CN113136185A - Organic water plugging gel for low-temperature hypersalinity oil reservoir - Google Patents
Organic water plugging gel for low-temperature hypersalinity oil reservoir Download PDFInfo
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- C09K8/504—Compositions based on water or polar solvents
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- C09K8/86—Compositions based on water or polar solvents containing organic compounds
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Abstract
The invention provides an organic water plugging gel for a low-temperature high-salinity oil reservoir, which consists of a main agent, a cross-linking agent, an accelerant, a regulator, a stabilizer and water, wherein the mass percentages of all the substances are as follows: 0.2-0.5% of main agent, anionic polyacrylamide is selected, and the weight-average molecular mass is 18 x 106‑24×106The degree of hydrolysis is 18-23%; 0.2 to 0.4 percent of cross-linking agent, and phenolic resin cross-linking agent is selected, wherein the content of hydroxymethyl is 28.49 to 45.28 percent; 0.05-0.2% of accelerator, and hydroquinone or resorcinol are selected; 0.03-0.1% of regulator, hydrochloric acid or oxalic acid is selected; 0.05 to 0.15 percent of stabilizer, and thiourea is selected; the balance of water. The water plugging gel has adjustable gelling time, the formed gel has high strength, good salt resistance and good stability, the plugging rate of the core reaches more than 93 percent, and the oil reservoir requirement can be met.
Description
Technical Field
The invention relates to the technical field of oilfield chemistry, in particular to an organic water plugging gel for a low-temperature hypersalinity oil reservoir.
Background
With the continuous development of oilfield flooding, the heterogeneity of the oilfield is stronger and stronger, the situation of sudden inflow and ineffective circulation of injected water is serious, and the profile control and water plugging technology is the most effective technology for solving the problem of high water content of the conventional oilfield. The profile control water shutoff technology is mainly divided into two types of mechanical and chemical water control water shutoff technologies, and compared with mechanical water control water shutoff, the chemical water control water shutoff technology has wider application in oil fields due to simple and convenient operation, controllable stratum depth, part of oil-water selectivity and the like. In the chemical water plugging and controlling technology, polymer jelly systems are widely applied. For example, in the ' evaluation of profile control performance of offshore oil field phenolic resin jelly ' (tension wave) ', a phenolic resin jelly system is provided, which has higher gelling strength, good thermal stability, high plugging rate and good injectivity. However, the system has the gelling time of 5-14 days at 65 ℃, the gelling time is longer for an oil reservoir with the temperature lower than 50 ℃, the gelling strength is weakened, and the applicable mineralization degree of the system is only 32000 mg/L. For oil reservoirs below 55 ℃, the most common water shutoff and profile control system is a chromium gel system, and in the research of a deep profile control crosslinking system (goldenvanic wave), the obtained chromium crosslinking system is suitable for preparing a water mineralization degree of less than 10000mg/L, but contains heavy metal ions, namely chromium ions, on one hand, the gelling time of a chromium example crosslinked polymer is too fast, on the other hand, the chromium ions are harmful to the environment and do not accord with the regulation of an environmental protection law. For reservoir temperatureBelow 55 deg.C and degree of mineralization greater than 1.0 × 105In mg/L oil fields, the polymer jelly is adopted to perform profile control and water shutoff operation on the oil reservoirs, which faces many technical challenges and is mainly summarized as the following two aspects: firstly, the high mineralization can compress the double electric layers of polymer molecules, so that the polymer molecules are coiled, the formed jelly structure is unstable, and a jelly system is easy to dehydrate; secondly, the temperature is low, so that the collision probability of polymer molecules and partial cross-linking agent molecules is reduced, the gelling time is prolonged, the cross-linking strength is weak, and the operation requirement cannot be met. In order to overcome the defects of polyacrylamide, CN106916249A provides a plugging agent system which adopts acrylamide as a main agent, the system has high gel strength, but the system adopts an acrylamide monomer with high toxicity, and the popularization and the application of the system in oil fields are not facilitated. In the inorganic water plugging gel, such as an inorganic coating plugging agent, calcium-magnesium salt precipitation and the like, although the preparation is simple and the price is low, the system has short gelling time and low gelling strength, cannot enter deep stratum and is limited in application in oil fields.
