CN106893573A - A kind of biological fracturing fluid system and its preparation and application - Google Patents
A kind of biological fracturing fluid system and its preparation and application Download PDFInfo
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- CN106893573A CN106893573A CN201510953618.4A CN201510953618A CN106893573A CN 106893573 A CN106893573 A CN 106893573A CN 201510953618 A CN201510953618 A CN 201510953618A CN 106893573 A CN106893573 A CN 106893573A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
- C09K8/685—Compositions based on water or polar solvents containing organic compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/90—Compositions based on water or polar solvents containing organic compounds macromolecular compounds of natural origin, e.g. polysaccharides, cellulose
- C09K8/905—Biopolymers
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/24—Bacteria or enzyme containing gel breakers
Abstract
Fracturing fluid system of the present invention, specifically a kind of new bio fracturing fluid system suitable for unconventional gas reservoir exploitation.By weight, constitute and be：The 4g/L of plant xanthan polymer 2；The 2g/L of biological bactericide 0.02；The 0.5g/L of biological cleanup additive 0.25；The 30g/L of clay stabilizer 10；PH value regulator；The 30mg/L of enzyme breaker 10；Balance of water.The characteristics of present invention is for unconventional gas reservoir reservoirs such as coal bed gas, shale gas, compact sandstone gas, the advantage for making seam and anti-leak-off of gelled fracturing fluid can farthest be played, and make Gel Breakdown thorough as gel breaker using biology enzyme, level of residue is few, the hole that reservoir is natural or pressure break goes out will not be blocked, so as to ensure pressing crack construction effect, effective row of returning, formation damage is reduced, non-conventional gas well capacity is improved, is the ideal New Fracturing Fluid system for being applied to unconventional gas reservoir exploitation.
Description
Technical field
The present invention relates to hydraulic fracturing reconstruction of oil and gas pools technology Related product development field, more particularly to a kind of new bio fracturing fluid system and its preparation suitable for unconventional gas reservoir exploitation.
Background technology
Hydraulic fracturing renovation technique is a kind of effective method for increasing for exploiting low osmoticing oil-gas layer.The dominant mechanism that it is applied to the unconventional gas reservoir fracturing yield increasing such as coal bed gas, shale gas, compact sandstone gas is：By in the crack occurred after original during high drive current clamp-on reservoir and pressure break, widening and stretching these cracks, and then more secondary fractures and crack are produced in reservoir, increase the gas permeability of reservoir.Compared with that can increase 5-20 times before pressure break, effect highly significant is adopted in increasing to post-flush production.
At present, hydraulic fracturing modification measures are the Main Means of domestic and international coal bed gas well volume increase, and domestic nearly all gas production is in 1000m3Coal bed gas well above is all by fracturing reform.And shale gas and Methed of Tight Sandstone Gas Layers because its reservoir ultra-low penetration, natural production capacity is low the characteristics of be also required to fracturing reform and can just carry out commercialization exploitation.
There is the most frequently used guanidine gum fracturing fluid higher making to stitch efficiency, prop-carrying capacity, and anti-filtration capacity is strong, and most common application has been obtained in the reservoir reconstruction of oil gas field.But the features such as in face of typical leak-off high, low temperature or the high temperature such as coal seam, shale and tight sand, complicated and reservoir the absorption high in crack, hyposmosis, strata pressure high, so that often with numerous damage factors while fracturing reform, and fracturing fluid is primary to the nocuity of reservoir.It is not thorough with the broken glue of regular oxidation gel breaker (such as ammonium persulfate APS), crosslinked gel fracturing fluid is caused to form cull in filter cake and seam in crack wall surface, fracturing fluid is injured up to 50%~90% to reservoir permeability, and this greatly reduces advantage of the guanidine gum fracturing fluid in unconventional gas reservoir exploitation.And other fracturing fluids there is also the various deficiencies such as leak-off is big, price is high.In addition, the fracturing fluid system of routine is chemical assistant due to what is used, its breaking glue solution causes very big injury to reservoir and environment.Therefore, it is badly in need of with reference to the unconventional gas reservoir reservoir such as coal bed gas, shale gas, compact sandstone gas the characteristics of and its pressure break rule develops a kind of new fracturing fluid system.
