CN116218497A - Gel profile control composition, gel profile control agent and application thereof - Google Patents
Gel profile control composition, gel profile control agent and application thereof Download PDFInfo
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- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 description 2
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/516—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls characterised by their form or by the form of their components, e.g. encapsulated material
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/50—Compositions for plastering borehole walls, i.e. compositions for temporary consolidation of borehole walls
- C09K8/504—Compositions based on water or polar solvents
- C09K8/506—Compositions based on water or polar solvents containing organic compounds
- C09K8/508—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/512—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/84—Compositions based on water or polar solvents
- C09K8/86—Compositions based on water or polar solvents containing organic compounds
- C09K8/88—Compositions based on water or polar solvents containing organic compounds macromolecular compounds
- C09K8/887—Compositions based on water or polar solvents containing organic compounds macromolecular compounds containing cross-linking agents
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
- C09K8/60—Compositions for stimulating production by acting on the underground formation
- C09K8/92—Compositions for stimulating production by acting on the underground formation characterised by their form or by the form of their components, e.g. encapsulated material
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B33/00—Sealing or packing boreholes or wells
- E21B33/10—Sealing or packing boreholes or wells in the borehole
- E21B33/13—Methods or devices for cementing, for plugging holes, crevices or the like
- E21B33/138—Plastering the borehole wall; Injecting into the formation
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Abstract
The invention relates to a gel profile control composition, a gel profile control agent and application thereof, and belongs to the technical field of profile control agents. The gel profile control composition comprises partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the cross-linking agent A is selected from one or any combination of 2-hydroxymethyl phenol, 3-hydroxymethyl phenol and 4-hydroxymethyl phenol; the cross-linking agent B consists of citric acid and oxalic acid; the mass ratio of the citric acid to the oxalic acid is 1 (0.3-3). The gel profile control composition is suitable for high-salt, high-hardness CaCl 2 The profile control system for reinjection sewage has good performanceThe gel-forming material has higher breakthrough pressure and plugging rate and better long-term heat stability.
Description
Technical Field
The invention relates to a gel profile control composition, a gel profile control agent and application thereof, and belongs to the technical field of profile control agents.
Background
The profile control technology ensures and improves the field application effect of chemical flooding, and becomes an important matching technology for improving the development effect of chemical flooding. The effect of the medicine is as follows: firstly, longitudinal and plane heterogeneity caused by long-term water injection scouring is relieved, and integral profile control is needed before chemical flooding; secondly, polymer channeling seriously affects the polymer oil displacement effect in the chemical flooding process, and profile control and channeling sealing are needed; thirdly, the polymer slug is easy to be broken through rapidly by the subsequent water drive, and the whole depth profile control should be performed in time when the polymer slug is injected.
At present, most of crosslinking agents adopted in the mature polyacrylamide gel profile control system in China are chromium crosslinking agents, are suitable for I-type low-temperature (30-60 ℃) oil reservoirs, and are mainly suitable for low-salt and low-hardness oil reservoirs and NaHCO 3 And (5) oil reservoirs with type water quality. However, the profile control system is not suitable for high-salinity and hypersalinited oil reservoirs, and is used for CaCl 2 When the oil reservoir with water quality is used, the oil reservoir cannot be glued and plays a role in profile control and channeling sealing.
Disclosure of Invention
The invention aims to provide a CaCl-suitable catalyst 2 Gel profile control composition for water quality oil reservoirs.
The second object of the invention is to provide a gel profile control agent.
The third object of the invention is to provide an application of the gel profile control agent in oil and gas reservoir exploitation.
In order to achieve the above purpose, the profile control composition of the present invention adopts the following technical scheme:
a gel profile control composition comprising partially hydrolyzed polyacrylamide, a cross-linking agent a, and a cross-linking agent B; the cross-linking agent A is selected from one or any combination of 2-hydroxymethyl phenol, 3-hydroxymethyl phenol and 4-hydroxymethyl phenol; the cross-linking agent B consists of citric acid and oxalic acid; the mass ratio of the citric acid to the oxalic acid is 1 (0.3-3).
