CN107312507A - A kind of clay stabilizer and its application - Google Patents
A kind of clay stabilizer and its application Download PDFInfo
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- CN107312507A CN107312507A CN201610269047.7A CN201610269047A CN107312507A CN 107312507 A CN107312507 A CN 107312507A CN 201610269047 A CN201610269047 A CN 201610269047A CN 107312507 A CN107312507 A CN 107312507A
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- epoxychloropropane
- clay stabilizer
- stabilizer
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/607—Compositions for stimulating production by acting on the underground formation specially adapted for clay formations
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/62—Compositions for forming crevices or fractures
- C09K8/66—Compositions based on water or polar solvents
- C09K8/68—Compositions based on water or polar solvents containing organic compounds
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2208/00—Aspects relating to compositions of drilling or well treatment fluids
- C09K2208/12—Swell inhibition, i.e. using additives to drilling or well treatment fluids for inhibiting clay or shale swelling or disintegrating
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- General Life Sciences & Earth Sciences (AREA)
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Abstract
The present invention relates to a kind of preparation method of the clay stabilizer for low permeability formation, comprise the following steps successively：In the aqueous solution that epoxychloropropane is added to unitary fatty amine, certain time is then reacted；Epoxychloropropane is added, is then heated up, is reacted；Then polyamine is added, epoxychloropropane is added, is then reacted, described clay stabilizer is obtained after drying.
Description
Technical field
The present invention relates to the auxiliary agent field used in oil-gas mining, and in particular to a kind of preparation method of clay stabilizer and its
Using.
Background technology
China's oil and gas reservoir all contains a certain amount of clay mineral, when clay content is higher in reservoir (such as：China Chuan Dong
The average clay content of southern Fuling Prefecture's shale gas reservoir is 32%, and fourth Mountain area reaches 40%-60%, and Peng River area reaches 20%-
50%), when the Water-based working liquid for electrical such as drilling well, well cementation, water filling, pressure break, acidifying, well workover are invaded, easily cause clay mineral expansion, divide
Dissipate and migrate, the throat of formation pore structure may be blocked, the permeability on stratum is reduced, oil well output is reduced, cause oil-gas Layer
Injury, it is therefore necessary to add clay stabilizer.
Clay stabilizer experienced inorganic salts, inorganic many nuclear polymers, cationic surfactant, organic cation polymerization
The thing stage.Wherein, organic cationic polymer clay stabilizer turns into popular research direction, and such as CN101921366 is by two allyls
Ammonium chloride and triallylammonium chloride synthesize three side chain cationic polymers, for stable clay in oil recovery process.But research
Show that the cationic polymer of HMW is not suitable for tight formation, easily form embolism in formation pore passage, from
And block stratum；Polymer is more containing cation group quantity due to molecular chain length simultaneously, easily with the processing containing anionic group
Agent reacts, extreme influence inorganic agent effect.Accordingly, it would be desirable to develop low relative molecular mass, protection stratum preserve from and
The good clay stabilizer with other inorganic agent compatibilities.
In applying at the scene, (such as drag reduction hydraulic pressure splits some work progress, it is desirable to the extremely low 0.1%- of clay stabilizer consumption
0.5%) consumption is controlled very strict.However, in a large amount of patents and document, often focus on consumption 1%~2% it is anti-swollen
Effect, evaluates less to the preventive effect of expansion of consumption 0.3%~1%, also tends to select higher dosage in the application, such is sticked at present
(1%~2% even more than) preventive effect of expansion is excellent when soil stabilizer has a high consumption, and low consumption (<0.5%) swollen effect is prevented when
Really poor the problem of, such as small molecule polyamine stabilizer EM (chemistry and bioengineering, 2010,27 (12)), consumption is in 1%-2%
When, anti-dilative reaches 72%-86%, but consumption, when being 0.5%, anti-dilative is only 43%.
