CN104628185A - Oil and gas field fracturing flow-back fluid treatment process - Google Patents
Oil and gas field fracturing flow-back fluid treatment process Download PDFInfo
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Abstract
The invention belongs to the technical field of wastewater treatment and in particular relates to an oil and gas field fracturing flow-back fluid centralized treatment process. The oil and gas field fracturing flow-back fluid centralized treatment process comprises the following steps: 1, collecting fracturing flow-back fluid into an adjusting tank, carrying out homogenizing and quantity equalizing treatment on the fracturing flow-back fluid, and enabling the fracturing flow-back fluid to enter a sand settling and oil removal tank to be subjected to sand settling and oil removal; 2, lifting effluent of the adjusting tank into a coagulation/air floatation tank, adding a flocculating agent, and removing floating oil and suspended matters through flocculation and air floatation; 3, enabling effluent of the air floatation tank to enter a primary oxidation unit, adding sodium hypochlorite, and primarily oxidizing and decomposing macromolecular organic compounds; 4, enabling effluent of a primary oxidation tank to enter a Fenton oxidation tower, and deeply oxidizing and decomposing by adopting a Fenton oxidizing agent; 5, enabling effluent of the Fenton oxidation tower to enter a sedimentation tank; and 6, enabling effluent of the sedimentation tank to enter an activated coke filtration and adsorption tank to be subjected to filtration and adsorption treatment, various indexes of effluent of the activated coke filtration and adsorption tank can reach the standard, and the effluent of the activated coke filtration and adsorption tank can be discharged or recycled. The oil and gas field fracturing flow-back fluid centralized treatment process is applicable to treatment of fracturing flow-back fluid in unconventional oil and gas field fracturing mining of petroleum, natural gas, shale gas and coal bed gas.
Description
Technical field
The invention belongs to technical field of waste water processing, be specifically related to a kind of oil-gas field fracturing and return discharge opeing and focus on technique.
Background technology
At present, at home and abroad in oil-gas field development, frac job is an important well stimulation, is generally adopted by each oil field.(generally after every mouthful of well pressure break, discharge opeing at least produces thickness waste liquid 300m to consequent fracturing waste liquor
3left and right) there is the features, particularly some wetting ability organic additives such as colourity is dark, acid by force, viscosity is large, CODcr is high, difficult degradation, be difficult to go out from waste water, if not treated direct discharge, severe contamination will be caused to surrounding enviroment.Immediate and mid-term, many scholars propose various means and measure both at home and abroad, can up to now, and the treatment technology of fracturing wastewater is still undesirable, can say and still be in the junior stage, and what really can be used in on-the-spot extensive process has no report.
At present, have the method that the process of oil field compression fracture waste water is generally taked: the combination treatment method that solidification method, biological process, chemical method or various technique combine.(1) solidification method: the dominant mechanism of curing technology utilizes certain chemical additive (solidifying agent) that fracturing waste liquor unstability is dewatered.Because solidifying agent is mostly the materials such as cement, lime or flyash, so processing cost is very low, but curing cycle is longer, and long-time heap releases the impact that may cause surrounding environment.(2) biological process: biological treatment mainly utilizes microorganism to reduce Organic substance in water content.Because fracturing wastewater has lower biochemical, so must the pre-treatment such as coagulation, absorption be carried out.Then cultivate bacterial classification, being dropped into by bacterial classification just can by the organic substance decomposing in sewage in some cycles in suitable Sewage Environment.The advantage utilizing biological process process fracturing wastewater is less investment, ecological, environmental protective and have stronger specific aim and feasibility; Shortcoming is that the required cycle is longer, and finding dominant bacteria is a problem needing to solve.