain thing admittedly---coagulation---leave standstill or filter removal and contain thing admittedly---advanced oxidation---leave standstill or filter removal and contain thing admittedly---chemical bases is analysed deposition---and leaving standstill or filter removal contains thing admittedly---secondary oxidation---leaves standstill or filter removal and contain thing admittedly ".
Above-mentioned treatment process specifically comprises the steps:
1) absorption: oil extraction waste water is carried out adsorption treatment, will adsorb effusive solution removal and contain thing admittedly, get treatment solution I.
Absorption preconditioning technique of the present invention can adopt the multiple adsorption unit of prior art; Its purpose is to remove part greasy dirt and suspended substance; The present invention preferably adopts sulphonated coal and/or boiler ash sediment and/or gac as adsorption medium absorption removal part greasy dirt and suspended substance; Above-mentioned sorbent material specific activity charcoal cost reduces a lot, and adsorption effect is same very significantly.When adopting sulphonated coal and/or boiler ash sediment, the particle diameter of sulphonated coal is 3-6mm, and the particle diameter of boiler ash sediment is the adsorptive power that 2-8mm helps to improve adsorption unit.After absorption flowed out solution left standstill 1-3 hour or filter after, treatment solution I, the particle diameter of preferred sulphonated coal is 4-5mm, the particle diameter of boiler ash sediment is 4-6mm, the solution left standstill after absorption is flowed out 2 hours.
Must note keep sulphonated coal, boiler ash sediment or amounts of activated carbon foot in the step 1, and in time change when saturated when it uses to reach more for a long time to adsorb.To realize better pretreating effect.
2) coagulation: in filtrating I, add coagulating agent, removal gets treatment solution II after containing thing admittedly;
Coagulating agent is added among the above-mentioned treatment solution I, stirred 2-8 minute earlier fast, stir about 15-25 minute at interval at a slow speed again leaves standstill or filters the back and removes and contain thing admittedly, treatment solution II, preferably stirred 5 minutes fast earlier, again stir about 20 minutes at interval at a slow speed.
Coagulating agent of the present invention is a quality than the compound ferro-aluminum suspension-s of 5-15% of concentration or for concentration is polymeric aluminum chlorides solution or the quality of the 5-20g/L 1.5-2.5% polyacrylamide solution than concentration, and add-on is that to make the volume by volume concentration in its waste water after adding be 0.8%; Or concentration is the polymeric aluminum chlorides solution of 10g/L, and add-on is that to make the volume by volume concentration in its waste water after adding be 3%.
Because different coagulating agent is discrepant to the coagulation effect of treatment solution; In order to filter out best coagulating agent; The contriver has carried out lot of test (the part test result sees table 1), adopts the coagulating agent of different mass specific concentration that treatment solution I is carried out coagulating treatment, is index with the COD clearance; Described COD clearance is in the coagulation process, the minimizing value of COD and the per-cent of handling COD value in the preceding waste water.Experimental result shows, the preferred compound ferro-aluminum of the coagulating agent of this oil extraction waste water, Poly aluminum Chloride (PAC), SEPIGEL 305.Earlier above-mentioned coagulating agent stirring and dissolving is made into certain density solution or suspension-s during use; Coagulating agent of the present invention is a quality than the compound ferro-aluminum suspension-s of 5-15% of concentration or for concentration is polymeric aluminum chlorides solution or the quality of the 5-20g/L 1.5-2.5% polyacrylamide solution than concentration, the 9% compound ferro-aluminum suspension-s or the concentration of preferred mass specific concentration are the polymeric aluminum chlorides solution of 10g/L.Coagulating agent is added among the above-mentioned treatment solution I, stirred 2-8 minute earlier fast, stir about 15-25 minute at interval at a slow speed again leaves standstill or filters the back and removes and contain thing admittedly, treatment solution II, preferably stirred 5 minutes fast earlier, again stir about 20 minutes at interval at a slow speed.In the alr mode; Stir the material thorough mixing that made in the treatment solution in 2-8 minute earlier fast; Stir about 15-25 minute at interval at a slow speed again, this moment coagulating agent can be fully with treatment solution in impurity combines formation to precipitate, whole whipping process was advisable in lasting 30-45 minute; Left standstill 1-3 hour or filtered remove contain thing admittedly after, treatment solution II.
