CN106833565B - It is a kind of can salinity control phase transition reversible emulsion, preparation method and phase inversion process - Google Patents
It is a kind of can salinity control phase transition reversible emulsion, preparation method and phase inversion process Download PDFInfo
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- CN106833565B CN106833565B CN201611266453.4A CN201611266453A CN106833565B CN 106833565 B CN106833565 B CN 106833565B CN 201611266453 A CN201611266453 A CN 201611266453A CN 106833565 B CN106833565 B CN 106833565B
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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
- C09K8/02—Well-drilling compositions
- C09K8/32—Non-aqueous well-drilling compositions, e.g. oil-based
- C09K8/36—Water-in-oil emulsions
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F222/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a carboxyl radical and containing at least one other carboxyl radical in the molecule; Salts, anhydrides, esters, amides, imides, or nitriles thereof
- C08F222/04—Anhydrides, e.g. cyclic anhydrides
- C08F222/06—Maleic anhydride
- C08F222/08—Maleic anhydride with vinyl aromatic monomers
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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
- C09K8/02—Well-drilling compositions
- C09K8/03—Specific additives for general use in well-drilling compositions
- C09K8/035—Organic additives
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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
- C09K8/02—Well-drilling compositions
- C09K8/04—Aqueous well-drilling compositions
- C09K8/26—Oil-in-water emulsions
- C09K8/28—Oil-in-water emulsions containing organic additives
Abstract
The present invention relates to it is a kind of can salinity control phase transition reversible emulsion, preparation method and phase inversion process.The reversible emulsion is by reversible emulsifier, water and oily phase composition, wherein the reversible emulsifier is made of P (St-co-MAn-co-PVBTEAB), neopelex, petroleum sodium sulfonate, perfluoroalkyl ethers carboxylic acid potassium salt FC-5.The present invention also provides can salinity control phase transition reversible emulsion preparation method and can salinity control phase transition reversible emulsion phase inversion process.Concentration by adjusting inorganic salts or reversal agent can be convenient quickly control emulsion and mutually convert between w/o type and O/W type, so that reversible emulsion is can adapt to the requirement of several work environment, and not can cause environmental pollution.
Description
Technical field
The present invention relates to reversible emulsion, preparation method and the phase inversions of a kind of achievable multiple phase transition of salinity control
Method belongs to Colloid and interface chemistry field.
Background technique
Emulsion refers to that a kind of liquid is dispersed in formed in another and its not miscible liquid with drops
Dispersion, have good physicochemical properties, oil field construction in be widely used and petrochemical industry in it is common
Grease existence form.On the one hand, due to oil field work progress complexity, the working solution of single mass is not able to satisfy various working
Requirement, therefore the property for changing working solution in the construction process is particularly important；On the other hand, due to water-in-oil emulsion and
Oil-in-water emulsion viscosity, conductivity, in terms of there are very big difference, can be allowed to by changing emulsion phase
More adapt to the condition of oil extraction, transport and storage.
With the raising of oil field fining degree, phase conversion of emulsion technology is widely used in oilfield exploitation procedure.
The factor for influencing emulsion phase can be summarized as formulation variables, four class of composition variable, emulsification scheme and environmental variance, wherein matching
Fang Bianliang includes emulsifier, water phase physical property, oil phase thing, and composition variable includes emulsifier content, grease volume ratio；Environment
Variable includes intensity of illumination, pH value, salinity and temperature.Although the factor for influencing phase conversion of emulsion is numerous, in oil field operation
In, emulsion system is primarily present in underground or pipeline, and formulation variables, composition variable and emulsification scheme are once it is determined that be all difficult
It is adjusted, therefore the key for controlling phase conversion of emulsion is development environment responsive type emulsifier.
The reversible phase inversion of emulsion refers to emulsion reversible transformation between w/o type and O/W type.Reversible emulsion not only has
There are all advantages of phase conversion of emulsion technology, also helps recycling for emulsifying working solution.
Chinese patent document CN105567182A provides a kind of reversible emulsus of pH value regulation that multiple phase transition can be achieved
Liquid and preparation method thereof.The raw material of the reversible emulsion forms are as follows: nano silica or nano oxidized titanium nano particle, N, N-
Two (2- ethoxy) amides, oil phase and water phase.Using N, (2- ethoxy) amide of N- bis- and nano particle jointly stabilizing emulsion.
The reversible emulsion acid adding of the pH value regulation of the invention can be changed into O/W type, then plus alkali can be changed into w/o type again, so repeatedly
Operation, is able to achieve multiple phase transition.But the invention is to need to change during phase inversion using the reversible emulsion of pH value regulation
The pH value of emulsion, and the problems such as the pH value for changing emulsion easily causes formation contaminant, corrosive pipeline.
