CN104787990A - Method for treating high-temperature, high-salinity difficult-degradation oil producing wastewater - Google Patents
Method for treating high-temperature, high-salinity difficult-degradation oil producing wastewater Download PDFInfo
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- CN104787990A CN104787990A CN201510226615.0A CN201510226615A CN104787990A CN 104787990 A CN104787990 A CN 104787990A CN 201510226615 A CN201510226615 A CN 201510226615A CN 104787990 A CN104787990 A CN 104787990A
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Abstract
The invention discloses a method for treating high-temperature, high-salinity difficult-degradation oil producing wastewater. An organic component, which can be degraded by a microbial agent R1 (4), in the oil producing wastewater is preferentially eliminated in a first-stage aerobic biochemical tank (2); supernate after solid-liquid separation is carried out enters a first-stage ozone pre-oxidizing tank (11) to be pre-oxidized, so that the biodegradability is increased; a biochemical organic matter is further degraded by a microbial agent R2 (21) added into a second-stage aerobic biochemical tank (18), into which outflow water flows; supernate after solid-liquid separation is carried out again flows into a high-stage oxidizing tank (28); little low-biodegradability organic matters remained in water can be thoroughly degraded under the synergistic effect of an ozone generator (15), an ultraviolet lamp light-emitting device (29) and an oxidizing agent adding system (31); and requirements of outflow water to indexes, such as sterilization and chroma, can be achieved. The method is accurate and controllable in target division of various process sections, simple to operate, low in drug adding amount and sludge yield and steady and reliable to output water. The method disclosed by the invention is conveniently popularized and used in the oil field wastewater treatment field.
Description
Technical field
The present invention relates to one and utilize one-level aerobic biochemical that---the combined method process high temperature and high salt difficult degradation oil extraction waste water of ozone pre-oxidation---secondary aerobic biochemical---advanced oxidation is to obtain wastewater to reach standard and arrange or the method for cycling and reutilization outward.
Background technology
Along with the development of modern industry, the mankind are also continuing to increase the demand of oil, a large amount of waste water will be produced in oil production and refining process, these waste water often have the features such as high temperature (>=50 DEG C), high salinity (>=3.5%TDS) and the unrecovered oil composition containing complexity, if not treated direct discharge, serious pollution and destruction certainly will be caused by environment to external world.At present, traditional treatment process is mainly dosing coagulation-precipitation-active carbon absorption technology or coagulation-filtration-ultrafiltration technology, to reach the emission request to the index such as oil, COD in country's discharge or reuse water quality standard.These techniques exist that equipment is many, reference mark is many, chemical feeding quantity is large, produce a large amount of unmanageable mud, active carbon adsorption equipment regeneration costly and there is serious secondary pollution problems in operational process.
Add the biological process of high temperature salt tolerant addicted to oily microbial inoculum, process petroleum wastewater expense be low, can degraded oil hydrocarbon pollutant and do not produce secondary pollution and be regarded as the new and high technology that has broad mass market prospect.But at present, the case application that high temperature salt tolerant is applied to practical engineering project addicted to oily microbial inoculum rarely had report, this is mainly because the loss of microbial inoculum makes will regularly to add a certain amount of microbial inoculum in practical engineering project, thus considerably increase the running cost of project, therefore find a kind of efficient microbial inoculum fixed form to become its prerequisite promoted the use of.
Water exploiting petroleum due to BOD/COD low (< 0.1) be difficult to by biochemical oxidation, especially former water is after one-level biochemical treatment, remaining organism major part is solubility hardly degraded organic substance, be difficult to again further by biochemical degradation, therefore need the process means adopting other to improve BOD/COD, be convenient to follow-up biochemical treatment unit.Ozone has very strong oxidisability, thus can decompose or various Persistent organic pollutants in degradation water.The oxidisability of ozone can directly utilize, also can in conjunction with UV, H
2o
2carry out advanced oxidation use.Existing ozonation technology, its object mainly allows the disposable degradable organism of ozone, and next is only raising wastewater biodegradability, and this processing mode ozone dosage is large, and running cost is high.
Summary of the invention
Many for the equipment existed in existing high temperature and high salt difficult degradation petroleum wastewater treatment method, control complicated, chemical feeding quantity is large, sludge yield is high, undesirable to hardly degraded organic substance treatment effect, there is serious secondary pollution problems, the invention provides the treatment process of such discharged wastewater met the national standard a kind of or cycling and reutilization.
Technical scheme of the present invention:
A treatment process for high temperature and high salt difficult degradation petroleum wastewater, the step of this treatment process comprises:
Step one, intake pump, by oil extraction waste water suction one-level aerobic biochemical pool, adds hydrophilic fibre bundle bio-carrier and microbiobacterial agent R in one-level aerobic biochemical pool
1, microbiobacterial agent is by manually to add or gravity chemicals dosing plant adds, and fibrous bundle bio-carrier packing ratio is Χ
1, microbiobacterial agent R
1add than being Y
1; Microbiobacterial agent R
1required dissolved oxygen is provided from bottom aeration head by aeration pump;
Step 2, the mixed solution after step one processes enters one-level solid-liquid separation tank by hydraulic pipe, and precipitating sludge is discharged by mud discharging mouth, and supernatant liquor overflows from the effluent weir of one-level solid-liquid separation tank;
Step 3, the supernatant liquor that step 2 is overflowed enters one-level ozone pre-oxidation pond by hydraulic pipe from top, one-level ozone pre-oxidation pond is made up of ozone reaction district and buffer zone two portions, and ozone needed for ozone reaction district is provided from bottom titanium alloy aeration head by ozonizer, supply ozone tolerance q
1, concentration C
1, reaction times t
1; Ozone reaction district forms communicating vessels with being communicated with bottom buffer zone; Bottom buffer zone, aeration is provided from bottom aeration head by aeration pump;
Step 4, the water after step 3 process enters in second-stage aerobic biochemical pool by hydraulic pipe overflow, adds granular biological carrier and microbiobacterial agent R in second-stage aerobic biochemical pool
2, microbiobacterial agent is by manually to add or gravity chemicals dosing plant adds, and granular biological carrier packing ratio is Χ
2, microbiobacterial agent R
2add than being Y
2; Dissolved oxygen in buffer zone water outlet in one-level ozone pre-oxidation pond can meet microbiobacterial agent R
2oxygen requirement, therefore without the need to two-pass aerating, biomembranous coming off is realized by agitator;
Step 5: the mixed solution after step 4 process enters secondary solid-liquid separation tank by hydraulic pipe, and precipitating sludge is discharged by mud discharging mouth, supernatant liquor overflows from the effluent weir of secondary solid-liquid separation tank;
Step 6: the supernatant liquor that step 5 is overflowed enters advanced oxidation pond by hydraulic pipe from top, top, advanced oxidation pond is provided with ultraviolet lamp light-emitting device and dosing mouth, oxygenant medicine system clearance dosing mouth adds related oxidized medicament in advanced oxidation pond, ozone needed for advanced oxidation pond is provided by bottom titanium alloy aeration head by ozonizer, supply ozone tolerance q
2, concentration C
2, reaction times t
2; Process water up to standard to discharge bottom advanced oxidation pond.