The different add-ons of several kinds of coagulating agent different concns of table 1 solution are to the influence of COD clearance (%)
Can find out from The above results; Adopt the compound ferro-aluminum suspension-s of 5-15% or for concentration be polymeric aluminum chlorides solution or the quality of 5-20g/L than the 15-25% polyacrylamide solution of concentration as coagulating agent; Single phase COD clearance (%) can reach 20-35%, and COD clearance (%) can reach more than 36% when to adopt quality be the polymeric aluminum chlorides solution of 10g/L than 9% compound ferro-aluminum suspension-s of concentration or for concentration.
3) advanced oxidation: with Fenton reagent solution II is carried out oxidative degradation, removal gets treatment solution III after containing thing admittedly; With the pH to 3.0-3.5 of hydrochloric acid adjusting treatment solution II, adding quality is the ydrogen peroxide 50 of 20-30% than concentration, presses Fe again
2+: H
2O-
2Be 1: 2-1: it is the FeSO of 0.5-1.5mol/L that 3 volume proportion adds concentration
47H
2O solution, FeSO
47H
2The add-on of O solution is 25-35mmol/L; Preferably regulate the pH to 32 of treatment solution II with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.5 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 30mmol/L.Carried out stirring reaction 35-45 minute preferred 40 minutes under the normal daylighting condition on room temperature, daytime.
Different oxidation technology is also bigger to the treatment effect influence of waste water.The inventor also selects for use the different oxidation agent at room temperature oil extraction waste water to be carried out the research of oxidation effectiveness on the basis of consulting amount of literature data and other similar experiment, and experimental result is seen table 2.
Different add-ons are to the influence of COD clearance (%) under the different pH values of several kinds of oxygenants of table 2
Can find out that from experimental result Fenton reagent has remarkable advantages, its oxidation effectiveness is better than other reagent greatly, and cheap more many than dioxide peroxide.
Generally carry out under the normal daylighting condition on room temperature, daytime.The rising of temperature can improve treatment effect significantly.Light also can help the degraded of pollutent by force.The increase reaction times also can be improved the effect of processing, but after 40 minutes, increases comparatively slow.
4) chemical bases is analysed deposition: in handling III, add precipitation agent, removal gets treatment solution IV after containing thing admittedly;
In treatment solution III, add precipitation agent, precipitation agent of the prior art has multiple, like quicklime, lime carbonate etc.And find in the practical application that adopt the effectively impurity in the precipitate and separate oil extraction waste water of above-mentioned precipitation agent, therefore, the contriver has done number of research projects to selecting for use of precipitation agent, has finally confirmed to be used for precipitation agent of the present invention.Precipitation agent is precipitation agent sodium hydroxide and the yellow soda ash of order number greater than 260 purpose fine powdered in the described step 4; It is 0.5-1.5% than concentration that their add-on makes its quality respectively; 1%-1.5%, it is 1%, 1.3% than concentration that the add-on of preferred sodium hydroxide, yellow soda ash makes its quality., after precipitation agent added, stirring reaction 1-3 minute, removal contained thing admittedly, got treatment solution IV, preferred stirring reaction 2 minutes.Adopt after A or the B, chemical bases of the present invention is analysed deposition single phase COD clearance and is surpassed 60%, and a large amount of experimental results that the contriver carries out are partly seen table 3.
The different add-ons of several kinds of precipitation agents of table 3 are to the influence of COD clearance (%)
The above results shows, adopt the specific precipitation agent of the present invention after, single phase COD clearance is up to 63.3%, water treatment effect is very obvious, and general precipitation agent does not almost have effect.
5) secondary oxidation: treatment solution IV is carried out secondary oxidation with Fenton reagent.
