CN109749019A - A kind of oil-well cement silane-modified polycarboxylate dispersant and preparation method and application - Google Patents
A kind of oil-well cement silane-modified polycarboxylate dispersant and preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of oil-well cement silane-modified polycarboxylate dispersant and preparation methods and application, the preparation method comprises the following steps: (1), by unsaturated polyether polymeric monomer, cationic monomer is added in distilled water, stirs to obtain mixed liquor；(2) silane monomer is taken, carboxylic acid type monomer is added distilled water, is stirred for A liquid；It takes initiator to be dissolved in distilled water, is stirred for B liquid；(3) A liquid and B liquid is added dropwise simultaneously in the mixed liquor obtained to step (1), after adding, is kept the temperature at 65-75 DEG C, adjusts pH, obtain oil-well cement with silane-modified polycarboxylate dispersant.The present invention takes water as a solvent, simple process and low cost；Dispersing agent can be effectively increased in the adsorbance of cement particle surface, improve the dispersion performance and rheological property of cement slurry, reduce the viscosity of cement slurry, to well adapting to property of oil-well cement.Retardation phenomenon is alleviated, resistance to sulfate ability is improved.The dispersibility and dispersion retentivity for improving cement slurry, improve the rheological characteristic of cement slurry.
Description
Technical field
The present invention relates to oil well cement additive technical field, in particular to the silane-modified polycarboxylic acids of a kind of oil-well cement
Dispersing agent and preparation method and application.
Background technique
In oil gas well cementing operation engineering, oil well cement additive is to improve cement slurry property, improves the effective of cementing quality
Auxiliary agent.Dispersing agent (also known as drag reducer) is a kind of important oil well cement additive, and main function is to adjust oil well cement paste
Rheological property reduces the viscosity of cement slurry, improves aid pumpability.At present applied to the dispersing agent of reinforcing oil well mainly with sulfonated ketone
Based on aldehyde polycondensate and naphthalene system dispersing agent, although these dispersing agents have certain dispersibility to cement slurry, there is flowing
The problem of retentivity difference, and preparation process is complicated, mostly uses the noxious materials such as formaldehyde in synthesis process, causes dirt to environment
Dye, and it is poor with other cement additive compatibilities, casing and cementing needs cannot be better meet.In recent years, polyocarboxy acid type disperses
Volume is low, good dispersion, structure-controllable and the excellent performance such as environmentally friendly are received significant attention because having for agent, therefore,
Many oil companies have started to be introduced into reinforcing oil well industry.
Polycarboxylate dispersant has very strong Molecular Design, mutually interpolymerized by using the monomer containing different functional groups
It closes, the polycarboxylate dispersant of available different performance.Chinese patent " polycarboxylate dispersant and its preparation for oil-well cement
Method " (application number: 201610543851.X) according to Polymer supported catalyst principle, using acrylic acid, N- ethenyl pyrrolidone
Ketone, itaconic acid, -2 methyl propane sulfonic acid of 2- propyl amides base, sodium vinyl sulfonate, vinylbenzenesulfonic acid sodium and the poly- second of allyl
Glycol is monomer, synthesizes the polycarboxylate dispersant with good high temperature resistant and rheological property, but above-mentioned dispersing agent is simultaneously uncomfortable
With in the higher oil-well cement of sulphates content.For the salt tolerance for improving polycarboxylate dispersant, Chinese patent " seawer system oil
Well water cement dispersant and preparation method thereof " (application number: 201610650154.4) synthesizing ampholyte copolymer by aqueous solution polymerization,
The dispersing agent can effectively control influence of the high volence metal ion to cement slurry mobility in seawater, but the stream of this dispersing agent
Dynamic retentivity is poor, is unfavorable for the long-term pumping of cement slurry.
In recent years, although being made some progress to oil-well cement with the research of polycarboxylate dispersant, have
Deficiency, because polycarboxylate dispersant is mainly the monomer containing carboxyl functional group at present, carboxyl can be adsorbed onto cement particle surface, press down
Hydrated cementitious process processed, causes the early strength of Behavior of Hardened Cement Paste to develop slowly, while when sulfate concentration is larger, sulfate ion
Competitive Adsorption can occur in cement particle surface with polycarboxylate dispersant, so that the dispersion of cement slurry and rheological characteristic is deteriorated, therefore difficult
To meet the requirement of regulation well cementing process cement slurry comprehensive performance.
