CN109824839A - Nano silica graft copolymer and its preparation method and application and drilling fluid and its application - Google Patents
Nano silica graft copolymer and its preparation method and application and drilling fluid and its application Download PDFInfo
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Abstract
The present invention relates to the drilling applications of petroleum industry, and in particular, to a kind of nano silica graft copolymer suitable for filtrate reducing with temperature resistance anticalcium ability and its preparation method and application and drilling fluid and its application.Nano silica graft copolymer of the invention contains one of structural unit shown in one of structural unit shown in one of structural unit shown in one of structural unit shown in following formula (1) or a variety of, formula (2) or a variety of, formula (3) or a variety of and formula (4) or a variety of.Copolymer provided by the invention, by structural unit shown in structural unit shown in structural unit shown in the formula (1) in the copolymer, formula (2), formula (3) and and formula (4) shown in mating reaction between structural unit, the copolymer successfully can be used for drilling fluid as the effect for when fluid loss additive, obtaining preferable anti-high calcium resistant to high temperatures.
Description
Technical field
The present invention relates to the drilling applications of petroleum industry, and in particular, to a kind of to be suitable for drop with temperature resistance anticalcium ability
Nano silica graft copolymer of leak-off and its preparation method and application and drilling fluid and its application.
Background technique
With the development of petroleum drilling technology and the reduction of conventional gas and oil reserves, the exploration and exploitation of petroleum resources gradually turn
To deep layer nontraditional reservoir.Drilling fluid as it is a kind of can satisfy drilling well work multiple functions circulation of fluid, cleaning shaft bottom,
Landwaste, cooling and lubrication drill bit etc. is carried to play an important role.However, with the increase of depth of stratum, drilling fluid must
It must experience long term high temperature and various cation contaminations.Although the performance of oil base drilling fluid is better than water-base drilling fluid, oil base drilling well
Liquid has the shortcomings that at high cost, liquid waste processing is difficult.Filtrate reducer for drilling fluid is to seep for reducing in drilling fluid liquid phase to stratum
The inorganic agent of the filter loss of leakage.The excessive borehole wall filter cake that will lead to of filter loss is blocked up in drilling fluid, fine clay particle can with filtrate into
Enter stratum, stratum is damaged, influences normal drilling well.The common fluid loss additive of drilling fluid has cellulose, humic acid, modified shallow lake
Powder, synthetic polymer etc..Wherein, the good combination of polymer fluid loss agent and clay enhances bentonitic structural stability.
Meanwhile the addition of some rigid radicals increases the temperature tolerance of polymer.The synthesis technology is simple, cheap, has obtained wide
General application.Gypsic horizon is a kind of good oil gas coating, and the oil gas coating of elephant nearly 30% is by gypsic horizon in the world
It is formed with rock salt.Contain a large amount of calcium and sodium ion in gypsic horizon, bentonitic aquation and dispersibility can be seriously affected, increased
Add drilling fluid filtration.Therefore, in current deep & ultra-deep well drilling process, polymer matrix water-base drilling fluid inorganic agent is not only
It needs to overcome problem of easy degradation under high temperature, but also must have good salt resistance, calcium fouling resistance performance, to keep handling
The good performance of agent.However, many researchs at present all concentrate on resistance to sodium ion pollution aspect, and to the drop under the conditions of high temperature high calcium
The research of vena caval filter is relatively fewer.
Drilling fluid often has with fluid loss additive at present: (1) carboxymethyl cellulose (CMC), using CMC as the cellulose products of representative
It is that dosage is maximum so far, one of widest filtrate reducer for drilling fluid of purposes.Why CMC can become important drilling fluid
Inorganic agent, because its raw material sources is abundant, relative low price, production technology is also easier.(2) sulfonated-methyl brown coal sulphur methyl is brown
Coal (SMC), the existing filtrate reducing effect of sulfonated-methyl brown coal have diluting effect again, thermostabilization height are mainly characterized by, 200~220
It can efficiently control the filter loss and viscosity of fresh-water drilling fluid at a high temperature of DEG C.(3) polymerization species are that current dosage is maximum
One of fluid loss additive, development speed are very fast.This quasi polymer is based on acrylic acid, acrylamide copolymer.
CMC molecular backbone is connected with ehter bond, and temperature resistance can only achieve 130-140 DEG C generally in drilling fluid, in addition its
Anti- high valence ion pollution, saline-alkaline tolerance are limited, and application is restricted in a wider context.The shortcomings that SMC is the salt resistance under high temperature
Performance is poor.Conventional propylene acylamide polymer fluid loss additive heat and salinity tolerance ability is weaker.
Summary of the invention
It is an object of the invention to which the defect of preferable temperature resistance and anticalcium ability cannot be had both for existing fluid loss additive,
Provide the nano silica graft copolymer and its system suitable for filtrate reducing that can obtain preferable temperature resistance and anticalcium performance
Preparation Method and application and drilling fluid and its application.
To achieve the goals above, in a first aspect, the present invention provides a kind of nano silica graft copolymer, feature
It is, which contains in structural unit shown in one of structural unit shown in following formula (1) or a variety of, formula (2)
One of structural unit shown in one of structural unit shown in one or more, formula (3) or a variety of and formula (4) is more
Kind:
Wherein, R1For the alkylidene of C0-C6；R1'And R1”It is each independently the alkyl of H and C1-C6；R2、R3And R4Respectively
Alkyl independently selected from H and C1-C6；R2'And R2”It is each independently the alkyl of H and C1-C6；R3'And R3”It is each independently
The alkyl of H and C1-C6；R4'And R4”It is each independently the alkyl of H and C1-C6；R5And R6It is each independently the alkylene of C1-C6
Base；M is H and alkali metal element；A is Nano particles of silicon dioxide.
Second aspect, the present invention provide a kind of preparation method of nano silica graft copolymer, which is characterized in that should
Method includes: in aqueous solvent, in the presence of redox type initiator, by formula (1-a) compound represented, formula (2-a)
Compound represented, formula (3-a) compound represented and formula (4-a) compound represented carry out copolymerization；
Wherein, R1For the alkylidene of C0-C6；R1'And R1”It is each independently the alkyl of H and C1-C6；R2、R3And R4Respectively
Alkyl independently selected from H and C1-C6；R2'And R2”It is each independently the alkyl of H and C1-C6；R3'And R3”It is each independently
The alkyl of H and C1-C6；R4'And R4”It is each independently the alkyl of H and C1-C6；R5And R6It is each independently the alkylene of C1-C6
Base；M is H and alkali metal element；A is Nano particles of silicon dioxide.
The third aspect, the present invention provide nano silica graft copolymer made from above-mentioned preparation method.