The pH value of regulating treatment solution IV is to suitable scope, to the Fenton reagent that wherein successively adds different proportionings.In ventilating kitchen, to stir and react, 30 minutes reaction times got final product.Finish Deng reaction, get supernatant after leaving standstill or filter after carry out result verification and measure.
With the pH to 3.0-3.5 of hydrochloric acid adjusting treatment solution IV, adding quality is the ydrogen peroxide 50 of 20-30% than concentration, presses Fe again
2+: H
2O
2Be 1: 2.5-1: it is the FeSO of 0.5-1.5mol/L that 3 volume proportion adds concentration
47H
2O solution, FeSO
47H
2The add-on of O solution is 2-8mmol/L; Preferably regulate the pH to 3.2 of treatment solution II with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.8 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 5mmol/L; Carried out stirring reaction 25-35 minute preferred 30 minutes under the normal daylighting condition on room temperature, daytime.
Once oxidation is adopted in processing for waste water in the prior art usually, and in actually operating, in order to reach the ideal oxidation effectiveness, needs the oxygenant of labor in the once oxidation process, and the one, cause cost high, the 2nd, increased the weight of the complexity of subsequent disposal.The contriver finds in test of many times; Earlier once oxidation is carried out in processing with Fenton reagent; Precipitating action through precipitation agent then; With Fenton reagent treatment solution IV is carried out secondary oxidation again, not only can reduce the usage quantity of oxygenant, and improved treatment effect unexpectedly greatly waste water.
In addition, in each step of the oil extraction waste water treatment method among the present invention, all need detect water sample.All to get the COD of wastewater sample measurement processing water sample in the front and back of above-mentioned each step, also will measure biochemical oxygen demand BOD sometimes
5, pH or turbidity.The mensuration of COD is used CTL-12 type COD tacheometer, makes COD value typical curve earlier, carries out water determination again.The biochemical incubator of TF-1A type is used in the measurement of BOD, and dilution method was measured in 5 days.PH uses PHS-25 type acidometer to measure, and turbidity uses SGZ-2P microcomputer turbidity analyser to measure.The detection of each parameter value of water sample can be adopted the detection method of any water sample in the prior art.
The treatment process of viscous crude provided by the invention, the extraordinary oil extraction waste water of high saliferous has following advantage:
1. preconditioning technique has adopted sulphonated coal, boiler ash sediment adsorption filtration to remove part greasy dirt and suspended substance, and specific activity charcoal cost reduces a lot, and effect is also fine.The coagulation stage has been found coagulating agent preferably, and removal effect is good.
2. in the depositing technology stage, found special precipitation agent, sedimentation effect is good, and single phase COD clearance surpasses 50%, and operating process is simple, convenient, rapid, and medicament expense is low.
3. in the aftertreatment technology of combined treatment process, adopted secondary oxidation or oxidation technology repeatedly, compare the consumption that traditional once oxidation treatment process has reduced oxygenant, improved the effect of handling.
4. bulk treatment technology is compared with physics, the chemical technology of other report, and equipment is simple, less investment, and processing ease, treatment effect is good, and processing cost is low.Demonstrate the total system advantage of this combination process.
5. compare with the biological process treatment process, simple to operate, the processing cycle is short, and is suitable for viscous crude, high-salt wastewater and the high temperature oil extraction waste water that biological process can not be handled, and can reach or be better than national oil extraction waste water emission standard.This treatment process high efficiency and time conservation has excellent industrial application foreground.
Embodiment
Embodiment 1
" sulphonated coal adsorbs-leaves standstill or filter-compound ferro-aluminum coagulation-leave standstill or filter-Fenton advanced oxidation-leave standstill or filter-precipitation agent sodium hydroxide precipitates-leaves standstill or filter-Fenton oxygenant secondary oxidation-deposition or filter ".
Oil extraction waste water poured into to be equipped with in the adsorption unit of sulphonated coal that particle diameter is 4-5mm carry out adsorption treatment, the solution removal after absorption is flowed out contains thing admittedly, treatment solution I.
