CN1887774A - Cement retardant and its application - Google Patents
Cement retardant and its application Download PDFInfo
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- CN1887774A CN1887774A CNA2006100148856A CN200610014885A CN1887774A CN 1887774 A CN1887774 A CN 1887774A CN A2006100148856 A CNA2006100148856 A CN A2006100148856A CN 200610014885 A CN200610014885 A CN 200610014885A CN 1887774 A CN1887774 A CN 1887774A
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- cement
- retardant
- grout
- temperature
- acid
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- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B24/00—Use of organic materials as active ingredients for mortars, concrete or artificial stone, e.g. plasticisers
- C04B24/16—Sulfur-containing compounds
- C04B24/161—Macromolecular compounds comprising sulfonate or sulfate groups
- C04B24/163—Macromolecular compounds comprising sulfonate or sulfate groups obtained by reactions only involving carbon-to-carbon unsaturated bonds
-
- C—CHEMISTRY; METALLURGY
- C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
- C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
- C04B2103/00—Function or property of ingredients for mortars, concrete or artificial stone
- C04B2103/20—Retarders
- C04B2103/22—Set retarders
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Ceramic Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Structural Engineering (AREA)
- Organic Chemistry (AREA)
- Curing Cements, Concrete, And Artificial Stone (AREA)
Abstract
The present invention belongs to the field of cement technology, and is especially one kind of cement retardant and its application. The cement retardant is prepared with 2-acrylamido -2-methyl propyl sulfonic acid 20-50 wt%, itaconic acid 30-70 wt% and sodium hypophoshorate 10-20 wt%, and through mixing to react while adding water in 180-230 wt% and ammonium persulfate in 0.5-4 wt% at 65-92 deg.c for 1-4 hr. The cement retardant is added into cement mortar and used at circulation temperature lower than 95 deg.c to prolong the thickening time of cement mortar effectively.
Description
Technical field
The invention belongs to the cementing concrete technical field, particularly cementing concrete retardant and application.
Background technology
The grout that normal open requires to contain cement, water and admixture by the ground pumping equipment in oil gas well cementing job and other underground flooding mud operation injects underground predetermined stratum, with the annular space between sealing stratum and the sleeve pipe.Typical grout is advanced in the sleeve pipe by pump and by returning annular space on the space between sleeve pipe and the stratum.Grout solidifies in annular space, forms a hard cement annulated column, this cement annulated column can and stratum and sleeve pipe between form glued.For reaching gratifying cementing job, realize a high-intensity gluing in case the fluid stopping body along the cement annulated column or within it portion to scurry logical be necessary, scurrying logical consequence is to pollute payzone or make resource loss.
The topmost purpose of cementing job is to stop the mobile of resident fluid and form glued with supporting sleeve.In addition, cemented purpose comprises that also protective casing is not corroded, sleeve pipe is not subjected to shock load, shutoff weak zone when boring deep-well.
One of most important design variable of cementing job is the thickening time.But it is the time that grout keeps liquid pump state substantially, therefore is the working lipe of implementing cementing job.When being mixed, can inject the degree of depth about 1800 meters safely with the no extended slurry of G class g cement preparation with suitable water cement ratio.Along with the rising of temperature, the hydration rate of cement is also accelerated.Therefore under higher temperature, retardant is used to slow down hydration rate, but makes grout keep the pump state.Along with bottom hole circulating temperature increases, it is crucial that the performance of these retardant becomes.
The performance of many factor affecting cement setting retarders, the type of cement itself, fineness, chemical constitution play a significant role at the enough pump time aspect of performances of acquisition.Even when using the cement of the same trade mark,, also can see the variation between the different lot number cement because the condition of starting material and kiln is variant.Obviously the chemical ingredients of retardant has significant feature, and when the variation of retardant and cement integrated, this just may go wrong in slurry design.The interaction of retardant and other admixture also is very important in slurry design.In many cases, retardant may have adverse influence to water retaining, especially in the high temperature design.Also can observe the disadvantageous effect of retardant, make cement consistency become extremely thick or extremely rare denseness.For very thick grout, need too high pumping pressure, this possibility pressure break stratum, and thin cement slurry may produce sedimentation and free liquid.Obtain no sedimentation grout and become of crucial importance in horizontal well completion, these adverse influences occur with too early agglomerative form at the thickening time duration of test usually.It grout may occur and condenses into lump under extreme case, and it has in fact just just formed hard gelinite.Can stir at this agglomerative grout in some cases and to change back to the primary denseness, denseness is increased.This gelinite may cause aforesaid too high pumping pressure, even may produce the grout bridge blinding in annular space, and ends cementing job fully.Ideal situation is that grout keeps suitable denseness during thickening time test or pumpdown, and then denseness increases fast, condenses, and forms effective ultimate compression strength.
