CN105086966B - Shallow well high molecular polymerization frozen glue sealing agent and preparation method thereof - Google Patents
Shallow well high molecular polymerization frozen glue sealing agent and preparation method thereof Download PDFInfo
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- CN105086966B CN105086966B CN201510576374.2A CN201510576374A CN105086966B CN 105086966 B CN105086966 B CN 105086966B CN 201510576374 A CN201510576374 A CN 201510576374A CN 105086966 B CN105086966 B CN 105086966B
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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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
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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
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/426—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for plugging
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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
- C09K2208/08—Fiber-containing well treatment fluids
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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
- C09K2208/18—Bridging agents, i.e. particles for temporarily filling the pores of a formation; Graded salts
Abstract
The present invention relates to a kind of shallow well high molecular polymerization frozen glue sealing agent and preparation method thereof, raw material components and weight content are purified cotton sodium salt solution：120 parts, acrylamide：75~85 parts, ammonium persulfate：13~17 parts, cerous sulfate：2~5 parts, β D mannuronic acids（M）：4 parts, ammonium dihydrogen phosphate：1~1.5 part, composite Portland cement slurry：100 parts, talcum powder：80~90 parts and mix type microfibre：20 parts；The ratio of mud of the composite Portland cement slurry is 0.44；Acrylamide, ammonium persulfate particle, cerous sulfate particle are added into purified cotton sodium salt solution successively and obtains high molecular polymerization frozen glue, adds β D mannuronic acids（M）, it is subsequently added into composite Portland cement slurry, talcum powder and mixes type microfibre, is eventually adding ammonium dihydrogen phosphate and stirs evenly to obtain shallow well high molecular polymerization frozen glue sealing agent.The shallow well high molecular polymerization frozen glue sealing agent heat resisting and pressure resisting, leak stopping are reliable.
Description
Technical field
The present invention relates to a kind of shallow well high molecular polymerization frozen glue sealing agent, the invention further relates to a kind of shallow well high molecular polymerization
The preparation method of frozen glue sealing agent, belong to petroleum drilling technology field.
Background technology
Leakage is the technical barrier frequently encountered in drilling process, can cause a large amount of losses of drilling fluid, cause drilling well into
This rising, while bottom pressure can be caused to change, induce the hair of the complex accidents such as borehole well instability, well slough, well kick, blowout
It is raw, seriously govern the raising of bit speed.
It is general using conventional stifled due to lacking new leakage stopping technology at present when oil drilling drilling strata misses section
Leak agent leak stopping.For the leakage of country's processing shallow well generally using bridge joint leak stopping, bridge joint leak stopping has economy, easy to use, construction peace
The advantages of complete, can solve partial loss and mistake as caused by hole and crack and return leakage.The bridge joint loss circulation material that the country uses
It is roughly divided into three classes：Hard fruit shell class, fibrous material and lamellar material.In Process of Leaking Stoppage, any kind material is independent
Use, it is all limited that it, which is acted on, and only above-mentioned three classes material is used in combination with rational ratio and grading, and can just receive should
Some effects, but deepening continuously with drilling, the temperature for missing stratum are also constantly raising, the hard being immersed in mud
Shell class material and plant fiber material such as walnut shell, hazelnut shell, cotton seed hulls and sawdust etc., high temperature, high pressure and strong in well
Under conditions of caustic corrosion, over time, these materials will slowly soften, corrode, or even some materials can be burnt, and cause
Bridge joint intensity is set drastically to decline, it is easy to cause leak stopping failure or secondary leakage, can not fundamentally solve the problem of leak stopping.
Well depth is that 2000~3000m is referred to as shallow well, and downhole temperature is generally at 80 DEG C~100 DEG C.Although conventional blocking method
Effect is played for the stoppage engineering of oil drilling, but simultaneously there is shortcoming or deficiency, temperature resistant capability is low, the term of validity is short, stifled
Leakage inefficient, loss circulation material consumption is big, plugging time is long, leak stopping safety coefficient is poor, down hole problem easily occurs, and these are lacked
Point directly affects probing development process, therefore traditional loss circulation material far from disclosure satisfy that growing Holes of Complicated Wells
Leak stopping demand, therefore it is very necessary to study a kind of shallow well sealing agent.
The content of the invention
The primary and foremost purpose of the present invention is, overcomes problems of the prior art, there is provided a kind of shallow well high molecular polymerization
Frozen glue sealing agent, leak stopping is reliable, and heat resisting and pressure resisting.