Disclosure of Invention
The invention overcomes the defects in the prior art, and the problems of long gelling time and low mineralization degree of the existing polymer gel system water shutoff gel under the low-temperature condition are solved, and the organic water shutoff gel for the low-temperature high-mineralization oil reservoir is provided, the gelling time of the water shutoff gel is adjustable, the formed gel has high strength, good salt resistance and good stability, the plugging rate of a rock core reaches more than 93 percent, and the oil reservoir requirements can be met.
The purpose of the invention is realized by the following technical scheme.
The organic water plugging gel for the low-temperature high-salinity oil reservoir comprises a main agent, a cross-linking agent, an accelerant, a regulator, a stabilizer and water, wherein the mass percentages of all the substances are as follows:
0.2-0.5% of main agent, anionic polyacrylamide is selected, and the weight-average molecular mass is 18 x 106-24×106The degree of hydrolysis is 18-23%;
0.2-0.4% of cross-linking agent, selecting phenolic resin cross-linking agent, wherein the content of hydroxymethyl is 28.49-45.28%, and the content of hydroxymethyl is detected according to the GB/T14074-2006 method;
0.05-0.2% of accelerator, and hydroquinone or resorcinol are selected;
0.03-0.1% of regulator, hydrochloric acid (the concentration of the hydrochloric acid solution is 37%) or oxalic acid is selected;
0.05 to 0.15 percent of stabilizer, and thiourea is selected;
the balance of water.
The relative molecular mass of anionic polyacrylamide used as the main agent is 2200 × 104-2300×104The degree of hydrolysis was 22.5%.
The organic water shutoff gel consists of 0.2 percent of main agent, 0.3 percent of cross-linking agent, 0.05 percent of accelerating agent, 0.05 percent of regulator, 0.05 percent of stabilizer and 99.35 percent of water.
The organic water shutoff gel consists of 0.5 percent of main agent, 0.2 percent of cross-linking agent, 0.1 percent of accelerating agent, 0.07 percent of regulator, 0.07 percent of stabilizer and 99.06 percent of water.
The organic water shutoff gel consists of 0.3 percent of main agent, 0.4 percent of cross-linking agent, 0.2 percent of accelerating agent, 0.1 percent of regulator, 0.1 percent of stabilizer and 98.90 percent of water.
The organic water shutoff gel consists of 0.4 percent of main agent, 0.2 percent of cross-linking agent, 0.1 percent of accelerating agent, 0.09 percent of regulator, 0.15 percent of stabilizer and 99.06 percent of water.
The organic water-plugging jelly is composed of 0.5% of main agent, 0.3% of cross-linking agent, 0.1% of accelerating agent, 0.07% of regulator, 0.1% of stabilizer and 98.93% of water.
The organic water-plugging jelly is composed of 0.2% of main agent, 0.4% of cross-linking agent, 0.08% of accelerating agent, 0.05% of regulator, 0.09% of stabilizer and 99.18% of water.
The organic water shutoff gel consists of 0.5 percent of main agent, 0.3 percent of cross-linking agent, 0.2 percent of accelerating agent, 0.1 percent of regulator, 0.1 percent of stabilizer and 98.80 percent of water.
The accelerator adopts a mixture of resorcinol and hydroquinone, wherein the mass ratio of resorcinol to hydroquinone is (2-3) to 1.
The gelling liquid viscosity of the organic water-plugging gel is 120-200000 mPa & s, the organic water-plugging gel is suitable for water-plugging profile control of an oil layer at the temperature of 40-50 ℃, the gelling time is 5-122h, and the strength of the formed gel is 30000-200000mPa & s.