Is that 9% compound ferro-aluminum suspension-s adds among the treatment solution I with quality than concentration, stirs 5 minutes fast earlier, and stir about 20 minutes is at interval at a slow speed again removed and contained thing admittedly, treatment solution II.
Regulate the pH to 3.2 of treatment solution II with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.5 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 30mmol/L.Add the back and carried out stirring reaction 40 minutes on room temperature, daytime under the normal daylighting condition, removal gets treatment solution III after containing thing admittedly.
In treatment solution III, add precipitation agent and be the order number greater than 260 purpose precipitation agent sodium hydroxide, it is 1% than concentration that add-on makes its quality, and after precipitation agent added, stirring reaction 2 minutes was removed and contained thing admittedly, treatment solution IV.
Regulate the pH to 3.2 of treatment solution IV with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.8 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 5mmol/L; Carry out stirring reaction under the normal daylighting condition on room temperature, daytime and remove after 30 minutes and contain thing admittedly, the water after the processing can directly be discharged.
The COD of the former water of oil extraction waste water is 5422mg/L, adopts technique scheme, and after sulphonated coal absorption, COD reduces to 5048mg/L, and has removed some swimmers and suspended substance.The COD that leaves standstill or filter the back water sample is 4 968mg/L, and behind the compound ferro-aluminum coagulating sedimentation, COD drops to 3538.2mg/L; Be 846.2mg/L behind the Fenton advanced oxidation, behind the adding precipitation agent, drop to 402.2mg/L; After carrying out the Fenton secondary oxidation again, drop to 185.3mg/L.Reach national oil extraction waste water emission standard.BOD
5/ COD also rises to 0.39 by 0.23 before handling, and biochemical property has also had bigger improvement.Residue after the filtration can landfill or is handled with burning method.
Embodiment 2
" boiler ash sediment adsorbs-leaves standstill or filter-Poly aluminum Chloride (PAC) coagulation-leave standstill or filter-Fenton advanced oxidation-leave standstill or filter-precipitation agent yellow soda ash precipitates-leaves standstill or filter-Fenton oxygenant secondary oxidation-deposition or filter ".
Oil extraction waste water poured into to be equipped with in the adsorption unit of boiler ash sediment that particle diameter is 4-6mm carry out adsorption treatment, the solution removal after absorption is flowed out contains thing admittedly, treatment solution I.
Is that the polymeric aluminum chlorides solution of 10g/L adds among the treatment solution I with quality than concentration, stirs 2 minutes fast earlier, and stir about 25 minutes is at interval at a slow speed again removed and contained thing admittedly, treatment solution II.
Regulate the pH to 3.5 of treatment solution II with hydrochloric acid, adding quality is 25% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.0 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 25mmol/L.Add the back and carried out stirring reaction 45 minutes on room temperature, daytime under the normal daylighting condition, removal gets treatment solution III after containing thing admittedly.
In treatment solution III, add precipitation agent and be the order number greater than 260 purpose precipitation agent yellow soda ash, it is 1.3% than concentration that its add-on makes its quality, and after precipitation agent added, stirring reaction 2 minutes was removed and contained thing admittedly, treatment solution IV.
Regulate the pH to 3.0 of treatment solution IV with hydrochloric acid, adding quality is 25% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.5 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 8mmol/L; Carry out stirring reaction under the normal daylighting condition on room temperature, daytime and remove after 25 minutes and contain thing admittedly, the water after the processing can directly be discharged.
The COD of the former water of oil extraction waste water is 5404mg/L, adopts technique scheme, and after sulphonated coal absorption, COD reduces to 5098mg/L, and has removed some swimmers and suspended substance.The COD that leaves standstill or filter the back water sample is 5 012.2mg/L, and behind the Poly aluminum Chloride (PAC) coagulating sedimentation, COD drops to 3 689.3mg/L; Be 968.2mg/L behind the Fenton advanced oxidation, behind the adding precipitation agent, drop to 478.4mg/L; After carrying out the Fenton secondary oxidation again, drop to 246.4mg/L.Reach national oil extraction waste water emission standard.BOD
5/ COD also rises to 0.31 by 0.23 before handling, and biochemical property has also had bigger improvement.