The content of the invention
The present invention is for existing clay stabilizer consumption is big, anti-dilative is low, and polymer clay stabilizer molecular weight is big, Yi Zao
The problem of into formation damage, the invention provides a kind of preparation method of clay stabilizer.Multicomponent prepared in accordance with the present invention
Clay stabilizer, its molecular weight is relatively low, also can effectively suppress clay hydration swelling under extremely low consumption and scattered
Migration.The clay stabilizer of the present invention is applicable to low permeability formation.Present invention also offers the application of the clay stabilizer.
According to an aspect of the invention, there is provided a kind of preparation method of clay stabilizer for low permeability formation, according to
It is secondary to comprise the following steps：
Epoxychloropropane is added in the aqueous solution of unitary fatty amine by a, then reacts certain time；
B adds epoxychloropropane into step a in reacted solution, then heats up, and is reacted；
C adds polyamine into step b in reacted solution, adds epoxychloropropane, is then reacted, and dries
Described clay stabilizer is obtained afterwards.
The method provided according to the present invention, clay stabilizer can be prepared in high conversion rate.The obtained clay is stable
Agent, by the reaction of monoamine fatty amine, epoxychloropropane and polyamine, forms the molecule knot that straight chain and network structure coexist
Structure, while multiple spot acts on electronegative clay particle, degree of absorption is high, it is achieved thereby that anti-dilative high mesh during low dosage
's.
One embodiment of the method provided according to the present invention, the unitary fatty amine is selected from dimethylamine, front three
At least one of amine, diethylamine and triethylamine.The polyamine is the compound containing at least two amidos.It is specific at one
In embodiment, the polyamine is triethylene tetramine and/or TEPA.It is described many in another specific embodiment
First amine is the mixture of triethylene tetramine and TEPA.And in one preferred embodiment, triethylene tetramine and four
The mol ratio of the amine of ethene five is 1:1-1:5.
The another embodiment of the method provided according to the present invention, the unitary fatty amine, total epoxy chloropropionate
The mol ratio of alkane and polyamine is 1:(0.9-1.5):(0.2-1).
Epoxychloropropane, step in the another embodiment of the method provided according to the present invention, the step a
The mol ratio of epoxychloropropane in b and the epoxychloropropane in step c is 1:(1-1.2):(0.2-1.5).The epoxy chlorine
Propane is to add by several times, it is possible to increase reaction transforming degree.It is used in described step a, b and c in a specific example
Epoxychloropropane feed postition for be added dropwise.Being added dropwise can be with control system temperature and the speed added.
The another embodiment of the method provided according to the present invention, the step a controls are carried out below 20 DEG C.
In a specific example, the certain time in step a is 0.5-2h, such as 0.5-1h or 1-2h.It is specific real at another
In example, in the aqueous solution of the unitary fatty amine, the mol ratio of unitary fatty amine and water is 1:(20-30).
The another embodiment of the method provided according to the present invention, in the step b, is warming up to 80-95 DEG C,
And/or the reaction time is 2-4h.In the step c, the temperature of reaction is 60-85 DEG C, and/or the time of reaction is 1-4h.
Resulting clay stabilizer is dry powder-shaped.
According to the specific embodiment of the present invention, it the described method comprises the following steps.According to mol ratio 1:(0.9-
1.5):(0.2-1):(10-30) weighs fatty monoamine, epoxychloropropane, polyamine and distilled water respectively.By the unitary of metering
In fatty amine and distilled water input reactor, stirring is opened, a certain amount of epoxychloropropane, control are added dropwise using constant pressure funnel
Certain reaction such as 1h are incubated after low temperature and rate of addition processed, completion of dropping；A certain amount of epoxychloropropane is added dropwise again, gradually heats up
To 80~95 DEG C, 2~4h of reaction time.The polyamine of metering is added in products therefrom, the epoxychloropropane of surplus is added dropwise,
60~85 DEG C are gradually heating to afterwards, 1~4h is reacted, and product is vacuum dried, obtains dry powder-shaped clay stabilizer.