The mineralization degree of the organic water-blocking gel is 2 multiplied by 10 at the temperature of 50 DEG C5After aging for 90 days under mg/L oil reservoir condition, dehydration phenomenon does not occur, the retention rate of the volume of water plugging jelly still reaches 100%, better integrity is kept, and the plugging rate of the core reaches 93-96%.
The invention has the beneficial effects that: the water-blocking jelly is suitable for the temperature of 40-50 deg.c and the mineralization degree of 2 x 105The mg/L (i.e. the high mineralization degree) oil deposit can improve the heterogeneity of the stratum, block a large pore canal of the stratum, promote the development of a medium-low permeable layer and further improve the recovery ratio of crude oil; the gel forming liquid of the water plugging jelly has the viscosity of 120-260 mPa.s, the viscosity is high, the starting pressure of a medium-low permeable layer is high, so that the water plugging jelly can enter a large pore passage of a stratum preferentially, after the gel forming liquid of the water plugging jelly is injected into the stratum, the water plugging jelly enters a high permeable layer flushed by injected water preferentially, a non-flowing high-strength system is formed under the oil reservoir condition, the liquid flow is diverted to enter the medium-low permeable layer, the water absorption profile of the water injection stratum is improved, and the sweep coefficient is improved; the water plugging gel has adjustable gelling time, the formed gel has high strength, good salt resistance and good stability, the plugging rate of the core reaches more than 93 percent, and the oil reservoir requirement can be met.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples.
And (3) evaluating and testing the prepared jelly system:
viscosity determination method (gel strength determination of gel system)
The crosslinker viscosity was measured using a Brookfield viscometer, USA, with a 0# spindle at 6rpm and 20 ℃.
The gel forming time and the gel forming strength of the gel system are tested by the following steps: and (3) sampling periodically to test the viscosity of the jelly system, wherein the time when the viscosity change is less than 5 percent is the gelling time, and the viscosity is the gelling strength.
Example 1
0.2g of polyacrylamide is added to 99.55g of clear water with stirring, and after stirring for 2 hours, the polymer solution is allowed to stand for 12 hours. Then 0.3g of phenolic crosslinking agent, 0.05g of resorcinol, 0.05g of oxalic acid and 0.05g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring. The gel system comprises, by mass, 0.2% of polyacrylamide, 0.3% of phenolic aldehyde crosslinking agent, 0.05% of resorcinol, 0.05% of oxalic acid, 0.05% of thiourea and 99.55% of water, and the gel forming time of the gel system is 114.3h at 50 ℃, and the strength of the formed gel is 62412mPa & s.
Example 2
0.5g of polyacrylamide is added into 99.06g of clear water while stirring, and after stirring for 2 hours, the polymer solution is kept stand for 12 hours. Then 0.2g of phenolic crosslinking agent, 0.1g of resorcinol, 0.07g of oxalic acid and 0.07g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring. The gel system comprises, by mass, 0.5% of polyacrylamide, 0.2% of phenolic aldehyde crosslinking agent, 0.1% of resorcinol, 0.07% of oxalic acid, 0.07% of thiourea and 99.06% of water, and the gel forming time of the gel system is 26.7h at 50 ℃, and the strength of the formed gel is 152372mPa & s.
Example 3
0.3g of polyacrylamide is added to 98.9g of clear water with stirring, and after stirring for 2 hours, the polymer solution is kept stand for 12 hours. Then 0.4g of phenolic crosslinking agent, 0.2g of accelerator (resorcinol and hydroquinone mixture with the mass ratio of 3:1), 0.1g of oxalic acid and 0.1g of thiourea are sequentially added into the polymer solution while stirring, and the gel is uniformly stirred to form a gel solution. The water-plugging gel system comprises, by mass, 0.3% of polyacrylamide, 0.4% of phenolic aldehyde crosslinking agent, 0.2% of resorcinol, 0.1% of oxalic acid, 0.1% of thiourea and 98.9% of water, and the gel-forming time of the water-plugging gel system is 19.5h at 50 ℃, so that the strength of the formed gel is 116471mPa & s.
