Hydrocarbyl tetralin polyethersulfonate, preparation method therefor and use thereof

Abstract

A hydrocarbyl tetralin polyethersulfonate, preparation method therefor and use thereof are provided. The hydrocarbyl tetralin polyethersulfonate is of formula (I-0),

##STR00001##

The hydrocarbyl tetralin polyethersulfonate has a high surface and interface activity, can be used in an oil reservoir exploitation, especially in a high-temperature and high-salt oil reservoir exploitation, to improve crude oil recovery.

Claims

1. A hydrocarbyl tetralin polyethersulfonate shown by formula (I-0), ##STR00007## wherein: R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are each independently H or C.sub.1-C.sub.30 hydrocarbyl, provided that at least one of R.sub.1, R.sub.2, R.sub.5 and R.sub.6 is not H; R.sub.3, R.sub.4 are independently selected from H, C.sub.1-C.sub.10 hydrocarbyl, C.sub.1-C.sub.10 hydrocarbon carbonyl, C.sub.1-C.sub.10 hydrocarbon sulfonic group, C.sub.1-C.sub.10 hydrocarbon alcohol sulfonic group, C.sub.1-C.sub.10 hydrocarbon carboxylic group or SO.sub.3(M).sub.n; X is selected from N and O atoms, provided that a=1 when group X is N, and a=0 when group X is O; -(Polyoxyalkylene.sub.1)- is a group formed by connecting one or more of (PO).sub.x1, (EO).sub.y1 and (BO).sub.z1, and -(Polyoxyalkylene.sub.2)- is a group formed by connecting one or more of (PO).sub.x2, (EO).sub.y2 and (BO).sub.z2; provided that x1+x2=030, y1+y2=130, z1+z2=030; M is selected from any one of alkali metal ion and alkaline earth metal ion; when M is an alkali metal ion, n is 1, and when M is an alkaline earth metal ion, n is 0.5; wherein the hydrocarbyl moiety of R.sub.1-R.sub.6 is not substituted, or is substituted or inserted by a heteroatom selected from O, S and N.

2. The hydrocarbyl tetralin polyethersulfonate according to claim 1, characterized in that the hydrocarbyl moieties of R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are selected from a linear or branched C.sub.1-C.sub.30 alkyl, preferably C.sub.1-C.sub.16 alkyl; C.sub.1-C.sub.30 alkoxy, preferably C.sub.1-C.sub.16 alkoxy; C.sub.3-C.sub.30 cycloalkyl, preferably C.sub.3-C.sub.14 cycloalkyl; C.sub.3-C.sub.30 heterocyclic group, preferably C.sub.3-C.sub.14 heterocyclic group; phenyl unsubstituted or substituted by one or more identical or different C.sub.1-C.sub.4 alkyl; five-or six-membered heteroaromatic group containing 1-4 N or S atoms.

3. The hydrocarbyl tetralin polyethersulfonate according to claim 2, characterized in that the sum of the carbon atom numbers of R.sub.1, R.sub.2, R.sub.5 and R.sub.6 is 8-16, preferably R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are each independently selected from alkyl.

4. The hydrocarbyl tetralin polyethersulfonate according to claim 1, characterized in that R.sub.5 and R.sub.6 are H and X is N.

5. The hydrocarbyl tetralin polyethersulfonate according to claim 4, having formula (I), ##STR00008## wherein R.sub.1 is C.sub.6-C.sub.30 hydrocarbyl; R.sub.2 is H or C.sub.1-C.sub.30 hydrocarbyl; R.sub.3, R.sub.4 are independently selected from H, C.sub.1-C.sub.10 hydrocarbyl, C.sub.1-C.sub.10 hydrocarbon carbonyl, C.sub.1-C.sub.10 hydrocarbon sulfonic group, C.sub.1-C.sub.10 hydrocarbon alcohol sulfonic group, C.sub.1-C.sub.10 hydrocarbon carboxylic group or SO.sub.3(M).sub.n; -(Polyoxyalkylene).sub.1- is one or more of (PO).sub.x1, (EO).sub.y1 and (BO).sub.z1; -(Polyoxyalkylene).sub.2- is one or more of (PO).sub.x2, (EO).sub.y2 and (BO).sub.z2; x1+x2=0-30, y1+y2=1-30, z1+z2=0-30; M is selected from any one of alkali metal ion and alkaline earth metal ion; when M is an alkali metal ion, n is 1, and when M is an alkaline earth metal ion, n is 0.5.