According to the specific embodiment of the present invention, the clay stabilizer is applied to low permeability formation, and methods described is system
The method of the standby clay stabilizer suitable for low permeability formation.
The method provided according to the present invention, is delivered and improves reaction transforming degree by several times by reaction raw materials；Added by priority
Enter monoamine a large amount of cation groups are introduced into strand with polyamine, form what is coexisted comprising linear chain structure and network structure
Multicomponent stabilizer, while multiple spot acts on electronegative clay particle, degree of absorption is high, it is achieved thereby that preventing during low dosage swollen
The high purpose of rate, anti-dilative is up to 73% under 0.3% dosage.
According to the clay stabilizer of the present invention, with low relative molecular mass (for example, number-average molecular weight is 250~5000
Left and right, based on 250~1300 component, accounts for 55-87%), it is solid dry powder-shaped, convenient transport and storage；It is not easily blocked
Stratum duct；Low permeability formation is particularly suitable for use in, does not cause formation damage；For in the operations such as drilling well, well cementation, water filling, acidifying, with
Conventional inorganic agent compatibility is good；Also there is anti-swollen property well and stabilizer under low addition.
According to another aspect of the present invention, a kind of application of clay stabilizer in oil-gas mining is additionally provided, including：
Clay stabilizer is prepared first with the above method, oil-gas mining is subsequently used for.Clay stabilizer prepared according to the methods of the invention
For oil-gas mining, be conducive to improving oil well output, it is to avoid or reduce reservoir damage.
Brief description of the drawings
Fig. 1 is the infrared spectrum of the stabilizer product according to one embodiment of the present of invention.
Embodiment
The invention will be further described with reference to embodiments, but does not constitute any limitation of the invention.
IR Characterization：The production of synthesis presses 1 with KBr:100 ratio mixing, tabletting after grinding is surveyed with infrared spectrometer
Its fixed spectrogram.
The measure of molecular weight：It is measured using gel permeation chromatography.
Embodiment 1：
1.2mol trimethylamines are added 10mol distilled water is added under three-necked flask, stirring condition, using constant pressure funnel
0.5mol epoxychloropropane is slowly added dropwise, control accelerates keeping temperature to be less than 20 DEG C, 1h is incubated after completion of dropping；Then add
0.5mol epoxychloropropane, is gradually heating to 90~95 DEG C of reaction 2h；0.4mol triethylene tetramines are added, 0.5mol rings are added dropwise
Oxygen chloropropane, is warming up to 65-70 DEG C of reaction 2h, clay stabilizer is obtained after product is vacuum dried.
Clay stabilizer is subjected to IR Characterization, as shown in Figure 1,1250cm-1、980cm-1For C-N characteristic absorption peaks,
2900~3000cm-1For C-H stretching vibration peaks in methyl, methylene, without N-H absworption peaks, 3330cm in the figure-1The hydroxyl at place
Peak is the characteristic peak of water after the pressing potassium bromide troche moisture absorption, it follows that containing quaternary ammonium group in stabilizer.
After tested, range of number-average molecular weight is about 250~5000, and wherein number-average molecular weight about 250~1300 accounts for 87%.
Embodiment 2：
1.2mol dimethylamine is added 10mol distilled water is added under three-necked flask, stirring condition, using constant pressure funnel
0.4mol epoxychloropropane is slowly added dropwise, control accelerates keeping temperature to be less than 20 DEG C, 1h is incubated after completion of dropping；Then add
0.4mol epoxychloropropane, is gradually heating to 80~85 DEG C of reaction 2h；0.4mol triethylene tetramines are added, 0.4mol rings are added dropwise
Oxygen chloropropane, is warming up to 65-70 DEG C of reaction 2h, clay stabilizer is obtained after product is vacuum dried.
After tested, quaternary ammonium group is contained in stabilizer.Range of number-average molecular weight is about 250~5000, wherein counting equal molecule
Amount about 250~1300 accounts for 85%.