Influence about salinity to emulsifier has paper to report inorganic salts and emulsifies to neopelex (SDBS)
The influence of the stability and phase inversion of dewatered oil and the stable O/W emulsion of deionized water, finds divalent and trivalent metal salt
It can be w/o type by phase conversion of emulsion, alkalescent sodium salt can generate synergistic effect with SDBS, be conducive to the stabilization of emulsion；Ginseng
See that Zhao repairs too etc. " influence of the inorganic salts to emulsion stability and phase inversion ", " inorganic chemicals industry " 2012 the 9th phase of volume 44
Page 25~28.The emulsion that paper experiment uses is that the SDBS of mass fraction 0.4% is prepared as emulsifier and crude oil, water
Oil-in-water emulsion is shown experimentally that, although divalent and trivalent metal salt can trigger the emulsion and phase inversion occur,
Emulsion stability after phase inversion is very poor.In addition, this article does not study the reverse phase process of its emulsion yet.So far, also
Do not find the report for having the method for the salinity control reversible phase inversion of emulsion.
In petroleum technology field, the reversible phase inversion of emulsion, salinity control are carried out relative to control intensity of illumination and temperature
The phase conversion of emulsion technology most application value of system.Key is to need a kind of reversible emulsus that phase transition is controlled by salinity
Liquid, but also to make the lotion after phase inversion sufficiently stable, just adapt to the requirement of various actual job environment.The applicant is thus
It is proposed the present invention.
Summary of the invention
In view of the deficiencies of the prior art, the present invention provide it is a kind of can salinity control phase transition reversible emulsion and its preparation
Method, the emulsion be it is stable by reversible emulsifier, by change salinity can realize multiple phase transition.
The present invention also provides it is a kind of can salinity control phase transition reversible emulsion phase inversion process.
Term explanation:
It is of the present invention that multiple phase transition can be achieved, it is directed to that high-valency metal salt is added in the emulsion, when high price
When concentration of metal ions is dominant, emulsion is w/o type from O/W type phase inversion, adds acid group or hydroxyl for high volence metal ion
It disposes, emulsion is again O/W type from w/o type phase inversion；High-valency metal salt is added thereto again, when the concentration of high volence metal ion
When being dominant again, phase inversion is w/o type to emulsion again, by being added or removing high volence metal ion, emulsion can be made in O/W type and
It carries out repeatedly mutually converting between w/o type.
Syneresis rate refers to that the ratio of the total volume of water in the volume and emulsion of water is precipitated in emulsion.
Condensate oil rate refers to that the ratio of total volume oily in the volume and emulsion of oil is precipitated in emulsion.
P (St-co-MAn-co-PVBTEAB): poly- (styrene-co- maleic anhydride-co- is to vinyl benzyl triethyl group bromine
Change ammonium).
PVBTEAB: to vinyl benzyl triethylammonium bromide.
Petroleum sodium sulfonate, abbreviation petroleum soap, commercial products.
Perfluoroalkyl ethers carboxylic acid potassium salt FC-5, molecular formula C15F29O6K, commercial products.
Technical scheme is as follows:
It is a kind of can salinity control phase transition reversible emulsion, raw material composition it is as follows:
Reversible 0.06~0.6 parts by weight of emulsifier, 40~60 parts by volume of water, oily 40~60 parts by volume of phase, and water and oily phase
Total volume be 100 parts by volume, the unit of the parts by weight/parts by volume are as follows: g/mL or kg/L；Wherein,
The reversible emulsifier is formulated by following component by mass percentage:
P (St-co-MAn-co-PVBTEAB) 15~25%,
Neopelex 30~40%,
Petroleum sodium sulfonate 25~35%,
Perfluoroalkyl ethers carboxylic acid potassium salt's FC-510~20%, the sum of each component are 100%.
It is preferred according to the present invention, it is described can salinity control phase transition reversible emulsion, raw material composition is as follows:
Reversible 0.1~0.3 parts by weight of emulsifier, 45~55 parts by volume of water, oily 45~55 parts by volume of phase, and water and oily phase
Total volume is 100 parts by volume, the unit of the parts by weight/parts by volume are as follows: g/mL or kg/L；Wherein,
The reversible emulsifier is formulated by following component by mass percentage:
P (St-co-MAn-co-PVBTEAB) 18~22%,
Neopelex 28~35%,
Petroleum sodium sulfonate 26~33%,
Perfluoroalkyl ethers carboxylic acid potassium salt's FC-514~19%, the sum of each component are 100%.
Preferred according to the present invention, the oil is mutually dewatered oil, white oil, diesel oil or kerosene.It is further preferably described
Oil be mutually dewatered oil, 5# white oil or -10# diesel oil.
Preferred according to the present invention, the water is deionized water.
According to the present invention, it is above-mentioned can the reversible emulsion of salinity control phase transition be oil-in-water emulsion.It is denoted as O/W
Emulsion.