6. The hydrocarbyl tetralin polyethersulfonate according to claim 1, characterized in that in formula (I) R.sub.1 is C.sub.8-C.sub.16 alkyl, preferably C.sub.8-C.sub.12 alkyl; and/or R.sub.2 is H or C.sub.1-C.sub.12 alkyl, preferably H or C.sub.1-C.sub.8 alkyl; and/or R.sub.3, R.sub.4 are independently selected from H, C.sub.1-C.sub.10 alkyl, C.sub.1-C.sub.10 alkyl carbonyl, C.sub.1-C.sub.10 alkyl sulfonic group, C.sub.1-C.sub.10 alkyl alcohol sulfonic group, C.sub.1-C.sub.10 alkyl carboxylic group or SO.sub.3(M).sub.n; preferably, R.sub.3, R.sub.4 are independently selected from H, C.sub.1-C.sub.6 alkyl or SO.sub.3(M).sub.n; more preferably, R.sub.3, R.sub.4 are independently selected from H, CH.sub.3, CH.sub.2CH.sub.3 or SO.sub.3(M).sub.n.

7. The hydrocarbyl tetralin polyethersulfonate according to claim 1, characterized in that z1 and z2 are zero, x1+x2=0-12, y1+y2=4-20; preferably, z1 and z2 are zero, x1+x2=0-8, y1+y2=4-12; more preferably, z1 and z2 are zero, x1+x2=0-4, y1+y2=4-8; and/or z1 and z2 are zero, x1+x2+y1+y2=1-50, preferably 5-20, more preferably 5-15; M is selected from any one of sodium ion, potassium ion, calcium ion, and magnesium ions and/or X is N.

8. The hydrocarbyl tetralin polyethersulfonate according to claim 1, characterized in that z1 and z2 are zero, x1+x2=1-6, y1+y2=4-8; and X is N.

9. The hydrocarbyl tetralin polyethersulfonate according to claim 1, characterized in that x1+x2=1-6, y1+y2=4-8, z1+z2=1-6; X is N; and/or N-(Polyoxyalkylene.sub.1)- and N-(Polyoxyalkylene.sub.2)- are each arranged in the way of NBO.sub.z1PO.sub.x1EO.sub.y1 or NBO.sub.z2PO.sub.x2EO.sub.y2.

10. A method for preparing the hydrocarbyl tetralin polyethersulfonate according to claim 1, comprising the steps of: S100. reacting the hydrocarbyl tetralin shown by formula (II-0) with a nitration reagent to produce hydrocarbyl nitrotetralin; ##STR00009## in formula (II-0), R.sub.1, R.sub.2, R.sub.5 and R.sub.6 are defined according to claim 1; S200. hydrotreating the hydrocarbyl nitrotetralin obtained in step S100 to obtain alkyl tetralin amine; S300. reacting the hydrocarbyl tetralin amine obtained in step S200 with one or more of epoxyethane, epoxypropane and epoxybutane to obtain hydrocarbyl tetralin amino polyether of formula (I-0); S400. reacting the hydrocarbyl tetralin amino polyether obtained in step S300 with a sulfonation reagent to obtain a sulfonated product which is hydrolyzed to obtain hydrocarbyl tetralin polyethersulfonate of formula (I-0).

11. The method according to claim 10, characterized in that the nitration reagent in step S100 is at least one of nitric acid and dinitrogen pentoxide, or a mixed acid composed of at least one of nitric acid and dinitrogen pentoxide and at least one selected from concentrated sulfuric acid, glacial acetic acid, acetic anhydride and phosphorus pentoxide; preferably, in the step S100, the molar ratio of the hydrocarbyl tetralin to the nitration reagent is 1:1-3; the reaction temperature is preferably 0-80 C.; the reaction time is preferably 1-10 hours; more preferably, the reaction temperature is 20-60 C. and the reaction time is 1-3 hours; preferably, the hydrotreatment in step S200 is carried out at a temperature of 20-150 C., preferably 50-70 C., and a pressure of less than 4 MPa, for example 1-3 MPa.

12. The method according to claim 10, characterized in that in step S300, the molar ratio of the epoxypropane to the hydrocarbyl tetralin amine is 0-30:1, preferably 0-12:1, more preferably 0-8:1, further preferably 0-4:1; the molar ratio of the epoxyethane to the hydrocarbyl tetralin amine is 1-30:1, preferably 4-20:1, more preferably 4-12:1, further preferably 4-8:1; the molar ratio of the epoxybutane to the hydrocarbyl tetralin amine is 0-30:1, preferably 0; and/or in step S300, the amount of the epoxybutane is zero, and the molar ratio of the total amount of the epoxypropane and epoxyethane to the hydrocarbyl tetralin amine is 1-50:1, preferably 5-20:1, more preferably 5-15:1; and/or in step S300, the reaction temperature is 135-200 C., preferably 140-180 C., more preferably 140-160 C.; the pressure is 0-5 MPa, preferably 0-3 MPa, more preferably 0-0.4 MPa.

13. The method according to claim 10, characterized in that the step S400 includes: S401. reacting the hydrocarbyl tetralin amino polyether with the sulfonation reagent in a molar ratio of 1:1-5 at a temperature of 20-80 C. for 0.5-10 hours to obtain a sulfonated product; S402. adjusting the pH value of the sulfonated product obtained in step S401 to 10-14 and hydrolyzing for 0.5-5 hours to obtain the hydrocarbyl tetralin polyethersulfonate.