Another ideal performance of cement setting retarder is the increase along with retardant content, and the thickening time can increase with reappearing, in many cases, will observe the thickening time sharp increase in case retardant content reaches certain when a certain amount of.Because in weighing retardant process, make mistakes and to cause the super slow setting of grout or owe slow setting, so this susceptibility is undesirable.Owing extended slurry obviously is the worst situation, because it may condense before cement replaces annular space fully.But the super slow-setting cement slurry also is undesirable, because it may cause greatly postponing the further operation of oil well.
On market, a lot of cement setting retarders can have been bought at present.Wherein some retardant comprises ligninsulfonate, hydrocarbon ethyl cellulose, methylol Natvosol and weak organic acid.Synthetic organic polymer just just was used as cement setting retarder at nearly 20 years.The most frequently used cement setting retarder may be wooden sodium sulfonate or wooden calcium sulfonate.These materials are the products of paying of the wooden pulp process of vitriol, are to be produced by the sulfurization that is present in the natural lignin in the timber.Because the amount of these material produce is big, so they are easy to buy, the charge is small, can play a role well under the about 90 ℃ temperature of circulation as retardant.One of its shortcoming is a discordance.Depend on that the source is hardwood or cork, even the asynchronism(-nization) of possibility trees felling can both be observed their difference.It is believed that these molecules are is polymer based with the phenyl-propane skeleton, in the pulp process, introduce the sulfonic group, also contain a large amount of hydroxyls and methoxyl group.Ligninsulfonate may also contain the impurity that quite a large amount of meetings influences their slow setting character, because unstable properties and have impurity, use ligninsulfonate need do a large amount of tests and determine the thickening time, so the more pleased use of the people comparatively stable retardant of performance of on testing, taking time less.
As mentioned above, the maximum temperature that ligninsulfonate can use is about 115 ℃, can make maximum temperature up to more than 200 ℃ by the slow setting toughener that mixes organic acid or water-soluble borate and so on.Normally used organic acid is tartrate or gluconic acid, a shortcoming of this way is the effect that organic acid tends to destroy some water retaining, even ligninsulfonate is quite effective under many circumstances, with their related problems attract again people to produce a kind of more uniform, have repeatability retardant.
One of effective ways that address these problems are to use a kind of synthetic polymer as cement setting retarder.Such admixture is easy to produce a collection ofly, and they is satisfied comprise desired performance requriements.The people who discloses this retardant the earliest is people such as Brothcrs, and they utilize a kind of 2-acrylamide-2-methyl propane sulfonic acid (AMPS) multipolymer, and this polymkeric substance is a kind of effectively retardant, but upper temperature limit is about 120 ℃ in fresh water.Under higher temperature, need certain slow setting toughener as ligninsulfonate.This retardant provides reproducible result for a certainty and produces the linear relationship that a kind of thickening time prolongs with the concentration increase.
As everyone knows, the polymkeric substance that contains carboxyl helps to delay condensing of cement.As acrylamide copolymer, the polymkeric substance of experience hydrolytic action may produce carboxyl on the spot in the pH of grout value environment.If there is the acrylamide of significant amounts in the multipolymer, under near the temperature more than 50 ℃, acrylamide will hydrolysis, will make the serious slow setting of cement.People may utilize this performance to make hydrolysate produce delayed coagulation.But this will be extremely difficult in practice.Therefore people would rather utilize the monomer that can not be hydrolyzed into carboxyl or have anti-this hydrolytic action.A kind of obvious selection as retardant is a kind of acrylic acid multipolymer, resembles the multipolymer AMPS (Chinese)/vinylformic acid.Vinylformic acid is the simplest monomer that can buy on the carboxylic market.And the AMPS monomer has very high resistance to hydrolysis, proves of great use as the polymkeric substance admixture of cement.For example, the vinylformic acid homopolymer can make cement retardative, but also can seriously make cementitious grout.A kind of AMPS/ acrylic copolymer also can make cement retardative, but does not almost have pectisation.
