CN115872649A - Oil-gas well cementing anti-corrosion additive and multi-component anti-corrosion cement paste system for ultra-high temperature acid gas well - Google Patents
Oil-gas well cementing anti-corrosion additive and multi-component anti-corrosion cement paste system for ultra-high temperature acid gas well Download PDFInfo
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Abstract
The application discloses a well cementation anticorrosion additive for an oil and gas well and a multi-component composite anticorrosion cement slurry system for an ultrahigh-temperature acid gas well, wherein the well cementation anticorrosion additive for the oil and gas well adopts the combination of two or more of blast furnace slag, metakaolin, biological ash, hydroxyapatite and basic zinc carbonate; the multi-element composite anti-corrosion cement paste system comprises the following components in parts by weight: 90-110 parts of Jiahua G-grade oil well cement, 30-40 parts of high-temperature stabilizer, 5-7 parts of functional composite emulsion, 4-6 parts of fluid loss additive, 3-5 parts of high-efficiency dispersant, 1-15 parts of oil and gas well cementing anticorrosion additive and 0.5-1.5 parts of expanding agent. The well cementation cement slurry system with the functions of resisting 220 ℃ ultrahigh temperature, resisting gas channeling and resisting CO2 corrosion can effectively meet the long-term sealing of an abnormal high-temperature acidic corrosion gas well, reduce the energy consumption requirement and provide guarantee for exploration and development, efficient production and environmental protection.
Description
Technical Field
The invention relates to the technical field of oil and gas well cementation, in particular to an oil and gas well cementation anticorrosion additive and a multi-component composite anticorrosion cement paste system for an ultrahigh-temperature acid gas well.
Background
In the ultra-high temperature acid gas well cementing operation, the cementing cement sheath is usually affected by acid corrosion, so that the oil and gas exploitation link is hindered. On one hand, the corrosive medium can destroy the cementation between the cement sheath and the stratum, so that the interlayer flees; on the other hand, the corrosive medium continues to move inwards along with the seepage channel and directly acts on the casing and the oil pipe, so that perforation occurs and even the whole well is scrapped. If the problem can not be effectively controlled, blowout or whole well abandonment can be caused, and major safety accidents are caused. Therefore, on the basis of ensuring that the basic performance of the oil well cement stone meets the requirements of conventional well cementation operation, the development of the research on corrosion resistance and gas channeling prevention of the cement stone is the key for improving the quality of complex well cementation and is the premise of ensuring long-term stable production of ultrahigh-temperature acid gas wells.
A great deal of research is carried out by scholars at home and abroad on improving the corrosion resistance of the well cementation cement stone. Yuan B et al use the film forming property and filling effect of nano-silicon latex (NL) to reduce the original permeability and average pore size of set cement by 3.35 times and 35.38% respectively. NL is also bound to Ca (OH) 2 The reaction generates tobermorite with low Ca/Si ratio, and the pH value of the cement is reduced. Rooby D et al investigated nano-CaCO 3 (CFC), nano SiO 2 (CFS) and nano ZrO 2 The influence of (CFZ) doping on the corrosion performance of the fly ash (CF) set cement shows that the nano material can inhibit the cracking of the set cement and obviously enhance the corrosion resistance. Krivenko P et al use surfactants and Na 3 PO 4 Soluble Sodium Silicate (SSS) was modified and its effect on slag based cement was subsequently explored. The result shows that the compactness of the slag-based set cement can be obviously improved and the mechanical property and the corrosion resistance can be enhanced by adopting the modified SSS. Zhang B, etc. with Sodium Styrene Sulfonate (SSS) and nano SiO 2 As emulsifier, soap-free emulsion (PSAC) is prepared by soap-free emulsion polymerization, and the prepared emulsion is used for PSAC cement at 90 deg.C and 3MPa CO 2 The carbonization performance under the conditions was evaluated. The PSAC has a typical core-shell structure and good heat resistance, the corrosion depth of the PSAC cement stone after 60d corrosion is only 2.16mm, the permeability is 0.0018mD, and the compressive strength is reduced by 6.65%. Xu B and the like construct a composite anti-corrosion additive (CRA) consisting of amorphous nano-silica, latex and resin, and research the corrosion performance of CRA set cement at 150 ℃. It was found that the original permeability of CRA set cement was reduced and that in the set cementThe CH phase of the cement is reduced, the hydration product Ca/Si is reduced, and the corrosion resistance of the cement stone is enhanced. Zuo J et al investigated the effect of epoxy resin emulsion in combination with Metakaolin (MK) on the corrosion performance of set cement, and found that the water absorption and chloride diffusion coefficient of epoxy resin emulsion set cement were significantly reduced after MK was added. In particular, 1250 mesh MK exhibited a maximum decrease in chloride diffusion coefficient of 73.1%.
