CN113797842B - Hydrocarbyl aryl anionic nonionic surfactant and preparation method thereof - Google Patents
Hydrocarbyl aryl anionic nonionic surfactant and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hydrocarbon aryl anion non-ionic surfactant and a preparation method thereof, which mainly solve the technical problems of poor emulsifying property and low activity of the surfactant in the existing enhanced oil recovery technology, in particular to the surfactant in the thick oil recovery. The alkyl aryl anionic nonionic surfactant is characterized by having at least one of the molecular general formulas shown in the formula (I), R 1 Is C 1 ～C 30 Any one of aliphatic hydrocarbon groups or aliphatic hydrocarbon group-substituted aromatic groups; r is R 2 Is any one of alkylene, alkenylene and arylene groups having 0 to 10 carbon atoms; m is an anionic group; n is any of cations or cationic groups; the technical scheme that m=0-100, n=0-90 and p=0-120, wherein m, n and p are all larger than 0 well solves the technical problem of poor emulsifying capacity of the existing surfactant, and can be used in the enhanced oil extraction process of an oil field.
Description
Technical Field
The invention relates to a hydrocarbon aryl anion surfactant and a preparation method thereof.
Background
The thick oil refers to crude oil with higher asphaltene and colloid content and higher viscosity. The relative density is generally greater than 0.92g/cm 3 Crude oils with a subsurface viscosity of more than 50 mPas, also called heavy oils, are known as thick oils (20 ℃). At present, the exploitation mode of thick oil is mainly divided into cold exploitation and hot exploitation. The thermal recovery method comprises the following steps: steam flooding, steam stimulation, steam Assisted Gravity Drainage (SAGD); the cold mining mode comprises the following steps: polymer flooding, surfactant flooding, foam flooding, solvent extraction (VAPEX), microbial flooding, and the like. Aiming at extra thick oil and super thick oil with viscosity more than 10,000mPa.s, a development mode of thermal recovery is often adopted.
The method is characterized in that the method mainly comprises single temple oil fields, winning lump three areas, grass bridge oil fields, island oil fields and the like of a winning oil field, nine areas, six eastern areas, red mountain mouth oil fields, and wind city thick oil areas of Xinjiang Kelamaiyi, an dawn one area, a Happy green thick oil area, a high lift oil field of a Liaohe oil field, a well-head oil field, an ancient city oil field and the like of a Henan oil field, a jujube garden oil field, a sheep three wood oil field and the like of a big harbor oil field. Wang Chunzhi et al designed a three-dimensional large-size core displacement experimental device for simulating the HDCS oil displacement process, and can monitor the pressure and temperature conditions of injection, well-stewed and recovery stages, thereby providing a laboratory simulation means for the recovery of thick oil. Experiments were performed using victory oilfield simulation oil and an SLKF series oil-soluble viscosity reducer. Experiments show that when the HDCS huff-puff experiment is carried out to a sixth period, the recovery water content reaches 85%, the oil reservoir pressure is reduced to below 5MPa, the condition of converting into steam flooding is achieved, then the steam flooding is changed, and meanwhile, the profile control agent is used for plugging the hypertonic layer belt, so that the recovery ratio can be improved.
At present, the most used tertiary oil recovery surfactants at home and abroad are surfactants such as petroleum sulfonate, olefin sulfonate and the like, such as patent documents such as CN1203935A, CN1426833A, US2010/0282467 and the like. The surfactant has the advantages of wide sources, low price and the like. However, as the oil field exploitation degree is deeper and deeper, the oil extraction stratum is deeper and deeper, the use temperature of the surfactant is higher and the mineralization degree of water quality is higher and higher. However, the above surfactants are poor in salt tolerance, particularly against divalent cations, resulting in their inability to be used in high temperature, high mineralization oilfield blocks. Therefore, the development of the novel temperature-resistant and salt-resistant surfactant has extremely important significance for the tertiary oil recovery industry.
Disclosure of Invention
One of the technical problems to be solved by the invention is that the surfactant in the prior art has poor emulsifying property and low activity on thick oil under the conditions of high temperature and high salt, and provides a novel alkyl aryl anion nonionic surfactant.
The second technical problem to be solved by the invention is to provide a preparation method of the alkyl aryl anionic nonionic surfactant corresponding to one of the technical problems. The method has the characteristics of simple process, mild reaction conditions and high product yield.
The third technical problem to be solved by the invention is to provide an application of the alkyl aryl anionic nonionic surfactant corresponding to one of the technical problems.
