CN101864286A - Mother liquor of oil displacement agent and preparation method thereof - Google Patents
Mother liquor of oil displacement agent and preparation method thereof Download PDFInfo
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- CN101864286A CN101864286A CN201010192373A CN201010192373A CN101864286A CN 101864286 A CN101864286 A CN 101864286A CN 201010192373 A CN201010192373 A CN 201010192373A CN 201010192373 A CN201010192373 A CN 201010192373A CN 101864286 A CN101864286 A CN 101864286A
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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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/584—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific surfactants
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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
- C09K8/58—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids
- C09K8/588—Compositions for enhanced recovery methods for obtaining hydrocarbons, i.e. for improving the mobility of the oil, e.g. displacing fluids characterised by the use of specific polymers
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- Oil, Petroleum & Natural Gas (AREA)
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Abstract
The invention discloses a mother liquor of an oil displacement agent and a preparation method thereof. The mother liquor of the oil displacement agent consists of a non-ionic surfactant, polyacrylamide and Suizhong 36-1 oil field water. In the mother liquor of the oil displacement agent, the non-ionic surfactant C18E10 and the polyacrylamide AP-P4 interact with each other so that the dissolution of the AP-P4 in high-mineralization oil field in-situ water can be quickened. Compared with the AP-P4 solution at the same concentration, the mother liquor of the oil displacement agent has the advantages that: the dissolving time of the AP-P4 is shortened; and the solution is more uniform.
Description
Technical field
The invention belongs to field of new, relate to a kind of mother liquor of oil displacement agent and preparation method thereof.
Background technology
After hydrophobic association polyacrylamide is meant and introduces a spot of hydrophobic grouping in water miscible acrylamide polymer, a class polyacrylamide derivative that still can be water-soluble.When hydrophobic association polyacrylamide is water-soluble, because of the extreme uncompatibility of hydrophobic grouping and water, assemble between hydrophobic grouping, form hydrophobic microcell.This microphase-separated characteristic that hydrophobic association polyacrylamide has makes it form physical cross-linked network in the aqueous solution, presents and remarkable different structure and the performances of conventional water-soluble polyacrylamide.At present, hydrophobic association polyacrylamide AP-P4 has entered suitability for industrialized production, and the hydrophobic association polyacrylamide technology of reservoir sweep has become offshore oilfield and increased substantially important gordian technique in the recovery efficiency technique.Simultaneously, because the existence of hydrophobic side group in the oil-displacing agent, make AP-P4 relatively poor in highly concentrated solution preparation link solvability with excellent properties, and then influenced the homogeneity of oil-displacing agent target solution, become the bottleneck of offshore oilfield technique of polymer flooding large-scale application, thereby be necessary the instant prescription of high density AP-P4 is studied.Laboratory experiment confirms the swelling of AP-P4 and is dissolved with obvious limit.AP-P4 dry powder dissolved key is to quicken the molecular diffusion motion of AP-P4 molecule in aqueous solvent in the swelling micelle.
Summary of the invention
The purpose of this invention is to provide a kind of mother liquor of oil displacement agent and preparation method thereof.
Mother liquor of oil displacement agent provided by the invention is made up of nonionogenic tenside, polyacrylamide and Suizhong 36-1 oil-field water.