The gel profile control composition is suitable for high-salt, high-hardness CaCl 2 The profile control system for reinjection sewage has good gel forming performance, and the gel forming material has higher breakthrough pressure and plugging rate and has better long-term thermal stability.
Preferably, the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is (1-2): 0.5-2.5. The proportion of the crosslinking agent A and the crosslinking agent B is within the above range, and effective gelling can be ensured. If the amount of the cross-linking agent A is too large (or the mass ratio of the cross-linking agent A to the cross-linking agent B is too large), the elasticity of the colloid-forming system is too high, and the colloid-forming system is easy to break. Too little amount of crosslinking agent A (or too small a mass ratio of crosslinking agent A to crosslinking agent B) may result in too low or even no gel strength. Too much amount of the cross-linking agent B (or too small mass ratio of the cross-linking agent A to the cross-linking agent B) can cause too slow gelling speed, and the cross-linking system cannot effectively gel in an oil reservoir and cannot play a role in profile control. Too little cross-linking agent B (or too large mass ratio of cross-linking agent A to cross-linking agent B) can cause too high gelling speed, the cross-linking system is blocked in a near wellbore zone, can not be transported to the deep part of an oil reservoir, and can not play a role in deep profile control.
Preferably, the molecular weight of the partially hydrolyzed polyacrylamide is not less than 1900 ten thousand. Because the gel profile control composition is suitable for oil reservoirs with lower temperature, the partially hydrolyzed polyacrylamide with lower molecular weight can meet the requirement, and in order to save the cost, the molecular weight of the partially hydrolyzed polyacrylamide is more preferably 1900-3500 ten thousand. For example, the molecular weight of the partially hydrolyzed polyacrylamide is 2288.7 ten thousand.
Preferably, the degree of hydrolysis of the partially hydrolyzed polyacrylamide is no greater than 42%. Further preferably, the degree of hydrolysis of the partially hydrolyzed polyacrylamide is 12 to 25%. For example, the degree of hydrolysis of the partially hydrolyzed polyacrylamide is 18.2%. The polymer has small viscosity due to the too small hydrolysis degree of the partially hydrolyzed polyacrylamide, and the adhesiveness is easy to be low; the degree of hydrolysis is too high, so that carboxylate ions in the partially hydrolyzed polyacrylamide are easy to react with divalent metal ions to generate precipitation, and the tackifying effect is not achieved.
The gel profile control agent adopts the following technical scheme:
the gel profile control agent mainly comprises water, a cross-linking agent A and a cross-linking agent B, wherein the cross-linking agent A is selected from one or any combination of 2-hydroxymethyl phenol, 3-hydroxymethyl phenol and 4-hydroxymethyl phenol, the cross-linking agent B comprises citric acid and oxalic acid, and the mass ratio of the citric acid to the oxalic acid is 1 (0.3-3); in the gel profile control agent, the concentration of the partially hydrolyzed polyacrylamide is more than or equal to 1000mg/L, the concentration of the cross-linking agent A is more than or equal to 1000mg/L, and the concentration of the cross-linking agent B is more than or equal to 500mg/L.
The gel profile control agent has good injectability, adjustable gel forming time, 100 percent of plugging efficiency, 6.06MPa/m of breakthrough pressure gradient and direct preparation and use of reinjection sewage with the mineralization degree of 90000mg/L and the calcium ion content of 6000mg/L. In the cross-linking agent B, the mass ratio of citric acid to oxalic acid is too small, so that the strength of a gel network structure is weaker, and the non-tackiness is easy to reduce. Too large a mass ratio of citric acid to oxalic acid can result in a jelly network structure that is too strong, easily resulting in a jelly that is too brittle, resulting in dehydration and failure to form a continuous gel dispersion.
It can be understood that when the gel profile control agent is used, water, partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B can be directly mixed into a whole for use, and also a part of water and the cross-linking agent A, a part of water and the cross-linking agent B can be prepared into a mixed solution for storage for standby.
Preferably, in the gel profile control agent, the molecular weight of the partially hydrolyzed polyacrylamide is not less than 1900 ten thousand. Further preferably, in the gel profile control agent, the molecular weight of the partially hydrolyzed polyacrylamide is 1800 to 3500 ten thousand. For example, in a gel profile control agent, the molecular weight of the partially hydrolyzed polyacrylamide is 2288.7 ten thousand.