As mentioned above, AMPS and methylene-succinic acid and inferior sodium phosphate, the synthetic multipolymer is than having stronger delayed coagulation with vinylformic acid synthetic multipolymer.Methylene-succinic acid is a kind of dicarboxylic acid, and vinylformic acid is a kind of monocarboxylic acid.This perhaps directly enlightens methylene-succinic acid will provide bigger delayed coagulation.But the mechanism of action of slow setting also imperfectly understands, even those people that are proficient in this field are also like this.Obviously retardant is by working to tricalcium aluminate and tricalcium silicate.Usually tricalcium aluminate is considered to the composition that reacts the fastest, and tricalcium silicate is considered to form the major cause of early anti pressured intension development.About delayed coagulation mechanism several theories have been proposed.The real situation of delayed coagulation may be all these theoretical synthesis result.It is believed that the retardant molecular adsorption on the hydrated cement particle surface, the protective layer that provides one deck water to attack.Also the someone thinks that the retardant that contains methylene-succinic acid can combine with surperficial each point better than acrylic acid carboxylate salt.Two carboxyls of methylene-succinic acid are always pressed close to mutually closely, and the degree of closeness of two carboxyls of vinylformic acid will depend on the kindliness of the alignment problem and the chain of acrylic acid groups on the main polymer chain.
Summary of the invention
The cement setting retarder that the purpose of this invention is to provide a kind of new synthetic copolymer, the composition of these multipolymers is applied in the oil gas well completion operation as the retardant of grout, can be according to the cemented needs of reality, regulate thickening time or the flowing time of grout under the pressurized conditions of heating, to guarantee the safety of cementing job.
Concrete technology contents of the present invention is:
1. the component of cement setting retarder and weight percent content:
2-acrylamido-2-methyl propane sulfonic acid (AMPS) 20-50%
Methylene-succinic acid 30-70%
Inferior sodium phosphate 10-20%.
By the various monomers of above-mentioned recipe ingredient weighing, in the water adding reactor with the monomer total amount, under agitation add various monomers respectively, the 0.5-4% ammonium persulfate initiator that adds the monomer total amount at last, temperature of reaction is controlled between 65-92 ℃, reaction times 1-4 hour, makes retardant.
2. be applied in the proportioning of the cement of oil well, gas well and other similar well, in 100 parts of cement weights:
(a) water is 44 parts
(b) retardant 0.4-1.2 part
(c) cement is 100 parts.
Retardant component among the present invention is added in the grout, is lower than in circulating temperature under 95 ℃ the condition to use, and can effectively prolong the thickening time of grout, avoids taking place grout and falls short of and interrupt the engineering accident that cementing job causes because of the thickening time; And can realize the circulation ratio of cement slurry thickening time between the different batches product preferably by this retardant of synthetic, reduce the workload of repetition test in the slurry design process.
The present invention has the following advantages:
1. production technique is simple, need not the interior airborne oxygen of removal system.
2. speed of response is fast, finishes in 30 minutes basically after polyreaction begins.
3. synthetic multipolymer retardant of the present invention can be used with multiple water retaining, does not destroy the energy of water retaining.
4. with multipolymer retardant preparation grout of the present invention, the neither excessive thickness of its slurry is spent only and is disperseed.
Embodiment
Embodiment 1:
Take by weighing various monomers in following ratio:
AMPS: methylene-succinic acid: inferior sodium phosphate=35: 50: 15
180% of each monomer total amount of adding deionized water is opened agitator in reactor, adds load weighted various monomer then, and adds 5% ammonium persulfate initiator of monomer total amount, temperature is controlled at 92 ℃ reacted 2 hours down, makes multipolymer.With the retardant code name of HX-RM01 as this multipolymer.