(3) chemical method: the chemical treatment method extensively adopted at present mainly contains Coagulation Method, Fenton oxidation method and Fe/C micro-electrolysis method etc.Wherein, 1. oxidation style: oxidation style refers to and is added among fracturing wastewater by oxygenant and related auxiliaries according to certain dosing method, and the macromolecule organic after question response for some time in waste water is removed by medicament.Oxidation style mainly comprises: Fenton reagent oxidation style, hypochlorite oxidation method, nano-photo catalytic oxidation style, Using Ferrate Oxidation Flocculation Method, supercritical water oxidation (SCWO), sonochemistry oxidation style etc.Mostly wherein applying comparatively is Fenton reagent oxidation style, hypochlorite oxidation method.Fenton reagent method is pointed especially to the removal of CODCr, meanwhile, as the raw material hydrogen peroxide of oxidizing reaction and reductibility iron cheap.2. Coagulation Method: Coagulation Method is the domestic method be most widely used in disposing polluted water in oil at present, and flocculating settling effectively can remove the suspended substance in waste water, also very high to the clearance of petroleum-type, turbidity, but undesirable to the removal effect of CODcr.And fracturing liquid waste water viscosity is very large, and dosage of PAC is large.The pre-treatment of Coagulation Method Chang Zuowei fracturing waste liquor process comes remove portion organism and suspended particle, next carries out advanced treatment again.3. Fe/C micro-electrolysis method: micro-electrolysis method is iron carbon dioxide process carbon electrode generation electrochemical reaction define electric field in the solution, makes the colloidal particle in water produce electrophoresis, by a series of effect loss of stability, condense and precipitate removal under the effect of electric field.But because potential difference is very little, the residence time is longer, and action effect is limited, cannot be applied to large-scale production practice.(4) Physical: 1. filtration method: the suspended particle in petroleum waste water, mainly by fast filtering technique, filters and removes, thus play turbid effect by filtration method, but very micro-for the fracturing fluid additive removal effect of solubility.Meanwhile, filtration process also comprises: the filtration of membrane filtration, reverse osmosis method, the filtration of osmosis method, ultra-filtration method etc.2. absorption method: absorption method drops in waste water by the agent of the Porous Medium Adsorption such as gac, clay, fully mix with it, particulate matter in the adsorbable waste water of sorbent material, also can make waste water be filtered by filter bed, and this method is also mainly play turbid effect.
Substantially be the combination of above-mentioned a few class technique putting into practice in engineering, but it is higher still to there is investment running cost, or treatment effect is not good, cannot the defect such as through engineering approaches, thus a kind of effective treatment process of exploitation is badly in need of, prevent the pollution of fracturing outlet liquid pollution to environment, reduce the Financial cost of oil-field development simultaneously.
Summary of the invention
The object of the invention is to: for the deficiencies in the prior art, provide a kind of low consumption, effectively, can the treatment process of fracturing outlet liquid of through engineering approaches.
For achieving the above object, the present invention is by the following technical solutions: a kind of oil-gas field fracturing returns the treatment process of discharge opeing, and its this treatment process comprises the following steps:
(1) oil-gas field fracturing is returned discharge opeing to collect equalizing tank and carry out after homogeneous all measures process, entering sand setting degreasing tank, sand setting oil removing; Wherein, equalizing tank adopts boring aeration pipe to carry out aeration, aeration air quantity 0.03 ~ 0.05m