Preferably, in the gel profile control agent, the degree of hydrolysis of the partially hydrolyzed polyacrylamide is not greater than 42%. Preferably, in the gel profile control agent, the degree of hydrolysis of the partially hydrolyzed polyacrylamide is 12-25%. For example, in a gel profile control agent, the degree of hydrolysis of the partially hydrolyzed polyacrylamide is 18.2%.
It will be appreciated that in general, the greater the mass to volume concentration of the partially hydrolyzed polyacrylamide, the more readily the gel profile control agent will gel, but in order to avoid excessive cost due to excessive mass to volume concentration of the partially hydrolyzed polyacrylamide, preferably the concentration of the partially hydrolyzed polyacrylamide in the gel profile control agent is from 1000 to 2000mg/L.
In general, the larger the mass-volume concentration of the crosslinking agent a, the more easily the gel profile control agent is gelled, but in order to avoid excessive cost due to the excessive mass-volume concentration of the crosslinking agent a, the concentration of the crosslinking agent a in the gel profile control agent is preferably 1000 to 2000mg/L.
In general, the greater the mass-volume concentration of the crosslinking agent B, the more easily the gel profile control agent is gelled, but in order to avoid excessive costs due to the excessive mass-volume concentration of the crosslinking agent B, the concentration of the crosslinking agent B in the gel profile control agent is preferably 500 to 2500mg/L.
Preferably, in the gel profile control agent, the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is (1-2): 0.5-2.5.
Preferably, the concentration of calcium ions in the gel profile control agent is not more than 6000mg/L.
The gel profile control agent is applied to oil and gas reservoir exploitation, and adopts the following technical scheme:
an application of the gel profile control agent in oil and gas reservoir exploitation.
The gel profile control agent provided by the invention is used in oil and gas reservoir exploitation, has good gel forming performance, has higher breakthrough pressure gradient after gel forming, and can effectively realize profile control and channeling sealing of high-salinity and high-mineralization oil reservoirs.
Preferably, the temperature of the reservoir is below 70 ℃. Further preferably, the temperature of the reservoir is 42-45 ℃.
Preferably, the mineralization degree of the oil and gas reservoir is not more than 120000mg/L, and the calcium ion content is not more than 6000mg/L.
Preferably, the application comprises the steps of: injecting the gel profile control agent into an oil and gas reservoir, and waiting for solidification.
Preferably, the waiting time is not less than 7d.
Drawings
FIG. 1 is a graph showing injection pressure versus injection pore volume ratio of the gel profile control agent of example 12 in Experimental example 5.
Detailed Description
The technical scheme of the invention is further described below with reference to specific embodiments.
The gel profile control compositions of examples 1-10 and the gel profile control agents of examples 11-22 and the partially hydrolyzed polyacrylamides of experimental examples 1-4 have a molecular weight of 2288.7 ten thousand, a degree of hydrolysis of 18.2%, a crosslinker a is 2-hydroxymethylphenol, and a crosslinker B consists of citric acid and oxalic acid in a mass ratio of 1:3.
1. Specific examples of gel profile control compositions of the present invention are as follows:
example 1
The gel profile control composition of the embodiment consists of partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is 1:1:0.5.
Example 2
The gel profile control composition of the embodiment consists of partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is 1:1:2.
Example 3
The gel profile control composition of the embodiment consists of partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is 1:1.5:0.5.
Example 4
The gel profile control composition of the embodiment consists of partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is 1:1.5:2.
Example 5
The gel profile control composition of the embodiment consists of partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is 2:1:0.5.
Example 6
The gel profile control composition of the embodiment consists of partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is 2:1:2.
Example 7
The gel profile control composition of the embodiment consists of partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is 2:1.5:0.5.
Example 8
The gel profile control composition of the embodiment consists of partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is 2:1.5:2.
Example 9
The gel profile control composition of the embodiment consists of partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is 1.5:1.2:1.
Example 10
The gel profile control composition of the embodiment consists of partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is 1.2:1.3:1.5.