In order to solve one of the technical problems, the invention adopts the following technical scheme: a hydrocarbyl aryl anionic nonionic surfactant, wherein the hydrocarbyl aryl anionic nonionic surfactant has at least one of the molecular formulas shown in formula (I):
in the formula (I), R 1 Is C 1 ～C 30 Any one of aliphatic hydrocarbon groups or aliphatic hydrocarbon group-substituted aromatic groups; r is R 2 Is any one of alkylene, alkenylene and arylene groups having 0 to 10 carbon atoms; m is an anionic group; n is any of cations or cationic groups; m=0 to 100, n=0 to 90, p=0 to 120, and m, n, p are all greater than 0.
In the above technical solution, R is 1 Is C 1 ～C 20 Any one of alkyl, alkenyl or alkylbenzene, alkenylbenzene; when R is 1 Is C 1 ～C 20 R is either alkyl benzene or alkenyl benzene 1 The benzene ring in (a) can form a naphthalene ring with the benzene ring in the structural formula.
In the above technical solution, preferably, m=0.5 to 50, n=1 to 75, and p=1 to 50; more preferably, n=1 to 50.
In the above technical solution, R is 2 Is any one of an alkylene group, an alkenylene group and an arylene group having 0 to 6 carbon atoms, wherein R is 2 When the number of carbon atoms is 0, the existence of a connecting group is not indicated, and M is directly connected with a benzene ring in the structural formula.
In the above technical scheme, N is any one of a cation or a cationic group, and does not represent the number of N, and is preferably any one selected from carboxylate, sulfonate, sulfate, and phosphate, more preferably any one selected from carboxylate and sulfonate, in order to balance the charges of the molecular formula.
In the above embodiment, the N is more preferably any one of alkali metal, alkaline earth metal and ammonium ion, and is more preferably Na + 、K + 、Mg 2+ 、Ca 2+ 、NH 4 + Any one of the following.
In order to solve the second technical problem, the technical scheme adopted by the invention is as follows: a process for preparing a hydrocarbyl aryl anionic nonionic surfactant comprising the steps of:
a) Carrying out alkoxylation reaction on an initiator and ethylene oxide, propylene oxide and butylene oxide in the presence of a catalyst to obtain polyether; wherein the initiator is C as substituent 1 ～C 30 Any one of aliphatic aromatic phenols;
b) Polyether sulfonate which is the alkyl aryl anion nonionic surfactant can be obtained by the sulfonation reaction or alkylation reaction of the polyether synthesized in the step a);
or:
c) And c), reacting the polyether synthesized according to the step a) with an etherification reagent to obtain polyether carboxylate, namely the alkyl aryl anionic 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 1 (1-50); the catalyst is alkali metal hydroxide, DMC bimetallic polyether catalyst or phosphazene catalyst, and the dosage is 0.001-2.0% of the weight of the initiator.
In the technical scheme, the mol ratio of the alkyl aryl polyether to the sulfonation reagent is 1 (1-3); the temperature of the sulfonation reaction is 20-80 ℃, and the sulfonation reaction time is 0.5-10 hours; the pH value after adding alkali is 10-14, and the hydrolysis reaction time is 0.5-5 hours.
In the above technical scheme, the carboxylate radical-containing initiator preferably has a substituent C 1 ～C 30 Aliphatic aromatic carboxylic acids, e.g. but not limited to, substituted with C 1 ～C 30 Alkyl salicylic acids such as dodecyl salicylic acid, octadecyl salicylic acid, and the like.
In order to solve the third technical problem, the technical scheme adopted by the invention is as follows: use of a hydrocarbyl aryl anionic nonionic surfactant.
In the above technical solution, the application is not particularly limited, for example, but not limited to, application in enhancing recovery of oil and gas fields, such as injection of an aqueous solution containing the surfactant of the present invention into the ground to enhance recovery of oil and gas fields, and the concentration of the surfactant is preferably 0.05w.t.% or more.
According to the alkyl aryl anion nonionic surfactant, through the block structure of which the molecular structure simultaneously comprises benzene rings and polyether functional groups (polyoxybutylene, polyoxypropylene and polyoxyethylene three blocks), the interaction with crude oil is enhanced, particularly the interaction with a thickened oil component is enhanced, so that 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 nonionic surfactant is used in tertiary oil recovery, particularly a heavy oil reservoir, and has the following advantages:
(1) The surfactant has high interfacial activity and strong emulsifying capacity. It can form 10 with underground crude oil at a concentration of above 0.05% -3 ～10 -4 The ultra-low interfacial tension of milli-newtons per meter and the solubilization parameters reach above 10.
