CN109868126B - Water plugging agent and preparation method and application thereof - Google Patents
Water plugging agent and preparation method and application thereof Download PDFInfo
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- CN109868126B CN109868126B CN201711252273.5A CN201711252273A CN109868126B CN 109868126 B CN109868126 B CN 109868126B CN 201711252273 A CN201711252273 A CN 201711252273A CN 109868126 B CN109868126 B CN 109868126B
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- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title claims abstract description 148
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 125
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000003431 cross linking reagent Substances 0.000 claims abstract description 33
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 28
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 17
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 16
- 239000003381 stabilizer Substances 0.000 claims abstract description 15
- 239000004115 Sodium Silicate Substances 0.000 claims abstract description 14
- 239000001110 calcium chloride Substances 0.000 claims abstract description 14
- 229910001628 calcium chloride Inorganic materials 0.000 claims abstract description 14
- 235000019795 sodium metasilicate Nutrition 0.000 claims abstract description 14
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910052911 sodium silicate Inorganic materials 0.000 claims abstract description 14
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims abstract description 12
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- 238000000034 method Methods 0.000 claims description 20
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- 239000005011 phenolic resin Substances 0.000 claims description 14
- 229920001568 phenolic resin Polymers 0.000 claims description 14
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 230000033558 biomineral tissue development Effects 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 7
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 5
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 claims description 5
- 238000002156 mixing Methods 0.000 claims description 4
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 4
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical group [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- 230000007062 hydrolysis Effects 0.000 claims description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims description 3
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- 150000003839 salts Chemical class 0.000 abstract description 16
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- 239000000378 calcium silicate Substances 0.000 description 2
- 229910052918 calcium silicate Inorganic materials 0.000 description 2
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 2
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Abstract
The invention provides a water shutoff agent and a preparation method and application thereof. The water shutoff agent comprises the following components: partially hydrolyzed polyacrylamide: 0.5-2%, organic cross-linking agent: 0.5-1.5%, antioxidant: 0.02-0.75%, stabilizer: 0.02-0.75%, anhydrous sodium metasilicate: 0-0.5%, calcium chloride: 0-0.2% and the balance of simulated water. The water shutoff agent provided by the invention has the advantages that through reasonable proportioning of simple components, the gelling time of the prepared water shutoff agent is appropriate, the heat stability after gelling is good, the strength is high, the salt resistance is good, and the requirements of certain special oil reservoir conditions with high temperature and high salt can be met.
Description
Technical Field
The invention relates to a water shutoff agent, a preparation method and application thereof, in particular to a high-temperature-resistant and salt-resistant gel water shutoff agent, and belongs to the technical field of oil field water shutoff.
Background
At present, after decades of enhanced exploitation, most oil fields in China enter the middle and later exploitation stages, and part of the oil fields successively enter the periods of high water content, high input and low output. Especially for western oil fields, due to high oil extraction speed, the bottom water of the oil reservoir is coning, the oil well is exposed to water too early, and the water content is increased too fast. And the pressure of the oil layer produced by most oil wells for years is reduced, and the water outlet pressure of the oil-water channel of most wells is greater than the oil outlet pressure of the oil producing layer. The water outlet problem of the oil well can bring serious influence to the oil field, for example, the energy of an oil layer is reduced due to the water outlet of the oil well, the pumping efficiency of a pumping unit is reduced, the pipelines and equipment are scaled and corroded, the load of a dehydration station is increased, the final recovery rate of the oil reservoir is reduced, and the like. In order to inhibit the oil field from entering a high water-cut period too early and improve the overall development effect of the oil field, it is necessary to adopt proper water shutoff measures, wherein the water shutoff agent is used most economically and effectively.
At present, the water shutoff agent capable of effectively plugging a high-temperature and high-salinity oil reservoir is mainly cement, but is difficult to be applied to a high-depth stratum due to the problems of poor injection performance, short solidification time and the like of cement, so that the cement water shutoff agent is gradually replaced by a gel water shutoff agent.