The content of the invention
It is not thorough for the broken glue of existing gel-type water-based fracturing liquid system, it is also easy to produce cull and blocks the deficiencies such as hole, the invention provides a kind of new bio fracturing fluid system hidden suitable for unconventionaloil pool.
Conventional chemical gel breaker, and the biological fracturing fluid system of optimization initiative on this basis are substituted using biological enzyme breaker.Physics is made seam technology and is combined together with the broken glue technological perfectionism of biology enzyme by it, the characteristics of giving full play to that the broken glue of biology enzyme is thorough and level of residue is few, long-lasting etc., cull and residue injury are thoroughly removed, improves individual well fracturing effect, farthest improve the exploitation of coal bed gas.Additionally, the system has environmentally safe, with strong points, process is simple, feasible high advantage.
The technical solution adopted by the present invention is：
In the biological fracturing fluid system of unconventional gas reservoir, it is that water-based fracturing liquid system mainly has natural plant gum, biological assistant, crosslinking agent, microorganism, water to be formulated for a kind of new application.Said components by weight, by plant xanthan polymer 2-4g/L；Biological bactericide 0.02-2g/L；Biological cleanup additive 0.25-0.5g/L；Clay stabilizer 10-30g/L；PH value regulator；Enzyme breaker 10-30mg/L；Balance of water.Said components are mixed according to a conventional method.Fracturing fluid of the present invention uses six rotating speed viscosimeter 170S-1Shear rate shearing, in 1h viscosity be more than 100mPa.s, after breaking gel level of residue be less than 200mg/L.Fracturing fluid of the present invention is less than 15% to rock core infiltration injury rate, and downhole temperature can be used below 80 DEG C, can the effective row of returning after pressure break.
Plant xanthan polymer is used as one or more that thickening agent is guar gum, HPG or CMHPG；
Biological bactericide is：Bacitracin, polymyxins or other have in the biological bactericide of same effect one or more；
Biological cleanup additive is：One or more in Lipopeptide Biosurfactants (surfactin, Iturin), rhamnolipid；
Biological enzyme breaker is：Acid-fast alkali-proof, the 'beta '-mannase of heatproof, cellulase, laccase or other have in the biology enzyme of same effect one or more；
Clay stabilizer is KCl.
PH adjusting agent is citric acid or sodium acid carbonate, and fracturing fluid system final ph is adjusted to 8.5-9.5 by it.
There is certain viscoelastic frozen glue shape water-based fracturing liquid system to obtain, the crosslinking agent used in pressure break system is borax or organic boron, and its consumption is：The aqueous solution of 1-1.5wt% boraxs or organic boron, crosslinking ratio is 100:5-100:10.
The preparation method of the water-based fracturing liquid system, it is the guar gum base fluid of 0.20-0.40% to prepare mass concentration first, again by biological cleanup additive, biological bactericide, clay stabilizer, biology enzyme, in described in claim 1 ratio add, it is eventually adding crosslinking agent to be crosslinked, becomes with certain viscoelastic frozen glue.
The beneficial effect of new bio fracturing fluid system of the present invention, gel breaking test (condition is carried out using it：Pressure break temperature 1h, fracturing fluid viscosity >=100mPa.s), its broken glue level of residue≤200mg/L breaks the glue time for 2-3h, and breaking glue solution viscosity is 1-5mPas, meets professional standard (SY/T 5107-2005).Pressing crack construction is carried out using this fracturing fluid system, fracturing fluid recovery (backflow) rate is high after construction, break glue thorough.
The present invention substitutes the chemistry aiding discharging agent in original aqueous fracturing fluid with biological cleanup additive, chemical bactericide is substituted with biological bactericide, chemical gel breaker is substituted with biological enzyme breaker, and add clay stabilizer and pH adjusting agent, then it is crosslinked with borate, the viscoplasticity frozen glue body of composite fracturing requirement can be formed, i.e., a kind of new application is in the biological fracturing fluid system of unconventional gas reservoir；Using this fracturing fluid system to well temperature for 20-80 DEG C of unconventional gas well carries out pressing crack construction, can reach that level of residue is few, breaking glue solution molecular weight is in 200-10, (referring to Fig. 4 and Fig. 6) between 000, pressure break injury it is low, enter well fracturing fluid return row lead it is high, improve effect of increasing production purpose.