Mix the cement slurry property of embodiment 3 retardant under the table 1 different tests condition
| Test conditions | Circulating temperature ℃ | 77 | 77 | 77 | 77 | 90 |
| Static temperature ℃ | 104 | 104 | 104 | 104 | 105 | |
| Pressure MPa | 61 | 61 | 61 | 35 | 45 | |
| Proportioning (weight ratio) | The G class g cement | 100 | 100 | 100 | 100 | 100 |
| Mixing water | 44 | 44 | 44 | 44 | 44 | |
| HX-RM01 | 0.44 | 0.75 | 1.00 | 0.75 | 0.75 | |
| Cement slurry property | Degree of mobilization cm | 24.5 | 24.5 | 25.0 | 24.5 | 24.5 |
| Free liquid content mL | 0.8 | 0.9 | 0.9 | 0.9 | 0.9 | |
| Thickening time min | 120 | 223 | 328 | 256 | 250 | |
| 24h ultimate compression strength MPa | 29.0 | 28.8 | 24.8 | 28.8 | 30.0 |
Embodiment 2:
Take by weighing various monomers in following ratio:
AMPS: methylene-succinic acid: inferior sodium phosphate=50: 30: 20
230% of each monomer total amount of adding deionized water is opened agitator in reactor, adds load weighted various monomer then, and adds 0.5% ammonium persulfate initiator of monomer total amount, temperature is controlled at 65 ℃ reacted 4 hours down, makes multipolymer.With the retardant code name of HX-RM02 as this multipolymer.
Mix the cement slurry property of embodiment 2 retardant under the table 2 different tests condition
| Test conditions | Circulating temperature ℃ | 40 | 55 | 70 | 80 | 90 |
| Static temperature ℃ | 55 | 70 | 95 | 100 | 110 | |
| Pressure MPa | 20 | 26 | 35 | 40 | 45 | |
| Proportioning (weight ratio) | The G class g cement | 100 | 100 | 100 | 100 | 100 |
| Mixing water | 44 | 44 | 44 | 44 | 44 | |
| HX-RM02 | 0.40 | 0.6 | 0.75 | 0.9 | 1.2 | |
| Cement slurry property | Degree of mobilization cm | 24.2 | 23.5 | 24.0 | 24.5 | 24.5 |
| Free liquid content mL | 0.8 | 0.9 | 0.9 | 0.9 | 0.9 | |
| Thickening time min | 210 | 202 | 231 | 230 | 243 | |
| 24h ultimate compression strength MPa | 23.0 | 22.8 | 25.8 | 27.8 | 29.0 |
Embodiment 3:
Take by weighing various monomers in following ratio:
AMPS: methylene-succinic acid: inferior sodium phosphate=20: 60: 20
200% of each monomer total amount of adding deionized water is opened agitator in reactor, adds load weighted various monomer then, and adds 3% ammonium persulfate initiator of monomer total amount, temperature is controlled at 85 ℃ reacted 3 hours down, makes multipolymer.With the retardant code name of HX-RM03 as this multipolymer.
Mix the cement slurry property of embodiment 3 retardant under the table 3 different tests condition
| Test conditions | Circulating temperature ℃ | 40 | 55 | 70 | 80 | 90 |
| Static temperature ℃ | 55 | 70 | 95 | 100 | 110 | |
| Pressure MPa | 20 | 26 | 35 | 40 | 45 | |
| Proportioning (weight ratio) | The G class g cement | 100 | 100 | 100 | 100 | 100 |
| Mixing water | 44 | 44 | 44 | 44 | 44 | |
| HX-RM03 | 0.40 | 0.6 | 0.75 | 0.9 | 1.2 | |
| Cement slurry property | Degree of mobilization cm | 24.2 | 23.5 | 24.0 | 24.5 | 24.5 |
| Free liquid content mL | 0.8 | 0.9 | 0.9 | 0.9 | 0.9 | |
| Thickening time min | 240 | 252 | 271 | 300 | 350 | |
| 24h ultimate compression strength MPa | 21.0 | 21.8 | 23.8 | 24.8 | 26.0 |
Claims (2)
1. cement setting retarder is characterized in that component and weight percent content are as follows:
2-acrylamido-2-methyl propane sulfonic acid 20-50%
Methylene-succinic acid 30-70%
Inferior sodium phosphate 10-20%;
By the various monomers of above-mentioned recipe ingredient weighing, in adding the reactor of entry, under agitation add various monomers, add the 0.5-4% ammonium persulfate initiator of monomer total amount at last, temperature of reaction reaction times 1-4 hour, makes retardant between 65-92 ℃.