However, the anti-corrosion additive has a plurality of problems, and the performance of the conventional polymer and resin materials is obviously reduced under the conditions of high temperature and ultrahigh temperature, and the conventional polymer and resin materials have great influence on the thickening process of cement paste; the acid-resistant particles have good slurry fluidity when the particle size is larger, but have poor settling stability, and the slurry fluidity is reduced when the particle size is smaller, so that the pumping difficulty is increased; most of the inorganic mineral powder has good compatibility with cement paste, but the early compressive strength of the set cement can be greatly reduced. In addition, the cement paste system is single in material, cannot meet complex actual working conditions, is mostly applied to medium and low temperature environments, and has few cases related to ultrahigh temperature corrosion research.
Disclosure of Invention
The invention aims to provide a cementing and anti-corrosion additive for an oil and gas well, which aims to solve the problem of poor corrosion resistance of a cement paste system.
In order to achieve the purpose, the invention provides an anticorrosive additive for cementing oil and gas wells, which is characterized by being prepared by mixing two or more than two components of blast furnace slag, metakaolin, biological ash, hydroxyapatite and basic zinc carbonate.
Furthermore, the composite material consists of 9-11 parts of blast furnace slag, 4-6 parts of metakaolin, 4-6 parts of biological ash and 4-6 parts of hydroxyapatite according to parts by weight.
A multi-component composite anticorrosive cement paste system for an ultrahigh-temperature acid gas well comprises the following components in parts by weight: 90-110 parts of Jiahua G-grade oil well cement, 30-40 parts of high-temperature stabilizer, 5-7 parts of functional composite emulsion, 4-6 parts of fluid loss additive, 3-5 parts of high-efficiency dispersant, 1-15 parts of oil and gas well cementing anticorrosion additive and 0.5-1.5 parts of expanding agent.
In order to improve the compactness of the cement stone substrate, the functional composite emulsion is a mixture of modified polystyrene emulsion, nano liquid silicon, alkali liquor and amine polymer.
Further, the mass ratio of the modified polystyrene emulsion, the nano liquid silicon, the alkali liquor and the amine polymer is 7.
In order to improve the fluidity of the cement paste, the dispersant is at least two combinations of sulfonated formaldehyde-acetone polycondensate, naphthalene sulfonate and polycarboxylic acid dispersant, the dispersant can avoid the problem of difficult pumping caused by overhigh consistency, and the engineering cost is reduced, and the dispersant combination is selected by integrating the temperature resistance, the dispersing effect and the mixing capability.
Preferably, the content of the sulphonated formaldehyde-acetone polycondensate is more than 70% of the total content of the dispersant.
To inhibit alpha-C 2 SH phase, and the high-temperature stabilizing agent is 200-250 mesh silica sand and/or nano liquid silicon emulsion.
In order to improve the high-temperature stability of the set cement, siO in the Jiahua G-grade oil well cement 2 The content is more than or equal to 20 percent, the CaO content is more than or equal to 61 percent, and the cement paste with the proportion has better basic performance and certain Ca content, and is beneficial to volcanic ash reaction with a high-temperature stabilizer.
Preferably, the multi-component composite anti-corrosion cement slurry system comprises the following components in parts by weight: 100 parts of Jiahua G-grade oil well cement, 35 parts of high-temperature stabilizer, 6 parts of functional composite emulsion, 4.8 parts of fluid loss additive, 3.4 parts of high-efficiency dispersant, 10-15 parts of oil-gas well cementing anticorrosive additive and 0.8 part of expansion agent.
