CN105273704B - Salt tolerant oil displacement surfactant and preparation method thereof - Google Patents
Salt tolerant oil displacement surfactant and preparation method thereof Download PDFInfo
- Publication number
- CN105273704B CN105273704B CN201410328886.2A CN201410328886A CN105273704B CN 105273704 B CN105273704 B CN 105273704B CN 201410328886 A CN201410328886 A CN 201410328886A CN 105273704 B CN105273704 B CN 105273704B
- Authority
- CN
- China
- Prior art keywords
- reaction
- sulfonic acid
- small
- ether
- oil displacement
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Lubricants (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)
Abstract
The present invention relates to salt tolerant oil displacement surfactant and preparation method thereof, mainly solves the problems, such as that oil displacement efficiency is low under the conditions of high salinity containing surfactant in the prior art.The present invention its entitled 3 (alkyl phenol polyethenoxy ether) 2 (hydroxypropyl sulfonic acid polyethenoxy ether) propane sulfonic acid salt by using salt tolerant oil displacement surfactant, shown in structure such as formula (I), wherein M1And M2It is independently selected from as any one in alkali metal, alkaline-earth metal, works as M1For alkali metal when n1For 1, work as M1For alkaline-earth metal when n1For 0.5, work as M2For alkali metal when n2For 1, work as M2For alkaline-earth metal when n2For 0.5, R C4~C20Alkyl, x=1~20, the technical solution of y=1~10, preferably solves the problems, such as this, available for oil field raising oil recovery factor production in.
Description
Technical field
The present invention relates to a kind of salt tolerant oil displacement surfactant and preparation method thereof.
Background technology
Oil field enter high water-cut stage after, remaining oil with discontinuous oil film by trap in the hole of reservoir rocks, make
Two main power on oil droplet are viscaps, if selecting suitable surfactant system, reduce oil
Interfacial tension between water, makes the interfacial tension between oil reservoirs grease be down to relatively low or ultralow value (10 from 20~30mN/m-3~10- 4MN/m), resistance caused by oil droplet deformation when moving remaining oil just can be reduced, so as to greatly improve oil displacement efficiency.
Most or petroleum sulfonate, heavy alkylbenzene sulfonate etc. the oil refining accessory substance of oil recovery surfactant application changes
Property surfactant, the characteristics of this kind of surfactant is that materials are extensive, cheap, still, this kind of surfactant
There is performance to be not sufficiently stable, salt tolerant especially the poor-performing of resistance to bivalent cation a series of problems, such as, it is impossible to suitable for high temperature, height
The oil field block of salt.The novel surfactant of multiple active function groups is introduced in same molecule, is greatly improved surface
Activity, and synergistic effect may be produced, increase salt-resistance.Patent U.S.Pat.No.4436672A alkylols are with shrinking
Glycerine reaction obtains alkylol polyglycidyl ether, then carries out sulfonation, obtains a kind of anion-nonionic surfactant；Patent
U.S.Pat.No.4466891A provides a kind of alkylphenol polyoxyethylene ether propane sulfonic acid salt；Patent
U.S.Pat.No.2011015111A1 is with alhpa olefin and 1, chloro- ethers of the 2- propyl alcohol reaction generation containing chloro base of 3- bis-, Ran Houjin
Row sulfonating reaction, obtains a kind of new anion surfactant containing two sulfo groups.But existing surfactant
Have much room for improvement in the oil displacement efficiency of high salt high temperature oil reservoir.
The content of the invention
The first technical problem to be solved by the present invention is that there are under high temperature, high salt conditions for surfactant in the prior art
The problem of oil displacement efficiency is low, there is provided a kind of new salt tolerant oil displacement surfactant, the surfactant have in high salinity bar
The characteristics of oil displacement efficiency is high under part.
The second technical problem to be solved by the present invention is to provide a kind of with solving one of technical problem corresponding salt tolerant
The preparation method of oil displacement surfactant.
The third technical problem to be solved by the present invention is that one of technical problem surfactant improves original in oil field
Application in oil recovery.
To solve one of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Salt tolerant oil displacement surfactant, its
Entitled 3- (alkyl phenol polyethenoxy ether) -2- (hydroxypropyl sulfonic acid polyethenoxy ether) propane sulfonic acid salt, shown in structure such as formula (I)：
Wherein M1And M2It is independently selected from as any one in alkali metal, alkaline-earth metal, works as M1For alkali metal when n1For 1, work as M1
For alkaline-earth metal when n1For 0.5, work as M2For alkali metal when n2For 1, work as M2For alkaline-earth metal when n2For 0.5, R C4~C20Hydrocarbon
Base, x=1~20, y=1~10.
In above-mentioned technical proposal, preferably x=2~8, y=2~4.
In above-mentioned technical proposal, the alkyl is preferably C7~C10Alkyl.
In above-mentioned technical proposal, as the most preferable technical solution：The alkyl is C8~C9Alkyl, x=4~6, y
=2-3.
To solve the two of above-mentioned technical problem, the technical solution adopted by the present invention is as follows：Described in one of above-mentioned technical problem
The preparation method of salt tolerant oil displacement surfactant, comprises the following steps：
A) under basic catalyst effect, alkyl phenol obtains alkyl phenol polyethenoxy ether with aequum reacting ethylene oxide；
Reaction temperature is preferably 85~160 DEG C, and pressure is preferably 0~0.40MPa (gauge pressure), when the reaction time is preferably 1~10 small；
B) alkyl phenol polyethenoxy ether obtained by step a) is dissolved into C6~C8In aromatic hydrocarbons, add alkali metal hydroxide or
At least one of alkaline earth metal hydroxide alkali, when alkalization 0.5~3 is small at 30~60 DEG C, adds 3- the third sulphurs of chlorine-2-hydroxyl
The alkali metal salt of acid, stirs lower reaction and obtains 3- (alkyl phenol polyethenoxy ether) -2- hydroxy-propanesulfonic acid salt；The alkyl phenol polyoxy
The molar ratio of vinethene and the alkali is preferably 1:(1~3)；Wherein described alkyl phenol polyethenoxy ether and 3- chlorine-2-hydroxyls third
The molar ratio of sulfonic acid alkali metal salts is preferably 1:(1~4)；Reaction temperature is preferably 30~80 DEG C；Reaction time is preferably 6~18
Hour；
C) by 3- (alkyl phenol polyethenoxy ether) -2- hydroxy-propanesulfonic acid salt obtained by step b), under basic catalyst effect,
React to obtain the 3- (alkyl phenol polyethenoxy ether) -2- (polyethenoxy ether) propane sulfonic acid salt with aequum propylene oxide；Reaction
Temperature is preferably 85~160 DEG C；Reaction pressure is preferably 0~0.40MPa (gauge pressure)；When reaction time preferably 1~10 is small；
D) by 3- (alkyl phenol polyethenoxy ether) -2- (polyethenoxy ether) propane sulfonic acid salt obtained by step c), it is dissolved into C6~C8
In aromatic hydrocarbons, at least one of alkali metal hydroxide or alkaline earth metal hydroxide alkali are added, alkalizes 0.5 at 30~60 DEG C
~3 it is small when, add the alkali metal salt of 3- chlorine-2-hydroxyl propane sulfonic acid, stir lower reaction and obtain 3- (alkyl phenol polyethenoxy ether) -2-
(hydroxypropyl sulfonic acid polyethenoxy ether) propane sulfonic acid salt；3- (alkyl phenol polyethenoxy ether) -2- (polyethenoxy ether) propane sulfonic acid
The molar ratio of salt and the alkali is preferably 1:(1~3)；The third sulphur of the 3- (alkyl phenol polyethenoxy ether) -2- (polyethenoxy ether)
The molar ratio of hydrochlorate and the alkali metal salt of 3- chlorine-2-hydroxyl propane sulfonic acid is preferably 1:(1~4)；Reaction temperature is preferably 30~80
℃；When reaction time is preferably 6~18 small.
