CN104531117A - Non thermo-sensitive type lyotropic liquid crystal soluble oil system, preparation method thereof and application - Google Patents
Non thermo-sensitive type lyotropic liquid crystal soluble oil system, preparation method thereof and application Download PDFInfo
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- CN104531117A CN104531117A CN201510018779.4A CN201510018779A CN104531117A CN 104531117 A CN104531117 A CN 104531117A CN 201510018779 A CN201510018779 A CN 201510018779A CN 104531117 A CN104531117 A CN 104531117A
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- 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
- C09K8/52—Compositions for preventing, limiting or eliminating depositions, e.g. for cleaning
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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
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
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Abstract
The invention provides a non thermo-sensitive type lyotropic liquid crystal soluble oil system. The system comprises, by weight, 55-85 parts of 20 wt%-50wt% of inorganic salt water solution, 5-10 parts of nonionic surfactant, 5-10 parts of ionic surfactant. The system does not contain cosurfactant. The non thermo-sensitive type lyotropic liquid crystal soluble oil system meets the various industrial requirements of environmental protection, and is easy to transport. The system is prepared from ordinary surfactant, the preparing method is simple, the manufacturing cost is low and the implementation is easy.
Description
Technical field
The application relates to but is not limited to the molten oil systems of a kind of solute liquid crystal, particularly, relates to molten oil systems of a kind of non-temperature sensitive type lytropic liquid crystals and its production and use.
Background technology
Lytropic liquid crystals is a kind of liquid crystal comprising two or more compound formation of solvated compounds, is to occur mesomorphic phase when solute molecule concentration is in certain limit in the solution.Structure type comprises hexagonal phase, Emission in Cubic or lamellar phase, and lamellar phase and hexagonal phase have typical birefringent phenomenon under polaroid, and Emission in Cubic does not have.The special rheological behavior of lytropic liquid crystals makes it have important effect in a lot of field, and lyotropic lamellar phase has the laminated structure of similar graphite, sheet interlayer energy relatively sliding, as U.S. Patent application US 6,130, described in 190 grades; It effectively can also improve the dispersion stabilization of solid matter, as US Patent No. 7, described in 931,824 grades.What is more important, lytropic liquid crystals has very strong solubilising, can the oil phase of some polar/non-polar of solubilising, form emulsion oil-in-water, such as, in " Functional Liquid ?Crystalline Assemblies:Self ?Organized SoftMaterials ", have detailed report.Wherein, cleaning process can be reduced to the dispersion of oil phase in water phase surfactant mixture, and dispersed in water of oil droplet will significantly improve cleaning efficiency.
The special construction of lytropic liquid crystals has important impact for its application, such as, as US Patent No. 7, and 791, report in 694, the change of temperature, salinity and pressure all can change the structure of former lytropic liquid crystals, and then affects the effect of lytropic liquid crystals.From current delivered document, had deep research abroad, make some progress for this field, the domestic report made a search for this field is less, only the application report of useful lyotropic liquid crystal flooding in patent CN101475796.But lytropic liquid crystals prepared in above-mentioned document all employs a large amount of auxiliary agent, dosage of surfactant is large, and saline-alkaline tolerance is poor and to temperature sensitive.Therefore, the lytropic liquid crystals of a kind of salt tolerant, temperature-insensitive has very important application prospect.
Summary of the invention
On the one hand, the object of the application is to provide a kind of non-temperature sensitive type lytropic liquid crystals molten oil systems.
Particularly, the application provides a kind of non-temperature sensitive type lytropic liquid crystals molten oil systems, and described system is made up of the component comprising following weight part: 20-50wt% inorganic salt solution 55-85 part; Nonionic surface active agent 5-10 part; Ionogenic surfactant 5-10 part; And described system is not containing cosurfactant.
In above or other embodiments, described nonionic surface active agent can be 5-8 part, and described ionogenic surfactant can be 5-8 part.
