CN103173196A - High-efficiency oil-displacing agent - Google Patents
High-efficiency oil-displacing agent Download PDFInfo
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- CN103173196A CN103173196A CN2012105538897A CN201210553889A CN103173196A CN 103173196 A CN103173196 A CN 103173196A CN 2012105538897 A CN2012105538897 A CN 2012105538897A CN 201210553889 A CN201210553889 A CN 201210553889A CN 103173196 A CN103173196 A CN 103173196A
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Abstract
The invention provides a high-efficiency oil-displacing agent which is prepared from 12-18 parts of sodium dodecyl benzene sulfonate, 15-20 parts of allyl polyethenoxy ether, 5-15 parts of sorbitan fatty acid ester, 15-20 parts of maleic anhydride, 80-120 parts of deionized water, 0.5-1.5 parts of ammonium persulfate, 20-35 parts of acrylamide, 10-25 parts of acrylic acid, 5-15 parts of isopropanol, and 30% sodium hydroxide. The preparation method of the high-efficiency oil-displacing agent comprises the following steps: sequentially adding the sodium dodecyl benzene sulfonate, allyl polyethenoxy ether, sorbitan fatty acid ester, maleic anhydride and deionized water into a reaction kettle, heating to 75+/-2 DEG C while stirring until the components are completely dissolved, adding the ammonium persulfate, reacting under reflux for 3.5-4 hours, heating to 85+/-2 DEG C, and respectively and dropwisely adding solutions of acrylic acid, acrylamide and isopropanol, wherein the dropwise addition time is respectively 28-32 minutes, 57-63 minutes and 115-125 minutes; and after finishing the dropwise addition, continuing the reaction for 145-155 minutes, cooling to 43-48 DEG C, regulating the pH value to 8-9 with the 30% sodium hydroxide, and cooling to room temperature, thereby obtaining the product.
Description
Technical field
The present invention relates to high-efficient oil-displacing agent synthetic, the oil-displacing agent energy decrease energy consumption of preparation improves its recovery ratio, and effect is splendid, and the method is simple, and important promotional value is arranged.
Background technology
Divide three phases according to the investment of oil production and oil-field development: primary oil recovery, secondary oil recovery and tertiary oil recovery; Primary oil recovery refers to utilize the exploitation of oil reservoir natural energy, and its recovery ratio is lower than 15%; Secondary oil recovery refers to adopt external complement producing energy (as water filling, gas injection), and to keep the raising of producing energy, its recovery ratio reaches 45%; Tertiary oil recovery refers to adopt physics, chemistry, heat, biology etc. by injecting other fluids, changes reservoir rocks and fluid properties, oil recovery after the raising water drive, and its recovery ratio reaches 50-90%.
Chemical flooding is divided into: polymer flooding, surfactant flooding, alkali drive, combination flooding.In tertiary oil recovery, everyly add chemical agent in injected water, to change interfacial property between displacement fluid properties, displacement fluid and crude oil, thereby all methods that are conducive to crude production all belong to the chemical flooding category, and corresponding chemical agent is called polymer oil-displacing agent, surfactant flooding agent, alkali oil-displacing agent, compound oil displacement agent.
Alkali drives and also makes alkaline solution drive or alkali reinforcement water drive, it is the method for the raising oil recovery factor of oil-displacing agent of doing with the aqueous solution of alkaline agent, but the example of mining site Success in Experiment still seldom, chief reason is the mechanism more complicated, alkali and rock interact and cause a large amount of alkaline consumptions, the alkali concn scope that produces low-tension is narrow, and the alkali concn scope that oil reservoir injects is restive.And the crude oil that acid number is larger, viscosity are generally all higher, and mobility control is more difficult, and therefore the mining site experimental project of simple caustic waterflooding reduces on the contrary to some extent in recent years.The most suitable tertiary oil recovery of surfactant flooding is the reasonable continuation of waterflooding, basically is not subjected to the restriction of water ratio, can obtain very high water drive irreducible oil recovery ratio.But expensive due to tensio-active agent invested highly, have a big risk, thereby its use range is very limited.Improving at present recovery ratio is mainly to use polymer flooding, and oneself is not simple polymer flooding for the polymer flooding that still adopts, but drives the complex body of combination with surfactant flooding and alkali.
