Alkylaniline Polyether Benzenesulfonate and Process of Producing Same

Abstract

A process for the conversion of methanol to olefins includes the steps of passing a feedstock comprising methanol to a fluidized bed reactor in contact with a catalyst to produce an olefin product, wherein the process at least partially deactivates the catalyst to form an at least partially deactivated catalyst; and passing spent catalyst from said at least partially deactivated catalyst to a regenerator for regeneration thereby forming regenerated catalyst and returning activated catalyst from said regenerated catalyst to said reactor via a regenerated catalyst line. An oxygen volume content in the gas-phase component at the outlet of the regenerated catalyst pipeline is controlled to be less than 0.1 percent, preferably less than 0.05% and more preferably less than 0.01% on the regenerated catalyst pipeline.

Claims

1. An alkylaniline polyether benzenesulfonate, having a structure shown in a formula (I): ##STR00006## in formula (I): R.sub.1 and R.sub.2 are independently selected from the group consisting of H, C.sub.1-C.sub.40 hydrocarbyl group or ##STR00007## and are not H at the same time; R.sub.3 was independently selected at each occurrence from the group consisting of H, C.sub.1-C.sub.10 hydrocarbyl group, C.sub.1-C.sub.10 carbonyl group, C.sub.1-C.sub.10 alkylsulfonic group, C.sub.1-C.sub.10 alkylolsulfonic group, C.sub.1-C.sub.10 alkylcarboxylic group, and —SO.sub.3(M).sub.n; -(Polyoxyalkylene).sub.1- is one or a combination of several of —(PO).sub.x1—, -(EO).sub.y1—, —(BO).sub.z1—; -(Polyoxyalkylene).sub.2- is one or a combination of several of —(PO).sub.x2—, -(EO).sub.y2—, —(BO).sub.z2—; x.sub.1, x.sub.2, y.sub.1, y.sub.2, z.sub.1, and z.sub.2 are each independently selected from any integer between 0 and 50, and x.sub.1+x.sub.2=0-50, y.sub.1+y.sub.2=1-50, and z.sub.1+z.sub.2=0-50; M is selected from alkali metals and alkaline earth metals, wherein n is 1 when M is an alkali metal, and n is 0.5 when M is an alkaline earth metal; and wherein PO is propoxy, EO is ethoxy, and BO is butoxy.

2. The alkylaniline polyether benzenesulfonate according to claim 1, characterized in that in formula (I), R.sub.1 is a C.sub.6-C.sub.30 hydrocarbyl group, preferably R.sub.1 is a C.sub.6-C.sub.30 alkyl or alkenyl group, R.sub.2 is H, a C.sub.1-C.sub.30 hydrocarbyl group or ##STR00008## R.sub.3 is independently at each occurrence H, —CH.sub.3, —CH.sub.2CH.sub.3, —CH.sub.2SO.sub.3(M).sub.n, —CH.sub.2(CHOH)SO.sub.3(M).sub.n, —CH.sub.2COO(M).sub.n or —SO.sub.3(M).sub.n, x.sub.1+x.sub.2=0-30, y.sub.1+y.sub.2=1-30, and z.sub.1+z.sub.2=0-30.

3. The alkylaniline polyether benzenesulfonate according to claim 1, wherein in formula (I), R.sub.1 is a C.sub.6-C.sub.20 hydrocarbyl group, preferably R.sub.1 is a C.sub.6-C.sub.20 alkyl or alkenyl group; R.sub.2 is H or a C.sub.1-C.sub.30 hydrocarbyl group; R.sub.3 is independently selected at each occurrence from H, —CH.sub.3 and —CH.sub.2CH.sub.3; x.sub.1+x.sub.2=0-20, preferably x.sub.1+x.sub.2=1-10, or preferably x.sub.1+x.sub.2=2-10; y.sub.1+y.sub.2=1-20, preferably y.sub.1+y.sub.2=2-20; z.sub.1+z.sub.2=0-20, preferably z.sub.1+z.sub.2=1-10, or preferably z.sub.1+z.sub.2=2-10; M is selected from sodium ion, potassium ion, calcium ion and magnesium ion.