In above or other embodiments, described nonionic surface active agent can be selected from sorbitan oleate class nonionogenic tenside (as Span20, Span40, Span60 or Span65), sorbitan monooleate polyethenoxy ether class nonionogenic tenside (as Tween20, Tween40, Tween60 or Tween80), polyoxyethylene nonionogenic tenside (as dodecyl polyoxyethylene 4 ether C
12eO
4, dodecyl polyoxyethylene 9 ether C
12eO
9, dodecyl polyoxyethylene 23 ether C
12eO
23) or its combination; Described ionogenic surfactant can be selected from Sulfonates, Sulfates, metal carboxylate (as sodium lauryl sulphate SDS, AMONYL 380LC CAB, sodium laurylsulfonate AS, polyoxyethylenated alcohol sodium sulfate AES), dodecanamide propyl decil lactone ionogenic surfactant or its combination.
In above or other embodiments, described inorganic salt can one or more for being selected from sodium salt, calcium salt or aluminium salt.Such as, water-soluble NaCl, CaCl
2.Further, the application mainly for be high calcium salt system.
In above or other embodiment, described inorganic salt solution is the calcium chloride water of mass percent 20%-40%.
On the other hand, the object of the application is to provide the purposes of above-mentioned system in the oil phase for dissolving polarity alkanes.
In above or other embodiments, described oil phase can be white oil or whiteruss.
In other respects, the application provides system as above for the purposes of completion scavenging solution.
In other, the application provides a kind of method for the preparation of the molten oil systems of above-described non-temperature sensitive type lytropic liquid crystals, comprise: get each component of formula ratio and be stirred to even, adhesive system, then sample and observe under polaroid, if observe oil stripping shape decorative pattern, and utilize the rheological property of rheometer measurement system, if rheological property is elastic modulus G ' parallel and is greater than viscous modulus G ", namely obtain the molten oil systems of described non-temperature sensitive type lytropic liquid crystals.
In above or other embodiments, wherein can by each component of formula ratio through water-bath, be stirred to even, adhesive system, be cooled to room temperature; The speed of wherein said stirring is 200-300 rev/min, and water solution temperature is 70-90 DEG C.
The molten oil systems of non-temperature sensitive type lytropic liquid crystals of the application is a kind of water phase surfactant mixture system being clean-out system with non-temperature sensitive type lytropic liquid crystals, good solubilising is had under high temperature, high salt condition, for the greasy dirt cleaning under the severe condition such as high temperature, high salinity provides possibility, have broad application prospects." non-temperature sensitive " described in the application refers within the scope of 25-75 DEG C, and structure, the rheological property of system do not change.
Further, the molten oil systems of non-temperature sensitive type lytropic liquid crystals of the application be a kind of low cost, low surfactant, to temperature-insensitive and the molten oil systems of the simple lytropic liquid crystals of preparation method.Further, the system of the application does not such as have stronger volatility containing surfactivity auxiliary agent and human body is had to the alcohols of certain injury.
The outward appearance of the molten oil systems of lytropic liquid crystals of the application is translucent bit bluish liquid, (at room temperature placement half a year, above outward appearance was unchanged to have certain permanent stability, namely without obvious layering and sedimentation phenomenon, sampling is observed under polaroid, observe oil stripping shape decorative pattern, and the elastic modulus G of the system utilizing rheometer to measure ' parallel and be greater than viscous modulus G ", show that the structure of system does not occur considerable change); High-temperature stability is good (place 15-18 hour at 120 DEG C after, outward appearance is without considerable change, namely without obvious layering and sedimentation phenomenon, sampling is observed under polaroid, observe oil stripping shape decorative pattern, and the elastic modulus G of the system utilizing rheometer to measure ' parallel and be greater than viscous modulus G ", illustrate that the high-temperature stability of lytropic liquid crystals is good); Low-temperature stability good (at being placed on-10-0 DEG C after 5-8 hour, outward appearance without considerable change, namely without obvious layering and sedimentation phenomenon.Sampling is observed under polaroid, observes oil stripping shape decorative pattern, and the elastic modulus G of the system utilizing rheometer to measure ' parallel and be greater than viscous modulus G ", illustrate that the low-temperature stability of lytropic liquid crystals is good).