In above-mentioned technical proposal, step a) and/or step c) the basic catalyst preferred alkali metal hydroxides or alkali
At least one of earth metal hydroxide.Step b) the alkyl phenol polyethenoxy ethers and 3- chlorine-2-hydroxyl propane sulfonic acid alkali gold
The molar ratio for belonging to salt is more preferably 1:(1~2), the reaction time be more preferably 6~10 it is small when.Step a) and/or step c) is described
Basic catalyst more preferably at least one of sodium hydroxide or potassium hydroxide.Step a) and/or the step c) reaction temperatures
More preferably 120~140 DEG C, the reaction time be more preferably 6~8 it is small when.
To solve the three of present invention problem, the technical solution adopted by the present invention is as follows：One of above-mentioned technical problem institute
State application of the surfactant in oil recovery factor is improved.
In above-mentioned technical proposal, the specific method of the application can be that will be asked in terms of parts by weight including the technology of the present invention
The oil displacement agent injection oil bearing bed of 100~2000 parts of 1 part of one of the topic surfactant and water.The water wherein used can be
Deionized water, river water, underground water, seawater, are preferably that total salinity scope is 80000-300000mg/L, Ca2++Mg2+For
The water of 1000-6000mg/L, for consideration easy for construction, saving water resource etc., more preferably oilfield injection water, such as
The Zhongyuan Oil Field Pu Chengxi Districts injection water that the embodiment of the present invention uses.In order to increase oil displacement efficiency, may be used also in oil displacement agent of the present invention
With including additive commonly used in the art, such as small molecule alcohol, DMSO, diethanol amine, CTAC etc..
The key problem in technology of the present invention is that surfactant employs new anion-nonionic surfactant, containing more
A hydrophilic radical, two sulfonic acid groups are located at molecule segment and the centre of polyoxyethylene and polyoxypropylene segment respectively.While by
The salt resistance of surfactant and the performance of anti-bivalent cation are considerably increased in the synergistic effect of multiple groups, with the prior art
In anion-nonionic surfactant compare, the surfactant salt resistance ability that uses of the present invention is stronger, available for high salinity
The oil reservoir displacement of reservoir oil, there is very high theory significance, and be with a wide range of applications and practical significance.
Surfactant of the present invention is in 85 DEG C of Zhongyuan Oil Field Pu Chengxi Districts formation temperature, salinity 80000-300000mg/
L, Ca2+、Mg2+Concentration still can form 10 under conditions of being 1000-6000mg/L with the block dewatered oil-3The mN/m orders of magnitude
Ultralow interfacial tension, so as to drive crude oil, improve recovery ratio more than 10%, achieve preferable technique effect.
Below by embodiment, the present invention is further elaborated.
Embodiment
【Embodiment 1】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
1.5mol ethylene oxide is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (3) ether.
B) nonylphenol polyoxyethylene ether (3) obtained by step a) is added to equipped with agitating device, condensation reflux unit and divided
In the reactor of water installations, 250 milliliters of benzene and 40 grams of sodium hydroxides are added, when alkalization 2 is small at 60 DEG C, add 0.61mol3-
Chlorine-2-hydroxyl propanesulfonate, at reflux, when reaction 8 is small.After reaction, hydrochloric acid that concentration is 6M is added dropwise by system
PH be transferred to 2, be extracted with ethyl acetate, after solvent is evaporated off in oil phase, neutralized with sodium hydroxide solution, then in volume ratio acetone:
Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (nonylphenol polyoxyethylene ether (3)) -2- hydroxy-propanesulfonic acid salt
(0.39mol)。
C) 3- (nonylphenol polyoxyethylene ether (3)) -2- hydroxy-propanesulfonic acid salt for synthesizing step b), is added to equipped with condensation
In the reactor of device, agitating device and gas distributor, 2 grams of sodium hydroxides and 20 grams of water are added, are heated to when leading to nitrogen
At 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, with nitrogen purge 4 times,
Then system reaction temperature is adjusted to 150 DEG C and is slowly passed through 0.39mol propylene oxide, control pressure≤0.40MPa is reacted；
After reaction, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain 3- (nonylphenol polyoxyethylene ether (3)) -2- (polyoxies
Propylene ether (1)) propane sulfonic acid salt (0.39mol).
D) 3- (nonylphenol polyoxyethylene ether (3)) -2- (polyethenoxy ether (1)) propane sulfonic acid salt for synthesizing step c)
(0.39mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.78mol), when alkalization 2 is small at 60 DEG C, adds 0.47mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (nonylphenol polyoxyethylene ether (3)) -2- (hydroxypropyl sulfonic acid polyethenoxy ether (1)) propane sulfonic acid salt
(0.36mol)。
2. surfactant properties are evaluated
Oil displacement agent is prepared:
The transparent oil displacement agent that above-mentioned 1 parts by weight of surfactant and Pu Chengxi Districts injection 500 parts by weight of water are mixed to get
For interfacial tension evaluation and oil displacement experiment.Injection water in Pu Chengxi Districts used wherein in all embodiments of the invention and comparative example
Composition is shown in Table 1.Composition for ease of comparing oil displacement agent is listed in table 2.
A) interfacial tension is evaluated
TX-500C rotating interfacial tensimeters, at 85 DEG C, rotating speed 4500 are produced using Texas ,Usa university
Under the conditions of rev/min, the interfacial tension measured between the dewatered oil of above-mentioned oil displacement agent and Pu Chengxi District extraction the results are shown in Table 3.
