CN104787990B - A kind of high temperature and high salt difficult degradation oil extraction waste water treatment method - Google Patents
A kind of high temperature and high salt difficult degradation oil extraction waste water treatment method Download PDFInfo
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Abstract
The invention discloses a kind of high temperature and high salt difficult degradation oil extraction waste water treatment method.Can be by microbial bacterial agent R in oil extraction waste water1(4) organic principle degraded preferentially is removed in one-level aerobic biochemical pool (2), after solid-liquid separation, supernatant carries out pre-oxidation into one-level ozone pre-oxidation pond (11) and improves biodegradability, the second-stage aerobic biochemical pool (18) that water outlet is flowed into, the microbial bacterial agent R added in pond2(21) further degrade biodegradability Organic substance, after solid-liquid separation, supernatant flows into advanced oxidation pond (28) again, under the synergism of ozonator (15), ultraviolet lamp lighting device (29) and oxidant medicine system (31) can thorough remaining a small amount of hardly degraded organic substance in degradation water, and reach requirement of the water outlet to indexs such as sterilization, colourities.The each process section target division of labor of the technique is clearly controllable, and flow operations are simple, and less developer, sludge yield are few, stable water outlet reliability.The inventive method is easy to promote the use of in oil field wastewater treatment field.
Description
Technical field
The present invention relates to a kind of, using one-level aerobic biochemical, --- ozone pre-oxidation --- two grades of aerobic biochemicals --- is senior
The method that the combined method of oxidation processes high temperature and high salt difficult degradation oil extraction waste water to obtain row or cycling and reutilization outside wastewater to reach standard.
Background technology
With the development of modern industry, the mankind, and were refined in oil exploitation also continuing to increase to the demand of oil
A large amount of waste water will be produced in journey, these waste water often have high temperature (>=50 DEG C), high salinity (>=3.5%TDS) and containing complexity
Unrecovered oil composition the features such as, if without process directly discharge, serious pollution and destruction certainly will be caused by environment to external world.Mesh
Before, traditional processing method is mainly dosing coagulation-precipitation-active carbon absorption technology or coagulation-filtration-ultrafiltration technology, to reach
Emission request in country's discharge or reuse water standard to indexs such as oil, COD.These techniques exist equipment it is many, control
Point is more, chemical feeding quantity is big, produces a large amount of intractable sludge, active carbon adsorption equipment and regenerate costly and exist tight in running
The secondary pollution problems of weight.
Add the bioanalysises of the thermophilic oily microbial inoculum of high temperature salt tolerant, process petroleum wastewater expense it is low, being capable of degraded oil hydrocarbon pollutant
And do not produce secondary pollution and be considered a new and high technology with broad mass market prospect.But at present, will be high temperature salt tolerant thermophilic
Oily microbial inoculum is applied to the case application of practical engineering project and rarely has report, and this loss for being primarily due to microbial inoculum causes Practical Project
A certain amount of microbial inoculum is periodically added in project, so as to considerably increase the operating cost of project, therefore is found a kind of efficient
Microbial inoculum fixed form becomes the premise which is promoted the use of.
Water exploiting petroleum is difficult by biochemical oxidation, the especially biochemical treatment of raw water Jing one-level due to BOD/COD low (＜ 0.1)
Afterwards, it is solubility hardly degraded organic substance that remaining Organic substance is most of, it is difficult to further pass through biochemical degradation, it is therefore desirable to adopt
BOD/COD is improved with other processing means, is easy to follow-up biochemical treatment unit.Ozone has very strong oxidisability, thus
Various persistent organic pollutants in energy decomposition or degradation water.The oxidisability of ozone directly can be utilized, also can be with reference to UV, H2O2
Carry out advanced oxidation use.Existing ozonation technology, its purpose mainly allow the disposable degradable Organic substance of ozone, secondly
Raising wastewater biodegradability is only, the processing mode ozone dosage is big, operating cost is high.
