CN113797842A - Alkyl aryl anionic nonionic surfactant and preparation method thereof - Google Patents

Alkyl aryl anionic nonionic surfactant and preparation method thereof Download PDF

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CN113797842A
CN113797842A CN202010539584.5A CN202010539584A CN113797842A CN 113797842 A CN113797842 A CN 113797842A CN 202010539584 A CN202010539584 A CN 202010539584A CN 113797842 A CN113797842 A CN 113797842A
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surfactant
anionic
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nonionic surfactant
oil
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CN113797842B (en
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李应成
张卫东
沙鸥
沈少春
翟晓东
孟勇
虞辰敏
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China Petroleum and Chemical Corp
Sinopec Shanghai Research Institute of Petrochemical Technology
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Abstract

The present invention relates to a hydrocarbonThe aryl anionic and nonionic surfactant and the preparation method thereof mainly solve the technical problems of poor emulsifying property and low activity of the surfactant in the prior intensified oil production technology, particularly in thickened oil production. The alkyl aryl anionic and nonionic surfactant is characterized in that the alkyl aryl anionic and nonionic surfactant has at least one of molecular formulas shown in a formula (I), R1Is C1~C30Any one of the aliphatic hydrocarbon group or the aliphatic hydrocarbon group-substituted aromatic group of (1); r2Any one of alkylene, alkenylene and arylene with carbon atoms of 0-10; m is an anionic group; n is any one of cation or cationic group; the technical scheme is that m is 0-100, n is 0-90, p is 0-120, and m, n and p are all larger than 0, so that the technical problem of poor emulsifying capacity of the existing surfactant is well solved, and the surfactant can be used in the enhanced oil recovery process of an oil field.

Description

Alkyl aryl anionic nonionic surfactant and preparation method thereof
Technical Field
The invention relates to a hydrocarbyl aryl anionic nonionic surfactant and a preparation method thereof.
Background
The thickened oil refers to crude oil with high content of asphaltene and colloid and high viscosity. The relative density is usually more than 0.92g/cm3(20 ℃) and the underground viscosity of the crude oil is more than 50 mPas, which is called thick oil and also called heavy oil. At present, the exploitation modes of the thickened oil mainly comprise cold exploitation and hot exploitation. Wherein the thermal recovery mode comprises: steam flooding, steam stimulation, Steam Assisted Gravity Drainage (SAGD); the cold mining method comprises the following steps: polymer flooding, surfactant flooding, foam flooding, solvent extraction (VAPEX), microbial flooding, and the like. For extra-thick oil and ultra-thick oil with the viscosity of more than 10,000mPa.s, a development mode of thermal recovery is often adopted.
China has rich thickened oil resources, which mainly comprises a single temple oil field, a victory lump three region, a haoqiao oil field, an island oil field and the like of a victory oil field, a nine region, a hexaeast region, a red mountain tip oil field and a Fengcheng thickened oil region of Craya, an eosin one region, a happy ridge thickened oil region and a high rising oil field of a Liaohe oil field, a shaft building oil field, an ancient city oil field and the like of a Henan oil field, a jujube garden oil field, a Yangsu oil field and the like of a Hongkong oil field. Wangchunzhi et al designed a three-dimensional large-sized core displacement experimental device for simulating the HDCS flooding process, monitoring the pressure and temperature conditions in the injection, soaking and recovery stages, and providing a laboratory simulation means for the exploitation of thick oil. Experiments were performed using victory oil field simulated oil and SLKF series oil soluble viscosity depressants. Experiments show that when the HDCS huff and puff experiment is carried out to the sixth period, the recovery water content reaches 85%, the oil reservoir pressure is reduced to be below 5MPa, the condition of transferring to steam flooding is achieved, then steam flooding is used, and meanwhile profile control agents are used for plugging a high-permeability zone, so that the recovery ratio can be improved.
