CN105110480A - Advanced treatment technology of high-salt-content degradation-resistant oil extraction sewage - Google Patents
Advanced treatment technology of high-salt-content degradation-resistant oil extraction sewage Download PDFInfo
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Abstract
The invention discloses a salt-tolerant Brevibacillus brevis and an application of complex microorganisms thereof in advanced treatment of high salt content degradation-resistant oil extraction sewage. The salt-tolerant Brevibacillus brevis is reserved in China General Microbiological Culture Collection Center, CGMCC for short, and the preservation number is CGMCC No.2148. The bacillus can bear high salinity which reaches 70000ppm, and has a wide applicable temperature range. The Brevibacillus brevis has a high COD degradation rate for petroleum hydrocarbon and salt-containing and oil-containing degradation-resistant sewage, and at 25-45 DEG C, the COD degradation rate for high salt content sewage (whose mineralization is higher than 30000ppm) reaches 60%. Brevibacillus brevis, Bacillus subtilis (registration number KC109003.1), Bacillus circulans Jordan (registration number JX893033.1), Bacillus amyloliquefaciens (registration number JX997921.1), Pseudomonas stutzeri (registration number KC113178.1) and Pseudomonas mendocina Marinobacter (registration number EU43329.1) compose complex microorganisms. A synergism is provided for high efficiency degradation of high salt content and oil containing degradation-resistant oil extraction sewage; the COD of incoming water is lower than 350ppm, and the COD of the discharged water after treatment is lower than 60ppm.
Description
Technical field:
The present invention relates to the application of compound salt tolerant bacillus group in high saliferous oily(waste)water advanced treatment of efficient degradation petroleum hydrocarbon.
Background technology:
In oil production process, the crude oil of extraction contains a large amount of moisture, and generally water ratio is up to more than 50%, and in the oil field in waterflooding later stage, extraction crude oil water containing is up to 95%.Oil extraction waste water is mainly extracted with crude oil, the waste water deviate from after gas-oil separation and processed.Secondly a large amount of waste water all constantly discharged by various devices such as electric desalting, the distillation tower etc. of crude refining.Oil extraction waste water have passed through the whole process of crude oil collection and preliminary working, and the impurity component in waste water and oil field character, oil bearing formation property, crude oil collection technology, Crude Oil Transportation condition etc. are closely related.
In recent years, along with Economic development is to the continuous growth of petroleum demand amount, petroleum exploration and development activity increases increasingly, and oil extraction waste water, except re-injection, is arranged outside some, but the general compliance rate of outer row's process is not high.And in recent years, environmental requirement externally discharged waste water reaches national grade one discharge standard.Therefore oil and gas industry also creates serious problem of environmental pollution while providing a large amount of clean energy and industrial chemicals.How effectively to administer exploitation and to use the environmental pollution caused in oil process, to have become the difficult problem that countries in the world face.
Oil extraction waste water except containing except complicated petroleum hydrocarbon, also containing high molecular weight polymer additive as polyacrylamide etc., chemical surfactant as emulsion splitter, wetting agent, viscosity-depression agent, water flood treatment additive as flocculation agent, sterilant, sustained release dosages etc., therefore form very complicated, intractability is very large.
Oil extraction waste water mainly adopts physico-chemical process process in early days, but process more complicated, and effluent quality is unstable, and running cost is high, and management difficulty is large, and there is the risk of secondary environmental pollution.Therefore the bioremediation of Environmental Safety is gradually adopted in recent years.
Biological treatment is the metabolism utilizing microorganism, makes to be converted into stable innoxious substance in the organic pollutant of dissolving, colloidal state in waste water.Main point Aerobic biological process and anaerobic biological treatment two kinds, and develop kinds of processes.It is low that Biochemical method oil extraction waste water has operation energy consumption, do not need in operational process to add chemical reagent, secondary pollution can not be caused to water body and surrounding environment, degradation of organic substances is thorough, final degraded product is water and carbonic acid gas, the advantages such as stable effluent quality are one of good methods of the development prospect of oil extraction waste water process from now on.Chinese patent CN102173503B discloses a kind of oil extraction-generated waste water biochemical treatment system rapid biofilm and starts technique.Earth's surface clear water is first carried out pre-hung film by this invention, and then pass into oil field oil-containing saline sewage and carry out biofilm, and select genus bacillus to be oil removing microbial inoculum, by biological reinforced dose that is made up of rapeseed cake and wheat bran and Inorganic phosphate ammonium salt, strengthen the tolerance level of microorganism to salinity and other biostats, effectively can improve microbic activity.In biochemical start-up course, improve salinity and microorganism salt tolerance and biological activity gradually, strengthen the adhesive ability of microorganism on filler, reach the object that oil-salts containing sewerage biological treatment system rapid biofilm starts.Result shows, this technique more conventional biofilm time shorten 60%, and oil removal efficiency reaches 98%, and stable water outlet.But biofilm process is very complicated, biological reinforced dose of consumption is large, long processing period.