3/ m
2.min, the residence time is not less than 4h; Sand setting degreasing tank adopts inclined tube oil removal settling tank, settling tank surface load 0.75 ~ 1.5m
3/ m
2.h; The residence time: 2h ~ 4h;
(2) water outlet after being processed by equalizing tank in step (1) promotes and enters coagulation floatation, removes oil slick and suspended substance; Wherein, air supporting mode adopts air-dissolving air-float, dissolving top hole pressure 0.4 ~ 0.5Mpa, air flotation pool surface load: 0.6 ~ 1.0m
3/ m
2.h, the coagulating agent that air flotation pool adds is aluminium chlorohydroxide PAC and polyacrylamide PAM, and pH value controls at 7.5 ~ 9, PAC dosage, 30 ~ 50ppm, PAM dosage 5 ~ 10ppm, both interval of adding 10 ~ 30s; The dosing reaction times: 5 ~ 10min;
(3) the water outlet lifting after air flotation pool process in step (2) is entered stair oxidation pond, add clorox, 10-40ml/l, pH control 3 ~ 5, reaction times 20 ~ 45min; Preliminary oxidation decomposes larger molecular organics;
(4) the water outlet lifting after stair oxidation pond process in step (3) is entered Fenton oxidation tower, carry out deep oxidation decomposition, add Fenton oxidation agent, ferrous sulfate and hydrogen peroxide ratio are: 4:1 ~ 8:1; Described hydrogen peroxide concentration specification is 30%, and ferrous sulfate dosage is that 3 ~ 6g/L, pH control 3 ~ 5,2 ~ 3 hours Fenton's reaction tower residence time, wherein said Fenton oxidation tower built-in elastic filler, if reaction reflux pump, quantity of reflux is 150% ~ 300%;
(5) the water outlet lifting in step (4) after the process of Fenton oxidation tower is entered coagulative precipitation tank, under agitation, dosing coagulant is PAC and PAM, pH value controls 7.5 ~ 9, PAC dosage 10 ~ 30ppm, PAM dosage 2 ~ 5ppm, both interval of adding 10 ~ 30s, dosing reaction times: 5 ~ 10min; Coagulative precipitation tank surface load 0.5 ~ 1.0m
3/ m
2.h, the residence time 2 ~ 4h;
(6) the water outlet lifting in step (5) after coagulative precipitation tank process is entered activated coke Filtration Adsorption pond, carry out filtration and adsorption treatment, activated coke Filtration Adsorption pond absorption 30 ~ 90min duration of contact, filtering velocity 1 ~ 3m/h, adopt air-water backwashing mode, washing intensity 3 ~ 6L/Sm
2, air purge intensity 10 ~ 20L/Sm2, backwash time 15 ~ 30min, backwash frequency, using water outlet SS<10mg/l as Con trolling index, can complete the process that oil-gas field fracturing returns discharge opeing.
The inclined tube that described sand setting degreasing tank adopts is polypropylene inclined tube, and it installs horizontal sextant angle is 60 °.Above-mentioned equipment and material are commercially available or known.
Beneficial effect of the present invention is, (1) equalizing tank adopts aeration tube homogeneous all to measure, and ensure that the stability of subsequent treatment process influent load.(2) adopt air supporting coagulation pretreatment, remove oil slick and suspended substance, alleviate the burden of subsequent treatment process, decrease chemical feeding quantity.(3) adopt 2 grades of oxidizing procesies, difficult degradation larger molecular organics discomposing effect is better.(4) adopt Fenton reagent as 2 grades of oxidizing procesies, its OH has higher reactive behavior, reacts rapidly with most of organic molecule indiscriminately, is oxidized more thorough.(5) Fenton oxidation technique adopts advanced reaction tower reactor, and supporting reaction reflux pump and filler, therefore waste water and the abundant contact reacts of Fenton reagent, oxidation efficiency is higher.(6) adopt the activated coke of central hole structure prosperity to do further Filtration Adsorption, its aperture meets the characteristic of waste water more, and adsorption effect is better, decreases the phenomenons such as filter stoppage saturate block simultaneously.The price that activated coke is cheap also reduces the running cost of wastewater treatment.(7) waste water after process can qualified discharge.
Accompanying drawing explanation
Below in conjunction with accompanying drawing, the present invention will be further described, Fig. 1 processing technological flow figure of the present invention.