At present, the most used tertiary oil recovery surfactants at home and abroad are petroleum sulfonate, olefin sulfonate and other surfactants, such as patent documents CN1203935A, CN1426833A, US2010/0282467 and the like. The surfactant has the advantages of wide source, low cost and the like. However, with the increasing depth of the exploitation degree of the oil field and the increasing depth of the oil extraction stratum, the use temperature of the surfactant is higher and higher, and the mineralization degree of water quality is higher and higher. However, the salt tolerance of the surfactant, especially the divalent cation tolerance, is poor, so that the surfactant cannot be applied to high-temperature and high-salinity oil field blocks. Therefore, the development of the novel temperature-resistant salt-resistant surfactant has great significance for the tertiary oil recovery industry.
Disclosure of Invention
The invention aims to solve the technical problems that the emulsifying property of a surfactant-containing heavy oil is poor and the activity is low under the conditions of high temperature and high salt in the prior art, and provides a novel alkyl aryl anionic and nonionic surfactant.
The second technical problem to be solved by the present invention is to provide a method for preparing alkyl aryl anionic surfactant corresponding to the first technical problem. The method has the characteristics of simple process, mild reaction conditions and high product yield.
The invention also provides an application of alkyl aryl anionic surfactant corresponding to one of the technical problems.
In order to solve one of the above technical problems, the technical scheme adopted by the invention is as follows: an alkyl aryl anionic surfactant, wherein the alkyl aryl anionic surfactant has at least one of the general molecular formulas shown in formula (I):
Figure BDA0002538445540000021
in the formula (I), R1Is C1~C30Any one of the aliphatic hydrocarbon group or the aliphatic hydrocarbon group-substituted aromatic group of (1); r2Any one of alkylene, alkenylene and arylene with carbon atoms of 0-10; m is an anionic group; n is any one of cation or cationic group; m is 0 to 100, n is 0 to 90, p is 0 to 120, and m, n, and p are all larger than 0.
In the above technical scheme, R1Is C1~C20Any one of alkyl, alkenyl or alkylbenzene, alkenylbenzene; when R is1Is C1~C20When any one of the alkyl benzene and alkenyl benzene is contained, R is1The benzene ring in (1) can form a naphthalene ring with the benzene ring in the structural formula.
In the above technical solution, preferably, m is 0.5 to 50, n is 1 to 75, and p is 1 to 50; more preferably, n is 1 to 50.
In the above technical scheme, R2Is any one of alkylene, alkenylene and arylene with 0-6 carbon atoms, and R is2When the number of carbon atoms is 0, the absence of a linking group is indicated, and M is directly linked to a benzene ring in the structural formula.
In the above technical solution, the N is any kind of cation or cationic group, represents the kind of cation or cationic group, does not represent the number of N, and is preferably selected from any one of carboxylate, sulfonate, sulfate and phosphate, and more preferably from any one of carboxylate and sulfonate, in order to balance the charges in the molecular formula.
In the above technical solution, said N is furtherPreferably any one of alkali metal, alkaline earth metal and ammonium ion, more preferably Na+、K+、Mg2+、Ca2+、NH4 +Any one of them.
To solve the second technical problem, the invention adopts the following technical scheme: a preparation method of alkyl aryl anionic nonionic surfactant comprises the following steps:
a) carrying out alkoxylation reaction on an initiator, ethylene oxide, propylene oxide and butylene oxide in the presence of a catalyst to obtain polyether; wherein the initiator is C1~C30Any one of aliphatic aromatic phenols;
b) polyether sulfonate can be obtained from the polyether synthesized in the step a) through sulfonation reaction or alkylation reaction, namely the alkyl aryl anionic and nonionic surfactant;
or:
c) reacting the polyether containing the carboxylate radical initiator synthesized in the step a) with an etherification reagent to obtain polyether carboxylate, namely the alkyl aryl anionic and nonionic surfactant.