In this mother liquor of oil displacement agent, described nonionogenic tenside is a polyoxyethylene octadecanol ether-10, and its structural formula is suc as formula shown in the I, and chemical formula is C
18H
37O (CH
2CH
2O)
10H also is C
18E
10
(formula I)
This non-ionic surfactant compound is available from Belgian ACROS Organics company, by the lark waffle agency of company limited that learns a skill.The viscosity-average molecular weight of described polyacrylamide is 1,200 ten thousand.Described polyacrylamide is preferably the polyacrylamide that is numbered AP-P4, and available from Sichuan light subfamily skill limited-liability company, solid content is 91.22%.Described Suizhong 36-1 oil-field water is preferably 36-1 oil field, Suizhong Simulated Water, and 36-1 oil field, described Suizhong Simulated Water is by water, Na
+, K
+, Ca
2+, Mg
2+, HCO
3 -, CO
3 2-, SO
4 2-And Cl
-Form described Na
+And K
+The concentration sum be 3091.96mg/L, described Ca
2+Concentration be 276.17mg/L, described Mg
2+Concentration be 158.68mg/L, described HCO
3 -Concentration be 311.48mg/L, described CO
3 2-Concentration be 14.21mg/L, described SO
4 2-Concentration be 85.29mg/L, described Cl
-Concentration be 5436.34mg/L.The concentration of described nonionogenic tenside in described mother liquor of oil displacement agent is 14.3～71.4mg/L, is specially 14.3-42.8mg/L or 42.8～71.4mg/L, preferred 42.8～71.4mg/L.The concentration of described polyacrylamide in described mother liquor of oil displacement agent is 4928.6～4985.7mg/L, is specially 4928.6-4957.2mg/L or 4957.2～4985.7mg/L, preferred 4928.6～4957.2mg/L.Described nonionogenic tenside and the total concn of described polyacrylamide in described mother liquor of oil displacement agent are 5000mg/L.
The method of the above-mentioned mother liquor of oil displacement agent of preparation provided by the invention comprises the steps: earlier described nonionogenic tenside to be mixed with described Suizhong 36-1 oil-field water, adds described polyacrylamide behind the mixing again, obtains described mother liquor of oil displacement agent behind the mixing.
In the mixing step of this method, temperature is 45 ± 0.5 ℃, and the method for mixing is a stirring and evenly mixing.In the described stirring and evenly mixing step, rotating speed is 400 ± 5r/min, and rotation radius is 35mm.
In order further to improve the effect of hydrophobic association polyacrylamide AP-P4 flooding system, the invention provides a kind of high density AP-P4 dissolved mother liquor of oil displacement agent of quickening 5000mg/L and preparation method thereof that is used to.This method adds an amount of nonionogenic tenside C in solution
18E
10The less tensio-active agent of these molecular weight is diffused in the solution rapidly, the spontaneous solubilising of its hydrophobic part is in the hydrophobic microcell of swelling micelle, and hydrophilic head base wraps up hydrophobic microcell and be dispersed in the water, thereby water molecules is penetrated into around the hydrophilic radical of polymkeric substance.Hydrophilic radical generation solvation effect, the molecular chain conformation changes extended configuration into from rolling up, and drives the hydrophobic grouping that is distributed on the molecular chain and breaks away from original hydrophobic microcell, forms new hydrophobic microcell with the hydrophobic grouping that closes on every side.The stretching, extension of the formation of hydrophobic microcell and molecular chain forms a running balance in the solution, and moves towards entropy increase direction.Therefore the average hydrophobic grouping quantity of forming hydrophobic microcell reduces gradually, but the hydrophobic microcell total amount in the solution is in continuous increase, and soltion viscosity increases gradually.In the mother liquor of oil displacement agent provided by the invention, nonionogenic tenside C
18E
10Interact with AP-P4, shortened the dissolution time of AP-P4, solution is more even.Method provided by the invention adds nonionic surface active agent when compounding high concentration AP-P4 solution, polymer dissolution is significantly improved, and dissolution time sharply shortens, and has good application prospects.
Description of drawings
Fig. 1 is the resistates quality per-cent of mother liquor of oil displacement agent ML1, ML2, ML3 and blank solution MBL and the relation curve of dissolution time.
Embodiment
The method for preparing mother liquor of oil displacement agent provided by the invention specifically comprises the steps:
(1) in the 5000mL beaker, takes by weighing non-ionic surfactant polyoxyethylene stearyl alcohol ether-10 shown in 0.0143～0.0714g formula I, compare experiment with the system of not adding nonionogenic tenside as blank, beaker is placed 45 ± 0.5 ℃ of waters bath with thermostatic control, fixing stirring rod, in beaker, add 1000mL Suizhong 36-1 oil field Simulated Water (condition of water quality sees Table 1), and adjust agitator speed to 400 ± 5r/min, constant temperature stirs 10 minutes to even;
Table 1,36-1 oil field, Suizhong Simulated Water water quality
(2) accurately take by weighing AP-P4 dry powder 4.9286～4.9857g, slowly equably AP-P4 dry powder is removed in the Simulated Water of constant temperature stirring, constant temperature (45 ℃) constant speed (400r/min) are that the agitator of 35mm stirs and to obtain mother liquor of oil displacement agent provided by the invention in 2 hours after even with rotation radius, wherein, described nonionogenic tenside and the total concn of described polyacrylamide in described mother liquor of oil displacement agent are 5000mg/L.