The content of the invention
For equipment present in existing high temperature and high salt difficult degradation petroleum wastewater treatment method it is many, control is complicated, chemical feeding quantity
Greatly, sludge yield is high, undesirable to hardly degraded organic substance treatment effect, there are serious secondary pollution problems, and the present invention is carried
For a kind of such discharged wastewater met the national standard or the processing method of cycling and reutilization.
Technical scheme：
The step of a kind of processing method of high temperature and high salt difficult degradation petroleum wastewater, processing method, includes：
Step one, intake pump are added in oil extraction waste water suction one-level aerobic biochemical pool in one-level aerobic biochemical pool hydrophilic
Property fibre bundle bio-carrier and microbial bacterial agent R1, microbial bacterial agent passes through manually to add or gravity chemicals dosing plant is added, fiber
Beam bio-carrier packing ratio is Χ1, microbial bacterial agent R1Add than for Y1；Microbial bacterial agent R1Required dissolved oxygen passes through aeration pump
There is provided from bottom aeration head；
Step 2, the mixed liquor Jing after step one process enter one-level solid-liquid separation tank by water-supply-pipe, and precipitating sludge leads to
Mud discharging mouth discharge is crossed, supernatant is overflowed from the effluent weir of one-level solid-liquid separation tank；
Step 3, the supernatant that step 2 is overflowed enter one-level ozone pre-oxidation pond from top by water-supply-pipe, and one-level is smelly
Oxygen pre-oxidation pond is made up of ozone reaction area and relief area two parts, and ozone needed for ozone reaction area is by ozonator from bottom
Titanium alloy aeration head is provided, supplied ozone tolerance q1, concentration C1, response time t1；Ozone reaction area connects shape with relief area bottom
Into linker；Relief area bottom aeration is provided from bottom aeration head by aeration pump；
Step 4, the water Jing after step 3 process are entered in second-stage aerobic biochemical pool by water-supply-pipe overflow, two grades of aerobic lifes
Granular biological carrier and microbial bacterial agent R are added in changing pond2, microbial bacterial agent passes through manually to add or gravity chemicals dosing plant is thrown
Plus, granular biological carrier packing ratio is Χ2, microbial bacterial agent R2Add than for Y2；Relief area in one-level ozone pre-oxidation pond goes out
Dissolved oxygen in water can meet microbial bacterial agent R2Oxygen demand, it is therefore without the need for two-pass aerating, biomembranous to come off by agitator
Realize；
Step 5：Mixed liquor Jing after step 4 process enters two grades of solid-liquid separation tanks by water-supply-pipe, and precipitating sludge leads to
Mud discharging mouth discharge is crossed, supernatant is overflowed from the effluent weir of two grades of solid-liquid separation tanks；
Step 6：The supernatant that step 5 is overflowed enters advanced oxidation pond, advanced oxidation Chi Ding from top by water-supply-pipe
Portion is provided with ultraviolet lamp lighting device and dosing mouth, and oxidant medicine system clearance dosing mouth adds related oxygen in advanced oxidation pond
Chemical medicine agent, ozone needed for advanced oxidation pond are provided by bottom titanium alloy aeration head by ozonator, supplied ozone tolerance q2,
Concentration C2, response time t2；Process water up to standard to discharge from advanced oxidation bottom of pond portion.
