CN105273706B - Suitable for the oil displacement surfactant on high salinity stratum - Google Patents
Suitable for the oil displacement surfactant on high salinity stratum Download PDFInfo
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- CN105273706B CN105273706B CN201410330757.7A CN201410330757A CN105273706B CN 105273706 B CN105273706 B CN 105273706B CN 201410330757 A CN201410330757 A CN 201410330757A CN 105273706 B CN105273706 B CN 105273706B
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Abstract
The present invention relates to oil displacement surfactant suitable for high salinity stratum 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 (carboxymethyl polyethenoxy ether) propane sulfonic acid salt by using the oil displacement surfactant suitable for high salinity stratum, shown in structure such as formula (I), wherein M1And M2Any one in alkali metal, alkaline-earth metal is independently selected from, 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 scheme of y=1~20, preferably solve the problem, available for oil field raising oil recovery factor production in.
Description
Technical field
The present invention relates to a kind of suitable for the oil displacement surfactant on high salinity stratum 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 rockses, make
Two main power on oil droplet are viscaps, if from suitable surfactant system, reduce oil
Interfacial tension between water, the interfacial tension between oil reservoirs profit is set to 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, be that materials are extensive, cheap the characteristics of this kind of surfactant, 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 synergy 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 APES 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, obtain 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
One of technical problems to be solved by the invention are that surfactant is present under high temperature, high salt conditions in the prior art
The problem of oil displacement efficiency is low, there is provided a kind of new oil displacement surfactant suitable for high salinity stratum, the surfactant
With oil displacement efficiency is high under the conditions of high salinity the characteristics of.
The two of the technical problems to be solved by the invention are to provide a kind of corresponding with solving one of technical problem be applicable
In the preparation method of the oil displacement surfactant on high salinity stratum.
The three of the technical problems to be solved by the invention are 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：One kind is with being applied to high salinity
The oil displacement surfactant of layer, its entitled 3- (alkyl phenol polyethenoxy ether) -2- (carboxymethyl polyethenoxy ether) propane sulfonic acid salt,
As shown in formula (I)：
Wherein M1And M2Any one in alkali metal, alkaline-earth metal is independently selected from, works as M1For alkali metal when n1For 1, work as M1For
N during alkaline-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=1~20.
In above-mentioned technical proposal, preferably x=2~8 and y=2~4.The alkyl is preferably C7~C10Alkyl.
In above-mentioned technical proposal, as the most preferable technical scheme：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
Suitable for the preparation method of the oil displacement surfactant on high salinity stratum, comprise the following steps：
A) under base 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, add alkali metal hydroxide or
At least one of alkaline earth metal hydroxide alkali, alkalized 0.5~3 hour at 30~60 DEG C, add 3- the third sulphurs of chlorine-2-hydroxyl
The alkali metal salt of acid, stir lower reaction and obtain 3- (alkyl phenol polyethenoxy ether) -2- hydroxy-propanesulfonic acid salt；The alkyl phenol polyoxy
The mol ratio of vinethene and the alkali is preferably 1:(1~3)；
C) by 3- (alkyl phenol polyethenoxy ether) -2- hydroxy-propanesulfonic acid salt obtained by step b), under base catalyst effect,
React to obtain the 3- (alkyl phenol polyethenoxy ether) -2- (polyethenoxy ether) propane sulfonic acid salt with aequum expoxy propane；
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 hours, chloroacetic alkali metal salt is added, lower reaction is stirred and obtains 3- (alkyl phenol polyethenoxy ether) -2- (carboxymethyl polyoxies
Propylene ether) propane sulfonic acid salt；Wherein, 3- (alkyl phenol polyethenoxy ether) -2- (polyethenoxy ether) the propane sulfonic acid salt and the alkali
Mol ratio be preferably 1:(1~3)；The temperature of the reaction is preferably 30~80 DEG C, and the time of the reaction is preferably 6~18
Hour.
In above-mentioned technical proposal, step a) and step c) the base catalyst preferred alkali metal hydroxides or alkaline earth gold
Belong at least one of hydroxide, more preferably at least one of sodium hydroxide or potassium hydroxide.