2. Specific examples of gel profile control agents of the present invention are as follows:
the gel profile control agents of examples 11-22 consisted of injected wastewater (mineralization 90000mg/L, calcium ion content 4000 mg/L) and the following mass volume concentrations: partially hydrolyzed polyacrylamide x mg/L, crosslinker Ay mg/L and crosslinker B z mg/L.
TABLE 1 concentration of partially hydrolyzed Polyacrylamide, crosslinker A and crosslinker B in gel profile control compositions of examples 11-22
3. Specific examples of applications of the gel profile control agent of the present invention in oil and gas reservoir exploitation are as follows:
injecting the gel profile control agent of any one of examples 11-22 into an oil reservoir with a temperature of 42-45 ℃ for candidate solidification; .
Experimental example 1
In order to examine the gel formation condition of the existing chromium crosslinking profile control agent system in high-salinity and hypersaline oil reservoirs, partially hydrolyzed polyacrylamide with different molecular weights and degrees of hydrolysis, a chromium crosslinking agent (an organic chromium crosslinking agent with the model of JL-I manufactured by Henan oil field application chemical plants) and reinjection sewage (the mineralization degree is 90000mg/L and the calcium ion content is 4000 mg/L) are prepared into a gel profile control agent (the concentration of the partially hydrolyzed polyacrylamide is 1500mg/L and the concentration of the chromium crosslinking agent is 300 mg/L), then the gel is cured for 7 days at 42 ℃, and the gel formation properties of the chromium crosslinking profile control agent system at different curing times are measured to evaluate. In the experimental example, the viscosity is measured by a Brookfield viscometer, and a No. 2 rotor is adopted in the test, and the rotating speed is 6r/min. The experimental results are shown in table 2.
TABLE 2 gel Properties of chromium crosslinked Profile control agent systems
The results show that the adoption ofWhen the chromium cross-linking agent and the partially hydrolyzed polyacrylamide are compounded and used, when the molecular weight of the partially hydrolyzed polyacrylamide is 1900 multiplied by 10 4 ～3382×10 4 In the range of (2), the adhesiveness of the gel profile control agent in 7d is greatly increased and then rapidly decreased, which indicates that the gel profile control agent prepared from the partially hydrolyzed polyacrylamide and the chromium crosslinking agent cannot play a good role in profile control.
Experimental example 2
In order to examine the influence of the concentrations of the partially hydrolyzed polyacrylamide, the cross-linking agent A and the cross-linking agent B on the gel forming performance of the gel profile control agent, the injected sewage (the mineralization degree is 90000mg/L, the calcium ion content is 4000 mg/L), the partially hydrolyzed polyacrylamide, the cross-linking agent A and the cross-linking agent B are prepared into the gel profile control agent, the mass volume concentrations of the partially Hydrolyzed Polyacrylamide (HPAM), the cross-linking agent A and the cross-linking agent B are controlled to prepare the gel profile control agent containing the partially Hydrolyzed Polyacrylamide (HPAM) with different concentrations, the cross-linking agent A and the cross-linking agent B, wherein the mass volume concentration of the partially hydrolyzed polyacrylamide is 500-2000 mg/L, the mass volume concentration of the cross-linking agent A is 500-2000 mg/L, the mass volume concentration of the cross-linking agent B is 0-2500 mg/L, and then the gel profile control agent with different proportions is subjected to 30d waiting for gel formation at the temperature of 42 ℃ to evaluate the influence of the mass concentrations of each component on the gel forming performance of the gel profile control agent. In the experimental example, the viscosity is measured by a Brookfield viscometer, and a No. 2 rotor is adopted in the test, and the rotating speed is 6r/min. The experimental results are shown in tables 3-6.
TABLE 3 influence of the concentration of Cross-linking agent A and Cross-linking agent B on the gel Forming Properties of the gel Profile control agent at 2000mg/L of HPAM
TABLE 4 influence of the concentration of Cross-linking agent A and Cross-linking agent B on the gel Forming Properties of the gel Profile control agent at 1500mg/L of HPAM
TABLE 5 influence of the concentration of Cross-linking agent A and Cross-linking agent B on the gel Forming Properties of the gel Profile control agent at 1000mg/L of HPAM
TABLE 6 influence of the concentration of Cross-linking agent A and Cross-linking agent B on the gel Forming Properties of the gel Profile control agent at 500mg/L of HPAM
The result shows that when the concentration of HPAM in the gel profile control agent is less than 1000mg/L, the concentration of the cross-linking agent A is 500-2000 mg/L, the concentration of the cross-linking agent B is 500-2500 mg/L, and after the gel profile control agent is cured for 7d at 42 ℃, the profile control agent is not glued or the glue forming system is not stable enough in strength and not big enough in glue forming strength; when the concentration of HPAM in the gel profile control agent is more than or equal to 1000mg/L, the concentration of the cross-linking agent A is 1000-2000 mg/L, the cross-linking agent B is 500-2500 mg/L, the viscosity of the profile control agent is larger than the initial viscosity after 3-5 d of waiting for coagulation, the cross-linking reaction of the profile control agent is shown, after 7d of waiting for coagulation, the gel is obviously gelled, the gel forming viscosity is 100 times higher than the initial viscosity (0 d), and most of high-concentration formula viscosity even reaches 5000 mPa.s.
Therefore, the critical gel forming concentration exists in the compound use of the cross-linking agent A and the cross-linking agent B, and the gel forming critical range of the gel profile control agent is as follows: HPAM concentration is more than or equal to 1000mg/L, cross-linking agent A concentration is 1000-2000 mg/L, and cross-linking agent B concentration is 500-2500 mg/L.
Therefore, during the application process of the mine field, the formulation of the gel profile control agent can be adjusted according to the conditions of oil layer permeability, injection pressure level, polymer crossflow degree and the like, but the concentration of HPAM, cross-linking agent A and cross-linking agent B needs to be controlled within the critical range of gel formation.
When the concentration of the partially hydrolyzed polyacrylamide, the crosslinking agent A and the crosslinking agent B is examined to influence the gel forming performance of the gel profile control agent according to the method when the crosslinking agent A is replaced by the 2-hydroxymethyl phenol and the 3-hydroxymethyl phenol and the 4-hydroxymethyl phenol, the obtained conclusion is consistent with the conclusion when the crosslinking agent A is the 2-hydroxymethyl phenol.
When the mass ratio of the citric acid to the oxalic acid in the cross-linking agent B is adjusted to be 1:0.3 and 1:2 from 1:3, the influence of the concentrations of the partially hydrolyzed polyacrylamide, the cross-linking agent A and the cross-linking agent B on the gel forming performance of the gel profile control agent is examined according to the method, and the obtained conclusion is consistent with the conclusion when the mass ratio of the citric acid to the oxalic acid in the cross-linking agent B is 1:3.
Experimental example 3
In order to verify the influence of other acidic compounds on the gel forming performance of the gel profile control agent, the gel profile control agent is prepared from injection sewage (the mineralization degree is 90000mg/L, the calcium ion content is 4000 mg/L), partially hydrolyzed polyacrylamide, a cross-linking agent A (2-hydroxymethyl phenol) and the acidic compound, wherein the mass volume concentration of the partially hydrolyzed polyacrylamide is 1500-2000 mg/L, the mass volume concentration of the cross-linking agent A is 1000-1500 mg/L, the mass volume concentration of the acidic compound is 1000-1500 mg/L, then the gel profile control agents with different proportions are subjected to weather coagulation for 30d under the temperature condition of 42 ℃, and the gel forming performances of the gel profile control agents are evaluated by measuring the gel forming viscosity at different weather coagulation times. In the experimental example, the viscosity is measured by a Brookfield viscometer, and a No. 2 rotor is adopted in the test, and the rotating speed is 6r/min. The experimental results are shown in table 7.
TABLE 7 influence of different acidic Compounds on gel Profile control agent gel Forming Properties
The results show that the gel profile control agent prepared by using the partially hydrolyzed polyacrylamide, the cross-linking agent A (2-hydroxymethyl phenol) and the acidic compound (citric acid, tartaric acid, butyric acid, oxalic acid and nonylmalonic acid) can be coagulated for 30d at the temperature of 42 ℃, and the viscosity is not obviously increased, so that the gel cannot be effectively formed.