Embodiment 3
" charcoal absorption-leave standstill or filter-compound ferro-aluminum coagulation-leave standstill or filter-Fenton advanced oxidation-leave standstill or filter-precipitation agent yellow soda ash precipitates-leaves standstill or filter-Fenton oxygenant secondary oxidation-deposition or filtration ".
Oil extraction waste water poured into carry out adsorption treatment in the adsorption unit that gac is housed, the solution removal after absorption is flowed out contains thing admittedly, treatment solution I.
Is that 9% compound ferro-aluminum suspension-s adds among the treatment solution I with quality than concentration, stirs 5 minutes fast earlier, and stir about 20 minutes is at interval at a slow speed again removed and contained thing admittedly, treatment solution II.
Regulate the pH to 3.0 of treatment solution II with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.0 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 25mmol/L.Add the back and carried out stirring reaction 40 minutes on room temperature, daytime under the normal daylighting condition, removal gets treatment solution III after containing thing admittedly.
In treatment solution III, add precipitation agent and be the order number greater than 260 purpose precipitation agent yellow soda ash, it is 1.5% than concentration that its add-on makes its quality,, after precipitation agent added, stirring reaction 2 minutes was removed and is contained thing admittedly, treatment solution IV.
Regulate the pH to 3.0 of treatment solution IV with hydrochloric acid, adding quality is 25% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 3.0 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 2mmol/L; Carry out stirring reaction under the normal daylighting condition on room temperature, daytime and remove after 30 minutes and contain thing admittedly, the water after the processing can directly be discharged.
The COD of the former water of oil extraction waste water is 5432mg/L, adopts technique scheme, and after charcoal absorption, COD reduces to 5021mg/L, and has removed some swimmers and suspended substance.The COD that leaves standstill or filter the back water sample is 4979.1mg/L, and behind the compound ferro-aluminum coagulating sedimentation, COD drops to 3562.3mg/L; Be 851.1mg/L behind the Fenton advanced oxidation, behind the adding precipitation agent, drop to 408.2mg/L; After carrying out the Fenton secondary oxidation again, drop to 195.39mg/L.Reach national oil extraction waste water emission standard.BOD
5/ COD also rises to 0.38 by 0.24 before handling, and biochemical property has also had bigger improvement.
Embodiment 4
" charcoal absorption-leave standstill or filter-compound ferro-aluminum coagulation-leave standstill or filter-Fenton advanced oxidation-leave standstill or filter-precipitation agent sodium hydroxide precipitates-leaves standstill or filter-Fenton oxygenant secondary oxidation-deposition or filtration ".
Oil extraction waste water poured into carry out adsorption treatment in the adsorption unit that gac is housed, the solution removal after absorption is flowed out contains thing admittedly, treatment solution I.
Is that 9% compound ferro-aluminum suspension-s adds among the treatment solution I with quality than concentration, stirs 5 minutes fast earlier, and stir about 20 minutes is at interval at a slow speed again removed and contained thing admittedly, treatment solution II.
Regulate the pH to 3.0 of treatment solution II with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.0 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 25mmol/L.Add the back and carried out stirring reaction 40 minutes on room temperature, daytime under the normal daylighting condition, removal gets treatment solution III after containing thing admittedly.
In treatment solution III, add precipitation agent and be the order number greater than 260 purpose precipitation agent sodium hydroxide, it is 1.% than concentration that its add-on makes its quality,, after precipitation agent added, stirring reaction 2 minutes was removed and is contained thing admittedly, treatment solution IV.
Regulate the pH to 3.0 of treatment solution IV with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 3.0 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 2mmol/L; Carry out stirring reaction under the normal daylighting condition on room temperature, daytime and remove after 30 minutes and contain thing admittedly, the water after the processing can directly be discharged.