In above-mentioned technical proposal, alkyl phenol polyethenoxy ether described in step b) and 3- chlorine-2-hydroxyl propane sulfonic acid alkali metal
The mol ratio of salt is preferably 1:(1~4) is more preferably 1:(1~2)；The temperature of reaction is preferably 30~80 DEG C, and the reaction time is excellent
Elect 6~18 hours, more preferably 6~10 hours as.
Step a) and/or step c) is preferably 85~160 DEG C in reaction temperature, more preferably 120~140 DEG C；Pressure is excellent
Elect 0~0.40MPa (gauge pressure) as.Reaction time is preferably 1~10 hour, more preferably 6~8 hours.
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 the application during surfactant improves oil recovery factor in oil field.
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, underground water, seawater, preferably total salinity scope are 80000-300000mg/L, Ca2++Mg2+For
1000-6000mg/L water, for the consideration of 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
Individual hydrophilic radical, wherein carboxymethyl are located at molecular chain-end, and propane sulfonic acid salt groups are located in polyoxyethylene and polyoxypropylene segment
Between, the degree of polymerization of polyoxyethylene and polyoxypropylene segment, the hydrophily of control surface activating agent can be passed through.It is simultaneously because multiple
The synergy of group considerably increases the salt resistance of surfactant and the performance of anti-bivalent cation, with the prior art only with
The anion-nonionic surfactant that one oxyethylene chain section connects is compared, and the surfactant that the present invention uses can be used for high ore deposit
The oil reservoir displacement of reservoir oil of change degree, 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
1.5mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (3) ether.
B) NPE (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, are alkalized 2 hours at 60 DEG C, add 0.61mol3-
Chlorine-2-hydroxyl propanesulfonate, at reflux, react 8 hours.After reaction terminates, 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- (NPE (3)) -2- hydroxy-propanesulfonic acid salt
(0.39mol)。
C) 3- (NPE (3)) -2- hydroxy-propanesulfonic acid salt for synthesizing step b), it 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 in logical nitrogen
At 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, is purged 4 times with nitrogen,
Then system reaction temperature is adjusted to 150 DEG C and is slowly passed through 0.39mol expoxy propane, control pressure≤0.40MPa is reacted；
After reaction terminates, system is purged with nitrogen, neutralizes, be dehydrated after cooling, obtain 3- (NPE (3)) -2- (polyoxies
Propylene ether (1)) propane sulfonic acid salt (0.39mol).
D) 3- (NPE (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), alkalized 2 hours at 60 DEG C, add 0.47mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (NPE (3)) -2- (carboxymethyl 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 the above-mentioned parts by weight of surfactant 1 and the Pu Chengxi Districts injection parts by weight of water 500 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 determined 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 terminates, 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
0.5mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 130 grams of Nonyl pheno (1) ethers.
B) 0.5mol NPEs (1) obtained by step a) are 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, alkalized 2 hours at 60 DEG C, add
0.6mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, 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- (NPE (1)) third sulphur of -2- hydroxyls
Hydrochlorate 0.38mol.
C) step b) is synthesized into 3- (NPE (1)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, add 1.5 grams of sodium hydroxides and 1.5 grams of water, side lead to nitrogen
While when being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, uses nitrogen
Purging 4 times, is then adjusted to 150 DEG C by system reaction temperature and is slowly passed through 1.52mol expoxy propane, control pressure≤0.40MPa
Reaction；After reaction terminates, system is purged with nitrogen, neutralizes, be dehydrated after cooling, obtain 3- (NPE (1)) -2-
(polyethenoxy ether (4)) propane sulfonic acid salt 0.37mol.
D) 3- (NPE (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), alkalized 2 hours at 60 DEG C, add 0.45mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (NPE (1)) -2- (carboxymethyl 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
1.0mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (2) ether.
B) 0.49mol NPEs (2) obtained by step a) are 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, alkalized 2 hours at 60 DEG C, add
0.59mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, 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- (NPE (2)) third sulphur of -2- hydroxyls
Hydrochlorate 0.38mol.
C) step b) is synthesized into 3- (NPE (2)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, add 1.5 grams of sodium hydroxides and 1.5 grams of water, side lead to nitrogen
While when being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, uses nitrogen
Purging 4 times, is then adjusted to 150 DEG C by system reaction temperature and is slowly passed through 0.76mol expoxy propane, control pressure≤0.40MPa
Reacted；After reaction terminates, system is purged with nitrogen, neutralizes, be dehydrated after cooling, obtain 3- (NPEs
(2)) -2- (polyethenoxy ether (2)) propane sulfonic acid salt 0.36mol.