In the technical scheme, the reaction temperature of the alkoxylation reaction is 140-200 ℃, the reaction pressure is 0-5 MPa, and the molar ratio of the initiator to the ethylene oxide, the propylene oxide or the butylene oxide is independently selected to be 1 (1-50); the catalyst is alkali metal hydroxide, DMC (dimethyl formamide) double metal polyether catalyst or phosphazene catalyst, and the using amount of the catalyst is 0.001-2.0% of the weight of the initiator.
In the technical scheme, the molar ratio of the alkyl aryl polyether to the sulfonation reagent is 1 (1-3); the sulfonation reaction temperature is 20-80 ℃, and the sulfonation reaction time is 0.5-10 hours; the pH value after the alkali is added is 10-14, and the hydrolysis reaction time is 0.5-5 hours.
In the above technical scheme, the carboxylate radical-containing initiator is preferably C as a substituent1~C30Aliphatic aromatic carboxylic acids, e.g. but not limited to C as substituent1~C30Alkyl salicylic acids, e.g. dodecylsalicylic acid, octadecaneSalicylic acid, and the like.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: an application of alkyl aryl anionic nonionic surfactant is disclosed.
In the above technical solution, the application is not particularly limited, for example, but not limited to the application in enhanced oil and gas field recovery, for example, the aqueous solution containing the surfactant of the present invention is injected into the underground for enhanced oil and gas field recovery, and the use concentration of the surfactant is preferably 0.05 w.t.% or more.
The molecular structure of the alkyl aryl anionic nonionic surfactant simultaneously contains a benzene ring and a segmented structure of polyether functional groups (polyoxybutylene, polyoxypropylene and polyoxyethylene triblock), so that the interaction with crude oil is enhanced, particularly the interaction with heavy oil components is enhanced, the technical problems of poor emulsifying property and low activity of the surfactant in the existing enhanced oil recovery technology are solved, and the oil displacement effect can be effectively improved.
The alkyl aryl anionic and nonionic surfactant is used in tertiary oil recovery, particularly heavy oil reservoirs, and has the following advantages:
(1) the surfactant has high interfacial activity and strong emulsifying capacity. When the concentration is more than 0.05 percent, 10 can be formed with underground crude oil-3~10-4The ultra-low interfacial tension of milli-Newton/m, the solubilization parameter reaches more than 10.
(2) High heat resistance and high salt resistance. Because the salt-resistant agent contains nonionic groups such as polyoxybutylene, polyoxypropylene and polyoxyethylene, the salt-resistant capability of the salt-resistant agent is obviously improved; different functional groups are connected through C-C bonds or C-O bonds, so that the hydrothermal stability is high.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Adding nonyl phenol and 1% KOH (potassium hydroxide) by mass as a catalyst into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging with nitrogen for 3-4 times to remove air in the system, raising the reaction temperature to 200 ℃, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. After the reaction is finished, cooling to 180 ℃, continuously and slowly introducing the calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding the calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), purging the system by using nitrogen, and removing unreacted ethylene oxide to obtain the alkyl aryl polyether nonionic surfactant.
Adding 2 times of molar amount of sulfur trioxide into the product, reacting for 1 hour at 60 ℃, then adding 3 times of molar amount of potassium hydroxide aqueous solution into a reaction system, and hydrolyzing for 6 hours at 80 ℃ to obtain the product, namely the potassium nonylphenol polyether sulfonate. Dissolving the product in ethanol/water (V/V ═ 7:3) mixed solution, passing through an acidic ion exchange column, neutralizing nonylphenol polyether sulfonic acid with sodium hydroxide aqueous solution, heating to 100 ℃, and removing the solvent under reduced pressure to obtain the nonylphenol polyether sodium sulfonate anionic/nonionic surfactant. The structure is shown in table 1.
[ example 2 ]
Adding octadecyl naphthol, 0.5 percent KOH by mass of the octadecyl naphthol and 30ppm of phosphazene catalyst into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging for 3-4 times by using nitrogen to remove air in the system, raising the reaction temperature to 200 ℃, slowly introducing metered epoxy butane, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. After the reaction is finished, cooling to 180 ℃, continuously and slowly introducing the calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding the calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), purging the system by using nitrogen, and removing unreacted ethylene oxide to obtain the alkyl aryl polyether nonionic surfactant.