The composite efficient oil-displacing agent that the invention provides a kind of existing tensio-active agent and have again polymer performance is exactly the preferably note to this product, and its preparation method does not change equipment, does not increase cost, popularization easy to operate, easy.
Summary of the invention
The object of the invention is to: the high-efficient oil-displacing agent that provides, can effectively reduce the adhesive power of crude oil and rock stratum, make crude oil easily be out of shape, peel off, improve its recovery ratio.
The present invention seeks to realize like this: a kind of high-efficient oil-displacing agent, raw material is prepared with parts by weight, implements step by step;
Raw material is comprised of Sodium dodecylbenzene sulfonate 12-18 part, allyl polyethenoxy ether 15-20 part, sorbitan-fatty acid ester 5-15 part, MALEIC ANHYDRIDE 15-20 part, deionized water 80-120 part, ammonium persulphate 0.5-1.5 part, acrylamide 20-35 part, vinylformic acid 10-25 part, Virahol 5-15 part and 30% sodium hydroxide;
the preparation of oil-displacing agent: with Sodium dodecylbenzene sulfonate, allyl polyethenoxy ether, sorbitan-fatty acid ester, MALEIC ANHYDRIDE and deionized water, add successively in reactor, stirring is warming up to 75 ± 2 ℃, until completely dissolved, add ammonium persulphate, back flow reaction 3.5-4 hour, after being warming up to 85 ± 2 ℃, drip respectively vinylformic acid, acrylamide, the solution of Virahol, vinylformic acid time for adding 28-32min wherein, acrylamide time for adding 57-63min, Virahol time for adding 115-125min, dropwise, continue reaction 145-155min, be cooled to 43-48 ℃, it is 8-9 that sodium hydroxide with 30% is regulated the pH value, be cooled to room temperature, namely get product,
When wherein preparing vinylformic acid, acrylamide, aqueous isopropanol, the consumption of deionized water accounts for 40% of total Water; The water consumption of namely preparing vinylformic acid, acrylamide, aqueous isopropanol is respectively 10%, 15%, 15%, and stirring and dissolving is rear the dropping fully.
The high-efficient oil-displacing agent that described method is obtained can make in oil water interfacial tension 60min and be reduced to 10
-3MN/m, 120min is reduced to 10 with interior
-4MN/m; Improve oil displacement efficiency more than 20%.
The mechanism of action of the present invention: the hydrophilic radical that high-efficient oil-displacing agent is provided is carboxyl and sulfonic group, hydrocarbon key in lipophilic group sulfonate, can effectively reduce the adhesive power of crude oil and rock stratum, make crude oil easily be out of shape, peel off, the crude oil that lumps in the dissolving stratum rapidly, rapid osmotic is in oil reservoir rock gap, effectively improve the resistance to flow of viscous crude, crude oil is dissolved and take out of, improve recovery ratio, and this oil-displacing agent does not need to add alkali, salt tolerant, make demonstration for enterprise energy-saving and cost-reducing, shown technical progress.
Description of drawings
Below in conjunction with accompanying drawing, invention is described further.
Fig. 1 is test products (example 1) interfacial tension temporal evolution graphic representation;
As shown in the figure: during 50min, interfacial tension is 0.0091mN/m, effectively interfacial tension is down to 10
-3MN/m, during 100min, interfacial tension is 0.0009mN/m, effectively interfacial tension is down to 10
-4MN/m;
Fig. 2 is test products (example 2) interfacial tension temporal evolution graphic representation;
As shown in the figure: during 50min, interfacial tension is 0.0094mN/m, effectively interfacial tension is down to 10
-3MN/m, during 100min, interfacial tension is 0.0009mN/m, effectively interfacial tension is down to 10
-4MN/m;
Fig. 3 is test products (example 3) interfacial tension temporal evolution graphic representation;
As shown in the figure: during 50min, interfacial tension is 0.0093mN/m, effectively interfacial tension is down to 10
-3MN/m, during 100min, interfacial tension is 0.0008mN/m, effectively interfacial tension is down to 10
-4MN/m;
Fig. 4 is test products (example 4) interfacial tension temporal evolution graphic representation;
As shown in the figure: during 50min, interfacial tension is 0.0089mN/m, effectively interfacial tension is down to 10
-3MN/m, during 100min, interfacial tension is 0.0009mN/m, effectively interfacial tension is down to 10
-4MN/m.