B) oil displacement experiment is evaluated
According to the composite oil-displacing system physical simulation flooding test in SY/T6424-2000 composite oil-displacing system performance test methods
Measure of merit, at 85 DEG C, length 30cm, a diameter of 2.5cm, permeability 1.5m2Rock core on to carry out imitation oil displacement experiment real
Test.Water drive first is carried out to aqueous 98% with Pu Chengxi Districts injection water, after water drive, on metaideophone 0.3pv (rock pore volume)
Oil displacement agent is stated, then water drive to aqueous 98%, improve oil recovery factor and the results are shown in Table 4.
【Embodiment 2】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
0.5mol ethylene oxide is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 130 grams of Nonyl pheno (1) ethers.
B) 0.5mol nonylphenol polyoxyethylene ether (1) obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 250 milliliters of benzene and 40 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.6mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, the salt that concentration is 6M is added dropwise
The pH of system is transferred to 2 by acid, is extracted with ethyl acetate, after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in volume
Compare acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (nonylphenol polyoxyethylene ether (1)) third sulphur of -2- hydroxyls
Hydrochlorate 0.38mol.
C) step b) is synthesized into 3- (nonylphenol polyoxyethylene ether (1)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, 1.5 grams of sodium hydroxides and 1.5 grams of water are added, while leading to nitrogen
While when being heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, use nitrogen
Purging 4 times, is then adjusted to 150 DEG C by system reaction temperature and is slowly passed through 1.52mol propylene oxide, control pressure≤0.40MPa
Reaction；After reaction, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain 3- (nonylphenol polyoxyethylene ether (1)) -2-
(polyethenoxy ether (4)) propane sulfonic acid salt 0.37mol.
D) 3- (nonylphenol polyoxyethylene ether (1)) -2- (polyethenoxy ether (4)) propane sulfonic acid salt for synthesizing step c)
(0.37mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.74mol), when alkalization 2 is small at 60 DEG C, adds 0.45mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (nonylphenol polyoxyethylene ether (1)) -2- (hydroxypropyl sulfonic acid polyethenoxy ether (4)) propane sulfonic acid salt
(0.35mol)。
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 3】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
1.0mol ethylene oxide is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (2) ether.
B) 0.49mol nonylphenol polyoxyethylene ether (2) obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 250 milliliters of benzene and 40 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.59mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, the salt that concentration is 6M is added dropwise
The pH of system is transferred to 2 by acid, is extracted with ethyl acetate, after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in volume
Compare acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (nonylphenol polyoxyethylene ether (2)) third sulphur of -2- hydroxyls
Hydrochlorate 0.38mol.
C) step b) is synthesized into 3- (nonylphenol polyoxyethylene ether (2)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, 1.5 grams of sodium hydroxides and 1.5 grams of water are added, while leading to nitrogen
While when being heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, use nitrogen
Purging 4 times, is then adjusted to 150 DEG C by system reaction temperature and is slowly passed through 0.76mol propylene oxide, control pressure≤0.40MPa
Reacted；After reaction, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain 3- (nonylphenol polyoxyethylene ether
(2)) -2- (polyethenoxy ether (2)) propane sulfonic acid salt 0.36mol.
D) 3- (nonylphenol polyoxyethylene ether (2)) -2- (polyethenoxy ether (2)) propane sulfonic acid salt for synthesizing step c)
(0.36mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.72mol), when alkalization 2 is small at 60 DEG C, adds 0.42mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (nonylphenol polyoxyethylene ether (2)) -2- (hydroxypropyl sulfonic acid polyethenoxy ether (2)) propane sulfonic acid salt
(0.33mol)。
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 4】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
2.0mol ethylene oxide is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (4) ether.
B) 0.49mol nonylphenol polyoxyethylene ether (4) obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 250 milliliters of benzene and 40 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, the salt that concentration is 6M is added dropwise
The pH of system is transferred to 2 by acid, is extracted with ethyl acetate, after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in volume
Compare acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (nonylphenol polyoxyethylene ether (4)) third sulphur of -2- hydroxyls
Hydrochlorate 0.38mol.
C) step b) is synthesized into 3- (nonylphenol polyoxyethylene ether (4)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, 2 grams of sodium hydroxides and 20 grams of water are added, when leading to nitrogen
When being heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, blown with nitrogen
Sweep 4 times, system reaction temperature then is adjusted to 150 DEG C is slowly passed through 0.76mol propylene oxide, control pressure≤0.40MPa into
Row reaction；After reaction, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (nonylphenol polyoxyethylene ether (4))-
2- (polyethenoxy ether (2)) propane sulfonic acid salt 0.37mol.
D) 3- (nonylphenol polyoxyethylene ether (2)) -2- (polyethenoxy ether (2)) propane sulfonic acid salt for synthesizing step c)
(0.36mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.72mol), when alkalization 2 is small at 60 DEG C, adds 0.42mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (nonylphenol polyoxyethylene ether (2)) -2- (hydroxypropyl sulfonic acid polyethenoxy ether (2)) propane sulfonic acid salt
(0.33mol)。
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 5】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
3.0mol ethylene oxide is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (6) ether.
B) 0.49mol nonylphenol polyoxyethylene ether (6) obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 500 milliliters of benzene and 40 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, the salt that concentration is 6M is added dropwise
The pH of system is transferred to 2 by acid, is extracted with ethyl acetate, after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in volume
Compare acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (nonylphenol polyoxyethylene ether (6)) third sulphur of -2- hydroxyls
Hydrochlorate 0.39mol.
C) step b) is synthesized into 3- (nonylphenol polyoxyethylene ether (6)) -2- hydroxy-propanesulfonic acid salt 0.39mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, 2 grams of sodium hydroxides and 20 grams of water are added, when leading to nitrogen
When being heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, blown with nitrogen
Sweep 4 times, system reaction temperature then is adjusted to 150 DEG C is slowly passed through 1.18mol propylene oxide, control pressure≤0.40MPa into
Row reaction；After reaction, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (nonylphenol polyoxyethylene ether (6))-
2- (polyethenoxy ether (3)) propane sulfonic acid salt 0.38mol.
D) 3- (nonylphenol polyoxyethylene ether (6)) -2- (polyethenoxy ether (3)) propane sulfonic acid salt for synthesizing step c)
(0.38mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.76mol), when alkalization 2 is small at 60 DEG C, adds 0.44mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (nonylphenol polyoxyethylene ether (6)) -2- (hydroxypropyl sulfonic acid polyethenoxy ether (3)) propane sulfonic acid salt
(0.35mol)。
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 6】
1. prepared by surfactant
The surfactant synthesized using embodiment 5, except that compound concentration.