Embodiment 3：
1.5mol dimethylamine is added 15mol distilled water is added under three-necked flask, stirring condition, using constant pressure funnel
0.7mol epoxychloropropane is slowly added dropwise, control accelerates keeping temperature to be less than 20 DEG C, 1h is incubated after completion of dropping；Then add
0.8mol epoxychloropropane, is gradually heating to 80~85 DEG C of reaction 2h；0.4mol triethylene tetramines are added, 0.2mol rings are added dropwise
Oxygen chloropropane, is warming up to 65-70 DEG C of reaction 2h, clay stabilizer is obtained after product is vacuum dried.
After tested, quaternary ammonium group is contained in stabilizer.Range of number-average molecular weight is about 250~5000, wherein counting equal molecule
Amount about 250~1300 accounts for 55%.
Embodiment 4：
1.5mol trimethylamines are added 20mol distilled water is added under three-necked flask, stirring condition, using constant pressure funnel
0.9mol epoxychloropropane is slowly added dropwise, control accelerates keeping temperature to be less than 20 DEG C, 1h is incubated after completion of dropping；Then add
0.9mol epoxychloropropane, is gradually heating to 90~85 DEG C of reaction 2h；0.3mol triethylene tetramines are added, 0.2mol rings are added dropwise
Oxygen chloropropane, is warming up to 65-70 DEG C of reaction 4h, clay stabilizer is obtained after product is vacuum dried.
After tested, quaternary ammonium group is contained in stabilizer.Range of number-average molecular weight is about 250~5000, wherein counting equal molecule
Amount about 250~1300 accounts for 59%.
Embodiment 5：
1.2mol trimethylamines are added 20mol distilled water is added under three-necked flask, stirring condition, using constant pressure funnel
0.4mol epoxychloropropane is slowly added dropwise, control accelerates keeping temperature to be less than 20 DEG C, 1h is incubated after completion of dropping；Then add
0.4mol epoxychloropropane, is gradually heating to 90~85 DEG C of reaction 2h；Add 0.3mol triethylene tetramines and 0.3mol tetrems
The mixture of the amine of alkene five, is added dropwise 0.6mol epoxychloropropane, is warming up to 65-70 DEG C of reaction 2h, is obtained after product is vacuum dried
Clay stabilizer.
After tested, quaternary ammonium group is contained in stabilizer.Range of number-average molecular weight is about 250~5000, wherein counting equal molecule
Amount about 250~1300 accounts for 87%.
The performance characterization of clay stabilizer and contrast：
1. the clay stabilizer of the present invention is contrasted with other stabilizers
Reference standard SY/T 5971-94《Water filling clay stabilizer method of evaluating performance》With Q/SH 0053-2010《It is viscous
Soil stabilizer technical requirements》Middle eccentricity method, is increased by determining bentonite in powder volumetric expansion in clay stabilizer solution and water
Amount evaluates anti-dilative.Determine respectively under the weight based on fracturing fluid, 0.3wt% dosages, clay stabilizer of the present invention and other
Conventional anti-dilative of the clay stabilizer in clear water, drag reduction water fracturing fluid；And the higher clay stabilizer of anti-dilative is selected, survey
Its water-fastness rate in clear water.Wherein, drag reduction hydraulic pressure splits formula of liquid and is：0.1wt% anionic polymers (acrylamide and third
Olefin(e) acid copolymer, molecular weight is more than 5,000,000, trade mark 80A-51) (pressure break cleanup additive, the trade mark is+0.1wt% surfactants
FC-117)+clear water, as a result as shown in table 1.
The anti-dilative of table 1, water-fastness rate comparing result
In table 1, CPCS series (development of CPCS series low relative molecular mass polyquaternium clay expansion-resisting agents, oil field
Learn, the 3rd phase of volume 26,2009, monoamine is made with epoxychloropropane for raw material)；
XFP-2 (new type high temperature clay stabilizer XFP-2 development and field application, Speciality Petrochemicals progress, volume 7
10th phase, 2006, monoamine is primary raw material)；
HAPEA and HFHEA (synthesis of organic amine expansion-resisting agent and its performance evaluation, Xi'an Petroleum University, master's degree opinion
Text, 2012), wherein HAPEA using monoamine and epoxychloropropane as primary raw material, HFHEA using polyamine and epoxychloropropane as
Primary raw material, clay stabilizer dosage is above 0.3% used in the measure of its anti-dilative, and anti-dilative is between 53%-71%.
As shown in Table 1, clay stabilizer of the invention is under 0.3wt% dosages, and the anti-dilative in riverfrac treatment liquid is equal
More than 65%, up to 73.6%；Anti-dilative in drag reduction water fracturing fluid is above 60%.
And in other control clay stabilizers, the anti-dilative under its 0.3wt% dosage is respectively less than the application.Wherein, CPCS
The clay stabilizer of series, XFP-2, HAPEA and HFHEA, even if addition is higher than the application, its anti-dilative is also far below this Shen
Please in stabilizer anti-dilative, not to mention, when its addition is identical with the application, its anti-dilative necessarily more below this
The anti-dilative of stabilizer in application.
By contrast, clay stabilizer of the invention, which has, prevents swollen advantage.Because the drag reducer in drag reduction water is anionic
Polymer, playing inhibitory action to cationic clay stabilizer has certain influence, therefore the anti-dilative in drag reduction water is less than
Clear water.The higher embodiment 1 of anti-dilative, embodiment 2, the water-fastness rate of the clay stabilizer of embodiment 5 are above 90%, are higher than
XFP-2 and HY-200.
2. influence of the clay stabilizer dosage to anti-dilative
Anti-dilative of the clay stabilizer of embodiment 1 in clear water under different dosages is determined, as a result as shown in table 2.
Influence result of the clay stabilizer dosage of table 2 to anti-dilative
3. viscosity test experiments
By embodiments of the invention 1, embodiment 2, embodiment 5 and high molecular weight cationic polymer formulation into 10%
Solution, its viscosity is determined using the fast viscosity instrument of Fann six, to characterize the size of relative molecular mass, for the same terms
Under product have it is certain comparative, as a result as shown in table 3.
The clay stabilizer solution viscosity of table 3 is contrasted
From table 3 it can be seen that because the clay stabilizer of the present invention has a low relative molecular mass, thus with equal dosage
High molecular polymer clay stabilizer compare, solution have lower viscosity.
4. compatibility is tested
Embodiment 1, embodiment 2, the clay stabilizer of embodiment 5 and existing drilling fluid, fracturing fluid are often entered with inorganic agent
Row compatibility is observed, as a result as shown in table 4：
The compatibility experimental result of the clay stabilizer of table 4
From table 4, it can be seen that the clay stabilizer of the present invention is mixed with conventional inorganic agent, no layering, precipitation and suspension are existing
As producing, compatibility is good.
Any numerical value mentioned in the present invention, if simply having two between any minimum and any of the highest value
The interval of unit, then include all values of one unit of each increase from minimum to peak.If for example, statement is a kind of
The amount of component, or the value of the state-variable such as temperature, pressure, time is 50-90, in this manual it means that specific
List 51-89,52-88 ... and the numerical value such as 69-71 and 70-71.For the value of non-integer, can with due regard to
0.1st, 0.01,0.001 or 0.0001 is a unit.This is only some special examples indicated.In this application, with similar side
Formula, the combination that is possible to of the numerical value between cited minimum and peak is considered to disclose.