14. A surfactant composition, comprising the hydrocarbyl tetralin polyethersulfonate according to claim 1.

15. An oil displacing agent composition, comprising the hydrocarbyl tetralin polyethersulfonate according to claim 1 and water, wherein the weight ratio of the hydrocarbyl tetralin polyethersulfonate to water is preferably 1:(50-2000), more preferably 1:(100-1000).

16. Use of said hydrocarbyl tetralin polyethersulfonate according to claim 1 in an oil reservoir exploitation.

Description

MODE OF CARRYING OUT THE INVENTION

[0078] The present invention is further illustrated below in combination with specific examples which, however, do not form any limitation to the present invention.

[0079] If there is no special restriction on the raw materials used in the examples and the comparative examples, they are all disclosed in the prior art, for example they are able to be directly purchased or prepared according to the preparation methods disclosed in the prior art.

EXAMPLE 1

1. Synthesis of 1-octyltetralin-5-amino polyoxypropylene (30) polyoxyethylene (16) ether-7-sodium sulfonate

[0080] a) 1.0 mol of 1-octyltetralin was added to a reactor equipped with a condensing device and a stirring device, and 2.1 mol of fuming nitric acid was added dropwise. The reaction temperature was controlled to 555 C. After the dropwise addition was completed, the reaction was continued for 2 hours. Let it stand to separate the solution, thereby obtaining 1-octyl-5-nitrotetralin. [0081] b) 1-octyl-5-nitrotetralin was added to a high pressure reactor, and a palladium carbon catalyst with a specification of 10% was added according to 0.5% of the weight of the reaction substrate, and the reactor was sealed. It was filled with nitrogen gas for replacement for 5 times, followed by a hydrogen gas replacement for 5 times. The temperature was raised to 60 C. and hydrogen began to be added. The system pressure was controlled at 3 MPa, and the reaction lasted for 6 hours to obtain 1-octyltetralin-5-amine. [0082] c) 1-octyltetralin-5-amine and 1% by mass of sodium hydroxide were added to a reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85 C. while nitrogen gas was introduced, and stirred to react for 1 hour. A vacuum system was turned on, and the reaction was heated to 90 C., vacuum dehydrated for 1 hour, then purged with nitrogen gas for 4 times to remove air from the system. Then the reaction temperature of the system was adjusted to 150 C., and epoxypropane and epoxyethane were introduced slowly in sequence, and the pressure was controlled to 0.40 MPa to carry out an etherification reaction; after the reaction, the system was purged with nitrogen gas, neutralized after cooling, and dehydrated to obtain 1-octyltetralin-5-amino polyoxypropylene (30) polyoxyethylene (16) ether. [0083] d) The octyltetralin amino polyoxypropylene (30) polyoxyethylene (16) ether synthesized in step c) was added to a reactor equipped with a condensing device, a dropwise addition device and a stirring device, and 20% fuming sulfuric acid was added dropwise in a molar ratio of 1:3. The reaction temperature was controlled to 50 C. After the dropwise addition was completed, the reaction was continued for 1 hour, and the excess acid was removed by water washing and extraction. The pH of the organic phase was adjusted to 9 by adding sodium hydroxide, thereby obtaining 0.75 mol of 1-octyltetralin-5-amino polyoxypropylene (30) polyoxyethylene (16) ether-7-sodium sulfonate.

2. Performance Evaluation

[0084] Formulation of an oil displacing agent composition: [0085] 1 part by weight of 1-octyltetralin-5-amino polyoxypropylene (30) polyoxyethylene (16) ether-7-sodium sulfonate was mixed with 1000 parts by weight of the injection water from the Zhongyuan Oilfield to obtain an oil displacing agent composition, which was used for an interfacial tension evaluation and an oil displacement experiment. The constitution of the used injection water from the Zhongyuan Oilfield is shown in Table 1. For the convenience of comparison, the constitution of the oil displacing agent composition is listed in Table 2. [0086] Interfacial tension evaluation: [0087] The interfacial tension between the above oil displacing agent composition and the dehydrated crude oil from the Zhongyuan Oilfield was measured using a TX-500C Spinning Drop Interfacial Tensiometer produced by the University of Texas of the United States at 80 C. and a rotational speed of 4500 rpm. The results are shown in Table 3.