2. oil displacement agent performance evaluation
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 7】
1. prepared by surfactant
The surfactant synthesized using embodiment 5, except that compound concentration.
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 8】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
4.0mol ethylene oxide is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (8) ether.
B) 0.49mol nonylphenol polyoxyethylene ether (8) obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 250 milliliters of benzene and 40 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, the salt that concentration is 6M is added dropwise
The pH of system is transferred to 2 by acid, is extracted with ethyl acetate, after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in volume
Compare acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (nonylphenol polyoxyethylene ether (8)) third sulphur of -2- hydroxyls
Hydrochlorate 0.39mol.
C) step b) is synthesized into 3- (nonylphenol polyoxyethylene ether (8)) -2- hydroxy-propanesulfonic acid salt 0.39mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, 1.5 grams of sodium hydroxides and 15 grams of water are added, while leading to nitrogen
While when being heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, use nitrogen
Purging 4 times, is then adjusted to 150 DEG C by system reaction temperature and is slowly passed through 1.17mol propylene oxide, control pressure≤0.40MPa
Reacted；After reaction, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain 3- (nonylphenol polyoxyethylene ether
(8)) -2- (polyethenoxy ether (3)) propane sulfonic acid salt 0.38mol.
D) 3- (nonylphenol polyoxyethylene ether (8)) -2- (polyethenoxy ether (3)) propane sulfonic acid salt for synthesizing step c)
(0.38mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.76mol), when alkalization 2 is small at 60 DEG C, adds 0.44mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (nonylphenol polyoxyethylene ether (8)) -2- (hydroxypropyl sulfonic acid polyethenoxy ether (3)) propane sulfonic acid salt
(0.35mol)。
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 9】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
2.0mol ethylene oxide is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (4) ether.
B) 0.49mol nonylphenol polyoxyethylene ether (4) obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 250 milliliters of benzene and 40 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, the salt that concentration is 6M is added dropwise
The pH of system is transferred to 2 by acid, is extracted with ethyl acetate, after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in volume
Compare acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (nonylphenol polyoxyethylene ether (4)) third sulphur of -2- hydroxyls
Hydrochlorate 0.39mol.
C) step b) is synthesized into 3- (nonylphenol polyoxyethylene ether (4)) -2- hydroxy-propanesulfonic acid salt 0.39mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, 2 grams of sodium hydroxides and 20 grams of water are added, when leading to nitrogen
When being heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, blown with nitrogen
Sweep 4 times, system reaction temperature then is adjusted to 150 DEG C is slowly passed through 0.39mol propylene oxide, control pressure≤0.40MPa into
Row reaction；After reaction, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (nonylphenol polyoxyethylene ether (4))-
2- (polyethenoxy ether (1)) propane sulfonic acid salt 0.39mol.
D) 3- (nonylphenol polyoxyethylene ether (4)) -2- (polyethenoxy ether (1)) propane sulfonic acid salt for synthesizing step c)
(0.39mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.78mol), when alkalization 2 is small at 60 DEG C, adds 0.48mol 3- chlorine-2-hydroxyl propanesulfonates, in reflux shape
Under state, when reaction 5 is small, 3- (nonylphenol polyoxyethylene ether (4)) -2- (hydroxypropyl sulfonic acid polyethenoxy ether (1)) propane sulfonic acid is obtained
Salt (0.36mol).
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 10】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
6.0mol ethylene oxide is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.5mol Nonyl phenos (12) ether.
B) 0.5mol nonylphenol polyoxyethylene ether (12) obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 400 milliliters of benzene and 40 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.6mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, the salt that concentration is 6M is added dropwise
The pH of system is transferred to 2 by acid, is extracted with ethyl acetate, after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in volume
Compare acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (nonylphenol polyoxyethylene ether (12)) -2- hydroxyls third
Sulfonate 0.38mol.
C) step b) is synthesized into 3- (nonylphenol polyoxyethylene ether (12)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, 2 grams of sodium hydroxides and 20 grams of water are added, when leading to nitrogen
When being heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, blown with nitrogen
Sweep 4 times, system reaction temperature is then adjusted to 150 DEG C and is slowly passed through 3.8mol propylene oxide, control pressure≤0.40MPa is carried out
Reaction；After reaction, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (nonylphenol polyoxyethylene ether (12))-
2- (polyethenoxy ether (10)) propane sulfonic acid salt 0.38mol.
D) 3- (nonylphenol polyoxyethylene ether (12)) -2- (polyethenoxy ether (10)) propane sulfonic acid salt for synthesizing step c)
(0.38mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.76mol), when alkalization 2 is small at 60 DEG C, adds 0.45mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (nonylphenol polyoxyethylene ether (12)) -2- (hydroxypropyl sulfonic acid polyethenoxy ether (10)) propane sulfonic acid
Salt (0.35mol).
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 11】
1. prepared by surfactant
A) 0.5mol octyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
1.5mol ethylene oxide is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol octylphenol polyethylenes ethylene oxide (3) ether.
B) 0.49mol octyl phenol polyoxyethylene ether (3) obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 300 milliliters of benzene and 38 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.58mol 3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, it is 6M's that concentration, which is added dropwise,
The pH of system is transferred to 2 by hydrochloric acid, is extracted with ethyl acetate, and after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in body
Product compares acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (octyl phenol polyoxyethylene ether (3)) -2- hydroxyls third
Sulfonate 0.38mol.
C) step b) is synthesized into 3- (nonylphenol polyoxyethylene ether (3)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, 1.5 grams of sodium hydroxides and 15 grams of water are added, while leading to nitrogen
While when being heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, use nitrogen
Purging 4 times, is then adjusted to 150 DEG C by system reaction temperature and is slowly passed through 1.2mol propylene oxide, control pressure≤0.40MPa into
Row reaction；After reaction, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (octyl phenol polyoxyethylene ether (3))-
2- (polyethenoxy ether (3)) propane sulfonic acid salt 0.38mol.
D) 3- (octyl phenol polyoxyethylene ether (3)) -2- (polyethenoxy ether (3)) propane sulfonic acid salt for synthesizing step c)
(0.38mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.76mol), when alkalization 2 is small at 60 DEG C, adds 0.44mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (octyl phenol polyoxyethylene ether (3)) -2- (hydroxypropyl sulfonic acid polyethenoxy ether (3)) propane sulfonic acid salt
(0.34mol)。
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 12】
1. prepared by surfactant
A) into the reactor equipped with condensing unit, agitating device and gas distributor add 0.5mol grams of octyl phenol and
1.5 grams of sodium hydroxides and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, 90
At a temperature of DEG C, vacuumize dehydration 1 it is small when, then purge 4 times with the air in removing system with nitrogen, system then reacted into temperature
Degree is adjusted to 150 DEG C and is slowly passed through 4.2mol ethylene oxide, and control pressure≤0.40MPa carries out ethoxylation；Reaction terminates
Afterwards, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain 0.5mol octylphenol polyethylenes ethylene oxide (8) ether.