The gel water shutoff agent is generally prepared by reacting a polymer solution with a proper cross-linking agent, wherein the polymer is mainly partially hydrolyzed polyacrylamide, and the cross-linking agent mainly comprises substances such as high-valence metal ions, low-molecular aldehydes and the like. The gel water shutoff agent prepared from partially hydrolyzed polyacrylamide and high-valence metal ions is the water shutoff agent which is most widely researched and applied at present, but the high-temperature resistance and the salt resistance of the gel water shutoff agent are poor, so that the gel water shutoff agent is difficult to be applied to Changqing oil fields (the stratum temperature is 80-100 ℃, and the mineralization degree of stratum water is 1.0 multiplied by 105mg/L，CaCl2Type), Tarim oil field (formation temperature 140 deg.C, formation water salinity 2.3X 105mg/L，CaCl2Type), etc. In addition, a part of gel water shutoff agents adopt low molecular aldehyde crosslinking agents, but in the process of water shutoff agent preparation and gelling, the aldehyde crosslinking agents and the partially hydrolyzed polyacrylamide have quick reaction time at high temperature, so that the gelling time is too short, and the field injection requirement cannot be met.
Therefore, how to provide the water shutoff agent has larger gel strength, better temperature resistance and salt resistance and proper gelling time, and has very important practical significance for the actual exploitation operation of high-temperature and high-salt oil fields such as Changqing oil fields, Tarim oil fields and the like.
Disclosure of Invention
The invention provides a water shutoff agent and a preparation method and application thereof, wherein the water shutoff agent has larger gel strength, better high temperature resistance and salt resistance and proper gelling time by reasonably selecting the components of the water shutoff agent and reasonably setting the proportion of the components. The invention also provides the application of the water shutoff agent in oil fields.
The invention provides a water shutoff agent, which comprises the following components in percentage by weight: partially hydrolyzed polyacrylamide: 0.5-2%, organic cross-linking agent: 0.5-1.5%, antioxidant: 0.02-0.75%, stabilizer: 0.02-0.75%, anhydrous sodium metasilicate: 0-0.5%, calcium chloride: 0-0.2% and the balance of simulated water.
The water shutoff agent provided by the invention is mainly a high molecular polymer gel with a three-dimensional network structure generated by the reaction of partially hydrolyzed polyacrylamide and an organic cross-linking agent, so that the water shutoff agent is actually a gel water shutoff agent. The inventor researches and discovers that the water shutoff agent has high strength and high temperature resistance, and analysis of the possible reason is that the partially hydrolyzed polyacrylamide and the organic cross-linking agent form the high polymer gel with the three-dimensional net structure in a covalent bond mode, but the conventional gel water shutoff agent, such as the water shutoff agent prepared by using high-valence metal ions as the cross-linking agent at present, forms the net structure of the gel in a coordination bond mode, and has high structural strength because the strength of the covalent bond is greater than that of the coordination bond, so that the high polymer gel can still maintain the structural stability even in a high-temperature and high-salt oil reservoir environment, and can be suitable for high-temperature and high-salt oil reservoirs such as Changqing oil fields and Tarim oil fields.
On the other hand, the inventor researches and discovers that by adopting the water plugging agent with the component proportion, the crosslinking reaction rate between the partially hydrolyzed polyacrylamide and the organic crosslinking agent is proper, so that the water plugging agent can be gelled after reaching a target oil layer, the gelling time of the water plugging agent can meet the actual field injection requirement, and the oil reservoir recovery rate is effectively improved.
The partially hydrolyzed polyacrylamide used in the water shutoff agent is not particularly limited, and conventional partially hydrolyzed polyacrylamide can be selected. In the specific embodiment of the invention, the weight average molecular weight of the polyacrylamide is 500-700 ten thousand, and the hydrolysis degree is 20-30%. Specifically, the mass content of the partially hydrolyzed polyacrylamide in the water shutoff agent is usually 0.75 to 1.50%.
The organic cross-linking agent used in the present invention is not particularly limited as long as it can cross-link with the partially hydrolyzed polyacrylamide to form an organic gel having a three-dimensional network structure, and the actual amount of the organic cross-linking agent can be set appropriately according to the degree of hydrolysis and the molecular weight of the partially hydrolyzed polyacrylamide.