The COD of the former water of oil extraction waste water is 5432mg/L, adopts technique scheme, and after charcoal absorption, COD reduces to 4987mg/L, and has removed some swimmers and suspended substance.The COD that leaves standstill or filter the back water sample is 4765.1mg/L, and behind the compound ferro-aluminum coagulating sedimentation, COD drops to 3476.3mg/L; Be 801.1mg/L behind the Fenton advanced oxidation, behind the adding precipitation agent, drop to 396.2mg/L; After carrying out the Fenton secondary oxidation again, drop to 178.39mg/L.Reach national oil extraction waste water emission standard.BOD
5/ COD also rises to 0.38 by 0.24 before handling, and biochemical property has also had bigger improvement.In technology, used activated carbon treatment technology instead, treatment effect is also better than instance 1.But consider that cost is bigger, should not adopt.
Embodiment 5
" sulphonated coal adsorbs-leaves standstill or filter-compound ferro-aluminum coagulation-leave standstill or filter-Fenton advanced oxidation-leave standstill or filter-precipitation agent sodium hydroxide precipitates-leaves standstill or filter-Fenton oxygenant secondary oxidation-deposition or filter ".
Oil extraction waste water poured into carry out adsorption treatment in the adsorption unit that sulphonated coal is housed, the solution removal after absorption is flowed out contains thing admittedly, treatment solution I.
Is that 5% compound ferro-aluminum suspension-s adds among the treatment solution I with quality than concentration, stirs 2 minutes fast earlier, and stir about 25 minutes is at interval at a slow speed again removed and contained thing admittedly, treatment solution II.
Regulate the pH to 3.0 of treatment solution II with hydrochloric acid, adding quality is 20% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 3 is the FeSO of 0.05mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 35mmol/L.Add the back and carried out stirring reaction 35 minutes on room temperature, daytime under the normal daylighting condition, removal gets treatment solution III after containing thing admittedly.
In treatment solution III, add precipitation agent and be the order number greater than 260 purpose precipitation agent sodium hydroxide, it is 1.5% than concentration that add-on makes its quality, and after precipitation agent added, stirring reaction 1 minute was removed and contained thing admittedly, treatment solution IV.
Regulate the pH to 3.0 of treatment solution IV with hydrochloric acid, adding quality is 20% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.5 is the FeSO of 0.5mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 8mmol/L; Carry out stirring reaction under the normal daylighting condition on room temperature, daytime and remove after 25 minutes and contain thing admittedly, the water after the processing can directly be discharged.
The COD of the former water of oil extraction waste water is 5420mg/L, adopts technique scheme, and after sulphonated coal absorption, COD reduces to 504lmg/L, and has removed some swimmers and suspended substance.The COD that leaves standstill or filter the back water sample is 4962mg/L, and behind the compound ferro-aluminum coagulating sedimentation, COD drops to 3536.4mg/L; Be 845.7mg/L behind the Fenton advanced oxidation, behind the adding precipitation agent, drop to 401.0mg/L; After carrying out the Fenton secondary oxidation again, drop to 181.2mg/L.
Embodiment 6
" boiler ash sediment adsorbs-leaves standstill or filter-Poly aluminum Chloride (PAC) coagulation-leave standstill or filter-Fenton advanced oxidation-leave standstill or filter-precipitation agent yellow soda ash precipitates-leaves standstill or filter-Fenton oxygenant secondary oxidation-deposition or filter ".
Oil extraction waste water poured into to be equipped with in the adsorption unit of boiler ash sediment that particle diameter is 6-8mm carry out adsorption treatment, the solution removal after absorption is flowed out contains thing admittedly, treatment solution I.
Is that the polymeric aluminum chlorides solution of 20g/L adds among the treatment solution I with quality than concentration, stirs 8 minutes fast earlier, and stir about 15 minutes is at interval at a slow speed again removed and contained thing admittedly, treatment solution II.