B) 0.5mol octyl phenol polyoxyethylene ether (8) obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 250 milliliters of benzene and 40 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.6mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, the salt that concentration is 6M is added dropwise
The pH of system is transferred to 2 by acid, is extracted with ethyl acetate, after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in volume
Compare acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (octyl phenol polyoxyethylene ether (8)) third sulphur of -2- hydroxyls
Hydrochlorate 0.38mol.
C) step b) is synthesized into 3- (octyl phenol polyoxyethylene ether (8)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, 1.5 grams of sodium hydroxides and 15 grams of water are added, while leading to nitrogen
While when being heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, use nitrogen
Purging 4 times, is then adjusted to 150 DEG C by system reaction temperature and is slowly passed through 2.0mol propylene oxide, control pressure≤0.40MPa into
Row reaction；After reaction, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (octyl phenol polyoxyethylene ether (8))-
2- (polyethenoxy ether (5)) propane sulfonic acid salt 0.38mol.
D) 3- (octyl phenol polyoxyethylene ether (8)) -2- (polyethenoxy ether (5)) propane sulfonic acid salt for synthesizing step c)
(0.38mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.76mol), when alkalization 2 is small at 60 DEG C, adds 0.45mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (octyl phenol polyoxyethylene ether (8)) -2- (hydroxypropyl sulfonic acid polyethenoxy ether (5)) propane sulfonic acid salt
(0.35mol)。
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 13】
1. prepared by surfactant
A) 0.5mol amylic phenols and 1 gram are added into the reactor equipped with condensing unit, agitating device and gas distributor
Sodium hydroxide and 10 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then system reaction temperature is adjusted to
150 DEG C are slowly passed through 2.6mol ethylene oxide, and control pressure≤0.40MPa carries out ethoxylation；After reaction, nitrogen is used
System is swept in air-blowing, is neutralized, is dehydrated after cooling, obtains 0.5mol amyl groups phenol polyethenoxy (5) ether.
B) 0.5mol amyl groups phenol polyethenoxy (5) ether obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 500 milliliters of benzene solvents and 40 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.6mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, excessive dilute hydrochloric acid is added dropwise
The pH of system is transferred to 2, is extracted with ethyl acetate, after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in volume ratio
Acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 0.36mol3- (amyl group phenol polyethenoxy (5) ether) -2- hydroxyls
Base propane sulfonic acid salt.
C) 3- (amyl group phenol polyethenoxy (5) ether) -2- hydroxy-propanesulfonic acid salt 0.35mol for synthesizing step b), are added to
In reactor equipped with condensing unit, agitating device and gas distributor, 1.5 grams of sodium hydroxides and 15 grams of water are added, while leading to nitrogen
When gas side is heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, use nitrogen
Air-blowing sweeps 4 times, and system reaction temperature then is adjusted to 150 DEG C is slowly passed through 0.72mol propylene oxide, and control pressure≤
0.40MPa is reacted；After reaction, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain 3- (amylic phenol polyoxy second
Alkene (5) ether) -2- (polyoxypropylene (2) ether) propane sulfonic acid salt 0.35mol.
D) 3- (amyl group phenol polyethenoxy (5) ether) -2- (polyoxypropylene (2) ether) propane sulfonic acid salt for synthesizing step c)
(0.35mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.70mol), when alkalization 2 is small at 60 DEG C, adds 0.40mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (amyl group phenol polyethenoxy (5) ether) -2- (hydroxypropyl sulfonic acid polyoxypropylene (2) ether) propane sulfonic acid salt
(0.31mol)。
2. surfactant properties are evaluated
In addition to oil displacement agent composition is different, method of evaluating performance is the same as embodiment 1.For ease of comparing the composition of oil displacement agent
Table 2 is listed in, evaluation result is listed in table 3 and table 4.
【Embodiment 14】
1. prepared by surfactant
A) into the reactor equipped with condensing unit, agitating device and gas distributor add 0.5mol dodecylphenols and
1.5 grams of sodium hydroxides and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, 90
At a temperature of DEG C, vacuumize dehydration 1 it is small when, then purge 4 times with the air in removing system with nitrogen, system then reacted into temperature
Degree is adjusted to 150 DEG C and is slowly passed through 1.1mol ethylene oxide, and control pressure≤0.40MPa carries out ethoxylation；Reaction terminates
Afterwards, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain 0.5mol dodecyls phenol polyethenoxy (2) ether.
B) 0.5mol dodecyls phenol polyethenoxy (2) ether obtained by step a) is added to equipped with agitating device, be condensed back to
In the reactor for flowing device and division box, 400 milliliters of benzene solvents and 30 grams of sodium hydroxides are added, when alkalization 2 is small at 60 DEG C,
0.6mol3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, when reaction 8 is small.After reaction, it is 6M concentration to be added dropwise
Hydrochloric acid the pH of system is transferred to 2, be extracted with ethyl acetate, after solvent is evaporated off in oil phase, neutralized with sodium hydroxide solution, Ran Hou
Volume ratio acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (dodecyl phenol polyethenoxy (2) ether) -2-
Hydroxy-propanesulfonic acid salt 0.36mol.
C) step b) is synthesized into 3- (dodecyl phenol polyethenoxy (2) ether) -2- hydroxypropionate sodium 0.36mol, added
Into the reactor equipped with condensing unit, agitating device and gas distributor, 1.5 grams of sodium hydroxides and 15 grams of water, Bian Tong are added
When nitrogen side is heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, use
Nitrogen purges 4 times, and system reaction temperature then is adjusted to 150 DEG C and is slowly passed through 1.5mol propylene oxide, and control pressure≤
0.40MPa is reacted；After reaction, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtaining 3-, (dodecylphenol gathers
Ethylene oxide (2) ether) -2- (polyoxypropylene (4) ether) sulfonate 0.36mol.
D) 3- (dodecyl phenol polyethenoxy (2) ether) -2- (polyoxypropylene (4) ether) sulfonate for synthesizing step c)
(0.36mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.72mol), when alkalization 2 is small at 60 DEG C, adds 0.42mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (dodecyl phenol polyethenoxy (2) ether) -2- (hydroxypropyl sulfonic acid polyoxypropylene (4) ether) sulfonic acid
Salt (0.33mol).