Specifically, the selected organic cross-linking agent can be a phenolic resin cross-linking agent or an aldehyde cross-linking agent. In the specific implementation process of the invention, the phenolic resin cross-linking agent is generated by the reaction of formaldehyde and hydroquinone or the reaction of formaldehyde and resorcinol. For example, hydroquinone, urotropine and other components of the water shutoff agent can be injected into an oil layer together, formaldehyde released by decomposition of the urotropine can react with the hydroquinone to generate phenolic resin in the gelling process, and the phenolic resin is used as a cross-linking agent and reacts with partially hydrolyzed polyacrylamide to generate gel with a three-dimensional network structure. The inventor researches and discovers that by adopting the mode and reasonably setting the adding amount of the polyacrylamide and the organic cross-linking agent, the water shutoff agent has a relatively proper gelling time, and the strength of the obtained gel is still gradually increased in the gelling process, which indicates that the release of formaldehyde, the generation of the phenolic resin cross-linking agent and the cross-linking reaction still occur after the water shutoff agent is injected into a stratum.
Meanwhile, as the formaldehyde used for generating the phenolic resin cross-linking agent is slowly released by the urotropine in the process of the cross-linking reaction, the mass and concentrated release of the formaldehyde is avoided, and the production safety is improved. Meanwhile, the crosslinking reaction can be slowly carried out for a long time by the formaldehyde which is slowly released, so that the maximum strength of the water plugging agent can be reached for a long time after the water plugging agent is gelatinized, and the water plugging agent can keep very high strength and performance stability for a long time under the conditions of high temperature and high salt.
The antioxidant and the stabilizer can enhance the stability of the high molecular polymer gel. The selection of the antioxidant and the stabilizer is not particularly limited, and conventional antioxidants and stabilizers in the field of water shutoff agents can be selected. Specifically, the stabilizer may be cobalt chloride; the antioxidant may be selected from at least one of thiourea and sodium sulfite. The inventors have found that the reducing antioxidant can further ensure that the reaction for producing the phenolic resin crosslinking agent proceeds smoothly and stably.
In the specific implementation process of the invention, the mass ratio of the antioxidant to the stabilizer is (1-2): 1, such as 1.5: 1.
in the specific implementation process of the invention, the components of the water shutoff agent also comprise anhydrous sodium metasilicate (also called zero-water sodium metasilicate) and calcium chloride, and the anhydrous sodium metasilicate has good water solubility, so that the anhydrous sodium metasilicate can react with the calcium chloride to generate water-insoluble calcium silicate precipitate, and the calcium silicate precipitate is filled into the high polymer gel with the three-dimensional network structure, so that the strength and the stability of the high polymer gel are further increased, and the performance of the water shutoff agent is improved.
In the specific implementation process of the invention, the mass ratio of the anhydrous sodium metasilicate to the calcium chloride is 1: (1-2).
The simulated water can be taken from the formation water of the actual oil field, and can also be self-configured according to indexes such as the mineralization degree of the formation water of the actual oil field. In the process of the invention, the degree of mineralization of the simulated water used should be at least not less than 1.0X 105mg/L, generally not less than 2.0X 105mg/L to reach high salt conditions of Changqing oil field and Tarim oil field.
The invention further provides a preparation method of the water shutoff agent, which comprises the following steps:
firstly, mixing partially hydrolyzed polyacrylamide with simulated water until the partially hydrolyzed polyacrylamide is completely dissolved, then adding an antioxidant, a stabilizer and a mixture of anhydrous sodium metasilicate and calcium chloride, uniformly mixing, and then adding an organic cross-linking agent to obtain the water plugging agent.
In the specific implementation process of the invention, anhydrous sodium metasilicate and calcium chloride are firstly mixed uniformly according to the proportion, and then the mixture is added into the mixed liquid of the components of the partially hydrolyzed polyacrylamide, the simulated water, the antioxidant and the like.
The configuration process can be carried out at normal temperature, for example, 20-30 ℃. In the specific implementation process of the invention, the water shutoff agent is configured on an oil field exploitation site, and then the configured water shutoff agent is injected into a stratum.
The invention also provides the application of the water shutoff agent in oilfield exploitation. The water shutoff agent provided by the invention has higher strength, good high temperature resistance and salt resistance and proper gel forming time, so that the water shutoff agent can be applied to high-temperature and high-salt oil reservoir conditions of Changqing oil fields, Tarim oil fields and the like, and can improve the oil reservoir exploitation efficiency.
