CN108641690A - A kind of green can energization temporarily block up preparation and its application method of diversion agent - Google Patents
A kind of green can energization temporarily block up preparation and its application method of diversion agent Download PDFInfo
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- CN108641690A CN108641690A CN201810518183.4A CN201810518183A CN108641690A CN 108641690 A CN108641690 A CN 108641690A CN 201810518183 A CN201810518183 A CN 201810518183A CN 108641690 A CN108641690 A CN 108641690A
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/5086—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
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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
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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
- C09K8/70—Compositions for forming crevices or fractures characterised by their form or by the form of their components, e.g. foams
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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
- C09K8/885—Compositions based on water or polar solvents containing organic compounds macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
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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
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices, or the like
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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
- E21B43/261—Separate steps of (1) cementing, plugging or consolidating and (2) fracturing or attacking the formation
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Abstract
The invention discloses be related to field of oilfield chemistry a kind of green can energization temporarily block up diversion agent preparation and its application method.After being modified to its polymer monomer, polymer-modified monomer and non-modified polymer monomer are polymerized by a certain percentage, when in use according to different well's conditions, a certain amount of pH adjusting agent, hardness regulator and degradation catalyst is added, execute-in-place is convenient and simple.Temporary stifled diversion agent prepared by the present invention has fabulous biocompatibility, can thoroughly be decomposed by biological enzyme in human body, can fundamentally solve the injury to human body and other biological.In the earth formation not only can be degradable, and carbon dioxide and methane caused by degradation can be stratum energization, and diversion agent is temporarily blocked up in degradable producible 670 895sm in stratum by calculating 1 ton of sheet3Mixed gas can also largely reduce viscosity of crude while to stratum energization, improve recovery ratio.
Description
Technical field
The present invention relates to technical field of oilfield chemistry, more particularly to a kind of green can energization temporarily block up diversion agent preparation and its
Application method.
Background technology
From nineteen thirty-seven, Halliburton companies of U.S. oilfield service company obtain the patent of invention of first chemical diverter
So far, diversion agent is temporarily blocked up in oil gas field stimulation work extensively using more than 80 years, also there are more than 20 years in China
Development and application.Diverting agent can be divided into insoluble particles diverting agent, oil-soluble and temporarily block up diversion agent and water-soluble temporarily stifled diversion agent at present
Three classes.It is 70-140 mesh ground quartz sand and 70-140 mesh powder pottery that insoluble particles diverting agent generally uses in oil field compression fracture
Grain, main purpose are temporary stifled stratum microcracks, artificial major fracture can not be carried out temporary stall to.Oil-soluble temporary plugging agent is general
In constructing applied to oil well acidation, pressing crack construction is because extensive injection aqueous fracturing fluid, oil-soluble temporarily block up diversion agent and will not meet
Oil, so temporarily blocking up diversion agent as insoluble particles diversion agent in pressing crack construction oil-soluble, can not play makes man-made fracture turn
To purpose.Water-soluble temporarily stifled diversion agent meet water can be formed viscosity 60-180mPa.s viscous liquid, into stratum after high score
Sub- paradigmatic structure group can be formed by pressing crack construction man-made fracture and effectively temporarily block up, and the net pressure in man-made fracture is made to increase
Add, when net pressure increases to certain numerical value, new man-made fracture will be reopened in crack wall surface, that is, man-made fracture occurs
Steering.The turning efficiency of water-soluble temporarily stifled diversion agent has gradually been recognized at home.
Temporarily most of stifled diversion agent is modified polypropene acyl salt, polyester fat class, polymerize virtue the water solubility that the country uses at present
The one or more of the fragrant same clan and biodegradable fiber etc. are composed.Although such temporarily stifled diversion agent can play good temporarily stifled
Turning efficiency, but still there are some disadvantages in practical operation at the scene.First, adding for diversion agent is temporarily blocked up when live pressing crack construction
The typically artificial filling of note, the grain size due to temporarily blocking up diversion agent temporarily block up the powder of diversion agent generally between 20-200 mesh
Grain easily misses inspiration by filling personnel and enters in human body, and there are prodigious security risks.Second, it is used at present all water-soluble temporary
Stifled diversion agent is limited in stratum palliating degradation degree, and degradation to oligomer state cannot be after generally under stratum high-temperature, condition of high voltage
Continuous degradation, a degree of injury can be caused to oil-gas reservoir.
Invention content
For practical problem existing for domestic existing temporarily stifled diversion agent, the present invention provides one kind to have good biological compatible
Property, and CO can be thoroughly degraded in stratum2、CH4、H2O and H2SO4The water solubility of equal small molecule structures temporarily blocks up diversion agent, with
And this temporarily blocks up preparation and its application method of diversion agent.