Generally speaking, the molten oil systems of the lytropic liquid crystals of the application has following benefit:
(1) the molten oil systems of non-temperature sensitive type lytropic liquid crystals of the application meets every industrial requirements of environmental protection, is easy to transport, and is obtained by conventional surfactants, and preparation method is simple, and production cost is low and easy to implement;
(2) the molten oil systems of non-temperature sensitive type lytropic liquid crystals of the application is to temperature-insensitive, and the change of temperature is on the almost no impact of its rheological;
(3) the molten oil systems of non-temperature sensitive type lytropic liquid crystals of the application can be used in the cleaning process in completion, has no report up to now, and this system is that oil production provides novel method.
Accompanying drawing explanation
The outside drawing of the molten oil systems of non-temperature sensitive type lytropic liquid crystals in the embodiment 1 of Fig. 1 the application under polarizing microscope after texture picture and molten oil (LC is lytropic liquid crystals, and 10%, 20% represents molten oil mass).
The rheological curves of the molten oil systems of non-temperature sensitive type lytropic liquid crystals in the embodiment 1 of Fig. 2 the application.
The molten oil systems of non-temperature sensitive type lytropic liquid crystals in the embodiment 1 of Fig. 3 the application apparent viscosity at different temperatures changes and the texture picture of lytropic liquid crystals under polaroid.
Embodiment
Describe the embodiment of the application below by embodiment, one of ordinary skill in the art appreciates that these specific embodiments only show object in order to reach the application and the enforcement technical scheme selected, is not the restriction to technical scheme.According to the instruction of the application, be obvious in conjunction with the improvement of prior art to technical scheme, all belong to the scope of the application's protection.
In following examples of the application, used chemical is commercial products.
Embodiment 1
The molten oil systems of non-temperature sensitive type lytropic liquid crystals, described system is made up of the component of following weight part:
The CaCl of 60 parts of 40wt%
2the aqueous solution, 5 parts of C
12eO
9(purchased from Japanese Nikkol company), 5 parts of AES (purchased from BASF Corp. of Germany), 5 parts of CAB (purchased from: Shandong Lv Sen Chemical Co., Ltd.).
Its preparation method is as follows:
Get above each component of formula ratio and be stirred to even, adhesive system, then sample and observe under polaroid, if observe oil stripping shape decorative pattern, and utilize the elastic modulus G of rheometer measurement system ' parallel and be greater than viscous modulus G ", namely obtain the molten oil systems of described non-temperature sensitive type lytropic liquid crystals.
Investigate the high-temperature stability of the molten oil systems of non-temperature sensitive type lytropic liquid crystals of preparation, permanent stability, low-temperature stability and the outward appearance of emulsion formed after adding oil phase and particle diameter respectively by the following method, wherein add oil phase to refer to add 25 parts of white oils to the molten oil systems of above-mentioned non-temperature sensitive type lytropic liquid crystals and stir with the rotating speed of 300 revs/min at 70 DEG C and be cooled to room temperature in 5 minutes, 70 DEG C wherein in the embodiment of the application temperature-rise periods mainly in simulated field application process.
The stability measurement of the molten oil systems of non-temperature sensitive type lytropic liquid crystals:
Permanent stability: by long-time for product static placement at 25 DEG C, observe outward appearance, note whether occurring layering clearly, sample and observe under polaroid, whether observe oil stripping shape decorative pattern, utilize simultaneously the elastic modulus G of rheometer measurement system ' with viscous modulus G " relation.
High-temperature stability: sample is placed on constant temperature 15-18 hour in 120 DEG C of High Temperature Furnaces Heating Apparatuss, observe outward appearance, whether layering or sedimentation, sample and observe under polaroid, whether observe oil stripping shape decorative pattern, utilize simultaneously the elastic modulus G of rheometer measurement system ' with viscous modulus G " relation.
Low-temperature stability: sample is placed on (about-10 DEG C) in refrigerator, observe outward appearance, whether layering or sedimentation, sample and observe under polaroid, whether observe oil stripping shape decorative pattern, utilize simultaneously the elastic modulus G of rheometer measurement system ' with viscous modulus G " relation.
Emulsion appearance and grain diameter measurement:
Under room temperature, the emulsion formed as stated above is left standstill after stablizing and observe outward appearance; The method measuring emulsion particle diameter according to dynamic light scattering (DLS) measures emulsion particle diameter, and measuring method is as described in document " HighlyStable Concentrated Nanoemulsions by the Phase Inversion Composition Method atElevated Temperature ".Wherein, after adding oil phase, emulsion particle diameter is less, then the stability of system is higher.
