CN105219365A - Middle-deep well cross-linked polymer gel plugging agent and preparation method thereof - Google Patents
Middle-deep well cross-linked polymer gel plugging agent and preparation method thereof Download PDFInfo
- Publication number
- CN105219365A CN105219365A CN201510577380.XA CN201510577380A CN105219365A CN 105219365 A CN105219365 A CN 105219365A CN 201510577380 A CN201510577380 A CN 201510577380A CN 105219365 A CN105219365 A CN 105219365A
- Authority
- CN
- China
- Prior art keywords
- polymer gel
- linked polymer
- plugging agent
- purified cotton
- deep well
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- 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
- C09K8/467—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 containing additives for specific purposes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F251/00—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof
- C08F251/02—Macromolecular compounds obtained by polymerising monomers on to polysaccharides or derivatives thereof on to cellulose or derivatives thereof
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Sealing Material Composition (AREA)
- Compositions Of Macromolecular Compounds (AREA)
Abstract
The present invention relates to a kind of middle-deep well cross-linked polymer gel plugging agent and preparation method thereof, feed composition and weight content be, purified cotton sodium salt solution: 120 parts, acrylamide: (75 ~ 85) part, ammonium persulphate: (13 ~ 17) part, cerous sulfate: (2 ~ 5) part, beta-D-mannuronic acid (M): 4 parts, primary ammonium phosphate: (1 ~ 1.5) part, composite Portland cement slurry: 100 parts and mix type primitive fiber: (150 ~ 200) part; The water cement ratio of described composite Portland cement slurry is 0.44; In purified cotton sodium salt solution, add acrylamide successively, ammonium persulphate particle, cerous sulfate particle obtain cross-linked polymer gel, add beta-D-mannuronic acid (M) again, then add composite Portland cement slurry and mix type primitive fiber, finally adding primary ammonium phosphate and stir evenly and obtain middle-deep well cross-linked polymer gel plugging agent.By force, leak stopping is reliable for this middle-deep well cross-linked polymer gel plugging agent high temperature resistance and anti-pressure ability.
Description
Technical field
The present invention relates to a kind of middle-deep well cross-linked polymer gel plugging agent, the invention still further relates to a kind of preparation method of middle-deep well cross-linked polymer gel plugging agent, belong to petroleum drilling technology field.
Background technology
Leakage is the technical barrier often run in drilling process, especially high temperature leakage can cause a large amount of losses of drilling fluid, cause the rising of drilling cost, bottomhole wellbore pressure can be caused to change simultaneously, bring out the generation of the complex accident such as borehole well instability, well slough, well kick, blowout, seriously govern the raising of drilling speed.
At present when high-temperature stratum leakage section met by petroleum drilling brill, owing to lacking the leakage stopping technology of high temperature resistance, the conventional plugging agent leak stopping of general employing.What domestic process high temperature leakage generally adopted is bridge joint leak stopping, and bridge joint leak stopping has economy, easy to use, the advantage of construction safety, can solve the partial loss that caused by hole and crack and leakage is returned in mistake.The bridge joint patching materials of domestic use is roughly divided into three classes: hard fruit shell class, fibrous material and lamellar material.In Process of Leaking Stoppage, any class material is used alone, its effect is all limited, only have above-mentioned three class materials with rational ratio and grating compound use, just can receive due effect, but along with deepening continuously of creeping into, the temperature on leakage stratum is also in continuous rising, be immersed in hard fruit shell class material in mud and plant fiber material as nut-shell, hazelnut shell, cotton seed hulls and sawdust etc., high temperature in well, under the condition of high pressure and alkali corrosion, As time goes on, these materials are by slowly deliquescing, corrosion, even some material can be burnt, bridge joint intensity is caused sharply to decline, be easy to cause leak stopping failure or secondary leakage, fundamentally cannot solve a difficult problem for high temperature leak stopping.
Well depth is that 4000 ~ 5000m is called middle-deep well, and downhole temperature is usually at 120 DEG C ~ 140 DEG C.Although the stoppage engineering that conventional blocking method is petroleum drilling has played effect, but there is shortcoming or deficiency simultaneously, high-temperature resistance is low, validity period is short, leak stopping efficiency is poor, patching materials consumption is large, plugging time is long, high temperature deep well and geothermal well leak stopping safety coefficient poor, easily there is down hole problem, these shortcomings directly affect the probing development process of hot hole and geothermal well, therefore traditional high temperature patching materials far from can meet the leak stopping demand of growing deep-well Holes of Complicated Wells, therefore it is very necessary for studying a kind of high temperature deep well high temperature resistance plugging agent.
Summary of the invention
Primary and foremost purpose of the present invention is, overcomes problems of the prior art, provides a kind of middle-deep well cross-linked polymer gel plugging agent, and by force, leak stopping is reliable for high temperature resistance and anti-pressure ability.