Summary of the invention
The purpose of the present invention is strong, the rheologies that overcomes the deficiencies of the prior art and provide a kind of pair of oil well cement paste dispersibility
Property it is good, with certain sulfate resistance ability and promote Behavior of Hardened Cement Paste early strength development the silane-modified polycarboxylic acids of oil-well cement
Dispersing agent.
A second object of the present invention is to provide a kind of oil-well cement preparation methods of silane-modified polycarboxylate dispersant.
Third object of the present invention is to provide a kind of applications of silane-modified polycarboxylate dispersant of oil-well cement.
Technical solution of the present invention is summarized as follows:
A kind of oil-well cement preparation method of silane-modified polycarboxylate dispersant, includes the following steps:
(1) ratio by weight, weighs 39.02-40.69 parts of unsaturated polyether polymeric monomers, 1.30-1.36 parts of cation monos
Body is added in 35-45 parts of distilled water, and stirring is warming up to 65-75 DEG C and obtains mixed liquor；
(2) 1.22-1.24 parts of silane monomers are weighed, 2.35-3.05 parts of carboxylic acid type monomers are added 30-40 parts of distilled water, stir
It mixes uniformly as A liquid；It weighs 0.80-1.0 parts of initiators and is dissolved in 25-35 parts of distilled water, be stirred for B liquid；
(3) A liquid and B liquid is added dropwise simultaneously in the mixed liquor obtained to step (1), after A liquid and B liquid all drip, continues
65-75 DEG C of heat preservation 2-4h adjusts pH=6-7, obtains oil-well cement with silane-modified polycarboxylate dispersant.
Step (1) is preferred are as follows: by weight example, weighs 40.02 parts of unsaturated polyether polymeric monomers, 1.34 parts of cation monos
Body is added in 40 parts of distilled water, and stirring is warming up to 70 DEG C and obtains mixed liquor.
Step (2) is preferred are as follows: weighs 1.23 parts of silane monomers, 35 parts of distilled water are added in 2.40 parts of carboxylic acid type monomers, stirring
It is uniformly A liquid；0.90 part of initiator is weighed, 30 parts of distilled water is dissolved in, is stirred for B liquid；
Unsaturated polyether polymeric monomer is preferably the allyl polyglycol or number-average molecular weight of number-average molecular weight 600-2400
The methacrylic polyethylene glycol of 600-2400.
Cationic monomer is preferably dimethyl diallyl ammonium chloride or MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
Silane monomer is preferably vinyltrimethoxysilane or 3- (isobutene acyl-oxygen) propyl trimethoxy silicane.
Carboxylic acid type monomer is preferably maleic anhydride, acrylic acid or itaconic acid.
Initiator is preferably ammonium persulfate, potassium peroxydisulfate or azo-bis-isobutyrate hydrochloride.
A kind of oil-well cement of above method preparation is with silane-modified polycarboxylate dispersant.
A kind of application of silane-modified polycarboxylate dispersant of above-mentioned oil-well cement.
Advantages of the present invention:
(1) present invention takes water as a solvent, and preparation process is simple, at low cost, is easy to realize industrial production.
(2) oil-well cement of the invention can effectively increase dispersing agent in cement with silane-modified polycarboxylate dispersant
Grain surface adsorbance, improve the dispersion performance and rheological property of cement slurry, reduce the viscosity of cement slurry, to oil-well cement have compared with
Good adaptability is suitable as oil well cement dispersant use.
(3) from Molecular Design angle, the functional silane monomer of siliceous oxygen groups is introduced as comonomer, substitution
Monomer of the part containing carboxyl functional group, alleviates carboxylic group bring retardation phenomenon, and improve resistance to sulfate ability.
(4) present invention is being increased by introducing anionic functional group's carboxyl, Cationic functional groups quaternary ammonium salt and Gui Yang functional group
The deferred action of carboxyl is effectively relieved while bonus point powder adsorption capacity, introducing, there is the polyether macromonomer of long side chain can mention
For steric hindrance, the dispersibility and dispersion retentivity of cement slurry are improved, improves the rheological characteristic of cement slurry, enhances the synthesis of cement slurry
Performance.
Detailed description of the invention
Fig. 1 is the oil-well cement infared spectrum of silane-modified polycarboxylate dispersant of the preparation of embodiment 1.
Fig. 2 is the oil-well cement nuclear magnetic resonance spectroscopy of silane-modified polycarboxylate dispersant of the preparation of embodiment 1.
Fig. 3 is that oil-well cement prepared by embodiment 1 is divided with the scanning electron microscope (A) and element of silane-modified polycarboxylate dispersant
It analyses spectrogram (B).