Adding 2 times of molar amount of sulfur trioxide into the product, reacting at 60 ℃ for 1 hour, then adding 3 times of molar amount of potassium hydroxide aqueous solution into the reaction system, and hydrolyzing at 80 ℃ for 6 hours. And dissolving the product in an ethanol/water (V/V ═ 7:3) mixed solution, passing through an acidic ion exchange column, neutralizing octadecyl (sulfonic acid) naphthol polyether by using a calcium hydroxide aqueous solution, heating to 80 ℃, and removing the solvent under reduced pressure to obtain the octadecyl naphthol polyether sulfonic acid calcium anionic non-surfactant. The structure is shown in table 1.
[ example 3 ]
Adding pentadecylphenol, 2.0% KOH by mass of the pentadecylphenol and 30ppm of phosphazene catalyst into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging for 3-4 times by using nitrogen to remove air in the system, raising the reaction temperature to 180 ℃, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 0.60MPa to carry out etherification reaction. And after the reaction is finished, continuously and slowly introducing the calculated amount of propylene oxide, after the reaction is finished, adding the calculated amount of ethylene oxide again, cooling to 150 ℃, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), purging the system by using nitrogen, and removing the unreacted ethylene oxide to obtain the pentadecylphenol polyether nonionic surfactant.
Adding formyl chloride with equal molar quantity into the product at normal temperature, adding aluminum trichloride after the reaction is finished, stirring and heating to 80 ℃, slowly dripping 4-chloro-2-butenoic acid, continuing the reaction for 5 hours after the dripping is finished, and carrying out post-treatment to obtain pentadecyl phenol-2-butenoic acid-polyether formate. Adding 2 times of molar weight of aqueous solution of sodium hydroxide into the reactant, heating to 80 ℃, stirring for 6 hours, adding solvent benzene, refluxing to remove water, filtering to remove the solid in the reactant to obtain the product pentadecylphenol-2-sodium butenoate-polyether formate anionic nonionic surfactant. The structure is shown in table 1.
[ example 4 ]
Adding octylphenol and 0.5% KOH catalyst by mass into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging with nitrogen for 3-4 times to remove air in the system, raising the reaction temperature to 200 ℃, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. After the reaction is finished, cooling to 180 ℃, continuously and slowly introducing the calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding the calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), purging the system by using nitrogen, and removing unreacted ethylene oxide to obtain the octyl phenol polyether nonionic surfactant.
Adding formyl chloride with equal molar quantity into the product at normal temperature, adding aluminum trichloride after the reaction is finished, stirring and heating to 80 ℃, slowly dripping 4-chloromethyl benzenesulfonic acid, continuing the reaction for 5 hours after the dripping is finished, and carrying out post-treatment to obtain the octyl phenol (4-methyl benzenesulfonic acid) polyether formate. Adding 2 times of magnesium hydroxide aqueous solution into the reactant, heating to 80 ℃, stirring for 6 hours, adding solvent benzene, refluxing to remove water, and filtering to remove the solid in the reactant to obtain the product octylphenol (4-sodium methyl benzene sulfonate) polyether anionic nonionic surfactant. The structure is shown in table 1.
[ example 5 ]
Adding m-pentadecyl phenol (cardanol) and 0.5% KOH catalyst by mass into a polymerization reaction kettle, heating the system to 170 ℃ under stirring, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 1.0MPa to carry out etherification reaction. And (3) after the reaction is finished, continuously and slowly introducing the calculated amount of propylene oxide, after the reaction is finished, adding the calculated amount of ethylene oxide again, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system by using nitrogen to remove the unreacted ethylene oxide to obtain the cardanol polyether nonionic surfactant.