For solving above technical problem, a kind of middle-deep well cross-linked polymer gel plugging agent of the present invention, feed composition and the weight content of this plugging agent are as follows, purified cotton sodium salt solution: 120 parts, acrylamide: (75 ~ 85) part, ammonium persulphate: (13 ~ 17) part, cerous sulfate: (2 ~ 5) part, beta-D-mannuronic acid (M): 4 parts, primary ammonium phosphate: (1 ~ 1.5) part, composite Portland cement slurry: 100 parts and mix type primitive fiber: (150 ~ 200) part; The water cement ratio of described 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 Mierocrystalline cellulose of crosslinking reaction; Acrylamide plays bridge formation adsorption, Mierocrystalline cellulose is flocculated, is cross-linked with each other; Ammonium persulphate causes crosslinking reaction, makes fiber destarch simultaneously; Cerous sulfate initiation polymer is polymerized, graft reaction; Composite Portland cement slurry can provide intensity and the anti-pressure ability of blob of viscose; Mix the effect that type primitive fiber plays bridge particle, provide the intensity of last formation " block wall " to ensure.2. this plugging agent adopts synthon and natural fiber to be cross-linked to form the net high-polymer polymkeric substance of mutual winding, and can resist the high temperature of more than 140 DEG C, anti-pressure ability reaches 15MPa, can meet the leak stopping requirement of 4000 ~ 5000m middle-deep well completely.3. the adding proportion mixing type primitive fiber in the present invention makes plugging agent have the highest intensity, if continue to improve the weight ratio mixing type primitive fiber, can disturb the chemically crosslinked effect of gel chemistries material on the contrary, can reduce the bearing capacity of its leak stopping on the contrary.
As preferred version of the present invention, the preparation method of described purified cotton sodium salt is as follows: 1. prepare the cotton fibre polymerization degree be 12000 ~ 14000 purified cotton and concentration expressed in percentage by weight be the sodium hydroxide solution of 17.5 ~ 18%, the weight ratio of purified cotton and sodium hydroxide solution is 5:2; 2. purified cotton is dropped in sodium hydroxide solution, stir at 60 DEG C and react more than 1.5 hours, until present uniform white suspension emulsion, obtain purified cotton sodium salt just solution; 3. carry out ultrasonic micro-vibration 30 minutes to the first solution of purified cotton sodium salt, obtain purified cotton sodium salt solution, ultrasonic frequency is 20kHz ~ 30kHz, and ultrasonication intensity is 2.0W/cm2 ~ 3.0W/cm2.Purified cotton and sodium hydroxide react and generate purified cotton sodium salt, and what make purified cotton inside obtains abundant moistening expansion, improves the reactive behavior of purified cotton, is conducive to further crosslinking reaction.Supersound process can improve the molecule link Zhi Chengdu of purified cotton sodium salt, for follow-up to provide with linking agent more meets Zhi Duan.Reaction mechanism is:
。
As preferred version of the present invention, described in mix type primitive fiber and evenly mixed by calcium carbonate crystal whisker and organic microfiber and form, the ratio of mixture of described calcium carbonate crystal whisker and organic microfiber is 0.8:1.Calcium carbonate crystal whisker and organic microfiber are dispersed in cross-linked polymer gel, are cross-linked to form with the high molecular polymer in cross-linked polymer gel the net high-polymer polymkeric substance be mutually wound around.Calcium carbonate crystal whisker provides the supporting role of physical property for forming " block wall ", its intensity is significantly promoted; Organic microfiber and calcium carbonate crystal whisker are wound around mutually, for " block wall " that formed provides the supporting role of physical property, its intensity are significantly promoted; Meanwhile, " block wall " is added by intensity when deforming under reservoir pressure effect.
As the further preferred version of the present invention, the length of described calcium carbonate crystal whisker 20 ~ 30 μm, diameter 0.5 ~ 1 μm, pH value 9.0 ~ 9.5, Young's modulus is 410 ~ 710GPa and tensile strength is not less than 2.058GPa; Described organic microfiber is made up of trevira and polypropylene fibre, and the weight of trevira and polypropylene fibre is 7:3; The diameter of described trevira 20 ~ 25 μm, length 6 ~ 9mm, elongation at break >=15%, tensile strength >=960MPa and Young's modulus >=9000MPa; The length of described polypropylene fibre is 10 ~ 20mm, filament number≤2.2dtex, tensile strength >=660MPa, Young's modulus >=350MPa.Polypropylene fibre can improve the intensity of " block wall ", improves " block wall " rebound performance after compressive deformation.Trevira can improve the anti-fatigue performance of " block wall ", resistance to cleavage and high temperature stability performance, effectively can improve the tension of " block wall ", resistance to compression, anti-shearing and resistance to impact shock, makes up the deficiency of polypropylene fibre in heat-resisting and ageing-resistant.
As the further preferred version of the present invention, described trevira and polypropylene fibre all soak 3 hours at 60 DEG C in hydrophilic finishing agent.Due to trevira and polypropylene fibre compound with regular structure but wetting ability is poor, be difficult to be uniformly dispersed in cross-linked polymer gel, hydrophilic finishing agent is adopted to carry out surface modification treatment to trevira and polypropylene fibre, its hydrophilicity can be improved, be conducive to them dispersed in polymer gel, make " block wall " structure and the even intensity of formation.
Another object of the present invention is, provides a kind of preparation method of middle-deep well cross-linked polymer gel plugging agent, the plugging agent that the method is prepared from, and by force, leak stopping is reliable for high temperature resistance and anti-pressure ability.
