CN102139971A - Method and process for advanced treatment of well drilling effluent - Google Patents
Method and process for advanced treatment of well drilling effluent Download PDFInfo
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- CN102139971A CN102139971A CN2011100323150A CN201110032315A CN102139971A CN 102139971 A CN102139971 A CN 102139971A CN 2011100323150 A CN2011100323150 A CN 2011100323150A CN 201110032315 A CN201110032315 A CN 201110032315A CN 102139971 A CN102139971 A CN 102139971A
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention relates to a method and processes for the advanced treatment of well drilling effluent. The method comprises the following processes of: chemically-enhanced solid-liquid separation, mechanical dehydration, treatment by the advanced oxidation technology and the like. The method comprises: adding 2 to 16 g/L of polyaluminium chloride into the well drilling effluent, stirring quickly and uniformly, adding 50 to 200 mg/L of cationic polyacrylamide, stirring at low speed for 10 to 15 minutes, so that the drilling waste liquid destabilized and agglutinated, and dehydrating in a centrifugal mode; and performing advanced oxidation treatment on the well drilling waste liquid from which solids are separated, regulating the pH value of the well drilling waste liquid to be 4, performing a reaction by taking hydrogen peroxide and ammonium persulfate as a composite oxidizing agent and ferrous sulfate as a catalyst under the condition of daylight or simulated daylight for 120 to 150 minutes, regulating the pH value of the well drilling waste liquid to be between 8 and 9 by using lime milk, clarifying, and discharging or performing the treatment in other modes. By the method, indexes such as the suspended solids, chromaticity, chemical oxygen demand (CODCr) and the like in the well drilling waste liquid are reduced substantially, so the method has a bright application prospect.
Description
Technical field
The present invention relates to the oil-gas field environmental protection technical field.
Background technology
Waste liquid of drilling mainly is meant the rejected well drilling liquid that discharges in the Process of Oil Well Drilling and the waste liquid of being made up of the scavenging solution of each implement, well liquid, sewage (part mud is carried in the rain-out well site and oily substance forms) etc., and wherein rejected well drilling liquid is a major portion.Wherein mainly pollute feature COD is arranged
CrHeight, high chroma such as disperses at characteristics among suspended solids content height and the Yi Zaishui.
Various chemical processing agent and tensio-active agent have been added in the rejected well drilling liquid, its composition more complicated, generally all contain heavy metal, oils, wilkinite, alkali and compound (comprising organism) etc. to people, animal and the deleterious material of environment, as chromium-iron lignosulfonate, sulfonated gilsonite, sulfonation tannin extract, sulfonated lignite etc., can cause the situ of drilling well surrounding environment to pollute dramatically, can not directly discharge.
Handling waste liquid of drilling (containing solid waste such as drilling cuttings) method at present mainly contains: methods such as directly discharging, re-injection, landfill, compost, soil cultivating, stabilization/curing, thermal desorption and burning.Directly discharging only is applicable to nontoxic waste liquid of drilling, and oil-containing or non-water-based drilling waste liquid and drilling cuttings absolute prohibition directly discharge.The re-injection method can only be eliminated the influence to ground environment or seabed water body, and pollution components such as oils, salinity and heavy metal do not obtain handling, and will produce secondary pollution if spill and leakage takes place.Landfill method has also just been eliminated the pollution of situ of drilling well, pollutent is not through handling, leachate is bigger to phreatic harm, and other effects limit such as landfill place are arranged, soil cultivating and compost have reduced the concentration of salinity and heavy metal components, petroleum-type and the biological degradation of part organic compound, but easily cause the pollution of surface water environment, also influential to underground shallow seated groundwater; The processing of waste volume increases if need clear up future, and has atmospheric pollution in various degree.Stabilization/solidification treatment pollution components stabilization treatment, the cured article leachate can be by test at present, and handling the back volume increases, and salinity and petroleum-type can reduce solidification effect and might go out by drop.Heat is taken off absorption and is burned and is used for the drilling well refuse that the handling oil base drilling fluid produces more, and energy consumption is big, acid compounds etching apparatus and existence atmospheric pollution in various degree under the high temperature.