D) 3- (NPE (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), alkalized 2 hours at 60 DEG C, add 0.42mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (NPE (2)) -2- (carboxymethyl 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
2.0mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (4) ether.
B) 0.49mol NPEs (4) obtained by step a) are 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, alkalized 2 hours at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, 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- (NPE (4)) third sulphur of -2- hydroxyls
Hydrochlorate 0.38mol.
C) step b) is synthesized into 3- (NPE (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, in logical nitrogen
When being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, is blown with nitrogen
Sweep 4 times, system reaction temperature is then adjusted to 150 DEG C and is slowly passed through 0.76mol expoxy propane, control pressure≤0.40MPa enters
Row reaction；Reaction terminate after, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (NPE (4))-
2- (polyethenoxy ether (2)) propane sulfonic acid salt 0.37mol.
D) 3- (NPE (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), alkalized 2 hours at 60 DEG C, add 0.42mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (NPE (2)) -2- (carboxymethyl 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
3.0mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (6) ether.
B) 0.49mol NPEs (6) obtained by step a) are 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, alkalized 2 hours at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, 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- (NPE (6)) third sulphur of -2- hydroxyls
Hydrochlorate 0.39mol.
C) step b) is synthesized into 3- (NPE (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, in logical nitrogen
When being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, is blown with nitrogen
Sweep 4 times, system reaction temperature is then adjusted to 150 DEG C and is slowly passed through 1.18mol expoxy propane, control pressure≤0.40MPa enters
Row reaction；Reaction terminate after, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (NPE (6))-
2- (polyethenoxy ether (3)) propane sulfonic acid salt 0.38mol.
D) 3- (NPE (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), alkalized 2 hours at 60 DEG C, add 0.44mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (NPE (6)) -2- (carboxymethyl 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
4.0mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (8) ether.
B) 0.49mol NPEs (8) obtained by step a) are 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, alkalized 2 hours at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, 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- (NPE (8)) third sulphur of -2- hydroxyls
Hydrochlorate 0.39mol.
C) step b) is synthesized into 3- (NPE (8)) -2- hydroxy-propanesulfonic acid salt 0.39mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, add 1.5 grams of sodium hydroxides and 15 grams of water, side lead to nitrogen
While when being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, uses nitrogen
Purging 4 times, is then adjusted to 150 DEG C by system reaction temperature and is slowly passed through 1.17mol expoxy propane, control pressure≤0.40MPa
Reacted；After reaction terminates, system is purged with nitrogen, neutralizes, be dehydrated after cooling, obtain 3- (NPEs
(8)) -2- (polyethenoxy ether (3)) propane sulfonic acid salt 0.38mol.
D) 3- (NPE (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), alkalized 2 hours at 60 DEG C, add 0.44mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (NPE (8)) -2- (carboxymethyl 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
2.0mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (4) ether.
B) 0.49mol NPEs (4) obtained by step a) are 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, alkalized 2 hours at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, 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- (NPE (4)) third sulphur of -2- hydroxyls
Hydrochlorate 0.39mol.
C) step b) is synthesized into 3- (NPE (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, in logical nitrogen
When being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, is blown with nitrogen
Sweep 4 times, system reaction temperature is then adjusted to 150 DEG C and is slowly passed through 0.39mol expoxy propane, control pressure≤0.40MPa enters
Row reaction；Reaction terminate after, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (NPE (4))-
2- (polyethenoxy ether (1)) propane sulfonic acid salt 0.39mol.
D) 3- (NPE (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), alkalized 2 hours at 60 DEG C, add 0.48mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (NPE (4)) -2- (carboxymethyl polyethenoxy ether (1)) propane sulfonic acid 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
6.0mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.5mol Nonyl phenos (12) ether.
B) 0.5mol NPEs (12) obtained by step a) are 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, alkalized 2 hours at 60 DEG C, add
0.6mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, 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- (NPE (12)) -2- hydroxyls third
Sulfonate 0.38mol.