The invention provides a water shutoff agent which has the following advantages through reasonable proportioning of simple components:
(1) a suitable viscosity of about 40mPa · s, and thus very good injection properties;
(2) the gel forming time is about 1 day, which meets the oil reservoir exploitation requirement;
(3) the water shutoff agent has very high strength after gelling, and the mineralization degree is 2.3 multiplied by 10 at the temperature of 140 DEG C5The strength of the product can be gradually increased to E level or above by a bottle test method under the conditions of high temperature and high salt of mg/L;
(4) very high viscosity retention, mineralization degree of 2.3X 10 at 140 deg.C5Under the conditions of high temperature and high salt of mg/L, the viscosity of the gel is more than 7500mPa & s for 2 months, and the viscosity of the gel is maintained at about 6000mPa & s even more than 7000mPa & s for 6 months, which shows that the gel of the water shutoff agent still keeps long-term stability under the conditions of high temperature and high salt.
Therefore, the water shutoff agent provided by the invention has very excellent injection performance and gelling time, meets the operation requirements of actual oil reservoir exploitation, and has very excellent high temperature resistance and salt resistance, so that the water shutoff agent is more suitable for high-temperature and high-salt oil reservoir conditions of Tarim oil reservoirs, Changqing oil fields and the like, and has very high strength and long-term stability under the high-temperature and high-salt conditions.
In addition, the water shutoff agent has simple components and wide raw material sources, and is suitable for large-scale production and popularization.
The invention also provides a preparation method of the water shutoff agent, which is simple and feasible, can be configured on the oilfield exploitation site, and does not release a large amount of formaldehyde in the configuration process, thereby improving the safety of production operation.
The invention also provides the application of the water shutoff agent in oilfield exploitation, and the water shutoff agent provided by the invention has the advantages, so that the water shutoff agent can be well applied to oilfield exploitation, especially to high-temperature and high-salt oil reservoir conditions such as Changqing oil fields and Tarim oil fields, and the oil reservoir exploitation efficiency can be improved.
Drawings
FIG. 1 is a photograph showing the strength of the water shutoff agent prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of the water plugging agent prepared in example 1 of the present invention;
FIG. 3 is a viscosity test curve of the water shutoff agent prepared in example 1 of the present invention;
FIG. 4 is a scanning electron micrograph of the water plugging agent prepared in example 2 of the present invention;
fig. 5 is a viscosity test curve of the water shutoff agent prepared in example 2 of the present invention.
FIG. 6 is a photograph showing the strength of the water-plugging agent prepared in comparative example 1 according to the present invention;
FIG. 7 is a scanning electron micrograph of the water plugging agent prepared in comparative example 1 according to the present invention;
fig. 8 is a viscosity test curve of the water shutoff agent prepared in comparative example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all, embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
In the following examples, the specific methods for measuring gel forming time and temperature resistance time were as follows: and (3) dripping the prepared water shutoff agent into an ampoule bottle, sealing, and then placing in a constant-temperature oven, wherein the set temperature is constant (generally, the temperature can be set according to the actual oil reservoir environment temperature). Periodically taking out the ampoule bottle filled with the water shutoff agent from the constant-temperature oven, and observing whether the ampoule bottle loses fluidity. The standard for judging the gelling and temperature resistance is as follows: and horizontally placing the ampoule bottle, and observing whether the angle formed by the front surface of the gel and the bottle wall is more than 45 degrees or not, so that the gel forming time and the temperature resistant time can be determined.
The strength of the water shutoff agent is measured by adopting a visual code method (also called a bottle test method), and the specific test method comprises the following steps: the ampoule bottle containing the water shutoff agent (gel) was inverted 45 °, the strength of the gel was observed and evaluated by the tongue-out condition of the gel, and the strength grade of the water shutoff agent prepared in this example was evaluated according to the gel strength grades (a to J) proposed by Sydansk et al.
Example 1
The present embodiment provides a water shutoff agent, and the components and the ratio thereof are shown in table 1.
TABLE 1 Water shutoff agent composition ratio (total mass content 100%)
The preparation method of the water shutoff agent comprises the following steps:
firstly, adding simulated water into a beaker, placing the beaker under a stirrer, and enabling the bottom of a stirring rod to be about 1cm away from the bottom of the beaker. Turning on a stirrer switch, adjusting the stirring speed to enable the simulated water to form a vortex, adding the partially hydrolyzed polyacrylamide into the beaker, and continuing stirring for about 2.5 hours until the partially hydrolyzed polyacrylamide is completely dissolved.