Adding formyl chloride with equal molar quantity into the product at normal temperature, adding aluminum trichloride after the reaction is finished, stirring and heating to 80 ℃, slowly dripping 3-chloropropanesulfonic acid, continuing the reaction for 5 hours after the addition is finished, and carrying out post-treatment to obtain cardanol (propanesulfonic acid) polyether formate. Adding 3 times of the molar weight of the aqueous solution of sodium hydroxide into the reactant, heating to 80 ℃, stirring for 6 hours, adding solvent benzene, refluxing to remove water, and filtering to remove the solid in the reactant to obtain the product of the cardanol polyether sodium propanesulfonate anionic nonionic surfactant. The structure is shown in table 1.
[ example 6 ]
Adding dodecyl salicylic acid, 1.5% KOH by mass and 30ppm of phosphazene catalyst into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging with nitrogen for 3-4 times to remove air in the system, raising the reaction temperature to 200 ℃, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. After the reaction is finished, cooling to 180 ℃, continuously and slowly introducing the calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding the calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), purging the system by using nitrogen, and removing unreacted ethylene oxide to obtain the dodecyl phenol polyether potassium carboxylate surfactant. The structure is shown in table 1.
[ example 7 ]
Adding octadecyl salicylic acid, 1.5 percent KOH by mass of the octadecyl salicylic acid and 30ppm of phosphazene catalyst into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, purging for 3-4 times by using nitrogen to remove air in the system, raising the reaction temperature to 200 ℃, slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. After the reaction is finished, cooling to 180 ℃, continuously and slowly introducing the calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding the calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), purging the system by using nitrogen to remove unreacted ethylene oxide, and obtaining the potassium octadecylphenol polyether carboxylate surfactant. The structure is shown in table 1.
[ example 8 ] evaluation of emulsifying Properties of surfactants
The phase evaluation was performed according to the SPE 113313 method to calculate the emulsifying capacity. The method mainly comprises the following steps: the desired volume and concentration of aqueous surfactant solution was added to the glass tube, and then crude oil was added to the solution, with a water-to-oil volume ratio (WOR) of 1.0. Sealing and mixing. It was then placed in a metal bath, heated to a set temperature, and periodically mixed to enhance mass transfer between the phases. Equilibrium is considered to be reached until the visual interface position does not change. Its emulsifying capacity is expressed by the solubilization parameter SP, i.e. the volume or mass of surfactant per unit volume or mass that solubilizes water in oil or oil in water. The results are shown in tables 2 and 3.
[ example 9 ] evaluation of surfactant interfacial Property
And measuring the interfacial tension change between the 0.3 wt% of surfactant and the crude oil by using a TX-500C rotary drop interfacial tension meter or a Dataphysics SVT20 under the conditions of reservoir temperature and rotating speed of 5000 r/min until oil drops are balanced. The results are shown in tables 2 and 3.
[ example 10 ] evaluation of oil-washing Performance of surfactant
Taking a certain amount of oil sand, according to the oil: sand 1: 4 (mass ratio) aging at the oil reservoir temperature for 10 days, and stirring for 5 minutes every 2 hours; the aged oil sand, 5g, was then removed, along with a 0.3 wt% surfactant solution as an oil sand: the mass ratio of the solution is 1: 10, mixing uniformly, aging for 48 hours at the oil reservoir temperature, extracting crude oil in the solution by using petroleum ether, fixing the volume by using a 50ml colorimetric tube, and carrying out colorimetric analysis by using a spectrophotometer at the wavelength of 430 nm. The crude oil concentration in the surfactant solution was calculated using a standard curve. The results are shown in tables 2 and 3.
[ example 11 ] evaluation of oil repellency of surfactant
According to the test of the physical simulated oil displacement effect of the composite oil displacement system in the SY/T6424-2000 composite oil displacement system performance test method, a simulated oil displacement experiment is carried out at the oil reservoir temperature. Firstly, using injected water to drive oil-free, then transferring 0.3PV (core pore volume) of the above-mentioned surfactant, then water-driving again to oil-free so as to raise crude oil recovery ratio. The results are shown in tables 2 and 3.
[ COMPARATIVE EXAMPLE 1 ]
The anionic nonionic surfactant of the alkyl aryl polyether was prepared by the method of example 1 except that propylene oxide and butylene oxide were not added and the performance evaluation was carried out, and the results are shown in tables 2 and 3.
[ COMPARATIVE EXAMPLE 2 ]
Surfactant C was prepared according to the method of US20110281779A18H17O-(BO)7-(PO)7-(EO)25-SO3Na, and the performance was evaluated, and the results are shown in tables 2 and 3.
Table 1 examples 1-7 surfactant compositions and structures
Figure BDA0002538445540000081
Table 2 examples 1-7 surfactant properties
And (3) testing conditions are as follows:
90 ℃, the degree of mineralization of 35,000mg/L, the content of divalent ions of 1,000mg/L, crude oil API 25 and the permeability of a rock core of 220mD
Examples Solubilization parameter Interfacial tension (mN/m) Wash oil Performance (%) Enhanced recovery (%)
1 14 0.00315 63 9.0
2 16 0.00038 79 13.7
3 13 0.00065 70 11.1
4 12 0.00436 61 7.8
5 14 0.00064 77 12.9
6 9 0.00171 66 8.7
7 15 0.00092 63 9.4
Comparative example 1 6 0.02572 31 4.1
Comparative example 2 7 0.00341 51 6.5
The surfactant prepared in example 2 was formulated at various concentrations and tested for oil-water interfacial tension with the crude oil described above, and the results are shown in table 3.
TABLE 3 oil-water interfacial tension between surfactant groups of different concentrations and crude oil
Figure BDA0002538445540000091
The results show that the surfactant disclosed by the invention has high oil-water interfacial activity on the tested thickened oil.
The surfactant of the invention is used for high-temperature high-salinity heavy oil reservoir again, and the oil-water interfacial tension of the surfactant is tested, and the result is shown in table 4.
Table 4 examples 1-7 surfactant properties
And (3) testing conditions are as follows:
the mineralization degree is 300,000mg/L at 120 ℃, the content of divalent ions is 10,000mg/L, crude oil API is 18, and the permeability of a rock core is 500mD
Examples Solubilization parameter Interfacial tension (mN/m) Wash oil Performance (%) Enhanced recovery ratio(%)
1 13 0.00091 73 11.1
2 15 0.00141 71 11.0
3 16 0.00427 62 8.3
4 12 0.00056 74 12.3
5 15 0.00261 70 10.9
6 16 0.00282 68 10.6
7 11 0.00314 63 9.0
Comparative example 1 3 0.08101 33 3.6
Comparative example 2 7 0.00443 52 7.0
As can be seen from the results in tables 2, 3 and 4, the surfactant prepared by the present invention has excellent properties, especially, solubilization capacity and oil washing performance under the same conditions, so that the surfactant of the present invention has an ultra-high effect of increasing the recovery ratio.

Claims (10)

1. An alkyl aryl anionic surfactant having at least one of the general molecular formulas of formula (I):
Figure FDA0002538445530000011
in the formula (I), R1Is C1~C30Any one of the aliphatic hydrocarbon group or the aliphatic hydrocarbon group-substituted aromatic group of (1); r2Any one of alkylene, alkenylene and arylene with carbon atoms of 0-10; m is an anionic group; n is any one of cation or cationic group; m is 0 to 100, n is 0 to 90,p is 0-120, and m, n and p are all larger than 0.
2. The hydrocarbyl aryl anionic nonionic surfactant of claim 1, wherein R is1Is C1~C20Any one of alkyl, alkenyl, alkylbenzene and alkenylbenzene of (1).
3. The hydrocarbyl aryl anionic nonionic surfactant of claim 1, wherein R is2Is any one of alkylene, alkenylene and arylene with 0-6 carbon atoms.
4. The anionic or nonionic hydrocarbyl aryl surfactant of claim 1, wherein m is 0.5 to 50, n is 1 to 75, and p is 1 to 50.
5. A process for the preparation of the hydrocarbyl aryl anionic surfactant as claimed in any one of claims 1 to 4, comprising the steps of:
a) carrying out etherification reaction on an initiator, butylene oxide, propylene oxide and ethylene oxide in the presence of a catalyst to obtain an etherification product; wherein the initiator is C1~C30Any one of aliphatic aromatic phenols;
b) the etherified product synthesized in the step a) is subjected to sulfonation reaction or alkylation reaction to obtain the alkyl aryl anionic and nonionic surfactant;
or:
a') carrying out etherification reaction on a carboxylate radical initiator serving as a raw material, butylene oxide, propylene oxide and ethylene oxide in the presence of a catalyst to obtain the alkyl aryl anionic and nonionic surfactant.
6. The method for preparing the anionic and nonionic hydrocarbyl aryl surfactant as claimed in claim 5, wherein the reaction temperature of the etherification reaction is 140-200 ℃ and the reaction pressure is 0-5 MPa.
7. The method for preparing the anionic and nonionic surfactant as claimed in claim 5, wherein the molar ratios of the initiator to butylene oxide, propylene oxide and ethylene oxide are respectively selected from 1 (0.5-50), 1 (1-75) and 1 (1-50).
8. The method of claim 5, wherein the catalyst is selected from the group consisting of alkali metal hydroxides, DMC double metal polyether catalysts and phosphazene catalysts, and the amount of the catalyst is 0.001-2.0% by weight of the initiator.
9. The method for preparing the anionic and nonionic surfactant with alkyl aryl according to claim 5, wherein the molar ratio of the etherification product to the sulfonation reagent is 1 (1-3); the sulfonation reaction temperature is 20-80 ℃, and the sulfonation reaction time is 0.5-10 hours; the pH value after the alkali is added is 10-14, and the hydrolysis reaction time is 0.5-5 hours.
10. Use of an alkyl aryl anionic surfactant as claimed in any one of claims 1 to 4.
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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4978780A (en) * 1987-10-16 1990-12-18 Basf Aktiengesellschaft Preparation of ether sulfonates and polyglycol ether sulfonates, and products prepared by this method
CN103768991A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Anion/nonionic sulphonate surfactant and preparation method thereof
CN103773347A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Surfactant combination for enhancing oil recovery and preparation method thereof
CN104726084A (en) * 2010-03-10 2015-06-24 巴斯夫欧洲公司 Method for producing crude oil using surfactants based on butylene oxide-containing alkyl alkoxylates
US20170226406A1 (en) * 2014-08-12 2017-08-10 China Petroleum & Chemical Corporation Surfactant composition and preparation method therefor and application thereof
CN107532077A (en) * 2015-04-30 2018-01-02 陶氏环球技术有限责任公司 Cosurfactant formation of foam composition for intensified oil reduction

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4978780A (en) * 1987-10-16 1990-12-18 Basf Aktiengesellschaft Preparation of ether sulfonates and polyglycol ether sulfonates, and products prepared by this method
CN104726084A (en) * 2010-03-10 2015-06-24 巴斯夫欧洲公司 Method for producing crude oil using surfactants based on butylene oxide-containing alkyl alkoxylates
CN103768991A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Anion/nonionic sulphonate surfactant and preparation method thereof
CN103773347A (en) * 2012-10-25 2014-05-07 中国石油化工股份有限公司 Surfactant combination for enhancing oil recovery and preparation method thereof
US20170226406A1 (en) * 2014-08-12 2017-08-10 China Petroleum & Chemical Corporation Surfactant composition and preparation method therefor and application thereof
CN107532077A (en) * 2015-04-30 2018-01-02 陶氏环球技术有限责任公司 Cosurfactant formation of foam composition for intensified oil reduction

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