2. the application of cement setting retarder as claimed in claim 1, the cement in oil well or gas well use is characterized in that in the proportioning of 100 parts of cement weights as follows:
44 parts in water
Retardant 0.4-1.2 part
100 parts of cement.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100148856A CN100368335C (en) | 2006-07-21 | 2006-07-21 | Cement retardant and its application |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100148856A CN100368335C (en) | 2006-07-21 | 2006-07-21 | Cement retardant and its application |
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| Publication Number | Publication Date |
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| CN1887774A true CN1887774A (en) | 2007-01-03 |
| CN100368335C CN100368335C (en) | 2008-02-13 |
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| CNB2006100148856A Expired - Fee Related CN100368335C (en) | 2006-07-21 | 2006-07-21 | Cement retardant and its application |
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Cited By (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101851317A (en) * | 2010-06-25 | 2010-10-06 | 中国科学院长春应用化学研究所 | Polymer used for high-temperature cement retarder and preparation method thereof |
| CN101870752A (en) * | 2010-06-25 | 2010-10-27 | 中国科学院长春应用化学研究所 | Polymer for high-temperature cement retarder and preparation method thereof |
| CN101870753A (en) * | 2010-06-25 | 2010-10-27 | 中国科学院长春应用化学研究所 | Polymer for high-temperature cement retarder and preparation method thereof |
| CN101402849B (en) * | 2008-11-17 | 2010-12-22 | 中国石油大学(华东) | Well cementing high-temperature inhibiting agent for oil gas well and preparation method |
| CN101994497A (en) * | 2010-10-15 | 2011-03-30 | 中国石油集团川庆钻探工程有限公司长庆固井公司 | Cement slurry process for exploratory well cementation in oil and gas field areas |
| CN102617061A (en) * | 2012-03-21 | 2012-08-01 | 中建商品混凝土有限公司 | Ultra retarder for concrete and preparation method for ultra retarder |
| CN104371065A (en) * | 2014-11-24 | 2015-02-25 | 卫辉市化工有限公司 | Preparation method of instant polymer retarder for oil well cement |
| CN105061661A (en) * | 2015-08-06 | 2015-11-18 | 中国石油集团渤海钻探工程有限公司 | Medium-high temperature delayed coagulant used for oil well cement and preparation method thereof |
| CN106008844A (en) * | 2016-07-11 | 2016-10-12 | 中国石油天然气集团公司 | High-inhibitive medium-high-temperature oil well cement retarder and preparation method thereof |
| CN106431054A (en) * | 2016-08-30 | 2017-02-22 | 卓达新材料科技集团威海股份有限公司 | High-efficiency set retarder used for 3D printing house slurry |
| CN106517852A (en) * | 2016-10-26 | 2017-03-22 | 中国石油大学(华东) | Modified aluminate cement retarder compounded from AMPS copolymer pre-chelated with aluminum ions, and borate and preparation method thereof |
| CN109503781A (en) * | 2017-09-14 | 2019-03-22 | 中石化石油工程技术服务有限公司 | A kind of inorganic-organic polymer oil well cement retarder, preparation method and application |
| CN109503760A (en) * | 2017-09-14 | 2019-03-22 | 中石化石油工程技术服务有限公司 | A kind of high temperature oil well cement retarder, preparation method and application |
| CN110577390A (en) * | 2019-10-25 | 2019-12-17 | 四川信敏绿色新建筑材料科技有限公司 | Concrete preparation process |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB8526438D0 (en) * | 1985-10-26 | 1985-11-27 | British Petroleum Co Plc | Cement setting retarding agents |
| CN1032332A (en) * | 1987-10-07 | 1989-04-12 | 重庆江南纤维素化工厂 | Cement setting retarder and manufacture method |