The synthetic method of P (St-co-MAn-co-PVBTEAB) of the present invention, comprises the following steps that
In the case where azodiisobutyronitrile (AIBN) and dibenzoyl peroxide (BPO) cause, in Isosorbide-5-Nitrae-dioxane solvent,
Make styrene (St), maleic anhydride (MA) and vinyl benzyl triethylammonium bromide (PVBTEAB) reacted under vacuum conditions,
75~85 DEG C of reaction temperature；Reaction product is separated, purified, is dried, P (St-co-MAn-co- is made
PVBTEAB).Preferably, styrene, maleic anhydride, to molar ratio=5.5~6.5 of vinyl benzyl triethylammonium bromide:
8.5~9.5:0.9~1.1；Azodiisobutyronitrile and styrene, maleic anhydride, to the sum of vinyl benzyl triethylammonium bromide
Molar ratio be 1:75~85；Dibenzoyl peroxide and styrene, maleic anhydride, to vinyl benzyl triethylammonium bromide it
The molar ratio of sum is 1:150~170.
It is one of the preferred embodiment of P provided by the invention (St-co-MAn-co-PVBTEAB) synthetic method below:
At room temperature, sequentially added in 100mL round-bottomed flask 30mmol styrene (St), 45mmol maleic anhydride (MA),
5mmol is to vinyl benzyl triethylammonium bromide (PVBTEAB), 1mmol azodiisobutyronitrile (AIBN), 0.5mmol peroxidating
Dibenzoyl (BPO) and 30mL Isosorbide-5-Nitrae-dioxane, stirring lead to nitrogen 20min until sufficiently dissolution, and liquid nitrogen frozen-pumping is true
Sky, so circulation three times afterwards seal flask, react 10h in 80 DEG C of oil baths；After reaction, product is cooled to room temperature,
Product is settled out in petroleum ether；Again with tetrahydrofuran (THF) for solvent, petroleum ether three times, is done for precipitating reagent purified polymer
It is dry to constant weight, obtain P (St-co-MAn-co-PVBTEAB).
P (St-co-MAn-co-PVBTEAB) of the invention is parents' random copolymer.The copolymer is existing lipophilic
There is hydrophily.
Monomer required for above-described P (St-co-MAn-co-PVBTEAB) synthesizes is to vinyl benzyl triethyl group bromine
Change ammonium (PVBTEAB) to be prepared as follows.
The preparation method of a kind of pair of vinyl benzyl triethylammonium bromide (PVBTEAB), comprises the following steps that
1. under dilauroyl peroxide (LPO) effect, in carbon tetrachloride (CCl4) in solvent, make p-methylstyrene and N-
Bromo-succinimide (NBS) is reacted, and 55~65 DEG C of reaction temperature；It is spin-dried for solvent, is made to bromometllylstyrene
(PBMS).Preferably, molar ratio=6.5 of p-methylstyrene and N- bromo-succinimide~7.5:5.5~6.5；Peroxide
The molar ratio for changing lauroyl and the sum of p-methylstyrene, N- bromo-succinimide is 1:125~135.
2. making to react bromometllylstyrene (PBMS) at room temperature with triethylamine (TEA) in tetrahydrofuran (THF)；
Reaction product is separated, carrying out washing treatment, is made to vinyl benzyl triethylammonium bromide (PVBTEAB).Preferably, to bromine
Molar ratio=0.9 of methyl styrene and triethylamine~1.1:0.9~1.1.
Described is the quick type monomer of salt to vinyl benzyl triethylammonium bromide (PVBTEAB).
It is further preferred that steps are as follows to the preparation method of vinyl benzyl triethylammonium bromide (PVBTEAB):
At room temperature, 70mmol p-methylstyrene, 60mmol N- bromo fourth two are sequentially added in 250ml round-bottomed flask
Acid imide (NBS), 1mmol dilauroyl peroxide (LPO) and 100ml carbon tetrachloride (CCl4), the back flow reaction in 60 DEG C of oil baths
7h；After reaction, succimide solid is filtered out, is spin-dried for solvent with Rotary Evaporators, obtains to bromometllylstyrene
(PBMS).At room temperature, 0.2mol is sequentially added in 250ml round-bottomed flask to bromometllylstyrene (PBMS), tri- second of 0.2mol
Amine (TEA) and 100ml tetrahydrofuran (THF), are stirred to react 20h；After reaction, solid product is obtained by filtration, and uses ether
Washing three times, is obtained to vinyl benzyl triethylammonium bromide (PVBTEAB).
According to the present invention, it is a kind of can salinity control phase transition reversible emulsion preparation method, comprising the following steps:
(1) according to the ratio, the reversible emulsifier is added to the water, stirs, is substantially dissolved in reversible emulsifier in water；
(2) according to the ratio, it takes oily phase to be sufficiently mixed with aqueous solution made from step (1), is stirred under the revolving speed of 12000r/min
8~10min is mixed, stable O/W emulsion, the reversible emulsion of salinity control as of the present invention are formed.
The reversible emulsion of salinity control of the present invention is for preparing reversible emulsion drilling fluid.
Based on it is above-mentioned can salinity control phase transition reversible emulsion, the present invention also provides a kind of turning for reversible emulsion
Phase method, details are as follows.