Above method all exists the deficiency of different aspect and degree, thereby the combination technique treatment process of the processing of waste liquid of drilling proposed, it mainly is materialization treatment process based on coagulation, this technology adds chemical coagulator in waste liquid of drilling and flocculation agent is handled, and still there is COD in the waste water of handling the back generation
Cr, parameter such as suspended solids exceeds standard.The coagulation of waste liquid of drilling-advanced oxidation treatment process is development in recent years a kind of combined treatment process that gets up, and wherein the advanced oxidation processing mode mainly contains Fenton reagent catalyzed oxidation, ozone O
3Oxidation, catalytic wet oxidation etc.Temperature required and the pressure condition of wet oxidation is higher, and equipment etc. is had relatively high expectations, and is difficult for realizing.Ozone O
3Oxidation has oxidation effectiveness preferably under alkaline condition, but requires load for the conversion unit result, and is stable to the entry water quality requirement; And situ of drilling well waste liquid composition is changeable, and change of water quality is big, is difficult for using at situ of drilling well.Fenton reagent catalyzed oxidation has higher oxide treatment ability, is a kind of processing mode of homogeneous catalysis oxidation, and also has the characteristics with pollutent generation coagulation in oxidising process, requires low to conversion unit.For improving the treatment effect of Fenton reagent catalyzed oxidation, photo-Fenton has been proposed in succession, electricity-Fenton, ultrasonic-senior oxide treatment technology such as Fenton, this class technology all is to produce difficult degradation pollutent in hydroxyl radical free radical (OH) elimination or the degrading waste water, and the biodegradability of raising waste water, but applying of these technology also has certain restriction.
Persulphate is a kind of common oxygenant, the sulphuric acid free radical (SO that its division back produces
4 -) have under certain condition than hydroxyl radical free radical (OH) redox potential more, most organism can be degraded fully by it.Persulphate self decomposition temperature is 70～100 ℃, and this requirement to heat credit is tried out at situ of drilling well and limited by certain condition.Can use ultraviolet ray, Co in addition
60Produce the transition metal ion (Co in the gamma-rays and the aqueous solution
2+, Cu
2+, Fe
2+And Ag
+) all can decompose by the catalysis persulphate.Based on the persulfate oxidation technology of sulphuric acid free radical, be subjected to the persulphate cost and etc. the restriction of aspect.
Summary of the invention
Purpose of the present invention, for the petroleum drilling waste liquid provides a kind of processing speed fast, the coagulation that treat effluent water quality is good-advanced oxidation combination technique utilizes this method can increase substantially the treatment effect of waste liquid of drilling, makes it qualified discharge.
Treatment process of the present invention is made up of several parts such as taking off steady-flocculation, solid-liquid separation, advanced oxidation, concrete grammar is: the aqueous solution that adds inorganic coagulant and organic coagulating agent in waste liquid of drilling successively, after high-speed stirring is even, stirred 10～15 minutes, with the waste liquid of drilling centrifuge dehydration of chemical enhanced solid-liquid separation, centrifuge speed is chosen in 2600～3400 rev/mins; Regulating the pH value in isolated coagulation water outlet is 4, adds hydrogen peroxide (30%), persulphate and ferrous sulfate successively, places under the radiation of daylight or solar simulated, reacts 120～150 minutes, and regulating the pH value with 10% milk of lime is 8～9.
Coagulation process provides novel inorganic coagulant and organic floculant among the present invention.
Wherein one or more form above-mentioned inorganic coagulant by Tai-Ace S 150, ferric sulfate, aluminum chloride, ferric sesquichloride, calcium chloride, calcium hydroxide, polymerize aluminum chloride and bodied ferric sulfate etc.Preferred inorganic coagulant is a polymerize aluminum chloride, and its working concentration is 2～16g/L.
Above-mentioned organic floculant is wherein one or both compositions such as non-ionic polyacrylamide, anionic polyacrylamide and cationic polyacrylamide.Preferred organic floculant is a cationic polyacrylamide, and its molecular weight is greater than 1000W, and cation ionization degree is 15%, and its consumption is 50～200mg/L.
Chemical enhanced solid-liquid separation process of the present invention, compound use inorganic coagulant polymerize aluminum chloride and organic floculant cationic polyacrylamide, become the coalescence effect of the capable suspended solids of negative electricity in the waste liquid of drilling by charge neutralization, cohesion and macromole bridging absorption, form the bulk flco, can be through centrifuge dehydration, isolate water cycle usefulness again,, clean drilling tool etc. as the configuring maintenance drilling fluid.
Separating water outlet generally has clear improvement in indexs such as colourity, suspended solids, COD and before handling, but for environmentally sensitive area and the higher area of environmental requirement, the separation water outlet that index such as chrominance C OD still is lower than emission standard in the water need be carried out further advanced treatment.