Embodiment
Embodiment 1, a kind of oil-gas field fracturing return the treatment process of discharge opeing, as shown in Figure 1, comprise connected successively by pipeline, valve, lift pump etc. equalizing tank, sand setting oil trap, air flotation pool, stair oxidation pond, Fenton oxidation tower, activated coke Filtration Adsorption pond.Wherein boring aeration pipe established by equalizing tank, blast aeration; Described sand setting oil trap establishes polypropylene inclined tube, and inclined tube installs horizontal sextant angle 60 °; Described air supporting coagulation basin is provided with chemicals dosing plant, and the coagulating agent added is PAC (polymerize aluminum chloride) and PAM (polyacrylamide), and air supporting mode adopts air-dissolving air-float; Described stair oxidation pond, the clorox added, as primary oxidizing agent, is provided with chemicals dosing plant and reaction whipping appts; Described Fenton oxidation tower adopts the form of reaction tower, the built-in filler of tower and auxiliary facility such as reaction stirrer, reflux pump etc.; Described activated coke Filtration Adsorption pond, using activated coke as filtering adsorbing material.
This technique by all measuring fracturing outlet liquid homogeneous, air supporting flocculation, secondary oxidation, the art breading such as Filtration Adsorption, finally realize water outlet indices and meet first discharge standard.
Adopt treatment process described above to carry out the process of fracturing outlet liquid, its treatment process comprises the steps:
(1) first fracturing outlet liquid is collected equalizing tank, in equalizing tank, grid is set, remove thicker suspended substance and floating matter in waste water.Equalizing tank blast aeration is carried out homogeneous and is all measured process, reduces the load impact to subsequent technique.Homogeneous all measure after waste water enter sand setting degreasing tank, precipitation is removed and is returned the silt that discharge opeing carries secretly, removes oil slick; In this step, equalizing tank adopts boring aeration pipe to carry out aeration, aeration air quantity 0.03 ~ 0.05m
3/ m
2.min.Sand setting degreasing tank adopts inclined tube oil removal settling tank, settling tank surface load 0.75 ~ 1.5m
3/ m
2.h.
(2) equalizing tank water outlet is promoted by lift pump and enters coagulation floatation, adopt the mode of air-dissolving air-float, under pneumatically supported effect, suspension oil in sewage and the holder of part oil in water emulsion are collected recovery to the water surface, dosing coagulant simultaneously, complete coagulation-flocculation process, throw out equally under pneumatically supported effect floating to the water surface, be collected into storage slag chute by scraper plate, reach the effect of removing oil slick and suspended substance; In this step, dissolving top hole pressure 0.4 ~ 0.5Mpa, air flotation pool surface load: 0.6 ~ 1.0m
3/ m
2.h.The coagulating agent that air flotation pool adds is PAC and PAM, and pH value controls at 7.5 ~ 9, PAC dosage, 30 ~ 50ppm, PAM dosage 5 ~ 10ppm, both interval of adding 10 ~ 30s.
(3) air flotation pool water outlet enters stair oxidation pond, regulates pH value, adds oxidizing agent sodium hypochlorite, abundant stirring reaction, oxygenolysis macromole organic pollutant.Stair oxidation pond adopts the structure of tube settler, outer row after sludge settling, and upper end water outlet promotes and enters Fenton oxidation tower; In this step, add clorox 10-40ml/l, PH controls 3 ~ 5, reaction times 20 ~ 45min.
(4) water outlet of stair oxidation pond is entering Fenton oxidation tower, regulates pH value, under agitation, adds Fenton oxidation agent and carry out deep oxidation decomposition.Fenton oxidation tower built-in elastic filler, if reaction reflux pump, ensures waste water and the abundant catalytic oxidation organism of oxygenant; In this step, ferrous sulfate and hydrogen peroxide ratio are: 4:1 ~ 8:1 (hydrogen peroxide concentration is 30%), and ferrous sulfate dosage is that 3 ~ 6g/L, PH control 3 ~ 5, and 2 hours residence time, reflux pump quantity of reflux is 150% ~ 300%.
(5) water outlet of Fenton oxidation tower enters coagulative precipitation tank; Under agitation, the coagulating agent added is PAC and PAM, and pH value controls at 7.5 ~ 9, PAC dosage, 10 ~ 30ppm, PAM dosage 2 ~ 5ppm, both interval of adding 10 ~ 30s.