Result is as shown in table 1:
| Product appearance | Transparent |
| Permanent stability | Place non-layering in six months |
| High-temperature stability | Stable |
| Low-temperature stability | Stable |
| The particle diameter (nm) of the emulsion formed after adding oil phase | 25 |
Table 1
Wherein, the lyotropic crystal system that Fig. 1 shows in embodiment 1 is adding the appearance change before and after oil phase; Fig. 2 is lyotropic crystal system rheological curves at normal temperatures, and rheological curves illustrates that system is with special structure; Fig. 3 shows the apparent viscosity variation with temperature situation of lyotropic crystal system, and apparent viscosity does not have variation with temperature and occurs obvious change as can be seen from Figure 3, does not also have too big-difference in appearance simultaneously, thus illustrates that this system is non-responsive to temperature type.
Embodiment 2
The molten oil systems of non-temperature sensitive type lytropic liquid crystals, described system is made up of the component of following weight part:
The CaCl of 70 parts of 20wt%
2the aqueous solution, 5 parts of C
12eO
9(purchased from Japanese Nikkol company), 5 parts of AES (purchased from BASF Corp. of Germany), 5 parts of CAB (purchased from: Shandong Lv Sen Chemical Co., Ltd.).
Its preparation method is as follows:
Get above each component of formula ratio and be stirred to even, adhesive system, then sample and observe under polaroid, if observe oil stripping shape decorative pattern, and utilize the elastic modulus G of rheometer measurement system ' parallel and be greater than viscous modulus G ", namely obtain the molten oil systems of described non-temperature sensitive type lytropic liquid crystals.
The high-temperature stability of the molten oil systems of non-temperature sensitive type lytropic liquid crystals prepared by investigating by the method in embodiment 1, permanent stability, low-temperature stability and add outward appearance and the particle diameter of the emulsion that molten oil is formed afterwards, wherein add molten oil and refer to add 15 parts of white oils to the molten oil systems of above-mentioned non-temperature sensitive type lytropic liquid crystals and stir with the rotating speed of 300 revs/min at 70 DEG C and be cooled to room temperature in 5 minutes.
Result is as shown in table 2:
| Product appearance | Translucent |
| Permanent stability | Place non-layering in six months |
| High-temperature stability | Stable |
| Low-temperature stability | Stable |
| The particle diameter (nm) of the emulsion formed after adding oil phase | 28 |
Table 2
Embodiment 3
The molten oil systems of non-temperature sensitive type lytropic liquid crystals, described system is made up of the component of following weight part:
The CaCl of 60 parts of 40wt%
2the aqueous solution, 10 parts of C
12eO
9(purchased from Japanese Nikkol company), 5 parts of AES (purchased from BASF Corp. of Germany), 5 parts of CAB (purchased from: Shandong Lv Sen Chemical Co., Ltd.).
Its preparation method is as follows:
Get above each component of formula ratio and be stirred to even, adhesive system, then sample and observe under polaroid, if observe oil stripping shape decorative pattern, and utilize the elastic modulus G of rheometer measurement system ' parallel and be greater than viscous modulus G ", namely obtain the molten oil systems of described non-temperature sensitive type lytropic liquid crystals.
The high-temperature stability of the molten oil systems of non-temperature sensitive type lytropic liquid crystals prepared by investigating by the method in embodiment 1, permanent stability, low-temperature stability and add outward appearance and the particle diameter of the emulsion that molten oil is formed afterwards, wherein add molten oil and refer to add 20 parts of white oils to the molten oil systems of above-mentioned non-temperature sensitive type lytropic liquid crystals and stir with the rotating speed of 300 revs/min at 70 DEG C and be cooled to room temperature in 5 minutes.