Fourth aspect, the present invention provide nano silica graft copolymer of the invention in drilling fluid as filtrate reducing
The application of agent.
5th aspect, the present invention provide, a kind of contain nano silica graft copolymer of the invention as filtrate reducing
The drilling fluid of agent.
6th aspect, the present invention propose application of the drilling fluid in oil/gas drilling.
Through the above technical solutions, the present invention has following beneficial effect.
(1) nano silica graft copolymer (M-PAAN) provided by the invention has excellent filtrate reducing effect,
Excellent filtrate reducing effect, especially high temperature are all had in fresh water base drilling fluid within the scope of 20-200 DEG C declines filtration effect,
The API filtration that 200 DEG C of bases after aging 16 hours are starched is only 8ml.
(2) M-PAAN provided by the invention has apparent anticalcium ionic soil to act at 170-180 DEG C.2 weight %'s
M-PAAN, which is added in the calcium contamination base slurry of 2 weight %, can make API filtration be reduced to 6ml from 188ml, and filtrate reducing effect is obvious.
(3) polymer and nano material graft are copolymerized by M-PAAN provided by the invention, have both highlighted polymer to clay
The raising of grain structure stability, and the temperature resistance of nano material is combined, make nano silica graft copolymer in high temperature
There is down excellent filtrate reducing effect, and there is good calcium fouling resistance ability.
Detailed description of the invention
Fig. 1 is to indicate to contain 2 weight % copolymer As 1 and 1 weight %CaCl under different aging temperatures2Base slurry particle
The figure of diameter.
Fig. 2 is the XRD diagram before each sample aging, wherein A: base slurry, B: base starches+2 weight % copolymer As 1, C: base slurry+1
Weight %CaCl2, D: base starches+2 weight % copolymer A 1+1 weight %CaCl2。
Fig. 3 is the XRD diagram after 180 DEG C of agings of each sample, wherein A: base slurry, B: base starches+2 weight % copolymer As 1, C: base
Starch+1 weight %CaCl2, D: base starches+2 weight % copolymer A 1+1 weight %CaCl2。
A in Fig. 4 is at 180 DEG C after aging 16 hours, and the TEM of 2 weight % copolymer As 1 in deionized water schemes
Picture；B in Fig. 4 is the TEM image of the base-material at 180 DEG C after aging 16 hours；C in Fig. 4 is that aging 16 is small at 180 DEG C
When after contain 2 weight %CaCl2Base slurry TEM image；D in Fig. 4 is to contain 2 weights after aging 16 hours at 180 DEG C
Measure %CaCl2The TEM image starched with the base of 2 weight % copolymer As 1；D1 in Fig. 4 is clearly total under the conditions of the d in Fig. 4
The TEM image of polymers A1 structure；D2 in Fig. 4 is the TEM image for amplifying 1 structure of copolymer A.
A in Fig. 5 is containing 2 weight % copolymer As 1 and 2 weight %CaCl2Base starch filter cake after 150 DEG C of agings
SEM image (3000 times of amplification)；B in Fig. 5 is containing 2 weight % copolymer As 1 and 2 weight %CaCl2Base slurry it is old at 180 DEG C
The SEM image (3000 times of amplification) of filter cake after change.
Specific embodiment
The endpoint of disclosed range and any value are not limited to the accurate range or value herein, these ranges or
Value should be understood as comprising the value close to these ranges or value.For numberical range, between the endpoint value of each range, respectively
It can be combined with each other between the endpoint value of a range and individual point value, and individually between point value and obtain one or more
New numberical range, these numberical ranges should be considered as specific open herein.
One aspect of the present invention provides a kind of nano silica graft copolymer (hereinafter also referred to as copolymer), the copolymerization
Object contain one of structural unit shown in one of structural unit shown in following formula (1) or a variety of, formula (2) or it is a variety of,
One of structural unit shown in one of structural unit shown in formula (3) or a variety of and formula (4) is a variety of:
Wherein, R1For the alkylidene of C0-C6；R1'And R1”It is each independently the alkyl of H and C1-C6；R2、R3And R4Respectively
Alkyl independently selected from H and C1-C6；R2'And R2”It is each independently the alkyl of H and C1-C6；R3'And R3”It is each independently
The alkyl of H and C1-C6；R4'And R4”It is each independently the alkyl of H and C1-C6；R5And R6It is each independently the alkylene of C1-C6
Base；M is H and alkali metal element；A is Nano particles of silicon dioxide.
According to the present invention, the alkyl of above-mentioned C1-C6 can be for example methyl, ethyl, n-propyl, isopropyl, normal-butyl, different
Butyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, n-hexyl etc..
The alkylidene that the alkyl of alkylidene and above-mentioned C1-C6 that the alkylidene of above-mentioned C0-C6 for example can be C0 is formed,
In, the alkylidene of C0 can consider that the group at the group both ends directly connects, so that the alkylidene of C0 exists with connecting key, it can also
It is considered to be not present.
In the case of, according to the invention it is preferred to, R1For the alkylidene of C0-C4；R1'And R1”It is each independently H's and C1-C4
Alkyl；R2、R3And R4It is each independently selected from the alkyl of H, C1-C4；R2'And R2”It is each independently the alkyl of H and C1-C4；R3'
And R3”It is each independently the alkyl of H and C1-C4；R4'And R4”It is each independently the alkyl of H and C1-C4；R5And R6For C2-C6
Alkylidene；M is H, Li, Na and K；A is Nano particles of silicon dioxide.
It is highly preferred that R1For the alkylidene ,-CH of C02-、-CH2-CH2Or-CH2-CH2-CH2-；R1'And R1”Each independently
For H, methyl, ethyl and propyl；R2、R3And R4It is each independently selected from H, methyl and ethyl；R2'And R2”Be each independently H,
Methyl, ethyl and propyl；R3'And R3”It is each independently H, methyl, ethyl and propyl；R4'And R4”It is each independently H, first
Base, ethyl and propyl；R5And R6For-CH2-CH2-、-CH2-CH2-CH2-、-CHCH3-CH2-、-CH2-CH2-CH2-CH2-、-C
(CH3)2-CH2-、-CH2-C(CH3)2Or-CH2-CHCH3-CH2-；M is H and Na；A is Nano particles of silicon dioxide.
In a preferred embodiment of the invention, R2、R3And R4For H.
According to the present invention, the partial size of the Nano particles of silicon dioxide is Nano grade, described in preferred situation
The partial size of Nano particles of silicon dioxide is 10-50nm, preferably 20-30nm.