The present invention compares had effect with existing technique：
The each process section of the present invention is with clearly defined objective controllable, and flow operations are simple, and sludge yield is few, can stablize and effectively go decontamination
The microorganisms such as easily biodegradable organicses, float, hardly degraded organic substance and antibacterial in water.One-level aerobic biochemical and solid-liquid separation
The function of process section is using the low microbial bacterial agent R of operating cost1The organic matter removal that can be degraded in water inlet is fallen, so as to
Mitigate the pressure of backend process section, for different water exploiting petroleum petrochina hydrocarbon components, add corresponding high-effect bacterial R1, pin
Strong to property, while filler used by aerobic biochemical pool is the strong compo material filler of adsorptivity, specific surface area is big, to microorganism
There is very strong fixed trapped function with the pollutant in water, microorganism fixes easy, and amount lost is few；Ozone pre-oxidation process section
Major function be not that hardly degraded organic substance is completely oxidized to into carbon dioxide and water, but by controlling the tolerance of ozone
q1, concentration C1, response time t1, hardly degraded organic substance is carried out into incomplete oxidation, larger molecular organicses chain rupture is organic into small molecule
Thing, so as to eliminate its refractory organics or toxicity, improves its biodegradability, and reducing ozone usage reduces operation investment operating cost
Simultaneously create more preferable condition for rear end biochemical process, the process section increases aeration relief area, its purpose be will remain in water it is smelly
Increase the oxygen content in water while oxygen stripping, realize preoxygenation, therefore rear end aerobic biochemical area without the need for carrying out aeration aerating again；
The function of two grades of aerobic biochemicals and solid-liquid separation process section is further to pass through microbial bacterial agent R2The pre- oxygen of biochemical degradation Jing ozone
After change in water body can biochemical Organic substance, microbial inoculum R is targetedly added according to the component of Organic substance in the stage water body2, fortune
Row low cost, effect is significant, the filler used by the process section are hydrophilic particle shape filler, and density and water quite, are 0.9 ρWater~
1.1ρWater, the fluidized state of filler is on the one hand facilitated implementation, treatment effeciency is improved, is on the other hand easy in the presence of stirring real
It is now biomembranous to come off and update；The major function of advanced oxidation processes section is by ozone, uviol lamp or oxidating chemicals (H2O2、
KMnO4) synergistic oxidation effect to remaining a small amount of bio-refractory Organic substance in water body thoroughly aoxidized generation water and
Carbon dioxide, while can remove the microorganisms such as the antibacterial in water body, reaches requirement of the effluent index to bacterial number.
Case：The technique is applied to North China Oilfield oil production waste water treatment station carries out pilot scale, processes water yield 1t/h, water inlet
Water quality index：45～50 DEG C of temperature, Cl-6000mg/L～12000mg/L, pH6～9, oil 50mg/L～100mg/L,
COD320mg/L～550mg/L, BOD/COD ＜ 0.1,80～150mg/L of ss suspended solid.Jing GC-MS are analyzed into Organic substance in water
Composition and content are respectively：Saturated straight chain alkane (being more than 40%), aromatic hydrocarbon (being more than 40%), organic acid (being less than 10%), be
Organic wastewater with difficult degradation thereby.During pilot plant test, using raw water as sole carbon source, screen from the profit bed mud of project scene
Acclimated microorganism, the good strain of Jing microbial identification adaptabilities are mainly Bacillus licheniformis and bacillus subtilises, and this two
Kind of bacterium is high temperature resistant and halophilic thermophilic oily bacterium, by isolate and purify and fermentation tank amplification culture after by both strains by 1:
Into microbial bacterial agent R1, during microbial inoculum dosage makes one-level aerobic biochemical pool, initial MLSS reaches 400～500mg/ to 1 proportions
L, the packing ratio of hydrophilic fibre filler beam is 60%, after the domestication biofilm of 30 days, the folding of microorganism on fiber filler beam
Calculation amount can be stablized up in more than 3000mg/L, and oil clearance of process section when time of staying HRT is 3h in water can be stablized
The clearance for reaching more than 80%, COD is 30%.
The response time in ozone pre-oxidation process section ozone reaction area be 15min, ozone add concentration 80mg/L～
110mg/L, ozone tolerance 8L/min, the process section oil clearance are 20% for the clearance of 10%, COD.To the pre- oxygen of ozone
Dissolve water and be analyzed discovery, its BOD/COD ＞ 0.3, dissolved oxygen DO are close to saturated dissolved oxygen state, the water outlet biochemical is good
Good, now water temperature is also down to 38 DEG C by more than 45 DEG C always intake, therefore two grades of aerobic biochemical section microbial bacterial agent R2 adopt expense
It is inoculated with cheap conventional municipal dewatered sludge.