Chinese patent CN102372403B discloses a kind of low permeability oil field oily(waste)water biochemical treatment process method.The method of this invention, first carries out aeration pre-treatment, and removing is containing the sulfide in sewage; Enter bio-contact oxidation system again, oily(waste)water Crude Oil is degraded; Bio-contact oxidation system comprises at least Two-Stage Biochemical pond of series connection, arranges hydrophilic composite filler, be provided with air aeration device at the bottom of the pond of biochemistry pool in biochemistry pool; Throw in initial start stage in biochemistry pool and have oil removing microbial inoculum, described oil removing microbial inoculum
By bacillus brevis (B.brevis), bacillus natto (B.natto), Bacillus licheniformis (B.lincheniformis),
The dry bacteria that bacillus cereus (B.cereus) forms, its mass ratio is 1: (0.9 ~ 1.1): (0.9 ~ 1.1): (0.9-1.1); Drop into biological reinforced dose that is made up of rapeseed cake, Semen Maydis powder, inorganic phosphate and inorganic ammonium salt with described oil removing microbial inoculum, rapeseed cake consumption is 0.2 ~ 0.4% of pond water weight, and Semen Maydis powder consumption is 0.1 ~ 0.2% of pond quality simultaneously.Then by extracellular polymeric and other bio-degradable organic efficient aeration settlement treatment: carry out extracellular polymeric and other bio-degradable organic efficient aeration settlement treatment again, enter water injection tank finally by after the process of ultrafiltration membrance filter system.The feature of the inventive method is that system sludge amount is little, film import sewage with oil is few, and Pollution of Ultrafiltration Membrane is little, and membrane flux is stable, the ultra-filtration membrane matting cycle is long, and system outlet water quality reaches low permeability oil field A level water quality standard.Oily(waste)water after this patented method process, can reach following effect: when import oil-containing≤200mg/L, COD≤400mg/L, BOD≤200mg/L, outlet oil-containing 0 ~ 2mg/L, COD≤100mg/L, BOD≤30mg/L.This patent is disposed of sewage for reinjection into reservoir, and treating processes is more complicated, and biological reinforced dose of consumption is large, and ultra-filtration membrane needs routine cleaning.
To the high salinity difficult degradation oil extraction waste water subject matter faced of carrying out a biological disposal upon be:
1. microorganism adaptedness is limited: conventional cultivation can not be used for effectively processing the waste water that saltiness is greater than 3 ~ 5%.Meanwhile, when being subject to without the affecting of salt medium, the salt adaptation of cultivation is easy to lose.
2. microorganism is sensitive to ionic strength reacting condition: the sharply change of salt concn between 0.5 ~ 2% can cause the destruction of biological treatment system.Even the operation after cultivating domestication also requires constant ion composition.Sharply changing the negative impact of biological treatment system of salt concn is more much bigger than slowly changing.
3. biological degradation is obvious by Effects of Salinity.The biological degradation rate of organic constituent declines along with the increase of salt concn.Therefore, brine waste should process under lower F/M (organic loading rate) condition.
4. sludge settling efficiency is low: the salt component in waste water can reduce the quantity of protozoon and filamentous bacterium, causes low sludge settling efficiency.
Therefore, bacteria agent and the further treatment technique thereof of the high saliferous difficult degradation oil extraction waste water of research and development is badly in need of.
Summary of the invention:
There is the compound Brevibacillus brevis group of efficient alkane degradation function, for the advanced treatment of high salinity oil extraction waste water under the object of this invention is to provide a kind of high salinity.
Object of the present invention is achieved through the following technical solutions:
One strain salt tolerant Brevibacillus brevis (Brevibacillusbrevis.) and composite flora thereof are applied in high saliferous difficult degradation oil extraction-generated waste water advanced treatment, this salt tolerant Brevibacillus brevis is by China Committee for Culture Collection of Microorganisms's common micro-organisms center preservation (referred to as CGMCC), address is Datun Road, Chaoyang District, Beijing City Institute of Microorganism, Academia Sinica, deposit number is CGMCCNo.2148, and the preservation time is on September 3rd, 2007.
The advanced treatment of high salinity difficult degradation oil extraction waste water, it is characterized in that, efficient degradation flora is salt tolerant Brevibacillus brevis (Brevibacillusbrevis.) and Bacillus subtillis (accession number KC109003.1), Bacillus circulans (accession number JX893033.1), bacillus amyloliquefaciens (accession number JX997921.1), Pseudomonas stutzeri (accession number KC113178.1), and pseudomonas mendocina sea bacillus (accession number EU043329.1) compound use, the high saliferous difficult degradation oil extraction-generated waste water of synergy degraded.
The salt tolerant Brevibacillus brevis under medium temperature condition with efficient degradation petroleum hydrocarbon and high salt oil production waste water COD thereof has following characteristics:
This bacterium bacterium colony is all rounded, rat, and oyster white, smooth surface is moistening.This bacterium is elongated rod shape, produces gemma, and gemma end is raw to be expanded.Gramstaining is all negative.Indole reaction is positive, and has growth in 0.5mol/lNaCl; Catalase is positive, oxidase negative.This bacterium is accredited as Brevibacillusbrevis through 16SrDNA, Brevibacillus brevis, and its gene order is as follows:
GCATGCCTGCAGGTCGACGATTGGTTACCTTGTTACGACTTCACCCCAGTCATCTACCCCACCTTCGGC
GGCTGGCTCCTTGCGGTTACCTCACCGACTTCGGGTGTTGCAAACTCCCGTGGTGTGACGGGCGGTGTG
TACAAGGCCCGGGAACGTATTCACCGCGGCATGCTGATCCGCGATTACTAGCGATTCCGACTTCATGTA
GGCGAGTTGCAGCCTACAATCCGAACTGAGATTGGTTTTAAGAGATTGGCGTCCTCTCGCGAGGTAGCA
TCCCGTTGTACCAACCATTGTAGCACGTGTGTAGCCCAGGTCATAAGGGGCATGATGATTTGACGTCAT
CCCCGCCTTCCTCCGTCTTGTCGACGGCAGTCTCTCTAGAGTGCCCAACTGAATGCTGGCAACTAAAGA
TAAGGGTTGCGCTCGTTGCGGGACTTAACCCAACATCTCACGACACGAGCTGACGACAACCATGCACCA
CCTGTCACCGCTGCCCCGAAGGGAAGCTCTGTCTCCAGAGCGGTCAGCGGGATGTCAAGACCTGGTAAG
GTTCTTCGCGTTGCTTCGAATTAAACCACATGCTCCACCGCTTGTGCGGGCCCCCGTCAATTCCTTTGA
GTTTCACTCTTGCGAGCGTACTCCCCAGGCGGAGTGCTTATTGCGTTAGCTGCGGCACTGAGGGTATTG
AAACCCCCAACACCTAGCACTCATCGTTTACGGCGTGGACTACCAGGGTATCTAATCCTGTTTGCTCCC
CACGCTTTCGCGCCTCAGCGTCAGTTACAGACCAGAAAGCCGCCTTCGCCACTGGTGTCCTCACATCTC
TACGCATTTCACCGCTACACGTGAATACCGCTTTCCTCTCTGCACTCAGCTACACAGTTTCGATGCGAA
CCGGGGTTGAGCCCGGGCTTAACACCAGACTTACATAGGCG
This bacterium energy decomposing petroleum hydrocarbon biosurfactant production, oil extraction loop diameter is respectively 4.8cm, and zone of hemolysis diameter is 6.0cm.This Brevibacillus brevis shows through performance test, and tolerance salinity reaches 70000ppm, temperature range 20-50 degree, and petroleum hydrocarbon degradation rate after 4 days of cultivating reaches 70%.
Have with the bacterium of Brevibacillus brevis Combined Processing height saliferous difficult degradation oil extraction waste water, the subtilis of salt tolerant is (with BacillussubtilisstrainRR-1, accession number KC109003.1 homology 100%), Bacillus circulans (BacilluscirculansstrainSD16, accession number JX893033.1 homology 100%), bacillus amyloliquefaciens is (with BacillusamyloliquefaciensstrainLZBA-Y1-3, accession number JX997921.1 homology 100%), Pseudomonas stutzeri (PseudomonasstutzeristrainKSI34 accession number KC113178.1 homology 100%), and pseudomonas mendocina (PseudomonasmendocinastrainPASS3-bpib accession number EU043329.1 homology 100%).These bacterium can decomposing petroleum hydrocarbon and other organic high molecular compound, is the major function bacterium of sewage disposal.Wherein subtilis is applied quite extensive in sewage disposal, is a kind of multi-functional microorganism; Bacillus circulans and bacillus amyloliquefaciens can produce multiple enzyme, degradation of organic substances, can also produce thing surfactant and antiseptic-germicide; Bacillus amyloliquefaciens is the function yeast of degradable carbon hydrate and intermediate product, plays a significant role in sewage disposal; Pseudomonas stutzeri and pseudomonas mendocina are a kind of energy multiple organic high molecular compound of degraded and the beneficial functions bacterium of biosurfactant production, are the major function bacterium of sewage disposal, distributed more widely, are suitable for high-salinity produced wastewater environmental facies.
Accompanying drawing illustrates:
Fig. 1 is certain Oil Field high salinity oil extraction Sewage advanced treatment schematic flow sheet.
Fig. 2 is water sample contrast photo before and after the biological reinforced Air Exposure in certain Oil Field high salinity oil extraction waste water SBR pond.
Embodiment:
Below in conjunction with specific embodiment, concrete further detailed description in detail is done to the present invention, but embodiments of the present invention are not limited thereto, and for the processing parameter do not indicated especially, can refer to routine techniques and carry out.
The seed selection of bacterial classification:
1. in, temperature is aerobic falls the screening that COD Brevibacillus brevis bacterial strain falls in hydrocarbon
1.1 isolation medium
1) enrichment medium (g/l): NaNO
32.0, Na
2hPO
412H
2o2.0, KH
2pO
40.6, MgSO
47H
2o0.25, yeast extract paste 2.0, CaCL
22H
2o0.06, NaCl30, pH7.5, carbon source is whiteruss 0.2%.
2) blood agar substratum (blood agar is bought from commercial company).
3) slant medium (g/L): extractum carnis 5.0, peptone 10.0, NaCl5.0, pH7.0.Sieve Shake flask medium again: identical with enrichment medium.
1.2 bacterial strain screening and cultural method
1) enrichment culture, by oil field mining liquid sample by 5% inoculum size access respectively in enrichment medium, 167rpm/min, at 37 DEG C in convolution shaking table cultivate 4d.
2) oil extraction circle sieve method, the distilled water adding 60ml in a glass dish (D=9cm) then adds the whiteruss of 8ml, the enrichment culture liquid removing thalline entering 1ml after on the water surface on its surface is uniformly distributed in until whiteruss, if produce oil extraction circle, then prove to there is biological surfactant in nutrient solution, otherwise then prove lifeless matter surfactant in this nutrient solution.
3) blood agar method, utilize biological table and promoting agent can the characteristic of haemolysis, the line of enrichment culture liquid and coating separation method that produce oil extraction circle are inoculated on blood agar, 37 DEG C of cultivation 24 ~ 48h, select on the large and transparent single colony inoculation inclined-plane of haemolysis circle, for further study.
4) slant culture, by bacterial strain after primary dcreening operation purifying after inclined-plane line, cultivates 24h, 4C Refrigerator store, for sieving again further for 37 DEG C.
5) sieve shake-flask culture again, will be inoculated in Shake flask medium after the bacterial strain activation culture of primary dcreening operation, 167rpm/min, 37 DEG C of shaking culture 4d, after fermented liquid is centrifugal, carry out multiple sieve and surface-active mensuration.
2. the seed selection of composite bacteria
With method separation screening subtilis (Bacillussubtilisstrain), Bacillus circulans (Bacilluscirculansstrain), bacillus amyloliquefaciens (Bacillusamyloliquefaciensstrain), Pseudomonas stutzeri (PseudomonasstutzeristrainKSI34), and pseudomonas mendocina (PseudomonasmendocinastrainPASS3-bpib).
Embodiment 1: certain Oil Field high-salinity produced wastewater advanced treatment:
High reactivity degraded COD bacterial classification-W2, W5,2D1 and 3D1 is added at aerobic aeration activated sludge tank, obtain the high-concentration bacterial liquid of 108CFU/ml, then 1# and 2#SBR (sequencingbatchreactor) treating pond is added to, and add carbon source sodium acetate, nitrogenous source and phosphorus source primary ammonium phosphate, C/N is than 5: 1, sodium acetate final concentration 100ppm, to improve 1# and 2#SBR treatment effect.From 2013/6/1 to 2013/6/10, the degraded COD bacterium liquid adding total 4.8 tons totally for four times, to 1# and 2#SBR pond, adds 0.6 ton respectively at every turn, added once every three days; 1# and 2#SBR degraded COD result shows, during import water sample COD≤350mg/L, the COD of outlet water sample is lower than 60mg/L; Import water sample COD scope is at 350mg/L-400mg/L, and the COD of outlet water sample is lower than 100mg/L.
Embodiment 2:
High concentration COD (being greater than 350mg/l) oil extraction waste water, after the process of SBR pond, exports outer draining COD at about 100mg/l, does not reach national grade one discharge standard.Get COD and pour shaking flask into again in the outer draining of about 100mg/l, inoculate 1% compound salt tolerant Brevibacillus brevis degradation flora, 140r/min process 24 hours, COD can be reduced to 57.92mg/l.
Claims (7)
1. the further treatment technique of high saliferous oily(waste)water, it is characterized in that, described high efficiency flora is salt tolerant Brevibacillus brevis (Brevibacillusbrevis.) and Bacillus subtillis (accession number KC109003.1), Bacillus circulans (accession number JX893033.1), bacillus amyloliquefaciens (accession number JX997921.1), Pseudomonas stutzeri (accession number KC113178.1), and pseudomonas mendocina sea bacillus (accession number EU043329.1) compound use, the high saliferous difficult degradation oily(waste)water of synergy degraded.
2. salt tolerant Brevibacillus brevis (Brevibacillusbrevis.) according to claim 1, it is characterized in that, described salt tolerant Brevibacillus brevis, by the center preservation of China Committee for Culture Collection of Microorganisms's common micro-organisms, it is referred to as CGMCC, its deposit number is CGMCCNo.2148, and the preservation time is on September 5th, 2007.
3. salt tolerant Brevibacillus brevis and Bacillus subtillis according to claim 1, Bacillus circulans, bacillus amyloliquefaciens, Pseudomonas aeruginosa, the composite floras such as sea bacillus are in the application of the high saliferous difficult degradation oily(waste)water advanced treatment of process, and it is characterized in that, this compound Brevibacillus brevis group is inoculated in active sludge, Air Exposure, for high saliferous oily(waste)water efficient degradation petroleum hydrocarbon and degraded COD.
4. the application of compound salt tolerant Brevibacillus brevis group according to claim 3, is characterized in that, described compound salt tolerant Brevibacillus brevis group is used for the oily(waste)water advanced treatment of salinity at more than 30000ppm.
5. the application of salt tolerant Brevibacillus brevis group according to claim 3, is characterized in that, described compound Brevibacillus brevis group is used for the high salinity oily(waste)water advanced treatment of temperature 20-50 degree.
6. the application of compound salt tolerant Brevibacillus brevis group according to claim 3, it is characterized in that, described high saliferous difficult degradation oily(waste)water is oil field produced petroleum waste water, and oleaginousness 5-50ppm, COD are lower than 350ppm.
7. according to claim 6 compound salt tolerant Brevibacillus brevis group in the application of high salinity oily(waste)water advanced treatment, it is characterized in that, oleaginousness 5-50ppm, COD is lower than the difficult degradation oil extraction-generated waste water of 350ppm, through being inoculated in composite flora Air Exposure in active sludge 8 hours, water outlet oleaginousness lower than 60ppm, reaches national grade one discharge standard lower than 1ppm, COD.
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CN106929454A (en) * | 2017-04-12 | 2017-07-07 | 大连民族大学 | One plant of bacterial strain CS07 and its application with oil degradation and cohesion performance |
CN106929454B (en) * | 2017-04-12 | 2020-07-31 | 大连民族大学 | Strain CS07 with petroleum degradation and condensation performance and application thereof |
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