In the case where, according to the invention it is preferred to, in the copolymer, structural unit shown in formula (1), shown in formula (2)
The molar ratio of structural unit shown in structural unit shown in structural unit, formula (3) and formula (4) can be 1:0.3-0.35:
0.5-0.6:0.05-0.06.In order to obtain the more excellent copolymer of performance, it is highly preferred that structure list shown in formula (1)
First, structural unit shown in structural unit and formula (4) shown in structural unit, formula (3) shown in formula (2) molar ratio is 1:
0.3-0.32:0.51-0.55:0.055-0.057, particularly preferably 1:0.3-0.32:0.51-0.55:0.055.
According to the present invention, the viscosity average molecular weigh of above-mentioned copolymer is 2.40 × 105~2.75 × 105It is carried out within the scope of g/mol
Selection, the heat and salinity tolerance and filtrate loss controllability for having gone out to improve gained copolymer consider, it is preferable that the viscous equal molecule of the copolymer
Amount is 2.42 × 105~2.67 × 105G/mol, more preferably 2.44 × 105~2.65 × 105g/mol。
According to the present invention, the silica graft copolymer contains shown in structural unit shown in formula (1), formula (2)
Structural unit shown in structural unit shown in structural unit, formula (3) and formula (4) is tied as shown in formula (1)
Structural unit shown in structure unit, formula (2), structural unit shown in structural unit and formula (4) shown in formula (3) constitute linear
Random copolymer.
According to another aspect of the present invention, a kind of preparation method of nano silica graft copolymer, this method are provided
Include: in aqueous solvent, in the presence of redox type initiator, will formula (1-a) compound represented, shown in formula (2-a)
Compound, formula (3-a) compound represented and formula (4-a) compound represented carry out copolymerization；
Wherein, R1For the alkylidene of C0-C6；R1'And R1”It is each independently the alkyl of H and C1-C6；R2、R3And R4Respectively
Alkyl independently selected from H and C1-C6；R2'And R2”It is each independently the alkyl of H and C1-C6；R3'And R3”It is each independently
The alkyl of H and C1-C6；R4'And R4”It is each independently the alkyl of H and C1-C6；R5And R6It is each independently the alkylene of C1-C6
Base；M is H and alkali metal element；A is Nano particles of silicon dioxide.
According to the present invention, above-mentioned formula (1-a) compound represented, formula (2-a) compound represented, shown in formula (3-a)
Compound and formula (4-a) compound represented and its each group being related to can be respectively according to formulas (1) described above
Shown in structural unit, structural unit shown in structural unit and formula (4) shown in structural unit, formula (3) shown in formula (2) into
The specific selection of row.
Wherein, the specific example of above-mentioned formula (1-a) compound represented for example may include following formula compound represented
One of or it is a variety of:
Formula (1-a-1): R1For the alkylidene of C0, R1'And R1”It is H (also referred to as acrylamide)；
Formula (1-a-2): R1For the alkylidene of C0, R1'For methyl, R1”For H (also referred to as Methacrylamide)；
Formula (1-a-3): R1For-CH2, R1'And R1”It is H.
Wherein, the specific example of above-mentioned formula (2-a) compound represented for example may include following formula compound represented:
Formula (2-a-1): R2、R3And R4For H, R2'And R2”It is H (n-vinyl pyrrolidone).
Wherein, the specific example of above-mentioned formula (3-a) compound represented for example may include following formula compound represented
One of or it is a variety of:
Formula (3-a-1): R5For-C (CH3)2-CH2, R3'And R3”It is H (2- acrylamide-2-methylpro panesulfonic acid) for H, M；
Formula (3-a-2): R5For-C (CH3)2-CH2, R3'And R3”It is Na (2- acrylamido -2- methyl-prop sulphur for H, M
Acid)；
Formula (3-a-3): R5For-C (CH3)2-CH2, R3'For methyl, R3”It is H (2- methacryl amido -2- first for H, M
Base propane sulfonic acid)；
Formula (3-a-4): R5For-C (CH3)2-CH2, R3'For methyl, R3”It is Na (2- methacryl amido -2- first for H, M
Base propanesulfonate).
Wherein, the specific example of above-mentioned formula (4-a) compound represented for example may include following formula compound represented:
Formula (3-a-1): R6For-CH2-CH2-CH2, R4'And R4”For H.
According to the present invention, above-mentioned formula (1-a) compound represented, formula (2-a) compound represented, shown in formula (3-a)
The dosage molar ratio of compound and formula (4-a) compound represented can be 1:0.3-0.35:0.5-0.6:0.05-0.06, be
The more excellent copolymer of performance can be obtained, it is preferable that change shown in above-mentioned formula (1-a) compound represented, formula (2-a)
The dosage molar ratio for closing object, formula (3-a) compound represented and formula (4-a) compound represented is 1:0.3-0.32:0.51-
0.55:0.055-0.057, particularly preferably 1:0.3-0.32:0.51-0.55:0.055.
In accordance with the present invention it is preferred that the copolymerization make resulting copolymer viscosity average molecular weigh be 2.40 ×
105~2.75 × 105G/mol, preferably 2.42 × 105~2.67 × 105G/mol is more preferably 2.44 × 105~2.65 ×
105g/mol。
According to the present invention, the aqueous solvent can be water, be also possible to containing not influencing copolymerization of the invention
Other solvents (such as methanol, ethyl alcohol, propyl alcohol etc.) water mixed liquor.The dosage of the aqueous solvent can be according to required
The molecular weight of copolymer is suitably adjusted, it is preferable that with aqueous solvent, formula (1-a) compound represented, formula (2-a) institute
On the basis of the total weight of compound, formula (3-a) compound represented and formula (4-a) compound represented for showing, the formula (1-a)
Compound represented, formula (2-a) compound represented, formula (3-a) compound represented and formula (4-a) compound represented it is total
Content is 15-35 weight %, more preferably 20-30 weight %, for example, 20-25 weight %.
According to the present invention, the present invention causes the poly- of above-mentioned monomer of the invention using redox type initiator system
It closes, there is no particular limitation for type of the present invention to the redox type initiator system, can be conventional using this field
Various redox type initiator systems.Preferably, the oxidant in the redox type initiator is ammonium persulfate, over cure
One of sour potassium, sodium peroxydisulfate, hydrogen peroxide, sodium hypochlorite, potassium permanganate, potassium perborate and sodium perborate are a variety of, excellent
It is selected as one of ammonium persulfate, potassium peroxydisulfate and sodium peroxydisulfate or a variety of.Preferably, in the redox type initiator
Reducing agent is one of sodium hydrogensulfite, potassium sulfite, sodium thiosulfate, potassium thiosulfate, vulcanized sodium and hydrogen sulfide or more
Kind, preferably sodium hydrogensulfite and/or potassium sulfate.In order to preferably cause to obtain the required copolymer of the present invention, preferably
Ground, the molar ratio of the Oxidizing and Reducing Agents in the redox type initiator are 1:0.5-2, preferably 1:0.5-1.3, more
Preferably 1:0.6-0.8.