Secondly, under the condition of maintaining stirring, uniformly and quickly adding the antioxidant thiourea and the stabilizer cobalt chloride into the beaker until the antioxidant and the stabilizer are completely dispersed.
And finally, adding hydroquinone and urotropine into the beaker, and uniformly dispersing to obtain the water shutoff agent.
The plugging agent prepared in the embodiment is placed in a constant-temperature oven at 140 ℃ (the stratum temperature of Tarim oil field oil reservoir), and gelling can be achieved after 1 day.
Fig. 1 is a photograph showing the gel strength of the water shutoff agent prepared in the present example, wherein a, b and c in fig. 1 are photographs showing the test at the time of heating (i.e., the time of standing in a constant temperature oven) for 30 days, 60 days and 90 days, respectively. The gel strength gradually increased with increasing heating time, and reached a maximum strength at about 60 days, and the strength rating was F as measured by jar test. Indicating that the gel still has a slow crosslinking process in the gelling process. Thereafter, the gel strength gradually decreased with the increase of the heating time, but no gel breaking was observed at 90 days. The temperature resistant time is more than 5 months after the temperature resistant time test.
Therefore, the water shutoff agent prepared by the embodiment has proper gelling time; at a temperature of 140 ℃ and a degree of mineralization of 2.3X 105The high-strength high-salinity oil-field well drilling fluid can still keep very high strength for a long time under the conditions of mg/L high temperature and high salinity, and can be particularly applied to the exploitation of high-temperature and high-salinity oil reservoirs such as Tarim oil field oil reservoirs.
The morphology of the microstructure of the three-dimensional network of the water shutoff agent after gelling is observed by a Scanning Electron Microscope (SEM), and fig. 2 is a scanning electron micrograph of a gel obtained by the water shutoff agent prepared in the present example after gelling at different magnifications. As can be seen from FIG. 2, the network structure of the gel is dense and uniform, and the size of the individual pores is about 5 μm. The three-dimensional network structure of the gel determines the gel strength to a certain extent, so that the gel strength of the water shutoff agent prepared by the embodiment is very high after gelling.
And measuring the viscosity of the water plugging agent and the gelled viscosity thereof by using a HAAKE rheometer. Wherein:
in fig. 3, a is a viscosity test result of the water shutoff agent prepared in the embodiment after the configuration is completed (the measurement rotating speed is 170S)-1At 30 ℃ for 5 min). It can be seen that the viscosity of the plugging agent obtained immediately after the preparation was about 39 mPas.
In FIG. 3, b and c are the results of the viscosity test of the water-blocking agent in a 140 ℃ constant temperature oven for 2 months and 6 months, respectively (measurement of the rotation speed of 1.5S)-1At 120 ℃ for 10 min). It can be seen that the water shutoff gel is at a temperature of 1Mineralization degree of 2.3X 10 at 40 deg.C5The viscosity of the mixture is about 8000mPa & s at the high temperature and high salt condition of mg/L for 2 months; the viscosity at 6 months was maintained at about 7100 mPas.
From the above viscosity test results, it can be seen that the water shutoff agent in the present embodiment has appropriate viscosity after completion of the configuration and excellent injection performance, and thus can meet the actual field injection requirements. The gel has outstanding thermal stability and salt tolerance after gelling, is suitable for being used as a water shutoff agent, and can be particularly applied to high-temperature and high-salt actual oil field exploitation operations such as Tarim oil field reservoirs and the like.
Example 2
The present embodiment provides a water shutoff agent, and the components and the ratio thereof are shown in table 2. The preparation method of the water shutoff agent comprises the following steps:
first, anhydrous sodium metasilicate and calcium chloride were mixed uniformly in the mass ratio shown in table 2 for use.
And secondly, adding simulated water into the beaker, placing the beaker under a stirrer, and enabling the bottom of the stirring rod to be about 1cm away from the bottom of the beaker. Turning on a stirrer switch, adjusting the stirring speed to enable the simulated water to form a vortex, adding the partially hydrolyzed polyacrylamide into the beaker, and continuing stirring for about 3.5 hours until the partially hydrolyzed polyacrylamide is completely dissolved.
And thirdly, rapidly and uniformly adding the antioxidant and the stabilizer into the beaker under the stirring, continuously adding the mixture of the anhydrous sodium metasilicate and the calcium chloride after uniformly stirring, and continuously and uniformly stirring.
And finally, adding the phenolic resin cross-linking agent into the beaker until the phenolic resin cross-linking agent is uniformly dispersed to obtain the water shutoff agent.
TABLE 2 component proportion (total mass content 100%) of water shutoff agent
The water shutoff agent prepared in the embodiment is placed in a constant-temperature oven at 140 ℃ (the stratum temperature of Tarim oil field reservoirs), gelling can be realized after 1 day, the strength of the gel is increased to the maximum in about 15 days, and the gel is grade E, which indicates that the gel has a slow crosslinking process in the gelling process. Thereafter, the gel strength gradually decreased with the lapse of time, but no gel breaking was observed at 90 days. The temperature resistant time is more than 5 months after the temperature resistant time test.
Therefore, the water shutoff agent prepared by the embodiment has proper gelling time; at a temperature of 140 ℃ and a degree of mineralization of 2.3X 105The high-strength high-salinity oil-field well drilling fluid can still keep very high strength for a long time under the conditions of mg/L high temperature and high salinity, and can be particularly applied to the exploitation of high-temperature and high-salinity oil reservoirs such as Tarim oil field oil reservoirs.
The morphology of the microstructure of the three-dimensional network of the water shutoff agent after gelling is observed by a Scanning Electron Microscope (SEM), and fig. 4 is a scanning electron microscope image of the gel obtained after gelling of the water shutoff agent prepared in the present example under different magnifications, which shows that the network structure of the gel is dense and uniform, and the size of a single hole of the network structure is measured to be about 37 μm. The three-dimensional network structure of the gel determines the gel strength to a certain extent, so that analysis and prediction can be performed, and the gel strength obtained after gelling of the water shutoff agent prepared by the embodiment is very high.
Adopting a HAAKE rheometer to measure the viscosity of the water plugging agent after gelling, wherein:
in fig. 5, a is a viscosity test result of the water shutoff agent of the present embodiment after the completion of the configuration (measurement rotation speed is 170S)-1At 30 ℃ for 5 min). It was found that the viscosity of the plugging agent obtained immediately after the preparation was maintained at about 44 mPas.
In FIG. 5, b and c are the results of the viscosity test when the water-blocking agent was placed in a 140 ℃ constant temperature oven for 2 months and 6 months, respectively (measurement of the rotation speed was 1.5S)-1At 120 ℃ for 10 min). As can be seen, the water shutoff agent has the mineralization degree of 2.3 multiplied by 10 at the temperature of 140 DEG C5The viscosity at 2 months was about 7800 mPas and the viscosity at 6 months was about 5900 mPas at high temperature and high salt conditions of mg/L.
According to the test results, the water shutoff agent in the embodiment has the advantages of small viscosity, proper viscosity after configuration and excellent injection performance, so that the water shutoff agent can meet the actual on-site injection requirement. The gel has outstanding thermal stability and salt tolerance after gelling, is suitable for being used as a water shutoff agent, and can be particularly applied to high-temperature and high-salt actual oil field exploitation operations such as Tarim oil field reservoirs and the like.
Comparative example 1
The comparative example provides a water shutoff agent, and the components and the proportion thereof are shown in table 3. The preparation method of the water shutoff agent comprises the following steps:
firstly, adding simulated water into a beaker, placing the beaker under a stirrer, and enabling a stirring rod to be about 1cm away from the bottom of the beaker. And opening a stirrer switch, adjusting the stirring speed to enable the simulated water to form a vortex, adding the partially hydrolyzed polyacrylamide into the beaker, continuously stirring for about 3 hours, and adding the phenolic resin cross-linking agent into the beaker under the condition of maintaining stirring until the phenolic resin cross-linking agent is uniformly dispersed to obtain the water shutoff agent.
TABLE 3 component proportion (total mass content is 100%) of water shutoff agent
The plugging agent prepared in the embodiment is placed in a constant-temperature oven at 140 ℃ (the stratum temperature of Tarim oil field oil reservoir), and gelling can be achieved after 1 day.