Regulate the pH to 3.5 of treatment solution II with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 3.0 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 25mmol/L.Add the back and carried out stirring reaction 40 minutes on room temperature, daytime under the normal daylighting condition, removal gets treatment solution III after containing thing admittedly.
In treatment solution III, add precipitation agent and be the order number greater than 260 purpose precipitation agent yellow soda ash, it is 1.3% than concentration that its add-on makes its quality, and after precipitation agent added, stirring reaction 2 minutes was removed and contained thing admittedly, treatment solution IV.
Regulate the pH to 3.5 of treatment solution IV with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 3.0 is the FeSO of 1.5mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 5mmol/L; Carry out stirring reaction under the normal daylighting condition on room temperature, daytime and remove after 35 minutes and contain thing admittedly, the water after the processing can directly be discharged.
The COD of the former water of oil extraction waste water is 5 400mg/L, adopts technique scheme, and after sulphonated coal absorption, COD reduces to 5 089mg/L, and has removed some swimmers and suspended substance.The COD that leaves standstill or filter the back water sample is 5 010.2mg/L, and behind the Poly aluminum Chloride (PAC) coagulating sedimentation, COD drops to 3687.5mg/L; Be 968.6mg/L behind the Fenton advanced oxidation, behind the adding precipitation agent, drop to 477.9mg/L; After carrying out the Fenton secondary oxidation again, drop to 245.2mg/L.Reach national oil extraction waste water emission standard.
Embodiment 7
" charcoal absorption-leave standstill or filter-compound ferro-aluminum coagulation-leave standstill or filter-Fenton advanced oxidation-leave standstill or filter-precipitation agent yellow soda ash precipitates-leaves standstill or filter-Fenton oxygenant secondary oxidation-deposition or filtration ".
Oil extraction waste water poured into carry out adsorption treatment in the adsorption unit that gac is housed, the solution removal after absorption is flowed out contains thing admittedly, treatment solution I.
Is that 15% compound ferro-aluminum suspension-s adds among the treatment solution I with quality than concentration, stirs 5 minutes fast earlier, and stir about 20 minutes is at interval at a slow speed again removed and contained thing admittedly, treatment solution II.
Regulate the pH to 3.0 of treatment solution II with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.0 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 25mmol/L.Add the back and carried out stirring reaction 40 minutes on room temperature, daytime under the normal daylighting condition, removal gets treatment solution III after containing thing admittedly.
In treatment solution III, add precipitation agent and be the order number greater than 260 purpose precipitation agent yellow soda ash, it is 0.5% than concentration that its add-on makes its quality, and after precipitation agent added, stirring reaction 3 minutes was removed and contained thing admittedly, treatment solution IV.
Regulate the pH to 3.2 of treatment solution IV with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O
2The volume proportion adding concentration that is 1: 2.5 is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 5mmol/L; Carry out stirring reaction under the normal daylighting condition on room temperature, daytime and remove after 30 minutes and contain thing admittedly, the water after the processing can directly be discharged.
Embodiment 8-11
Compare with embodiment 1, distinctive points only is:
Embodiment in the foregoing description can further make up or replace; And embodiment describes the preferred embodiments of the present invention; Be not that design of the present invention and scope are limited; Under the prerequisite that does not break away from design philosophy of the present invention, the various changes and modifications that the professional and technical personnel makes technical scheme of the present invention in this area all belong to protection scope of the present invention.
Claims (11)
1. the treatment process of an oil extraction waste water is characterized in that, described method comprises the steps:
1) absorption-: oil extraction waste water is carried out adsorption treatment, and the solution after absorption is flowed out removes to contain admittedly thing, gets the treatment solution I;
2) coagulation: in the treatment solution I, add coagulating agent, removal gets the treatment solution II after containing thing admittedly;
3) advanced oxidation: with Fenton reagent the treatment solution II is carried out oxidative degradation, removal gets the treatment solution III after containing thing admittedly;
4) chemical bases is analysed deposition: in the treatment solution III, add precipitation agent, removal gets the treatment solution IV after containing thing admittedly;
Precipitation agent is solid precipitation agent sodium hydroxide or the yellow soda ash of order number greater than 260 purpose fine powdered in the described step 4; It is 0.5-1.5% than concentration that their add-on makes its quality respectively; 1%-1.5%, after precipitation agent adds the treatment solution III, stirring reaction 1-3 minute; Removal contains thing admittedly, gets the treatment solution IV;
5) secondary oxidation: the treatment solution IV is carried out secondary oxidation with Fenton reagent.