It is a kind of can salinity control phase transition reversible emulsion phase inversion process, including reversible emulsion above-mentioned (O/W cream
Shape liquid), it comprises the following steps that
It is 80~120g/L inorganic salt solution, 0.8~4.0mL, stirring, emulsus that concentration is added into the reversible emulsion
Liquid is w/o type by O/W type phase inversion；1.0~3.0mL of reversal agent is continuously added, is stirred, phase inversion is O/W type to emulsion again；
The inorganic salt solution high-valency metal salt is soluble in water to be made, and the high-valency metal salt is selected from MgCl2、
CaCl2、SrCl2、MnCl2、ZnCl2、CuCl2、BaCl2、CrCl3Or FeCl3；It is preferred that inorganic salt solution concentration is 100g/L.
The reversal agent is the compound containing acid group or contains alkali hydroxy solution obtained soluble in water, and concentration 80~
120g/L；Preferred concentration is 100g/L.The compound containing acid group is selected from Na2SO4、K2SO4、H2SO4、Na2CO3、K2CO3、
Na2SiO3、K2SiO3、H3PO4、Na3PO4Or K3PO4；It is described to be selected from NaOH or KOH containing alkali hydroxy.
Preferably, the stirring is 8~15min of stirring under 5000~15000r/min revolving speed.It is preferred that 8000~
10min is stirred under 12000r/min revolving speed.
In more detail, it is a kind of can salinity control phase transition reversible emulsion phase inversion process, comprise the following steps that
(1) preparation of inorganic salt solution
High-valency metal salt is soluble in water, and compound concentration is the inorganic salt solution of 80~120g/L；
The high-valency metal salt is selected from MgCl2、CaCl2、SrCl2、MnCl2、ZnCl2、CuCl2、BaCl2、CrCl3Or
FeCl3；
(2) preparation of reversal agent
By containing acid group compound or containing alkali hydroxy it is soluble in water, compound concentration be 80~120g/L solution；
The compound containing acid group is selected from Na2SO4、K2SO4、H2SO4、Na2CO3、K2CO3、Na2SiO3、K2SiO3、
H3PO4、Na3PO4Or K3PO4；
It is described to be selected from NaOH or KOH containing alkali hydroxy；
(3) phase inversion
To inorganic salt solution made from 0.8~4.0mL step (1) is added in the reversible emulsion (O/W type), 8000
8~15min is stirred under the revolving speed of~12000r/min, emulsion is w/o type by O/W type phase inversion；
(4) phase is reversed
Into above-mentioned w/o type emulsion, solution made from 1.0~3.0mL step (2) is added, in 8000~12000r/
8~15min is stirred under the revolving speed of min, phase inversion is O/W type to emulsion again.
O/W type emulsion after phase inversion obtained as above is pressed into step (3) repetitive operation, reversible emulsus of the present invention can be made
Liquid realizes multiple phase transition between O/W type and w/o type.
Preferred according to the present invention, the high-valency metal salt is selected from CaCl2、BaCl2·2H2O、MgCl2·6H2O or
CrCl3·6H2O.It is preferred that inorganic salt solution concentration is 100g/L.
Preferred according to the present invention, the compound containing acid group is selected from Na2CO3、Na2SiO3Or Na3PO4, contain hydrogen-oxygen
The alkali of root is selected from NaOH.Chemical element contained by such compound is consistent with chemical element contained by water flooding itself, can avoid over the ground
Layer pollution.It is preferred that reversal agent solution concentration is 100g/L.
The phase inversion process of the above reversible emulsion of the present invention can be convenient by adjusting inorganic salt concentration or reversal agent concentration
Quickly control emulsion is mutually converted between w/o type and O/W type, and emulsifying working solution is made to can adapt to several work environment
Requirement, and not can cause environmental pollution.
Reversible emulsifier hydrophily used in the present invention is stronger, and energy Jiang Shui is mutually emulsified into stable O/W emulsion with oil.
When high price inorganic salt solution is added, the surface charge that high-valency metal salt shields P (St-co-MAn-co-PVBTEAB) causes it
Zeta current potential absolute value reduces, and also promotes the dissociation of carboxylic acid to a certain extent, enhances surface hydrophobic；High price gold simultaneously
Belong to the diffusion electric double layer that salt also has compressed sulfonate hydrophilic radical, reduces its hydrophily, in addition formd with sulfonate ion
The sulfonate of high price, hydrophobicity enhancing, initiation phase conversion of emulsion are w/o type.Acid group or hydroxyl, high-valency metal salt and acid is added
Root or hydroxyl, which combine, forms insoluble salt, removes the high volence metal ion in emulsion, phase inversion is O/W type to emulsion again.
So reprocessing, emulsion can realize multiple phase transition between O/W type and w/o type.
Excellent results of the invention:
1, the reversible emulsion of salinity of the invention control can realize multiplicating phase inversion, in practical applications, can be significant
Improve the utilization rate of emulsifying working solution；Emulsion during defeated to oil recovery sum aggregate, can be convenient and efficient according to the requirement of environment
Change its phase.