Example 4
0.4g of polyacrylamide is added into 99.06g of clear water while stirring, and after stirring for 2 hours, the polymer solution is kept stand for 12 hours. Then 0.2g of phenolic crosslinking agent, 0.1g of resorcinol, 0.09g of oxalic acid and 0.15g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring. The gel system comprises, by mass, 0.4% of polyacrylamide, 0.2% of phenolic aldehyde crosslinking agent, 0.1% of resorcinol, 0.09% of oxalic acid, 0.15% of thiourea and 99.06% of water, and the gel forming time of the gel system is 97.2h at 40 ℃, and the strength of the formed gel is 89415mPa & s.
Example 5
0.5g of polyacrylamide is added to 98.93g of clear water with stirring, and after stirring for 2 hours, the polymer solution is allowed to stand for 12 hours. Then 0.3g of phenolic crosslinking agent, 0.1g of resorcinol, 0.07g of oxalic acid and 0.1g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring. The gel system comprises, by mass, 0.5% of polyacrylamide, 0.3% of phenolic aldehyde crosslinking agent, 0.1% of resorcinol, 0.07% of oxalic acid, 0.1% of thiourea and 98.93% of water, and the gel forming time of the gel system is 23.8h at 50 ℃, and the strength of the formed gel is 168573mPa & s.
Example 6
49.59g of clear water, 0.1g of polyacrylamide is added with stirring, and after stirring for 2 hours, the polymer solution is kept stand for 12 hours. Then 0.2g of phenolic crosslinking agent, 0.04g of resorcinol, 0.025g of oxalic acid and 0.045g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring to form a gel solution. The gel system comprises, by mass, 0.2% of polyacrylamide, 0.4% of phenolic crosslinking agent, 0.08% of resorcinol, 0.05% of oxalic acid, 0.09% of thiourea and 99.18% of water, and the gel system has the gel forming time of 106.7h at 50 ℃ and the strength of the formed gel is 85677mPa & s.
Example 7
0.5g of polyacrylamide is added to 98.8g of clear water with stirring, and after stirring for 2 hours, the polymer solution is allowed to stand for 12 hours. Then 0.3g of phenolic crosslinking agent, 0.2g of resorcinol, 0.1g of oxalic acid and 0.1g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring. The gel system comprises, by mass, 0.5% of polyacrylamide, 0.3% of phenolic aldehyde crosslinking agent, 0.2% of resorcinol, 0.1% of oxalic acid, 0.1% of thiourea and 98.8% of water, and the gel forming time of the gel system is 51.6h at 45 ℃ to form the strength of the gel of 146827mPa & s.
Example 8
0.3g of polyacrylamide is added to 99.2g of clear water while stirring, and after stirring for 2 hours, the polymer solution is kept stand for 12 hours. Then 0.3g of phenolic crosslinking agent, 0.08g of resorcinol, 0.07g of oxalic acid and 0.05g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring. The gel system comprises, by mass, 0.3% of polyacrylamide, 0.3% of phenolic aldehyde crosslinking agent, 0.08% of resorcinol, 0.07% of oxalic acid, 0.05% of thiourea and 99.2% of water, and the gel forming time of the gel system is 42.4h at 50 ℃, and the strength of the formed gel is 91365mPa & s.
Example 9
0.4g of polyacrylamide was added to 99.16g of clear water with stirring, and after stirring for 2 hours, the polymer solution was allowed to stand for 12 hours. Then 0.2g of phenolic crosslinking agent, 0.1g of resorcinol, 0.06g of oxalic acid and 0.08g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring. The gel system comprises, by mass, 0.4% of polyacrylamide, 0.2% of phenolic crosslinking agent, 0.1% of resorcinol, 0.06% of oxalic acid, 0.08% of thiourea and 99.16% of water, and the gel forming time of the gel system is 56.2h at 45 ℃, and the strength of the formed gel is 96741mPa & s.