Result is as shown in table 3:
| Product appearance | Muddy |
| Permanent stability | Place non-layering in six months |
| High-temperature stability | Stable |
| Low-temperature stability | Stable |
| The particle diameter (nm) of the emulsion formed after adding oil phase | 78 |
Table 3
Embodiment 4
The molten oil systems of non-temperature sensitive type lytropic liquid crystals, described system is made up of the component of following weight part:
The CaCl of 55 parts of 40wt%
2the aqueous solution, 10 parts of C
12eO
9(purchased from Japanese Nikkol company), 5 parts of AES (purchased from BASF Corp. of Germany), 10 parts of CAB (purchased from: Shandong Lv Sen Chemical Co., Ltd.).
Its preparation method is as follows:
Get above each component of formula ratio and be stirred to even, adhesive system, then sample and observe under polaroid, if observe oil stripping shape decorative pattern, and utilize the elastic modulus G of rheometer measurement system ' parallel and be greater than viscous modulus G ", namely obtain the molten oil systems of described non-temperature sensitive type lytropic liquid crystals.
The high-temperature stability of the molten oil systems of non-temperature sensitive type lytropic liquid crystals prepared by investigating by the method in embodiment 1, permanent stability, low-temperature stability and add outward appearance and the particle diameter of the emulsion that molten oil is formed afterwards, wherein add molten oil and refer to add 20 parts of white oils to the molten oil systems of above-mentioned non-temperature sensitive type lytropic liquid crystals and stir with the rotating speed of 300 revs/min at 70 DEG C and be cooled to room temperature in 5 minutes.
Result is as shown in table 4:
| Product appearance | Slightly, light blue translucent |
| Permanent stability | Place non-layering in six months |
| High-temperature stability | Stable |
| Low-temperature stability | Stable |
| The particle diameter (nm) of the emulsion formed after adding oil phase | 90 |
Table 4
Embodiment 5
The molten oil systems of non-temperature sensitive type lytropic liquid crystals, described system is made up of the component of following weight part:
The CaCl of 80 parts of 40wt%
2the aqueous solution, 5 parts of C
12eO
9(purchased from Japanese Nikkol company), 5 parts of AES (purchased from BASF Corp. of Germany), 10 parts of CAB (purchased from: Shandong Lv Sen Chemical Co., Ltd.).
Its preparation method is as follows:
Get above each component of formula ratio and be stirred to even, adhesive system, then sample and observe under polaroid, if observe oil stripping shape decorative pattern, and utilize the elastic modulus G of rheometer measurement system ' parallel and be greater than viscous modulus G ", namely obtain the molten oil systems of described non-temperature sensitive type lytropic liquid crystals.
The high-temperature stability of the molten oil systems of non-temperature sensitive type lytropic liquid crystals prepared by investigating by the method in embodiment 1, permanent stability, low-temperature stability and add outward appearance and the particle diameter of the emulsion that molten oil is formed afterwards, wherein add molten oil and refer to add 5 parts of white oils to the molten oil systems of above-mentioned non-temperature sensitive type lytropic liquid crystals and stir with the rotating speed of 300 revs/min at 70 DEG C and be cooled to room temperature in 5 minutes.
Result is as shown in table 5:
| Product appearance | Transparent |
| Permanent stability | Place non-layering in six months |
| High-temperature stability | Stable |
| Low-temperature stability | Stable |
| The particle diameter (nm) of the emulsion formed after adding oil phase | 73 |
Table 5
Embodiment 6
The molten oil systems of non-temperature sensitive type lytropic liquid crystals, described system is made up of the component of following weight part:
The CaCl of 55 parts of 40wt%
2the aqueous solution, 5 parts of C
12eO
9(purchased from Japanese Nikkol company), 5 parts of AES (purchased from BASF Corp. of Germany), 5 parts of CAB (purchased from: Shandong Lv Sen Chemical Co., Ltd.).
Its preparation method is as follows:
Get above each component of formula ratio and be stirred to even, adhesive system, then sample and observe under polaroid, if observe oil stripping shape decorative pattern, and utilize the elastic modulus G of rheometer measurement system ' parallel and be greater than viscous modulus G ", namely obtain the molten oil systems of described non-temperature sensitive type lytropic liquid crystals.
The high-temperature stability of the molten oil systems of non-temperature sensitive type lytropic liquid crystals prepared by investigating by the method in embodiment 1, permanent stability, low-temperature stability and add outward appearance and the particle diameter of the emulsion that molten oil is formed afterwards, wherein add molten oil and refer to add 30 parts of white oils to the molten oil systems of above-mentioned non-temperature sensitive type lytropic liquid crystals and stir with the rotating speed of 300 revs/min at 70 DEG C and be cooled to room temperature in 5 minutes.
