CN110790553A - Alkali-activated slag well cementation cement system capable of being regulated and controlled and method for regulating and controlling thickening time - Google Patents
Alkali-activated slag well cementation cement system capable of being regulated and controlled and method for regulating and controlling thickening time Download PDFInfo
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- CN110790553A CN110790553A CN201911098688.0A CN201911098688A CN110790553A CN 110790553 A CN110790553 A CN 110790553A CN 201911098688 A CN201911098688 A CN 201911098688A CN 110790553 A CN110790553 A CN 110790553A
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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
- C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
- C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
- C04B28/08—Slag cements
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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
- C04B40/00—Processes, in general, for influencing or modifying the properties of mortars, concrete or artificial stone compositions, e.g. their setting or hardening ability
- C04B40/0028—Aspects relating to the mixing step of the mortar preparation
- C04B40/0039—Premixtures of ingredients
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
- C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
- C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
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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
- C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
- C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
- C04B2111/00724—Uses not provided for elsewhere in C04B2111/00 in mining operations, e.g. for backfilling; in making tunnels or galleries
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Abstract
The invention discloses an adjustable alkali-activated slag well-cementing cement system and a method for adjusting and controlling thickening time of alkali-activated slag well-cementing cement slurry. The basic principle of the invention is that after sodium carbonate, calcium hydroxide, slag and water are prepared into alkali slag cement slurry, the sodium carbonate and the calcium hydroxide react to generate sodium hydroxide excited slag, and under the action of a retarder sodium gluconate, the sodium gluconate can delay the generation rate of the sodium hydroxide by delaying the reaction of the sodium carbonate and the calcium hydroxide, thereby delaying the hydration of the alkali slag cement. The method has the characteristics of simplicity, easiness in operation, low cost and good performance of the formed cement paste, and can meet the requirements of field well cementation.
Description
Technical Field
The invention relates to a method for regulating and controlling an alkali-activated slag cement system and thickening time, which is simple to operate, wide in source of used raw materials and low in price, and the formed alkali-activated slag cement slurry has excellent performance and can better meet the needs of oil field well cementation operation.
Background
With the recent decline of international oil prices and the prosperous trend of the petroleum industry, various large petroleum companies try to develop new technologies and search for new materials to reduce the cost and improve the profit. Meanwhile, with the increasing requirement for environmental protection in China, the production limit and production stop of cement plants are in a normal state, and the price of oil well cement is continuously increased. In order to solve the contradiction between the low price of petroleum and the rising of oil well cement, the low-cost well cementing material is urgently needed to be searched and developed. The alkali-activated slag material has good early strength performance, belongs to industrial waste, has wide sources and low cost, and is widely applied to the fields of construction and well cementation. However, the activator used in the conventional alkali-activated slag material is sodium hydroxide or a compound of sodium hydroxide and sodium silicate and the like (national peace. low-density slag MTC system research [ D ]. China Petroleum university, 2010; old Fusong, army, Juxiang, and the like; research progress of alkali-slag gelled materials and retarders thereof [ J ]. fly ash, 2012,24(1): 8-10.). The cost of the sodium hydroxide is high, the sodium hydroxide is used as an activator, the cost of the alkali-activated slag material is greatly increased, and certain danger exists when the sodium hydroxide is used. In addition, under the condition of adopting sodium hydroxide as an activator, the traditional cement retarder can not effectively delay the hydration speed of the alkali-activated slag material, so that the setting time or thickening time of the traditional alkali-activated slag material is difficult to control. The conventional portland cement has a hydration mechanism that silicate is gradually and slowly dissolved after contacting with water to form silicate ions, calcium ions and the like, the ions react again to generate hydration products such as C-S-H gel, calcium hydroxide and the like, and the retarder can delay the hydration speed of the portland cement by absorbing on the surface of portland cement particles to delay the dissolution of the cement, chelate the calcium ions, inhibit the growth of crystal nuclei and the like. The hydration mechanism of the alkali slag cement slurry is obviously different from that of silicate cement, alkali has a strong destructive effect on the vitreous body of slag, and slag is gradually disintegrated and hydrated under the action of alkali to form a large amount of C-S-H gel, so that an alkali-excited slag cement slurry system is coagulated and hardened, the hydration speed of the alkali-slag cement is related to the alkalinity, and the coagulation and hardening speed of the alkali slag cement is higher when the alkali content is higher. However, because the slag is dissolved too fast under the action of alkali, particularly strong alkali, and a common retarder cannot delay the slag dissolution process, the conventional cement retarder is difficult to delay the hydration of alkali slag cement so as to control the setting time or thickening time of the alkali slag cement.