Fig. 6 is a test photograph of the gel strength of the water shutoff agent prepared in the present comparative example, wherein a, b, c and d in fig. 6 are test photographs of the heating time (i.e., the standing time in the constant temperature oven at 140 ℃) of 1 day, 15 days, 30 days and 60 days, respectively. The gel strength gradually increased with the increase of the heating time, and the strength reached the maximum in about 15 days, and the strength grade was C as measured by a bottle test method. Thereafter, the gel strength gradually decreased with the increase of the heating time.
The morphology of the microstructure of the three-dimensional network of the gel obtained after gelling of the water shutoff agent is observed by a Scanning Electron Microscope (SEM), and fig. 7 is SEM photographs of the gel obtained when the water shutoff agent prepared in this example is placed in an oven at 140 ℃ for 15 days under different magnifications, and the average size of the single pores in the gel network structure is measured to be about 62 μm. The three-dimensional network structure of the gel determines the gel strength to a certain extent, and analysis and prediction can be performed, so that the gel strength of the water shutoff agent prepared by the embodiment after gelling is general.
Adopting a HAAKE rheometer to measure the viscosity of the water plugging agent after gelling, wherein:
in fig. 8, a is a viscosity test result (measured rotation speed of 170S) of the water shutoff agent prepared in the present embodiment after the configuration is completed-1At 30 ℃ for 5min), it can be seen that the viscosity of the water plugging agent just prepared is about 30 mPas.
In FIG. 8, b and c are the results of the viscosity test when the water-blocking agent was placed in a 140 ℃ constant temperature oven for 2 months and 6 months, respectively (measurement of the rotation speed was 1.5S)-1At 120 ℃ for 10 min). It can be seen that the water shutoff agent gel has the mineralization degree of 2.3 multiplied by 10 at the temperature of 140 DEG C5The viscosity of the mixture is about 4000mPa & s at 2 months under the conditions of high temperature and high salt of mg/L; the viscosity at 6 months was about 3200 mPas.
According to the test results, the water shutoff agent in the comparative example has proper viscosity after the preparation, but has poor thermal stability and salt tolerance after the gelling, and cannot be applied to the high-temperature and high-salt actual oil field exploitation operation such as a Tarim oil field reservoir.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.
Claims (4)
1. The water shutoff agent is characterized by comprising the following components in percentage by weight:
partially hydrolyzed polyacrylamide: 0.5-2%, organic cross-linking agent: 0.5-1.5%, antioxidant: 0.02 &0.75%, stabilizer: 0.02-0.75%, anhydrous sodium metasilicate: 0-0.5%, calcium chloride: 0-0.2 percent of water, and the balance of simulated water, wherein the mineralization degree of the simulated water is more than or equal to 1.0 multiplied by 105mg/L；
The weight average molecular weight of the partially hydrolyzed polyacrylamide is 500-700 ten thousand, and the hydrolysis degree is 20-30%;
the organic cross-linking agent is a phenolic resin cross-linking agent or an aldehyde cross-linking agent;
the phenolic resin cross-linking agent is generated by the reaction of formaldehyde and hydroquinone, or the phenolic resin cross-linking agent is generated by the reaction of formaldehyde and resorcinol, wherein the formaldehyde is obtained by decomposing urotropine;
the antioxidant is selected from at least one of thiourea and sodium sulfite; the stabilizer is cobalt chloride;
the mass ratio of the antioxidant to the stabilizer is (1-2): 1.
2. the plugging agent according to claim 1, wherein the mass ratio of anhydrous sodium metasilicate to calcium chloride is 1: (1-2).
3. The method for preparing a water shutoff agent according to claim 1 or 2, which comprises:
firstly, mixing the partially hydrolyzed polyacrylamide with simulated water until the partially hydrolyzed polyacrylamide is completely dissolved, then adding an antioxidant, a stabilizer and a mixture of anhydrous sodium metasilicate and calcium chloride, uniformly mixing, and then adding an organic cross-linking agent to obtain the water shutoff agent.