Result is as shown in table 6:
| Product appearance | Oyster white, muddiness |
| Permanent stability | Place non-layering in three months |
| High-temperature stability | Stable |
| Low-temperature stability | Stable |
| The particle diameter (nm) of the emulsion formed after adding oil phase | 65 |
Table 6
Be only the preferred embodiment of the application described in upper, not any formal and substantial restriction made to the application.Those skilled in the art, not departing from the scope of technical scheme, a little change made, modifies the Equivalent embodiments being the application with the equivalent variations of differentiation when utilizing disclosed above technology contents; Meanwhile, all substantial technological according to the application to the change of any equivalent variations that above embodiment is done, modify with differentiation etc. all in the scope defined by claim of the application.
Claims (10)
1. the molten oil systems of non-temperature sensitive type lytropic liquid crystals, described system is made up of the component comprising following weight part: 20-50wt% inorganic salt solution 55-85 part; Nonionic surface active agent 5-10 part; Ionogenic surfactant 5-10 part; And described system is not containing cosurfactant.
2. system according to claim 1, wherein, described nonionic surface active agent is 5-8 part, and described ionogenic surfactant is 5-8 part.
3. system according to claim 1, wherein, described nonionic surface active agent is selected from sorbitan oleate class nonionogenic tenside, sorbitan monooleate polyethenoxy ether class nonionogenic tenside, polyoxyethylene nonionogenic tenside or its combination; Described ionogenic surfactant is selected from Sulfonates, Sulfates, metal carboxylate, dodecanamide propyl decil lactone ionogenic surfactant or its combination.
4. system according to claim 1, wherein, described inorganic salt be selected from sodium salt, calcium salt or aluminium salt one or more.
5. system according to claim 4, wherein, described inorganic salt solution is the calcium chloride water of mass percent 20%-40%.
6. the purposes of the system according to any one of claim 1-5 in the oil phase for dissolving polarity alkanes.
7. purposes according to claim 6, wherein, described oil phase is white oil or whiteruss.
8. the system according to any one of claim 1-5 is used for the purposes of completion scavenging solution.
9. the method for the preparation of the molten oil systems of non-temperature sensitive type lytropic liquid crystals such as according to any one of claim 1-5, comprise: get each component of formula ratio and be stirred to even, adhesive system, then sample and observe under polaroid, if observe oil stripping shape decorative pattern, and utilize the rheological property of rheometer measurement system, if rheological property is elastic modulus G ' parallel and is greater than viscous modulus G ", namely obtain the molten oil systems of described non-temperature sensitive type lytropic liquid crystals.
10. method as claimed in claim 9, wherein by each component of formula ratio through water-bath, be stirred to even, adhesive system, be cooled to room temperature; The speed of wherein said stirring is 200-300 rev/min, and water solution temperature is 70-90 DEG C.
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| CN107474814A (en) * | 2017-08-02 | 2017-12-15 | 山东大学 | A kind of emulsion-type oil base mud cleans liquid and preparation method thereof |
| CN111019618A (en) * | 2019-11-18 | 2020-04-17 | 中国石油天然气股份有限公司 | Temperature-sensitive shunt temporary plugging agent and preparation method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107118753A (en) * | 2017-05-10 | 2017-09-01 | 中国石油天然气股份有限公司 | Without high molecular variable viscosity oil displacement agent composition and preparation method and application |
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| CN111019618B (en) * | 2019-11-18 | 2022-07-05 | 中国石油天然气股份有限公司 | Temperature-sensitive shunt temporary plugging agent and preparation method thereof |
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|---|---|
| CN104531117B (en) | 2018-05-08 |
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Address after: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee after: China Oilfield Services Limited Patentee after: China Offshore Oil Group Co., Ltd. Address before: 100010 Chaoyangmen North Street, Dongcheng District, Dongcheng District, Beijing Co-patentee before: China Oilfield Services Limited Patentee before: China National Offshore Oil Corporation |