According to the present invention, the dosage of the redox type initiator can be carried out according to the molecular weight of required copolymer
It suitably adjusts, it is preferable that relative to shown in formula (1-a) compound represented, formula (2-a) compound represented, formula (3-a)
The total weight of compound and formula (4-a) compound represented, the dosage of the redox type initiator are 0.05-2 weight %,
Preferably 0.2-1 weight %, more preferably 0.2-0.5 weight %.
In the case of, according to the invention it is preferred to, the condition of the copolymerization includes: that pH value is 7-8, temperature 50-70
DEG C, the time is 3-8h (preferably 4-7h).Wherein, the pH value of reaction system can be adjusted using the bronsted lowry acids and bases bronsted lowry of this field routine
The reaction system that section, usually above-mentioned monomer provide is acidity, thus can using alkali metal hydroxide (such as sodium hydroxide,
Potassium hydroxide etc.) it is adjusted.
According to the present invention, further include that deoxygenation is carried out to reaction system before carrying out copolymerization, the present invention is kept with this
The activity of used redox type initiator, for example, by using being passed through non-interactive gas (nitrogen, helium, neon, argon gas etc.
One of or it is a variety of) mode, being passed through the time for example can be 10-60min.
In a preferred embodiment of the invention, the above method includes: by formula (1-a) compound represented, formula
(2-a) compound represented, formula (3-a) compound represented, formula (4-a) compound represented and aqueous solvent are mixed,
And pH to 8-9 is adjusted, it is then passed through the deoxygenation of non-interactive gas, when temperature reaches copolymerization temperature, introduces oxidation
Reduced form initiator is to carry out the copolymerization.
According to the present invention, in order to obtaining the copolymer of the invention of solid form, this method further include: will it is described from
It is dried by the product of base polymerization reaction.The condition of the drying for example may include: that temperature is 50-100 DEG C, time 20-
60h.To dry mode, there is no particular limitation, can be carried out using the various drying modes of this field routine, such as dry
Method, freeze-drying and spray drying process.
The present invention also provides the copolymers as prepared by the above method.Although there is no particular limitation by the present invention,
The copolymer may be considered above described in one of copolymer or a variety of copolymers mixture.Certainly, it answers
When understanding, copolymer prepared by the above method typically refer to the above method without purification direct product (or only
After the above drying), the product of even now may be the mixture of multiple polymers, but the present invention is also by this
The case where sample, is included within the scope of the invention.
The present invention also provides above-mentioned copolymers or the copolymer as prepared by the above method in drilling fluid as drop
The application of fluid loss agents.
The present invention also provides a kind of drilling fluids for containing above-mentioned copolymer as fluid loss additive.
According to the present invention, it is applied to drilling fluid for above-mentioned copolymer as fluid loss additive, which is in aqueous solution
Polymer wrapped nano silica microsphere body, grain diameter can play excellent between 200-400nm in water-base drilling fluid
Different filtrate reducing effect, and filtrate reducing effect is especially apparent at high temperature, temperature resistance is up to 200 DEG C.Also, the copolymer can be with
At 180 DEG C after aging, partial polymer chain is stretched and forms Nano-meter SiO_22The linear structure of polymer chain.In stretching
A large amount of amide, sulfonic group and annular rigid group are exposed on polymer chain, are connected by hydrogen bond with argillic horizon, are strengthened this
Connection between copolymer and argillic horizon, it is therefore prevented that Ca2+A large amount of ion exchanges between argillic horizon.Therefore, Ca can be resisted2 +The decrease of caused caly structure intensity and the reunion of argillic horizon.At this point, the particle diameter distribution of clay particle is more extensive, it is some
The Nano-meter SiO_2 being grafted on particle and polymer chain having a size of 1-10um2The micro-nano hole on filter cake can be blocked together.This
When, at 170-180 DEG C, the copolymer can resist the calcium ion pollution of 2 weight %, and filter loss is lower than 6ml, thus may be used
See, the copolymer as in fluid loss additive water-base drilling fluid at high temperature with excellent filtrate loss controllability and special anti-
Calcium contamination performance.
According to the present invention, it is applied to drilling fluid for above-mentioned copolymer as fluid loss additive, gained drilling fluid can be in high temperature
Lower filter loss is still maintained in high calcium environment, can preferably maintain wellbore stability, is that high temperature is high especially suitable for underground
The exploitation of the deep layer, ultra deep petroleum resources of calcium environment.There is no particular limitation for content of the present invention to the copolymer, can adopt
With the dosage of conventional filtrate reducer for drilling fluid, naturally it is also possible to be suitably adjusted according to the case where different wells, preferably
Ground, the content of the copolymer are 2-3 weight % (total weight relative to drilling fluid).
According to the present invention, there is no particular limitation to above-mentioned drilling fluid system by the present invention, can be each of this field routine
Kind drilling fluid system, as long as being added into copolymer of the invention into these conventional drilling fluid systems.As such
Conventional drilling liquid system can be for example one in potassium chloride-polyglycol drilling fluid, silicone drilling fluid and cationic drilling fluid
Kind is a variety of.Various potassium chloride-polymeric alcohols that the potassium chloride-polyglycol drilling fluid can be well known to those skilled in the art
Drilling fluid, such as can be potassium chloride-PEG drilling fluid, potassium chloride-polypropylene glycol drilling fluid, potassium chloride-ethylene glycol/the third
One of diol copolymer drilling fluid, potassium chloride-polyglycerol drilling fluid and potassium chloride-polyethylene glycol drilling fluid are more
Kind；The various silicone drilling fluids that the silicone drilling fluid can be well known to those skilled in the art, the organosilicon bore
Organosilicon in well liquid can be for selected from one of methyl silicon sodium alcoholate, methyl silanol potassium and organic silicone potassium humate or a variety of.
The various cationic drilling fluids that the cationic drilling fluid can be well known to those skilled in the art, the cationic drilling fluid
In cation can for selected from 2,3- epoxypropyltrimethylchloride chloride, 3- chloro-2-hydroxypropyl-trimethyl ammonium chloride and sun from
One of sub- polyacrylamide is a variety of.
According to the present invention, the drilling fluid is preferably water-base drilling fluid, can be with other than water and above-mentioned copolymer
Containing other additives as water-base drilling fluid, under preferable case, drilling fluid of the invention contains bentonite, tackifier, anti-
Collapse one of agent, lubricant, calcium chloride, sodium carbonate etc. or a variety of.
Wherein, the bentonite refers to the clay using montmorillonite as main mineral constituent, has imparting drilling fluid is viscous to cut
The effect of power and leak-off wave making machine, such as can be sodium bentonite and/or calcium-base bentonite, preferably sodium bentonite.More
Preferably, the bentonitic content is 2-4 weight %, more preferably 3-4 weight %.