EXAMPLE 2

1. Synthesis of 1-dodecyltetralin-5-amino polyoxyethylene (6) ether-7-sodium sulfonate

[0088] a) 1.0 mol of 1-dodecyltetralin was added to a reactor equipped with a condensing device and a stirring device, and 1.1 equivalents of 65% nitric acid and 50 g of 98% concentrated sulfuric acid were added dropwise according to a molar ratio. The reaction temperature was controlled to 20 C. After the dropwise addition was completed, the reaction was continued for 1 hour. Let it stand to separate the solution, thereby obtaining 1-dodecyl-5-nitrotetralin. [0089] b) 1-dodecyl-5-nitrotetralin was added to a high pressure reactor, and a palladium carbon with a specification of 10% was added according to 0.5% of the weight of the reaction substrate, and the reactor was sealed. It was filled with nitrogen gas for replacement for 5 times, followed by hydrogen gas replacement for 5 times. The temperature was raised to 60 C. and hydrogen began to be added. The system pressure was controlled at 3 MPa, and the reaction lasted for 6 hours to obtain 1-dodecyl-5-tetralinamine. [0090] c) 1-dodecyl-5-tetralinamine and 1% by mass of sodium hydroxide were added to a reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85 C. while nitrogen gas was introduced, and stirred to react for 1 hour. A vacuum system was turned on, and the reaction was heated to 90 C., vacuum dehydrated for 1 hour, then purged with nitrogen gas for 4 times to remove air from the system. Then the reaction temperature of the system was adjusted to 150 C., and epoxyethane was introduced slowly, and the pressure was controlled to 0.40 MPa to carry out an etherification reaction; after the reaction, the system was purged with nitrogen gas, neutralized after cooling, and dehydrated to obtain 1-dodecyltetralin-5-amino polyoxyethylene (6) ether. [0091] d) The 1-dodecyltetralin-5-amino polyoxyethylene (6) ether synthesized in step c) was added to a reactor equipped with a condensing device, a dropwise addition device and a stirring device, and 3 equivalents of 20% fuming sulfuric acid were added dropwise according to a molar ratio. The reaction temperature was controlled to 50 C. After the dropwise addition was completed, the reaction was continued for 1 hour. Then sodium hydroxide was added to adjust the pH to 13, followed by a hydrolysis reaction for 2 hours to obtain 0.78 mol of 1-dodecyltetralin-5-amino polyoxyethylene (6) ether-7-sodium sulfonate.

2. Performance Evaluation

[0092] According to the method in Example 1, the oil displacing agent composition was formulated and the interfacial tension was measured. For the convenience of comparison, the constitution of the oil displacing agent composition is listed in Table 2, and the evaluation results are shown in Table 3.

EXAMPLE 3

1. Synthesis of 1-dodecyl-4-octyltetralin-5-amino polyoxypropylene (4) polyoxyethylene (8) ether-7-sodium sulfonate

[0093] a) 1.0 mol of 1-dodecyl-4-octyltetralin was added to a reactor equipped with a condensing device and a stirring device, and 1.2 equivalents of 65% nitric acid and 0.3 equivalents of 98% concentrated sulfuric acid were added dropwise according to a molar ratio. The reaction temperature was controlled to 20 C. After the dropwise addition was completed, the reaction was continued for 1 hour. Let it stand to separate the solution, thereby obtaining 1-dodecyl-4-octyl-5-nitrotetralin. [0094] b) 1-dodecyl-4-octyl-5-nitrotetralin was added to a high pressure reactor, and a palladium carbon with a specification of 10% was added according to 1.0% of the weight of the reaction substrate, and the reactor was sealed. It was filled with nitrogen gas for replacement for 5 times, followed by hydrogen gas replacement for 5 times. The temperature was raised to 60 C. and hydrogen began to be added. The system pressure was controlled at 3 MPa, and the reaction lasted for 6 hours to obtain 1-dodecyl-4-octyltetralin-5-amine. [0095] c) 1-dodecyl-4-octyltetralin-5-amine and 1% by mass of sodium hydroxide were added to a reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85 C. while nitrogen gas was introduced, and stirred to react for 1 hour. A vacuum system was turned on, and the reaction was heated to 90 C., vacuum dehydrated for 1 hour, then purged with nitrogen gas for 4 times to remove air from the system. Then the reaction temperature of the system was adjusted to 150 C., and epoxypropane and epoxyethane were introduced slowly in sequence, and the pressure was controlled to 0.40 MPa to carry out an etherification reaction; after the reaction, the system was purged with nitrogen gas, neutralized after cooling, and dehydrated to obtain 1-dodecyl-4-octyltetralin-5-amino polyoxypropylene (4) polyoxyethylene (8) ether. [0096] d) The 1-dodecyl-4-octyltetralin-5-amino polyoxypropylene (4) polyoxyethylene (8) ether synthesized in step c) was added to a reactor equipped with a condensing device, a dropwise addition device and a stirring device, and 4 equivalents of 50% fuming sulfuric acid were added dropwise according to a molar ratio. The reaction temperature was controlled to 20 C. After the dropwise addition was completed, the reaction was continued for 1 hour. Then sodium hydroxide was added to adjust the pH to 13, followed by hydrolysis reaction for 2 hours to obtain 0.83 mol of 1-dodecyl-4-octyltetralin-5-amino polyoxypropylene (4) polyoxyethylene (8) ether-7-sodium sulfonate.