Has the advantages that:
1. the inorganic powder in the anti-corrosion additive mainly has two forms of pore filling and alkaline-excited secondary cementation. Wherein, the pore canal filling mainly utilizes an anti-corrosion additive to match with a compact calcium carbonate layer formed by carbonizing the cement stone to prevent the infiltration of acidic corrosive media. In addition, the protective layer can reduce Ca at high temperature and high pressure 2+ The loss speed is reduced, thereby slowing down Ca (OH) 2 And corrosion of C-S-H phases. While the other part of the anti-corrosion additive can be excited to a certain degreeThe cement paste shows the gelling property under the action, so that the micro-pores of the cement paste are effectively reduced, and the corrosion resistance of the cement paste is improved;
2. the functional composite emulsion can effectively reduce the primary pores in the cement stone, thereby obviously improving the compactness of the cement stone matrix, effectively reducing the water loss of cement paste at high temperature, and avoiding the problems of weight loss, gas channeling and the like caused by water loss of well cementation cement paste. In addition, the alkaline particles in the composite emulsion can excite the inorganic mineral powder to form a crystalline phase, so that the matrix compactness of the set cement is improved; 3. the siliceous high-temperature stabilizer has different particle size distributions, so that the siliceous high-temperature stabilizer has better interactivity with the particle size of mud particles, the formed stacking pores are smaller, the higher suspension property can be kept, a silicon powder concentration area is not easy to form, and the method is favorable for alpha-C 2 Inhibition of SH phase; 4. the oil-gas well cementing multi-component composite anticorrosive cement paste system has the characteristics of 220 ℃ ultrahigh temperature resistance, gas channeling resistance and CO resistance 2 The corroded well cementation cement slurry system can effectively meet the long-term sealing of the abnormal high-temperature acidic corrosion gas well, reduce the energy consumption requirement and provide guarantee for exploration and development, efficient production and environmental protection.
Drawings
FIG. 1 is a graph comparing the corrosion ages of examples 1-4;
FIG. 2 shows the microstructure of a corroded area of the multi-element composite anticorrosive set cement (the combined addition of the anticorrosive additive is 10%);
FIG. 3 shows the microstructure of the non-corroded area of the multi-component corrosion-resistant set cement.
Detailed Description
The present invention will be described in further detail with reference to examples, but the embodiments of the present invention are not limited thereto. The invention is further illustrated by reference to the following examples, which include, but are not limited to, the following. The Jiahua G-grade oil well cement is provided by Jiahua special cement, inc., the 300/800 mesh silicon powder and the expanding agent are commercially available products, and the anticorrosion additive combination, the functional composite emulsion, the defoaming agent, the fluid loss agent and the dispersing agent are provided by Jiahua science and technology, inc., jingzhou. The examples are given by weight unless otherwise specified.
Example 1
A multi-component composite anti-corrosion cement slurry system suitable for an ultrahigh-temperature acid gas well relates to the technical field of oil and gas well cementation, adopts Jiahua G-grade oil well cement, a high-temperature stabilizer and an expanding agent as main ash components, takes functional composite emulsion as a micropore filling agent and an anti-channeling agent, and specifically comprises the following components:
wherein, the SiO in Jiahua G-grade oil well cement 2 The content is 21 percent, and the CaO content is 70 percent; the functional composite emulsion is a mixture of modified polystyrene emulsion, nano liquid silicon, alkali liquor and amine polymer; the high-temperature stabilizer is 300-mesh silica sand, and the dispersant is a combination of 7 parts of sulfonated formaldehyde-acetone polycondensate and 3 parts of naphthalene sulfonate; the functional composite emulsion comprises 6 parts of modified temperature-resistant latex and 1 part of stabilizer, 6 parts of nano liquid silicon, 0.2 part of NaOH solid-phase particles and 9 parts of amine polymer.
Weighing the raw materials according to the specific component ratio in the table, mixing, and preparing cement slurry according to SY/T5546-92, wherein the name is 0% BFs.
Example 2
In this example, on the basis of example 1, two or more of blast furnace slag, metakaolin, biological ash, hydroxyapatite, basic zinc carbonate and inorganic powder are used as anticorrosive additives, and the specific composition is as follows:
the anti-corrosion additive comprises 10 parts of blast furnace slag, 5 parts of metakaolin, 5 parts of biological ash and 5 parts of hydroxyapatite according to parts by weight.
The raw materials are weighed according to the specific component proportion in the table, mixed and prepared into cement slurry according to SY/T5546-92, and the cement slurry is named as 5% BFs.
Example 3
In the embodiment, based on the embodiment 2, the proportion of the anticorrosive additive is continuously increased, and the specific composition is as follows:
weighing the raw materials according to the specific component ratio in the table, mixing, preparing cement slurry according to SY/T5546-92, and naming as 10% BFs.