2. surfactant properties are evaluated
Method of evaluating performance is the same as embodiment 1.Composition for ease of comparing oil displacement agent is listed in table 2, and evaluation result is listed in
Table 3 and table 4.
【Embodiment 15】
1. prepared by surfactant
A) into the reactor equipped with condensing unit, agitating device and gas distributor add 0.5mol cetyls phenol and
2 grams of sodium hydroxides and 20 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, at 90 DEG C
At a temperature of, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature
It is adjusted to 150 DEG C and is slowly passed through 2.5mol ethylene oxide, control pressure≤0.40MPa carries out ethoxylation；After reaction,
System is purged with nitrogen, neutralizes, be dehydrated after cooling, obtain 0.49mol cetyls phenol polyethenoxy (5) ether.
B) 0.49mol cetyls phenol polyethenoxy (5) ether obtained by step a) is added to equipped with agitating device, be condensed back to
In the reactor for flowing device and division box, 400 milliliters of benzene solvents and 26 grams of sodium hydroxides are added, when alkalization 2 is small at 60 DEG C,
0.58mol3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, when reaction 8 is small.After reaction, it is 6M concentration to be added dropwise
Hydrochloric acid the pH of system is transferred to 2, be extracted with ethyl acetate, after solvent is evaporated off in oil phase, neutralized with sodium hydroxide solution, Ran Hou
Volume ratio acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (cetyl phenol polyethenoxy (5) ether) -2-
Hydroxy-propanesulfonic acid salt 0.36mol.
C) step b) is synthesized into 3- (cetyl phenol polyethenoxy (5) ether) -2- hydroxy-propanesulfonic acid salt 0.36mol, added
Into the reactor equipped with condensing unit, agitating device and gas distributor, 1 gram of sodium hydroxide and 10 grams of water are added, while leading to nitrogen
When gas side is heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, use nitrogen
Air-blowing is swept 4 times, and system reaction temperature then is adjusted to 150 DEG C and is slowly passed through 1.8mol propylene oxide, control pressure≤0.40MPa
Reacted；After reaction, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain 3- (cetyl phenol polyethenoxies
(5) ether) -2- (polyoxypropylene (5) ether) propane sulfonic acid salt 0.35mol.
D) 3- (cetyl phenol polyethenoxy (5) ether) -2- (polyoxypropylene (5) ether) propane sulfonic acid salt for synthesizing step c)
(0.35mol) is added in the reactor equipped with agitating device, condensation reflux unit and division box, add 200 milliliters of benzene and
Sodium hydroxide (0.70mol), when alkalization 2 is small at 60 DEG C, adds 0.40mol3- chlorine-2-hydroxyl propanesulfonates, in reflux state
Under, when reaction 5 is small, obtain 3- (cetyl phenol polyethenoxy (5) ether) -2- (hydroxypropyl sulfonic acid polyoxypropylene (5) ether) third sulphur
Hydrochlorate (0.31mol).
2. surfactant properties are evaluated
Oil displacement agent is prepared:
3- (cetyl phenol polyethenoxy (5) ether) -2- (polyoxypropylene (5) ether) propane sulfonic acid that above-mentioned steps c) is synthesized
When 1 parts by weight of salt, 0.5 parts by weight of diethanol amine and small Pu Chengxi Districts 500 parts by weight of injection water mixing 1, obtain a kind of equal
Even transparent oil displacement agent.Other performance evaluation method is the same as embodiment 1.Composition for ease of comparing oil displacement agent is listed in table 2, will comment
The results are shown in table 3 and table 4 for valency.
【Comparative example 1】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
3.0mol ethylene oxide is slowly passed through to 150 DEG C, when control pressure≤0.40MPa progress ethoxylations 4 are small, is then passed to
1.5mol propylene oxide, the reaction was continued 4 it is small when；After reaction, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain
0.49mol Nonyl phenos (6) polyoxypropylene (3) ether.
B) 0.49mol Nonyl phenos (6) polyoxypropylene (3) ether obtained by step a) is added to equipped with stirring dress
Put, in the reactor of condensation reflux unit and division box, add 500 milliliters of benzene and 40 grams of sodium hydroxides, alkalize 2 at 60 DEG C
Hour, 0.58mol3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, when reaction 8 is small.After reaction, it is added dropwise dense
Spend and the pH of system be transferred to 2 for the hydrochloric acid of 6M, be extracted with ethyl acetate, after solvent is evaporated off in oil phase, neutralized with sodium hydroxide solution,
Then in volume ratio acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (Nonyl pheno (6) polyoxies
Propylene (3) ether) -2- hydroxy-propanesulfonic acid salt 0.38mol, structure is as follows：
2. surfactant properties are evaluated
By 1 parts by weight of 3- (Nonyl pheno (6) polyoxypropylene (3) ether) -2- hydroxy-propanesulfonic acids salt of above-mentioned synthesis
With Pu Chengxi Districts injection water 500 parts by weight be mixed 1 it is small when, obtain displacement of reservoir oil agent solution.
A) interfacial tension is evaluated
TX-500C rotating interfacial tensimeters, at 85 DEG C, rotating speed 4500 are produced using Texas ,Usa university
Under the conditions of rev/min, the interfacial tension result between above-mentioned oil displacement agent and Pu Chengxi District injection water and the dewatered oil of extraction is measured
It is shown in Table 5.
B) oil displacement experiment is evaluated
According to the composite oil-displacing system physical simulation flooding test in SY/T6424-2000 composite oil-displacing system performance test methods
Measure of merit, at 85 DEG C, length 30cm, a diameter of 2.5cm, permeability 1.5m2Rock core on to carry out imitation oil displacement experiment real
Test.Water drive first is carried out to aqueous 98% with Pu Chengxi Districts injection water, after water drive, on metaideophone 0.3pv (rock pore volume)
Oil displacement agent is stated, then water drive to aqueous 98%, improve oil recovery factor and the results are shown in Table 5.
【Comparative example 2】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
1.5mol propylene oxide is slowly passed through to 150 DEG C, when control pressure≤0.40MPa reactions 4 are small, obtains nonyl phenol poly-oxypropylene
(3) ether, then passes to 3.0mol ethylene oxide, the reaction was continued 4 it is small when；After reaction, with nitrogen purge system, after cooling in
With, dehydration, obtain 0.49mol nonyl phenol poly-oxypropylenes (3) polyoxyethylene (6) ether.