Fig. 4 is that the hydration heat rate profile that the cement slurry of dispersing agent is 30 DEG C in curing temperature is added.
Specific embodiment
The present invention is further illustrated combined with specific embodiments below.
Embodiment 1
A kind of oil-well cement preparation method of silane-modified polycarboxylate dispersant, includes the following steps:
(1) the methacrylic polyethylene glycol that 40.02g number-average molecular weight is 2400,1.34g dimethyl diallyl are weighed
Ammonium chloride is added in 40g distilled water, and stirring is warming up to 70 DEG C and obtains mixed liquor；
(2) 1.23g vinyltrimethoxysilane is weighed, 2.40g acrylic acid is added 35g distilled water, is stirred for A
Liquid；It weighs 0.90g ammonium persulfate and is dissolved in 30g distilled water, be stirred for B liquid；
(3) A liquid and B liquid is added dropwise simultaneously in the mixed liquor obtained to step (1), after A liquid and B liquid all drip, continues
70 DEG C of heat preservation 2h adjust pH=7 with NaOH, obtain oil-well cement with silane-modified polycarboxylate dispersant.
Embodiment 2
A kind of oil-well cement preparation method of silane-modified polycarboxylate dispersant, includes the following steps:
(1) the methacrylic polyethylene glycol that 39.02g number-average molecular weight is 600,1.30g dimethyl diallyl are weighed
Ammonium chloride is added in 35g distilled water, and stirring is warming up to 65 DEG C and obtains mixed liquor；
(2) 3- (isobutene acyl-oxygen) propyl trimethoxy silicane of 1.22g is weighed, 40g distillation is added in 2.35g itaconic acid
Water is stirred for A liquid；It weighs 0.80g potassium peroxydisulfate and is dissolved in 25g distilled water, be stirred for B liquid；
(3) A liquid and B liquid is added dropwise simultaneously in the mixed liquor obtained to step (1), after A liquid and B liquid all drip, continues
65 DEG C of heat preservation 4h adjust pH=6 with NaOH, obtain oil-well cement with silane-modified polycarboxylate dispersant.
Embodiment 3
A kind of oil-well cement preparation method of silane-modified polycarboxylate dispersant, includes the following steps:
(1) allyl polyglycol that 40.69g number-average molecular weight is 600,1.36g methylacryoyloxyethyl three are weighed
Ammonio methacrylate is added in 45g distilled water, and stirring is warming up to 75 DEG C and obtains mixed liquor；
(2) 3- (isobutene acyl-oxygen) propyl trimethoxy silicane of 1.24g is weighed, 3.05g maleic anhydride is added 30g and steams
Distilled water is stirred for A liquid；It weighs 1.0g azo-bis-isobutyrate hydrochloride and is dissolved in 35g distilled water, be stirred for B liquid；
(3) A liquid and B liquid is added dropwise simultaneously in the mixed liquor obtained to step (1), after A liquid and B liquid all drip, continues
75 DEG C of heat preservation 2h adjust pH=7 with NaOH, obtain oil-well cement with silane-modified polycarboxylate dispersant.
Embodiment 4
(1) ratio by weight weighs the allyl polyglycol that 40.02g number-average molecular weight is 2400,1.34g methyl-prop
Alkene acyloxyethyl trimethyl ammonium chloride is added in 40g distilled water, and stirring is warming up to 65 DEG C and obtains mixed liquor；
(2) 1.23g vinyltrimethoxysilane is weighed, 2.40g itaconic acid is added 35g distilled water, is stirred for A
Liquid；It weighs 0.90g azo-bis-isobutyrate hydrochloride and is dissolved in 30g distilled water, be stirred for B liquid；
(3) A liquid and B liquid is added dropwise simultaneously in the mixed liquor obtained to step (1), after A liquid and B liquid all drip, continues
65 DEG C of heat preservation 3h adjust pH=6.5 with NaOH, obtain oil-well cement with silane-modified polycarboxylate dispersant.
Comparative example 1
A kind of oil-well cement preparation method of polycarboxylate dispersant, includes the following steps:
(1) the methacrylic polyethylene glycol that 40.59g number-average molecular weight is 2400 is dissolved in 35g distilled water, 1.36g
Dimethyl diallyl ammonium chloride is added in 40g distilled water, and stirring is warming up to 70 DEG C and obtains mixed liquor；
(2) it weighs 3.04g acrylic acid and is dissolved in 35g distilled water, be stirred for A liquid；0.90g ammonium persulfate is weighed to be dissolved in
30g distilled water is stirred for B liquid；
(3) A liquid and B liquid is added dropwise simultaneously in the mixed liquor obtained to step (1), after A liquid and B liquid all drip, continues
70 DEG C of heat preservation 2h adjust pH=7 with NaOH, obtain oil-well cement and use polycarboxylate dispersant.
Oil-well cement prepared by embodiment 1 structured testing of silane-modified polycarboxylate dispersant.
Fig. 1 is the oil-well cement infared spectrum of silane-modified polycarboxylate dispersant of the preparation of embodiment 1.It can from figure
Out, 3446cm-1And 1115cm-1It is the stretching vibration of the-OH and-C-O-C- on methacrylic polyethylene glycol (HPEG) respectively
Peak, 2886cm-1It is-CH3Characteristic absorption peak；1723cm-1And 1467cm-1It is the symmetrical of-COOH on acrylic acid (AA) respectively
With antisymmetric stretching vibration peak, 1335cm-1And 966cm-1It is-C-N on dimethyl diallyl ammonium chloride (DMDAAC) respectively
With-N+R3Characteristic absorption peak；835cm-1It is the stretching vibration peak of-Si-O- on vinyltrimethoxysilane (VTMO), table
Bright all monomers both participate in polymerization reaction, thus oil-well cement with silane-modified polycarboxylate dispersant be function monomer HPEG, AA,
The quadripolymer of DMDAAC, VTMO.
Fig. 2 is the oil-well cement nuclear magnetic resonance spectroscopy of silane-modified polycarboxylate dispersant of the preparation of embodiment 1.It can from figure
To find out, 2.5ppm is dimethyl sulfoxide (DMSO) solvent peak, and 2.32ppm is the feature of-CH- in main chain AA in polymer respectively
Proton uptake peak, 3.31ppm are-NCH in DMDAAC3Diagnostic protons absorption peak, 3.40-3.60ppm is-CH in HPEG2-
CH2- Si-O-CH in-O- and VTMO3In proton characteristic absorption peak.Analysis is it is found that tetra- kinds of monomers of HPEG, AA, DMDAAC, VTMO
It is both present in polymer molecular chain.
Fig. 3 is that oil-well cement prepared by embodiment 1 is divided with the scanning electron microscope (A) and element of silane-modified polycarboxylate dispersant
It analyses spectrogram (B).From scanning electron microscope (SEM) photograph as can be seen that oil-well cement with silane-modified polycarboxylate dispersant is in club shaped structure, and phase
It is mutually intertwined, can be seen that the presence of element silicon in silane-modified polycarboxylate dispersant from elemental analysis spectrogram, it was demonstrated that
Vinyltrimethoxysilane takes part in polymerization reaction.
The preparation of cement slurry and performance test methods are carried out referring to GB/T19139-2012 " oil-well cement test method ".
The fluidity of the dispersing agent of embodiment and comparative example, rheological property, first final setting time and compressive property are evaluated, evaluation knot
Fruit such as table 1, table 2, shown in table 3 and table 4.
Fluidity of 1 dispersing agent of table in different hydration times
Note: cement-slurry method are as follows: dispersing agent+a certain amount of sodium sulphate of G grades of 500g good magnificent oil-well cement+difference dosages+
220g fresh water.
As shown in Table 1, when dispersing agent dosage is 0.2wt%, the dispersing agent of embodiment 1 is because of early stage cement fast hydration meeting
A large amount of hydrated products are generated, hydrated product can coat dispersing agent and form organic mineral facies, and a large amount of dispersing agents, which are consumed, causes cement
Slurry slightly declines in aquation early flow degree；When dispersing agent dosage is 0.4wt%, compared with the dispersing agent of comparative example 1, implement
The dispersing agent of example 1 has good dispersibility and dispersion retentivity to mortar architecture in 120min；The sulphur of 0.5wt% is added
Sour sodium, the dispersing agent of embodiment 1 still have good dispersion performance, illustrate that the dispersing agent of embodiment 1 has certain sulfuric-resisting
Salt ability.
The dispersing agent of embodiment 1 can pass through-COOH the anion and-N of main chain+R3Cation and cement particle surface
Chemical bonding effect and polyoxyethylene branched chain occur for charge adsorption effect, silicon oxygen bond and hydrated product in cement particle surface
Steric hindrance effect, destroys the flocculent structure of cement granules and discharges Free water, so that cement slurry be made to have good fluidity
With flowing retentivity, and then improve cement slurry dispersion performance.