Embodiment
Comparative examples of the present invention is described further.
Embodiment 1
Add successively Sodium dodecylbenzene sulfonate 12kg, allyl polyethenoxy ether 15kg, sorbitan-fatty acid ester 5kg, MALEIC ANHYDRIDE 15kg and deionized water 48kg in reactor, stirring is warming up to 75 ± 2 ℃, until completely dissolved, added ammonium persulphate 0.5kg back flow reaction 3.5 hours, make a liquid, be warming up to 85 ± 2 ℃;
Keep 85 ± 2 ℃ of temperature, respectively vinylformic acid 10kg being added water 8kg, acrylamide 20kg adds water 12kg, Virahol 5kg and adds water 12kg and be configured to solution, add in a liquid in the mode that drips, wherein vinylformic acid 30min dropwises, acrylamide 60min dropwises, Virahol 120min dropwises, and continues reaction 150min; Be cooled to 43 ℃, with mass concentration be 30% sodium hydroxide to regulate pH be 8.6, be cooled to room temperature, namely get high-efficient oil-displacing agent.
Reduce the oil water interfacial tension situation: testing tool TX-500 type interfacial tensimeter, the profit system is Crude Oils From Tahe Oilfield and mineralized water, and the oil-displacing agent dosage is 4 ‰, 75 ℃ of probe temperatures, rotating speed is 5000 rev/mins, and interfacial tension temporal evolution curve as shown in Figure 1.
Oil displacement efficiency: it is that 0.4% the aqueous solution is estimated oil displacement efficiency with the self-control rock sample that the simulation oil field recovered water is configured to mass concentration with this high-efficient oil-displacing agent, the crude oil of getting is the system in Tahe Oilfield oil well, bringing crude oil in the rock sample is 5.86ml, initial water repelling crude oil 3.15ml, pool efficient 53.75%, oil-displacing agent repelling crude oil 1.32ml, increase oil displacement efficiency 22.53% newly subsequently.
Embodiment 2
Add successively Sodium dodecylbenzene sulfonate 18kg, allyl polyethenoxy ether 20kg, sorbitan-fatty acid ester 15kg, MALEIC ANHYDRIDE 20kg and deionized water 60kg in reactor, stirring is warming up to 75 ± 2 ℃, until completely dissolved, added ammonium persulphate 1.2kg back flow reaction 4 hours, make a liquid, be warming up to 85 ± 2 ℃.
Keep 85 ± 2 ℃ of temperature, respectively vinylformic acid 18kg being added water 10kg, acrylamide 30kg adds water 15kg, Virahol 14kg and adds water 15kg and be configured to solution and add in a liquid in the mode that drips, wherein vinylformic acid 30min dropwises, acrylamide 60min dropwises, Virahol 120min dropwises, and continues reaction 150min;
Be cooled to 48 ℃, with mass concentration be 30% sodium hydroxide to regulate pH be 9.0, be cooled to room temperature and namely get high-efficient oil-displacing agent.
Reduce the oil water interfacial tension situation: testing tool TX-500 type interfacial tensimeter, the profit system is Crude Oils From Tahe Oilfield and mineralized water, and the oil-displacing agent dosage is 5 ‰, 75 ℃ of probe temperatures, rotating speed is 5000 rev/mins, and interfacial tension temporal evolution curve as shown in Figure 2.
Oil displacement efficiency: it is that 1.5% the aqueous solution is estimated oil displacement efficiency with the self-control rock sample that the simulation oil field recovered water is configured to mass concentration with this high-efficient oil-displacing agent, the crude oil of getting is the system in Tahe Oilfield oil well, bringing crude oil in the rock sample is 6.83ml, initial water repelling crude oil 3.22ml, pool efficient 47.14%, oil-displacing agent repelling crude oil 1.66ml, increase oil displacement efficiency 24.30% newly subsequently.