B) 0.49mol nonyl phenol poly-oxypropylenes (3) polyoxyethylene (6) ether obtained by step a) is added to equipped with stirring dress
Put, in the reactor of condensation reflux unit and division box, add 500 milliliters of benzene and 40 grams of sodium hydroxides, alkalize 2 at 60 DEG C
Hour, 0.58mol 3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, when reaction 8 is small.After reaction, it is added dropwise dense
Spend and the pH of system be transferred to 2 for the hydrochloric acid of 6M, be extracted with ethyl acetate, after solvent is evaporated off in oil phase, neutralized with sodium hydroxide solution,
Then in volume ratio acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (nonyl phenol poly-oxypropylene (3) polyoxies
Ethene (6) ether) -2- hydroxy-propanesulfonic acid salt 0.38mol, structure is as follows：
2. surfactant properties are evaluated
During by above-mentioned 1 parts by weight of surfactant and small Pu Chengxi Districts 500 parts by weight of injection water mixing 1, one is obtained
The oil displacement agent of kind homogeneous transparent.Other same comparative examples 1, for ease of comparing the results are shown in table 5.
【Comparative example 3】
1. prepared by surfactant
A) 0.5mol nonyl phenols and 1.5 are added into the reactor equipped with condensing unit, agitating device and gas distributor
Gram sodium hydroxide and 15 grams of water, when 85 DEG C are heated to when leading to nitrogen, when stirring reaction 1 is small.Vacuum system is opened, in 90 DEG C of temperature
Under degree, vacuumize dehydration 1 it is small when, then with nitrogen purge 4 times with the air in removing system, then by system reaction temperature tune
3.0mol ethylene oxide is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (6) ether.
B) 0.49mol nonylphenol polyoxyethylene ether (6) obtained by step a) is added to equipped with agitating device, condensing reflux dress
Put in the reactor with division box, add 500 milliliters of benzene and 40 grams of sodium hydroxides, when alkalization 2 is small at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, when reaction 8 is small.After reaction, the salt that concentration is 6M is added dropwise
The pH of system is transferred to 2 by acid, is extracted with ethyl acetate, after solvent is evaporated off in oil phase, is neutralized with sodium hydroxide solution, then in volume
Compare acetone:Ethanol:Water is 2:1:1 in the mixed solvent is recrystallized to give 3- (nonylphenol polyoxyethylene ether (6)) third sulphur of -2- hydroxyls
Hydrochlorate 0.39mol.
C) step b) is synthesized into 3- (nonylphenol polyoxyethylene ether (6)) -2- hydroxy-propanesulfonic acid salt 0.39mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, 2 grams of sodium hydroxides and 20 grams of water are added, when leading to nitrogen
When being heated to 85 DEG C, when stirring reaction 1 is small.Open vacuum system, at a temperature of 90 DEG C, vacuumize dehydration 1 it is small when, blown with nitrogen
Sweep 4 times, system reaction temperature then is adjusted to 150 DEG C is slowly passed through 1.18mol propylene oxide, control pressure≤0.40MPa into
Row reaction；After reaction, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (nonylphenol polyoxyethylene ether (6))-
2- (polyethenoxy ether (3)) propane sulfonic acid salt 0.38mol, structure are as follows：
2. surfactant properties are evaluated
During by above-mentioned 1 parts by weight of surfactant and small Pu Chengxi Districts 500 parts by weight of injection water mixing 1, one is obtained
The oil displacement agent of kind homogeneous transparent.Other same comparative examples 1, for ease of comparing the results are shown in table 5.
Water is injected in 1 Zhongyuan Oil Field Pu Chengxi Districts of table
| Project | Na++K+ | Mg2+ | Ca2+ | Cl- | SO4 2- | HCO3 - | TDS |
| mg/L | 85066 | 367 | 3840 | 138006 | 1089 | 282 | 228650 |
2 embodiment 1-15 oil displacement agents of table form
3 embodiment 1-15 oil displacement agent interfacial tension performances of table
| Embodiment | Interfacial tension (mN/m) |
| 1 | 0.0065 |
| 2 | 0.0074 |
| 3 | 0.0026 |
| 4 | 0.0018 |
| 5 | 0.0012 |
| 6 | 0.0002 |
| 7 | 0.0065 |
| 8 | 0.0015 |
| 9 | 0.0058 |
| 10 | 0.0073 |
| 11 | 0.0040 |
| 12 | 0.0041 |
| 13 | 0.0235 |
| 14 | 0.0082 |
| 15 | 0.0043 |
4 embodiment 1-15 oil displacement experiment results of table
| Embodiment | Improve recovery ratio % |
| 1 | 5.8 |
| 2 | 5.3 |
| 3 | 7.4 |
| 4 | 10.5 |
| 5 | 10.1 |
| 6 | 11.8 |
| 7 | 4.6 |
| 8 | 8.1 |
| 9 | 6.9 |
| 10 | 5.0 |
| 11 | 7.5 |
| 12 | 6.4 |
| 13 | 4.3 |
| 14 | 4.4 |
| 15 | 5.9 |
5 comparative example 1-3 the performance test results of table
| Comparative example | Interfacial tension (mN/m) | Improve recovery ratio % |
| 1 | 0.011 | 4.3 |
| 2 | 0.023 | 4.6 |
| 3 | 0.045 | 3.5 |
Claims (10)
1. salt tolerant oil displacement surfactant, its entitled 3- (alkyl phenol polyethenoxy ether) -2- (hydroxypropyl sulfonic acid polyoxypropylene
Ether) propane sulfonic acid salt, shown in structure such as formula (I)：
Wherein M1And M2It is independently selected from as any one in alkali metal, alkaline-earth metal, works as M1For alkali metal when n1For 1, work as M1For alkali
N during earth metal1For 0.5, work as M2For alkali metal when n2For 1, work as M2For alkaline-earth metal when n2For 0.5, R C4~C20Alkyl, x=
1~20, y=1~10.
2. salt tolerant oil displacement surfactant according to claim 1, it is characterised in that x=2~8, y=2~4.
3. salt tolerant oil displacement surfactant according to claim 2, it is characterised in that the alkyl is C7~C10Alkyl.
4. the preparation method of the salt tolerant oil displacement surfactant described in claim 1, comprises the following steps：
A) under basic catalyst effect, alkyl phenol obtains alkyl phenol polyethenoxy ether with aequum reacting ethylene oxide；
B) alkyl phenol polyethenoxy ether obtained by step a) is dissolved into C6~C8In aromatic hydrocarbons, alkali metal hydroxide or alkaline earth are added
At least one of metal hydroxides alkali, when alkalization 0.5~3 is small at 30~60 DEG C, adds 3- chlorine-2-hydroxyl propane sulfonic acid
Alkali metal salt, stirs lower reaction and obtains 3- (alkyl phenol polyethenoxy ether) -2- hydroxy-propanesulfonic acid salt；
C) by 3- (alkyl phenol polyethenoxy ether) -2- hydroxy-propanesulfonic acid salt obtained by step b), under basic catalyst effect, with institute
Requirement propylene oxide reacts to obtain the 3- (alkyl phenol polyethenoxy ether) -2- (polyethenoxy ether) propane sulfonic acid salt；
D) by 3- (alkyl phenol polyethenoxy ether) -2- (polyethenoxy ether) propane sulfonic acid salt obtained by step c), it is dissolved into C6~C8Aromatic hydrocarbons
In, at least one of alkali metal hydroxide or alkaline earth metal hydroxide alkali are added, the alkalization 0.5~3 at 30~60 DEG C
Hour, the alkali metal salt of 3- chlorine-2-hydroxyl propane sulfonic acid is added, lower reaction is stirred and obtains 3- (alkyl phenol polyethenoxy ether) -2- (hydroxyls
Propyl sulfonic acid polyethenoxy ether) propane sulfonic acid salt.
5. the preparation method of salt tolerant oil displacement surfactant according to claim 4, it is characterized in that step a) and/or step
C) basic catalyst is at least one of alkali metal hydroxide or alkaline-earth metal.
6. the preparation method of salt tolerant oil displacement surfactant according to claim 4, it is characterized in that the step b) alkyl
The molar ratio of phenol polyethenoxy ether and 3- chlorine-2-hydroxyl propane sulfonic acid alkali metal salts is 1:(1~2), the reaction time are 6~10
Hour.
7. the preparation method of salt tolerant oil displacement surfactant according to claim 5, it is characterized in that step a) and step c)
The basic catalyst is at least one of sodium hydroxide or potassium hydroxide.
8. the preparation method of salt tolerant oil displacement surfactant according to claim 4, it is characterized in that step a) and/or step
C) reaction temperature is 120~140 DEG C, when the reaction time is 6~8 small.
9. application of the surfactant described in claim 1 in oil recovery factor is improved.
10. application according to claim 9, it is characterized in that application process is that will be lived in terms of parts by weight including the surface
Property 100~2000 parts of 1 part of agent and water oil displacement agent inject oil bearing bed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410328886.2A CN105273704B (en) | 2014-07-11 | 2014-07-11 | Salt tolerant oil displacement surfactant and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410328886.2A CN105273704B (en) | 2014-07-11 | 2014-07-11 | Salt tolerant oil displacement surfactant and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105273704A CN105273704A (en) | 2016-01-27 |
| CN105273704B true CN105273704B (en) | 2018-05-11 |
Family
ID=55143559
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410328886.2A Active CN105273704B (en) | 2014-07-11 | 2014-07-11 | Salt tolerant oil displacement surfactant and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105273704B (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111087608B (en) * | 2018-10-23 | 2022-08-12 | 中国石油化工股份有限公司 | Oil-displacing surfactant and composition of alkyl phenol polyether bisbenzenesulfonate, and preparation method and application thereof |
| CN111088013B (en) * | 2018-10-23 | 2022-07-12 | 中国石油化工股份有限公司 | Anion-cation composite oil displacement surfactant, preparation method thereof and oil displacement method |
| CN111088014B (en) * | 2018-10-23 | 2022-02-01 | 中国石油化工股份有限公司 | Yin-yang composite surfactant for oil extraction, preparation method thereof and oil displacement method |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560178A (en) * | 2004-02-25 | 2005-01-05 | 石油大学(华东) | Anti-salt type thicking oil reducing viscosity agent and preparation process thereof |
| CN101279937A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Alkyl phenol sulfonic polyoxyethylene ether sulfonate and preparation thereof |
| CN101279936A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Alkyl phenol sulfonic polyoxyethylene ether sulfate and preparation thereof |
-
2014
- 2014-07-11 CN CN201410328886.2A patent/CN105273704B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1560178A (en) * | 2004-02-25 | 2005-01-05 | 石油大学(华东) | Anti-salt type thicking oil reducing viscosity agent and preparation process thereof |
| CN101279937A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Alkyl phenol sulfonic polyoxyethylene ether sulfonate and preparation thereof |
| CN101279936A (en) * | 2007-04-04 | 2008-10-08 | 中国石油化工股份有限公司 | Alkyl phenol sulfonic polyoxyethylene ether sulfate and preparation thereof |
Non-Patent Citations (1)
| Title |
|---|
| 烷基酚阴离子表面活性剂的合成与应用进展;孙守双，等;《化学研究与应用》;20130131;第25卷(第1期);2 Extended 型表面活性剂 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105273704A (en) | 2016-01-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106590582B (en) | Salt tolerant oil displacement surfactant and preparation method thereof | |
| CN105273704B (en) | Salt tolerant oil displacement surfactant and preparation method thereof | |
| CN104277808B (en) | Surfactant oil displacement and preparation method thereof | |
| CN104559988B (en) | Beet alkali surface activator, preparation method and the application in intensified oil reduction | |
| CN105273706B (en) | Suitable for the oil displacement surfactant on high salinity stratum | |
| CN104277812B (en) | Tertiary oil recovery surfactant and preparation method thereof | |
| CN111088013B (en) | Anion-cation composite oil displacement surfactant, preparation method thereof and oil displacement method | |
| CN104277813B (en) | Oil extraction in oil field composition and preparation method thereof | |
| CN104109524B (en) | Reinforced foam flooding composition for high salinity reservoirs, and preparation method thereof | |
| CN105315980B (en) | Displacement composition and preparation method thereof | |
| CN104559989B (en) | Alkylamine polyoxyethylene ether polyethenoxy ether sulfonate type glycine betaine | |
| CN105273705B (en) | Salt tolerant displacement composition and preparation method thereof | |
| CN106590584B (en) | Oil displacement surfactant for high salinity reservoir | |
| CN106590581B (en) | Salt tolerant displacement composition and preparation method thereof | |
| CN104277809B (en) | Displacement composition and preparation method thereof | |
| CN111088014B (en) | Yin-yang composite surfactant for oil extraction, preparation method thereof and oil displacement method | |
| CN104559990B (en) | Chemical flooding surface activator composition and its application | |
| CN104559986B (en) | Binary is driven poly- table pack thing and its is applied in intensified oil reduction | |
| CN104277815B (en) | Oil-displacement composition and preparation method thereof | |
| CN104277810B (en) | Enhanced oil recovery surfactant and preparation method thereof | |
| CN104559987A (en) | Amide polyoxyethylene ether sulfonate betaine surfactant | |
| CN106590564B (en) | Temperature-resistant salt-resistant low-tension foam flooding composition and preparation method and application thereof | |
| CN111087601B (en) | Surfactant and composition for oil extraction and preparation method thereof | |
| CN104276983B (en) | The preparation method of oil recovery tensio-active agent | |
| CN104277811B (en) | The preparation method of intensified oil reduction surfactant |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |