CN103880202A - Rejection processing technology for gas production wastewater in sulfur acid containing gas field - Google Patents
Rejection processing technology for gas production wastewater in sulfur acid containing gas field Download PDFInfo
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- CN103880202A CN103880202A CN201210537451.XA CN201210537451A CN103880202A CN 103880202 A CN103880202 A CN 103880202A CN 201210537451 A CN201210537451 A CN 201210537451A CN 103880202 A CN103880202 A CN 103880202A
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Abstract
The invention discloses a rejection processing technology for gas production wastewater in sulfur acid containing gas field. The rejection processing technology for gas production wastewater in sulfur acid containing gas field comprises the following steps: enabling the sulfur acid containing gas field gas production wastewater to be successively subjected to suspension and oil removal processing, aeration sulfur removal, chemical oxidation sulfur removal, coagulation and flocculation processing, settlement, sterilization, double-medium filter filtering, fiber bundle filter filtering, ultrafiltration, and corrosion and scale inhibition. The invention also provides a corrosion and scale inhibition agent which comprises hydroxyethylidene diphosphonic acid, sodium sulfonate and benzotriazole. The gas production wastewater rejection processing technology is simple in flow, relatively low in operation cost and simple in management, and is capable of effectively processing sulfur acid containing gas field gas production wastewater, and discharged water reaches A3 standard in Recommended Index for the Injection Water Quality for Clastic Reservoir in People's Republic of China petroleum and Natural Gas Industry Standards SY/T5329/94.
Description
Technical field
The present invention relates to sulfuric acid gas field gas production waste water reinjection treatment process.
Background technology
The shortage of water resources has caused the concern of international community already, and there is more than 100 national lack of water in the whole world, comprising China.The gross amount of water resources of China is considerable, occupies the 4th, the world, but water resources comes the 109th, the world per capita.Approximately 30,000,000,000 tons of the annual blowdown flow rates in the whole nation.Each big city, whole nation underground water is polluted in various degree.78 trunk rivers in the whole nation have 54 to be polluted. the large water system of China seven: the Changjiang river, the Zhujiang River, Song Hua River, the Yellow River, Huaihe River, Haihe River, the Liaohe River.In seven large water systems, have half section to be polluted, 86% section, city is polluted and is exceeded standard, and more serious has: the Yellow River, Huaihe River, the Liaohe River, Taihu Lake, Chaohu, the rivers and lakes such as Dian Chi.
In China, natural gas source is the important lifeblood of national economy, Oil And Gas Exploration And Development project is in giving the Social benefit and economic benefit that social creativity is huge, caused certain pollution and destruction also to ecotope around, atmosphere, water body, soil, the biology of construction of natural gas fields meeting on exploratory development region causes complicated and diversified impact.Construction of natural gas fields activity is the most serious to the pollution of water resources.Water is lifespring, the pollution of water can directly cause soil and crop pollution, the pollution of crop promotes again the enrichment of toxic substance in domestic animal, poultry and human body, the health that finally jeopardizes people in whole food chain, and therefore the processing of Sweet natural gas gas production waste water reinjection should strictly be processed and prevent outer row.
In gas production process, generally carry out gas production waste water reinjection.According to the characteristic of gas field gas production water re-injection layer position, should be noted that following problem:
1) in injected water, should not carry a large amount of suspended substances, organic sludge, oil and emulsion, with prevent from stopping up water injection well, stratum venturi, layer gap.
2) stratum of institute's injected water stop slime bacteria and saprophytic microorganism growth, prevent from therefore stopping up water filling path.
3) adopt the water filling of fully-closed system, anoxybiotic as far as possible in injected water, to prevent that many oxide from generating, particularly Fe
3+precipitation.
4) injected water should be with corrosive medium as far as possible, to prevent the corrosion to water treating equipment, water pipe and well casing.
5) injected water is not answered fouling, to prevent damage equipment and to reduce water-injection capability.