For solving above technical problem, the preparation method of a kind of middle-deep well cross-linked polymer gel plugging agent of the present invention, in turn include the following steps: (1) prepare raw material by following component and weight content, purified cotton sodium salt solution: 120 parts, acrylamide: (75 ~ 85) part, ammonium persulphate: (13 ~ 17) part, cerous sulfate: (2 ~ 5) part, beta-D-mannuronic acid (M): 4 parts, primary ammonium phosphate: (1 ~ 1.5) part, composite Portland cement slurry: 100 parts and mix type primitive fiber: (150 ~ 200) part; The water cement ratio of described composite Portland cement slurry is 0.44; (2) in purified cotton sodium salt solution, add acrylamide, carry out high-speed stirring with the rotating speed of 400r/min and within 10 minutes, make both fully mixing, then carry out moderate-speed mixer with the rotating speed of 300r/min, be heated to 60 DEG C while moderate-speed mixer and keep constant temperature; (3) continue to pass into nitrogen in step reaction product (2) and reaction vessel, pass into nitrogen and at remaining on constant temperature 60 DEG C, slowly add ammonium persulphate particle at maintenance moderate-speed mixer after 3 minutes, reaction is until after particulate matter disappears, continue back flow reaction 1.5 hours; (4) temperature be increased to 80 DEG C and keep constant temperature, under maintenance moderate-speed mixer, slowly add cerous sulfate particle, then the charging opening of off-response container, promote the charge of nitrogen, keep the pressure in reaction vessel to be 1.3MPa, back flow reaction more than 3 hours, until reactant presents white emulsion shape, obtains cross-linked polymer gel; Detect the molecular weight of described cross-linked polymer gel more than 4,000,000; (5), under the state keeping moderate-speed mixer, in above-mentioned cross-linked polymer gel, slowly add beta-D-mannuronic acid (M), continue moderate-speed mixer after adding 10 minutes, and adjust ph is 7 ~ 7.5; (6) in step reaction product (5), add composite Portland cement slurry and mix type primitive fiber, moderate-speed mixer more than 15 minutes is until mix; (7) in step reaction product (6), add primary ammonium phosphate, moderate-speed mixer 10 minutes, obtain middle-deep well cross-linked polymer gel plugging agent.
Relative to prior art, the present invention achieves following beneficial effect: 1. purified cotton sodium salt provides the Mierocrystalline cellulose of crosslinking reaction, and acrylamide plays bridge formation adsorption, Mierocrystalline cellulose is flocculated, is cross-linked with each other.Ammonium persulphate causes crosslinking reaction, makes fiber destarch simultaneously; Before adding ammonium persulphate, pass into nitrogen, guarantee reaction environment anaerobic, avoid Mierocrystalline cellulose to rise in cross-linking process sticky, affect the molecular weight of final cross-linking products; Back flow reaction 1.5h guarantees under the effect of crosslinking reaction initiator, and purified cotton fibre element builds bridge that adsorbing acrylamide is full cross-linked, copolyreaction with can provide, and makes cellulose molecular chain elongated, and molecular weight sharp increase.Cerous sulfate further between cellulose initiated and acrylamide, Mierocrystalline cellulose and acrylamide be by between ammonium persulphate copolymerzation with cross-linking reaction product and mutual grafting between Mierocrystalline cellulose and copolymerzation with cross-linking reactant, make the molecular weight of the high molecular polymer of generation larger, molecular chain has more side chain, there is provided more side chain for forming gel after formation under the effect of thixotropic agent, the gel-strength of formation is higher.Reaction mechanism is:
。
2. the molecular weight of cross-linked polymer gel illustrate more than 4,000,000 crosslinked, copolymerization, graft reaction very abundant, for the intensity forming " block wall " is given security.3. after adding beta-D-mannuronic acid (M) in cross-linked polymer gel, the amide group in the sodium ion of beta-D-mannuronic acid (M) and cross-linked polymer gel exchanges, and carries out ionic replacement at carboxyl position, thus gelling reaction occurs, and forms blob of viscose.Beta-D-mannuronic acid (M) viscosity when pH reduces can increase, and there is viscosity thixotropic, have certain alkali-resistivity when pH is 6.7, and when pH is 7 ~ 7.5, the blob of viscose of formation has better shear thinning behavior, for pumping provides favourable condition.4. after cross-linked polymer gel gelling, if wherein do not have enough bridge particles, the blob of viscose intensity of formation only can reach 1 ~ 2MPa, can not meet the pressurization sealing requirement of middle-deep well; Mix the effect that type primitive fiber can play bridge particle, under the high-temperature condition of down-hole, high molecular polymerization frozen glue slowly starts gelling, after complete gelation, the intensity forming blob of viscose can reach 15MPa, the high temperature of more than 140 DEG C can be resisted, the leak stopping needs of the middle-deep well of well depth 4000 ~ 5000m can be met.The adding proportion mixing type primitive fiber in the present invention makes plugging agent have the highest intensity, if continue to improve the weight ratio mixing type primitive fiber, can disturb the chemically crosslinked effect of gel chemistries material on the contrary, can reduce the bearing capacity of its leak stopping on the contrary.5. the primary ammonium phosphate of ratio of the present invention is added, gelling can be controlled in suitable time range, both ensured before gelling, plugging agent can be pumped to drop ply, replacing in drilling rod and well can be completed again starch before gelling, there is gelling in time after plugging agent can also be made to arrive drop ply, make leak stopping slurries stop living at drop ply.
As preferred version of the present invention, the preparation method of described purified cotton sodium salt is as follows: 1. prepare the cotton fibre polymerization degree be 12000 ~ 14000 purified cotton and concentration expressed in percentage by weight be the sodium hydroxide solution of 17.5 ~ 18%, the weight ratio of purified cotton and sodium hydroxide solution is 5:2; 2. purified cotton is dropped in sodium hydroxide solution, stir at 60 DEG C and react more than 1.5 hours, until present uniform white suspension emulsion, obtain purified cotton sodium salt just solution; 3. carry out ultrasonic micro-vibration 30 minutes to the first solution of purified cotton sodium salt, obtain purified cotton sodium salt solution, ultrasonic frequency is 20kHz ~ 30kHz, and ultrasonication intensity is 2.0W/cm2 ~ 3.0W/cm2.