Example 4
In the embodiment, based on the embodiment 2, the proportion of the anticorrosive additive is continuously increased, and the anticorrosive additive comprises the following specific components:
weighing the raw materials according to the specific component ratio in the table, mixing, and preparing cement slurry according to SY/T5546-92, wherein the name is 15% BFs.
According to the testing of the corrosion depth of the set cement of the ultra-high temperature oil well, the set cement is mainly distinguished by naked eyes and is subjected to auxiliary observation by combining a microscope, the center line of the set cement at a constant corrosion age is split, four corrosion thicknesses are selected from the side edge of a corrosion layer to be recorded, and then the average value is obtained to obtain the corrosion depth value. Examples 1-4 were tested based on this method and the results are shown in the figure.
As can be seen from the attached figure 1, in the range of the age of 60d, the corrosion depth of the multi-component composite anti-corrosion cement paste shows regular change along with the increase of the corrosion curing age, and is consistent with the corrosion depth development rule of the conventional clean paste cement paste, and all the corrosion depths accord with the fitting relational expression of y = A + B sqrt (x). Along with the increase of the addition of the anti-corrosion additive, the corrosion depth of the set cement is gradually reduced, wherein the corrosion depths of the set cement under 10 percent and 15 percent of the anti-corrosion additive are closer, so that a more effective anti-corrosion effect can be obtained by controlling the addition of the anti-corrosion additive to be about 10 percent.
According to a method for testing the compressive strength of a corrosion experiment, the compressive strength of cement before and after corrosion is measured according to the national standard GB// T199139-2012 'method for testing well cementation cement stones', and the compressive strength degradation rate is calculated. The results are shown in Table 1.
TABLE 1 compressive Strength decay Rate
As can be seen from the table, with the increasing of the addition of the anti-corrosion additive, the initial compressive strength of the multi-component composite anti-corrosion cement stone shows a situation of firstly decreasing and then increasing, and the change rate of the compressive strength after 60d corrosion gradually decreases, and when the addition of the anti-corrosion additive is respectively 10% and 15%, the fluctuation range of the compressive strength of the multi-component composite anti-corrosion cement stone at 60d is +/-4.5% compared with that before corrosion, which indicates that in the multi-component composite anti-corrosion cement stone, when the addition of the anti-corrosion additive is 10% or more, more stable corrosion performance can be obtained.
According to the multi-element composite anti-corrosion cement, permeability of the cement sample is measured by adopting an HKY-200 pulse attenuation gas permeability tester according to American Petroleum institute standard (API RP-40), and the test results are shown in Table 2.
TABLE 2 Permeability measurement results
As can be seen from the table, the permeability change rate of the multi-component composite anti-corrosion set cement corroded by 60d gradually decreases with the increasing of the addition amount of the anti-corrosion additive, and when the addition amount of the anti-corrosion additive is 10% and 15%, respectively, the permeability of the multi-component composite anti-corrosion set cement corroded by 60d fluctuates within plus or minus 3.5% compared with that before corrosion, and the multi-component composite anti-corrosion set cement also shows relatively stable corrosion performance.
In order to analyze the influence of the corrosion performance of the multi-component composite anticorrosive set cement, a scanning electron microscope is adopted to observe the section of the multi-component composite anticorrosive set cement when the corrosion additive is 10% and the multi-component composite anticorrosive set cement is corroded for 28 days, and the change of the microstructure of the multi-component composite anticorrosive set cement corrosion layer is judged, and the result is shown in fig. 2.
As can be seen from FIG. 2, a small amount of scattered CaCO is present in the multi-component corrosion-resistant cemented carbide corrosion layer 3 Crystalline phase, majority CaCO 3 The crystalline phase is present as aggregates and a small amount of polymer coating is visible, not shown as xonotlite, ca (OH) 2 The profile shows good structural integrity. The method is characterized in that in the multi-element composite anti-corrosion cement stone, the original hole structure of the hydration product is cemented and filled by the recrystallization of the alkali-activated mineral, so that the compactness of the cement stone matrix is effectively improved, the coverage of the cemented object is enlarged, and in addition, an anti-corrosion additive and a polymer can be matched in the corrosion process, so that the integrity of the section structure is further improved.