Example 10
0.5g of polyacrylamide is added to 98.8g of clear water with stirring, and after stirring for 2 hours, the polymer solution is allowed to stand for 12 hours. Then 0.4g of phenolic crosslinking agent, 0.1g of resorcinol, 0.1g of oxalic acid and 0.1g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring. The gel system comprises, by mass, 0.5% of polyacrylamide, 0.4% of phenolic aldehyde crosslinking agent, 0.1% of resorcinol, 0.1% of oxalic acid, 0.1% of thiourea and 98.8% of water, and the gel forming time of the gel system is 12.6h at 50 ℃, and the strength of the formed gel is 186415mPa & s.
And (3) evaluating the salt-tolerant stability of the water-plugging gel by adopting a static simulation method:
the experimental process comprises the following steps: taking the degree of mineralization as 2 x 10599.2g of sodium chloride brine in mg/L was added to the formation 0.3g of polyacrylamide with stirring for 2h, and the polymer solution was allowed to stand for 12 h. Then 0.3g of phenolic crosslinking agent, 0.08g of resorcinol, 0.07g of oxalic acid and 0.05g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring. The jelly systemThe plates were placed in an incubator at 50 ℃ and periodically taken out to observe the change in strength and the retention rate was recorded. The formula of conservation rate is eta ═ V2/V1X 100%, wherein, V1Is the glue-forming liquid volume injected, V2The volume of the gelatinized liquid is a value measured at room temperature. The results are shown in Table 1.
TABLE 1 salt resistance stability of Water-plugging jelly according to the invention
For the plugging performance of the organic water plugging jelly, the plugging performance of the artificial core is evaluated by adopting the artificial core to determine the plugging rate of the jelly:
the experimental process comprises the following steps: (1) taking the degree of mineralization as 2 x 10599.2g of sodium chloride brine in mg/L was added to the formation 0.3g of polyacrylamide with stirring for 2h, and the polymer solution was allowed to stand for 12 h. Then 0.3g of phenolic crosslinking agent, 0.08g of resorcinol, 0.07g of oxalic acid and 0.05g of thiourea are sequentially added into the polymer solution while stirring, and the gel is obtained after uniform stirring. (2) Marking two artificial rock cores with the length of 10cm and the inner diameter of 2.5cm as 1# and 2# respectively, and measuring the permeability k before plugging after water is driven to stable pressure0Then reverse injecting 0.3Vp(core pore volume) to form glue solution, and then injecting 0.1VpDisplacing water, sealing the sand filling pipe, placing the sealed sand filling pipe in an electronic constant temperature box at 40 ℃/50 ℃, driving water again until the pressure is stable after the water-blocking jelly becomes gel, and measuring the permeability k after the plugging of the rock core1And according to the formula E ═ k0-k1)/k1And calculating the core plugging rate E, wherein the experimental result is shown in a table 2.
TABLE 2 plugging Properties of the Water plugging jelly of the present invention
| Core | Temperature of experiment | Permeability before plugging | Permeability after plugging | Plugging rate |
| 1# | 40℃ | 832mD | 61mD | 92.7％ |
| 2# | 50℃ | 786mD | 53mD | 93.3％ |
Experimental results show that the jelly provided by the invention has strong plugging performance under the condition of a low-temperature high-salinity oil reservoir, and can effectively plug a stratum high-permeability layer, so that the sweep efficiency is improved, and the effects of oil stabilization and water reduction are achieved.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (10)
1. The organic water plugging gel for the low-temperature hypersalinity oil reservoir is characterized by comprising the following components in parts by weight: the composite material consists of a main agent, a cross-linking agent, an accelerating agent, a regulator, a stabilizer and water, wherein the mass percentages of the substances are as follows:
0.2-0.5% of main agent, and anionic type is selectedPolyacrylamide with a weight average molecular mass of 18X 106-24×106The degree of hydrolysis is 18-23%;
0.2 to 0.4 percent of cross-linking agent, and phenolic resin cross-linking agent is selected, wherein the content of hydroxymethyl is 28.49 to 45.28 percent;
0.05-0.2% of accelerator, and hydroquinone or resorcinol are selected;
0.03-0.1% of regulator, hydrochloric acid or oxalic acid is selected;
0.05 to 0.15 percent of stabilizer, and thiourea is selected;
the balance of water.