2. method according to claim 1; It is characterized in that: described step 1 is: oil extraction waste water is poured in the adsorption unit that sulphonated coal and/or boiler ash sediment and/or gac are housed carried out adsorption treatment; The particle diameter of sulphonated coal is 3-6mm, and the particle diameter of boiler ash sediment is 2-8 mm, and the particle diameter of gac is 0.5-3mm; After absorption flowed out solution left standstill 1-3 hour or filter after, the treatment solution I.
3. method according to claim 2; It is characterized in that: described step 1 is: oil extraction waste water is poured in the adsorption unit that sulphonated coal and/or boiler ash sediment and/or gac are housed carried out adsorption treatment, the particle diameter of sulphonated coal is 4-5mm, and the particle diameter of boiler ash sediment is 4-6 mm; The particle diameter of gac is 1-2mm; Solution left standstill after absorption flowed out 2 hours is removed and is contained thing admittedly, the treatment solution I.
4. method according to claim 1 is characterized in that: described step 2 is: coagulating agent is added in the above-mentioned treatment solution I, and quick earlier the stirring 2-8 minute stirred 15-25 minute at a slow speed more at interval, removed after leaving standstill or filtering to contain thing admittedly, got the treatment solution II.
5. method according to claim 4 is characterized in that: described step 2 is: coagulating agent is added in the above-mentioned treatment solution I, and elder generation stirred 5 minutes fast, stirred 20 minutes at interval at a slow speed again, and removal gets the treatment solution II after containing thing admittedly.
6. method according to claim 4 is characterized in that: described coagulating agent be quality than the compound ferro-aluminum suspension-s of 5-15% of concentration or for concentration be polymeric aluminum chlorides solution or the quality of 5-20g/L 1.5-2.5% polyacrylamide solution than concentration.
7. method according to claim 6 is characterized in that: described coagulating agent is the 9% compound ferro-aluminum suspension-s of quality than concentration, and add-on is that to make the volume by volume concentration in its waste water after adding be 0.8%; Or concentration is the polymeric aluminum chlorides solution of 10g/L, and add-on is that to make the volume by volume concentration in its waste water after adding be 3%.
8. method according to claim 1 is characterized in that: described step 3 is: regulate the pH to 3.0-3.5 of treatment solution II with hydrochloric acid, adding quality is the ydrogen peroxide 50 of 20-30% than concentration, presses Fe again
2+: H
2O-
2For the volume proportion of 1:2-1:3 adds concentration is the FeSO of 0.5-1.5mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 25-35mmol/L.
9. method according to claim 8 is characterized in that: described step 3 is: regulate the pH to 3.2 of treatment solution II with hydrochloric acid, adding quality is 30% ydrogen peroxide 50 than concentration, presses Fe again
2+: H
2O-
2For the volume proportion of 1:2.5 adds concentration is the FeSO of 1mol/L
47H
2O solution, FeSO
47H
2The add-on of O solution is 30mmol/L.
10. method according to claim 1; It is characterized in that: precipitation agent is solid precipitation agent sodium hydroxide or the yellow soda ash of order number greater than 260 purpose fine powdered in the described step 4; It is 1%, 1.3% than concentration that the add-on of sodium hydroxide, yellow soda ash makes its quality, after precipitation agent adds the treatment solution III, and stirring reaction 2 minutes; Removal contains thing admittedly, gets the treatment solution IV.
11. method according to claim 1 is characterized in that: also comprise the COD of water sample among the described method steps 1-5, the mensuration of BOD, pH and turbidity.
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