Using municipal dehydration activity sludge seeding second-stage aerobic biochemical pool, inoculum concentration causes initial MLSS ＞ in pond
1000mg/L, the packing ratio 40% of granular filler, hydraulic detention time HRT are 2h, and after the domestication biofilm of 15 days, granule is filled out
Biological conversion amount on material can be stablized in 2500～3000mg/L, the oil clearance 5% of the process section, and the clearance of COD is
Up to 30%～35%, in the case of not extra aeration, dissolved oxygen DO meets aerobic to DO up to 2～5mg/L to the process section
Requirement.
Water petrochina content into advanced oxidation processes section has been less than 5mg/L, and COD is less than 80mg/L, and the process section is selected
With 135W low pressure ultraviolet lamps 2, ozone adds concentration 80mg/L～110mg/L, ozone tolerance 16L/min, response time
30min, the pilot scale process section do not add any oxidating chemicals.
The effluent index Jing after the PROCESS FOR TREATMENT：Oil is not detected, COD ＜ 45mg/L, and ss suspended solid ＜ 2mg/L can stablize
Oil field extracted water re-injection (A2, A3) or discharge standard (oil ＜ 8mg/L, COD ＜ 50mg/L, float ＜ 3mg/L) are reached, should
Process operation cost can be controlled in 2.5～3.5 yuan/ton of water, common process reach identical effluent index operating cost then 4～
8 yuan/ton of water, the pilot plant test have highlighted the characteristics of operational effect of the present invention is stable, and operating cost is low.
Description of the drawings
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；2nd, one-level aerobic biochemical pool；3rd, hydrophilic fibre beam bio-carrier；4th, microbial bacterial agent R1；
5th, aeration pump；6th, one-level aerobic biochemical area aeration head；8th, one-level solid-liquid separation tank；12nd, one-level ozone pre-oxidation pond；13rd, ozone
Reaction zone；14th, relief area；15th, ozonator；19th, second-stage aerobic biochemical pool；20th, granular biological carrier；21st, microbial bacteria
Agent R2；22nd, agitator；24th, two grades of solid-liquid separation tanks；28th, advanced oxidation pond；29th, ultraviolet lamp lighting device；30th, dosing mouth；
31st, oxidant medicine system.
Specific embodiment
With reference to accompanying drawing, the invention will be further described.
1. a kind of handling process of organic wastewater with difficult degradation thereby, it is characterised in that：The step of handling process, includes：
Step one, intake pump 1 add parent by oil extraction waste water suction one-level aerobic biochemical pool 2 in one-level aerobic biochemical pool 2
Aqueous fiber beam bio-carrier 3 and microbial bacterial agent R14, microbial bacterial agent passes through manually to add or gravity chemicals dosing plant is added,
Fibre bundle bio-carrier packing ratio is Χ1, microbial bacterial agent R14 add than for Y1；Microbial bacterial agent R1Needed for 4, dissolved oxygen passes through
Aeration pump 5 is provided from bottom aeration head 6；
Step 2, the mixed liquor Jing after step one process enter one-level solid-liquid separation tank 8, precipitating sludge by water-supply-pipe 7
Discharged by mud discharging mouth 9, supernatant is overflowed from the effluent weir 10 of one-level solid-liquid separation tank 8；
Step 3, step 2 overflow supernatant by water-supply-pipe 11 from top enter one-level ozone pre-oxidation pond 12, one
Level ozone pre-oxidation pond 12 is made up of ozone reaction area 13 and 14 two parts of relief area, and ozone needed for ozone reaction area is sent out by ozone
Raw device 15 is provided from bottom titanium alloy aeration head 16, supplied ozone tolerance q1, concentration C1, response time t1；13 He of ozone reaction area
14 bottom of relief area connects to form linker；14 bottom aeration of relief area is provided from bottom aeration head 17 by aeration pump 5；
Step 4, the water Jing after step 3 process are entered in second-stage aerobic biochemical pool 19 by 18 overflow of water-supply-pipe, and two grades good
Granular biological carrier 20 and microbial bacterial agent R are added in oxygen biochemistry pool 19221, microbial bacterial agent passes through manually to add or gravity adds
Medicine device is added, and 20 packing ratio of granular biological carrier is Χ2, microbial bacterial agent R221 add than for Y2；One-level ozone pre-oxidation pond
The dissolved oxygen in 14 water outlet of relief area in 12 can meet microbial bacterial agent R221 oxygen demand, therefore without the need for two-pass aerating, it is biological
Being come off for film realized by agitator 22；
Step 5, the mixed liquor Jing after step 4 process enter two grades of solid-liquid separation tanks 24 by water-supply-pipe 23, and precipitation is dirty
Mud is discharged by mud discharging mouth 25, and supernatant is overflowed from the effluent weir 26 of two grades of solid-liquid separation tanks 24；
Step 6, the supernatant that step 5 is overflowed enter advanced oxidation pond 28, advanced oxidation from top by water-supply-pipe 27
Ultraviolet lamp lighting device 29 and dosing mouth 30 are provided with the top of pond 28,31 clearance dosing mouth 30 of oxidant medicine system is to advanced oxidation
Related oxidized medicament is added in pond 28, ozone needed for advanced oxidation pond 28 passes through bottom titanium alloy aeration head by ozonator 15
32 provide, supplied ozone tolerance q2, concentration C2, response time t2；Process water up to standard to discharge from 28 bottom of advanced oxidation pond.
8, two grades of solid-liquid separation tanks 24 of one-level solid-liquid separation tank used in the present invention have all in accordance with handled difficult degradation
The flow of machine waste water and according in design manual to related process section requirement design.
The above, is the general case study on implementation of the present invention, not the present invention is imposed any restrictions, every according to the present invention
Any simple modification, change and equivalent structure change that technical spirit is made to above example, still fall within skill of the present invention
In the protection domain of art scheme.
Claims (8)
1. a kind of processing method of high temperature and high salt difficult degradation oil extraction waste water, it is characterised in that：The step of processing method, includes：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), two
Level solid-liquid separation tank (24) and advanced oxidation pond (28)；
Step one, intake pump in oil extraction waste water suction one-level aerobic biochemical pool, will add hydrophilic fine in one-level aerobic biochemical pool
Dimension beam bio-carrier and microbial bacterial agent R1；Microbial bacterial agent R1Required dissolved oxygen is exposed from one-level aerobic biochemical area by aeration pump
Gas head is provided；
Step 2, the mixed liquor Jing after step one process enter one-level solid-liquid separation tank by water-supply-pipe, and precipitating sludge is by row
Mud mouth is discharged, and supernatant is overflowed from the effluent weir of one-level solid-liquid separation tank；
Step 3, the supernatant that step 2 is overflowed enter one-level ozone pre-oxidation pond from top by water-supply-pipe；One-level ozone is pre-
Oxidation pond is made up of ozone reaction area (13) and relief area (14) two parts, and ozone needed for ozone reaction area (13) is occurred by ozone
Device (15) is provided from bottom titanium alloy aeration head (16), supplied ozone tolerance q1, concentration C1, response time t1；Ozone reaction area
(13) connect to form linker with relief area (14) bottom；Relief area (14) bottom aeration is by aeration pump (5) from bottom aeration head
(17) provide；
Step 4, the water Jing after step 3 process are entered in second-stage aerobic biochemical pool by water-supply-pipe overflow, second-stage aerobic biochemical pool
Middle addition granular biological carrier and microbial bacterial agent R2, microbial bacterial agent passes through manually to add or gravity chemicals dosing plant is added；Plus
The granular biological carrier for entering is hydrophilic plastic material, and density is 0.9 ρWater～1.1 ρWater；
Step 5：Mixed liquor Jing after step 4 process enters two grades of solid-liquid separation tanks by water-supply-pipe, and precipitating sludge is by row
Mud mouth is discharged, and supernatant is overflowed from the effluent weir of two grades of solid-liquid separation tanks；
Step 6：The supernatant that step 5 is overflowed enters advanced oxidation pond from top by water-supply-pipe, processes water up to standard from height
Discharge level oxidation pond bottom.
2. the processing method of high temperature and high salt difficult degradation oil extraction waste water according to claim 1, it is characterised in that the one-level
With certain packing ratio Χ in aerobic biochemical pool (2)1Add hydrophilic fibre beam bio-carrier (3).
3. the processing method of high temperature and high salt difficult degradation oil extraction waste water according to claim 1, it is characterised in that for difference
Oil field water exploiting petroleum petrochina hydrocarbon component, adds corresponding high-effective microorganism microbial inoculum R1(4), microbial bacterial agent R1(4) add ratio
For Y1, can be using manually adding or chemicals dosing plant is added.
4. the processing method of high temperature and high salt difficult degradation oil extraction waste water according to claim 2, it is characterised in that used hydrophilic
Property fibre bundle bio-carrier (3) is compo material, 2000 ㎡ of specific surface area ＞/m3, with lipophile and adsorptivity.
5. the processing method of high temperature and high salt difficult degradation oil extraction waste water according to claim 1, it is characterised in that described two grades
Granular biological carrier (20) is added in aerobic biochemical pool (19), carrier packing ratio is Χ2。
6. the processing method of high temperature and high salt difficult degradation oil extraction waste water according to claim 1, it is characterised in that described two grades
For organic constituentses in the stage waste water in aerobic biochemical pool (19), corresponding high-effective microorganism microbial inoculum R is added2(21) it is, high
Effect microbial bacterial agent R2(21) add than for Y2。
7. the processing method of high temperature and high salt difficult degradation oil extraction waste water according to claim 1, is further characterized in that, leading portion one
The dissolved oxygen in relief area (14) water outlet in level ozone pre-oxidation pond (12) can meet microbial bacterial agent R2(21) oxygen demand,
Without the need for secondary aeration aerating, on granular biological carrier (20), length has microbial bacterial agent R2(21) biofilm detachment is updated by stirring
Mix device (22) realization.
8. the processing method of high temperature and high salt difficult degradation oil extraction waste water according to claim 1, it is characterised in that advanced oxidation
Ultraviolet lamp lighting device (29) and dosing mouth (30) are provided with the top of pond (28), oxidant medicine system (31) is by dosing mouth (30)
Related oxidized medicament is added in advanced oxidation pond (28), ozone is passed through by ozonator (15) needed for advanced oxidation pond (28)
Bottom titanium alloy aeration head (32) provides, supplied ozone tolerance q2, concentration C2, response time t2；Water after process is from advanced oxidation
Pond (28) bottom standard discharge or reuse.
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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 |
| 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 |
| CN113105063B (en) * | 2020-01-13 | 2023-07-04 | 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 |
| CN117706055B (en) * | 2024-02-06 | 2024-07-02 | 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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| CN1919756A (en) * | 2006-09-14 | 2007-02-28 | 天津市塘沽区鑫宇环保科技有限公司 | Processing method of collecting and displacing oil-field sewage and detritus sewage |
| CN101723539A (en) * | 2008-10-24 | 2010-06-09 | 周兆宇 | Method for treating or recycling waste water with high salt content and applications |
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| CN1919756A (en) * | 2006-09-14 | 2007-02-28 | 天津市塘沽区鑫宇环保科技有限公司 | Processing method of collecting and displacing oil-field sewage and detritus sewage |
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Effective date of registration: 20170810 Address after: 100083, Beijing, Haidian District learning Road 16, learning Hin room 2002 Patentee after: Beijing Zhi think Feng Technology Co. Ltd. Address before: 100044 Beijing city Haidian District Xizhimen Shangyuan Village No. 3 Patentee before: Beijing Jiaotong University |