It is that biological fracturing fluid system of the invention and gelled fracturing fluid system conventional at present are contrasted it is a technical advantage that：
1) all characteristics with the crosslinking of traditional aqueous fracturing fluid frozen glue and rheological characteristic；
2) biological assistant (gel breaker, cleanup additive, bactericide) for substituting used is biodegradable low toxicity or nontoxic green bio preparation；
3) break glue thoroughly, break the glue time controllable；
4) Applicable temperature of biological enzyme breaker is wide (20-80 DEG C) used by, and can significantly improve traditional chemical gel breaker cannot break glue or the halfway shortcoming of broken glue at low temperature, is particularly suited for the broken glue of non-conventional gas low temperature well pressure break；
5) System On Core injury is less than 15% (chemical method 30-37%), than conventional fracturing fluid system reduction 10-20%, due to the long-lasting sustainable raising fracture condudtiviy of enzyme breaker；
6) after this fracturing fluid system pressing crack construction, can the effective row of returning.
Brief description of the drawings：
The various concentrations biology enzyme fracturing fluid shearing curve of accompanying drawing 1；
The 20ppm biology enzymes of accompanying drawing 2 are formulated rheology linearity curve；
The ammonium persulfate breaking glue solution of accompanying drawing 3 (reaction 48h) graph of molecular weight distribution (30 DEG C)；
The biology enzyme breaking glue solution of accompanying drawing 4 (reaction 48h) guar gum rheological characteristic figure (30 DEG C)；
The ammonium persulfate breaking glue solution of accompanying drawing 5 (reaction 48h) guar gum rheological characteristic figure (60 DEG C)；
The biology enzyme breaking glue solution of accompanying drawing 6 (reaction 48h) guar gum rheological characteristic figure (60 DEG C).
Specific embodiment
Embodiment 1
A kind of new application is achieved in the following ways in the preparation of the biological fracturing fluid system of unconventional gas reservoir：
1) plant xanthan polymer (specially HPG) 0.20g is weighed by weight, under conditions of high-speed stirred, is at the uniform velocity added in the water of 100mL, be configured to guar gum base fluid.
2) biological bactericide (specially bacitracin) 0.02g is added, biological cleanup additive (specially surfactin) 0.025g, clay stabilizer (specially KCl) 2g, biological enzyme breaker (specially 'beta '-mannase) 30mg/L.
3) pH adjusting agent is added to adjust pH value to 8.5-9.5.
4) crosslinking agent is added to be crosslinked, crosslinking agent is 1.5wt% borax solutions, and addition is 5mL, while being gently mixed, you can obtain the frozen glue for pressure break.
Embodiment 2
A kind of new application is achieved in the following ways in the preparation of the biological fracturing fluid system of unconventional gas reservoir：
1) plant xanthan polymer (specially HPG) 0.20g is weighed by weight, under conditions of high-speed stirred, is at the uniform velocity added in the water of 100mL, be configured to guar gum base fluid.
2) biological bactericide (specially polymyxins) 0.02g is added, biological cleanup additive (specially surfactin) 0.025g, clay stabilizer (specially KCl) 2g, biological enzyme breaker (specially 'beta '-mannase) 30mg/L.
3) pH adjusting agent is added to adjust pH value to 8.5-9.5.
4) crosslinking agent is added to be crosslinked, crosslinking agent is 1.5wt% borax solutions, and addition is 5mL, while being gently mixed, you can obtain the frozen glue for pressure break.
Embodiment 3
A kind of new application is achieved in the following ways in the preparation of the biological fracturing fluid system of unconventional gas reservoir：
1) plant xanthan polymer (specially CMHPG) 0.20g is weighed by weight, under conditions of high-speed stirred, is at the uniform velocity added in the water of 100mL, be configured to guar gum base fluid.
2) biological bactericide (specially polymyxins) 0.02g is added, biological cleanup additive (specially rhamnolipid) 0.003g, clay stabilizer (specially KCl) 2g, biological enzyme breaker (specially 'beta '-mannase) 30mg/L.
3) pH adjusting agent is added to adjust pH value to 8.5-9.5.
4) crosslinking agent is added to be crosslinked, crosslinking agent is 1.5wt% borax solutions, and addition is 5mL, while being gently mixed, you can obtain the frozen glue for pressure break.
Application examples 1
Rheological characteristic is tested
According to method shown in embodiment 1 prepare system base fluid, with pure water prepare 1% biological enzyme breaker (β-galactomannans enzyme) dilution, enzyme dilution is added in above-mentioned base fluid make its final concentration of 5,10,20,30ppm；Add crosslinking agent to be crosslinked, form frozen glue；The frozen glue is placed in rheometer, it is persistently overheating to 100 DEG C, in 170s-1Heatproof resistant to shearing experiment is carried out under shearing force.Result of the test shows that the fracturing fluid containing 5-30ppm enzyme breakers is in 170s-1Under shearing force, viscosity is positively retained at more than 100mPa.s in 1h, and enzyme breaker concentration declines rapidly in the fracturing fluid of more than 10ppm after 1h, and fracturing fluid thoroughly breaks glue after 3h, and viscosity is in below 5mPa.s.Therefore, the biological enzyme breaker can meet heatproof endurance of cutting and the rheological characteristic requirement of fracturing fluid.
Application examples 2
Breaking glue solution surface and interface tension force and level of residue are analyzed：
Method prepares system base fluid as shown in embodiment 1, is separately added into biology enzyme or ammonium persulfate and is crosslinked as gel breaker and with borax crosslinkers, carries out gel breaking test assessment：
Table 1 is with ammonium persulfate as gel breaker
Note：Breaking glue solution surface tension：27.35mN/m；Interfacial tension is 6.10mN/m, residue content
It is 178.0mg/L.
Table 2 is with biology enzyme as gel breaker
Note：Breaking glue solution surface tension：24.21mN/m；Interfacial tension is 2.18mN/m, and residue content is 122.0mg/L.
Simultaneously, ammonium persulfate and biology enzyme under different temperatures breaking glue solution molecular weight after breaking gel is analyzed, result shows, biology enzyme is gel breaker thorough compared with the fracturing liquid rubber-breaking that ammonium persulfate is gel breaker, guar gum is more easy to be degraded to small molecule carbohydrate (Fig. 3-6), and polysaccharide molecular weight is concentrated mainly on 250-3800 intervals during 48h.And apply ammonium persulfate as in the breaking glue solution of gel breaker, molecular weight does not have obvious absworption peak below 5000.Illustrate that the broken glue effect of biological enzyme breaker is better than chemical gel breaker ammonium persulfate.Application examples 3
Level of residue is reduced, following experiment is done with core permeability analyzer, core porosity analyzer, rock core vacuum pressed saturation device etc..Base fluid is prepared as described in Example 1, and from three blocks of rock cores on same stratum, rock core primary data is as follows：
The rock core physical parameter table of table 3.
Breaking glue solution by 1# rock cores is that, with ammonium persulfate as gel breaker, the breaking glue solution by 2# rock cores is with biology enzyme as gel breaker.Use Instrument measuring core damage.Experiment flow is as follows：
1st, the positive injection kerosene of rock core, until saturation.Inlet pressure is maintained at 20MPa or so, and outlet pressure is maintained at 0.2MPa or so.Determine permeability.
2nd, after breaking glue solution filtering, inverse injection rock core, injection rate reaches 2PV.
3rd, it is positive again to inject kerosene, until saturation.Determine permeability.
4th, core damage is calculated by front and rear permeability variation relation.
Table 4. is evaluated and level of residue result
Shown by above-mentioned experimental data, core damage is done using biology fracturing fluid system of the invention to test, injury rate have decreased to 10.7% from original 31.6%, and level of residue dropped to 234mg/L from former 548mg/L, it is seen that this invention is to reducing rock stratum injury effect clearly.
The characteristics of present invention is for unconventional gas reservoir reservoirs such as coal bed gas, shale gas, compact sandstone gas, the advantage for making seam and anti-leak-off of gelled fracturing fluid can farthest be played, and make Gel Breakdown thorough as gel breaker using biology enzyme, level of residue is few, the hole that reservoir is natural or pressure break goes out will not be blocked, so as to ensure pressing crack construction effect, effective row of returning, formation damage is reduced, non-conventional gas well capacity is improved, is the ideal New Fracturing Fluid system for being applied to unconventional gas reservoir exploitation.
Claims (7)
1. a kind of biological fracturing fluid system, it is water-based fracturing liquid system, it is characterised in that：
By weight, the composition of the fracturing fluid system is：Plant xanthan polymer 2-4g/L；Biology is killed
Microbial inoculum 0.02-2g/L；Biological cleanup additive 0.25-0.5g/L；Clay stabilizer 10-30g/L；Enzyme breaks glue
Agent 10-30mg/L；The aqueous solution of 1-1.5wt% crosslinking agents, water and crosslinking in water-based fracturing liquid system
The volume ratio of agent solution is 100:5-100:10；PH value regulator adjusts fracturing fluid system final ph
It is 8.5-9.5；Balance of water.
2. fracturing fluid system according to claim 1, it is characterised in that：
Plant xanthan polymer is one kind of guar gum, HPG or CMHPG；
Biological bactericide is at least one in bacitracin, gramicidins or polymyxins；
Biological cleanup additive is rhamnolipid, alkyl polyglycoside, at least one of her withered grass element；
Clay stabilizer is KCl.
3. fracturing fluid system according to claim 1, it is characterised in that：
Enzyme breaker be acid-fast alkali-proof, the 'beta '-mannase of heatproof, cellulase, laccase at least
It is a kind of；
PH adjusting agent is citric acid, glutamic acid, aspartic acid or sodium acid carbonate, and it is by fracturing fluid system
Final ph is adjusted to 8.5-9.5.
4. fracturing fluid system according to claim 1, it is characterised in that：Have necessarily to obtain
Viscoelastic frozen glue shape water-based fracturing liquid system, crosslinking agent used in pressure break system for borax or
Organic boron, its consumption is：The aqueous solution of 1-1.5wt% boraxs or organic borate cross-linker, aqueous fracturing fluid
Water and the volume ratio of cross-linking agent solution in system are 100:5-100:10.
5. the preparation method of fracturing fluid system described in claim 1-4, it is characterised in that：
It is the natural plant gum polymer base fluid of 2g/L-40g/L to prepare mass concentration first, then biology is helped
Row's agent, biological bactericide, clay stabilizer, enzyme breaker desired proportions are added, and are adjusted using pH
It is 8.5-9.5 that system pH is adjusted in section agent, is eventually adding crosslinking agent and is crosslinked, and is become with one
Fixed viscoelastic frozen glue.
6. fracturing liquid ties up to coal bed gas, shale gas, compact sandstone gas etc. according to claim 1
The application of unconventional gas reservoir pressure break exploitation, it is characterised in that：Glue reality is carried out brokenly using this fracturing fluid system
Test, be incubated 1h at a temperature of pressure break, fracturing fluid viscosity >=100mPa.s, its broken glue level of residue≤200mg/L,
The broken glue time is 2-3h, and breaking glue solution viscosity is 1-5mPas.
7. application according to claim 6, it is characterised in that：Carried out using this fracturing fluid system
Pressing crack construction, fracturing fluid recovery (backflow) rate is high after construction, breaks glue thorough.
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| CN108708704A (en) * | 2018-05-15 | 2018-10-26 | 重庆交通大学 | A kind of method that coalbed methane reservoir reduces leak-off |
| CN109705833A (en) * | 2018-12-28 | 2019-05-03 | 北京大德广源石油技术服务有限公司 | High-efficiency activated supermolecule fracturing fluid |
| CN111040752A (en) * | 2018-10-11 | 2020-04-21 | 中国石油化工股份有限公司 | Low-adsorption fracturing fluid system and preparation method thereof |
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| CN109705833A (en) * | 2018-12-28 | 2019-05-03 | 北京大德广源石油技术服务有限公司 | High-efficiency activated supermolecule fracturing fluid |
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