The rheological parameter of the mortar architecture of 2 dispersing agent of table
Note: cement-slurry method are as follows: dispersing agent+a certain amount of sodium sulphate of G grades of 500g good magnificent oil-well cement+difference dosages+
220g fresh water.
Well cementation industry it is generally believed that the liquidity index n of cement slurry be the bigger the better, consistency coefficient K value it is the smaller the better, such water
Mud viscosity is smaller, and fluidity is big, is easy to pump.As shown in Table 2, it corresponds to for comparative example 1, the case where same dosage
Under, the liquidity index of the mortar architecture of the dispersing agent containing embodiment 1 is larger, and consistency coefficient is smaller, and the stream of cement slurry
Variable element can according to need the adjusting for carrying out dosage, to substantially improve the rheological property of mortar architecture.
When 0.5wt% sodium sulphate is added, added with the mortar architecture stream still with higher of the dispersing agent of embodiment 1
It is good to illustrate that the dispersing agent of embodiment 1 still has in the presence of sulfate ion for sex index and lower consistency coefficient
Rheological property.
The first final setting time of the mortar architecture of 3 dispersing agent of table
Note: cement-slurry method are as follows: the dispersing agent+220g fresh water of G grades of 500g good magnificent oil-well cement+difference dosages
As shown in Table 3, it corresponds to for comparative example 1, first final setting time phase corresponding to the dispersing agent containing embodiment 1
It is poor little, and the time difference between just final set is shorter, compared with comparative example 1, illustrates the dispersing agent for having embodiment 1 to cement slurry
Setting time does not have an adverse effect.
Compression strength of 4 dispersing agent of table in different curing times
Note: cement-slurry method are as follows: G grades of 500g good magnificent oil-well cement+0.4wt% dispersing agent+220g fresh water.(/ % refers to
Mass percentage of the dispersing agent in G grades of good magnificent oil-well cements)
As shown in Table 4, it corresponds to for striaght cement, cement slurry corresponding to the dispersing agent containing embodiment 1 is at 60 DEG C
Under the conditions of compression strength early-stage development it is rapid, chemical action occurs for silicon oxygen bond in silane monomer and cement granules, increases in water
The adsorption site of mud particle enhances silane-modified polycarboxylate dispersant to the peptizaiton of cement slurry, makes mortar architecture more
It is stable and evenly dispersed, to promote the early strength development of Behavior of Hardened Cement Paste, illustrate to have the dispersing agent of embodiment 1 can promote water
The early strength of mudstone develops.
Fig. 4 is that the hydration heat rate profile that the cement slurry of dispersing agent is 30 DEG C in curing temperature is added.It can be with from figure
Find out, compared with striaght cement, added with the time delay that the maximum heatrelease rate of dispersing agent occurs, and the peak of maximum heatrelease rate
Value also reduces, the reason is that inhibiting hydrated cementitious since with calcium ion chelation can occur for the carboxyl in dispersing agent；With comparative example
1 compares, and the addition of silane monomer promotes hydrated cementitious in the dispersing agent of embodiment 1, and silane-modified polycarboxylate dispersant is to cement
The inhibition level of aquation weakens, to promote the generation of hydrated product, is conducive to the early strength development of Behavior of Hardened Cement Paste, this and early stage
Compression strength data match.
The testing result of embodiment 2,3,4 is similar to Example 1.
Oil-well cement of the invention has preparation process simple with silane-modified polycarboxylate dispersant, at low cost and be easy to store up
The advantages that depositing.The silane-modified polycarboxylate dispersant has introduced cationic monomer, anionic monomer and the silicon containing silicon oxygen bond
Alkane monomer increases physics and chemisorption site of the dispersing agent in cement particle surface, plays well to mortar architecture
Dispersion effect, at the same have the polymeric monomer of long side chain cement particle surface generate space steric effect, prevent cement granules it
Between flocculation, improve cement slurry dispersibility with dispersion retentivity.Mortar architecture containing the silane-modified polycarboxylate dispersant
With good rheological property and higher early strength, in the higher situation of sulfate concentration, still there is preferable dispersion
It is in general a kind of added with the excellent combination property of the mortar architecture of silane-modified polycarboxylate dispersant with rheological property
High-efficiency oil well cement dispersing agent.