To solve above technical problem, a kind of shallow well high molecular polymerization frozen glue sealing agent of the invention, the original of the sealing agent
Expect that component and weight content are as follows, purified cotton sodium salt solution：120 parts, acrylamide：（75~85）Part, ammonium persulfate：（13~
17）Part, cerous sulfate：（2~5）Part, beta-D-mannuronic acid：4 parts, ammonium dihydrogen phosphate：（1~1.5）Part, composite Portland cement
Slurry：100 parts, talcum powder：（80~90）Part and mix type microfibre：20 parts；The ratio of mud of composite Portland cement slurry is
0.44。
Relative to prior art, the present invention achieves following beneficial effect：1. purified cotton sodium salt provides the fibre of cross-linking reaction
Dimension element；Acrylamide plays bridge formation suction-operated, cellulose is flocculated, and is cross-linked with each other；Ammonium persulfate triggers cross-linking reaction,
Make fiber destarch simultaneously；Cerous sulfate triggers polymer that polymerization, graft reaction occurs；Talcum powder and mix type microfibre and play frame
The effect of bridge particles, there is provided the intensity for eventually forming " block wall " ensures.2. the sealing agent uses synthetic fibers and natural fiber
Be cross-linked to form the net high-polymer polymer of mutual winding, can more than 100 DEG C of heatproof, anti-pressure ability reaches 5MPa, completely
It disclosure satisfy that the leak stopping requirement of 2000~3000m shallow wells.3. the adding proportion for mixing type microfibre in the present invention causes sealing agent
With highest intensity, if continuing to improve the weight ratio for mixing type microfibre, the chemistry of gel chemistries material can be disturbed on the contrary
Crosslinked action, the bearing capacity of its leak stopping can be reduced on the contrary.
It is as follows as the preferred scheme of the present invention, the preparation method of the purified cotton sodium salt：1. prepare the cotton fiber degree of polymerization
The sodium hydroxide solution that purified cotton and concentration expressed in percentage by weight for 12000~14000 are 17.5~18%, purified cotton and hydroxide
The weight ratio of sodium solution is 5:2；2. will purified cotton put into sodium hydroxide solution in, stirred at 60 DEG C and react 1.5 hours with
On, until uniform white suspension emulsion is presented, obtain purified cotton sodium salt just solution；3. solution at the beginning of purified cotton sodium salt is surpassed
Sound micro-vibration 30 minutes, purified cotton sodium salt solution is obtained, supersonic frequency is 20kHz~30kHz, and ultrasonication intensity is 2.0 W/
Cm2~3.0W/cm2.Purified cotton and sodium hydroxide reaction generation purified cotton sodium salt so that be sufficiently humidified so as to inside purified cotton
Expansion, improves the reactivity of purified cotton, is advantageous to further cross-linking reaction.Supersound process can improve purified cotton sodium salt
Molecule link Zhi Chengdu, more meet Zhi Duan subsequently to be provided with crosslinking agent.Reaction mechanism is：
。
As the preferred scheme of the present invention, the type microfibre that mixes is carried out uniformly by calcium carbonate crystal whisker and organic microfiber
Mix and form, the mixing ratio of the calcium carbonate crystal whisker and organic microfiber is 0.8:1.Calcium carbonate crystal whisker and organic microfiber are uniform
Be dispersed in high molecular polymerization frozen glue, be cross-linked to form with the high molecular polymer in high molecular polymerization frozen glue mutually wind it is netted
High molecular polymer.Calcium carbonate crystal whisker is to form " block wall " to provide physical supporting role, and its intensity is substantially improved；Have
Machine microfibre is mutually wound with calcium carbonate crystal whisker, is provided physical supporting role for " block wall " of formation, is made its intensity big
Width is lifted；Meanwhile add the intensity of " block wall " when being deformed under being acted on by strata pressure.
As the further preferred scheme of the present invention, 20~30 μm of the length of the calcium carbonate crystal whisker, 0.5~1 μm of diameter,
PH value 9.0~9.5, modulus of elasticity is 410~710GPa and tensile strength is not less than 2.058GPa；The organic microfiber is by gathering
The weight ratio of ester fiber and polypropylene fibre composition, polyester fiber and polypropylene fibre is 7:3；The diameter 20 of the polyester fiber
~25 μm, 6~9mm of length, elongation at break >=15%, tensile strength >=960MPa and modulus of elasticity >=9000MPa；It is described poly-
The length of tacryl is 10~20mm, filament number≤2.2dtex, tensile strength >=660MPa, modulus of elasticity >=350MPa.
Polypropylene fibre can improve the intensity of " block wall ", improve the rebound performance of " block wall " after compressive deformation.Polyester fiber can
Improve anti-fatigue performance, cracking resistance and the high temperature stability performance of " block wall ", the tension of " block wall " can be effectively improved, resisted
Pressure, anti-shearing and impact strength, make up deficiency of the polypropylene fibre at heat-resisting and ageing-resistant aspect.