(2) The temperature resistance and the salt resistance are strong. The anti-salt capability of the modified polyurethane is obviously improved because the modified polyurethane contains nonionic groups such as polyoxybutylene, polyoxypropylene, polyoxyethylene and the like; and different functional groups are connected through a C-C bond or a C-O bond, so that the hydrothermal stability of the compound is high.
The invention is further illustrated by the following examples.
Detailed Description
[ example 1 ]
Adding nonylphenol and KOH with the mass percentage of 1% as a catalyst into a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then slowly introducing metered epoxybutane after the reaction temperature is raised to 200 ℃, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. And after the reaction is finished, cooling to 180 ℃, continuously and slowly introducing calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the hydrocarbon aryl polyether nonionic surfactant.
Adding 2 times molar quantity of sulfur trioxide into the product, reacting for 1 hour at 60 ℃, then adding 3 times molar quantity of aqueous solution of potassium hydroxide into a reaction system, and hydrolyzing for 6 hours at 80 ℃ to obtain the product of the nonylphenol polyether potassium sulfonate. The product is dissolved in ethanol/water (V/V=7:3) mixed solution and passes through an acid ion exchange column, then sodium hydroxide aqueous solution is used for neutralizing the nonylphenol polyether sulfonic acid, the temperature is raised to 100 ℃, the solvent is removed under reduced pressure, and the nonylphenol polyether sodium sulfonate anionic non-surfactant is obtained. The structure is shown in Table 1.
[ example 2 ]
Adding octadecyl naphthol, 0.5% KOH and 30ppm phosphazene catalyst in a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then raising the reaction temperature to 200 ℃, slowly introducing metered epoxybutane, and controlling the reaction pressure to be less than 2.0MPa to carry out etherification reaction. And after the reaction is finished, cooling to 180 ℃, continuously and slowly introducing calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the hydrocarbon aryl polyether nonionic surfactant.
To the above product, 2 times molar amount of sulfur trioxide was added, and the reaction was carried out at 60℃for 1 hour, then 3 times molar amount of an aqueous solution of potassium hydroxide was added to the reaction system, and the reaction system was hydrolyzed at 80℃for 6 hours. The product of the potassium stearyl naphthol polyether sulfonate is obtained, the product is dissolved in ethanol/water (V/V=7:3) mixed solution and passes through an acid ion exchange column, then calcium hydroxide aqueous solution is used for neutralizing the stearyl (sulfonic acid) naphthol polyether, the temperature is raised to 80 ℃ and the solvent is removed under reduced pressure, so that the calcium stearyl naphthol polyether sulfonate anionic non-surfactant is obtained. The structure is shown in Table 1.
[ example 3 ]
Pentadecyl phenol, 2.0% KOH and 30ppm phosphazene catalyst by mass are added into a polymerization reaction kettle, the system temperature is heated to 80-90 ℃ under stirring, a vacuum system is started, dehydration is carried out for 1 hour, nitrogen is used for purging 3-4 times to remove air in the system, then the reaction temperature is raised to 180 ℃, then metered epoxybutane is slowly introduced, and the reaction pressure is controlled to be less than 0.60MPa for etherification reaction. And after the reaction is finished, continuously and slowly introducing calculated amount of propylene oxide, after the reaction is finished, adding calculated amount of ethylene oxide again, cooling to 150 ℃, and carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the pentadecyl phenol polyether nonionic surfactant.
Adding formyl chloride with the same molar quantity into the product at normal temperature, adding aluminum trichloride after the reaction, stirring and heating to 80 ℃, slowly dropwise adding 4-chloro-2-butenoic acid, continuing the reaction for 5 hours after the addition, and obtaining pentadecyl phenol-2-butenoic acid-polyether formate through aftertreatment. Adding 2 times molar quantity of 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 solids in the reactant to obtain the pentadecyl phenol-2-sodium butenoate-polyether formate anionic nonionic surfactant. The structure is shown in Table 1.
[ example 4 ]
Adding octyl phenol 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, then purging with nitrogen for 3-4 times to remove air in the system, then slowly introducing metered epoxybutane after the reaction temperature is raised to 200 ℃, 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 calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the octyl phenol polyether nonionic surfactant.
Adding formyl chloride with the same molar quantity into the product at normal temperature, adding aluminum trichloride after the reaction, stirring and heating to 80 ℃, slowly dropwise adding 4-chloromethylbenzenesulfonic acid, continuing the reaction for 5 hours after the addition, and obtaining the octyl phenol (4-methylbenzenesulfonic acid) polyether formate through aftertreatment. 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 solids in the reactant to obtain the product of the octyl phenol (4-sodium methylbenzenesulfonate) polyether anionic 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, then slowly introducing metered butylene oxide, and controlling the reaction pressure to be less than 1.0MPa for etherification reaction. And after the reaction is finished, continuously and slowly introducing calculated amount of propylene oxide, after the reaction is finished, adding calculated amount of ethylene oxide again, and carrying out etherification again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the cardanol polyether nonionic surfactant.