2. Performance Evaluation

[0097] According to the method in Example 1, the oil displacing agent composition was formulated and the interfacial tension was measured. For the convenience of comparison, the constitution of the oil displacing agent composition is listed in Table 2, and the evaluation results are shown in Table 3.

EXAMPLE 4

1. Synthesis of 1-triacontyltetralin-5-amino polyoxypropylene (10) polyoxyethylene (20) ether-7-sodium sulfonate

[0098] a) 1.0 mol of 1-triacontyltetralin was added to a reactor equipped with a condensing device and a stirring device, and 1.1 equivalents of 65% nitric acid and 0.2 equivalents of 98% concentrated sulfuric acid were added dropwise according to a molar ratio. The reaction temperature was controlled to 20 C. After the dropwise addition was completed, the reaction was continued for 1 hour. Let it stand to separate the solution, thereby obtaining 1-triacontyl-5-nitrotetralin. [0099] b) 1-triacontyl-5-nitrotetralin was added to a high pressure reactor, and a palladium carbon with a specification of 10% was added according to 5.0% of the weight of the reaction substrate, and the reactor was sealed. It was filled with nitrogen gas for replacement for 5 times, followed by hydrogen gas replacement for 5 times. The temperature was raised to 60 C. and hydrogen began to be added. The system pressure was controlled at 3 MPa, and the reaction lasted for 6 hours to obtain 1-triacontyltetralin-5-amine. [0100] c) 1-triacontyltetralin-5-amine and 1% by mass of sodium hydroxide based on the reaction substrate were added to a reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85 C. while nitrogen gas was introduced, and stirred to react for 1 hour. A vacuum system was turned on, and the reaction was heated to 90 C., vacuum dehydrated for 1 hour, then purged with nitrogen gas for 4 times to remove air from the system. Then the reaction temperature of the system was adjusted to 150 C., and epoxypropane and epoxyethane were introduced slowly in sequence, and the pressure was controlled to 0.40 MPa to carry out an etherification reaction; after the reaction, the system was purged with nitrogen gas, neutralized after cooling, and dehydrated to obtain 1-triacontyltetralin-5-amino polyoxypropylene (10) polyoxyethylene (20) ether. [0101] d) The 1-triacontyltetralin-5-amino polyoxypropylene (10) polyoxyethylene (20) ether synthesized in step c) was added to a reactor equipped with a condensing device, a dropwise addition device and a stirring device, and 5 equivalents of 98% fuming sulfuric acid were added dropwise according to a molar ratio. The reaction temperature was controlled to 50 C. After the dropwise addition was completed, the reaction was continued for 1 hour. Then sodium hydroxide was added to adjust the pH to 13, followed by hydrolysis reaction for 2 hours to obtain 0.79 mol of 1-triacontyltetralin-5-amino polyoxypropylene (10) polyoxyethylene (20) ether-7-sodium sulfonate.

2. Performance Evaluation

[0102] According to the method in Example 1, the oil displacing agent composition was formulated and the interfacial tension was measured. For the convenience of comparison, the constitution of the oil displacing agent composition is listed in Table 2, and the evaluation results are shown in Table 3.

EXAMPLE 5

[0103] The oil displacing agent composition was formulated and the interfacial tension was measured according to the method in Example 1 using the surfactant synthesized in Example 3. For the convenience of comparison, the constitution of the oil displacing agent composition is listed in Table 2, and the evaluation results are shown in Table 3.

EXAMPLE 6

1. Synthesis of 1-ethyl-2-butyl-3-propyl-4-ethyltetralin-5-amino polyoxybutene (2) polyoxypropylene (2) polyoxyethylene (6) ether-7-sodium sulfonate