As the further preferred scheme of the present invention, the polyester fiber and polypropylene fibre are at 60 DEG C hydrophilic whole
Soaked 3 hours in reason agent.Due to polyester fiber and polypropylene fibre compound with regular structure but hydrophily is poor, in high molecular polymerization frozen glue
It is difficult to be uniformly dispersed, surface modification treatment is carried out using hydrophilic finishing agent to polyester fiber and polypropylene fibre, its parent can be improved
It is water-based can, be advantageous to that they are dispersed in polymer gel, make " block wall " structure and the even intensity to be formed.
, should it is a further object of the invention to provide a kind of preparation method of shallow well high molecular polymerization frozen glue sealing agent
The sealing agent that method is prepared, leak stopping is reliable, and heat resisting and pressure resisting.
For solve above technical problem, a kind of preparation method of shallow well high molecular polymerization frozen glue sealing agent of the invention, according to
It is secondary to comprise the following steps：(1) raw material, purified cotton sodium salt solution are prepared by following components and weight content：120 parts, acrylamide：
（75~85）Part, ammonium persulfate：（13~17）Part, cerous sulfate：（2~5）Part, beta-D-mannuronic acid：4 parts, ammonium dihydrogen phosphate：
（1~1.5）Part, composite Portland cement slurry：100 parts, talcum powder：（80~90）Part and mix type microfibre：20 parts；It is described multiple
The ratio of mud for closing silicate grout is 0.44；(2) acrylamide is added into purified cotton sodium salt solution, with turning for 400r/min
Speed, which carries out high-speed stirred, is sufficiently mixed both in 10 minutes, then carries out moderate-speed mixer, moderate-speed mixer with 300r/min rotating speed
While be heated to 60 DEG C and keep constant temperature；(3) nitrogen is continually fed into step reaction product (2) and reaction vessel, be passed through
Nitrogen, in the case where keeping moderate-speed mixer and being maintained at 60 DEG C of constant temperature, is slowly added to ammonium persulfate particle, reaction is until particle after 3 minutes
After thing disappears, continue back flow reaction 1.5 hours；(4) temperature is increased to 80 DEG C and keeps constant temperature, in the case where keeping moderate-speed mixer, delayed
It is slow to add cerous sulfate particle, the charge door of reaction vessel is then shut off, lifts the charge of nitrogen, keeps the pressure in reaction vessel
Power is 1.3MPa, and back flow reaction obtains high molecular polymerization frozen glue in more than 3 hours up to reactant presentation white emulsion shape；Detection
The molecular weight of the high molecular polymerization frozen glue is more than 4,000,000；(5) in the state of moderate-speed mixer is kept, to above-mentioned polyphosphazene polymer
Close in frozen glue and be slowly added to beta-D-mannuronic acid, continue moderate-speed mixer 10 minutes after addition, and adjust pH value for 7~
7.5；(6) composite Portland cement slurry, talcum powder are added into step reaction product (5) and mixes type microfibre, moderate-speed mixer
More than 15 minutes until well mixed；(7) ammonium dihydrogen phosphate is added into step reaction product (6), moderate-speed mixer 10 minutes, obtained
To shallow well high molecular polymerization frozen glue sealing agent.
Relative to prior art, the present invention achieves following beneficial effect：1. purified cotton sodium salt provides the fibre of cross-linking reaction
Dimension element, acrylamide play bridge formation suction-operated, cellulose is flocculated, be cross-linked with each other.Ammonium persulfate triggers cross-linking reaction,
Make fiber destarch simultaneously；Nitrogen is passed through before ammonium persulfate is added, it is ensured that reaction environment anaerobic, avoids cellulose in cross-linking process
In rise viscous, influence the molecular weight of final cross-linking products；Back flow reaction 1.5h is ensured in the presence of cross-linking reaction initiator, is refined
Gossypin and can provide bridge formation suction-operated acrylamide is full cross-linked, copolyreaction, make cellulose molecular chain elongated, and
Molecular weight increases severely.Cerous sulfate further triggers between cellulose and acrylamide, cellulose and acrylamide pass through ammonium persulfate