Adding equimolar amount of formyl chloride into the product at normal temperature, adding aluminum trichloride after the reaction, stirring and heating to 80 ℃, slowly dropwise adding 3-chloropropanesulfonic acid, continuing the reaction for 5 hours after the addition, and obtaining the cardanol (propanesulfonic acid) polyether formate through aftertreatment. Adding 3 times molar quantity of 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 solid in the reactant to obtain the product cardanol polyether sodium propane sulfonate anionic nonionic surfactant. The structure is shown in Table 1.
[ example 6 ]
Adding dodecyl salicylic acid, 1.5% KOH and 30ppm phosphazene catalyst in a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then raising the reaction temperature to 200 ℃, slowly introducing metered epoxybutane, 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 calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the dodecyl phenol polyether carboxylic acid potassium surfactant. The structure is shown in Table 1.
[ example 7 ]
Adding octadecylsalicylic acid, 1.5% KOH and 30ppm phosphazene catalyst in a polymerization reaction kettle, heating the system to 80-90 ℃ under stirring, starting a vacuum system, dehydrating for 1 hour, then purging with nitrogen for 3-4 times to remove air in the system, then raising the reaction temperature to 200 ℃, slowly introducing metered epoxybutane, 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 calculated amount of propylene oxide, after the reaction is finished, cooling to 150 ℃ again, adding calculated amount of ethylene oxide, carrying out etherification reaction again until the reaction is finished (the reaction pressure is unchanged), and purging the system with nitrogen to remove unreacted ethylene oxide to obtain the octadecyl phenol polyether carboxylic acid potassium surfactant. The structure is shown in Table 1.
Example 8 evaluation of emulsifying Properties of surfactant
The emulsification capacity was calculated by evaluating the phase state according to SPE 113313 method. The method mainly comprises the following steps: an aqueous surfactant solution of the desired volume and concentration was added to the glass tube, and then crude oil was added to the solution at a water-to-oil volume ratio (WOR) of 1.0. And mixing after sealing. It is then placed in a metal bath, heated to a set temperature, and the sample mixture is periodically removed to enhance mass transfer between the phases. The equilibrium was considered to be reached until there was no change in visual interface position. Its emulsifying capacity is expressed in terms of the solubilization parameter SP, i.e., the volume or mass of surfactant per unit volume or mass of water in or of oil. The results are shown in tables 2 and 3.
[ example 9 ] evaluation of interfacial Property of surfactant
The interfacial tension change between the surfactant and crude oil at 0.3wt% was measured using a TX-500C spin drop interfacial tensiometer or DataPhysics SVT20 at reservoir temperature and rotational speed of 5000 rpm until the oil drops equilibrated. The results are shown in tables 2 and 3.
Example 10 evaluation of surfactant wash oil Performance
Taking a certain amount of oil sand according to the following oil: sand=1: 4 (mass ratio) aging for 10 days at reservoir temperature, stirring for 5 minutes every 2 hours; and then taking out 5g of the aged oil sand, and mixing the aged oil sand with 0.3wt% of surfactant solution according to the weight percentage of the oil sand: solution mass ratio = 1:10, aging for 48 hours at the reservoir temperature, extracting crude oil in the solution by using petroleum ether, fixing the volume by using a 50ml colorimetric tube, and performing colorimetric analysis at a wavelength of 430nm by using a spectrophotometer. The concentration of crude oil in the surfactant solution was calculated using a standard curve. The results are shown in tables 2 and 3.
Example 11 evaluation of oil displacement performance of surfactant
According to the test of the physical simulated oil displacement effect of the compound oil displacement system in the SY/T6424-2000 compound oil displacement system performance test method, a simulated oil displacement experiment is carried out at the oil reservoir temperature. Firstly, water is injected to drive to be oil-free, then the surfactant with the volume of 0.3PV (core pore volume) is injected, then water is again driven to be oil-free, and the crude oil recovery ratio is calculated and improved. The results are shown in tables 2 and 3.
[ comparative example 1 ]
A hydrocarbon-based aryl polyether anionic nonionic surfactant was prepared as in example 1 except that propylene oxide and butylene oxide were not added, and performance evaluation was performed, and the results are shown in tables 2 and 3.