(6) coagulative precipitation tank water outlet gravity flow enters activated coke Filtration Adsorption pond and carries out filtration and adsorption treatment, and remove floc particle further, water outlet meets emission standard.Regularly carry out air-water backwashing according to water quality and adsorption effect, recover the adsorptivity of filtrate, saturated active coke uses by hot recycling heavy burden; In this step, activated coke Filtration Adsorption pond adopts central hole structure flourishing, and the relatively excellent honest and clean activated coke of price is absorption filtering material.Particle diameter of filter medium 3-5mm, iodine number >600mg/g, methylenum coeruleum >120mg/g, tear strength >90%.Activated coke Filtration Adsorption pond absorption 30 ~ 90min duration of contact, filtering velocity 1 ~ 3m/h.Air-water backwashing intensity: washing intensity 3 ~ 6L/Sm
2, gas intensity 10 ~ 20L/Sm2, backwash 15min, backwash frequency is using water outlet SS<10mg/l as Con trolling index.Can arrange outward after the sludge dehydrating and drying that treating processes produces, saturated activated coke can be reused by hot recycling, and treated fracturing outlet liquid can meet first discharge standard.
Embodiment 2, with treatment process of the present invention, the fracturing outlet liquid produced in certain oil extraction in oil field process to be processed.Design by running continuously 24 hours every days.
1, influent quality is designed
2, process parameters design
(1) in equalizing tank, grid is set, removes thicker suspended substance and floating matter in waste water.Equalizing tank adopts boring aeration pipe blast aeration air quantity 0.05m
3/ m
2.min.Equalizing tank residence time 4h; Homogeneous all measure after waste water enter sand setting degreasing tank, surface load 0.75m
3/ m
2.h, inclined tube length 1 meter, by horizontal sextant angle 60 ° installation, precipitation removes the silt returning discharge opeing and carry secretly, removes oil slick; (2) equalizing tank water outlet promotes and enters coagulation floatation.Air flotation pool adopts the mode of air-dissolving air-float, dissolving top hole pressure 0.5Mpa, air flotation pool surface load: 0.6m
3/ m
2.h.Regulate pH value 7, stir and add PAC50ppm, add PAM:10ppm, both interval of adding 10 ~ 30s;
(3) air flotation pool water outlet enters stair oxidation pond, regulates pH value 4, adds clorox 10ml/l (waste water), abundant stirring reaction, reaction times 45min;
(4) water outlet of stair oxidation pond promotes and enters Fenton oxidation tower, regulates pH value 4, under agitation, adds Fenton oxidation agent.Ferrous sulfate and hydrogen peroxide ratio are: 6:1 (hydrogen peroxide concentration is 30%), and ferrous sulfate dosage is 6g/L, 2 hours residence time, and reflux pump quantity of reflux is 300%;
(5) water outlet of Fenton oxidation tower enters coagulative precipitation tank, and the coagulating agent added is PAC and PAM, and pH value controls at 9, PAC dosage 30ppm, PAM dosage 5ppm, both interval of adding 10 ~ 30s, settling tank surface load: 0.6m
3/ m
2.h.Mud is outer row after being collected by sludge bucket;
(6) coagulative precipitation tank water outlet gravity flow enters activated coke Filtration Adsorption pond.Activated coke Filtration Adsorption pond absorption 90min duration of contact, filtering velocity 3m/h.Air-water backwashing intensity: washing intensity 5L/Sm
2, gas intensity 15L/Sm2, backwash 15min, backwash frequently
Rate is using water outlet SS<10mg/l as Con trolling index.
All the other processing parameters are as crossed the water treatment routinely such as mill weir load, via hole flow velocity, stirring velocity etc., pond body structure process
Design requirements process.