C) step b) is synthesized into 3- (NPE (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, in logical nitrogen
When being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, is blown with nitrogen
Sweep 4 times, system reaction temperature is then adjusted to 150 DEG C and is slowly passed through 3.8mol expoxy propane, control pressure≤0.40MPa is carried out
Reaction；Reaction terminate after, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (NPE (12))-
2- (polyethenoxy ether (10)) propane sulfonic acid salt 0.38mol.
D) 3- (NPE (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), alkalized 2 hours at 60 DEG C, add 0.45mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (NPE (12)) -2- (carboxymethyl 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
1.5mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol octyl phenols polyoxyethylene (3) ether.
B) 0.49mol OPEOs (3) obtained by step a) are 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, alkalized 2 hours at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, 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- (OPEO (3)) third sulphur of -2- hydroxyls
Hydrochlorate 0.38mol.
C) step b) is synthesized into 3- (NPE (3)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, add 1.5 grams of sodium hydroxides and 15 grams of water, side lead to nitrogen
While when being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, uses nitrogen
Purging 4 times, is then adjusted to 150 DEG C by system reaction temperature and is slowly passed through 1.2mol expoxy propane, control pressure≤0.40MPa enters
Row reaction；Reaction terminate after, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (OPEO (3))-
2- (polyethenoxy ether (3)) propane sulfonic acid salt 0.38mol.
D) 3- (OPEO (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), alkalized 2 hours at 60 DEG C, add 0.44mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (OPEO (3)) -2- (carboxymethyl 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, 90
At a temperature of DEG C, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, system is then reacted into temperature
Degree is adjusted to 150 DEG C and is slowly passed through 4.2mol oxirane, and control pressure≤0.40MPa carries out ethoxylation；Reaction terminates
Afterwards, system is purged with nitrogen, neutralizes, is dehydrated after cooling, obtain 0.5mol octyl phenols polyoxyethylene (8) ether.
B) 0.5mol OPEOs (8) obtained by step a) are 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, alkalized 2 hours at 60 DEG C, add
0.6mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, 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- (OPEO (8)) third sulphur of -2- hydroxyls
Hydrochlorate 0.38mol.
C) step b) is synthesized into 3- (OPEO (8)) -2- hydroxy-propanesulfonic acid salt 0.38mol, is added to dress
In the reactor for having condensing unit, agitating device and gas distributor, add 1.5 grams of sodium hydroxides and 15 grams of water, side lead to nitrogen
While when being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, uses nitrogen
Purging 4 times, is then adjusted to 150 DEG C by system reaction temperature and is slowly passed through 2.0mol expoxy propane, control pressure≤0.40MPa enters
Row reaction；Reaction terminate after, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (OPEO (8))-
2- (polyethenoxy ether (5)) propane sulfonic acid salt 0.38mol.
D) 3- (OPEO (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), alkalized 2 hours at 60 DEG C, add 0.45mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (OPEO (8)) -2- (carboxymethyl 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, is then adjusted to system reaction temperature
150 DEG C are slowly passed through 2.6mol oxirane, and control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, 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, alkalized 2 hours at 60 DEG C, add
0.6mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, excessive watery 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, add 1.5 grams of sodium hydroxides and 15 grams of water, side lead to nitrogen
When gas side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, uses nitrogen
Air-blowing sweeps 4 times, and system reaction temperature then is adjusted into 150 DEG C is slowly passed through 0.72mol expoxy propane, and control pressure≤
0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralizes, be 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), alkalized 2 hours at 60 DEG C, add 0.40mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (amyl group phenol polyethenoxy (5) ether) -2- (carboxymethyl 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, 90
At a temperature of DEG C, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, system is then reacted into temperature
Degree is adjusted to 150 DEG C and is slowly passed through 1.1mol oxirane, 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, condensed back
In the reactors for flowing device and division box, 400 milliliters of benzene solvents and 30 grams of sodium hydroxides are added, are alkalized 2 hours at 60 DEG C,
0.6mol3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, are reacted 8 hours.After reaction terminates, dropwise addition concentration is 6M
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, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, uses
Nitrogen is purged 4 times, and system reaction temperature then is adjusted into 150 DEG C and is slowly passed through 1.5mol expoxy propane, and control pressure≤
0.40MPa is reacted；After reaction terminates, system is purged with nitrogen, neutralizes, be dehydrated after cooling, obtaining 3-, (dodecylphenol gathers