[0104] a) 1.0 mol of 1-ethyl-2-butyl-3-propyl-4-ethyltetralin was added to a reactor equipped with a condensing device and a stirring device, and 1.05 equivalents of 65% nitric acid and 0.2 equivalents of 98% concentrated sulfuric acid were added dropwise according to a molar ratio. The reaction temperature was controlled to 30 C. After the dropwise addition was completed, the reaction was continued for 1 hour. Let it stand to separate the solution, thereby obtaining 1-ethyl-2-butyl-3-propyl-4-ethyl-5-nitrotetralin. [0105] b) 1-ethyl-2-butyl-3-propyl-4-ethyl-5-nitrotetralin was added to a high pressure reactor, and a palladium carbon with a specification of 10% was added according to 0.2% of the weight of the reaction substrate, and the reactor was sealed. It was filled with nitrogen gas for replacement for 5 times, followed by hydrogen gas replacement for 5 times. The temperature was raised to 60 C. and hydrogen began to be added. The system pressure was controlled at 1-3 MPa, and the reaction lasted for 6 hours to obtain 1-ethyl-2-butyl-3-propyl-4-ethyl-5-nitrotetralin amine. [0106] c) 1-ethyl-2-butyl-3-propyl-4-ethyl-5-nitrotetralin amine and 0.5% by mass of sodium hydroxide were added to a reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85 C. while nitrogen gas was introduced, and stirred to react for 1 hour. A vacuum system was turned on, and the reaction was heated to 90 C., vacuum dehydrated for 0.5 hours, then purged with nitrogen gas for 4 times to remove air from the system. Then the reaction temperature of the system was adjusted to 150 C., and epoxybutane, epoxypropane and epoxyethane were introduced slowly in sequence, and the pressure was controlled to 0.40 MPa to carry out an etherification reaction; after the reaction, the system was purged with nitrogen gas, neutralized after cooling, and dehydrated to obtain 1-ethyl-2-butyl-3-propyl-4-ethyltetralin-5-amino polyoxybutene (2) polyoxypropylene (2) polyoxyethylene (6) ether. [0107] d) The 1-ethyl-2-butyl-3-propyl-4-ethyltetralin-5-amino polyoxybutene (2) polyoxypropylene (2) polyoxyethylene (6) ether synthesized in step c) was dissolved in dichloroethane. The reaction temperature was controlled to 30 C. Sulfonation was carried out by introducing sulfur trioxide, and the reaction lasted for 0.5 hours. Then sodium hydroxide was added to adjust the pH to 12, followed by hydrolysis reaction at 80 C. for 2 hours to obtain 0.81 mol of 1-ethyl-2-butyl-3-propyl-4-ethyltetralin-5-amino polyoxybutene (2) polyoxypropylene (2) polyoxyethylene (6) ether-7-sodium sulfonate.

2. Performance Evaluation

[0108] According to the method in Example 1, the oil displacing agent composition was formulated and the interfacial tension was measured. For the convenience of comparison, the constitution of the oil displacing agent composition is listed in Table 2, and the evaluation results are shown in Table 3.

EXAMPLE 7

1. Synthesis of 1-butoxy-2-methyl-3-propyltetralin-5-amino polyoxybutene (3) polyoxypropylene (4) polyoxyethylene (8) ether-7-sodium sulfonate

[0109] a) 1.0 mol of 1-butoxy-2-methyl-3-propyltetralin was added to a reactor equipped with a condensing device and a stirring device, and 1.02 equivalents of nitric acid and 0.2 equivalents of acetic anhydride were added dropwise according to a molar ratio. The reaction temperature was controlled to 30 C. After the dropwise addition was completed, the reaction was continued for 1 hour. Let it stand to separate the solution, thereby obtaining 1-butoxy-2-methyl-3-propyl-5-nitrotetralin. [0110] b) 1-butoxy-2-methyl-3-propyl-5-nitrotetralin was added to a high pressure reactor, and a palladium carbon with a specification of 10% was added according to 0.1% of the weight of the reaction substrate, and the reactor was sealed. It was filled with nitrogen gas for replacement for 5 times, followed by hydrogen gas replacement for 5 times. The temperature was raised to 80 C. and hydrogen began to be added. The system pressure was controlled at 1-3 MPa, and the reaction lasted for 6 hours to obtain 1-butoxy-2-methyl-3-propyl-5-nitrotetralin amine. [0111] c) 1-butoxy-2-methyl-3-propyl-5-nitrotetralin amine and 0.5% by mass of sodium hydroxide were added to a reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85 C. while nitrogen gas was introduced, and stirred to react for 1 hour. A vacuum system was turned on, and the reaction was heated to 90 C., vacuum dehydrated for 0.5 hours, then purged with nitrogen gas for 4 times to remove air from the system. Then the reaction temperature of the system was adjusted to 150 C., and epoxybutane, epoxypropane and epoxyethane were introduced slowly in sequence, and the pressure was controlled to 0.50 MPa to carry out an etherification reaction; after the reaction, the system was purged with nitrogen gas, neutralized after cooling, and dehydrated to obtain 1-butoxy-2-methyl-3-propyltetralin-5-amino polyoxybutene (3) polyoxypropylene (4) polyoxyethylene (8) ether. [0112] d) The 1-butoxy-2-methyl-3-propyltetralin-5-amino polyoxybutene (3) polyoxypropylene (4) polyoxyethylene (8) ether synthesized in step c) was dissolved in dichloroethane. The reaction temperature was controlled to 30 C. Sulfonation was carried out by introducing sulfur trioxide, and the reaction lasted for 0.5 hours. Then sodium hydroxide was added to adjust the pH to 12, followed by hydrolysis reaction at 80 C. for 2 hours to obtain 0.83 mol of 1-butoxy-2-methyl-3-propyltetralin-5-amino polyoxybutene (3) polyoxypropylene (4) polyoxyethylene (8) ether-7-sodium sulfonate.