Therefore must carry out strict effectively processing to re-injection water, in prior art, now a lot of for sulfuric acid gas field gas production waste water reinjection treatment process method, mainly comprise Physical, chemical method, biological process and physico-chemical processes, generally take array mode for reaching target processing effect.Wherein, Physical, chemical method, physical chemistry have the stable function that is easy to adjusting for the treatment of effect for this class strong toxicity and the large waste water that fluctuates.Although biological process processing cost is low, for its even collapse that is easily hit of waste water of this type of feature, need the cycle of recovery long, affect the safety and stability processing of waste water.For the treatment process of the existing general use oxidation sulphur removal+coagulating sedimentation+single filter of sulfuric acid gas field gas production waste water reinjection treatment process, effluent quality situation after treatment is generally: SS is 60～100mg/L, median particle size 15 μ m～20 μ m, oil 10mg/L～25mg/L, sulphur 18mg/L～55mg/L, 100, SRB bacterium/mL～500/mL, 3000, TGB bacterium/mL～8000/mL, 3000 of iron bacterias/mL～5000/mL, total iron 5mg/L～20mg/L, erosion rate 0.180mm/a～0.850mm/a.Processed waste water water quality difficulty reaches the A3 standard in SY/T5329-94 petroclastic rock reservoir water water quality proposed standard as stated above.If be above standard for a long time water filling, can damage water injecting pipeline, affect the work-ing life of water injection well, even can affect groundwater quality, this present situation is urgently to be resolved hurrily.
Summary of the invention
Technology to be solved by this invention is, the technique of processing gas production waste water in sulfuric acid gas field in order to overcome in prior art is difficult to reach the A3 standard in SY/T5329-94 petroclastic rock reservoir water water quality proposed standard, finally cause damaging water injecting pipeline, affect the work-ing life of water injection well, even can affect the defect of groundwater quality, and a kind of sulfuric acid gas field gas production waste water reinjection treatment process is provided.Gas production waste water reinjection processing technological flow of the present invention is easy, running cost is lower, management is simple, can effectively process sulfuric acid gas field gas production waste water, and water outlet reaches the A3 standard in the oil and gas industry standard SY/T5329-94 of People's Republic of China (PRC) petroclastic rock reservoir water water quality fertilizer index.
The invention provides sulfuric acid gas field gas production waste water reinjection treatment process, it comprises the steps: sulfuric acid gas field gas production waste water successively through oil removal and oil removal treatment, aeration sulphur removal, chemical oxidation sulphur removal, coagulation and flocculation treatment, precipitation, sterilization, the filtration of two medium filter, fiber bundle filter filtration, ultrafiltration and corrosion-mitigation scale-inhibition; In described corrosion-mitigation scale-inhibition, the corrosion inhibiting and descaling agent of employing comprises 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, sodium sulfonate and benzotriazole.
Described sulfuric acid gas field gas production waste water is the sulfuric acid gas field gas production waste water described in the routine of this area, general SS is 200～800mg/L, median particle size 45 μ m～120 μ m, oil 48mg/L～125mg/L, sulphur 118mg/L～1250mg/L, 10000, SRB bacterium/mL～30000/mL, 100000, TGB bacterium/mL～800000/mL, 100000 of iron bacterias/mL～500000/mL, total iron 25mg/L～70mg/L, erosion rate 2.250mm/a～9.560mm/a.
In the present invention, described oil removing and oil removal processing can be oil removing and the oil removal processing of this area routine, are preferably through air-dissolving air-float processing.
Described air-dissolving air-float is processed and is preferably adopted the processing of nitrogen air-dissolving air-float.The device of the device preferred nitrogen air-dissolving air-float of described air-dissolving air-float.
The processing parameter of described nitrogen dissolved air flotation device can be selected with reference to the processing parameter of conventional nitrogen dissolved air flotation device.
Described preferred 10s～20s of the nitrogen air-dissolving air-float residence time.
Preferably 10 DEG C～70 DEG C of the treatment temps of the device of described nitrogen air-dissolving air-float.
During described nitrogen air-dissolving air-float is processed, the preferred 0.3MPa～0.4MPa of pressure of the molten gas of nitrogen.
During described nitrogen air-dissolving air-float is processed, the preferred 15m/s～20m/s of molten gas velocity in the molten gas releasing tube of nitrogen air dissolving system.
During described nitrogen air-dissolving air-float is processed, nitrogen air dissolving system release head discharges the preferred 0.5m/s～1.0m/s of flow velocity.
During described nitrogen air-dissolving air-float is processed, nitrogen air dissolving system discharges the preferably 30 μ m～50 μ m of diameter of bubble.
In the present invention, described aeration sulphur removal can be the aeration sulphur removal of this area routine, and its device, condition and step all can be selected according to routine.
The device of described aeration sulphur removal is preferably a closed unit and is connected with spray-type hydrogen sulfide absorption tower.
The each processing parameter of device of described aeration sulphur removal is as described in routine.