Wherein, the tackifier can be improved the viscous shear force of drilling fluid, such as can be polyacrylamide sylvite (KPAM), poly-
One of anionic cellulose (such as PAC141) and acrylamide and the copolymer (such as the trade mark is 80A51) of sodium acrylate
Or a variety of, preferably polyacrylamide sylvite.It is highly preferred that the content of the tackifier is 0.2-0.5 weight %, more preferably
0.3-0.5 weight %.
Wherein, the anti-sloughing agent can assist bionical shale control agent to prevent hole collapse, improve borehole wall stability, example
It such as can be one in potassium humate (KHM), organosilicon (such as the trade mark is GF-1) and sulfonated gilsonite (such as the trade mark is FT-1A)
Kind is a variety of, preferably potassium humate.It is highly preferred that the content of the anti-sloughing agent is 2-4 weight %.
Wherein, the lubricant can be improved drilling fluid lubricating performance, prevent the undergrounds such as bit freezing complicated state, such as can be with
For sulfonation oil foot (such as the trade mark is FK-10), diesel oil and surfactant mixture (such as trade mark is FRH) and fatty glyceride
(such as trade mark is one of FK-1) or a variety of, preferably FK-10 with surfactant mixture.It is highly preferred that the lubrication
The content of agent is 2-4 weight %.
Wherein, the content of calcium chloride be for example can be 0.5-1 weight %, the content of sodium carbonate be for example can be 0.2-
0.3 weight %.
The various substances that above-mentioned additive is can be commercially available product, can also be made according to the method for this field routine, this
In repeat no more.
The present invention also provides application of the above-mentioned drilling fluid in oil/gas drilling.
The present invention will be described in detail by way of examples below.
In following embodiment and comparative example,
AM: acrylamide, purity are 99 weight %, are purchased from Aladdin；
AMPS:2- acrylamide-2- methyl-1-propane sulfonic acid, purity are 98 weight %, are purchased from Aladdin；
NVP:N- vinyl pyrrolidone, purity are 99 weight %, are purchased from Aladdin；
M-SiO2: the modified nano silica of methacryloxypropyl trimethoxy silane (KH570), titanium dioxide
Silicon grain diameter is 20nm, and purity is 99 weight %, is purchased from Emperor XianFeng chemical reagents corporation.
Viscosity average molecular weigh is measured using Ubbelohde viscometer.
X-ray photoelectron spectroscopy is measured using the D8ADVANCE polycrystal X ray diffractometer of Germany.
Polymer preparation example 1
10g AM (0.14mol) and 15g AMPS (0.07mol) is substantially dissolved in 100ml water, with sodium hydroxide tune
The pH value of solution is saved to 8, the M-SiO of 2g is then added2(0.008mol), which is sufficiently stirred, to be made it dissolve.Aqueous solution is transferred to three
In mouth reaction flask, it is added 5ml NVP (0.046mol).By the way of heating water bath, reaction flask is placed in 55 DEG C of thermostatted water
In bath, the stirring of 300r/min rate after heat preservation 30 minutes, the sodium hydrogensulfite of the ammonium persulfate of 60mg and 20mg is added molten
In liquid, catalysis is reacted, and whole process is passed through nitrogen and is protected in reaction process.After reaction 4 hours, milky thick liquid is obtained,
It is dried in 60 DEG C of baking oven, crushes, obtain M-PAAN nano silica graft copolymer A1.
It is detected through infrared, nuclear magnetic resonance spectroscopy and carbon spectrum analysis, acrylamide, N- ethenyl pyrrolidone in gained copolymer
Ketone, 2- acrylamide-2-methylpro panesulfonic acid and M-SiO2The molar ratio of the structural unit of offer is 1:0.32:0.51:
0.055, the viscosity average molecular weigh of the copolymer is 2.6 × 105g/mol。
Polymer preparation example 2
10.5g AM (0.15mol) and 20g AMPS (0.1mol) is substantially dissolved in 100ml water, with sodium hydroxide tune
The pH value of solution is saved to 8, the M-SiO of 2g is then added2(0.008mol), which is sufficiently stirred, to be made it dissolve.Aqueous solution is transferred to three
In mouth reaction flask, it is added 5ml NVP (0.046mol).By the way of heating water bath, reaction flask is placed in 55 DEG C of thermostatted water
In bath, the stirring of 300r/min rate after heat preservation 30 minutes, the sodium hydrogensulfite of the ammonium persulfate of 60mg and 20mg is added molten
In liquid, catalysis is reacted, and whole process is passed through nitrogen and is protected in reaction process.After reaction 4 hours, colourless viscous liquid is obtained,
It is dried in 60 DEG C of baking oven, crushes, obtain M-PAAN nano silica graft copolymer A2.
It is detected through infrared, nuclear magnetic resonance spectroscopy and carbon spectrum analysis, acrylamide, N- ethenyl pyrrolidone in gained copolymer
Ketone, 2- acrylamide-2-methylpro panesulfonic acid and M-SiO2The molar ratio of the structural unit of offer is 1:0.3:0.53:0.055,
The viscosity average molecular weigh of the copolymer is 2.65 × 105g/mol。
Polymer preparation example 3
10g AM (0.14mol) and 15g AMPS (0.07mol) is substantially dissolved in 100ml water, with sodium hydroxide tune
The pH value of solution is saved to 8, the M-SiO of 2g is then added2(0.008mol), which is sufficiently stirred, to be made it dissolve.Aqueous solution is transferred to three
In mouth reaction flask, it is added 5ml NVP (0.046mol).By the way of heating water bath, reaction flask is placed in 55 DEG C of thermostatted water
In bath, the stirring of 300r/min rate after heat preservation 30 minutes, the sodium hydrogensulfite of the ammonium persulfate of 70mg and 30mg is added molten
In liquid, catalysis is reacted, and whole process is passed through nitrogen and is protected in reaction process.After reaction 4 hours, colourless viscous liquid is obtained,
It is dried in 60 DEG C of baking oven, crushes, obtain M-PAAN nano silica graft copolymer A3.
It is detected through infrared, nuclear magnetic resonance spectroscopy and carbon spectrum analysis, acrylamide, N- ethenyl pyrrolidone in gained copolymer
Ketone, 2- acrylamide-2-methylpro panesulfonic acid and M-SiO2The molar ratio of the structural unit of offer is 1:0.32:0.55:
0.055, the viscosity average molecular weigh of the copolymer is 2.72 × 105g/mol。
Polymer prepares comparative example 1
It is carried out according to the method for embodiment 3, unlike, it is added without M-SiO2, obtain copolymer D1.