As preferred version of the present invention, described in mix type primitive fiber and evenly mixed by calcium carbonate crystal whisker and organic microfiber and form, the ratio of mixture of calcium carbonate crystal whisker and organic microfiber is 0.8:1.
As the further preferred version of the present invention, the length of described calcium carbonate crystal whisker 20 ~ 30 μm, diameter 0.5 ~ 1 μm, pH value 9.0 ~ 9.5, Young's modulus is 410 ~ 710GPa and tensile strength is not less than 2.058GPa; Described organic microfiber is made up of trevira and polypropylene fibre, and the weight of trevira and polypropylene fibre is 7:3; The diameter of described trevira 20 ~ 25 μm, length 6 ~ 9mm, elongation at break >=15%, tensile strength >=960MPa and Young's modulus >=9000MPa; The length of described polypropylene fibre is 10 ~ 20mm, filament number≤2.2dtex, tensile strength >=660MPa, Young's modulus >=350MPa.
As the further preferred version of the present invention, described trevira and polypropylene fibre all soak 3 hours at 60 DEG C in hydrophilic finishing agent.
Embodiment
Embodiment one
The preparation method of a kind of middle-deep well cross-linked polymer gel plugging agent of the present invention, in turn includes the following steps:
(1) following component and weight content prepare raw material, purified cotton sodium salt solution: 120 parts, acrylamide: 75 parts, ammonium persulphate: 13 parts, cerous sulfate: 2 parts, beta-D-mannuronic acid (M): 4 parts, primary ammonium phosphate: 1 part, composite Portland cement slurry: 100 parts and mix type primitive fiber: 150 parts; The water cement ratio of described composite Portland cement slurry is 0.44;
(2) add acrylamide in purified cotton sodium salt solution, carry out high-speed stirring with the rotating speed of 400r/min and within 10 minutes, make both fully mixing, then carry out moderate-speed mixer with the rotating speed of 300r/min, be heated to 60 DEG C while moderate-speed mixer and keep constant temperature;
(3) continue to pass into nitrogen in step reaction product (2) and reaction vessel, pass into nitrogen and at remaining on constant temperature 60 DEG C, slowly add ammonium persulphate particle at maintenance moderate-speed mixer after 3 minutes, reaction is until after particulate matter disappears, continue back flow reaction 1.5 hours;
(4) temperature be increased to 80 DEG C and keep constant temperature, under maintenance moderate-speed mixer, slowly add cerous sulfate particle, then the charging opening of off-response container, promote the charge of nitrogen, keep the pressure in reaction vessel to be 1.3MPa, back flow reaction 3 hours, until reactant presents white emulsion shape, obtains cross-linked polymer gel; Detect the molecular weight of described cross-linked polymer gel more than 4,000,000;
(5), under the state keeping moderate-speed mixer, in above-mentioned cross-linked polymer gel, slowly add beta-D-mannuronic acid (M), continue moderate-speed mixer after adding 10 minutes, and adjust ph is 7;
(6) in step reaction product (5), add composite Portland cement slurry and mix type primitive fiber, moderate-speed mixer more than 15 minutes is until mix;
(7) in step reaction product (6), add primary ammonium phosphate, moderate-speed mixer 10 minutes, obtain middle-deep well cross-linked polymer gel plugging agent.
Embodiment two
The preparation method of a kind of middle-deep well cross-linked polymer gel plugging agent of the present invention, in turn includes the following steps:
(1) following component and weight content prepare raw material, purified cotton sodium salt solution: 120 parts, acrylamide: 80 parts, ammonium persulphate: 15 parts, cerous sulfate: 3 parts, beta-D-mannuronic acid (M): 4 parts, primary ammonium phosphate: 1.2 parts, composite Portland cement slurry: 100 parts and mix type primitive fiber: 180 parts; The water cement ratio of described composite Portland cement slurry is 0.44;
(2) add acrylamide in purified cotton sodium salt solution, carry out high-speed stirring with the rotating speed of 400r/min and within 10 minutes, make both fully mixing, then carry out moderate-speed mixer with the rotating speed of 300r/min, be heated to 60 DEG C while moderate-speed mixer and keep constant temperature;
(3) continue to pass into nitrogen in step reaction product (2) and reaction vessel, pass into nitrogen and at remaining on constant temperature 60 DEG C, slowly add ammonium persulphate particle at maintenance moderate-speed mixer after 3 minutes, reaction is until after particulate matter disappears, continue back flow reaction 1.5 hours;
(4) temperature be increased to 80 DEG C and keep constant temperature, under maintenance moderate-speed mixer, slowly add cerous sulfate particle, then the charging opening of off-response container, promote the charge of nitrogen, keep the pressure in reaction vessel to be 1.3MPa, back flow reaction 3.5 hours, until reactant presents white emulsion shape, obtains cross-linked polymer gel; Detect the molecular weight of described cross-linked polymer gel more than 4,000,000;
(5), under the state keeping moderate-speed mixer, in above-mentioned cross-linked polymer gel, slowly add beta-D-mannuronic acid (M), continue moderate-speed mixer after adding 10 minutes, and adjust ph is 7.5;
(6) in step reaction product (5), add composite Portland cement slurry and mix type primitive fiber, moderate-speed mixer more than 15 minutes is until mix;
(7) in step reaction product (6), add primary ammonium phosphate, moderate-speed mixer 10 minutes, obtain middle-deep well cross-linked polymer gel plugging agent.