Claims (10)
1. a kind of oil-well cement preparation method of silane-modified polycarboxylate dispersant, it is characterized in that including the following steps:
(1) ratio by weight, weighs 39.02-40.69 parts of unsaturated polyether polymeric monomers, 1.30-1.36 parts of cationic monomers add
Enter in 35-45 parts of distilled water, stirring is warming up to 65-75 DEG C and obtains mixed liquor；
(2) 1.22-1.24 parts of silane monomers are weighed, 30-40 parts of distilled water are added in 2.35-3.05 parts of carboxylic acid type monomers, and stirring is equal
Even is A liquid；It weighs 0.80-1.0 parts of initiators and is dissolved in 25-35 parts of distilled water, be stirred for B liquid；
(3) A liquid and B liquid is added dropwise simultaneously in the mixed liquor obtained to step (1), after A liquid and B liquid all drip, continues in 65-75
DEG C heat preservation 2-4h, adjust pH=6-7, obtain oil-well cement with silane-modified polycarboxylate dispersant.
2. according to the method described in claim 1, it is characterized in that the step (1) are as follows: ratio by weight weighs 40.02 parts not
It is saturated polyether macromonomer, 1.34 parts of cationic monomers are added in 40 parts of distilled water, and stirring is warming up to 70 DEG C and obtains mixed liquor.
3. according to the method described in claim 1, it is characterized in that the step (2) are as follows: weigh 1.23 parts of silane monomers, 2.40 parts
Carboxylic acid type monomer is added 35 parts of distilled water, is stirred for A liquid；It weighs 0.90 part of initiator and is dissolved in 30 parts of distilled water, stirring is equal
Even is B liquid.
4. method according to claim 1 or 2, it is characterized in that the unsaturated polyether polymeric monomer is number-average molecular weight 600-
2400 allyl polyglycol or the methacrylic polyethylene glycol of number-average molecular weight 600-2400.
5. method according to claim 1 or 2, it is characterized in that the cationic monomer is dimethyl diallyl ammonium chloride
Or MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride.
6. method according to claim 1 or 3, it is characterized in that the silane monomer is vinyltrimethoxysilane or 3-
(isobutene acyl-oxygen) propyl trimethoxy silicane.
7. method according to claim 1 or 3, it is characterized in that the carboxylic acid type monomer is maleic anhydride, acrylic acid or clothing
Health acid.
8. method according to claim 1 or 3, it is characterized in that the initiator is ammonium persulfate, potassium peroxydisulfate or azo
Two NSC 18620 hydrochlorides.
9. a kind of oil-well cement prepared by the method for one of claim 1-8 is with silane-modified polycarboxylate dispersant.
10. a kind of application of silane-modified polycarboxylate dispersant of oil-well cement of claim 9.
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| WO2022033588A1 (en) * | 2020-08-14 | 2022-02-17 | 中国石油化工股份有限公司 | Polymer having dispersing function, oil well cement dispersant, and preparation method therefor and use thereof |
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| WO2022033588A1 (en) * | 2020-08-14 | 2022-02-17 | 中国石油化工股份有限公司 | Polymer having dispersing function, oil well cement dispersant, and preparation method therefor and use thereof |
| CN112142362A (en) * | 2020-09-04 | 2020-12-29 | 中交第二航务工程局有限公司 | Efficient seawater slurry regulator |
| CN112142362B (en) * | 2020-09-04 | 2022-04-29 | 中交第二航务工程局有限公司 | Efficient seawater slurry regulator |
| CN114426408A (en) * | 2020-10-13 | 2022-05-03 | 中国石油化工股份有限公司 | Oil well cement dispersant, preparation method and application thereof |
| CN112250799A (en) * | 2020-10-19 | 2021-01-22 | 上海是大高分子材料有限公司 | Organic silicon modified polycarboxylate dispersant, and preparation method and application thereof |
| CN113563539A (en) * | 2021-07-21 | 2021-10-29 | 中国石油大学(华东) | Water-based drilling fluid surface hydration inhibitor and preparation method and application thereof |
| CN113563539B (en) * | 2021-07-21 | 2024-02-23 | 中国石油大学(华东) | Water-based drilling fluid surface hydration inhibitor and preparation method and application thereof |
| CN116535146A (en) * | 2023-05-24 | 2023-08-04 | 天津大学 | Self-repairing agent for well cementation cement suitable for high-mineralization water environment |
| CN116535146B (en) * | 2023-05-24 | 2023-11-24 | 天津大学 | Self-repairing agent for well cementation cement suitable for high-mineralization water environment |
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Application publication date: 20190514 |