Adopt high-level oxidation technology that waste liquid of drilling is separated water outlet among the present invention and carry out advanced treatment, its concrete grammar is: the pH value of regulating waste liquid of drilling separation water outlet is 4, in water, add oxygenant and catalyzer then respectively, place under the UV, visible light illumination, after reaction for some time, regulating the pH value with alkali is 8～9, and subsequent processes is discharged or entered to termination reaction.
Above-mentioned advanced oxidation treatment process has H
2O
2/ Fe
2+, H
2O
2/ Fe
2+-complexing agent, UV-Vis/H
2O
2/ Fe
2+, UV-Vis/H
2O
2/ Fe
2+-complexing agent, H
2O
2/ S
2O
8 2-/ Fe
2+Or H
2O
2/ HSO
5 -/ Fe
2+, UV-Vis/H
2O
2/ S
2O
8 2-/ Fe
2+Or UV-Vis/H
2O
2/ HSO
5 -/ Fe
2+In one or more technology.Preferred advanced oxidation processes is UV-Vis/H
2O
2/ S
2O
8 2-/ Fe
2+And UV-Vis/H
2O
2/ HSO
5 -/ Fe
2+
Above-mentioned advanced oxidation treatment process, S
2O
8 2-Be ammonium salt, sodium salt or the sylvite of persulfuric acid, HSO
5 -Be Potassium Monopersulfate double salt.Preferred persulphate is an ammonium persulphate.
Above-mentioned advanced oxidation treatment process, illumination condition are UV-light, ultraviolet-visible, daylight and solar simulated illumination conditions such as (xenon long-arc lamp radiation), and preferred illumination condition is daylight or solar simulated (xenon long-arc lamp radiation).
Above-mentioned advanced oxidation treatment process, in 1.5～4 hours reaction times, the preferred reaction times is 120～150 minutes.
Above-mentioned advanced oxidation treatment process, the acid adjusting used sulfuric acid, and alkalescence is regulated and is used 10% milk of lime.
Embodiment
Embodiment 1
The discarded organosilicon drilling fluid of certain oil field discharging, add 12g/L inorganic coagulant polymerize aluminum chloride and 100mg/L organic floculant cationic polyacrylamide, (300r/min) stirs 90s at a high speed, and low speed (20r/min) stirred 10～15 minutes, with whizzer 3400r/min centrifugation 2min.Separating the residual turbidity of water outlet is 18FTU (being 10530FTU before handling), and residual colourity is 5 times (handling preceding 10000 times), COD
CrFor 1100mg/L (handles preceding 1.4 * 10
4Mg/L), clearance all reaches more than 99%.To separate water outlet adjusting pH value is 4, adds hydrogen peroxide (30%) 7ml/L then, the 1.5g/L ammonium persulphate, and the 0.5mmol/L ferrous sulfate, under 15～20 ℃, regulating pH value with milk of lime with sun exposure after 120 minutes is 8～9, catalyzed oxidation water outlet COD
CrBe 147.6mg/L; Radiation is after 120 minutes in the external lighting type photochemical reactor with solar simulated (xenon long-arc lamp), and regulating the pH value is 8～9, COD
CrBe 135.2mg/L.Heavy metal ion content after such waste drilling fluids disposal sees Table 1.
Table 1 waste polymer drilling fluid different process stage water outlet heavy metal ion content
Annotate: "-" expression " not detecting "
Embodiment 2
The waste polymer drilling fluid of certain oil field discharging, add 16g/L inorganic coagulant polymerize aluminum chloride and 120mg/L organic floculant cationic polyacrylamide, (300r/min) stirs 90s at a high speed, and low speed (20r/min) stirred 10～15 minutes, with whizzer 3400r/min centrifugation 2min.Separating the residual turbidity of water outlet is 8FTU (being 8150FTU before handling), and residual colourity is 10 times (handling preceding 8000 times), COD
CrFor 730mg/L (handles preceding 6.6 * 10
4Mg/L), clearance all reaches more than 99%.To separate water outlet adjusting pH value is 4, adds hydrogen peroxide (30%) 7ml/L then, the 1.5g/L ammonium persulphate, and the 0.5mmol/L ferrous sulfate, under 15～20 ℃, regulating pH value with milk of lime with sun exposure after 120 minutes is 8～9, catalyzed oxidation water outlet COD
CrBe 147.2mg/L; Radiation is after 120 minutes in the external lighting type photochemical reactor with solar simulated (xenon long-arc lamp), and regulating the pH value is 8～9, COD
CrBe 94.2mg/L.Heavy metal ion content after such waste drilling fluids disposal sees Table 2.