Embodiment three
The preparation method of a kind of middle-deep well cross-linked polymer gel plugging agent of the present invention, in turn includes the following steps:
(1) following component and weight content prepare raw material, purified cotton sodium salt solution: 120 parts, acrylamide: 85 parts, ammonium persulphate: 17 parts, cerous sulfate: 5 parts, beta-D-mannuronic acid (M): 4 parts, primary ammonium phosphate: 1.5 parts, composite Portland cement slurry: 100 parts and mix type primitive fiber: 200 parts; The water cement ratio of described composite Portland cement slurry is 0.44;
(2) add acrylamide in purified cotton sodium salt solution, carry out high-speed stirring with the rotating speed of 400r/min and within 10 minutes, make both fully mixing, then carry out moderate-speed mixer with the rotating speed of 300r/min, be heated to 60 DEG C while moderate-speed mixer and keep constant temperature;
(3) continue to pass into nitrogen in step reaction product (2) and reaction vessel, pass into nitrogen and at remaining on constant temperature 60 DEG C, slowly add ammonium persulphate particle at maintenance moderate-speed mixer after 3 minutes, reaction is until after particulate matter disappears, continue back flow reaction 1.5 hours;
(4) temperature be increased to 80 DEG C and keep constant temperature, under maintenance moderate-speed mixer, slowly add cerous sulfate particle, then the charging opening of off-response container, promote the charge of nitrogen, keep the pressure in reaction vessel to be 1.3MPa, back flow reaction 3.5 hours, until reactant presents white emulsion shape, obtains cross-linked polymer gel; Detect the molecular weight of described cross-linked polymer gel more than 4,000,000;
(5), under the state keeping moderate-speed mixer, in above-mentioned cross-linked polymer gel, slowly add beta-D-mannuronic acid (M), continue moderate-speed mixer after adding 10 minutes, and adjust ph 7.5;
(6) in step reaction product (5), add composite Portland cement slurry and mix type primitive fiber, moderate-speed mixer more than 15 minutes is until mix;
(7) in step reaction product (6), add primary ammonium phosphate, moderate-speed mixer 10 minutes, obtain middle-deep well cross-linked polymer gel plugging agent.
One, initial set, final setting time test are carried out to the plugging agent of the embodiment of the present invention two
Standard with reference to GB/T50080-2002 is tested plugging agent initial set at different temperatures and final setting time, and the initial set of record plugging agent and final setting time are as table 1.
Table 1
。
As can be seen from Table 1, at 30 DEG C, the plugging agent presetting period can reach 135 minutes, and final setting time can reach 420 minutes, but along with the raising of temperature, gelation time shortens fast.When wherein reaching 60 DEG C, the presetting period is 21 minutes, and when reaching 120 DEG C, the presetting period is only 3min, substantially belongs to and has started glue instantaneously, but becomes steady higher than final setting time after 60 DEG C.
Two, slit formation plugging test is carried out to the plugging agent of the embodiment of the present invention one to embodiment three
Test is pressed SY/T5840-2007 " People's Republic of China's oil and gas industry standard well liquid bridge joint patching materials Experimental Method in Laboratory " and is performed.With the DLM-01 type sealing Analog Device that Bohai Sea drilling project institute produces, can heat to 150 DEG C, can 7.0MPa be forced into.Select vertical slit die plate, thickness 5mm, stitches high 50mm, and stitching wide is 3mm.
The plugging agent Heating temperature of embodiment one is 80 DEG C, the plugging agent Heating temperature of embodiment two is 120 DEG C, the plugging agent Heating temperature of embodiment three is 140 DEG C, plugging agent 2000mL of the present invention is injected in test chamber, plugging agent enters rapidly template gap and flows out from the lower part outlet of device, record plugging agent stops the elution time, and be blocking time, test-results gathers as following table 2.
Table 2
。
After above shutoff success, leave standstill 4 hours respectively, then pour into clear water, then embodiment one is still heated to 80 DEG C and keeps constant temperature, and embodiment two is still heated to 120 DEG C and keeps constant temperature, embodiment three is still heated to 140 DEG C and keeps constant temperature, carry out plugging test under being forced into different pressures, under each pressure, maintain 300 seconds, observe leakage situation, judge plugging effect, test-results is as shown in table 3.
Table 3
。
Three, osmosis type plugging test is carried out to the plugging agent of the embodiment of the present invention one to embodiment three
Test is pressed SY/T5840-2007 " People's Republic of China's oil and gas industry standard well liquid bridge joint patching materials Experimental Method in Laboratory " and is performed.With the DLM-01 type sealing Analog Device that Bohai Sea drilling project institute produces, the filtration area 2289mm2 of casting bed, casting bed thickness 35mm.
The plugging agent Heating temperature of embodiment one is 80 DEG C, the plugging agent Heating temperature of embodiment two is 120 DEG C, the plugging agent Heating temperature of embodiment three is 140 DEG C, plugging agent 2000mL of the present invention is injected in test chamber, plugging agent enters casting bed rapidly and flows out from the lower part outlet of device, record plugging agent stops the elution time, and be blocking time, test-results gathers as shown in table 4 below.
Table 4
。
Embodiment three does not have plugging agent to flow out at 140 DEG C, and plugging agent infiltrates casting bed 3/4 and is shutoff success.
After above shutoff success, leave standstill 4 hours respectively, then pour into clear water, then embodiment one is still heated to 80 DEG C and keeps constant temperature, and embodiment two is still heated to 120 DEG C and keeps constant temperature, embodiment three is still heated to 140 DEG C and keeps constant temperature, carry out plugging test under being forced into different pressures, under each pressure, maintain 300 seconds, observe leakage situation, judge plugging effect, test-results is as shown in table 5.