2. Performance Evaluation

[0113] According to the method in Example 1, the oil displacing agent composition was formulated and the interfacial tension was measured. For the convenience of comparison, the constitution of the oil displacing agent composition is listed in Table 2, and the evaluation results are shown in Table 3.

[0114] Table 1 constitution of the injection water from the Zhongyuan Oilfield

TABLE-US-00001 item, mg/L Na.sup.+ + K.sup.+ Mg.sup.2+ Ca.sup.2+ Cl.sup. SO.sub.4.sup.2 HCO.sub.3.sup. CO.sub.3.sup.2 TDS 24719 2871 592 37101 13939 217 24719 79439

[0115] Table 2 constitutions of the oil displacing agent compositions in Examples 1-7

TABLE-US-00002 surfactant [00006] injection water from the Zhongyuan parts by Oilfield, parts by Examples structural parameters weight weight 1 R.sub.1 = C.sub.8, R.sub.2 = H, R.sub.3 = SO.sub.3Na, R.sub.4 = SO.sub.3Na, 1 1000 R.sub.5 = H, R.sub.6 = H, n = 1, x1 + x2 = 30, y1 + y2 = 16, z1 + z2 = 0, M = Na, X = N 2 R.sub.1 = C.sub.12, R.sub.2 = H, R.sub.3 = H, R.sub.4 = H, R.sub.5 = H, R.sub.6 = H, 1 300 n = 1, x1 + x2 = 0, y1 + y2 = 6, z1 + z2 = 0, M = Na, X = N 3 R.sub.1 = C.sub.12, R.sub.2 = C.sub.8, R.sub.3 = H, R.sub.4 = H, R.sub.5 = H, R.sub.6 = H, 1 300 n = 1, x1 + x2 = 4, y1 + y2 = 8, z1 + z2 = 0, M = Na, X = N 4 R.sub.1 = C.sub.30, R.sub.2 = H, R.sub.3 = H, R.sub.4 = H, R.sub.5 = H, R.sub.6 = H, 1 500 n = 1, x1 + x2 = 10, y1 + y2 = 20, z1 + z2 = 0, M = Na, X = N 5 R.sub.1 = C.sub.12, R.sub.2 = C.sub.8, R.sub.3 = H, R.sub.4 = H, R.sub.5 = H, R.sub.6 = H, 1 100 n = 1, x1 + x2 = 4, y1 + y2 = 8, z1 + z2 = 0, M = Na, X = N 6 R.sub.1 = C.sub.2, R.sub.2 = C.sub.2, R.sub.3 = H, R.sub.4 = H, R.sub.5 = C.sub.4, 1 200 R.sub.6 = C.sub.3, n = 1, x1 + x2 = 2, y1 + y2 = 6, z1 + z2 = 2, M = Na, X = N 7 R.sub.1 = C.sub.2H.sub.110O, R.sub.2 = H, R.sub.3 = H, R.sub.4 = H, R.sub.5 = C.sub.1, 1 200 R.sub.6 = C.sub.3, n = 1, x1 + x2 = 4, y1 + y2 = 8, z1 + z2 = 3, M = Na, X = N

[0116] Table 3 interfacial tension performance of the oil displacing agent compositions in Examples 1-7

TABLE-US-00003 Examples interfacial tension (mN/m) 1 0.028 2 0.0035 3 0.0079 4 0.015 5 0.0013 6 0.0011 7 0.0021

Oil Displacement Effect Test

[0117] According to the physical simulation oil displacement effect test of the composite oil displacement system in the SY/T6424-2000 composite oil displacement system performance testing method, a simulation oil displacement experiment was conducted on a core with a length of 30 cm, a diameter of 2.5 cm and a permeability of 1.5 m.sup.2 at 80 C. First, the injection water from the Zhongyuan Oilfield was used for waterflooding to a water content of 98%. After the water flooding was completed, 0.3 pv (pore volume of the core) of the above oil displacing agent was injected, followed by waterflooding to a water content of 98% to calculate the increase in the crude oil recovery.

[0118] The oil displacing agents prepared in Example 3 and Example 5 were evaluated through oil displacement experiments according to the above method, and the results showed an increase in the crude oil recovery of 7.8% and 9.7%, respectively.

COMPARATIVE EXAMPLE 1

[0119] Sodium petroleum sulfonate (Shengli Oilfield) was used to replace the 1-dodecyl-4-octyltetralin-5-amino polyoxypropylene (4) polyoxyethylene (8) ether-7-sodium sulfonate surfactant in Example 3 to formulate an oil displacing agent composition, and the interfacial tension was measured. The interfacial tension between the oil displacing agent composition in Comparative Example 1 and the crude oil from the Zhongyuan Oilfield was 0.23 mN/m.

[0120] The above oil displacement effect test was used to measure the increase in the oil recovery of the oil displacing agent composition in Comparative Example 1, and the crude oil recovery was increased by 2.7%.