Oxygen ethene (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), alkalized 2 hours at 60 DEG C, add 0.42mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (dodecyl phenol polyethenoxy (2) ether) -2- (carboxymethyl polyoxypropylene (4) ether) sulfonate (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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, at 90 DEG C
At a temperature of, dehydration 1 hour is vacuumized, then 4 times are purged with nitrogen 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 oxirane, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates,
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, condensed back
In the reactors for flowing device and division box, 400 milliliters of benzene solvents and 26 grams of sodium hydroxides are added, are alkalized 2 hours at 60 DEG C,
0.58mol3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, are reacted 8 hours.After reaction terminates, dropwise addition concentration is 6M
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, add 1 gram of sodium hydroxide and 10 grams of water, side lead to nitrogen
When gas side is heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, uses nitrogen
Air-blowing is swept 4 times, and system reaction temperature then is adjusted into 150 DEG C and is slowly passed through 1.8mol expoxy propane, control pressure≤0.40MPa
Reacted；After reaction terminates, system is purged with nitrogen, neutralizes, be 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), alkalized 2 hours at 60 DEG C, add 0.40mol sodium chloroacetates, at reflux, reaction 5 is small
When, obtain 3- (cetyl phenol polyethenoxy (5) ether) -2- (carboxymethyl polyoxypropylene (5) ether) propane sulfonic acid salt (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
The parts by weight of salt 1, the parts by weight of diethanol amine 0.5 and Pu Chengxi Districts injection water 500 parts by weight mix 1 hour, 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
Valency result is listed in table 3 and table 4.
【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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
3.0mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation 4 hours, then passes to
1.5mol expoxy propane, continue reaction 4 hours；After reaction terminates, system is purged with nitrogen, neutralizes, be 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, are reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend and the pH of system be transferred to 2 for 6M hydrochloric acid, 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 the parts by weight of 3- (Nonyl pheno (6) polyoxypropylene (3) ether) -2- hydroxy-propanesulfonic acids salt 1 of above-mentioned synthesis
Mixed 1 hour with Pu Chengxi Districts injection water 500 parts by weight, 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 determined
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 terminates, 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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
1.5mol expoxy propane is slowly passed through to 150 DEG C, control pressure≤0.40MPa reacts 4 hours, obtains nonyl phenol poly-oxypropylene
(3) ether, 3.0mol oxirane is then passed to, continues reaction 4 hours；Reaction terminate after, 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, 0.58mol3- chlorine-2-hydroxyl propanesulfonates are added, at reflux, are reacted 8 hours.After reaction terminates, it is added dropwise dense
Spend and the pH of system be transferred to 2 for 6M hydrochloric acid, 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
The above-mentioned parts by weight of surfactant 1 and Pu Chengxi Districts injection water 500 parts by weight are mixed 1 hour, obtain one
The oil displacement agent of kind homogeneous transparent.Other same comparative examples 1, result is listed in table 5 for ease of comparing.
【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 being heated to 85 DEG C in logical nitrogen, stirring reaction 1 hour.Vacuum system is opened, in 90 DEG C of temperature
Under degree, dehydration 1 hour is vacuumized, then 4 times is purged with the air in removing system with nitrogen, then adjusts system reaction temperature
3.0mol oxirane is slowly passed through to 150 DEG C, control pressure≤0.40MPa carries out ethoxylation；After reaction terminates, use
Nitrogen purges system, neutralizes, is dehydrated after cooling, obtains 0.49mol Nonyl phenos (6) ether.
B) 0.49mol NPEs (6) obtained by step a) are 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, alkalized 2 hours at 60 DEG C, add
0.58mol3- chlorine-2-hydroxyl propanesulfonates, at reflux, react 8 hours.After reaction terminates, 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- (NPE (6)) third sulphur of -2- hydroxyls
Hydrochlorate 0.39mol.
C) step b) is synthesized into 3- (NPE (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, in logical nitrogen
When being heated to 85 DEG C, stirring reaction 1 hour.Vacuum system is opened, at a temperature of 90 DEG C, dehydration 1 hour is vacuumized, is blown with nitrogen
Sweep 4 times, system reaction temperature is then adjusted to 150 DEG C and is slowly passed through 1.18mol expoxy propane, control pressure≤0.40MPa enters
Row reaction；Reaction terminate after, with nitrogen purge system, after cooling neutralize, be dehydrated, obtain 3- (NPE (6))-
2- (polyethenoxy ether (3)) propane sulfonic acid salt 0.38mol, structure are as follows：
2. surfactant properties are evaluated
The above-mentioned parts by weight of surfactant 1 and Pu Chengxi Districts injection water 500 parts by weight are mixed 1 hour, obtain one
The oil displacement agent of kind homogeneous transparent.Other same comparative examples 1, result is listed in table 5 for ease of comparing.