The microstructure of the non-corroded area inside the multi-component corrosion-resistant set cement is shown in FIG. 3.
As can be seen from FIG. 3, the non-corroded area of the multi-element composite anti-corrosion set cement contains a large amount of alkali-excited minerals, has high structural integrity, and can see a large amount of acicular tobermorite and a small amount of long-sheet anti-corrosion materials. In addition, the matrix filler in the section of the multi-element composite anti-corrosion cement stone sample has larger coverage area and higher integrity and compactness, thereby improving the invasion difficulty of an acid corrosion medium.
Claims (10)
1. An oil and gas well cementing anticorrosion additive is characterized in that: it is prepared by mixing two or more than two components of blast furnace slag, metakaolin, biological ash, hydroxyapatite and basic zinc carbonate.
2. The oil and gas well cementing anti-corrosive additive of claim 1, which is characterized in that: the biological ash comprises, by weight, 9-11 parts of blast furnace slag, 4-6 parts of metakaolin, 4-6 parts of biological ash and 4-6 parts of hydroxyapatite.
3. The multi-element composite anti-corrosion cement paste system for the ultrahigh-temperature acid gas well, which adopts the anti-corrosion additive of claim 1 or 2, is characterized by comprising the following components in parts by weight: 90-110 parts of Jiahua G-grade oil well cement, 30-40 parts of high-temperature stabilizer, 5-7 parts of functional composite emulsion, 4-6 parts of fluid loss additive, 3-5 parts of high-efficiency dispersant, 1-15 parts of oil and gas well cementing anticorrosion additive and 0.5-1.5 parts of expanding agent.
4. The multi-element composite anti-corrosion cement slurry system according to claim 3, characterized in that: the functional composite emulsion is a mixture of modified polystyrene emulsion, nano liquid silicon, alkali liquor and amine polymer.
5. The multi-element composite anticorrosive cement paste system according to claim 4, wherein: the mass ratio of the modified polystyrene emulsion, the nano liquid silicon, the alkali liquor and the amine polymer is 7.
6. The multi-element composite anti-corrosion cement slurry system according to any one of claims 3 to 5, characterized in that: the dispersant is at least two combinations of sulfonated formaldehyde-acetone polycondensate, naphthalene sulfonate and polycarboxylic acid dispersant.
7. The multi-element composite anti-corrosion cement slurry system according to claim 6, characterized in that: the content of the sulfonated formaldehyde-acetone polycondensate is more than 70 percent of the total content of the dispersing agent.
8. The multi-element composite anticorrosive cement paste system according to any one of claims 3 to 7, wherein: the high-temperature stabilizing agent is 200-250 mesh silica sand and/or nano liquid silicon emulsion.
9. The multi-element composite anticorrosive cement paste system according to any one of claims 3 to 7, wherein: siO in the Jiahua G-grade oil well cement 2 The content is more than or equal to 20 percent, and the content of CaO is more than or equal to 61 percent.
10. The multi-component anticorrosion cement paste system according to claim 9, wherein the multi-component anticorrosion cement paste system comprises, in parts by weight: 100 parts of Jiahua G-grade oil well cement, 35 parts of high-temperature stabilizer, 6 parts of functional composite emulsion, 4.8 parts of fluid loss additive, 3.4 parts of high-efficiency dispersant, 10-15 parts of oil-gas well cementing anticorrosive additive and 0.8 part of expansion agent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211628194.0A CN115872649A (en) | 2022-12-17 | 2022-12-17 | Oil-gas well cementing anti-corrosion additive and multi-component anti-corrosion cement paste system for ultra-high temperature acid gas well |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202211628194.0A CN115872649A (en) | 2022-12-17 | 2022-12-17 | Oil-gas well cementing anti-corrosion additive and multi-component anti-corrosion cement paste system for ultra-high temperature acid gas well |
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| Publication Number | Publication Date |
|---|---|
| CN115872649A true CN115872649A (en) | 2023-03-31 |
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| CN202211628194.0A Withdrawn CN115872649A (en) | 2022-12-17 | 2022-12-17 | Oil-gas well cementing anti-corrosion additive and multi-component anti-corrosion cement paste system for ultra-high temperature acid gas well |
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| Country | Link |
|---|---|
| CN (1) | CN115872649A (en) |
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- 2022-12-17 CN CN202211628194.0A patent/CN115872649A/en not_active Withdrawn
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