Preferred 2h～the 3h of the residence time of the device of described aeration sulphur removal.
Preferably (20:1) of the gas-water ratio of the aeration rate of described aeration sulphur removal～(100:1).
Preferred 2m/s～the 5m/s of gas flow rate of described spray-type hydrogen sulfide absorption tower air inlet.
Described spray-type hydrogen sulfide absorption tower preferably adopts volution nozzle.
In described spray-type hydrogen sulfide absorption tower, fogdrop diameter is 100 μ m～200 μ m preferably.
In described spray-type hydrogen sulfide absorption tower, add the gas medicine of sodium hydroxide than preferred 1m
3: (20g～100g).
In described spray-type hydrogen sulfide absorption tower, add the gas medicine of clorox than preferred 1m
3: (50g～500g).
In described spray-type hydrogen sulfide absorption tower, the preferred 100m of specific liquid rate
3/ m
2﹒ h～160m
3/ m
2﹒ h.
In the present invention, described chemical oxidation sulphur removal can be the chemical oxidation sulphur removal of this area routine, and its each processing condition and step all can be selected by the routine of this area.
In described chemical oxidation sulphur removal, pharmacy optimization clorox used.
In described chemical oxidation sulphur removal, described clorox preferably contains the clorox that massfraction is 10% available chlorine, the preferred 2500mg/L～30000mg/L of its dosage.Described available chlorine refers to oxidation state chlorine contained in chlorine-containing compound.
Preferred 0.2h～the 0.5h of the residence time of described chemical oxidation sulphur removal.
In described chemical oxidation sulphur removal, agent mixer preferred pipeline formula mixing tank.In described duct type mixing tank, the preferred 2m of mixinglength.
In the present invention, described coagulation and flocculation can be coagulation and the flocculation of this area routine, and its each processing condition and step all can be selected with reference to routine.
In described coagulation and flocculation treatment, generally first carry out coagulation and flocculate again.
In described coagulation and flocculation treatment, the polymerize aluminum chloride that coagulating agent preferential oxidation aluminium content used is 30%, described percentage ratio is mass percent.Preferred 80mg/L～the 300mg/L of dosage of described polymer alumina.
In described coagulation and flocculation treatment, the preferred 20min～30min of reaction times of coagulation.
In described coagulation and flocculation treatment, flocculation agent preferred cationic flocculation agent.Described cationic flocculant optimization polypropylene acid amides.Preferred 1mg/L～the 4mg/L of dosage of described polyacrylamide.
In described coagulation and flocculation treatment, preferred 5min～10min of flocculation reaction time.
Described precipitation is generally carried out in settling vessel.The general tube settling that adopts in described settling vessel.
Preferred 1h～the 2h of time of described precipitation.
The preferred 1m of surface load of described tube settling
3/ m
2﹒ h～2m
3/ m
2﹒ h.
In the present invention, the process of described sterilization can be the sterilization process of this area routine, and its processing step and condition all can be selected by the routine of this area.
The preferred clorox of described sterilant.Preferred 5mg/l～the 10mg/l/ of dosage of described sterilant.
It is 10% available chlorine that described clorox preferably contains massfraction.Described available chlorine refers to oxidation state chlorine contained in chlorine-containing compound.
In the present invention, the two medium filters that adopt during described two medium filters filter can be two medium filters of this area routine, and its processing condition and step all can be selected according to routine.
The filtrate upper strata of described two medium filters is preferably hard coal, and lower floor is preferably quartz sand.
The filtering velocity of described two medium filters is preferably 5.0m/h～17.0m/h.
In the filler of described two medium filters, the preferred 0.4mm～0.65mm of the particle diameter of quartz sand (nonuniformity coefficient < 2).
In the filler of described two medium filters, the preferred 0.8mm～1.6mm of anthracitic particle diameter (nonuniformity coefficient < 2).
In the present invention, the fiber bundle filter using during described fiber bundle filter filters can be the fiber bundle filter of this area routine, and its processing condition and step all can be selected according to routine.
The filtering velocity of described fiber bundle filter is preferably 10.0m/h～15.0m/h.
The filtrate filament diameter of described fiber bundle filter is 20 μ m preferably.
In the present invention, ultrafiltration membrance filter is preferably used in described ultrafiltration.
The membrane pore size of described ultra-filtration membrane is 0.1 μ m～0.001 μ m preferably, unit surface water production rate 25L/m
2h.
Preferred 0.10MPa～0.25MPa is pressed in the operation of described ultrafiltration.
In the present invention, described corrosion-mitigation scale-inhibition processing can be the corrosion-mitigation scale-inhibition processing of this area routine, and its processing condition and step all can be selected according to this area routine.
In described corrosion-mitigation scale-inhibition, the preferred 9.0mg/L-14.0mg/L of the dosage of described 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid.
In described corrosion-mitigation scale-inhibition, the preferred 21.0mg/L-26.0mg/L of the dosage of described sodium sulfonate.
In described corrosion-mitigation scale-inhibition, the preferred 2.5mg/L-3.5mg/L of the dosage of described benzotriazole.
The present invention also provides a kind of corrosion inhibiting and descaling agent, and it comprises 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, sodium sulfonate and benzotriazole.
In described corrosion inhibiting and descaling agent, the preferred 9.0mg/L-14.0mg/L of the dosage of described 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid.
In described corrosion inhibiting and descaling agent, the preferred 21.0mg/L-26.0mg/L of the dosage of described sodium sulfonate.
In described corrosion inhibiting and descaling agent, the preferred 2.5mg/L-3.5mg/L of the dosage of described benzotriazole.
Agents useful for same of the present invention and raw material equal commercially available obtaining except specified otherwise.
In the present invention, without prejudice to the field on the basis of common sense, above-mentioned each technical characterictic optimum condition can arbitrary combination obtain preferred embodiments.
Positive progressive effect of the present invention is: sulfuric acid of the present invention gas field gas production waste water reinjection processing technological flow is easy, Construction and operation cost is lower, management is simple, can effectively process sulfuric acid gas field gas production waste water, and realize water outlet and reach the A3 standard in the oil and gas industry standard SY/T 5329-94 of People's Republic of China (PRC) petroclastic rock reservoir water water quality fertilizer index.This technique extends the duration of service of reinjection well greatly, guarantees that non-wastewater discharge is to water body; This technique is simply easy to apply, and has fabulous application prospect.
Brief description of the drawings
Fig. 1 is sulfuric acid gas field gas production waste water reinjection processing technological flow schematic diagram in embodiment 1.
Embodiment
Mode below by embodiment further illustrates the present invention, but does not therefore limit the present invention among described scope of embodiments.The experimental technique of unreceipted actual conditions in the following example, according to ordinary method and condition, or selects according to catalogue.
The water quality control of sulfuric acid gas field gas production waste water reinjection processing is according to the A3 standard in the oil and gas industry standard SY/T 5329-94 of People's Republic of China (PRC) petroclastic rock reservoir water water quality fertilizer index and analytical procedure: SS≤3.0mg/L, median particle size≤2.0 μ m, oil≤8.0mg/L, sulphur≤6.0mg/L, SRB bacterium≤25/mL, TGB bacterium≤1000/mL, iron bacteria≤1000/mL, total iron≤0.5mg/L, erosion rate≤0.076mm/a.
In following embodiment, the detection method of SS, median particle size, oil, sulphur, SRB bacterium, TGB bacterium, iron bacteria, total iron and erosion rate is all by the oil and gas industry standard SY/T 5329-94 of People's Republic of China (PRC) petroclastic rock reservoir water water quality fertilizer index and analytical procedure.
Embodiment 1
Certain gas field gas production waste water has been carried out to trial production test (referring to accompanying drawing 1), this system design water yield 360m
3/ d, water inlet (most of data) index is: general SS is 230～680mg/L, median particle size 55 μ m～115 μ m, oil 55mg/L～100mg/L, sulphur 250mg/L～1200mg/L, 10000, SRB bacterium/mL～30000/mL, 300000, TGB bacterium/mL～800000/mL, 100000 of iron bacterias/mL～400000/mL, total iron 25mg/L～60mg/L, erosion rate 2.350mm/a～9.500mm/a.
Described all treating processess are in encloses container carries out, technical process used is: by acid gas field gas production waste water through oil removing and suspended substance, then through aeration sulphur removal, again through chemical oxidation sulphur removal, after coagulation, enter again settling vessel and carry out mud-water separation, then carry out sterilization two medium filters of going forward side by side and filter, then enter fiber bundle filter and filter, through ultrafiltration membrance filter, finally carry out corrosion-mitigation scale-inhibition and process rear re-injection again.