Mutually it is grafted between copolymerzation with cross-linking reaction product and between cellulose and copolymerzation with cross-linking reactant, makes caused high molecular polymer
Molecular weight it is bigger, strand has more side chains, for after formation in the presence of thixotropic agent formed gel provide more
Side chain, the gel strength of formation are higher.Reaction mechanism is：
。
2. the molecular weight of high molecular polymerization frozen glue 4,000,000 it is described above crosslinking, copolymerization, graft reaction very fully,
Guarantee is provided to form the intensity of " block wall ".3. after adding beta-D-mannuronic acid in high molecular polymerization frozen glue, β-D- sweet dews
The sodium ion of uronic acid exchanges with the amide groups in high molecular polymerization frozen glue, ionic compartmentation is carried out at carboxyl position, so as to occur
Gelling reaction, form blob of viscose.Beta-D-mannuronic acid viscosity when pH is reduced can increase, and viscosity thixotropic be present when pH is 6.7,
With certain alkali resistance, when pH is 7~7.5, the blob of viscose of formation has more preferable shear thinning behavior, and favourable bar is provided for pumping
Part.4. after the gelling of high molecular polymerization frozen glue, if without enough bridge particles, the blob of viscose intensity of formation is only capable of reaching 1
~2MPa, it is impossible to meet the pressurization sealing requirement of shallow well；Talcum powder and mix type microfibre and can play a part of bridge particle,
In underground, high molecular polymerization frozen glue slowly starts to be gelled, and after complete gelation, the intensity for forming blob of viscose can reach 5MPa, being capable of heatproof
100 DEG C, the leak stopping needs of 2000~3000m of well depth shallow well can be met.Mix the adding proportion of type microfibre in the present invention
So that sealing agent has highest intensity, if continuing to improve the weight ratio for mixing type microfibre, gel chemistries can be disturbed on the contrary
The chemical crosslinking effect of material, the bearing capacity of its leak stopping can be reduced on the contrary.5. the ammonium dihydrogen phosphate of ratio of the present invention is added, can
So that gelling control in suitable time range, both to be ensured before gelling, sealing agent can be pumped to drop ply, and and can enough exists
Drilling rod is completed before gelling with replacing slurry in well, additionally it is possible to sealing agent is gelled in time after reaching drop ply so that leak stopping is starched
Liquid stops to live in drop ply.
It is as follows as the preferred scheme of the present invention, the preparation method of the purified cotton sodium salt：1. prepare the cotton fiber degree of polymerization
The sodium hydroxide solution that purified cotton and concentration expressed in percentage by weight for 12000~14000 are 17.5~18%, purified cotton and hydroxide
The weight ratio of sodium solution is 5:2；2. will purified cotton put into sodium hydroxide solution in, stirred at 60 DEG C and react 1.5 hours with
On, until uniform white suspension emulsion is presented, obtain purified cotton sodium salt just solution；3. solution at the beginning of purified cotton sodium salt is surpassed
Sound micro-vibration 30 minutes, purified cotton sodium salt solution is obtained, supersonic frequency is 20kHz~30kHz, and ultrasonication intensity is 2.0 W/
Cm2~3.0W/cm2.
As the preferred scheme of the present invention, the type microfibre that mixes is carried out uniformly by calcium carbonate crystal whisker and organic microfiber
Mix and form, the mixing ratio of calcium carbonate crystal whisker and organic microfiber is 0.8:1.
As the further preferred scheme of the present invention, 20~30 μm of the length of the calcium carbonate crystal whisker, 0.5~1 μm of diameter,
PH value 9.0~9.5, modulus of elasticity is 410~710GPa and tensile strength is not less than 2.058GPa；The organic microfiber is by gathering
The weight ratio of ester fiber and polypropylene fibre composition, polyester fiber and polypropylene fibre is 7:3；The diameter 20 of the polyester fiber
~25 μm, 6~9mm of length, elongation at break >=15%, tensile strength >=960MPa and modulus of elasticity >=9000MPa；It is described poly-
The length of tacryl is 10~20mm, filament number≤2.2dtex, tensile strength >=660MPa, modulus of elasticity >=350MPa.
As the further preferred scheme of the present invention, the polyester fiber and polypropylene fibre are at 60 DEG C hydrophilic whole
Soaked 3 hours in reason agent.