2. The organic water plugging gel for the low-temperature hypersalinity oil reservoir according to claim 1, which is characterized in that: the relative molecular mass of anionic polyacrylamide used as the main agent is 2200 × 104-2300×104The degree of hydrolysis was 22.5%.
3. The organic water plugging gel for the low-temperature hypersalinity oil reservoir according to claim 1, which is characterized in that: the organic water shutoff gel consists of 0.2 percent of main agent, 0.3 percent of cross-linking agent, 0.05 percent of accelerating agent, 0.05 percent of regulator, 0.05 percent of stabilizer and 99.35 percent of water.
4. The organic water plugging gel for the low-temperature hypersalinity oil reservoir according to claim 1, which is characterized in that: the organic water shutoff gel consists of 0.5 percent of main agent, 0.2 percent of cross-linking agent, 0.1 percent of accelerating agent, 0.07 percent of regulator, 0.07 percent of stabilizer and 99.06 percent of water.
5. The organic water plugging gel for the low-temperature hypersalinity oil reservoir according to claim 1, which is characterized in that: the organic water shutoff gel consists of 0.3 percent of main agent, 0.4 percent of cross-linking agent, 0.2 percent of accelerating agent, 0.1 percent of regulator, 0.1 percent of stabilizer and 98.90 percent of water.
6. The organic water plugging gel for the low-temperature hypersalinity oil reservoir according to claim 1, which is characterized in that: the organic water shutoff gel consists of 0.4 percent of main agent, 0.2 percent of cross-linking agent, 0.1 percent of accelerating agent, 0.09 percent of regulator, 0.15 percent of stabilizer and 99.06 percent of water.
7. The organic water plugging gel for the low-temperature hypersalinity oil reservoir according to claim 1, which is characterized in that: the organic water-plugging jelly is composed of 0.5% of main agent, 0.3% of cross-linking agent, 0.1% of accelerating agent, 0.07% of regulator, 0.1% of stabilizer and 98.93% of water.
8. The organic water plugging gel for the low-temperature hypersalinity oil reservoir according to claim 1, which is characterized in that: the organic water-plugging jelly is composed of 0.2% of main agent, 0.4% of cross-linking agent, 0.08% of accelerating agent, 0.05% of regulator, 0.09% of stabilizer and 99.18% of water.
9. The organic water plugging gel for the low-temperature hypersalinity oil reservoir according to claim 1, which is characterized in that: the organic water shutoff gel consists of 0.5 percent of main agent, 0.3 percent of cross-linking agent, 0.2 percent of accelerating agent, 0.1 percent of regulator, 0.1 percent of stabilizer and 98.80 percent of water.
10. The application of the organic water plugging gel for the low-temperature hypersalinity oil reservoir according to any one of claims 1 to 9 in water plugging of the oil reservoir, which is characterized in that: the gelling liquid viscosity of the organic water-plugging gel is 120-200000 mPa & s, the organic water-plugging gel is suitable for water-plugging profile control of an oil layer at the temperature of 40-50 ℃, the gelling time is 5-122h, and the strength of the formed gel is 30000-200000mPa & s.
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| CN115819910A (en) * | 2022-12-01 | 2023-03-21 | 中国石油大学(华东) | Solid-free gel composition, solid-free gel system, preparation method and application thereof |
| CN115819910B (en) * | 2022-12-01 | 2023-08-11 | 中国石油大学(华东) | Solid-free gel composition, solid-free gel system, preparation method and application thereof |
| CN116285921A (en) * | 2023-03-07 | 2023-06-23 | 郭伟 | Chemical plugging composition for offshore oil field and preparation method and application thereof |
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Application publication date: 20210720 |