Water is injected in the Zhongyuan Oil Field Pu Chengxi Districts of table 1
| Project | Na++K+ | Mg2+ | Ca2+ | Cl- | SO4 2- | HCO3 - | TDS |
| mg/L | 85066 | 367 | 3840 | 138006 | 1089 | 282 | 228650 |
The embodiment 1-15 oil displacement agents of table 2 form
The embodiment 1-15 oil displacement agent interfacial tension performances of table 3
| Embodiment | Interfacial tension (mN/m) |
| 1 | 0.0075 |
| 2 | 0.0084 |
| 3 | 0.0034 |
| 4 | 0.0021 |
| 5 | 0.0014 |
| 6 | 0.0002 |
| 7 | 0.0068 |
| 8 | 0.0018 |
| 9 | 0.0063 |
| 10 | 0.0075 |
| 11 | 0.0035 |
| 12 | 0.0038 |
| 13 | 0.0148 |
| 14 | 0.0086 |
| 15 | 0.0045 |
The embodiment 1-15 oil displacement experiment results of table 4
| Embodiment | Improve recovery ratio % |
| 1 | 5.8 |
| 2 | 5.2 |
| 3 | 7.1 |
| 4 | 9.3 |
| 5 | 9.8 |
| 6 | 11.6 |
| 7 | 4.5 |
| 8 | 8.2 |
| 9 | 6.5 |
| 10 | 4.8 |
| 11 | 7.1 |
| 12 | 6.1 |
| 13 | 4.1 |
| 14 | 4.3 |
| 15 | 5.8 |
The comparative example 1-3 the performance test results of table 5
| 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. suitable for the oil displacement surfactant on high salinity stratum, its entitled 3- (alkyl phenol polyethenoxy ether) -2- (carboxylic first
Base polyethenoxy ether) propane sulfonic acid salt, shown in structure such as formula (I)：
Wherein M1And M2Any one in alkali metal, alkaline-earth metal is independently selected from, works as M1For alkali metal when n1For 1, work as M1For alkaline earth
N during 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=1~20.
2. the oil displacement surfactant according to claim 1 suitable for high salinity stratum, it is characterised in that x=2~
8, y=2~4.
3. the oil displacement surfactant according to claim 2 suitable for high salinity stratum, it is characterised in that the hydrocarbon
Base is C7~C10Alkyl.
4. the preparation method of the oil displacement surfactant suitable for high salinity stratum described in claim 1, including following step
Suddenly：
A) under base 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, alkalized 0.5~3 hour at 30~60 DEG C, add 3- chlorine-2-hydroxyl propane sulfonic acid
Alkali metal salt, stir lower reaction and obtain 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 base catalyst effect, with institute
Requirement expoxy propane 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, chloroacetic alkali metal salt is added, lower reaction is stirred and obtains 3- (alkyl phenol polyethenoxy ether) -2- (carboxymethyl polyoxies third
Alkene ether) propane sulfonic acid salt；
5. the preparation method of the oil displacement surfactant according to claim 4 suitable for high salinity stratum, its feature
It is step a) and the step c) base catalysts is at least one of alkali metal hydroxide or alkaline earth metal hydroxide.
6. the preparation method of the oil displacement surfactant according to claim 4 suitable for high salinity stratum, its feature
It is step b) the alkyl phenol polyethenoxy ethers and the mol ratio of 3- chlorine-2-hydroxyl propane sulfonic acid alkali metal salts is 1:(1~4).
7. the preparation method of the oil displacement surfactant according to claim 5 suitable for high salinity stratum, its feature
It is step a) and the step c) base catalysts is at least one of sodium hydroxide or potassium hydroxide.
8. the preparation method of the oil displacement surfactant according to claim 4 suitable for high salinity stratum, its feature
Be step a) and/or step c) in reaction temperature it is 85~160 DEG C, pressure is 0~0.40MPa.
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.
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