At present, methods for controlling the setting time or thickening time of alkali slag cement mainly include alkalinity reduction (reduction of the amount of an alkali activator added or use of a low-alkaline activator) (sunreping. analysis of influence factors of alkali-slag cement rapid setting [ J ] building materials world, 2011(01):16-18.) or development of a novel alkali slag cement retarder (CN 102249594A; dawn. research of delaying alkali-slag cement setting [ D ]. north Hebei institute of science, 2003.; Fusong, Luo Xiaojun, Zhuxiang, etc.. research of alkali-slag cement and a retarder thereof [ J ]. fly ash, 2012,24(1):8-10.) and the like. The setting or thickening time of alkali slag cement can be prolonged to some extent by the method of reducing alkalinity, but this has a large adverse effect on the strength of set cement, especially the early strength (queen peak, dazzling, songqiang, etc.. research on alkali-activated slag geopolymers with NaOH [ J ] non-metallic minerals, 2008(03): 12-14.). The research and development of the effective novel alkali slag cement retarder requires a longer period and can influence the popularization and application of alkali-activated slag materials to a certain extent.
Therefore, the development of a method which can conveniently adjust the setting or thickening time of the alkali slag cement is necessary for promoting the popularization of the alkali slag cement.
Disclosure of Invention
The invention aims to provide a method for regulating and controlling an alkali-activated slag well-cementing cement system and the thickening time of alkali-activated slag well-cementing cement slurry, which has the characteristics of simplicity, easiness in operation, low cost and good performance of the formed cement slurry and can meet the field well-cementing requirement.
In order to achieve the purpose, the invention adopts the following technical scheme:
the adjustable alkali-activated slag well-cementing cement system comprises slag and water, wherein sodium carbonate and calcium hydroxide are selected as activators, and sodium gluconate is selected as a retarder.
Preferably, the slag used in the cement paste provided by the invention can be selected from S95 granulated blast furnace slag, and the specific surface area is not less than 400 square meters per kilogram.
Preferably, the weight ratio of the calcium hydroxide to the sodium carbonate in the invention is 7: 10.
preferably, the weight ratio of the activator to the retarder in the invention is 13.6: (1-5), and the optional ratio is 13.6: (1 to 2.3)
Preferably, the components in the invention are as follows in parts by weight: 100 parts of slag, 13.6 parts of activating agent, 1-5 parts of retarder and 45-55 parts of water.
The used slag is a silicon dioxide-aluminum oxide composite system, and the mineral components and percentage composition of the slag are as follows: 51% of calcium oxide, 24% of silicon dioxide, 13% of aluminum oxide, 2% of sulfur trioxide, 1% of titanium dioxide and the balance of trace elements. The microelements comprise manganese oxide, potassium oxide, etc.
A method for regulating and controlling thickening time of alkali-activated slag cement slurry selects sodium carbonate and calcium hydroxide as activators and selects sodium gluconate as a retarder.
Preferably, the thickening time of the cement paste is adjusted by adjusting the addition amount of the retarder.
The basic principle of the invention is that after sodium carbonate and calcium hydroxide, slag and water are prepared into alkali slag cement slurry, the sodium carbonate and the sodium hydroxide react to generate sodium hydroxide excited slag, and finally slag cement stone with similar performance to the sodium hydroxide excited slag cement slurry is formed, thereby meeting the field requirement. Under the action of the retarder sodium gluconate, the sodium gluconate can delay the generation rate of sodium hydroxide by delaying the reaction of sodium carbonate and calcium hydroxide, so that the hydration of the alkali slag cement is delayed.