Experimental example 4
In order to verify the influence of other phenolic compounds on the gelling performance of the gel profile control agent, the injected sewage (mineralization degree is 90000mg/L, calcium ion content is 4000 mg/L), partially hydrolyzed polyacrylamide, phenolic compounds and a crosslinking agent B (consisting of citric acid and oxalic acid in a mass ratio of 1:3) are prepared into the gel profile control agent, wherein the mass volume concentration of the partially hydrolyzed polyacrylamide is 1500mg/L, the mass volume concentration of the phenolic compounds is 1500mg/L, the mass volume concentration of the crosslinking agent B is 1500mg/L, then each gel profile control agent is subjected to waiting 30d at a temperature of 42 ℃, and the gelling degree at different waiting times is measured to evaluate the gelling performance of each gel profile control agent. In the experimental example, the viscosity is measured by a Brookfield viscometer, and a No. 2 rotor is adopted in the test, and the rotating speed is 6r/min. The experimental results are shown in table 8.
TABLE 8 influence of different phenolic Compounds on gel Profile control agent gel Forming Properties
The results show that the gel profile control agent prepared from the partially hydrolyzed polyacrylamide, phenolic compounds (phenol, hydroquinone, resorcinol, catechol and phenolic resin) and the crosslinking agent B can be cured for 30d at the temperature of 42 ℃, the viscosity is not obviously increased, and the gel cannot be effectively formed.
Experimental example 5
Good injection performance and gel forming performance are key to ensuring the success of the gel profile control agent field test. The injectability of the gel profile control agent can be represented by the characteristic of a change curve of injection pressure along with the pore volume multiple of the core; if the injection pressure rises and changes steadily, the gel profile control agent has good injectability; if the injection pressure is rapidly increased and is difficult to stabilize, the gel profile control agent has poor injectability. Therefore, the injectability of the gel profile control agent can be analyzed according to the injection pressure gradient change characteristics of the gel profile control agent, and the underground gel forming performance of the profile control agent can be analyzed and evaluated according to the injection pressure change, the breakthrough pressure gradient and the core plugging efficiency of the injected gel profile control agent.
In order to further evaluate the injectability, the underground gel forming performance and the plugging efficiency of the gel profile control agent, the permeability is selected to be 1500 multiplied by 10 -3 ～2000×10 -3 μm 2 And (3) performing a plugging experiment on the core. The experimental method is as follows: the high permeability well section of the main oil reservoir of the simulated target oil reservoir polymer flooding is selected from a medium-high permeability core (K=1500x10) with the diameter of 2.5cm and the length of 8-10 cm -3 ～2000×10 -3 μm 2 ) Initial aqueous phase permeability K was measured with simulated wastewater (mineralization degree 120000mg/L, hardness 6000 mg/L) wb The method comprises the steps of carrying out a first treatment on the surface of the Injecting gel profile control agent with a volume of more than 6 times of pore volume at a flow rate of 30mL/h (which is equivalent to the underground Darcy seepage velocity of 1.5 m/d), and monitoring injection pressure in the injection process of the gel profile control agent at regular time; waiting for the gel profile control agent to solidify in the rock core for 7-30 d at 42 ℃ (simulating the temperature of the oil layer); then, cleaning gel on the inlet end face of the core (scraping, grinding and water flushing), carrying out subsequent water flooding (the volume of water is 5 times of the pore volume) at the same flow rate (30 mL/h), monitoring the injection pressure of the subsequent water flooding at fixed time, and measuring the water phase permeability K after profile control after the injection pressure and the flow rate are stable wa The method comprises the steps of carrying out a first treatment on the surface of the Drawing a relation curve of injection pressure or pressure gradient and injection pore volume multiple, and calculating the plugging efficiency of the gel profile control agent after gel formation: ηk (%) = (K) wb -K wa )/K wa ×100。
The relation curve of the injection pressure and the injection pore volume multiple of the gel profile control agent of example 12 is shown in fig. 1, the breakthrough pressure gradient obtained by the test after the gel profile control agent of example 12 plugs the rock core is 6.06MPa/m, and the plugging efficiency is 100%; the gel profile control agents of examples 11 and 13-22 have a breakthrough pressure gradient of 6-10 MPa/m after plugging the core, and the plugging efficiency is 100%.