2, the important component P (St-co-MAn-co-PVBTEAB) of reversible emulsifier of the present invention is that parents are randomly total
Polymers, the existing lipophilicity of the copolymer also have hydrophily.P (St-co-MAn-PVBTEAB) synthesis monomer styrene tool used
There is lipophilicity, maleic anhydride has hydrophily.Styrene monomer, maleic anhydride monomer random arrangement, PVBTEAB on main chain
Monomer is unordered in the form of micro- block to be distributed on main chain, and glass transition and heat distortion temperature are increased.
3, the reversible emulsion of salinity of the invention control can be used in drilling process, prepare reversible emulsion drilling fluid.This
Kind drilling fluid is w/o type drilling fluid in drilling phase, has the characteristics that good lubricity, strong inhibition capability and protection oil reservoir, is similar to
Oil base drilling fluid；It is O/W type by the emulsion drilling fluid phase inversion in completion phase, has filter cake easy-clear, cementing strength high
The features such as, it is similar to water-base drilling fluid；It is W/O by the emulsion drilling fluid again phase inversion after drilling fluid returns and is discharged to ground
Type can continue on for drillng operation.
4, in the present invention, used inorganic salts and control reverse used chemical combination during phase during control phase inversion
Chemical element contained by object is consistent with chemical element contained by water flooding itself, will not pollute stratum.
Detailed description of the invention
Fig. 1 is the O/W emulsion before the phase inversion in embodiment 2；
Fig. 2 is the O/W emulsion type qualification test before the phase inversion in embodiment 2；
Fig. 3 is the microphoto of 1200 times of O/W emulsion amplification before the phase inversion in embodiment 2；
Fig. 4 is the W/O emulsion after the phase inversion in embodiment 2；
Fig. 5 is the W/O emulsion type qualification test after the phase inversion in embodiment 2；
Fig. 6 is the microphoto of 1200 times of W/O emulsion amplification after the phase inversion in embodiment 2.
Fig. 7 is the O/W emulsion after the reverse phase in embodiment 2；
Fig. 8 is the O/W emulsion type qualification test after the reverse phase in embodiment 2；
Fig. 9 is the microphoto of 1200 times of O/W emulsion amplification after the reverse phase in embodiment 2.
Specific embodiment
The present invention is discussed in detail below by way of specific embodiment.The present invention will be further described in conjunction with the embodiments, but
It is not intended to limit the present invention.
% as described in the examples is mass percent.
Unless otherwise indicated, raw materials used in embodiment is commercially available material.Petroleum sodium sulfonate, perfluoroalkyl ethers carboxylic acid
It is Chemical Co., Ltd., Shanghai Ci Tai Yilong Industry Co., Ltd. that sylvite FC-5 is purchased from Guangzhou U.S.A respectively.
The synthesis of embodiment 1, monomer P (St-co-MAn-co-PVBTEAB)
1,70mmol p-methylstyrene, 60mmol N- bromo fourth at room temperature, are sequentially added in 250ml round-bottomed flask
Imidodicarbonic diamide (NBS), 1mmol dilauroyl peroxide (LPO) and 100ml carbon tetrachloride (CCl4), it flows back in 60 DEG C of oil baths anti-
Answer 7h；After reaction, succimide solid is filtered out, is spin-dried for solvent with Rotary Evaporators, obtains yellow oil pair
Bromometllylstyrene (PBMS).
At room temperature, 0.2mol is sequentially added in 250ml round-bottomed flask to bromometllylstyrene (PBMS), tri- second of 0.2mol
Amine (TEA) and 100ml tetrahydrofuran (THF), are stirred to react 20h；After reaction, yellow solid product is obtained by filtration, is used in combination
Ether washs three times, obtains the quick type monomer of salt to vinyl benzyl triethylammonium bromide (PVBTEAB).
2,30mmol styrene (St), 45mmol maleic anhydride at room temperature, are sequentially added in 100mL round-bottomed flask
(MA), 5mmol is to vinyl benzyl triethylammonium bromide (PVBTEAB), 1mmol azodiisobutyronitrile (AIBN), 0.5mmol mistake
Dibenzoyl (BPO) and 30mL Isosorbide-5-Nitrae-dioxane are aoxidized, stirring leads to nitrogen 20min, liquid nitrogen frozen-pumping until sufficiently dissolution
Vacuum, so circulation three times afterwards seal flask, react 10h in 80 DEG C of oil baths；After reaction, product is cooled to room
Temperature settles out product in petroleum ether；Again with tetrahydrofuran (THF) be solvent, petroleum ether be precipitating reagent purified polymer three times,
Drying obtains parents' random copolymer P (St-co-MAn-co-PVBTEAB) to constant weight.
Monomer P (St-co-MAn-co-PVBTEAB) used in following example 2-5 is the production that above embodiments 1 synthesize
Object.
Embodiment 2, it is a kind of can salinity control phase transition reversible emulsion, its preparation and phase inversion process
It is a kind of can salinity control phase transition reversible emulsion, raw material composition it is as follows:
Reversible emulsifier 0.18g, Si Kalan 5# white oil 100mL, deionized water 100mL.Wherein, the reversible emulsifier
It is formulated by mass percentage by following component:
P (St-co-MAn-co-PVBTEAB) 20%,
Neopelex 30%,
Petroleum sodium sulfonate 32%,
Perfluoroalkyl ethers carboxylic acid potassium salt FC-5 18%；
The preparation method of reversible emulsion:
The reversible emulsifier of 0.18g is mixed with 100mL deionized water, is stirred with glass bar until being completely dissolved；It is added
100mL Si blocks orchid 5# white oil, and 10min is stirred under the revolving speed of 12000r/min, forms milky O/W emulsion (such as Fig. 1, figure
3), reversible emulsion as of the invention is denoted as A1 emulsion.
The O/W type identification test of the A1 emulsion is as shown in Figure 2.
Stability experiment shows: syneresis rate is 8% after A1 emulsion stands 5 hours.
It is a kind of can salinity control phase transition reversible emulsion phase inversion process, use above-mentioned reversible emulsion (O/W cream
Shape liquid), steps are as follows:
(1) by 10gCrCl3·6H2O solid is mixed with 100mL deionized water, with glass bar stirring until CrCl3·6H2O
Solid is completely dissolved, and obtains CrCl3·6H2O solution.
(2) by 10gNa2CO3Solid is mixed with 100mL deionized water, with glass bar stirring until Na2CO3Solid is completely molten
Solution, obtains Na2CO3Solution.
(3) CrCl described in 1.4mL phase inversion process: is added in the A1 emulsion of Xiang Suoshu3·6H2O solution, uses glass bar
It stirs evenly, 10min is then stirred under the revolving speed of 12000r/min, form milky W/O emulsion, be denoted as A2 emulsion.
As shown in figs. 4 and 6.
The W/O type identification test of the A2 emulsion is as shown in Figure 5.
Stability experiment shows: A2 emulsion breakdown voltage is 153V, and condensate oil rate is 10% after standing 5 hours.
(4) it reverses phase process: Na described in 2.5mL being added in Xiang Suoshu A2 emulsion2CO3Solution is stirred equal with glass bar
It is even, 10min is then stirred under the revolving speed of 12000r/min, is formed O/W emulsion, is denoted as A3 emulsion.Such as Fig. 7, Fig. 9 institute
Show.
The O/W type identification test of the A3 emulsion is as shown in Figure 8.
Stability experiment shows: syneresis rate is 3% after A3 emulsion stands 5 hours.
Embodiment 3
It is a kind of can salinity control phase transition reversible emulsion, raw material composition it is as follows:
Reversible emulsifier 0.24g, dewatered oil 110mL, deionized water 90mL.Wherein, the reversible emulsifier presses matter
Amount percentage is formulated by following component:
The reversible emulsion the preparation method is as follows:
The reversible emulsifier of 0.24g is mixed with 90mL deionized water, is stirred with glass bar until being completely dissolved；It is added
110mL dewatered oil stirs 10min under the revolving speed of 12000r/min, forms milky O/W emulsion, as of the invention
Reversible emulsion is denoted as B1 emulsion.
Stability experiment shows: syneresis rate is 9% after B1 emulsion stands 5 hours.
It is a kind of can salinity control phase transition reversible emulsion phase inversion process, use above-mentioned reversible emulsion (O/W cream
Shape liquid), steps are as follows:
(1) by 10gBaCl2·2H2O solid is mixed with 100mL deionized water, with glass bar stirring until BaCl2·2H2O
Solid is completely dissolved, and obtains BaCl2·2H2O solution.
(2) by 10gNa2SiO3Solid is mixed with 100mL deionized water, with glass bar stirring until Na2SiO3Solid is complete
Dissolution, obtains Na2SiO3Solution.
(3) BaCl described in 3.6mL phase inversion process: is added in the B1 emulsion of Xiang Suoshu2·2H2O solution, uses glass bar
It stirs evenly, 10min is then stirred under the revolving speed of 8000r/min, form milky W/O emulsion, be denoted as B2 emulsion.
Stability experiment shows: B2 emulsion breakdown voltage is 123V, and condensate oil rate is 14% after standing 5 hours.
(4) it reverses phase process: Na described in 2.3mL being added in Xiang Suoshu B2 emulsion2SiO3Solution is stirred with glass bar
Uniformly, 10min is then stirred under the revolving speed of 8000r/min, is formed O/W emulsion, is denoted as B3 emulsion.
Stability experiment shows: syneresis rate is 5% after B3 emulsion stands 5 hours.
Embodiment 4
It is a kind of can salinity control phase transition reversible emulsion, raw material composition it is as follows:
Reversible emulsifier 0.26g, -10# diesel oil 100mL, deionized water 100mL.Wherein, the reversible emulsifier presses matter
Amount percentage is formulated by following component:
The reversible emulsion the preparation method is as follows:
The reversible emulsifier of 0.26g is mixed with 100mL deionized water, is stirred with glass bar until being completely dissolved；It is added
100mL-10# diesel oil stirs 10min under the revolving speed of 12000r/min, forms milky O/W emulsion, as of the invention
Reversible emulsion is denoted as C1 emulsion.
Stability experiment shows: syneresis rate is 7% after C1 emulsion stands 5 hours.
It is a kind of can salinity control phase transition reversible emulsion phase inversion process, use above-mentioned reversible emulsion (O/W cream
Shape liquid), steps are as follows:
(1) by 10gCaCl2Solid is mixed with 100mL deionized water, with glass bar stirring until CaCl2Solid is completely molten
Solution, obtains CaCl2Solution.
(2) by 10gNa3PO4Solid is mixed with 100mL deionized water, with glass bar stirring until Na3PO4Solid is completely molten
Solution, obtains Na3PO4Solution.
(3) CaCl described in 1.2mL phase inversion process: is added in the C1 emulsion of Xiang Suoshu2Solution is stirred equal with glass bar
It is even, 10min is then stirred under the revolving speed of 10000r/min, is formed milky W/O emulsion, is denoted as C2 emulsion.
Stability experiment shows: C2 emulsion breakdown voltage is 133V, and condensate oil rate is 13% after standing 5 hours.
(4) it reverses phase process: Na described in 1.6mL being added in Xiang Suoshu C2 emulsion3PO4Solution is stirred equal with glass bar
It is even, 10min is then stirred under the revolving speed of 10000r/min, is formed O/W emulsion, is denoted as C3 emulsion.
Stability experiment shows: syneresis rate is 4% after C3 emulsion stands 5 hours.
Embodiment 5
It is a kind of can salinity control phase transition reversible emulsion, raw material composition it is as follows:
Reversible emulsifier 0.16g, Si Kalan 5# white oil 90mL, deionized water 110mL.Wherein, the reversible emulsifier
It is formulated by mass percentage by following component:
P (St-co-MAn-co-PVBTEAB) 21%,
Neopelex 35%,
Petroleum sodium sulfonate 29%,
Perfluoroalkyl ethers carboxylic acid potassium salt FC-515%.
The reversible emulsion the preparation method is as follows:
The reversible emulsifier of 0.16g is mixed with 110mL deionized water, is stirred with glass bar until being completely dissolved；It is added
90mL Si blocks orchid 5# white oil, and 8min is stirred under the revolving speed of 12000r/min, forms milky O/W emulsion, as of the invention
Reversible emulsion, be denoted as D1 emulsion.
Stability experiment shows: syneresis rate is 12% after D1 emulsion stands 5 hours.
It is a kind of can salinity control phase transition reversible emulsion phase inversion process, use above-mentioned reversible emulsion (O/W cream
Shape liquid), steps are as follows:
(1) by 10gCrCl3·6H2O solid is mixed with 100mL deionized water, with glass bar stirring until CrCl3·6H2O
Solid is completely dissolved, and obtains CrCl3·6H2O solution.
(2) 10gNaOH solid is mixed with 100mL deionized water, with glass bar stirring until NaOH solid is completely dissolved,
Obtain NaOH solution.
(3) CrCl described in 0.8mL phase inversion process: is added in the D1 emulsion of Xiang Suoshu3·6H2O solution, uses glass bar
It stirs evenly, 10min is then stirred under the revolving speed of 12000r/min, form milky W/O emulsion, be denoted as D2 emulsion.
Stability experiment shows: D2 emulsion breakdown voltage is 187V, and condensate oil rate is 9% after standing 5 hours.
(4) it reverses phase process: NaOH solution described in 1.0mL step (2) being added in Xiang Suoshu D2 emulsion, uses glass bar
It stirs evenly, 10min is then stirred under the revolving speed of 12000r/min, form O/W emulsion, be denoted as D3 emulsion.
Stability experiment shows: syneresis rate is 7% after D3 emulsion stands 5 hours.
Claims (13)
1. one kind can salinity control phase transition reversible emulsion, it is characterised in that raw material composition it is as follows:
Reversible 0.06~0.6 parts by weight of emulsifier, 40~60 parts by volume of water, oily 40~60 parts by volume of phase, and water are total with oily phase
Volume is 100 parts by volume, the unit of the parts by weight/parts by volume are as follows: g/mL or kg/L；Wherein,
The reversible emulsifier is formulated by following component by mass percentage:
2. as described in claim 1 can salinity control phase transition reversible emulsion, which is characterized in that raw material composition it is as follows:
The totality of reversible 0.1~0.3 parts by weight of emulsifier, 45~55 parts by volume of water, oily 45~55 parts by volume of phase, and water and oily phase
Product is 100 parts by volume, the unit of the parts by weight/parts by volume are as follows: g/mL or kg/L；Wherein,
The reversible emulsifier is formulated by following component by mass percentage:
3. as claimed in claim 1 or 2 can salinity control phase transition reversible emulsion, which is characterized in that the oily phase
It is dewatered oil, white oil, diesel oil or kerosene.
4. as claimed in claim 1 or 2 can salinity control phase transition reversible emulsion, which is characterized in that the oil is mutually
Dewatered oil, 5# white oil or -10# diesel oil.
5. as claimed in claim 1 or 2 can salinity control phase transition reversible emulsion, it is characterised in that the P (St-
Co-MAn-co-PVBTEAB it) synthesizes by the following method:
In the case where azodiisobutyronitrile and dibenzoyl peroxide cause, in Isosorbide-5-Nitrae-dioxane solvent, make styrene (St), horse
Carry out acid anhydrides (MA) and vinyl benzyl triethylammonium bromide (PVBTEAB) is reacted under vacuum conditions, reaction temperature 75~85
℃；Reaction product is separated, purified, is dried, is made P (St-co-MAn-co-PVBTEAB).
6. as claimed in claim 5 can salinity control phase transition reversible emulsion, which is characterized in that the styrene, horse
Come acid anhydrides, molar ratio=5.5~6.5:8.5~9.5:0.9~1.1 to vinyl benzyl triethylammonium bromide；Azo two is different
Butyronitrile and styrene, maleic anhydride are 1:75~85 to the molar ratio of the sum of vinyl benzyl triethylammonium bromide；Peroxidating two
Benzoyl and styrene, maleic anhydride are 1:150~170 to the molar ratio of the sum of vinyl benzyl triethylammonium bromide.
7. as claimed in claim 5 can salinity control phase transition reversible emulsion, it is characterised in that it is described to vinyl benzyl
Base triethylammonium bromide (PVBTEAB) is prepared as follows:
Under dilauroyl peroxide effect, in carbon tetrachloride solvent, make p-methylstyrene and N- bromo-succinimide into
Row reaction, 55~65 DEG C of reaction temperature；It is spin-dried for solvent, is made to bromometllylstyrene (PBMS)；P-methylstyrene and N- bromine
For molar ratio=6.5~7.5:5.5~6.5 of succimide；Dilauroyl peroxide and p-methylstyrene, N- bromo fourth two
The molar ratio of the sum of acid imide is 1:125~135；
In tetrahydrofuran, make to react bromometllylstyrene (PBMS) at room temperature with triethylamine (TEA)；By reaction product into
Row separation, carrying out washing treatment, are made to vinyl benzyl triethylammonium bromide (PVBTEAB)；To bromometllylstyrene and triethylamine
Molar ratio=0.9~1.1:0.9~1.1.
8. described in a kind of any one of claim 1-7 can salinity control phase transition reversible emulsion preparation method, including with
Lower step:
(1) according to the ratio, the reversible emulsifier is added to the water, stirs, is substantially dissolved in reversible emulsifier in water；
(2) according to the ratio, take it is oily be mutually sufficiently mixed with aqueous solution made from step (1), stir 8 under the revolving speed of 12000r/min~
10min forms stable O/W emulsion.
9. claim 1-7 it is described in any item can salinity control phase transition reversible emulsion application, it is reversible for preparing
Emulsion drilling fluid.
10. one kind can salinity control phase transition reversible emulsion phase inversion process, including claim 1-7 is described in any item
Can salinity control phase transition reversible emulsion, steps are as follows:
Into the reversible emulsion be added concentration be 80~120g/L inorganic salt solution, 0.8~4.0mL, stirring, emulsion by
O/W type phase inversion is w/o type；1.0~3.0mL of reversal agent is continuously added, is stirred, phase inversion is O/W type to emulsion again；
The inorganic salt solution is with high-valency metal salt MgCl2、CaCl2、SrCl2、MnCl2、ZnCl2、CuCl2、BaCl2、CrCl3
Or FeCl3It is soluble in water to be made；
The reversal agent is for the compound containing acid group or containing alkali hydroxy solution obtained soluble in water, 80~120g/ of concentration
L；
The compound containing acid group is selected from Na2SO4、K2SO4、H2SO4、Na2CO3、K2CO3、Na2SiO3、K2SiO3、H3PO4、
Na3PO4Or K3PO4；It is described to be selected from NaOH or KOH containing alkali hydroxy.
11. as claimed in claim 10 can salinity control phase transition reversible emulsion phase inversion process, it is characterised in that institute
The high-valency metal salt stated is selected from CaCl2、BaCl2·2H2O、MgCl2·6H2O or CrCl3·6H2O。
12. as claimed in claim 10 can salinity control phase transition reversible emulsion phase inversion process, it is characterised in that institute
Stating stirring is 8~15min of stirring under 5000~15000r/min revolving speed.
13. as claimed in claim 10 can salinity control phase transition reversible emulsion phase inversion process, which is characterized in that institute
Stating stirring is to stir 10min under 8000~12000r/min revolving speed.
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| CN105642186A (en) * | 2016-01-13 | 2016-06-08 | 中国石油大学(华东) | PH-responded reversible emulsifier composition as well as preparation method and application thereof |
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| CN105642186A (en) * | 2016-01-13 | 2016-06-08 | 中国石油大学(华东) | PH-responded reversible emulsifier composition as well as preparation method and application thereof |
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