A kind of green can energization temporarily block up diversion agent, it is characterised in that including following components, shared by each component and each component
Mass percent be：Polymer monomer, 1.5-3.5% sulfonating agents, 0.5-3.0%pH conditioning agents A, 0.5- of 5.0-10.0%
3.0%pH conditioning agent B, 0.5-3.0% hardness regulator, 0.5-1.0% degradation catalysts, 85-95% water.
A kind of a kind of green described in basis can energization temporarily block up the method for preparation and use of diversion agent comprising following step
Suddenly：
（1）Polymer monomer is first carried out to sulfonation in sulfonating agent, obtains sulfonated polymer monomer；
（2）Using infrared spectrometer, x-ray photoelectron spectroscopy, scanning electron microscope to obtained sulfonated polymer monomer
Phenetic analysis is carried out, determines that the hydroxyl in polymer monomer is replaced by sulfonate radical；
（3）The polymer monomer of obtained sulfonated polymer monomer and unsulfonated is mixed in a certain ratio uniformly, is polymerize
Reaction, obtains sulfonated polymer；
（4）Obtained sulfonated polymer is crushed to, is cut into the particle of 20-200 mesh, you can obtain green can the temporary stall of energization to
Agent solid particle；
（5）It is separately added into pH adjusting agent A, pH adjusting agent B, hardness regulator and degradation catalyst in clear water, stirs evenly；
（6）At the uniform velocity by step（4）The green prepared can energization temporarily block up diversion agent solid particle step be added（5）It is described to regulate
Aqueous solution in, quickly stirring to viscosity is more than 60mPa.s up to temporarily stifled diversion agent of the present invention.
The temporary stifled diversion agent of the present invention has advantageous effect compared to existing temporarily stifled diversion agent.One kind provided by the present invention
Green can energization temporarily to block up diversion agent main synthon be D-lactic acid, IUPAC scientific name L-2- hydracrylic acids.D-lactic acid and its
Polymer poly D-lactic acid is the universally acknowledged renewable environment-friendly products of green.Poly L-lactic acid is a kind of with good biological phase
Capacitive and can natural degradation polymer, also can be completely decomposed into CO under the action of lactic acid bacteria in vivo2And H2O.Equally,
In pressing crack construction with a certain amount of degradation catalyst is noted, Poly L-lactic acid can thoroughly be degraded to CO under the aerobic environment of stratum2
And H2O；It can thoroughly be degraded to CH under the oxygen-free environment of stratum4And H2O。
Since, there are a large amount of ester bond, hydrophily is poor, degradation cycle is uncontrollable, and China not yet exists in Poly L-lactic acid
It is used in pressing crack construction.The present invention introduces hydrophilic functional groups sulfonate radical in Poly L-lactic acid, can effectively improve poly- left-handed
The hydrophily of lactic acid, and can be by the mixed proportion of D-lactic acid and sulfonation D-lactic acid when adjusting polymerization, after polymerization
Obtained sulfonation Poly L-lactic acid hydrophily is controlled to adjust.In pressing crack construction, according to the difference of individual well hole condition and water quality,
It, can be by the hydrolysis of sulfonation Poly L-lactic acid and drop using pH adjusting agent A, pH adjusting agent B, hardness regulator and degradation catalyst
Time control is solved in the range of 1 minute to 10 days, realizes controlled degradation.
Sulfonation Poly L-lactic acid meet water hydrolyzable be D-lactic acid, sulfonation D-lactic acid and its oligomer, it is small after hydrolysis
Molecular structure further can thoroughly be degraded to CO under stratum high-temperature effect2、CH4、H20 and H2SO4.By calculating, 1 ton of this hair
The bright green can energization temporarily block up diversion agent particle, degradable generation 670-895sm under the action of degradation catalyst3CO2With
CH4Mixed gas, and gas energization technology is in China that each major oil and gas field gets the nod, and wide popularization and application.
Specific implementation mode
Below by embodiment, the present invention is further described, purpose be only that be better understood from the present invention and it is unrestricted
Protection scope of the present invention.