The alkali-activated slag well cementation cement slurry has the following four advantages: (1) the raw materials are wide in source, low in price and environment-friendly, and the cost can be greatly reduced; (2) calcium hydroxide and sodium carbonate are used for replacing sodium hydroxide to excite slag to obtain alkali-excited slag well cement, and the strength of formed set cement is higher than that of set cement obtained by exciting sodium hydroxide; (3) the alkali-activated slag well-cementing cement prepared by adopting calcium hydroxide and sodium carbonate as activators has lower cost than the alkali-activated slag well-cementing cement prepared by adopting sodium hydroxide; (4) when the sodium carbonate and the calcium hydroxide are used as an activator, the sodium carbonate and the calcium hydroxide can be dry-mixed with slag to facilitate the field slurry preparation operation, and the sodium hydroxide needs to be dissolved in water in advance when in use, so that certain safety risk exists; (5) the thickening time of the alkali-activated slag cement prepared from sodium hydroxide is difficult to adjust by using sodium gluconate, while the thickening time of the alkali-activated slag cement prepared from calcium hydroxide and sodium carbonate can be well adjusted by using sodium gluconate, and the cement paste thickening curve is smooth and has excellent right-angle thickening performance, thereby being beneficial to the operation requirements of field well cementation, gas channeling prevention and the like.
The invention provides a novel alkali-activated slag well cementation cement slurry system which has reliable technology, convenient field construction, low cost, environmental protection and good thickening performance and has the potential to replace portland cement, and provides a very valuable cement slurry system for the field of domestic well cementation materials.
Drawings
The above and/or additional aspects and advantages of the present invention will become apparent and readily appreciated from the following description of the embodiments, taken in conjunction with the accompanying drawings of which:
FIG. 1 is a graph of the thickening profile of a cement slurry prepared according to the present invention.
Detailed Description
The embodiments described below with reference to the accompanying drawings are illustrative only for the purpose of explaining the present invention, and are not to be construed as limiting the present invention.
The experimental method comprises the following steps:
preparing cement paste according to a well cementation test standard API RP 10B, and measuring the cement paste performance and the compression strength of a set cement.
Comparative example 1
100 parts of S95 slag, 49 parts of water, 6 parts of sodium hydroxide and 0 part of sodium gluconate.
Comparative example 2
100 parts of S95 slag, 49 parts of water, 6 parts of sodium hydroxide and 2 parts of sodium gluconate.
Comparative example 3
100 parts of S95 slag, 49 parts of water, 6 parts of sodium hydroxide and 4 parts of sodium gluconate.
Comparative example 4
100 parts of S95 slag, 49 parts of water, 6 parts of sodium hydroxide and 6 parts of sodium gluconate.
Example 1
100 parts of S95 slag, 52 parts of water, 5.6 parts of calcium hydroxide, 8 parts of sodium carbonate and 0 part of sodium gluconate.
Example 2
100 parts of S95 slag, 52 parts of water, 5.6 parts of calcium hydroxide, 8 parts of sodium carbonate and 1 part of sodium gluconate.
Example 3
100 parts of S95 slag, 52 parts of water, 5.6 parts of calcium hydroxide, 8 parts of sodium carbonate and 2.3 parts of sodium gluconate.
The results are shown in Table 1
TABLE 1 Experimental results Table
FIG. 1 is the thickening curve for example 3. As can be seen from figure 1, the cement slurry thickening curve using calcium hydroxide and sodium carbonate as activators is stable, the time of the cement slurry thickness from 30 to 100Bc is only 12min, and the method is very favorable for ensuring the gas channeling prevention and the well cementation quality.
While embodiments of the invention have been shown and described, it will be understood by those of ordinary skill in the art that: various changes, modifications, substitutions and alterations can be made to the embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the claims and their equivalents.