Table 5
。
Four, ultimate compressive ability test is carried out to the blob of viscose that the plugging agent of the embodiment of the present invention two is formed
The plugging agent getting the embodiment of the present invention two is gelling 4 hours and 12 hours respectively at 140 DEG C, carries out mechanical pressurization respectively to the blob of viscose obtained, and tests to cause its structure and to be badly deformed loose force value.Test-results is as shown in table 6.
Table 6
。
Can find out, along with the increase of gelation time, the blob of viscose ultimate compression strength of formation increases, the highest can resistance to compression 15MPa.
The present invention purified cotton used be evenly loose, without the White Flocculus of the impurity such as wood chip, bamboo bits, silt, greasy dirt, metal object.Its raw material is linters, and main chemical compositions is Mierocrystalline cellulose, xylogen and hemicellulose.It is elementary composition by carbon, hydrogen, oxygen three kinds, the mass ratio of its composition: carbon 44.4%, hydrogen 6.17%, oxygen 49.39%.The general formula of purified cotton is: (C6H1005) n, n represents the cellulosic polymerization degree, and the polymerization degree is generally 12000 ~ 14000.
It is the composite Portland cement (P.C) that Beijing Jinyu cement Trade Co., Ltd. produces that composite Portland cement of the present invention starches composite Portland cement used.
The present invention's hydrophilic finishing agent used is the TD-5512 type durable hydrophilic finishing composition that Shenzhen Tianding Fine Chemical Engineering Manufacturing Co., Ltd produces.
The foregoing is only the better possible embodiments of the present invention, non-ly therefore limit to scope of patent protection of the present invention.In addition to the implementation, the present invention can also have other embodiments.All employings are equal to the technical scheme of replacement or equivalent transformation formation, all drop in the protection domain of application claims.The technical characteristic that the present invention does not describe to the greatest extent can pass through or adopt existing techniques in realizing, does not repeat them here.
Claims (10)
1. a middle-deep well cross-linked polymer gel plugging agent, it is characterized in that, feed composition and the weight content of this plugging agent are as follows, purified cotton sodium salt solution: 120 parts, acrylamide: (75 ~ 85) part, ammonium persulphate: (13 ~ 17) part, cerous sulfate: (2 ~ 5) part, beta-D-mannuronic acid (M): 4 parts, primary ammonium phosphate: (1 ~ 1.5) part, composite Portland cement slurry: 100 parts and mix type primitive fiber: (150 ~ 200) part; The water cement ratio of described composite Portland cement slurry is 0.44.
2. middle-deep well cross-linked polymer gel plugging agent according to claim 1, it is characterized in that, the preparation method of described purified cotton sodium salt is as follows: 1. prepare the cotton fibre polymerization degree be 12000 ~ 14000 purified cotton and concentration expressed in percentage by weight be the sodium hydroxide solution of 17.5 ~ 18%, the weight ratio of purified cotton and sodium hydroxide solution is 5:2; 2. purified cotton is dropped in sodium hydroxide solution, stir at 60 DEG C and react more than 1.5 hours, until present uniform white suspension emulsion, obtain purified cotton sodium salt just solution; 3. carry out ultrasonic micro-vibration 30 minutes to the first solution of purified cotton sodium salt, obtain purified cotton sodium salt solution, ultrasonic frequency is 20kHz ~ 30kHz, and ultrasonication intensity is 2.0W/cm2 ~ 3.0W/cm2.
3. middle-deep well cross-linked polymer gel plugging agent according to claim 1, is characterized in that, described in mix type primitive fiber and evenly mixed by calcium carbonate crystal whisker and organic microfiber and form, the ratio of mixture of described calcium carbonate crystal whisker and organic microfiber is 0.8:1.
4. middle-deep well cross-linked polymer gel plugging agent according to claim 3, it is characterized in that, the length of described calcium carbonate crystal whisker 20 ~ 30 μm, diameter 0.5 ~ 1 μm, pH value 9.0 ~ 9.5, Young's modulus is 410 ~ 710GPa and tensile strength is not less than 2.058GPa; Described organic microfiber is made up of trevira and polypropylene fibre, and the weight of trevira and polypropylene fibre is 7:3; The diameter of described trevira 20 ~ 25 μm, length 6 ~ 9mm, elongation at break >=15%, tensile strength >=960MPa and Young's modulus >=9000MPa; The length of described polypropylene fibre is 10 ~ 20mm, filament number≤2.2dtex, tensile strength >=660MPa, Young's modulus >=350MPa.
5. middle-deep well cross-linked polymer gel plugging agent according to claim 4, is characterized in that, described trevira and polypropylene fibre all soak 3 hours at 60 DEG C in hydrophilic finishing agent.