3, treatment effect
4, conclusion: by the known treatment process of the present invention of above processing data, high to the removal efficiency such as CODcr, suspended substance, turbidity of fracturing outlet liquid, treatment effect is good, can meet the table 4 first discharge standard requirement in " integrated wastewater discharge standard " (GB8978-1996) after these several leading indicator process.In addition, present device less investment, technical process is simple, less developer, and running cost is low, and the concentrating of fracturing outlet liquid of applicable high viscosity, high density processes continuously, has a extensive future.
Claims (2)
1. oil-gas field fracturing returns a treatment process for discharge opeing, it is characterized in that: this treatment process comprises the following steps:
(1) oil-gas field fracturing is returned discharge opeing to collect equalizing tank and carry out after homogeneous all measures process, entering sand setting degreasing tank, sand setting oil removing; Wherein, equalizing tank adopts boring aeration pipe to carry out aeration, aeration air quantity 0.03 ~ 0.05m
3/ m
2.min, the residence time is not less than 4h; Sand setting degreasing tank adopts inclined tube oil removal settling tank, settling tank surface load 0.75 ~ 1.5 m
3/ m
2.h; The residence time: 2h ~ 4h;
(2) water outlet after being processed by equalizing tank in step (1) promotes and enters coagulation floatation, removes oil slick and suspended substance; Wherein, air supporting mode adopts air-dissolving air-float, dissolving top hole pressure 0.4 ~ 0.5Mpa, air flotation pool surface load: 0.6 ~ 1.0 m
3/ m
2.h, the coagulating agent that air flotation pool adds is aluminium chlorohydroxide PAC and polyacrylamide PAM, and pH value controls at 7.5 ~ 9, PAC dosage, 30 ~ 50ppm, PAM dosage 5 ~ 10ppm, both interval of adding 10 ~ 30s; The dosing reaction times: 5 ~ 10min;
(3) the water outlet lifting after air flotation pool process in step (2) is entered stair oxidation pond, add clorox, 10-40ml/l, pH control 3 ~ 5, reaction times 20 ~ 45min; Preliminary oxidation decomposes larger molecular organics;
(4) the water outlet lifting after stair oxidation pond process in step (3) is entered Fenton oxidation tower, carry out deep oxidation decomposition, add Fenton oxidation agent, ferrous sulfate and hydrogen peroxide ratio are: 4:1 ~ 8:1; Described hydrogen peroxide concentration specification is 30%, and ferrous sulfate dosage is that 3 ~ 6g/L, pH control 3 ~ 5,2 ~ 3 hours Fenton's reaction tower residence time, wherein said Fenton oxidation tower built-in elastic filler, if reaction reflux pump, quantity of reflux is 150% ~ 300%;
(5) the water outlet lifting in step (4) after the process of Fenton oxidation tower is entered coagulative precipitation tank, under agitation, dosing coagulant is PAC and PAM, pH value controls 7.5 ~ 9, PAC dosage 10 ~ 30ppm, PAM dosage 2 ~ 5ppm, both interval of adding 10 ~ 30s, dosing reaction times: 5 ~ 10min; Coagulative precipitation tank surface load 0.5 ~ 1.0m
3/ m
2.h, the residence time 2 ~ 4h;
(6) the water outlet lifting in step (5) after coagulative precipitation tank process is entered activated coke Filtration Adsorption pond, carry out filtration and adsorption treatment, activated coke Filtration Adsorption pond absorption 30 ~ 90min duration of contact, filtering velocity 1 ~ 3m/h, adopt air-water backwashing mode, washing intensity 3 ~ 6L/Sm
2, air purge intensity 10 ~ 20L/Sm2, backwash time 15 ~ 30min, backwash frequency, using water outlet SS<10mg/l as Con trolling index, can complete the process that oil-gas field fracturing returns discharge opeing.
2. treatment process according to claim 1, is characterized in that: the inclined tube that described sand setting degreasing tank adopts is polypropylene inclined tube, and it installs horizontal sextant angle is 60 °.
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