The results show that the gel profile control agent of example 12 has better injectability as shown in the injection pressure change curve of fig. 1, the injection pressure tends to be stable after 2PV is injected into the core, 6PV is accumulated, and the injection pressure is relatively stable. After the gel profile control agent is gelled in the core, the injection pressure of the subsequent water flooding continuously rises, which indicates that the gel profile control agent completes the gelling in the porous medium, the plugging efficiency is close to 100%, the breakthrough pressure gradient is 6.06MPa/m, and indicates that the gel profile control agent of the embodiment 12 effectively plugs the core. The gel profile control agents of examples 11, 13-22 also effectively block the core.
Experimental example 6
When deionized water, partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B are adopted to prepare the gel profile control agent, when the concentration of the partially hydrolyzed polyacrylamide is 1000-2000 mg/L, the concentration of the cross-linking agent A is 1000-1500 mg/L and the concentration of the cross-linking agent B is 500-2000 mg/L, the gel profile control agent can be effectively gelled after waiting for 7-30 d at 42 ℃. The concentration of the partially hydrolyzed polyacrylamide is 1500mg/L, the concentration of the crosslinking agent A is 1500mg/L, the concentration of the crosslinking agent B is 1500mg/L, and the viscosity after 7d of the weather is 15000 mPa.s.
Claims (10)
1. A gel profile control composition, which is characterized by comprising partially hydrolyzed polyacrylamide, a cross-linking agent A and a cross-linking agent B; the cross-linking agent A is selected from one or any combination of 2-hydroxymethyl phenol, 3-hydroxymethyl phenol and 4-hydroxymethyl phenol; the cross-linking agent B consists of citric acid and oxalic acid; the mass ratio of the citric acid to the oxalic acid is 1 (0.3-3).
2. The gel profile control composition according to claim 1, wherein the mass ratio of the partially hydrolyzed polyacrylamide, the cross-linking agent A and the cross-linking agent B is (1-2): 0.5-2.5.
3. The gel profile control composition according to claim 1 or 2, wherein the molecular weight of the partially hydrolyzed polyacrylamide is not less than 1900 ten thousand.
4. The gel profile control composition of claim 1 or 2, wherein the partially hydrolyzed polyacrylamide has a degree of hydrolysis of no greater than 42%.
5. The gel profile control agent is characterized by mainly comprising water, a cross-linking agent A and a cross-linking agent B, wherein the cross-linking agent A is selected from one or any combination of 2-hydroxymethyl phenol, 3-hydroxymethyl phenol and 4-hydroxymethyl phenol, the cross-linking agent B is composed of citric acid and oxalic acid, and the mass ratio of the citric acid to the oxalic acid is 1 (0.3-3); in the gel profile control agent, the concentration of the partially hydrolyzed polyacrylamide is more than or equal to 1000mg/L, the concentration of the cross-linking agent A is more than or equal to 1000mg/L, and the concentration of the cross-linking agent B is more than or equal to 500mg/L.
6. The gel profile control agent according to claim 5, wherein the molecular weight of the partially hydrolyzed polyacrylamide is not less than 1900 tens of thousands; the degree of hydrolysis of the partially hydrolyzed polyacrylamide is not greater than 42%.
7. The gel profile control agent according to claim 5, wherein the mass ratio of the partially hydrolyzed polyacrylamide to the cross-linking agent A to the cross-linking agent B is (1-2): 0.5-2.5.
8. The gel profile control agent according to claim 5, wherein in the gel profile control agent, the concentration of the partially hydrolyzed polyacrylamide is 1000 to 2000mg/L; the concentration of the cross-linking agent A is 1000-2000 mg/L; the concentration of the cross-linking agent B is 500-2500 mg/L.
9. The gel profile control agent of any one of claims 5-8, wherein the concentration of calcium ions in the gel profile control agent is no greater than 6000mg/L.
10. Use of a gel profile control agent according to any one of claims 5-9 in oil and gas reservoir production.
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