The treatment temp of described nitrogen dissolved air flotation device is 20 DEG C～35 DEG C;
The described nitrogen air-dissolving air-float residence time is 15s～20s;
Molten gas velocity 15m/s～20m/s in the described molten gas releasing tube of nitrogen high pressure air dissolving system;
It is 0.5m/s～1.0m/s that described nitrogen high pressure air dissolving system release head discharges flow velocity;
Described nitrogen high pressure air dissolving system discharges the diameter 30 μ m～50 μ m of bubble.
The described aeration desulfurizing device residence time is 2.0h～2.5h;
The gas-water ratio of the aeration rate of described aeration sulphur removal is 50:1～100:1;
Described spray-type hydrogen sulfide absorption tower adopts volution nozzle, fogdrop diameter 100 μ m～200 μ m;
Gas flow rate 2m/s～the 5m/s of described spray-type hydrogen sulfide absorption tower air inlet;
In described spray-type hydrogen sulfide absorption tower, add sodium hydroxide gas medicine than being 1m
3: 20g～100g and clorox gas medicine compare 1m
3: 50g～500g;
Described specific liquid rate is 100m
3/ m
2﹒ h～160m
3/ m
2﹒ h.
Described chemical oxidation sulfur elimination clorox dosage is 3700mg/L～25000mg/L.
The polymerize aluminum chloride that the coagulating agent that described coagulating sedimentation uses is alumina content 30%, flocculation agent is cationic flocculant;
The dosage of the coagulating agent that described coagulating sedimentation uses is 80mg/L～300mg/L;
The flocculation agent that described coagulating sedimentation uses is polyacrylamide, and dosage is 1mg/L～3.5mg/L;
The described coagulating sedimentation reaction times is 20min～30min;
The described flocculation reaction time is 5min～8min;
The sedimentation time of described coagulating sedimentation is 1h～2h;
The surface load of described tube settling is 1m
3/ m
2﹒ h～1.5m
3/ m
2﹒ h.
Described two medium filter filtrates upper strata is hard coal, and lower floor is quartz sand;
Described two medium filter filtering velocitys are 10.0m/h～15.0m/h;
Described two medium filter filler quartz sand 0.4mm～0.65mm (nonuniformity coefficient < 2), hard coal 0.8mm～1.6mm (nonuniformity coefficient < 2).
Described fiber bundle filter filtering velocity is 11.0m/h～14.0m/h;
Described fiber bundle filter filtrate filament diameter 20 μ m.
Described ultra-filtration membrane membrane pore size 0.1 μ m～0.01 μ m, unit surface water production rate 25L/m
2h.
The composite medicine of described corrosion inhibiting and descaling agent is: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid dosage 12.0mg/L, sodium sulfonate dosage 24.0mg/L, benzotriazole 3.0mg/L.
Start with operation result and show, this system run all right, treatment effect is fine.
After testing, effluent quality: SS≤3mg/L, median particle size≤2.0 μ m, oil≤3.0mg/L, sulphur≤2.0mg/L, SRB≤100, TGB≤100, iron bacteria≤100, total iron≤0.1mg/L, erosion rate≤0.010mm/a, water quality meets the oil and gas industry standard SY/T5329-94 of People's Republic of China (PRC) petroclastic rock reservoir water water quality fertilizer index and analytical procedure.
Embodiment 2
Certain gas field gas production waste water has been carried out to trial production test (referring to accompanying drawing 1), this system design water yield 150m
3/ d.Water inlet (most of data) index is: general SS is 200～650mg/L, median particle size 45 μ m～100 μ m, oil 50mg/L～95mg/L, sulphur 120mg/L～1200mg/L, 10000, SRB bacterium/mL～30000/mL, 300000, TGB bacterium/mL～700000/mL, 300000 of iron bacterias/mL～400000/mL, total iron 25mg/L～50mg/L, erosion rate 2.350mm/a～8.950mm/a.
Described all treating processess are in encloses container carries out, technical process used is: by acid gas field gas production waste water through oil removing and suspended substance, then through aeration sulphur removal, again through chemical oxidation sulphur removal, after coagulation, enter again settling vessel and carry out mud-water separation, then carry out sterilization two medium filters of going forward side by side and filter, then enter fiber bundle filter and filter, through ultrafiltration membrance filter, finally carry out corrosion-mitigation scale-inhibition and process rear re-injection again.
The treatment temp of described nitrogen dissolved air flotation device is 20 DEG C～35 DEG C;
The described nitrogen air-dissolving air-float residence time is 15s～20s;
Molten gas velocity 15m/s～20m/s in the described molten gas releasing tube of nitrogen high pressure air dissolving system;
It is 0.5m/s～1.0m/s that described nitrogen high pressure air dissolving system release head discharges flow velocity;
Described nitrogen high pressure air dissolving system discharges the diameter 30 μ m～50 μ m of bubble.
The described aeration desulfurizing device residence time is 2.0h～3.0h;
The gas-water ratio of the aeration rate of described aeration sulphur removal is 50:1～80:1;
Described spray-type hydrogen sulfide absorption tower adopts volution nozzle, fogdrop diameter 100 μ m～200 μ m;
Gas flow rate 2m/s～the 4m/s of described spray-type hydrogen sulfide absorption tower air inlet;
In described spray-type hydrogen sulfide absorption tower, add sodium hydroxide gas medicine than being 1m
3: 20g～80g and clorox gas medicine compare 1m
3: 50g～450g;
Described specific liquid rate is 100m
3/ m
2﹒ h～130m
3/ m
2﹒ h.
Described chemical oxidation sulfur elimination clorox dosage is 3400mg/L～24000mg/L.
The polymerize aluminum chloride that the coagulating agent that described coagulating sedimentation uses is alumina content 30%, flocculation agent is cationic flocculant;
The dosage of the coagulating agent that described coagulating sedimentation uses is 80mg/L～250mg/L;
The flocculation agent that described coagulating sedimentation uses is polyacrylamide, and dosage is 1.5mg/L～3.0mg/L;
The described coagulating sedimentation reaction times is 20min～30min;
The described flocculation reaction time is 5min～10min;
The sedimentation time of described coagulating sedimentation is 1h～2h;
The surface load of described tube settling is 1.5m
3/ m
2﹒ h～2.0m
3/ m
2﹒ h.
Described two medium filter filtrates upper strata is hard coal, and lower floor is quartz sand;
Described two medium filter filtering velocitys are 10.0m/h～14.0m/h;
Described two medium filter filler quartz sand 0.4mm～0.65mm (nonuniformity coefficient < 2), hard coal 0.8mm～1.6mm (nonuniformity coefficient < 2).
Described fiber bundle filter filtering velocity is 11.0m/h～14.0m/h;
Described fiber bundle filter filtrate filament diameter 20 μ m.
Described ultra-filtration membrane membrane pore size 0.1 μ m～0.01 μ m, unit surface water production rate 25L/m
2h.
The composite medicine of described corrosion inhibiting and descaling agent is: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid dosage 13.0mg/L, sodium sulfonate dosage 23.0mg/L, benzotriazole 3.5mg/L.
Start with operation result and show, this system run all right, treatment effect is fine.
After testing, effluent quality: SS≤3mg/L, median particle size≤2.0 μ m, oil≤3.0mg/L, sulphur≤2.0mg/L, SRB≤100, TGB≤1000, iron bacteria≤100, total iron≤0.1mg/L, erosion rate≤0.020mm/a, water quality meets the oil and gas industry standard SY/T5329-94 of People's Republic of China (PRC) petroclastic rock reservoir water water quality fertilizer index and analytical procedure.
Embodiment 3
Certain gas field gas production waste water has been carried out to trial production test (referring to accompanying drawing 1), this system design water yield 120m
3/ d.Water inlet (most of data) index is: general SS is 240～760mg/L, median particle size 55 μ m～120 μ m, oil 55mg/L～80mg/L, sulphur 200mg/L～800mg/L, 10000, SRB bacterium/mL～30000/mL, 300000, TGB bacterium/mL～800000/mL, 300000 of iron bacterias/mL～400000/mL, total iron 25mg/L～50mg/L, erosion rate 1.350mm/a～8.550mm/a.
Described all treating processess are in encloses container carries out, technical process used is: by acid gas field gas production waste water through oil removing and suspended substance, then through aeration sulphur removal, again through chemical oxidation sulphur removal, after coagulation, enter again settling vessel and carry out mud-water separation, then carry out sterilization two medium filters of going forward side by side and filter, then enter fiber bundle filter and filter, through ultrafiltration membrance filter, finally carry out corrosion-mitigation scale-inhibition and process rear re-injection again.
The treatment temp of described nitrogen dissolved air flotation device is 20 DEG C～35 DEG C;
The described nitrogen air-dissolving air-float residence time is 15S～20S;
Molten gas velocity 15m/s～20m/s in the described molten gas releasing tube of nitrogen high pressure air dissolving system;
It is 0.5m/s～1.0m/s that described nitrogen high pressure air dissolving system release head discharges flow velocity;
Described nitrogen high pressure air dissolving system discharges the diameter 30 μ m～50 μ m of bubble.
The described aeration desulfurizing device residence time is 2.0h～2.6h;
The gas-water ratio of the aeration rate of described aeration sulphur removal is 60:1～80:1;
Described spray-type hydrogen sulfide absorption tower adopts volution nozzle, fogdrop diameter 100 μ m～200 μ m;
Gas flow rate 2m/s～the 3m/s of described spray-type hydrogen sulfide absorption tower air inlet;
In described spray-type hydrogen sulfide absorption tower, add sodium hydroxide gas medicine than being 1m
3: 30g～90g and clorox gas medicine compare 1m
3: 40g～400g;
Described specific liquid rate is 100m
3/ m
2﹒ h～150m
3/ m
2﹒ h.
Described chemical oxidation sulfur elimination clorox dosage is 3500mg/L～28000mg/L.
The polymerize aluminum chloride that the coagulating agent that described coagulating sedimentation uses is alumina content 30%, flocculation agent is cationic flocculant;
The dosage of the coagulating agent that described coagulating sedimentation uses is 80mg/L～200mg/L;
The flocculation agent that described coagulating sedimentation uses is polyacrylamide, and dosage is 2.0mg/L～3.5mg/L;
The described coagulating sedimentation reaction times is 20min～30min;
The described flocculation reaction time is 5min～10min;
The sedimentation time of described coagulating sedimentation is 1h～2h;
The surface load of described tube settling is 1.5m
3/ m
2﹒ h～2.0m
3/ m
2﹒ h.
Described two medium filter filtrates upper strata is hard coal, and lower floor is quartz sand;
Described two medium filter filtering velocitys are 10.0m/h～15.0m/h;
Described two medium filter filler quartz sand 0.4mm～0.65mm (nonuniformity coefficient < 2), hard coal 0.8mm～1.6mm (nonuniformity coefficient < 2).
Described fiber bundle filter filtering velocity is 11.0m/h～14.0m/h;
Described fiber bundle filter filtrate filament diameter 20 μ m.
Described ultra-filtration membrane membrane pore size 0.1 μ m～0.01 μ m, unit surface water production rate 25L/m
2h.
The composite medicine of described corrosion inhibiting and descaling agent is: 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid dosage 11.0mg/L, sodium sulfonate dosage 22.0mg/L, benzotriazole 2.0mg/L.
Start with operation result and show, this system run all right, treatment effect is fine.
After testing, effluent quality: SS≤3mg/L, median particle size≤2.0 μ m, oil≤3.0mg/L, sulphur≤2.0mg/L, SRB≤100, TGB≤100, iron bacteria≤100, total iron≤0.1mg/L, erosion rate≤0.015mm/a, water quality meets the oil and gas industry standard SY/T5329-94 of People's Republic of China (PRC) petroclastic rock reservoir water water quality fertilizer index and analytical procedure.
Claims (14)
1. sulfuric acid gas field gas production waste water reinjection treatment process, it is characterized in that comprising the steps: by sulfuric acid gas field gas production waste water successively through oil removing and oil removal processing, aeration sulphur removal, chemical oxidation sulphur removal, coagulation and flocculation treatment, precipitation, sterilization, the filtration of two medium filter, fiber bundle filter filtration, ultrafiltration and corrosion-mitigation scale-inhibition; In described corrosion-mitigation scale-inhibition, the corrosion inhibiting and descaling agent of employing comprises 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, sodium sulfonate and benzotriazole.
2. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, it is characterized in that: in described sulfuric acid gas field gas production waste water, SS is 200～800mg/L, median particle size 45 μ m～120 μ m, oil 48mg/L～125mg/L, sulphur 118mg/L～1250mg/L, 10000, SRB bacterium/mL～30000/mL, 100000, TGB bacterium/mL～800000/mL, 100000 of iron bacterias/mL～500000/mL, total iron 25mg/L～70mg/L, erosion rate 2.250mm/a～9.560mm/a.
3. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: described oil removing and oil removal are treated to through air-dissolving air-float processing; Described air-dissolving air-float is processed and is adopted the processing of nitrogen air-dissolving air-float; Wherein, the nitrogen air-dissolving air-float residence time is 10s～20s; The treatment temp of the device of described nitrogen air-dissolving air-float is 10 DEG C～70 DEG C; During described nitrogen air-dissolving air-float is processed, the pressure of the molten gas of nitrogen is 0.3MPa～0.4MPa; During described nitrogen air-dissolving air-float is processed, in the molten gas releasing tube of nitrogen air dissolving system, molten gas velocity is 15m/s～20m/s; During described nitrogen air-dissolving air-float is processed, it is 0.5m/s～1.0m/s that nitrogen air dissolving system release head discharges flow velocity; During described nitrogen air-dissolving air-float is processed, the diameter that nitrogen air dissolving system discharges bubble is 30 μ m～50 μ m.
4. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: the device of described aeration sulphur removal is a closed unit and is connected with spray-type hydrogen sulfide absorption tower; The residence time of the device of described aeration sulphur removal is 2h～3h; The gas-water ratio of the aeration rate of described aeration sulphur removal is (20:1)～(100:1); The gas flow rate of described spray-type hydrogen sulfide absorption tower air inlet is 2m/s～5m/s; Described spray-type hydrogen sulfide absorption tower adopts volution nozzle; In described spray-type hydrogen sulfide absorption tower, fogdrop diameter is 100 μ m～200 μ m; In described spray-type hydrogen sulfide absorption tower, add the gas medicine of sodium hydroxide than being 1m
3: (20g～100g); In described spray-type hydrogen sulfide absorption tower, add the gas medicine of clorox than being 1m
3: (50g～500g); In described spray-type hydrogen sulfide absorption tower, specific liquid rate is 100m
3/ m
2﹒ h～160m
3/ m
2﹒ h.
5. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: in described chemical oxidation sulphur removal, medicament used is clorox; Described clorox is to contain the clorox that massfraction is 10% available chlorine, and its dosage is 2500mg/L～30000mg/L; The residence time of described chemical oxidation sulphur removal is 0.2h～0.5h; In described chemical oxidation sulphur removal, agent mixer is duct type mixing tank; In described duct type mixing tank, mixinglength is 2m.
6. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: in described coagulation and flocculation treatment, first carry out coagulation and flocculate; In described coagulation and flocculation treatment, coagulating agent used is that alumina content is 30% polymerize aluminum chloride, and described percentage ratio is mass percent; The dosage of described polymer alumina is 80mg/L～300mg/L; In described coagulation and flocculation, the reaction times of coagulation is 20min～30min.
7. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: in described coagulation and flocculation treatment, flocculation agent is cationic flocculant; Described cationic flocculant is polyacrylamide; The dosage of described polyacrylamide is 1mg/L～4mg/L; In described coagulation and flocculation, the flocculation reaction time is 5min～10min.
8. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: described being deposited in settling vessel carried out; In described settling vessel, adopt tube settling; The time of described precipitation is 1h～2h; The surface load of described tube settling is 1m
3/ m
2﹒ h～2m
3/ m
2﹒ h.
9. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: the sterilant adopting in described sterilization is clorox; The dosage of described sterilant is 5mg/l～10mg/l; It is 10% available chlorine that described clorox contains massfraction.
10. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: the filtrate upper strata of described two medium filters is hard coal, lower floor is quartz sand; The filtering velocity of described two medium filters is 5.0m/h～17.0m/h; In the filler of described two medium filters, the particle diameter of quartz sand is 0.4mm～0.65mm, nonuniformity coefficient < 2; In the filler of described two medium filters, anthracitic particle diameter is 0.8mm～1.6mm, nonuniformity coefficient < 2.
11. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: the filtering velocity of described fiber bundle filter is 10.0m/h～15.0m/h; The filtrate filament diameter of described fiber bundle filter is 20 μ m.
12. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: described ultrafiltration ultrafiltration membrance filter; The membrane pore size of described ultra-filtration membrane is 0.1 μ m～0.001 μ m, unit surface water production rate 25L/m
2h; The operation of described ultrafiltration is pressed as 0.10MPa～0.25MPa.
13. sulfuric acid as claimed in claim 1 gas field gas production waste water reinjection treatment process, is characterized in that: in described corrosion inhibiting and descaling agent, the dosage of described 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid is 9.0mg/L ~ 14.0mg/L; The dosage of described sodium sulfonate is 21.0mg/L-26.0mg/L; The dosage of described benzotriazole is 2.5mg/L-3.5mg/L.
14. 1 kinds of corrosion inhibiting and descaling agents, is characterized in that: contain 1-Hydroxy Ethylidene-1,1-Diphosphonic Acid, sodium sulfonate and benzotriazole.
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