It should be noted that embodiment described above is only used for explaining the present invention, do not constitute to any of the present invention
Limitation.By referring to exemplary embodiments, invention has been described, it should be appreciated that wherein word used is descriptive
With explanatory vocabulary, rather than limited vocabulary.The present invention can be made within the scope of the claims by regulation
Modification, and the present invention is revised in without departing substantially from scope and spirit of the present invention.Although the present invention described in it is related to
And specific method, material and embodiment, it is not intended that the present invention is limited to wherein disclosed particular case, on the contrary, this hair
It is bright to can be extended to other all methods and applications with identical function.
Claims (10)
1. a kind of preparation method of clay stabilizer, comprises the following steps successively：
Epoxychloropropane is added in the aqueous solution of unitary fatty amine by a, then reacts certain time；
B adds epoxychloropropane into step a in reacted solution, then heats up, and is reacted；
C adds polyamine into step b in reacted solution, adds epoxychloropropane, is then reacted, after drying
To described clay stabilizer.
2. according to the method described in claim 1, it is characterised in that the unitary fatty amine is selected from dimethylamine, trimethylamine, diethyl
At least one of amine and triethylamine.
3. method according to claim 1 or 2, it is characterised in that the polyamine is triethylene tetramine and/or four ethene
Five amine.
4. method according to claim 3, it is characterised in that the polyamine is triethylene tetramine and TEPA
The mol ratio of mixture, preferably triethylene tetramine and TEPA is 1:1-1:5.
5. the method according to any one in claim 1-4, it is characterised in that the unitary fatty amine, total epoxy
The mol ratio of chloropropane and polyamine is 1:(0.9-1.5):(0.2-1)；And/or in the aqueous solution of the unitary fatty amine, one
The mol ratio of first fatty amine and water is 1:(20-30).
6. the method according to any one in claim 1-5, it is characterised in that epoxychloropropane in the step a,
The mol ratio of epoxychloropropane in step b and the epoxychloropropane in step c is 1:(1-1.2):(0.2-1.5)；And/or institute
The feed postition of epoxychloropropane used in step a, b and c is stated to be added dropwise.
7. the method according to any one in claim 1-6, it is characterised in that the step a controls are below 20 DEG C
Carry out, the certain time in preferred steps a is 0.5-2h, preferably 0.5-1h.
8. the method according to any one in claim 1-7, it is characterised in that in the step b, be warming up to 80-
95 DEG C, and/or the reaction time is 2-4h.
9. the method according to any one in claim 1-8, it is characterised in that in the step c, the temperature of reaction
For 60-85 DEG C, and/or the time of reaction is 1-4h；And/or the clay stabilizer is dry powder-shaped.
10. a kind of application of clay stabilizer in oil-gas mining, including：First with described in any one in claim 1-9
Method prepares the clay stabilizer, is subsequently used for oil-gas mining.
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| CN108329902A (en) * | 2018-01-23 | 2018-07-27 | 中国石油天然气股份有限公司 | Salt-tolerant clay stabilizer for preparing fracturing fluid from oilfield effluent and preparation method thereof |
| CN108485633A (en) * | 2018-03-31 | 2018-09-04 | 青岛大学 | A kind of preparation method of the poly- quaternary amine oil/gas well shale expansion-resisting agent of novel netted |
| CN108485633B (en) * | 2018-03-31 | 2021-10-08 | 青岛大学 | Preparation method of shale anti-swelling agent for net-shaped polyquaternary amine oil and gas well |
| CN109097006A (en) * | 2018-09-14 | 2018-12-28 | 中国石油集团渤海钻探工程有限公司 | Drilling fluid borehole wall anti-sloughing agent and preparation method thereof |
| CN109097006B (en) * | 2018-09-14 | 2020-09-29 | 中国石油集团渤海钻探工程有限公司 | Borehole wall anti-sloughing agent for drilling fluid and preparation method thereof |
| CN110452375A (en) * | 2019-07-12 | 2019-11-15 | 东北石油大学 | A kind of highly cationic clay stabilizer and preparation method thereof |
| CN110452375B (en) * | 2019-07-12 | 2022-06-03 | 东北石油大学 | High-cationic-degree clay stabilizer and preparation method thereof |
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