Claims (6)
1. The adjustable alkali-activated slag well-cementing cement system comprises slag and water and is characterized in that sodium carbonate and calcium hydroxide are selected as activators, and sodium gluconate is selected as a retarder.
2. The adjustable alkali-activated slag cement system for well cementation according to claim 1, wherein the slag is S95 granulated blast furnace slag, and the specific surface area is not less than 400 square meters per kilogram.
3. The regulated alkali-activated slag cement system according to claim 1, wherein the weight ratio of calcium hydroxide to sodium carbonate is 7: 10.
4. the adjustable alkali-activated slag cement system according to claim 1, wherein the adjustable alkali-activated slag cement system comprises the following components in parts by weight: 100 parts of slag, 13.6 parts of activating agent, 1-5 parts of retarder and 45-55 parts of water.
5. A method for regulating and controlling thickening time of alkali-activated slag cement slurry is characterized in that sodium carbonate and calcium hydroxide are selected as activators, and sodium gluconate is selected as a retarder.
6. The method for controlling the thickening time of alkali-activated slag cementing cement slurry according to claim 5, wherein the thickening time of the cement slurry is adjusted by adjusting the addition amount of the retarder.
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| CN201911098688.0A CN110790553A (en) | 2019-11-12 | 2019-11-12 | Alkali-activated slag well cementation cement system capable of being regulated and controlled and method for regulating and controlling thickening time |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551930A (en) * | 2020-12-11 | 2021-03-26 | 河南理工大学 | Coated excitant for alkali slag cement and preparation method thereof |
| CN113636766A (en) * | 2021-08-20 | 2021-11-12 | 广西大学 | Slag carbonization modification method, carbonization modified slag cementing material and preparation method thereof |
| CN114105548A (en) * | 2022-01-25 | 2022-03-01 | 中国石油大学(华东) | Geopolymer well cementing fluid with controllable thickening time |
| CN114956614A (en) * | 2022-05-30 | 2022-08-30 | 中国地质大学（武汉） | Slag cement based on synergistic excitation of sodium citrate and caustic alkali and preparation method thereof |
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| US5553670A (en) * | 1993-12-30 | 1996-09-10 | Shell Oil Company | Optimizing blast furnace slag cements |
| US6068055A (en) * | 1998-06-30 | 2000-05-30 | Halliburton Energy Services, Inc. | Well sealing compositions and methods |
| US20050166803A1 (en) * | 2003-08-22 | 2005-08-04 | Bj Services Company | Ultra low density cementitious slurries for use in cementing of oil and gas wells |
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2019
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Patent Citations (5)
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| US5423379A (en) * | 1989-12-27 | 1995-06-13 | Shell Oil Company | Solidification of water based muds |
| CN1086577A (en) * | 1992-10-22 | 1994-05-11 | 国际壳牌研究有限公司 | The method of drilling well and well cementation |
| US5553670A (en) * | 1993-12-30 | 1996-09-10 | Shell Oil Company | Optimizing blast furnace slag cements |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112551930A (en) * | 2020-12-11 | 2021-03-26 | 河南理工大学 | Coated excitant for alkali slag cement and preparation method thereof |
| CN113636766A (en) * | 2021-08-20 | 2021-11-12 | 广西大学 | Slag carbonization modification method, carbonization modified slag cementing material and preparation method thereof |
| CN113636766B (en) * | 2021-08-20 | 2022-07-22 | 广西大学 | Slag carbonization modification method, carbonization modified slag cementing material and preparation method thereof |
| CN114105548A (en) * | 2022-01-25 | 2022-03-01 | 中国石油大学(华东) | Geopolymer well cementing fluid with controllable thickening time |
| US11834605B2 (en) | 2022-01-25 | 2023-12-05 | China University Of Petroleum (East China) | Geopolymer cementing fluid with controllable thickening time |
| CN114956614A (en) * | 2022-05-30 | 2022-08-30 | 中国地质大学（武汉） | Slag cement based on synergistic excitation of sodium citrate and caustic alkali and preparation method thereof |
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