Measure the dissolution rate of mother liquor of oil displacement agent provided by the invention according to following method:
(1) is sprinkled into the water fully from AP-P4 and picks up counting, got equal volume (38mL) solution once in 20 minutes at interval, with the aperture is that 149 μ m (100 order) stainless (steel) wire filters under pressure reduction 0.01MPa, pressurizeed 20 minutes, resistates is changed in the crucible together with stainless (steel) wire, and the washing and filtering device is also integrated with crucible with solution;
(2) crucible is placed 100 ℃ of baking ovens dry to constant weight (36 hours), crucible is changed over to reduce to room temperature in the moisture eliminator, weigh rapidly.
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.Used hydrophobic association polyacrylamide is the hydrophobic association polyacrylamide that is numbered AP-P4 available from Sichuan light subfamily skill limited-liability company among the following embodiment, and solid content is 91.22%, and its viscosity-average molecular weight is 1,200 ten thousand.Used agitator is available from Jiangyin, Jiangsu Poly scientific research apparatus company limited.Used polyoxyethylene octadecanol ether-10 is available from Belgian ACROS Organics company, by the lark waffle agency of company limited that learns a skill.
Embodiment 1
1) with (C of non-ionic surfactant polyoxyethylene stearyl alcohol ether-10 shown in the 0.0143g formula I
18H
37O (CH
2CH
2O)
10H) be dissolved in the Simulated Water of the oil field of Suizhong 36-1 shown in the 1000mL table 1, constant temperature (45 ℃) constant speed (400r/min) are the agitator stirring dissolving fully in 10 minutes of 35mm with rotation radius;
2) slowly in having added the Simulated Water of polyoxyethylene octadecanol ether-10, described step 1) adds 4.9857gAP-P4 dry powder equably, constant temperature (45 ℃) constant speed (400r/min) are that the agitator of 35mm stirs after 2 hours to even and obtains mother liquor of oil displacement agent provided by the invention with rotation radius, wherein the total concn of nonionogenic tenside and AP-P4 is 5000mg/L, is numbered ML1.
The resistates quality per-cent of this mother liquor of oil displacement agent ML1 and the relation curve of dissolution time are as shown in Figure 1.
Embodiment 2
1) with (C of non-ionic surfactant polyoxyethylene stearyl alcohol ether-10 shown in the 0.0428g formula I
18H
37O (CH
2CH
2O)
10H) be dissolved in the Simulated Water of the oil field of Suizhong 36-1 shown in the 1000mL table 1, constant temperature (45 ℃) constant speed (400r/min) are the agitator stirring dissolving fully in 10 minutes of 35mm with rotation radius;
2) slowly in having added the Simulated Water of polyoxyethylene octadecanol ether-10, described step 1) adds 4.9572gAP-P4 dry powder equably, constant temperature (45 ℃) constant speed (400r/min) are that the agitator of 35mm stirs and to obtain mother liquor of oil displacement agent provided by the invention in 2 hours after even with rotation radius, wherein the total concn of nonionogenic tenside and AP-P4 is 5000mg/L, is numbered ML2.
The resistates quality per-cent of this mother liquor of oil displacement agent ML2 and the relation curve of dissolution time are as shown in Figure 1.
Embodiment 3
1) with (C of non-ionic surfactant polyoxyethylene stearyl alcohol ether-10 shown in the 0.0714g formula I
18H
37O (CH
2CH
2O)
10H) be dissolved in the Simulated Water of the oil field of Suizhong 36-1 shown in the 1000mL table 1, constant temperature (45 ℃) constant speed (400r/min) are the agitator stirring dissolving fully in 10 minutes of 35mm with rotation radius;
2) slowly in having added the Simulated Water of polyoxyethylene octadecanol ether-10, described step 1) adds 4.9286gAP-P4 dry powder equably, constant temperature (45 ℃) constant speed (400r/min) are that the agitator of 35mm stirs and to obtain mother liquor of oil displacement agent provided by the invention in 2 hours after even with rotation radius, wherein the total concn of nonionogenic tenside and AP-P4 is 5000mg/L, is numbered ML3.
The resistates quality per-cent of this mother liquor of oil displacement agent ML3 and the relation curve of dissolution time are as shown in Figure 1.
Reference examples
According to the identical Step By Condition of the foregoing description 1-3, only nonionogenic tenside will do not added in the step 1), step 2) consumption of used hydrophobic association polyacrylamide AP-P4 dry powder replaces with 5.0000g in, obtain oil-displacing agent as blank, be numbered MBL, the total concn of hydrophobic association polyacrylamide AP-P4 is 5000mg/L described in this MBL oil-displacing agent, and the relation curve of its resistates quality per-cent and dissolution time as shown in Figure 1.
As shown in Figure 1, when dissolution time reached more than 80 minutes, partly soluble AP-P4 blank solution was extruded by filter screen under 0.01MPa pressure, and undissolved AP-P4 is blocked and remains on the filter screen, and residuals content is less than 100%.And add shown in the formula I that concentration do not wait behind the non-ionic surfactant polyoxyethylene stearyl alcohol ether-10, AP-P4 solution was promptly arranged by filter screen in several minutes, illustrate that polyoxyethylene octadecanol ether-10 can make AP-P4 be dissolved in rapidly in the Simulated Water, the formation homogeneous solution.
According to preceding method mother liquor of oil displacement agent provided by the invention is carried out the mensuration of dissolution rate, the gained result is as shown in table 2.
The add-on of the ether-10 of non-ionic surfactant polyoxyethylene stearyl alcohol shown in table 2, the formula I is to the influence of mother liquor of oil displacement agent dissolution rate
aDissolution time is 30 minutes.
As shown in Table 2, when dissolution time is 30 minutes, the solution of the ether-10 of non-ionic surfactant polyoxyethylene stearyl alcohol shown in the adding type I is by behind the filter screen, residual polymer content reduces, and illustrates that the adding of nonionogenic tenside can be shortened the dissolution time of AP-P4 in the high salinity Simulated Water.
Because in the practical application, total mineral degree in the 36-1 oil-field water of Suizhong near but a little less than 36-1 oil field, used Suizhong Simulated Water in the table 1 of the present invention, use Simulated Water to prepare mother liquor as solvent, its performance evaluation result can prove that more this mother liquor of oil displacement agent can obtain good effect in actual applications.
Claims (10)
1. a mother liquor of oil displacement agent is made up of nonionogenic tenside, polyacrylamide and Suizhong 36-1 oil-field water.
2. mother liquor of oil displacement agent according to claim 1 is characterized in that: described nonionogenic tenside is a polyoxyethylene octadecanol ether-10, and its structural formula is suc as formula shown in the I,
(formula I).
3. mother liquor of oil displacement agent according to claim 1 and 2 is characterized in that: the viscosity-average molecular weight of described polyacrylamide is 1,200 ten thousand.
4. according to the arbitrary described mother liquor of oil displacement agent of claim 1～3, it is characterized in that: described Suizhong 36-1 oil-field water is 36-1 oil field, a Suizhong Simulated Water;
36-1 oil field, described Suizhong Simulated Water is by water, Na
+, K
+, Ca
2+, Mg
2+, HCO
3 -, CO
3 2-, SO
4 2-And Cl
-Form described Na
+And K
+The concentration sum be 3091.96mg/L, described Ca
2+Concentration be 276.17mg/L, described Mg
2+Concentration be 158.68mg/L, described HCO
3 -Concentration be 311.48mg/L, described CO
3 2-Concentration be 14.21mg/L, described SO
4 2-Concentration be 85.29mg/L, described Cl
-Concentration be 5436.34mg/L.
5. according to the arbitrary described mother liquor of oil displacement agent of claim 1～4, it is characterized in that: the concentration of described nonionogenic tenside in described mother liquor of oil displacement agent is 14.3～71.4mg/L, preferred 42.8～71.4mg/L.
6. according to the arbitrary described mother liquor of oil displacement agent of claim 1～5, it is characterized in that: the concentration of described polyacrylamide in described mother liquor of oil displacement agent is 4928.6～4985.7mg/L, preferred 4928.6～4957.2mg/L; Described nonionogenic tenside and the total concn of described polyacrylamide in described mother liquor of oil displacement agent are 5000mg/L.
7. according to the arbitrary described mother liquor of oil displacement agent of claim 1～6, it is characterized in that: described mother liquor of oil displacement agent is to get according to the arbitrary described method preparation of claim 8-1O.
8. method for preparing the arbitrary described mother liquor of oil displacement agent of claim 1～7, comprise the steps: earlier described nonionogenic tenside to be mixed with described Suizhong 36-1 oil-field water, add described polyacrylamide behind the mixing again, obtain described mother liquor of oil displacement agent behind the mixing.
9. method according to claim 8 is characterized in that: in the described mixing step, temperature is 45+0.5 ℃, and the method for mixing is a stirring and evenly mixing;
Described Suizhong 36-1 oil-field water is 36-1 oil field, a Suizhong Simulated Water; 36-1 oil field, described Suizhong Simulated Water is by water, Na
+, K
+, Ca
2+, Mg
2+, HCO
3 -, CO
3 2-, SO
4 2-And Cl
-Form described Na
+And K
+The concentration sum be 3091.96mg/L, described Ca
2+Concentration be 276.17mg/L, described Mg
2+Concentration be 158.68mg/L, described HCO
3 -Concentration be 311.48mg/L, described CO
3 2-Concentration be 14.21mg/L, described SO
4 2-Concentration be 85.29mg/L, described Cl
-Concentration be 5436.34mg/L;
The concentration of described nonionogenic tenside in described mother liquor of oil displacement agent is 14.3～71.4mg/L, preferred 42.8～71.4mg/L; The concentration of described polyacrylamide in described mother liquor of oil displacement agent is 4928.6～4985.7mg/L, preferred 4928.6～4957.2mg/L; Described nonionogenic tenside and the total concn of described polyacrylamide in described mother liquor of oil displacement agent are 5000mg/L.
10. method according to claim 9 is characterized in that: in the described stirring and evenly mixing step, rotating speed is 400 ± 5r/min, and rotation radius is 35mm.
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| CN102453167A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Polymer displacement agent, preparation method thereof, and oil displacement method for oil reservoirs |
| CN104311733A (en) * | 2014-10-30 | 2015-01-28 | 孙安顺 | Viscosity-maintaining polymer and preparation method thereof |
| CN106867496A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | Online injection type oil displacement agent containing hydrophobic associated polymer emulsion and preparation method thereof |
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| CN102453167B (en) * | 2010-10-25 | 2013-09-04 | 中国石油化工股份有限公司 | Polymer oil displacement agent, preparation method thereof, and oil displacement method for oil reservoirs |
| CN104311733A (en) * | 2014-10-30 | 2015-01-28 | 孙安顺 | Viscosity-maintaining polymer and preparation method thereof |
| CN106867496A (en) * | 2015-12-14 | 2017-06-20 | 中国石油化工股份有限公司 | Online injection type oil displacement agent containing hydrophobic associated polymer emulsion and preparation method thereof |
| CN106867496B (en) * | 2015-12-14 | 2020-05-01 | 中国石油化工股份有限公司 | Online injection type oil displacement agent containing hydrophobically associating polymer emulsion and preparation method thereof |
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| CN101864286B (en) | 2014-09-10 |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant after: China National Offshore Oil Corporation Applicant after: CNOOC Research Institute Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Applicant before: China National Offshore Oil Corporation Applicant before: CNOOC Research Center |
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Address after: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee after: CNOOC research institute limited liability company Patentee after: China Offshore Oil Group Co., Ltd. Address before: 100010 Beijing, Chaoyangmen, North Street, No. 25, No. Co-patentee before: CNOOC Research Institute Patentee before: China National Offshore Oil Corporation |