4. Use of the water shutoff agent of claim 1 or 2 in oilfield exploitation.
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| CN110205109A (en) * | 2019-07-10 | 2019-09-06 | 中海石油(中国)有限公司秦皇岛32-6作业公司 | A kind of low-viscosity gel water shutoff agent of resisting high temperature, high salt |
| CN113308231B (en) * | 2020-02-26 | 2023-01-10 | 中国石油天然气股份有限公司 | Water shutoff agent, preparation method, experimental method and water shutoff method thereof |
| CN115960599B (en) * | 2021-10-11 | 2024-04-09 | 中国石油天然气股份有限公司 | Inorganic microgel-polymer composite gel system and preparation method and application thereof |
| CN116445141A (en) * | 2023-04-14 | 2023-07-18 | 中海油田服务股份有限公司 | Rigid nanoparticle plugging agent for improving recovery ratio |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4940091A (en) * | 1989-01-03 | 1990-07-10 | Mobil Oil Corporation | Method for selectively plugging a zone having varying permeabilities with a temperature activated gel |
| CN1177053A (en) * | 1997-10-21 | 1998-03-25 | 辽河石油勘探局钻采工艺研究院 | Single liquid method combined with two liquid method for water sealing in borehole |
| CN102559159A (en) * | 2011-12-14 | 2012-07-11 | 中国石油天然气股份有限公司 | High-temperature-resistant phenolic resin weak gel profile control water plugging agent |
| CN103740348A (en) * | 2013-12-31 | 2014-04-23 | 东营泰尔石油技术有限公司 | Leaking stoppage reinforcing agent |
| CN103937474A (en) * | 2014-03-24 | 2014-07-23 | 四川仁智油田技术服务股份有限公司 | Environment-friendly high strength profile control water shut-off agent and preparation method thereof |
| CN105505354A (en) * | 2015-12-10 | 2016-04-20 | 中国石油天然气股份有限公司 | High-temperature profile control agent and preparation method thereof |
| CN106590558A (en) * | 2016-11-28 | 2017-04-26 | 中国石油大学(北京) | Temperature resisting cross-linking polymeric microsphere modifying and flooding agent and preparation method thereof |
| CN106634908A (en) * | 2016-10-09 | 2017-05-10 | 中国石油化工股份有限公司 | Heat-resisting interpenetrating polymer network plural gel profile control agent and preparation method thereof |
| CN106947450A (en) * | 2017-03-10 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of in-depth profile control with low initial viscosity and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103834373A (en) * | 2012-11-27 | 2014-06-04 | 中国石油天然气股份有限公司 | Inorganic modified copolymer plugging agent |
-
2017
- 2017-12-01 CN CN201711252273.5A patent/CN109868126B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4940091A (en) * | 1989-01-03 | 1990-07-10 | Mobil Oil Corporation | Method for selectively plugging a zone having varying permeabilities with a temperature activated gel |
| CN1177053A (en) * | 1997-10-21 | 1998-03-25 | 辽河石油勘探局钻采工艺研究院 | Single liquid method combined with two liquid method for water sealing in borehole |
| CN102559159A (en) * | 2011-12-14 | 2012-07-11 | 中国石油天然气股份有限公司 | High-temperature-resistant phenolic resin weak gel profile control water plugging agent |
| CN103740348A (en) * | 2013-12-31 | 2014-04-23 | 东营泰尔石油技术有限公司 | Leaking stoppage reinforcing agent |
| CN103937474A (en) * | 2014-03-24 | 2014-07-23 | 四川仁智油田技术服务股份有限公司 | Environment-friendly high strength profile control water shut-off agent and preparation method thereof |
| CN105505354A (en) * | 2015-12-10 | 2016-04-20 | 中国石油天然气股份有限公司 | High-temperature profile control agent and preparation method thereof |
| CN106634908A (en) * | 2016-10-09 | 2017-05-10 | 中国石油化工股份有限公司 | Heat-resisting interpenetrating polymer network plural gel profile control agent and preparation method thereof |
| CN106590558A (en) * | 2016-11-28 | 2017-04-26 | 中国石油大学(北京) | Temperature resisting cross-linking polymeric microsphere modifying and flooding agent and preparation method thereof |
| CN106947450A (en) * | 2017-03-10 | 2017-07-14 | 中国石油化工股份有限公司 | A kind of in-depth profile control with low initial viscosity and preparation method thereof |
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