Table 2 waste polymer drilling fluid different process stage water outlet heavy metal ion content
Annotate: "-" expression " not detecting "
Embodiment 3
The discarded sylvite polymer drilling fluid of certain oil field discharging, add 12g/L inorganic coagulant polymerize aluminum chloride and 60mg/L organic floculant cationic polyacrylamide, (300r/min) stirs 90s at a high speed, low speed (20r/min) stirred 10～15 minutes, with whizzer 3400r/min centrifugation 2min.Separating the residual turbidity of water outlet is 8FTU (being 32600FTU before handling), and residual colourity is 20 times (handling preceding 13500 times), COD
CrFor 1059.6mg/L (handles preceding 4.4 * 10
4Mg/L), clearance all reaches more than 99%.To separate water outlet adjusting pH value is 4, adds hydrogen peroxide (30%) 7ml/L then, the 1.0g/L ammonium persulphate, and the 0.5mmol/L ferrous sulfate, under 15～20 ℃, regulating pH value with milk of lime with sun exposure after 120 minutes is 8～9, catalyzed oxidation water outlet COD
CrBe 190.8mg/L; Radiation is after 120 minutes in the external lighting type photochemical reactor with solar simulated (xenon long-arc lamp), and regulating the pH value is 8～9, COD
CrBe 112.8mg/L.Heavy metal ion content after such waste drilling fluids disposal sees Table 3.
Table 3 waste polymer drilling fluid different process stage water outlet heavy metal ion content
Annotate: "-" expression " not detecting "
Claims (9)
1. new waste liquid of drilling method for innocent treatment and technology, concrete grammar: at first waste liquid of drilling is handled through chemical enhanced solid-liquid separation process, after the mechanical separation method separation, the waste liquid of drilling after separating is carried out the advanced oxidation advanced treatment, discharge then.
2. according to described waste liquid of drilling method for innocent treatment of claim 1 and technology, it is characterized in that: compound use inorganic coagulant of the chemical enhanced solid-liquid separation process of waste liquid of drilling and organic floculant, at first in waste liquid of drilling, add inorganic coagulant, the broken glue of suspensoid is taken off surely; Add organic floculant then, make and take off steady colloid and sign an undertaking bigger flco, realize chemical enhanced solid-liquid separation.
3. comprise Tai-Ace S 150, ferric sulfate, aluminum chloride, ferric sesquichloride, calcium chloride, calcium hydroxide, polymerize aluminum chloride and bodied ferric sulfate etc. according to used inorganic coagulant in the chemical enhanced reinforcement solid-liquid separation process described in the claim 2; Organic floculant comprises: non-ionic polyacrylamide, anionic polyacrylamide and cationic polyacrylamide.
4. be polymerize aluminum chloride according to the used inorganic coagulant of chemical enhanced solid-liquid separation process described in the right 2; Organic floculant is a cationic polyacrylamide, and molecular weight is greater than 1000w, and cationic degree is 15～20%.
5. according to method for innocent treatment of waste liquid of drilling described in the claim 1 and technology, it is characterized in that: solid-liquid separating method adopts modes such as press filtration, vacuum filtration, centrifuge dehydration, selects centrifugation that waste liquid of drilling is carried out solid-liquid separation.
6. according to method for innocent treatment of waste liquid of drilling described in the claim 1 and technology, it is characterized in that the well-drilling waste water after the mechanical separation adopts the high-level oxidation technology advanced treatment.
7. according to the advanced oxidation of waste liquid of drilling described in the claim 6 treatment process, it is characterized in that: adopt H
2O
2/ Fe
2+, H
2O
2/ Fe
2+-complexing agent, UV-Vis/H
2O
2/ Fe
2+, UV-Vis/H
2O
2/ Fe
2+-complexing agent, H
2O
2/ S
2O
8 2-/ Fe
2+Or H
2O
2/ HSO
5 -/ Fe
2+, UV-Vis/H
2O
2/ S
2O
8 2-/ Fe
2+Or UV-Vis/H
2O
2/ HSO
5 -/ Fe
2+In a kind of advanced oxidation treatment technology.
8. according to the advanced oxidation of waste liquid of drilling described in the claim 6 treatment process, it is characterized in that: adopt UV-Vis/H
2O
2/ HSO
5 -/ Fe
2+The advanced oxidation treatment technology, regulating wastewater pH with sulfuric acid is 3～4, adopts daylight or solar simulated as illumination condition, reaction finishes the back and regulates the pH value with 10% milk of lime.
9. according to advanced oxidation treatment process described in the right 6, S
2O
8 2-Be ammonium salt, sodium salt or the sylvite of persulfuric acid, HSO
5 -Be Potassium Monopersulfate double salt.
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