6. a preparation method for middle-deep well cross-linked polymer gel plugging agent, is characterized in that, in turn includes the following steps:
(1) prepare raw material by following component and weight content, purified cotton sodium salt solution: 120 parts, acrylamide: (75 ~ 85) part, ammonium persulphate: (13 ~ 17) part, cerous sulfate: (2 ~ 5) part, beta-D-mannuronic acid (M): 4 parts, primary ammonium phosphate: (1 ~ 1.5) part, composite Portland cement slurry: 100 parts and mix type primitive fiber: (150 ~ 200) part; The water cement ratio of described composite Portland cement slurry is 0.44;
(2) in purified cotton sodium salt solution, add acrylamide, carry out high-speed stirring with the rotating speed of 400r/min and within 10 minutes, make both fully mixing, then carry out moderate-speed mixer with the rotating speed of 300r/min, be heated to 60 DEG C while moderate-speed mixer and keep constant temperature;
(3) continue to pass into nitrogen in step reaction product (2) and reaction vessel, pass into nitrogen and at remaining on constant temperature 60 DEG C, slowly add ammonium persulphate particle at maintenance moderate-speed mixer after 3 minutes, reaction is until after particulate matter disappears, continue back flow reaction 1.5 hours;
(4) temperature be increased to 80 DEG C and keep constant temperature, under maintenance moderate-speed mixer, slowly add cerous sulfate particle, then the charging opening of off-response container, promote the charge of nitrogen, keep the pressure in reaction vessel to be 1.3MPa, back flow reaction more than 3 hours, until reactant presents white emulsion shape, obtains cross-linked polymer gel; Detect the molecular weight of described cross-linked polymer gel more than 4,000,000;
(5), under the state keeping moderate-speed mixer, in above-mentioned cross-linked polymer gel, slowly add beta-D-mannuronic acid (M), continue moderate-speed mixer after adding 10 minutes, and adjust ph is 7 ~ 7.5;
(6) in step reaction product (5), add composite Portland cement slurry and mix type primitive fiber, moderate-speed mixer more than 15 minutes is until mix;
(7) in step reaction product (6), add primary ammonium phosphate, moderate-speed mixer 10 minutes, obtain middle-deep well cross-linked polymer gel plugging agent.
7. the preparation method of middle-deep well cross-linked polymer gel plugging agent according to claim 6, it is characterized in that, the preparation method of described purified cotton sodium salt is as follows: 1. prepare the cotton fibre polymerization degree be 12000 ~ 14000 purified cotton and concentration expressed in percentage by weight be the sodium hydroxide solution of 17.5 ~ 18%, the weight ratio of purified cotton and sodium hydroxide solution is 5:2; 2. purified cotton is dropped in sodium hydroxide solution, stir at 60 DEG C and react more than 1.5 hours, until present uniform white suspension emulsion, obtain purified cotton sodium salt just solution; 3. carry out ultrasonic micro-vibration 30 minutes to the first solution of purified cotton sodium salt, obtain purified cotton sodium salt solution, ultrasonic frequency is 20kHz ~ 30kHz, and ultrasonication intensity is 2.0W/cm2 ~ 3.0W/cm2.
8. the preparation method of middle-deep well cross-linked polymer gel plugging agent according to claim 6, it is characterized in that, the described type primitive fiber that mixes evenly is mixed by calcium carbonate crystal whisker and organic microfiber and forms, and the ratio of mixture of calcium carbonate crystal whisker and organic microfiber is 0.8:1.
9. the preparation method of middle-deep well cross-linked polymer gel plugging agent according to claim 8, it is characterized in that, the length of described calcium carbonate crystal whisker 20 ~ 30 μm, diameter 0.5 ~ 1 μm, pH value 9.0 ~ 9.5, Young's modulus is 410 ~ 710GPa and tensile strength is not less than 2.058GPa; Described organic microfiber is made up of trevira and polypropylene fibre, and the weight of trevira and polypropylene fibre is 7:3; The diameter of described trevira 20 ~ 25 μm, length 6 ~ 9mm, elongation at break >=15%, tensile strength >=960MPa and Young's modulus >=9000MPa; The length of described polypropylene fibre is 10 ~ 20mm, filament number≤2.2dtex, tensile strength >=660MPa, Young's modulus >=350MPa.
10. the preparation method of middle-deep well cross-linked polymer gel plugging agent according to claim 9, is characterized in that, described trevira and polypropylene fibre all soak 3 hours at 60 DEG C in hydrophilic finishing agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510577380.XA CN105219365B (en) | 2015-09-11 | 2015-09-11 | Middle-deep well cross-linked polymer gel sealing agent and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510577380.XA CN105219365B (en) | 2015-09-11 | 2015-09-11 | Middle-deep well cross-linked polymer gel sealing agent and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105219365A true CN105219365A (en) | 2016-01-06 |
| CN105219365B CN105219365B (en) | 2017-11-24 |
Family
ID=54988653
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510577380.XA Active CN105219365B (en) | 2015-09-11 | 2015-09-11 | Middle-deep well cross-linked polymer gel sealing agent and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105219365B (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749925A (en) * | 2016-11-22 | 2017-05-31 | 中国地质大学（北京） | Colloidal sol modified cellulose and its preparation method and application |
| CN109054778A (en) * | 2018-09-05 | 2018-12-21 | 中石化石油工程技术服务有限公司 | Water-based film-forming agent and preparation method thereof and water-base drilling fluid and its application |
| CN110144198A (en) * | 2019-06-13 | 2019-08-20 | 中国石油集团长城钻探工程有限公司 | A kind of oil base drilling fluid GEL USED FOR PLUGGING WELL LOST CIRCULATION and preparation method thereof |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519585A (en) * | 2009-03-31 | 2009-09-02 | 荆州市弘利化工科技有限公司 | Shearing cross-linking sensitive plugging agent and preparation method thereof |