COMPARATIVE EXAMPLE 2

[0121] The following method was used to synthesize 1-dodecyl-4-octylnaphthalene-5-amino polyoxypropylene (4) polyoxyethylene (8) ether-7-sodium sulfonate. [0122] a) 1.0 mol of 1-dodecyl-4-octylnaphthalene was added to a reactor equipped with a condensing device and a stirring device, and 1.1 equivalents of 65% nitric acid and 0.2 equivalents of 98% concentrated sulfuric acid were added dropwise according to a molar ratio. The reaction temperature was controlled to 30 C. After the dropwise addition was completed, the reaction was continued for 1 hour. Let it stand to separate the solution, thereby obtaining 1-dodecyl-4-octyl-5-nitronaphthalene. [0123] b) 1-dodecyl-4-octyl-5-nitronaphthalene was added to a high pressure reactor, and a palladium carbon with a specification of 10% was added according to 0.5% of the weight of the reaction substrate, and the reactor was sealed. It was filled with nitrogen gas for replacement for 5 times, followed by hydrogen gas replacement for 5 times. The temperature was raised to 80 C. and hydrogen began to be added. The system pressure was controlled at 3 MPa, and the reaction lasted for 5 hours to obtain 1-dodecyl-4-octylnaphthalene-5-amine. [0124] c) 1-dodecyl-4-octylnaphthalene-5-amine and 1% by mass of sodium hydroxide were added to a reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85 C. while nitrogen gas was introduced, and stirred to react for 0.5 hours. A vacuum system was turned on, and the reaction was heated to 90 C., vacuum dehydrated for 0.5 hours, then purged with nitrogen gas for 4 times to remove air from the system. Then the reaction temperature of the system was adjusted to 140 C., and epoxypropane and epoxyethane were introduced slowly in sequence, and the pressure was controlled to 0.50 MPa to carry out an etherification reaction; after the reaction, the system was purged with nitrogen gas, neutralized after cooling, and dehydrated to obtain 1-dodecyl-4-octylnaphthalene-5-amino polyoxypropylene (4) polyoxyethylene (8) ether. [0125] d) The 1-dodecyl-4-octylnaphthalene-5-amino polyoxypropylene (4) polyoxyethylene (8) ether synthesized in step c) was added to a reactor equipped with a condensing device, a dropwise addition device and a stirring device, and 4 equivalents of 50% fuming sulfuric acid were added dropwise according to a molar ratio. The reaction temperature was controlled to 30 C. After the dropwise addition was completed, the reaction was continued for 1 hour. Then sodium hydroxide was added to adjust the pH to 12, followed by hydrolysis reaction at 80 C. for 2 hours to obtain 0.79 mol of 1-dodecyl-4-octylnaphthalene-5-amino polyoxypropylene (4) polyoxyethylene (8) ether-7-sodium sulfonate.

[0126] 1-dodecyl-4-octylnaphthalene-5-amino polyoxypropylene (4) polyoxyethylene (8) ether-7-sodium sulfonate was used to replace the 1-dodecyl-4-octyltetralin-5-amino polyoxypropylene (4) polyoxyethylene (8) ether-7-sodium sulfonate surfactant in Example 3 to formulate an oil displacing agent composition, and the interfacial tension was measured. The interfacial tension between the oil displacing agent composition in Comparative Example 2 and the crude oil from the Zhongyuan Oilfield is 0.012 mN/m.

[0127] The above oil displacement effect test was used to measure the increase in the oil recovery of the oil displacing agent composition in Comparative Example 2, and the crude oil recovery was increased by 4.6%.

[0128] Therefore, the hydrocarbyl tetralin polyethersulfonate of the present invention has a high surface and interface activity and can improve the recovery of crude oil.

[0129] For any values mentioned in the present invention, if there is only a two-unit interval between any lowest value and any highest value, it includes all the values that increase by one unit each time from the lowest value to the highest value. For example, if it is declared that the amount of a component or the value of process variables such as temperature, pressure, time, etc. is 50-90, it means in the present specification that the values such as 51-89, 52-88 . . . , 69-71, and 70-71 are specifically listed. For non-integer values, it is appropriate to consider using 0.1, 0.01, 0.001 or 0.0001 as one unit. These are only some specially specified examples. In the present application, all possible combinations of the values between the lowest value and the highest value listed are considered to have been disclosed in a similar manner.

[0130] It should be noted that the above examples are only used to explain the present invention and do not form any limitation to the present invention. The present invention is described by referring to typical examples, but it should be understood that the words used therein are descriptive and explanatory vocabulary, rather than restrictive vocabulary. The present invention may be amended within the scopes of the claims of the present invention according to the stipulations, and may be revised without deviating from the scope and spirit of the present invention. Although the present invention described herein relates to specific methods, materials, and examples, it does not mean that the present invention is limited to the specific examples disclosed herein. On the contrary, the present invention can be extended to all other methods and uses with the same function.