| CN1223543C (en) * | 2002-12-31 | 2005-10-19 | 中国石油化工股份有限公司 | Oil well cement slow coagulation agent |
-
2006
- 2006-07-21 CN CNB2006100148856A patent/CN100368335C/en not_active Expired - Fee Related
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| CN101402849B (en) * | 2008-11-17 | 2010-12-22 | 中国石油大学(华东) | Well cementing high-temperature inhibiting agent for oil gas well and preparation method |
| CN101851317A (en) * | 2010-06-25 | 2010-10-06 | 中国科学院长春应用化学研究所 | Polymer used for high-temperature cement retarder and preparation method thereof |
| CN101870752A (en) * | 2010-06-25 | 2010-10-27 | 中国科学院长春应用化学研究所 | Polymer for high-temperature cement retarder and preparation method thereof |
| CN101870753A (en) * | 2010-06-25 | 2010-10-27 | 中国科学院长春应用化学研究所 | Polymer for high-temperature cement retarder and preparation method thereof |
| CN101994497A (en) * | 2010-10-15 | 2011-03-30 | 中国石油集团川庆钻探工程有限公司长庆固井公司 | Cement slurry process for exploratory well cementation in oil and gas field areas |
| CN101994497B (en) * | 2010-10-15 | 2013-09-18 | 中国石油集团川庆钻探工程有限公司长庆固井公司 | Cement slurry process for exploratory well cementation in oil and gas field areas |
| CN102617061A (en) * | 2012-03-21 | 2012-08-01 | 中建商品混凝土有限公司 | Ultra retarder for concrete and preparation method for ultra retarder |
| CN102617061B (en) * | 2012-03-21 | 2013-10-02 | 中建商品混凝土有限公司 | Ultra retarder for concrete and preparation method for ultra retarder |
| CN104371065A (en) * | 2014-11-24 | 2015-02-25 | 卫辉市化工有限公司 | Preparation method of instant polymer retarder for oil well cement |
| CN105061661A (en) * | 2015-08-06 | 2015-11-18 | 中国石油集团渤海钻探工程有限公司 | Medium-high temperature delayed coagulant used for oil well cement and preparation method thereof |
| CN106008844A (en) * | 2016-07-11 | 2016-10-12 | 中国石油天然气集团公司 | High-inhibitive medium-high-temperature oil well cement retarder and preparation method thereof |
| CN106008844B (en) * | 2016-07-11 | 2018-11-27 | 中国石油天然气集团公司 | A kind of strong rejection capability high temperature oil well cement retarder and preparation method thereof |
| CN106431054A (en) * | 2016-08-30 | 2017-02-22 | 卓达新材料科技集团威海股份有限公司 | High-efficiency set retarder used for 3D printing house slurry |
| CN106517852A (en) * | 2016-10-26 | 2017-03-22 | 中国石油大学(华东) | Modified aluminate cement retarder compounded from AMPS copolymer pre-chelated with aluminum ions, and borate and preparation method thereof |
| CN109503781A (en) * | 2017-09-14 | 2019-03-22 | 中石化石油工程技术服务有限公司 | A kind of inorganic-organic polymer oil well cement retarder, preparation method and application |
| CN109503760A (en) * | 2017-09-14 | 2019-03-22 | 中石化石油工程技术服务有限公司 | A kind of high temperature oil well cement retarder, preparation method and application |
| CN109503781B (en) * | 2017-09-14 | 2021-05-04 | 中石化石油工程技术服务有限公司 | Inorganic-organic polymer oil well cement retarder, and preparation method and application thereof |
| CN109503760B (en) * | 2017-09-14 | 2021-06-01 | 中石化石油工程技术服务有限公司 | Medium-high temperature oil well cement retarder, and preparation method and application thereof |
| CN110577390A (en) * | 2019-10-25 | 2019-12-17 | 四川信敏绿色新建筑材料科技有限公司 | Concrete preparation process |
| CN110577390B (en) * | 2019-10-25 | 2022-01-18 | 四川信敏绿色新建筑材料科技有限公司 | Concrete preparation process |
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| CN100368335C (en) | 2008-02-13 |
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