Embodiment 1：Utilize SO3Sulfonation method carries out sulfonation in injection circulation reactor to 50.0g D-lactic acids；By institute
Obtained sulfonation D-lactic acid and D-lactic acid in mass ratio 1:3 ratio is uniformly mixed, and recycles batch type anti-
It answers device and double screw extruder to carry out melt polycondensation to the mixed solution of sulfonation D-lactic acid and D-lactic acid, obtains the poly- breast of sulfonation
Acid；The sulfonation polylactic acid for preparing gained is crushed, is cut into the particle of 60-100 mesh for future use；It is added in 50ml fresh water
1.0gCaCl2, it is stirring evenly and then adding into 10.0g aforementioned prepared sulfonation particles of polylactic acid and 1.0g lactic acid bacterias, accelerates stirring
To viscosity be more than 60mPa.s, obtain green can energization temporarily block up diversion agent；
Embodiment 2：Utilize SO3Sulfonation method carries out sulfonation in injection circulation reactor to 50.0g D-lactic acids；It will be acquired
Sulfonation D-lactic acid and D-lactic acid in mass ratio 1:3 ratio is uniformly mixed, and recycles batch stirred reactor
Melt polycondensation is carried out to the mixed solution of sulfonation D-lactic acid and D-lactic acid with double screw extruder, obtains sulfonation polylactic acid；
The sulfonation polylactic acid for preparing gained is crushed, is cut into the particle of 60-100 mesh for future use；It is added in 50ml fresh water
1.0gCaCl2、0.5gNa2CO3, it is stirring evenly and then adding into 10.0g aforementioned prepared sulfonation particles of polylactic acid and 1.0g lactic acid
Bacterium, accelerate stirring to viscosity be more than 60mPa.s, obtain green can energization temporarily block up diversion agent；
Embodiment 3：Utilize SO3Sulfonation method carries out sulfonation in injection circulation reactor to 50.0g D-lactic acids；It will be acquired
Sulfonation D-lactic acid and D-lactic acid in mass ratio 1:3 ratio is uniformly mixed, and recycles batch stirred reactor
Melt polycondensation is carried out to the mixed solution of sulfonation D-lactic acid and D-lactic acid with double screw extruder, obtains sulfonation polylactic acid；
The sulfonation polylactic acid for preparing gained is crushed, is cut into the particle of 60-100 mesh for future use；It is added in 50ml fresh water
1.0gCaCl2, 2.5ml 20%HCl, be stirring evenly and then adding into the aforementioned prepared sulfonation particles of polylactic acid of 10.0g and 1.0g breasts
Sour bacterium, accelerate stirring to viscosity be more than 60mPa.s, obtain green can energization temporarily block up diversion agent.
It can energization temporarily stifled diversion agent progress core damage experiment and degradation examination to 1-3 of the embodiment of the present invention greens prepared
It tests.
Core damage test method：The artificial core of length 10cm, diameter 5cm are put into rock core rheometer, in 40MPa
Under constant-pressure conditions, by 10ml prepare green can energization temporarily block up diversion agent from the inlet of rock core rheometer inject, to artificial
Rock core carries out displacement, records infiltration capacity variation per minute, and calculating green can energization temporarily stifled injury of the diversion agent to artificial core
Recovery rate.
Green prepared by 1 embodiment of the present invention of table can energization temporarily block up core damage test result of the diversion agent at 30 DEG C
Green prepared by 2 embodiment of the present invention of table can energization temporarily block up core damage test result of the diversion agent at 60 DEG C
Green prepared by 3 embodiment of the present invention of table can energization temporarily block up core damage test result of the diversion agent at 90 DEG C
Degrading experiment method：500ml round-bottomed flasks are placed in electric-heated thermostatic water bath, are added into 500ml round-bottomed flasks
The green that 10ml is prepared can energization temporarily block up diversion agent, measure and generated after the degradation of sulfonation Poly L-lactic acid under different oxygen content
CO2And CH4Content.Experiment process is followed successively by electric heating constant temperature heating water bath 500ml round-bottomed flasks, and the gas for generation of degrading is logical first
Overrich H2SO4The gas of generation is dried in drying bottle；Using soda lime spherical shape drying tube, pass through the increased matter of soda lime
Amount, which calculates, generates CO2Standard state volume；Gas collecting apparatus finally is drained using 500mL, measures and generates CH4Chamber interior volume.
Green prepared by Fig. 1 embodiment of the present invention can energization temporarily block up diversion agent Degrading experiment installation drawing
Green prepared by 4 embodiment of the present invention of table can energization temporarily block up Degrading experiment result of the diversion agent at 30 DEG C
Green prepared by 5 embodiment of the present invention of table can energization temporarily block up Degrading experiment result of the diversion agent at 60 DEG C
Green prepared by 6 embodiment of the present invention of table can energization temporarily block up Degrading experiment result of the diversion agent at 90 DEG C
By a kind of green prepared by the present invention it can be seen from core damage test result can energization temporarily block up diversion agent in different pH
Under value, different solutions hardness, different temperatures, hydrolysis time has prodigious difference, although in practical fracturing process, formation temperature is not
Able person in order to control, but can by temporarily block up diversion agent be sent into liquid pH value and hardness adjusting, to realize to temporary stall
Artificial control to agent hydrolysis time.Meanwhile temporarily stifled diversion agent of the present invention can be hydrolyzed thoroughly at different temperatures, water
For rock core recovery rate after solution 99% or more, effect is much better than currently used temporarily stifled diversion agent.
In conjunction with Degrading experiment interpretation of result, it can be seen that a kind of green provided by the present invention can energization temporarily to block up diversion agent thorough
Bottom degradation is divided into two stages, and first stage is the hydrolytic process of temporarily stifled diversion agent, under the action of hydrone in polymer
Ester bond start to be hydrolyzed to D-lactic acid, sulfonation D-lactic acid and its oligomer, after the completion of hydrolysis, core permeability is opened
Begin gradually to restore；Second stage is D-lactic acid, sulfonation D-lactic acid and its oligomer under the action of oxidant or bacterium,
Continue to be degraded to CO2、CH4、H20 and H2SO4, wherein the CO for generation of degrading2It is the good stratum energization gas of application effect, and
CH4Stratum energy can not only be increased, oil viscosity can also be reduced, improve recovery ratio to a certain extent.
Above-described is only the optimization test scheme of the present invention, not does any type of limitation to the present invention.
Claims (10)
1. a kind of green can energization temporarily block up diversion agent, it is characterised in that：Its component and mass ratio are：5.0%-10.0% polymer lists
Body, 1.5%-3.5% sulfonating agents, 0.5%-3.0%pH conditioning agent A, 0.5%-3.0%pH conditioning agent B, 0.5%-3.0% hardness regulator,
0.5%-1.0% degradation catalysts, 85%-95% water.
2. a kind of green according to claim 1 can energization temporarily block up diversion agent, it is characterised in that：The polymer monomer
For D-lactic acid, IUPAC scientific names：L-2- hydracrylic acids.
3. a kind of green according to claim 1 can energization temporarily block up diversion agent, it is characterised in that：The sulfonating agent includes
It is one or more in sulfuric acid, oleum, sulfur trioxide, chlorosulfonic acid.
4. a kind of green according to claim 1 can energization temporarily block up diversion agent, it is characterised in that：The pH adjusting agent A
Including sodium hydroxide, sodium carbonate, sodium bicarbonate, sodium formate, sodium acetate, potassium hydroxide, potassium carbonate, saleratus, potassium formate, second
It is one or more in sour potassium.
5. a kind of green according to claim 1 can energization temporarily block up diversion agent, it is characterised in that：The pH adjusting agent B
Including one or more in hydrochloric acid, formic acid, acetic acid, nitric acid, hydrofluoric acid.
6. a kind of green according to claim 1 can energization temporarily block up diversion agent, it is characterised in that：The hardness regulator
Including one or more in calcium chloride, calcium nitrate, magnesium chloride, magnesium nitrate, zinc chloride, zinc nitrate.
7. a kind of green according to claim 1 can energization temporarily block up diversion agent, it is characterised in that：The degradation catalyst
Including one or more in lactic acid bacteria, Penicillium notatum, rotten plant bacterium, reaping hook enzyme candida albicans, hydrogen peroxide, ammonium persulfate.
8. according to the preparation and application required by claim 1-7, it is characterised in that：It comprises the steps of：It first will polymerization
Object monomer carries out sulfonating reaction in sulfonating agent；Again according to a certain percentage by sulfonated polymer monomer and non-sulfonated polymer monomer
It is polymerize, the difference of the two ratio can make the sulfonated polymer hydrophily finally prepared different；Then the sulphur of gained will be prepared
Fluidized polymer is crushed, be cut into 20-200 mesh particle to get green can energization temporarily block up diversion agent solid particle；Finally according to pressure break
Construction operation condition is different, will after a certain amount of pH adjusting agent A, pH adjusting agent B, hardness regulator are added in construction water
The green of preparation can energization temporarily block up diversion agent solid particle and be added, selectively add degradation catalyst according to actual conditions, stir
Stratum can uniformly be injected.
9. a kind of green according to claim 8 can energization temporarily block up diversion agent preparation and application, it is characterised in that：
It is sulfonate radical that the sulfonating reaction, which is by the hydroxyl modification in D-lactic acid,.
10. a kind of green according to claim 8 can energization temporarily block up the preparation and application of diversion agent, feature exists
In：The certain proportion refer to the accounting of sulfonated polymer be a, the accounting of non-sulfonated polymer is（1-a）, 0≤a≤
100%。
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