Embodiment
Embodiment one
A kind of preparation method of shallow well high molecular polymerization frozen glue sealing agent of the present invention, in turn includes the following steps：
(1) following components and weight content prepare raw material, purified cotton sodium salt solution：120 parts, acrylamide：75 parts, over cure
Sour ammonium：13 parts, cerous sulfate：2 parts, beta-D-mannuronic acid：4 parts, ammonium dihydrogen phosphate：1 part, composite Portland cement slurry：100
Part, talcum powder：80 parts and mix type microfibre：20 parts；The ratio of mud of the composite Portland cement slurry is 0.44；
(2) acrylamide is added in purified cotton sodium salt solution, carrying out high-speed stirred with 400r/min rotating speed makes two in 10 minutes
Person is sufficiently mixed, and then carries out moderate-speed mixer with 300r/min rotating speed, is heated to 60 DEG C and keeps permanent while moderate-speed mixer
Temperature；
(3) nitrogen is continually fed into step reaction product (2) and reaction vessel, is passed through nitrogen after 3 minutes in holding
Speed is stirred and is maintained at 60 DEG C of constant temperature, is slowly added to ammonium persulfate particle, and reaction continues backflow instead until after particulate matter disappearance
Answer 1.5 hours；
(4) temperature is increased to 80 DEG C and keeps constant temperature, in the case where keeping moderate-speed mixer, be slowly added to cerous sulfate particle, then
The charge door of reaction vessel is closed, lifts the charge of nitrogen, it is 1.3MPa to keep the pressure in reaction vessel, back flow reaction 3
Hour until reactant presentation white emulsion shape, obtains high molecular polymerization frozen glue；Detect the molecule of the high molecular polymerization frozen glue
Amount is more than 4,000,000；
(5) in the state of moderate-speed mixer is kept, β-D-MANNOSE aldehyde is slowly added into above-mentioned high molecular polymerization frozen glue
Acid, continues moderate-speed mixer 10 minutes after addition, and adjusts pH value as 7；
(6) composite Portland cement slurry, talcum powder are added into step reaction product (5) and mixes type microfibre, middling speed
Stir more than 15 minutes until well mixed；
(7) ammonium dihydrogen phosphate is added into step reaction product (6), moderate-speed mixer 10 minutes, obtain shallow well polyphosphazene polymer
Close frozen glue sealing agent.
Embodiment two
A kind of preparation method of shallow well high molecular polymerization frozen glue sealing agent of the present invention, in turn includes the following steps：
(1) following components and weight content prepare raw material, purified cotton sodium salt solution：120 parts, acrylamide：80 parts, over cure
Sour ammonium：15 parts, cerous sulfate：3 parts, beta-D-mannuronic acid：4 parts, ammonium dihydrogen phosphate：1.2 parts, composite Portland cement slurry：100
Part, talcum powder：85 parts and mix type microfibre：20 parts；The ratio of mud of the composite Portland cement slurry is 0.44；
(2) acrylamide is added in purified cotton sodium salt solution, carrying out high-speed stirred with 400r/min rotating speed makes two in 10 minutes
Person is sufficiently mixed, and then carries out moderate-speed mixer with 300r/min rotating speed, is heated to 60 DEG C and keeps permanent while moderate-speed mixer
Temperature；
(3) nitrogen is continually fed into step reaction product (2) and reaction vessel, is passed through nitrogen after 3 minutes in holding
Speed is stirred and is maintained at 60 DEG C of constant temperature, is slowly added to ammonium persulfate particle, and reaction continues backflow instead until after particulate matter disappearance
Answer 1.5 hours；
(4) temperature is increased to 80 DEG C and keeps constant temperature, in the case where keeping moderate-speed mixer, be slowly added to cerous sulfate particle, then
The charge door of reaction vessel is closed, lifts the charge of nitrogen, it is 1.3MPa to keep the pressure in reaction vessel, back flow reaction
3.5 hours until reactant presentation white emulsion shape, obtains high molecular polymerization frozen glue；Detect point of the high molecular polymerization frozen glue
Son amount is more than 4,000,000；
(5) in the state of moderate-speed mixer is kept, β-D-MANNOSE aldehyde is slowly added into above-mentioned high molecular polymerization frozen glue
Acid, continues moderate-speed mixer 10 minutes after addition, and adjusts pH value as 7.5；
(6) composite Portland cement slurry, talcum powder are added into step reaction product (5) and mixes type microfibre, middling speed
Stir more than 15 minutes until well mixed；
(7) ammonium dihydrogen phosphate is added into step reaction product (6), moderate-speed mixer 10 minutes, obtain shallow well polyphosphazene polymer
Close frozen glue sealing agent.
Embodiment three
A kind of preparation method of shallow well high molecular polymerization frozen glue sealing agent of the present invention, in turn includes the following steps：
(1) following components and weight content prepare raw material, purified cotton sodium salt solution：120 parts, acrylamide：85 parts, over cure
Sour ammonium：17 parts, cerous sulfate：5 parts, beta-D-mannuronic acid：4 parts, ammonium dihydrogen phosphate：1.5 parts, composite Portland cement slurry：100
Part, talcum powder：90 parts and mix type microfibre：20 parts；The ratio of mud of the composite Portland cement slurry is 0.44；
(2) acrylamide is added in purified cotton sodium salt solution, carrying out high-speed stirred with 400r/min rotating speed makes two in 10 minutes
Person is sufficiently mixed, and then carries out moderate-speed mixer with 300r/min rotating speed, is heated to 60 DEG C and keeps permanent while moderate-speed mixer
Temperature；
(3) nitrogen is continually fed into step reaction product (2) and reaction vessel, is passed through nitrogen after 3 minutes in holding
Speed is stirred and is maintained at 60 DEG C of constant temperature, is slowly added to ammonium persulfate particle, and reaction continues backflow instead until after particulate matter disappearance
Answer 1.5 hours；
(4) temperature is increased to 80 DEG C and keeps constant temperature, in the case where keeping moderate-speed mixer, be slowly added to cerous sulfate particle, then
The charge door of reaction vessel is closed, lifts the charge of nitrogen, it is 1.3MPa to keep the pressure in reaction vessel, back flow reaction
3.5 hours until reactant presentation white emulsion shape, obtains high molecular polymerization frozen glue；Detect point of the high molecular polymerization frozen glue
Son amount is more than 4,000,000；
(5) in the state of moderate-speed mixer is kept, β-D-MANNOSE aldehyde is slowly added into above-mentioned high molecular polymerization frozen glue
Acid, continues moderate-speed mixer 10 minutes after addition, and adjusts pH value 7.5；
(6) composite Portland cement slurry, talcum powder are added into step reaction product (5) and mixes type microfibre, middling speed
Stir more than 15 minutes until well mixed；
(7) ammonium dihydrogen phosphate is added into step reaction product (6), moderate-speed mixer 10 minutes, obtain shallow well polyphosphazene polymer
Close frozen glue sealing agent.
First, the sealing agent to the embodiment of the present invention two carries out initial set, final setting time is tested
The pre-hardening and final setting time of sealing agent at different temperatures is tested with reference to GB/T50080-2002 standard,
Record initial set and the final setting time such as table 1 of sealing agent.
Table 1
。
As can be seen from Table 1, at 30 DEG C, the sealing agent presetting period can reach 130 minutes, and final setting time can reach 410
Minute, but as the raising of temperature, gelling time quickly shorten.The presetting period is 20 minutes when wherein reaching 60 DEG C, reaches 120
DEG C when the presetting period be only 3min, substantially belonging to moment has started glue, but higher than 60 DEG C after final setting time become steady.
2nd, slit formation plugging test is carried out to the sealing agent of the embodiment of the present invention one to embodiment three
SY/T 5840-2007 are pressed in experiment《People's Republic of China's oil and gas industry standard well liquid is stifled with bridge joint
Leak material Experimental Method in Laboratory》Perform.The DLM-01 type sealing Analog Devices produced with Bohai Sea drilling project institute, can be heated up to 150
DEG C, 7.0MPa can be forced into.The vertical slit die plate of selection, thickness 5mm, stitches high 50mm, slit width 3mm.
The sealing agent heating-up temperature of embodiment one is 80 DEG C, and the sealing agent heating-up temperature of embodiment two is 100 DEG C, embodiment
Three sealing agent heating-up temperature is 120 DEG C, and the sealing agent 2000mL of the present invention is injected into test chamber, and sealing agent quickly enters
Template gap is simultaneously flowed out from the lower part outlet of device, and record sealing agent stops the delivery time, as blocking time, and result of the test is converged
Total such as table 2 below.
Table 2
。
After blocking successfully above, 4 hours are stood respectively, then pours into clear water, then embodiment one is still heated up to 80 DEG C
And constant temperature is kept, embodiment two still heats up to 100 DEG C and keeps constant temperature, and embodiment three still heats up to 120 DEG C and keeps permanent
Temperature, it is forced under different pressures and carries out plugging test, maintained 300 seconds under each pressure, observe leakage situation, judges closure effect
Fruit, result of the test are as shown in table 3.
Table 3
。
3rd, osmosis type plugging test is carried out to the sealing agent of the embodiment of the present invention one to embodiment three
SY/T 5840-2007 are pressed in experiment《People's Republic of China's oil and gas industry standard well liquid is stifled with bridge joint
Leak material Experimental Method in Laboratory》Perform.The DLM-01 type sealing Analog Devices produced with Bohai Sea drilling project institute, the filtering surface of casting bed
Product 2289mm2, casting bed thickness 35mm.
The sealing agent heating-up temperature of embodiment one is 80 DEG C, and the sealing agent heating-up temperature of embodiment two is 100 DEG C, embodiment
Three sealing agent heating-up temperature is 120 DEG C, and the sealing agent 2000mL of the present invention is injected into test chamber, and sealing agent quickly enters
Casting bed simultaneously flows out from the lower part outlet of device, and record sealing agent stops the delivery time, as blocking time, result of the test collect as
Shown in table 4 below.
Table 4
。
After blocking successfully above, 4 hours are stood respectively, then pours into clear water, then embodiment one is still heated up to 80 DEG C
And constant temperature is kept, embodiment two still heats up to 100 DEG C and keeps constant temperature, and embodiment three still heats up to 120 DEG C and keeps permanent
Temperature, it is forced under different pressures and carries out plugging test, maintained 300 seconds under each pressure, observe leakage situation, judges closure effect
Fruit, result of the test are as shown in table 5.
Table 5
。
As can be seen that the sealing agent of the present invention, at 100 DEG C, bearing capacity can reach 5MPa, can meet shallow well leak stopping
Need.
Purified cotton used in the present invention is that uniformly white loose, without impurity such as wood chip, bamboo scraps, silt, greasy dirt, metal objects is wadded a quilt with cotton
Shape thing.Its raw material is cotton linter, and main chemical compositions are cellulose, lignin and hemicellulose.It is by carbon, hydrogen, three kinds of oxygen
Element forms, its mass ratio formed：Carbon 44.4%, hydrogen 6.17%, oxygen 49.39%.The formula of purified cotton is：（C6H1005）
N, n represent the degree of polymerization of cellulose, and the degree of polymerization is generally 12000~14000.
Composite Portland cement used in composite Portland cement slurry of the present invention is given birth to for Beijing Jinyu cement Trade Co., Ltd.
The composite Portland cement of production（P.C）.
Hydrophilic finishing agent used in the present invention is that the TD-5512 types of Shenzhen Tianding Fine Chemical Engineering Manufacturing Co., Ltd's production are durable
Property hydrophilic finishing agent.
It the foregoing is only the preferable possible embodiments of the present invention, non-therefore the limitation present invention patent protection model
Enclose.In addition to the implementation, the present invention can also have other embodiment.All skills formed using equivalent substitution or equivalent transformation
Art scheme, all falls within the protection domain of application claims.The technical characteristic that the present invention does not describe to the greatest extent can be by or using now
There is technology realization, will not be repeated here.
Claims (10)
1. a kind of shallow well high molecular polymerization frozen glue sealing agent, it is characterised in that the raw material components and weight content of the sealing agent are such as
Under, purified cotton sodium salt solution：120 parts, acrylamide：（75~85）Part, ammonium persulfate：（13~17）Part, cerous sulfate：（2~5）
Part, beta-D-mannuronic acid：4 parts, ammonium dihydrogen phosphate：（1~1.5）Part, composite Portland cement slurry：100 parts, talcum powder：（80
~90）Part and mix type microfibre：20 parts；The ratio of mud of the composite Portland cement slurry is 0.44.
2. shallow well high molecular polymerization frozen glue sealing agent according to claim 1, it is characterised in that the purified cotton sodium salt
Preparation method is as follows：1. prepare purified cotton that the cotton fiber degree of polymerization is 12000~14000 and concentration expressed in percentage by weight be 17.5~
The weight ratio of 18% sodium hydroxide solution, purified cotton and sodium hydroxide solution is 5:2；2. it is molten that purified cotton is put into sodium hydroxide
In liquid, stir and react more than 1.5 hours at 60 DEG C, until uniform white suspension emulsion is presented, obtain purified cotton sodium salt
First solution；3. carrying out ultrasonic micro-vibration 30 minutes to solution at the beginning of purified cotton sodium salt, purified cotton sodium salt solution is obtained, supersonic frequency is
20kHz~30kHz, ultrasonication intensity are 2.0 W/cm2~3.0W/cm2.
3. shallow well high molecular polymerization frozen glue sealing agent according to claim 1, it is characterised in that described to mix type microfibre
By calcium carbonate crystal whisker and organic microfiber uniformly mix and form, the mixing ratio of the calcium carbonate crystal whisker and organic microfiber is
0.8:1。
4. shallow well high molecular polymerization frozen glue sealing agent according to claim 3, it is characterised in that the calcium carbonate crystal whisker
20~30 μm of length, 0.5~1 μm of diameter, pH value 9.0~9.5, modulus of elasticity is 410~710GPa and tensile strength is not less than
2.058GPa；The organic microfiber is made up of polyester fiber and polypropylene fibre, the weight of polyester fiber and polypropylene fibre
Than for 7:3；20~25 μm, 6~9mm of length of the diameter of the polyester fiber, elongation at break >=15%, tensile strength >=
960MPa and modulus of elasticity >=9000MPa；The length of the polypropylene fibre is 10~20mm, filament number≤2.2dtex, is resisted
Tensile strength >=660MPa, modulus of elasticity >=350MPa.
5. shallow well high molecular polymerization frozen glue sealing agent according to claim 4, it is characterised in that the polyester fiber and poly-
Tacryl soaks 3 hours at 60 DEG C in hydrophilic finishing agent.
6. a kind of preparation method of shallow well high molecular polymerization frozen glue sealing agent, it is characterised in that in turn include the following steps：
(1) raw material, purified cotton sodium salt solution are prepared by following components and weight content：120 parts, acrylamide：（75~85）Part,
Ammonium persulfate：（13~17）Part, cerous sulfate：（2~5）Part, beta-D-mannuronic acid：4 parts, ammonium dihydrogen phosphate：（1~1.5）Part,
Composite Portland cement is starched：100 parts, talcum powder：（80~90）Part and mix type microfibre：20 parts；The complex silicate salt solution
The ratio of mud of mud is 0.44；
(2) acrylamide is added into purified cotton sodium salt solution, carrying out high-speed stirred with 400r/min rotating speed makes both in 10 minutes
It is sufficiently mixed, moderate-speed mixer is then carried out with 300r/min rotating speed, is heated to 60 DEG C and keeps constant temperature while moderate-speed mixer；
(3) nitrogen is continually fed into step reaction product (2) and reaction vessel, is passed through nitrogen and is keeping middling speed to stir after 3 minutes
Mix and be maintained at 60 DEG C of constant temperature, be slowly added to ammonium persulfate particle, reaction continues back flow reaction until after particulate matter disappearance
1.5 hour；
(4) temperature is increased to 80 DEG C and keeps constant temperature, in the case where keeping moderate-speed mixer, be slowly added to cerous sulfate particle, be then shut off
The charge door of reaction vessel, lifts the charge of nitrogen, and it is 1.3MPa to keep the pressure in reaction vessel, back flow reaction 3 hours
Above until white emulsion shape is presented in reactant, high molecular polymerization frozen glue is obtained；Detect the molecule of the high molecular polymerization frozen glue
Amount is more than 4,000,000；
(5) in the state of moderate-speed mixer is kept, beta-D-mannuronic acid is slowly added into above-mentioned high molecular polymerization frozen glue, is added
Continue moderate-speed mixer after entering 10 minutes, and adjust pH value as 7~7.5；
(6) composite Portland cement slurry, talcum powder are added into step reaction product (5) and mixes type microfibre, moderate-speed mixer
More than 15 minutes until well mixed；
(7) ammonium dihydrogen phosphate is added into step reaction product (6), moderate-speed mixer 10 minutes, obtains shallow well high molecular polymerization jelly
Glue sealing agent.
7. the preparation method of shallow well high molecular polymerization frozen glue sealing agent according to claim 6, it is characterised in that the essence
The preparation method of cotton sodium salt processed is as follows：1. prepare the purified cotton and concentration expressed in percentage by weight that the cotton fiber degree of polymerization is 12000~14000
For 17.5~18% sodium hydroxide solution, the weight ratio of purified cotton and sodium hydroxide solution is 5:2；2. purified cotton is put into hydrogen
In sodium hydroxide solution, stir and react more than 1.5 hours at 60 DEG C, until uniform white suspension emulsion is presented, obtain essence
The first solution of cotton sodium salt processed；3. carrying out ultrasonic micro-vibration 30 minutes to solution at the beginning of purified cotton sodium salt, purified cotton sodium salt solution is obtained, is surpassed
Acoustic frequency is 20kHz~30kHz, and ultrasonication intensity is 2.0 W/cm2~3.0W/cm2.
8. the preparation method of shallow well high molecular polymerization frozen glue sealing agent according to claim 6, it is characterised in that described mixed
Miscellaneous type microfibre by calcium carbonate crystal whisker and organic microfiber uniformly mix and formed, calcium carbonate crystal whisker and organic microfiber it is mixed
Composition and division in a proportion is 0.8:1.
9. the preparation method of shallow well high molecular polymerization frozen glue sealing agent according to claim 8, it is characterised in that the carbon
20~30 μm of the length of sour calcium pyroborate, 0.5~1 μm of diameter, pH value 9.0~9.5, modulus of elasticity are 410~710GPa and tension
Intensity is not less than 2.058GPa；The organic microfiber is made up of polyester fiber and polypropylene fibre, polyester fiber and polypropylene
The weight ratio of fiber is 7:3；20~25 μm, 6~9mm of length of the diameter of the polyester fiber, elongation at break >=15%, tension
Intensity >=960MPa and modulus of elasticity >=9000MPa；The length of the polypropylene fibre is 10~20mm, filament number≤
2.2dtex, tensile strength >=660MPa, modulus of elasticity >=350MPa.
10. the preparation method of shallow well high molecular polymerization frozen glue sealing agent according to claim 8, it is characterised in that described
Polyester fiber and polypropylene fibre soak 3 hours at 60 DEG C in hydrophilic finishing agent.
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