[ comparative example 2 ]
Preparation of surfactant C according to the method of US20110281779A1 8 H 17 O-(BO) 7 -(PO) 7 -(EO) 25 -SO 3 Na, and performance evaluation was performed, and the results are shown in tables 2 and 3.
Table 1 examples 1-7 surfactant compositions and structures
Table 2 examples 1-7 surfactant properties
Test conditions:
90 ℃, mineralization degree of 35,000mg/L, divalent ion content of 1,000mg/L, crude oil API=25, core permeability of 220mD
| Examples | Solubilization parameters | 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 of crude oil and surfactant groups at different concentrations
The results show that the surfactant provided by the invention has high oil-water interfacial activity on the tested thickened oil.
The surfactant of the invention is used for a high-temperature high-salt heavy oil reservoir again, the oil-water interfacial tension of the surfactant is tested, and the results are shown in Table 4.
Table 4 examples 1-7 surfactant properties
Test conditions:
120 ℃, mineralization degree 300,000mg/L, divalent ion content 10,000mg/L, crude oil API=18, core permeability 500mD
| Examples | Solubilization parameters | Interfacial tension (mN/m) | Wash oil performance (%) | Enhanced recovery (%) |
| 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, under the same conditions, the surfactant prepared by the invention has excellent performance, especially solubilization capacity and wash oil performance, so that the surfactant has an ultrahigh recovery ratio improving effect.
Claims (9)
1. A hydrocarbyl aryl anionic nonionic surfactant characterized by at least one of the molecular formulas of formula (I):
a compound of formula (I);
in the formula (I), R 1 Is C 18 H 37 -C 4 H 3 ，R 1 Forms a naphthalene ring with the benzene ring in the formula (I), R 2 The number of carbon atoms of (2) is 0; or alternatively, the process may be performed,
R 1 is C 15 H 29 ，R 1 Is alkenyl, R 2 Is CH 2 Ch=ch; or alternatively, the process may be performed,
R 1 is C 8 H 17 ，R 2 Is CH 2 C 6 H 4 ，R 2 Is a substituted arylene group; or alternatively, the process may be performed,
R 1 is C 15 H 27 ，R 1 Is alkenyl, R 2 Is CH 2 CH 2 CH 2 ；
M is an anionic group; n is any one of cations or cationic groups; m=1 to 50, n=7 to 50, and p=35 to 50.
2. The alkylaryl anionic nonionic surfactant according to claim 1, wherein N is any one of alkali metal, alkaline earth metal, ammonium ion.
3. The alkylaryl anionic nonionic surfactant according to claim 2, characterized in that said N is Na + 、K + 、Mg 2+ 、Ca 2+ 、NH 4 ＋ Any one of the following.
4. A process for preparing a hydrocarbyl aryl anionic nonionic surfactant according to any one of claims 1 to 3 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 C as substituent 1 ～C 30 Any one of aliphatic aromatic phenols;
b) The etherification product synthesized in the step a) is subjected to sulfonation reaction or alkylation reaction to obtain the alkyl aryl anionic surfactant;
or:
and a') carrying out etherification reaction on a carboxylate initiator serving as a raw material and butylene oxide, propylene oxide and ethylene oxide in the presence of a catalyst to obtain the alkyl aryl anionic nonionic surfactant.
5. The process for producing a hydrocarbon-based aryl anionic nonionic surfactant according to claim 4, wherein the etherification reaction is carried out at a reaction temperature of 140 to 200℃and a reaction pressure of 0 to 5MPa.
6. The process for producing a hydrocarbon-based aryl anionic nonionic surfactant according to claim 4, wherein the molar ratio of the initiator to butene oxide, propylene oxide and ethylene oxide is 1 (0.5-50), 1 (1-75) and 1 (1-50), respectively.
7. The process for preparing a hydrocarbon-based aryl anionic nonionic surfactant according to claim 4, wherein the catalyst is an alkali metal hydroxide, DMC bimetallic polyether catalyst or phosphazene catalyst in an amount of 0.001 to 2.0% by weight of the initiator.
8. The process for producing a alkylaryl anionic nonionic surfactant according to claim 4, characterized in that the molar ratio of the etherification product to the sulfonation reagent is 1 (1-3); the temperature of the sulfonation reaction is 20-80 ℃, and the time of the sulfonation reaction is 0.5-10 hours.
9. Use of a hydrocarbyl aryl anionic nonionic surfactant according to any one of claims 1 to 3.
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| 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 |
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| 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 |
| 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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| WO2016023139A1 (en) * | 2014-08-12 | 2016-02-18 | 中国石油化工股份有限公司 | Surfactant composition and preparation method therefor and application thereof |
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| 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 |
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