| CN102453475A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Leak-stopping agent for petroleum drilling, preparation method, and application thereof |
| CN102775503A (en) * | 2012-08-14 | 2012-11-14 | 常熟威怡科技有限公司 | Preparation method of high-salt resistance high-viscosity sodium carboxymethylcellulose |
| CN103409119A (en) * | 2013-06-04 | 2013-11-27 | 哈尔滨理工大学 | Degradable quick plugging agent |
| US20140048265A1 (en) * | 2012-07-17 | 2014-02-20 | Csi Technologies, Llc | Cohesive settable cement system |
| CN104513653A (en) * | 2014-12-31 | 2015-04-15 | 大港油田集团有限责任公司 | Double-gel oil-water well blocking agent and preparation method thereof |
| CN104726078A (en) * | 2015-03-13 | 2015-06-24 | 商南天和泥浆有限公司 | Gel plugging agent and preparation method thereof |
-
2015
- 2015-09-11 CN CN201510577380.XA patent/CN105219365B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101519585A (en) * | 2009-03-31 | 2009-09-02 | 荆州市弘利化工科技有限公司 | Shearing cross-linking sensitive plugging agent and preparation method thereof |
| CN102453475A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Leak-stopping agent for petroleum drilling, preparation method, and application thereof |
| US20140048265A1 (en) * | 2012-07-17 | 2014-02-20 | Csi Technologies, Llc | Cohesive settable cement system |
| CN102775503A (en) * | 2012-08-14 | 2012-11-14 | 常熟威怡科技有限公司 | Preparation method of high-salt resistance high-viscosity sodium carboxymethylcellulose |
| CN103409119A (en) * | 2013-06-04 | 2013-11-27 | 哈尔滨理工大学 | Degradable quick plugging agent |
| CN104513653A (en) * | 2014-12-31 | 2015-04-15 | 大港油田集团有限责任公司 | Double-gel oil-water well blocking agent and preparation method thereof |
| CN104726078A (en) * | 2015-03-13 | 2015-06-24 | 商南天和泥浆有限公司 | Gel plugging agent and preparation method thereof |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106749925A (en) * | 2016-11-22 | 2017-05-31 | 中国地质大学（北京） | Colloidal sol modified cellulose and its preparation method and application |
| CN106749925B (en) * | 2016-11-22 | 2019-05-21 | 中国地质大学（北京） | Colloidal sol modified cellulose and its preparation method and application |
| CN109054778A (en) * | 2018-09-05 | 2018-12-21 | 中石化石油工程技术服务有限公司 | Water-based film-forming agent and preparation method thereof and water-base drilling fluid and its application |
| CN109054778B (en) * | 2018-09-05 | 2021-03-16 | 中石化石油工程技术服务有限公司 | Water-based film forming agent, preparation method thereof, water-based drilling fluid and application thereof |
| CN110144198A (en) * | 2019-06-13 | 2019-08-20 | 中国石油集团长城钻探工程有限公司 | A kind of oil base drilling fluid GEL USED FOR PLUGGING WELL LOST CIRCULATION and preparation method thereof |
| CN110144198B (en) * | 2019-06-13 | 2021-12-03 | 中国石油天然气集团有限公司 | Gel plugging agent for oil-based drilling fluid and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105219365B (en) | 2017-11-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105368409B (en) | A kind of oil base drilling fluid compound sealing agent and preparation method thereof | |
| CN106986584B (en) | Low-temperature high-strength and high-toughness cement slurry as well as preparation method and application thereof | |
| CN101353569B (en) | Controllable cross linked gel water blockage plugging material | |
| CN102093864B (en) | Temporary plugging diversion agent for refracturing of oil-water well and preparation method thereof | |
| CN105419753A (en) | novel leakage-preventing while drilling agent for oil-based drilling fluid and application | |
| WO2021196740A1 (en) | Temporary plugging agent and preparation method therefor, and temporary plugging deflection fracturing method for high temperature reservoir | |
| CN105524600A (en) | Plugging while drilling agent for oil-based drilling fluid and preparation method of plugging while drilling agent | |
| CN104087274A (en) | Multi-stage blocking pressure-bearing plugging agent | |
| CN110079288B (en) | Expansive temporary plugging agent and preparation method thereof | |
| CN1309798C (en) | Follow-drilling plugging agent and its preparation method and use | |
| CN106398669B (en) | A kind of preparation method of drilling fluid pressurization sealing agent | |
| WO2009046980A1 (en) | Fusing materials for prevention of lost circulation | |
| CN108865088B (en) | Temporary plugging agent, preparation method thereof, drilling fluid and application of drilling fluid in plugging of fractured reservoir while drilling | |
| CN104861953A (en) | Oil field fracture temporary plugging agent and preparation method thereof | |
| CN105114032B (en) | A kind of method that use cross-linked polymer gel sealing agent carries out middle-deep well leak stopping | |
| CN109180084B (en) | Active self-repairing cement slurry system responding to oil gas | |
| CN105219365A (en) | Middle-deep well cross-linked polymer gel plugging agent and preparation method thereof | |
| CN114479778A (en) | Plugging agent for oil-based drilling fluid and application | |
| CN104291733A (en) | Toughened anti-channeling agent for cement and toughened cement for cementing shale gas horizontal well | |
| CN109913186B (en) | Petroleum drilling auxiliary and preparation method thereof | |
| CN103468237A (en) | Clean fracturing fluid and preparation method thereof | |
| CN105086966A (en) | Shallow-well high-polymer gel plugging agent and preparation method thereof | |
| CN105153361B (en) | A kind of part branched moiety cross-linked polymer oil-displacing agent and preparation method thereof | |
| Yang et al. | Laboratory evaluation of a controllable self-degradable temporary plugging agent in fractured reservoir | |
| CN105112031A (en) | Method for shallow well leaking stoppage by adopting macromolecular polymerization jelly leaking stoppage agent |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |