CN101935615A - Composite bacterial agent and biological method for treating flow-back fracturing fluid to obtain oil displacement active water - Google Patents
Composite bacterial agent and biological method for treating flow-back fracturing fluid to obtain oil displacement active water Download PDFInfo
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Abstract
The invention discloses a composite bacterial agent and a biological method for treating flow-back fracturing fluid to obtain oil displacement active water, which relate to biotransformation and reutilization technology of fracturing flow-back fluid. In the method, the fracturing flow-back fluid is treated by a microbial fermentation method, and a residual organic substance harmful to environment in the flow-back fluid is transformed into biological active water with certain function. The composite bacterial agent and the method are applied to reinjection water of water injection wells, reinjection water for single-well soaking, reinjection water for oil field blockage removal, reinjection water for other purposes, water for medicament preparation in a technical process and the like. The composite bacterial agent comprises biosurfactant, organic acid, organic ester, organic ketone, biogas and other metabolites produced by microbial metabolism of the fracturing flow-back fluid.
Description
Technical field
The present invention relates to a kind of bio-transformation reutilization technology of fracturing outlet liquid.Its characteristics are to utilize the method for composite microbial fermentation that fracturing outlet liquid is handled, and residual environmentally harmful organic substance is converted into the bioactive water with certain function in the discharge opeing with returning, and its range of application is a water injection well re-injection water; Single well stimulation re-injection water; De-plugging of well re-injection water; Other use re-injection water; Medicament is prepared water etc. in the technical process.Its main component is: generation bio-surfactant, organic acid, organic ester, organic ketone and other meta-bolites of biogas that fracturing outlet liquid produces through microbial metabolism.
Background technology
Fracturing outlet liquid is very harmful to environment.Because its inherent pollutent composition is complicated and more stable, is difficult to be degraded under the effect of natural force (as oxygen).These chemical substances enter the normal operation that will seriously upset production system after the water treatment system, treatment effect as mass consumption water treatment agent or reduction water conditioner, influence the removal of oil and harmful ion in the water body, the sludge settling that influences in the water treatment procedure to be produced, severe contamination filtrate etc., and its most salinity is higher, contain objectionable impuritiess such as crude oil, polyose and phenols, water quality to the locality has considerable influence, thereby cause and handle back water quality and do not reach the injection water quality requirement, the production and the long term growth in oil field caused bigger loss.
Because oil-gas field production characteristics and borehole operation character have determined that the frac job wastewater flow rate is little, disperseed, can not focus on, can only handle on the spot and utilization again; In addition, because pressure break contains and contains organism such as a certain amount of suspended solid, oil and various tensio-active agents in the sugared waste liquid, make the composition and property of waste liquid extremely complicated, intractability is very big, the technical finesse cost that uses is high now, the sewage water treatment method of present various routines all can not be handled oil-gas field fracturing waste liquor economically, therefore must be in conjunction with composition and property, the characteristics of underground fracture operating feature and frac job waste liquid, in conjunction with the integrated demand in the oilfield development process, development research goes out the borehole operation waste liquid and efficiently handles new technology.
Summary of the invention
Purpose of the present invention is for providing a kind of composite fungus agent and application of handling fracturing outlet liquid, by COD, BOD in the composite microbial fermentation reduction fermented liquid of special formulation, deleterious larger molecular organics, irreducible oil, aromatic compounds are converted into the form that can utilize once more originally in the discharge opeing returning by its metabolism simultaneously.Its range of application: water injection well transfer drive re-injection water; De-plugging of well re-injection water; Other use re-injection water; Medicament is prepared water etc. in the technical process.
To achieve these goals, the present invention has taked physics pre-treatment-two kinds of method bonded of biological treatment technology to returning discharge opeing, comprises the steps:
1. the preparation of microbiobacterial agent: Rhodococcus equi BS001 (Rhodococcus equi.), Pseudomonas aeruginosa BS002 (Pseudomonas aeruginosa), the basket bacterium BP001 of rough thorn (Talaromycestrachyspermus), subtilis BS003 (Bacillus subtilis), bacillus cereus BC001 (Bacillus cereus), variotin BP002 (Paecilomyces sp.).Above Rhodococcus equi is to screen in the Daqing oil field crude oil pollution soil to obtain producing the tensio-active agent microorganism, and in China Committee for Culture Collection of Microorganisms's common micro-organisms center preservation, preserving number is CGMCC3885, and all the other bacterial strains are general bacterial strain.Prescription is (pressing dry weight basis): Rhodococcus equi BS001,30%～40%; Pseudomonas aeruginosa BS002,30%～40%; The basket bacterium BP001 of rough thorn, 15%～20%; Subtilis BS003,5%～10%; Bacillus cereus BC001,5%～10%; Variotin BP002,5%～10%.
Above bacterial strain rhodococcus screens from Daqing oil field and obtains producing the tensio-active agent microorganism, and in China Committee for Culture Collection of Microorganisms's common micro-organisms center preservation, preserving number is CGMCC3885, and all the other bacterial strains are general commonly used common bacterial strain.The polysaccharide growth that the bacterial classification that microbial inoculum adopts produces for utilizing breaking glue solution residue or broken glue can produce bio-surfactant class bacterial classification simultaneously.
2.1) bacterial strain can be used for handling fracturing outlet liquid (oil field fracturing outlet liquid main component is basic identical) after composite in the described composite fungus agent, the discharge opeing of returning after the processing can be used as bioactive water and is recycled into oil well or well, and it has certain oil-displacement capacity; Make fracturing outlet liquid have the recyclable performance of utilizing.
2) microbiobacterial agent fermented liquid preparation process is as follows:
Preparation seed liquor substratum: peptone, 10g/L; Yeast powder, 5g/L; NaCl, 5g/L; Molasses, 1% (volume ratio); KH
2PO
4, 3g/L; K
2HPO
4, 1.5g/L; Nature pH; 115 ℃ of 15min that sterilize down; Insert composite good microbiobacterial agent, the volume inoculum size is that 1～5%, 30～37 ℃ of following 150rpm shaking tables are cultivated 24h, gets seed liquor;
Configuration fermention medium: guar gum breaking glue solution monose (hundred mans of great strength, 160 enzymes break glue) 5g; NH
4NO
3, 2.0g; K
2HPO
43H
2O, 3.0g; NaH
2PO
42H
2O, 10g; MgSO
47H
2O, 0.2g; MnCl
24H
2O, 2ppm; Yeast extract paste 0.2g; Transfer pH=7.0 with NaOH solution; Insert seed liquor by 1～5% volume inoculum size, 30～37 ℃ of fermentation culture 24-36h get fermented liquid.
3. utilize composite bacteria fermentation liquid to handle fracturing outlet liquid:
Fracturing outlet liquid at first leaves standstill the 24h sedimentation and filtration, removes and returns particulate contamination in the discharge opeing; Add acid-base modifier as required and adjust its pH value between the 5.0-9.0; Add composite good microbiobacterial agent fermented liquid, add-on is 1～5kg/m
3, aeration is handled, and aeration rate is 25L/h, hydraulic detention time 24-96h; The centrifugal thalline of removing of fermented liquid, supernatant liquor is bioactive water;
Wherein acid-base modifier is K
2HPO
4With KH
2PO
4Regulate the processing requirement of returning discharge opeing pH value to reach, provide enough K, P elements for its recycling simultaneously, concrete add-on changes to some extent according to the initial pH value difference of returning discharge opeing, regulating the final pH value is between the 5.0-9.0, to satisfy the growth requirement of most of bacterial strains in the composite microbiobacterial agent.
Fracturing outlet liquid is removed and is returned the nutrition source that adds strain growth necessity in the discharge opeing after the particulate contamination simultaneously according to following dosage: contain in every 1000mL water: NH
4NO
31.0-4.0g, K
2HPO
43H
2O3-5g, NaH
2PO
42H
2O 7-15g, MgSO
47H
2O 0.1-0.3g, MnCl
24H
2O 1-10ppm.
The bioactive water that is obtained can be used as oil field re-injection water and injects oil reservoir, and its low surface tension can effectively be peeled off difficult moving crude oil in the reservoir; Improve the interfacial tension between crude oil-water-rock, improve degree of rock wettability, make the easy extraction of crude oil; Be rich in simultaneously elements such as nitrogen that microorganism growth needs, phosphorus in the active water, can effectively activate indigenous microorganism in the oil reservoir, make its a large amount of breedings, produce surface-active substance, biogas etc., comprehensively reach the purpose that improves oil recovery factor.
The present invention has following advantage:
1. the entire treatment process is used is biotechnological formulation and a spot of small molecules chemotrophy source, environmental protection, the macromolecular chemistry additive of no environment difficulty self degradation, compound oil field HSE standard.
2. solved the handling problem of fracturing outlet liquid, made it to change the bioactive water that can reuse displacement of reservoir oil effect into from environmentally harmful sewage, turned waste into wealth, reached the recycling of resource, efficient, low-carbon (LC), environmental protection have huge economic benefit.
3. bacterial strain is handled the efficient of returning discharge opeing and is improved greatly through after composite, and more single thalline is handled and effectively shortened hydraulic detention time, thereby reduces aeration rate, the consumption of save energy; Owing to be composite microbial inoculum, strengthen the ability of its processing simultaneously, made it the original state of returning discharge opeing is required to reduce, enlarged its use range.
Description of drawings
Fig. 1 bio-surfactant high performance liquid phase spectrogram;
The relation of Fig. 2 bacterial strain polysaccharide yield and growth curve, viscosity;
Rhodococcus equi BS001, classification name: Rhodococcus equi Rhodococcus equi., be preserved in China Committee for Culture Collection of Microorganisms common micro-organisms center, address: No. 3 Institute of Microorganism, Academia Sinica in Yard 1, BeiChen xi Road, Chaoyang District, Beijing City, deposit number: CGMCC No3885, preservation date on 06 01st, 2010.
Embodiment
Embodiment 1: microbiobacterial agent composite
The bacterium that grows in the oil-well strata water is carried out enrichment culture, afterwards through the line of LB agar plate, cultivated 16 hours for 37 ℃, the single bacterium colony of picking through screening, obtains a kind of bacterial strain, through being accredited as Rhodococcus equi, is numbered BS001;
Get known commercial bacterial strain simultaneously: with Pseudomonas aeruginosa, the basket bacterium of rough thorn, subtilis, bacillus cereus, variotin are numbered BS002, BP001, BS003, BC001, BP002 respectively.
Configuration seed liquor substratum, filling a prescription is: peptone, 10g/L; Yeast powder, 5g/L; NaCl, 5g/L; Molasses, 1% (volume ratio); KH
2PO
4, 3g/L; K
2HPO
4, 1.5g/L; Nature pH.115 ℃ of 15min that sterilize down.Liquid amount is that liquid amount 100mL/250mL bottle is long-pending, in every bottle respectively the above-mentioned 6 kinds of bacterial strain list bacterium colony constant temperature shaking speed of picking be 150rpm, temperature is 30-37 ℃, cultivate after 24～48 hours, 1: 1 adding 70% glycerine, lyophilize is powdered.
Each bacterial strain is composite according to prescription, and specific practice is: take by weighing above bacterial strain lyophilized powder: Rhodococcus equi BS001,30g; Pseudomonas aeruginosa BS002,30g; The basket bacterium BP001 of rough thorn, 15g; Subtilis BS003,5g; Bacillus cereus BC001,10g; Variotin BP002,10g is mixing in beaker, packing.
Embodiment 2: composite microbial inoculum produces the checking of thing tensio-active agent
The measurement of surface tension of fermented liquid is the JYW-200 full automatic watch/interfacial tensimeter that detects company limited with the prosperous trier in Chengde, at room temperature measures the surface tension of fermented liquid, measures triplicate at every turn, averages.Capillary concrete operations are: get the centrifugal 10min of 30mL fermented liquid 8000rpm, get supernatant liquor in measuring cup, measure surface tension with the platinum ring.
Liquid fermentation medium following (by weight):
Guar gum breaking glue solution monose ['beta '-mannase, hundred Tai Gang difficult to understand (Dalian) bio tech ltds] 5g, NH
4NO
32.0g, K
2HPO
43H
2O 3.0g, NaH
2PO
42H
2O 10g, MgSO
47H
2O0.2g, MnCl
24H
2O 2ppm, yeast extract paste 0.2g transfers pH=7.0 with NaOH solution.
Above-mentioned cultivation specifically consists of: peptone, 10g/L by the seed liquor of composite microbial inoculum in the step 2 of inoculum size 5% (V/V) access summary of the invention; Yeast powder, 5g/L; NaCl, 5g/L; Molasses, 1% (volume ratio); KH
2PO
4, 3g/L; K
2HPO
4, 1.5g/L, liquid amount 100mL/250mL bottle is long-pending, and 150rpm, cultivates 48h by 30～37 ℃; Through 8000rpm, after centrifugal 10 minutes, remove bacterial sediment, obtain supernatant liquor.
To not insert microbial inoculum in contrast simultaneously, only insert single microbial inoculum BS001, BS003, BS003 respectively as a reference, operate by said process;
Each 1000mL of the supernatant liquor of above-mentioned substratum after the lyophilize, uses methyl alcohol Hui Rong, discards insolubles; With the Rotary Evaporators evaporation, get the yellow-green colour viscous liquid; NaHCO with 0.05mol/mL
3The solution dissolving adds HCl and regulates pH value to 2.0, and solution becomes pale brown look suspension liquid; After 4 ℃ of placements are spent the night, centrifugal abandoning supernatant, precipitation methyl alcohol extracting obtains primary extract.
Each primary extract sample of above-mentioned acquisition, be made into 10 μ M solution, measure its surface tension, dilute 10 times, 25 times, 50 times, 100 times, 200 times, 400 times of surface tension value of measuring different concns solution, determine the curved line relation between surface tension and the concentration, the CMC value of determining this surfactant is 15 μ g/mL.
Detect the tensio-active agent that is extracted, result such as Fig. 1 with high performance liquid chromatography simultaneously
As can be seen from the above table, the minimum 28.84mN/m that reaches of the fermented liquid surface tension of composite microbial inoculum injects oil well as re-injection water and can effectively reduce surface and interface tension force between the profit, makes the easier extraction of crude oil, reaches the purpose of volume increase.
Embodiment 3: bacterial strain utilizes breaking glue solution to produce the checking of thing polymkeric substance
The present invention has carried out surfactivity and sugar degree experiment thereof for the bioactive water of preparation; Substratum screening is that surface tension value with fermented liquid is as screening index.
Liquid fermentation medium following (by weight):
Guar gum breaking glue solution monose ['beta '-mannase, hundred Tai Gang difficult to understand (Dalian) bio tech ltds] 5g, NH
4NO
32.0g, K
2HPO
43H
2O 3.0g, NaH
2PO
42H
2O 10g, MgSO
47H
2O0.2g, MnCl
24H
2O 2ppm, yeast extract paste 0.2g transfer pH=7.0 with NaOH solution.
Above-mentioned cultivation specifically consists of: peptone, 10g/L by the seed liquor of composite microbial inoculum in inoculum size 5% (V/V) the access summary of the invention step 2; Yeast powder, 5g/L; NaCl, 5g/L; Molasses, 1% (volume ratio); KH
2PO
4, 3g/L; K
2HPO
4, 1.5g/L, liquid amount 100mL/250mL bottle is long-pending, 150rpm, 37 ℃, to cultivate 30 hours, dull and stereotyped dilution coating method is measured colony number.
Through 8000rpm, behind the centrifugal 10min, remove bacterial sediment, obtain supernatant liquor, product formula viscometer determining viscosity; The phenol sulfuric acid process is measured polymer output.
As shown in Figure 2, produce the large number of biological polymkeric substance in the thalli growth process, its output reaches 18mg/mL stationary phase to growing.Fracturing outlet liquid is rich in biological polymer after composite fungus agent is handled, can be used as re-injection water and inject, and plays the effect that activates indigenous microorganism, reaches the purpose of volume increase.
Embodiment 4: the application 1-of composite fungus agent returns discharge opeing and handles the bioactive water re-injection that obtains through composite microbial inoculum and carry out water filling and drive
Utilization is returned bioactive water re-injection that discharge opeing handles and is carried out water filling and drive in the following manner and realize:
Carry out the water drive experiment in the Liaohe Oil Field on August 29th, 2009, replace traditional water drive water to carry out water drive with bioactive water.Concrete technology is as follows:
1) oil pick-up tube and oil pump are taken out, well-flushing: pump truck pumps into about 20m
3Clear water.
2) pump into bioactive water: pump truck pumps into 5m
3Bioactive water.
3) pump into 2m
3Clear water is as displacing liquid.
The normal operation that drives a well after 2～3 days of vexed well.Well recovery condition of production contrast in 60 days is as follows:
Shown by above-mentioned single well stimulation experimental data: daily oil production can reach 2 times more than.Because active water is rich in materials such as bio-surfactant, organic acid, organic ketone, biogas, is injected in the oil well as water drive, effectively changes down-hole rock-water-oil meter interfacial tension, the moving crude oil of the difficulty in the rock crevice is peeled off out.The double of output shows that this invention increase oil recovery effect is very obvious.
Embodiment 5: tensio-active agent polysorbate60, polymer poly acrylamide that the application 2-bioactive water of composite fungus agent adds external source carry out transfer drive
Bioactive water adds external source tensio-active agent polysorbate60, the polymer poly acrylamide carries out transfer drive and realizes in the following manner:
Whole transfer drive technology is divided into four sections:
1) injection of spearhead: volume accounts for total injection rate about 15～20% and is spearhead, uses bioactive water to add tensio-active agent and strengthens the displacement of reservoir oil, makes difficult moving viscous crude peel off rock, and is fully emulsified.
2) slug injects before the biological polymer: volume accounts for total injection rate about 40～50%, use the biological polymer of bioactive water preparation, inject stratum chance highly mineralized formation brines and become after the glue, form slug, the water string of the high infiltration of shutoff drives, and reaches the purpose of profile control and water plugging.
3) slug injects behind the biological polymer: it is about 20～30% that volume accounts for total injection rate, uses the chemical superpolymer of bioactive water preparation, injects the stratum and form the high strength slug, and the water string of the high infiltration of shutoff drives, and reaches the purpose of profile control and water plugging.
4) injection of displacing liquid: it is about 10% that volume accounts for total injection rate, and using the pure water compound concentration is 5% biological activity water diluent, injects pit shaft.
Its construction results is as follows:
Show that by above-mentioned water injection well transfer drive experimental data daily oil production can reach 2～3 times more than.Adopt bioactive water of the present invention and external source tensio-active agent and polymkeric substance coupling to be used for the water injection well transfer drive, can effectively improve the test pit produce oil and imitate.As seen this invention increase oil recovery effect is very obvious.
Above-mentioned oil field compression fracture returns discharge opeing and handles composite microbial inoculum and using method and the bioactive water that is obtained, and can be used as the oil field and uses with oily water treatment and environment remediation technology; The bioactive water of gained can be used as re-injection water and injects oil well, and its low surface and interface tension force and micromolecular carbohydrate have bioavailability, behind new injection stratum, have drag reduction, viscosity reduction, wetting, the big area displacement of reservoir oil in rock stratum, improves the function of recovery ratio.
Claims (6)
1. composite fungus agent is characterized in that:
Press dry weight basis, filling a prescription is: Rhodococcus equi BS001,30%～40%; Pseudomonas aeruginosa BS002,30%～40%; The basket bacterium BP001 of rough thorn, 15%～20%; Subtilis BS003,5%～10%; Bacillus cereus BC001,5%～10%; Variotin BP002,5%～10%;
In the above bacterial strain, rhodococcus obtains from the Daqing oil field screening, and it is for can produce the tensio-active agent microorganism, in China Committee for Culture Collection of Microorganisms's common micro-organisms center preservation, preserving number is CGMCC 3885, and all the other bacterial strains are general commonly used common bacterial strain.
2. handling the row's of returning fracturing liquid according to the described composite fungus agent of claim 1 is the biological method of displacement of reservoir oil active water, it is characterized in that: can be used to handle fracturing outlet liquid after bacterial strain is composite, the discharge opeing of returning after the processing can be used as bioactive water and is recycled into oil well or well, and it has certain oil-displacement capacity; Make fracturing outlet liquid have the recyclable performance of utilizing.
3. biological method according to claim 2 is characterized in that: fracturing outlet liquid at first leaves standstill the 24h sedimentation and filtration, removes and returns particulate contamination in the discharge opeing; Add acid-base modifier as required and adjust its pH value between the 5.0-9.0; Add composite good microbiobacterial agent fermented liquid, add-on is 1～5kg/m
3Fracturing outlet liquid, aeration is handled, and aeration rate is 25L/h, hydraulic detention time 24-96h; The centrifugal thalline of removing of fermented liquid, supernatant liquor is bioactive water;
Wherein acid-base modifier is K
2HPO
4With KH
2PO
4Regulate the processing requirement of returning discharge opeing pH value to reach, provide enough K, P elements for its recycling simultaneously, concrete add-on changes to some extent according to the initial pH value difference of returning discharge opeing, regulating the final pH value is between the 5.0-9.0, to satisfy the growth requirement of most of bacterial strains in the composite microbiobacterial agent.
4. biological method according to claim 3 is characterized in that: the bioactive water that it obtained can be used as oil field re-injection water and injects oil reservoir, and its low surface tension can effectively be peeled off difficult moving crude oil in the reservoir; Improve the interfacial tension between crude oil-water-rock, improve the rock stratum degree of wetting, make the easy extraction of crude oil; Be rich in simultaneously elements such as nitrogen that microorganism growth needs, phosphorus in the active water, can effectively activate indigenous microorganism in the oil reservoir, make its a large amount of breedings, produce surface-active substance, biogas etc., comprehensively reach the purpose that improves oil recovery factor.
5. biological method according to claim 3 is characterized in that:
Described microbiobacterial agent fermented liquid preparation process is as follows:
1) preparation seed liquor substratum: peptone, 10g/L; Yeast powder, 5g/L; NaCl, 5g/L; Molasses, 1% (volume ratio); KH
2PO
4, 3g/L; K
2HPO
4, 1.5g/L; Nature pH; 115 ℃ of 15min that sterilize down; Insert the described composite fungus agent of claim 1, the volume inoculum size is 1-5%, and 30-37 ℃ of following 150rpm shaking table cultivated 24h, gets seed liquor;
2) configuration fermention medium: guar gum breaking glue solution monose (hundred mans of great strength, 160 enzymes break glue) 5g; NH
4NO
3, 2.0g; K
2HPO
43H
2O, 3.0g; NaH
2PO
42H
2O, 10g; MgSO
47H
2O, 0.2g; MnCl
24H
2O, 2ppm; Yeast extract paste 0.2g; Transfer pH=7.0 with NaOH solution; Insert seed liquor by 1～5% volume inoculum size, 30～37 ℃ of fermentation culture 24-36h get fermented liquid.
6. biological method according to claim 3 is characterized in that: fracturing outlet liquid is removed and is returned the nutrition source that adds strain growth necessity in the discharge opeing after the particulate contamination simultaneously according to following dosage: add in every 1000mL water: NH
4NO
31.0-4.0g, K
2HPO
43H
2O 3-5g, NaH
2PO
42H
2O7-15g, MgSO
47H
2O 0.1-0.3g, MnCl
24H
2O 1-10ppm.
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