Embodiment 3
Add successively Sodium dodecylbenzene sulfonate 18kg, allyl polyethenoxy ether 18kg, sorbitan-fatty acid ester 15kg, MALEIC ANHYDRIDE 20kg and deionized water 72kg in reactor, stirring is warming up to 75 ± 2 ℃, until completely dissolved, add ammonium persulphate 1.5kg back flow reaction 3.5min, make a liquid, be warming up to 85 ± 2 ℃.
Keep 85 ± 2 ℃ of temperature, respectively vinylformic acid 20kg being added water 12kg, acrylamide 35kg adds water 18kg, Virahol 15kg and adds water 18kg and be configured to solution and add in a liquid in the mode that drips, wherein vinylformic acid 30min dropwises, acrylamide 60min dropwises, Virahol 120min dropwises, and continues reaction 150min;
Be cooled to 45 ℃, with mass concentration be 30% sodium hydroxide to regulate pH be 8.0, be cooled to room temperature and namely get high-efficient oil-displacing agent.
Reduce the oil water interfacial tension situation: testing tool TX-500 type interfacial tensimeter, the profit system is Karamay oilfield crude oil and mineralized water, and the oil-displacing agent dosage is 4 ‰, 85 ℃ of probe temperatures, rotating speed is 5000 rev/mins, and interfacial tension temporal evolution curve as shown in Figure 3.
Oil displacement efficiency: it is that 1.5% the aqueous solution is estimated oil displacement efficiency with the self-control rock sample that the simulation oil field recovered water is configured to mass concentration with this high-efficient oil-displacing agent, the crude oil of getting is the Karamay oilfield oil well, bringing crude oil in the rock sample is 6.27ml, initial water repelling crude oil 3.41ml, pool efficient 54.38%, oil-displacing agent repelling crude oil 1.37ml, increase oil displacement efficiency 21.85% newly subsequently.
Embodiment 4
Add successively Sodium dodecylbenzene sulfonate 14kg, allyl polyethenoxy ether 18kg, sorbitan-fatty acid ester 14kg, MALEIC ANHYDRIDE 16kg and deionized water 60kg in reactor, stirring is warming up to 75 ± 2 ℃, until completely dissolved, added ammonium persulphate 1.2kg back flow reaction 24 hours, make a liquid, be warming up to 85 ± 2 ℃.
Keep 85 ± 2 ℃ of temperature, respectively vinylformic acid 25kg being added water 10kg, acrylamide 20kg adds water 15kg, Virahol 12kg and adds water 15kg and be configured to solution and add in a liquid in the mode that drips, wherein vinylformic acid 30min dropwises, acrylamide 60min dropwises, Virahol 120min dropwises, and continues reaction 150min;
Be cooled to 45 ℃, with mass concentration be 30% sodium hydroxide to regulate pH be 8.4, be cooled to room temperature and namely get high-efficient oil-displacing agent.
Reduce the oil water interfacial tension situation: testing tool TX-500 type interfacial tensimeter, the profit system is breathed out crude oil and mineralized water for telling, and the oil-displacing agent dosage is 5 ‰, 85 ℃ of probe temperatures, rotating speed is 5000 rev/mins, and interfacial tension temporal evolution curve as shown in Figure 4.
Oil displacement efficiency: it is that 1.5% the aqueous solution is estimated oil displacement efficiency with the self-control rock sample that the simulation oil field recovered water is configured to mass concentration with this high-efficient oil-displacing agent, institute's crude oil of getting is breathed out the oil field oil well for telling, bringing crude oil in the rock sample is 5.88ml, initial water repelling crude oil 2.62ml, pool efficient 44.56%, oil-displacing agent repelling crude oil 1.26ml, increase oil displacement efficiency 21.43% newly subsequently.
The Sodium dodecylbenzene sulfonate that product of the present invention is selected is provided by circle, upper tableland chemical industry company limited by the two Long Huaxuepinchang buyings in Shanghai, allyl polyethenoxy ether; Sorbitan-fatty acid ester is provided by sea, Zibo outstanding chemical industry company limited; MALEIC ANHYDRIDE is provided by Suzhou letter thousand ancient cooking vessel trade Co., Ltds; Ammonium persulphate is provided by Chengdu upright chemical industry company limited; Vinylformic acid is provided by brilliant Shanghai, Shanghai chemical industry company limited; Acrylamide effluent Nanchang chemical industry far away provides; Virahol is provided by Shanghai De Mao chemical industry; Sodium hydroxide is provided by safe chemical limited-liability company in Xinjiang.
The relevant criterion of this product: by SY/T6315 2006 heavy crude reservoir high temperature relative permeabilities and oil displacement efficiency measuring method; By SY-T6424-2000 composite oil-displacing system performance test methods.
Claims (2)
1. high-efficient oil-displacing agent, it is characterized in that: raw material is prepared with parts by weight, implements step by step;
Raw material is comprised of Sodium dodecylbenzene sulfonate 12-18 part, allyl polyethenoxy ether 15-20 part, sorbitan-fatty acid ester 5-15 part, MALEIC ANHYDRIDE 15-20 part, deionized water 80-120 part, ammonium persulphate 0.5-1.5 part, acrylamide 20-35 part, vinylformic acid 10-25 part, Virahol 5-15 part and 30% sodium hydroxide;
the preparation of oil-displacing agent: with Sodium dodecylbenzene sulfonate, allyl polyethenoxy ether, sorbitan-fatty acid ester, MALEIC ANHYDRIDE and deionized water, add successively in reactor, stirring is warming up to 75 ± 2 ℃, until completely dissolved, add ammonium persulphate, back flow reaction 3.5-4 hour, after being warming up to 85 ± 2 ℃, drip respectively vinylformic acid, acrylamide, the solution of Virahol, vinylformic acid time for adding 28-32min wherein, acrylamide time for adding 57-63min, Virahol time for adding 115-125min, dropwise, continue reaction 145-155min, be cooled to 43-48 ℃, it is 8-9 that sodium hydroxide with 30% is regulated the pH value, be cooled to room temperature, namely get product,
When wherein preparing vinylformic acid, acrylamide, aqueous isopropanol, the consumption of deionized water accounts for 40% of total Water; The water consumption of namely preparing vinylformic acid, acrylamide, aqueous isopropanol is respectively 10%, 15%, 15%, and stirring and dissolving is rear the dropping fully.
2. method according to claim 1, it is characterized in that: the high-efficient oil-displacing agent that the method is obtained can make in oil water interfacial tension 60min and be reduced to 10
-3MN/m, 120min is reduced to 10 with interior
-4MN/m; Improve oil displacement efficiency more than 20%.
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| CN103173196B CN103173196B (en) | 2015-01-07 |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437699A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Oil washing agent and preparation method and application thereof |
| CN115028785A (en) * | 2022-06-16 | 2022-09-09 | 陕西科技大学 | Temperature-resistant salt-tolerant oil displacement surfactant and preparation method thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935934A (en) * | 2006-09-28 | 2007-03-28 | 大庆石油管理局 | Ternary composite drive-collect-convey system anti-deposition agent and its preparing method |
| CN101260171A (en) * | 2008-04-22 | 2008-09-10 | 山东大学 | Comb-type structure activity polymer and its preparation technique and application |
| US20110297377A1 (en) * | 2010-06-07 | 2011-12-08 | Halliburton Energy Services, Inc. | Stable organic-based fluid loss additive containing an organophilic clay-based suspending agent for use in a well |
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2012
- 2012-12-19 CN CN201210553889.7A patent/CN103173196B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1935934A (en) * | 2006-09-28 | 2007-03-28 | 大庆石油管理局 | Ternary composite drive-collect-convey system anti-deposition agent and its preparing method |
| CN101260171A (en) * | 2008-04-22 | 2008-09-10 | 山东大学 | Comb-type structure activity polymer and its preparation technique and application |
| US20110297377A1 (en) * | 2010-06-07 | 2011-12-08 | Halliburton Energy Services, Inc. | Stable organic-based fluid loss additive containing an organophilic clay-based suspending agent for use in a well |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN114437699A (en) * | 2020-10-20 | 2022-05-06 | 中国石油化工股份有限公司 | Oil washing agent and preparation method and application thereof |
| CN114437699B (en) * | 2020-10-20 | 2023-07-21 | 中国石油化工股份有限公司 | Oil washing agent and preparation method and application thereof |
| CN115028785A (en) * | 2022-06-16 | 2022-09-09 | 陕西科技大学 | Temperature-resistant salt-tolerant oil displacement surfactant and preparation method thereof |
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