It is detected through infrared, nuclear magnetic resonance spectroscopy and carbon spectrum analysis, acrylamide, N- ethenyl pyrrolidone in gained copolymer
The molar ratio for the structural unit that ketone, 2- acrylamide-2-methylpro panesulfonic acid provide is 1:0.32:0.55, which glues
Average molecular weight is 3.5 × 105g/mol。
Test case 1
This test case is for illustrating drilling fluid and its application of the invention.
Base drilling fluid formula: by 1000g water, 40g sodium bentonite (be purchased from Shandong Weifang Hua Wei bentonite company, with
Under it is identical) and 2.5g natrium carbonicum calcinatum mixed, and high-speed stirred 20min is old in closed container under room temperature (about 25 DEG C)
Change for 24 hours, obtains base drilling fluid Y.
Above-described embodiment and the resulting copolymer of comparative example of 2 weight % is added in base drilling fluid Y respectively, and respectively
Before ageing and after 140 DEG C of aging 16h and after 200 DEG C of aging 16h, after being down to room temperature (about 25 DEG C), each system is measured
Apparent viscosity, plastic viscosity, yield value (YP), middle filter pressing loss (API) and high temperature and high pressure filter loss (HTHL), are as a result shown in respectively
Shown in table 1, in which:
Viscosity is measured using the fast viscosimeter of Viscometry instrument-six, calculation method are as follows:
Apparent viscosity: μa=1/2 θ600, θ600For the degree under 600 turns/min；
Plastic viscosity: μp=θ600-θ300, θ600For the degree under 600 turns/min, θ300For the degree under 300 turns/min.Its
In, plastic viscosity reflects in laminar flow conditions, in drilling fluid grid structure destruction with restore in dynamic equilibrium when, hang
The power of interior rubbing action between floating solid phase and liquid phase and inside Continuous Liquid Phase.Higher expression large rock-carrying ability is better, but
It is excessively high, it will increase cyclic pressure dissipation, pump, the down hole problems such as bit balling are suppressed in generation.
Yield value (YP) is using the fast viscosimeter method according to specified in standard GB/T/T29170-2012 of normal form six
It measures, YP=0.5 (2 θ300-θ600), unit Pa.
API refers to middle filter pressing loss, is that filters pressing is committed a breach of etiquette and surveyed according to the method in SY/T 5621-93 standard in using
Amount, unit mL.
Table 1
Test case 2
This test case is for illustrating drilling fluid and its application of the invention.
Base drilling fluid formula: by water, sodium bentonite (be purchased from Shandong Weifang Hua Wei bentonite company, same as below) and
Sodium carbonate is mixed according to the weight ratio of 400:16:1, and high-speed stirred 20min, under room temperature (about 25 DEG C) in closed container
Aging for 24 hours, obtains base drilling fluid Y.
Above-described embodiment and the resulting copolymer of comparative example and CaCl is added in base drilling fluid Y respectively2Aqueous solution
(dosage is as shown in table 1), and room temperature is down to (about before ageing and after 80 DEG C of aging 16h and after 180 DEG C of aging 16h respectively
25 DEG C) after, the apparent viscosity, plastic viscosity, yield value (YP) and middle filter pressing loss (API) of each system are measured, is as a result distinguished
It is shown in Table 2, in which:
Viscosity is measured using the fast viscosimeter of Viscometry instrument-six, calculation method are as follows:
Apparent viscosity: μa=1/2 θ600, θ600For the degree under 600 turns/min；
Plastic viscosity: μp=θ600-θ300, θ600For the degree under 600 turns/min, θ300For the degree under 300 turns/min.Its
In, plastic viscosity reflects in laminar flow conditions, in drilling fluid grid structure destruction with restore in dynamic equilibrium when, hang
The power of interior rubbing action between floating solid phase and liquid phase and inside Continuous Liquid Phase.Higher expression large rock-carrying ability is better, but
It is excessively high, it will increase cyclic pressure dissipation, pump, the down hole problems such as bit balling are suppressed in generation.
Yield value (YP) is using the fast viscosimeter method according to specified in standard GB/T/T29170-2012 of normal form six
It measures, YP=0.5 (2 θ300-θ600), unit Pa.
API refers to middle filter pressing loss, is that filters pressing is committed a breach of etiquette and surveyed according to the method in SY/T 5621-93 standard in using
Amount, unit mL.
Table 2
Note: "/" expression is not tested；CaCl2Content with Ca2+Meter.
Test case 3
Base drilling fluid formula: by water, sodium bentonite (be purchased from Shandong Weifang Hua Wei bentonite company, same as below) and
Sodium carbonate is mixed according to the weight ratio of 400:16:1, and high-speed stirred 20min, under room temperature (about 25 DEG C) in closed container
Aging for 24 hours, obtains base drilling fluid Y.
It prepares base slurry, base under different temperatures after aging and starches+2 weight % copolymer As 1 ,+1 weight %CaCl of base slurry2, base
Starch+2 weight % copolymer A 1+1 weight %CaCl2Sample, take fluid sample carry out granularmetric analysis (laser particle analyzer, Dandong
Hundred is special, Bettersize2000)；Tem analysis is carried out after 1000 times of liquid diluting；Fluid sample is dry in 60 DEG C of baking oven
And pulverize, powder sample carries out X-ray diffraction analysis (XRD) (Bruker D8Advance)；It takes and finishes API filtration
The filter cake of test carries out surface sweeping Electronic Speculum (SEM) (Jeol Ltd., JSM7401) analysis.
(1) granularmetric analysis
Fig. 1 is shown contains 2 weight % copolymers and 1 weight %CaCl under different aging temperatures2Drilling fluid in
Granule size.It can be seen from the figure that partial size when temperature is 180 DEG C is minimum, median particle diameter is 54.94 μm, and in aging
It is preceding and 150 DEG C, the partial size after 200 DEG C of agings be respectively 346.1 μm, 303.2 μm and 90.41 μm.Therefore, contain after 180 DEG C of agings
Grain diameter in calcium drilling fluid is minimum, shows the dispersibility of clay particle at this moment preferably, advantageously forms fine and close filter cake.
(2) XRD analysis
X-ray diffraction analysis (XRD) is the most important evidence for analyzing clay interlamellar spacing.The interlamellar spacing of clay is with clay
The insertion of aquation and chemical substance and change.Add copolymer A 1 and CaCl2The variation of clay interlamellar spacing such as Fig. 2 and Fig. 3 institute afterwards
Show.From figure 2 it can be seen that the copolymer A 1 that 2 weight % are added at room temperature makes bentonitic interlamellar spacing d(001)By 1.23nm
1.26nm is increased to, and 1 weight %CaCl is added2By d(001)Increase to 1.48nm.Calcium ion (Ca2+) in the absorption of surface of clay
Significantly increase d(001).It is added to by the copolymer A 1 of 2 weight % containing 1 weight %CaCl2Base slurry in after, d(001)From
1.48nm slightly drops to 1.45nm.As shown in figure 3, at 180 DEG C after aging 16 hours, base slurry contains 2 weight % copolymers
The base of A1 is starched, and 1 weight %CaCl is contained2Base slurry and contain 2 weight % copolymer As 1 and 1 weight %CaCl2Base slurry in it is viscous
Grogs diameter drops to 1.21,1.21,1.39,1.29nm from 1.23,1.26,1.48,1.45nm respectively.At high temperature, due to layer
Between water disappearance, the interlamellar spacing of clay can reduce.At this time as can be seen that copolymer A 1 makes containing CaCl2Base slurry in argillic horizon
Spacing is substantially reduced from 1.39nm to 1.29nm, shows that copolymer A 1 prevents Ca2+In the absorption of surface of clay, Ca is reduced2+
The phenomenon that coalescing clay particle, simultaneously enhances the dispersion of clay in aqueous solution.However, containing after copolymer A 1 is added at room temperature
The bentonitic d of calcium ion(001)It is not substantially reduced.
(3) tem analysis
It is observed and grain size analysis and the consistent result of XRD analysis (Fig. 4) by TEM image.It can from a in Fig. 4
It is grafted with Nano-meter SiO_2 out2Finely dispersed linear polymer molecules A1, the polymer chain of stretching leads to higher fluid viscosity
With lower filtration volume.It can see transparent argillic horizon in b in Fig. 4, but argillic horizon is reunited after adding calcium
(c in Fig. 4).When 2 weight % copolymer A 1 is added, argillic horizon is in CaCl2In the presence of still well dispersion (in Fig. 4
d).At this point it is possible to observe the copolymer A 1 (d1 in Fig. 4) more stretched, and linear structure also becomes apparent from (in Fig. 4
d2).Copolymer A 1 structure from chain winding become chain-unfolding after, more amides, sulfonic group and annular rigid group exposure
On polymer chain.Nano-meter SiO_22Good adsorption and copolymer A 1 and clay between hydrogen bond and other power make polymer and viscous
Native close connection, it is therefore prevented that Ca2+A large amount of ion exchanges between argillic horizon, reduce the reunion of clay.
(4) sem analysis
As shown in a in Fig. 5, contain 2 weight % copolymer As 1 and 2 weight %CaCl2Base slurry it is small in 150 DEG C of agings 16
Shi Hou occurs " recess and summit " on filter cake, illustrates that filter cake is to loosen.And as shown in the b in Fig. 5, it is small in 180 DEG C of agings 16
When after filter cake it is finer and close and smooth, this shows between copolymer A 1 and clay particle that interaction forms dense film, exactly
Since this smooth and fine and close filter cake is formed such that filter loss can be effectively reduced in copolymer A 1.
By above-mentioned analysis it is found that at 170-180 DEG C or so, partial polymer chain is stretched and forms Nano-meter SiO_22It is poly-
Close the linear structure of object chain.A large amount of amide, sulfonic group and annular rigid group are exposed on the polymer chain of stretching, are passed through
Hydrogen bond is connected with argillic horizon, strengthens the connection between copolymer A 1 and argillic horizon, it is therefore prevented that Ca2+It is a large amount of between argillic horizon
Ion exchange.Therefore, copolymer A 1 effectively resists Ca2+The decrease of caused caly structure intensity and the reunion of argillic horizon.This
When, the particle diameter distribution of clay particle is more extensive, the nanometer being grafted on some particles and polymer chain having a size of 1-10um
SiO2The micro-nano hole on filter cake can be blocked together.
The preferred embodiment of the present invention has been described above in detail, and still, the present invention is not limited thereto.In skill of the invention
In art conception range, can with various simple variants of the technical solution of the present invention are made, including each technical characteristic with it is any its
Its suitable method is combined, and it should also be regarded as the disclosure of the present invention for these simple variants and combination, is belonged to
Protection scope of the present invention.
Claims (12)
1. a kind of nano silica graft copolymer, which is characterized in that the copolymer contains structural unit shown in following formula (1)
One of or a variety of, formula (2) shown in one of structural unit shown in one of structural unit or a variety of, formula (3)
Or one of structural unit shown in a variety of and formula (4) or a variety of:
Wherein, R1For the alkylidene of C0-C6；R1'And R1”It is each independently the alkyl of H and C1-C6；R2、R3And R4It is respectively independent
Ground is selected from the alkyl of H and C1-C6；R2'And R2”It is each independently the alkyl of H and C1-C6；R3'And R3”Be each independently H and
The alkyl of C1-C6；R4'And R4”It is each independently the alkyl of H and C1-C6；R5And R6It is each independently the alkylidene of C1-C6；
M is H and alkali metal element；A is Nano particles of silicon dioxide.
2. nano silica graft copolymer according to claim 1, wherein R1For the alkylidene of C0-C4；R1'And R1”
It is each independently the alkyl of H and C1-C4；R2、R3And R4It is each independently selected from the alkyl of H, C1-C4；R2'And R2”Respectively solely
It is on the spot the alkyl of H and C1-C4；R3'And R3”It is each independently the alkyl of H and C1-C4；R4'And R4”Be each independently H and
The alkyl of C1-C4；R5And R6For the alkylidene of C2-C6；M is H, Li, Na and K；A is Nano particles of silicon dioxide；
Preferably, R1For the alkylidene ,-CH of C02-、-CH2-CH2Or-CH2-CH2-CH2-；R1'And R1”It is each independently H, first
Base, ethyl and propyl；R2、R3And R4It is each independently selected from H, methyl and ethyl；R2'And R2”It is each independently H, methyl, second
Base and propyl；R3'And R3”It is each independently H, methyl, ethyl and propyl；R4'And R4”Be each independently H, methyl, ethyl and
Propyl；R5And R6For-CH2-CH2-、-CH2-CH2-CH2-、-CHCH3-CH2-、-CH2-CH2-CH2-CH2-、-C(CH3)2-CH2-、-
CH2-C(CH3)2Or-CH2-CHCH3-CH2-；M is H and Na；A is Nano particles of silicon dioxide.
3. nano silica graft copolymer according to claim 1 or 2, wherein structural unit shown in formula (1),
Structural unit shown in formula (2), structural unit shown in structural unit and formula (4) shown in formula (3) molar ratio be 1:0.3-
0.35:0.5-0.6:0.05-0.06, preferably 1:0.3-0.32:0.51-0.55:0.055-0.057；
Preferably, the viscosity average molecular weigh of the nano silica graft copolymer is 2.44 × 105~2.65 × 105g/mol。
4. a kind of preparation method of nano silica graft copolymer, which is characterized in that this method comprises: in aqueous solvent
In, in the presence of redox type initiator, by formula (1-a) compound represented, formula (2-a) compound represented, formula (3-a)
Compound represented and formula (4-a) compound represented carry out copolymerization；
Wherein, R1For the alkylidene of C0-C6；R1'And R1”It is each independently the alkyl of H and C1-C6；R2、R3And R4It is respectively independent
Ground is selected from the alkyl of H and C1-C6；R2'And R2”It is each independently the alkyl of H and C1-C6；R3'And R3”Be each independently H and
The alkyl of C1-C6；R4'And R4”It is each independently the alkyl of H and C1-C6；R5And R6It is each independently the alkylidene of C1-C6；
M is H and alkali metal element；A is Nano particles of silicon dioxide.
5. according to the method described in claim 4, wherein, R1For the alkylidene of C0-C4；R1'And R1”It is each independently H and C1-
The alkyl of C4；R2、R3And R4It is each independently selected from the alkyl of H, C1-C4；R2'And R2”It is each independently the alkane of H and C1-C4
Base；R3'And R3”It is each independently the alkyl of H and C1-C4；R4'And R4”It is each independently the alkyl of H and C1-C4；R5And R6
For the alkylidene of C2-C6；M is H, Li, Na and K；A is Nano particles of silicon dioxide；
Preferably, R1For the alkylidene ,-CH of C02-、-CH2-CH2Or-CH2-CH2-CH2-；R1'And R1”It is each independently H, first
Base, ethyl and propyl；R2、R3And R4It is each independently selected from H, methyl and ethyl；R2'And R2”It is each independently H, methyl, second
Base and propyl；R3'And R3”It is each independently H, methyl, ethyl and propyl；R4'And R4”Be each independently H, methyl, ethyl and
Propyl；R5And R6For-CH2-CH2-、-CH2-CH2-CH2-、-CHCH3-CH2-、-CH2-CH2-CH2-CH2-、-C(CH3)2-CH2-、-
CH2-C(CH3)2Or-CH2-CHCH3-CH2-；M is H and Na；A is Nano particles of silicon dioxide.
6. method according to claim 4 or 5, wherein chemical combination shown in formula (1-a) compound represented, formula (2-a)
The dosage molar ratio of object, formula (3-a) compound represented and formula (4-a) compound represented is 1:0.3-0.35:0.5-0.6:
0.05-0.06, preferably 1:0.3-0.32:0.51-0.55:0.055-0.057.
7. method according to claim 4 or 5, wherein the oxidant in the redox type initiator is persulfuric acid
One of ammonium, potassium peroxydisulfate, sodium peroxydisulfate, hydrogen peroxide, sodium hypochlorite, potassium permanganate, potassium perborate and sodium perborate or
It is a variety of；Reducing agent in the redox type initiator is sodium hydrogensulfite, potassium sulfite, sodium thiosulfate, thiosulfuric acid
Potassium, vulcanized sodium and hydrogen sulfide and one of or it is a variety of；
Preferably, the molar ratio of the Oxidizing and Reducing Agents in the redox type initiator be 1:0.5-2, preferably 1:
0.5-1.3；
Preferably, relative to formula (1-a) compound represented, formula (2-a) compound represented, formula (3-a) compound represented
With the total weight of formula (4-a) compound represented, the dosage of the redox type initiator is 0.05-2 weight %, preferably
0.2-1 weight %；
Preferably, to change shown in aqueous solvent, formula (1-a) compound represented, formula (2-a) compound represented, formula (3-a)
On the basis of the total weight for closing object and formula (4-a) compound represented, shown in formula (1-a) compound represented, formula (2-a)
The total content of compound, formula (3-a) compound represented and formula (4-a) compound represented is 15-35 weight %, preferably
20-30 weight %；
Preferably, it is 7-8 that the condition of the copolymerization, which includes: pH value, and temperature is 50-70 DEG C, time 3-8h.
8. nano silica graft copolymer made from a kind of method as described in any one of claim 4-7.
9. nano silica graft copolymer described in any one of claim 1-3 and 8 is in drilling fluid as drop filter
Lose the application of agent.
10. a kind of contain nano silica graft copolymer described in any one of claim 1-3 and 8 as filtrate reducing
The drilling fluid of agent.
11. drilling fluid according to claim 10, wherein the content of the nano silica graft copolymer is 0.5-
2 weight %.
12. application of the drilling fluid described in claim 10 or 11 in oil/gas drilling.
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| CN113024746A (en) * | 2021-03-04 | 2021-06-25 | 中国石油大学(北京) | Star-structure copolymer for reducing fluid loss, preparation method and application thereof, drilling fluid and application thereof |
| CN113355073A (en) * | 2021-06-22 | 2021-09-07 | 西南石油大学 | Synthesis of self-adaptive external flexible and internal rigid type nano plugging agent and water-based drilling fluid |
| CN113773440A (en) * | 2021-10-12 | 2021-12-10 | 中国石油大学(华东) | Water-based drilling fluid filtrate reducer capable of inhibiting natural gas hydrate decomposition and preparation method and application thereof |
| CN114163587A (en) * | 2021-11-30 | 2022-03-11 | 中国石油天然气集团有限公司 | Nano-silica graft polymer, preparation method and application thereof, and fluid loss additive |
| CN114163587B (en) * | 2021-11-30 | 2024-01-23 | 中国石油天然气集团有限公司 | Nano silicon dioxide grafted polymer, preparation method and application thereof, and filtrate reducer |
| CN114685736A (en) * | 2021-12-14 | 2022-07-01 | 中国石油天然气集团有限公司 | High-temperature-resistant high-salt-resistant hydrophobic blocking agent and preparation method thereof |
| CN114736339A (en) * | 2022-05-21 | 2022-07-12 | 库尔勒明洋工贸有限责任公司 | Synthesis method of filtrate reducer without residual monomers and filtrate reducer prepared by same |
| CN114736339B (en) * | 2022-05-21 | 2024-03-12 | 库尔勒明洋工贸有限责任公司 | Method for synthesizing residual monomer-free filtrate reducer and filtrate reducer prepared by same |
| CN115975133A (en) * | 2022-12-02 | 2023-04-18 | 中国石油大学(华东) | Suspension stabilizer for high-temperature high-density well cementing cement slurry, preparation method and application |
| CN116396491A (en) * | 2023-03-30 | 2023-07-07 | 任丘市鸿运石油化工有限公司 | Modified lubricant and preparation method and application thereof |
| CN116396491B (en) * | 2023-03-30 | 2023-11-03 | 任丘市鸿运石油化工有限公司 | Modified lubricant and preparation method and application thereof |
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