The present invention compares had effect with existing technique:
The each process section of the present invention is with clearly defined objective controlled, and flow operations is simple, and sludge yield is few, can stablize the microorganisms such as the effective easily biodegradable organics removed in sewage, suspended substance, hardly degraded organic substance and bacterium.The function of one-level aerobic biochemical and solid-liquid separation process section is the microbiobacterial agent R utilizing working cost low
1the organic matter removal that can be degraded in water inlet is fallen, thus alleviates the pressure of backend process section, for different water exploiting petroleum Petroleum Hydrocarbon components, add corresponding high-effect bacterial R
1, with strong points, aerobic biochemical pool filler used is the compo material filler that adsorptivity is strong simultaneously, and specific surface area is large, all has very strong fixed trapped function to the pollutent in microorganism and water, and Microorganism incubation is easy, and amount lost is few; The major function of ozone pre-oxidation process section is not that hardly degraded organic substance is completely oxidized to carbonic acid gas and water, but by controlling the tolerance q of ozone
1, concentration C
1, reaction times t
1hardly degraded organic substance is carried out incomplete oxidation, larger molecular organics chain rupture becomes small organic molecule, thus eliminate its refractory organics or toxicity, improve its biodegradability, reducing while ozone usage reduces operation investment running cost is that rear end biochemical process creates better condition, this process section increases aeration buffer zone, its object is the oxygen level that will increase while residue ozone stripping in water in water, and realize preoxygenation, therefore aerobic biochemical district in rear end is without the need to carrying out aeration aerating again; The function of secondary aerobic biochemical and solid-liquid separation process section is further by microbiobacterial agent R
2biochemical degradation after ozone pre-oxidation in water body can biochemical organism, add microbial inoculum R targetedly according to organic component in this stage water body
2, running cost is low, Be very effective, and this process section filler used is hydrophilic particle shape filler, and density and aqueous phase are worked as, and are 0.9 ρ
water~ 1.1 ρ
water, be on the one hand convenient to the fluidized state realizing filler, improve processing efficiency, be convenient on the other hand to realize under the effect of stirring biomembranously come off and upgrade; The major function of advanced oxidation processes section is by ozone, ultraviolet lamp or oxidating chemicals (H
2o
2, KMnO
4) synergistic oxidation effect a small amount of bio-refractory organism remaining in water body be oxidized thoroughly generate water and carbonic acid gas, the microorganisms such as the bacterium in water body can be removed simultaneously, reach the requirement of effluent index to bacterial number.
Case: this process application is carried out pilot scale in North China Oilfield oil production waste water treatment station, process water yield 1t/h, influent quality index: temperature 45 ~ 50 DEG C, Cl
-6000mg/L ~ 12000mg/L, pH6 ~ 9, oil 50mg/L ~ 100mg/L, COD320mg/L ~ 550mg/L, BOD/COD < 0.1, ss suspended solid 80 ~ 150mg/L.Analyze organic components and content in water inlet through GC-MS to be respectively: saturated straight chain alkane (being greater than 40%), aromatic hydrocarbon (being greater than 40%), organic acid (being less than 10%) are organic wastewater with difficult degradation thereby.In pilot plant test process, adopt former water as sole carbon source, acclimated microorganism is screened from the on-the-spot profit bed mud of project, Bacillus licheniformis and subtilis is mainly through the bacterial classification that microorganism identification adaptability is good, these two kinds of bacterium are high temperature resistant and halophilic addicted to oily bacterium, by these two kinds of bacterial classifications being become microbiobacterial agent R1 by the proportions of 1:1 after separation and purification and fermentor tank amplification culture, microbial inoculum dosage makes initial MLSS in one-level aerobic biochemical pool reach 400 ~ 500mg/L, the packing ratio of hydrophilic fibre filler beam is 60%, after the domestication biofilm of 30 days, on fibrous bundle filler, the conversion amount Absorbable organic halogens of microorganism reaches at more than 3000mg/L, the oil clearance Absorbable organic halogens of this process section when residence time HRT is 3h in water reaches more than 80%, the clearance of COD is 30%.
The reaction times in ozone pre-oxidation process section ozone reaction district is 15min, and ozone adds concentration 80mg/L ~ 110mg/L, ozone tolerance 8L/min, and this process section oil clearance is the clearance of 10%, COD is 20%.Carry out analysis to ozone pre-oxidation water outlet to find, its BOD/COD > 0.3, dissolved oxygen DO is close to saturated dissolved oxygen state, this water outlet biochemical is good, now water temperature is also down to 38 DEG C by more than 45 DEG C that always intake, and therefore secondary aerobic biochemical section microbiobacterial agent R2 adopts the conventional municipal dewatered sludge of low cost to inoculate.
Adopt municipal dehydration activity sludge seeding second-stage aerobic biochemical pool, inoculum size makes initial MLSS > 1000mg/L in pond, the packing ratio 40% of granular filler, hydraulic detention time HRT is 2h, after the domestication biofilm of 15 days, biology conversion amount Absorbable organic halogens on granular filler is at 2500 ~ 3000mg/L, the oil clearance 5% of this process section, the clearance of COD is for can reach 30% ~ 35%, this process section is when not extra aeration, dissolved oxygen DO can reach 2 ~ 5mg/L, meets the aerobic requirement to DO.
The water PetroChina Company Limited. content entering advanced oxidation processes section is less than 5mg/L, and COD is less than 80mg/L, and this process section selects 135W low pressure ultraviolet lamp 2, ozone adds concentration 80mg/L ~ 110mg/L, ozone tolerance 16L/min, reaction times 30min, this process section of pilot scale does not add any oxidating chemicals.
Effluent index after this art breading: oil does not detect, COD < 45mg/L, ss suspended solid < 2mg/L, Absorbable organic halogens reaches oil field extracted water re-injection (A2, or emission standard (oil < 8mg/L A3), COD < 50mg/L, suspended substance < 3mg/L), this process operation cost can be controlled in 2.5 ~ 3.5 yuan/ton of water, common process reaches identical effluent index running cost then at 4 ~ 8 yuan/ton of water, this pilot plant test has highlighted operating performance of the present invention and has stablized, the feature that running cost is low.
Accompanying drawing explanation
Fig. 1 is a kind of high temperature and high salt degree difficult degradation oil extraction waste water treatment method schematic diagram.
In figure, 1, intake pump; 2, one-level aerobic biochemical pool; 3, hydrophilic fibre bundle bio-carrier; 4, microbiobacterial agent R
1; 5, aeration pump; 6, one-level aerobic biochemical district aeration head; 8, one-level solid-liquid separation tank; 12, one-level ozone pre-oxidation pond; 13, ozone reaction district; 14, buffer zone; 15, ozonizer; 19, second-stage aerobic biochemical pool; 20, granular biological carrier; 21, microbiobacterial agent R
2; 22, agitator; 24, secondary solid-liquid separation tank; 28, advanced oxidation pond; 29, ultraviolet lamp light-emitting device; 30, dosing mouth; 31, oxygenant medicine system.
Embodiment
The invention will be further described by reference to the accompanying drawings.
1. a treatment process for organic wastewater with difficult degradation thereby, is characterized in that: the step of this treatment process comprises:
Step one, intake pump 1, by oil extraction waste water suction one-level aerobic biochemical pool 2, adds hydrophilic fibre bundle bio-carrier 3 and microbiobacterial agent R in one-level aerobic biochemical pool 2
14, microbiobacterial agent is by manually to add or gravity chemicals dosing plant adds, and fibrous bundle bio-carrier packing ratio is Χ
1, microbiobacterial agent R
14 add than being Y
1; Microbiobacterial agent R
1dissolved oxygen needed for 4 is provided from bottom aeration head 6 by aeration pump 5;
Step 2, the mixed solution after step one processes enters one-level solid-liquid separation tank 8 by hydraulic pipe 7, and precipitating sludge is discharged by mud discharging mouth 9, and supernatant liquor overflows from the effluent weir 10 of one-level solid-liquid separation tank 8;
Step 3, the supernatant liquor that step 2 is overflowed enters one-level ozone pre-oxidation pond 12 by hydraulic pipe 11 from top, one-level ozone pre-oxidation pond 12 is made up of ozone reaction district 13 and buffer zone 14 two portions, ozone needed for ozone reaction district is provided from bottom titanium alloy aeration head 16 by ozonizer 15, supply ozone tolerance q
1, concentration C
1, reaction times t
1; Ozone reaction district 13 forms communicating vessels with being communicated with bottom buffer zone 14; Bottom buffer zone 14, aeration is provided from bottom aeration head 17 by aeration pump 5;
Step 4, the water after step 3 process enters in second-stage aerobic biochemical pool 19 by hydraulic pipe 18 overflow, adds granular biological carrier 20 and microbiobacterial agent R in second-stage aerobic biochemical pool 19
221, microbiobacterial agent is by manually to add or gravity chemicals dosing plant adds, and granular biological carrier 20 packing ratio is Χ
2, microbiobacterial agent R
221 add than being Y
2; Dissolved oxygen in buffer zone 14 water outlet in one-level ozone pre-oxidation pond 12 can meet microbiobacterial agent R
2the oxygen requirement of 21, therefore without the need to two-pass aerating, biomembranous coming off is realized by agitator 22;
Step 5, the mixed solution after step 4 process enters secondary solid-liquid separation tank 24 by hydraulic pipe 23, and precipitating sludge is discharged by mud discharging mouth 25, and supernatant liquor overflows from the effluent weir 26 of secondary solid-liquid separation tank 24;
Step 6, the supernatant liquor that step 5 is overflowed enters advanced oxidation pond 28 by hydraulic pipe 27 from top, top, advanced oxidation pond 28 is provided with ultraviolet lamp light-emitting device 29 and dosing mouth 30, oxygenant medicine system 31 clearance dosing mouth 30 adds related oxidized medicament in advanced oxidation pond 28, ozone needed for advanced oxidation pond 28 is provided by bottom titanium alloy aeration head 32 by ozonizer 15, supply ozone tolerance q
2, concentration C
2, reaction times t
2; Process water up to standard to discharge bottom advanced oxidation pond 28.
One-level solid-liquid separation tank 8 used in the present invention, secondary solid-liquid separation tank 24 are all according to the flow of handled organic wastewater with difficult degradation thereby and design the requirement of related process section according in design manual.
The above; for general case study on implementation of the present invention; not the present invention is imposed any restrictions, every above embodiment is done according to the technology of the present invention essence any simple modification, change and equivalent structure change, all still belong in the protection domain of technical solution of the present invention.
Claims (10)
1. a treatment process for high temperature and high salt difficult degradation oil extraction waste water, is characterized in that: the step of this treatment process comprises: one-level aerobic biochemical pool (2), one-level solid-liquid separation tank (8), one-level ozone pre-oxidation pond (12), second-stage aerobic biochemical pool (19), secondary solid-liquid separation tank (24) and advanced oxidation pond (28).
2. one-level aerobic biochemical pool (2) according to claim 1, is characterized in that, with certain packing ratio Χ in this biochemistry pool
1add anchoring fiber bundle bio-carrier (3).
3. one-level aerobic biochemical pool (2) according to claim 1, is characterized in that, for different oil fields water exploiting petroleum Petroleum Hydrocarbon component, adds corresponding high-effective microorganism microbial inoculum R
1(4), microbiobacterial agent R
1(4) add than being Y
1, can adopt and manually to add or chemicals dosing plant adds.
4. one-level aerobic biochemical pool (2) according to claim 2, is characterized in that anchoring fiber bundle bio-carrier (3) used is compo material, specific surface area > 2000 ㎡/m
3, there is lipophilicity and adsorptivity.
5. one-level ozone pre-oxidation pond (12) according to claim 1, it is characterized in that, described oxidation pond is made up of ozone reaction district (13) and buffer zone (14) two portions, the required ozone in ozone reaction district (13) is provided from bottom titanium alloy aeration head (16) by the raw device (15) of ozone, supply ozone tolerance q
1, concentration C
1, reaction times t
1; Ozone reaction district (13) is communicated with formation communicating vessels with buffer zone (14) bottom; Bottom, buffer zone (14) aeration is provided from bottom aeration head (17) by aeration pump (5).
6. second-stage aerobic biochemical pool according to claim 1 (19), is characterized in that, adds granular biological carrier (20) in described second-stage aerobic biochemical pool (19), and carrier packing ratio is Χ
2.
7. second-stage aerobic biochemical pool according to claim 6 (19), is characterized in that, the granular biological carrier (20) added is hydrophilic plastic material, and density is 0.9 ρ
water~ 1.1 ρ
water.
8. second-stage aerobic biochemical pool according to claim 1 (19), is characterized in that, for organic constituents in this stage waste water in described second-stage aerobic biochemical pool (19), adds corresponding high-effective microorganism microbial inoculum R
2(21), high-effective microorganism microbial inoculum R
2(21) add than being Y
2.
9. second-stage aerobic biochemical pool according to claim 1 (19), is further characterized in that, the dissolved oxygen in buffer zone (14) water outlet in leading portion one-level ozone pre-oxidation pond (12) can meet microbiobacterial agent R
2(21) oxygen requirement, without the need to secondary aeration aerating, the upper length of granular biological carrier (20) has microbial inoculum R
2(21) biofilm detachment is upgraded and is realized by agitator (22).
10. advanced oxidation pond (28) according to claim 1, it is characterized in that, advanced oxidation pond (28) top is provided with ultraviolet lamp light-emitting device (29) and dosing mouth (30), oxygenant medicine system (31) adds related oxidized medicament by dosing mouth (30) in advanced oxidation pond (28), the required ozone in advanced oxidation pond (28) is provided by bottom titanium alloy aeration head (32) by ozonizer (15), supply ozone tolerance q
2, concentration C
2, reaction times t
2; Water after process is from advanced oxidation pond (28) bottom standard discharge or reuse.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105540820A (en) * | 2016-02-24 | 2016-05-04 | 中国石油化工股份有限公司 | Device and method for treating electro-desalting wastewater through ozone |
| CN105858861A (en) * | 2016-04-21 | 2016-08-17 | 中国石油化工股份有限公司 | Device and method for treating production wastewater of butadiene styrene rubber by utilizing ozone |
| EP3309130A1 (en) * | 2016-10-11 | 2018-04-18 | Suez International | Process and facility for treating produced water from an oil & gas field |
| CN111187742A (en) * | 2020-02-26 | 2020-05-22 | 上海淳渊环境科技有限公司 | Composite biological agent and method and system for treating salt-containing organic matter wastewater |
| CN111849798A (en) * | 2019-08-30 | 2020-10-30 | 上海傲江生态环境科技有限公司 | Microbial flora compound liquid and petroleum hydrocarbon polluted soil treatment method |
| CN113105063A (en) * | 2020-01-13 | 2021-07-13 | 中国石油天然气股份有限公司 | Oil extraction sewage treatment process |
| CN115259573A (en) * | 2022-08-24 | 2022-11-01 | 南京工大环境科技有限公司 | Treatment method of high-sulfate organic wastewater in petroleum refining industry |
| CN117706055A (en) * | 2024-02-06 | 2024-03-15 | 天津创业环保集团股份有限公司 | Integrated method and device for analyzing organic matter full-component characteristics of municipal sewage |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105540820A (en) * | 2016-02-24 | 2016-05-04 | 中国石油化工股份有限公司 | Device and method for treating electro-desalting wastewater through ozone |
| CN105858861A (en) * | 2016-04-21 | 2016-08-17 | 中国石油化工股份有限公司 | Device and method for treating production wastewater of butadiene styrene rubber by utilizing ozone |
| EP3309130A1 (en) * | 2016-10-11 | 2018-04-18 | Suez International | Process and facility for treating produced water from an oil & gas field |
| WO2018069344A1 (en) * | 2016-10-11 | 2018-04-19 | Suez International | Process and facility for treating produced water from an oil & gas field |
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| CN111849798A (en) * | 2019-08-30 | 2020-10-30 | 上海傲江生态环境科技有限公司 | Microbial flora compound liquid and petroleum hydrocarbon polluted soil treatment method |
| CN113105063A (en) * | 2020-01-13 | 2021-07-13 | 中国石油天然气股份有限公司 | Oil extraction sewage treatment process |
| CN111187742A (en) * | 2020-02-26 | 2020-05-22 | 上海淳渊环境科技有限公司 | Composite biological agent and method and system for treating salt-containing organic matter wastewater |
| CN115259573A (en) * | 2022-08-24 | 2022-11-01 | 南京工大环境科技有限公司 | Treatment method of high-sulfate organic wastewater in petroleum refining industry |
| CN117706055A (en) * | 2024-02-06 | 2024-03-15 | 天津创业环保集团股份有限公司 | Integrated method and device for analyzing organic matter full-component characteristics of municipal sewage |
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