4. The alkylaniline polyether benzenesulfonate according to claim 1, wherein in the formula (I), R.sub.1 or R.sub.2 is ##STR00009##

5. The alkylaniline polyether benzenesulfonate according to claim 1, wherein each occurrence of R.sub.3 is the same.

6. The alkylaniline polyether benzenesulfonate according to claim 1, wherein R.sub.3 is —SO.sub.3(M).sub.n, preferably each M occurring in the formula (I) is the same.

7. A surfactant composition comprising one or more of the alkylaniline polyether benzenesulfonates according to claim 1.

8. A process for producing the alkylaniline polyether benzenesulfonate according to claim 1, comprising the steps of: Step 1, reacting alkylaniline serving as an initiator with an epoxy compound, and optionally performing blocking treatment on the reaction product by using a blocking agent, to obtain alkylaniline polyether; Step 2, sulfonating the alkylaniline polyether by using a sulfonating reagent, to obtain the alkylaniline polyether benzenesulfonate.

9. The process according to claim 8, characterized in that the alkylaniline is of the formula: R.sub.1-Ph-NH.sub.2, wherein Ph represents phenyl and R.sub.1 is selected from the group consisting of H, C.sub.1-C.sub.40 hydrocarbyl group or ##STR00010## and are not H at the same time.

10. The process according to claim 8, characterized in that step 1′ and step 1″ are carried out before step 1: Step 1′, taking alkylbenzene as a raw material, and carrying out nitration treatment to obtain alkyl nitrobenzene; Step 1″, carrying out hydrotreatment on the alkyl nitrobenzene to obtain the alkylaniline.

11. The process according to claim 10, characterized in that in step 1′, the alkylbenzene is nitrated with a nitrating agent and optionally an activator, wherein the nitrating agent is selected from nitric acid and dinitrogen pentoxide, and the activator is selected from concentrated sulfuric acid, glacial acetic acid, acetic anhydride, and phosphorus pentoxide.

12. The process according to claim 11, characterized in that the molar ratio of the nitrating reagent to alkylbenzene is (1-5):1, preferably (1-3):1; and/or the nitration treatment of step 1′ is carried out at 0-80° C., preferably 20-65° C. for 1-10 hours, preferably 2-8 hours.

13. The process according to claim 10, characterized in that in step 1″, the hydrotreatment is carried out in the presence of a hydrogenation catalyst selected from palladium on carbon and Raney nickel; and/or the hydrogenation catalyst is used in an amount of 0.1-10 wt %, and preferably 1.0-5.0 wt %, relative to the alkyl nitrobenzene; and/or the hydrotreatment described in step 1″ is carried out at 20 to 150° C., preferably 50 to 110° C., under 0 to 5 MPa, preferably 0.5 to 4 MPa.

14. The process according to claim 8, characterized in that in step 1, the epoxy compound is selected from C.sub.2-C.sub.6 epoxy compounds, preferably from propylene oxide and ethylene oxide; and/or in step 1, the molar ratio of the epoxy compound to the alkylaniline is (1-150):1, preferably (1-90):1, more preferably (1-60):1, and even more preferably (1-40):1 or (2-40):1; and/or step 1 is carried out in the presence of a basic catalyst; preferably, the basic catalyst is selected from the group consisting of alkali metals, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates and alkali metal oxides; more preferably, the basic catalyst is used in an amount of 0.1 wt % to 10 wt %, preferably 0.5 wt % to 5.0 wt % of the total weight of the reactants; and in step 1, the reaction conditions comprise: a reaction temperature of 140-200° C., and a reaction pressure of 0-5 MPa.

15. The process according to claim 8, characterized in that in step 1, the blocking agent is selected from R′.sub.3—X or R″.sub.3—X′—R″.sub.3, wherein R′.sub.3 is a C.sub.1-C.sub.10 hydrocarbyl group or C.sub.1-C.sub.10 carbonyl group, X is selected from halogens or hydroxyl, for which when X is hydroxyl, R′.sub.3 is a C.sub.1-C.sub.10 carbonyl group; R″.sub.3 is selected from C.sub.1-C.sub.10 carbonyls and X′ is selected from 0; preferably the halogen is F, Cl or Br, R′.sub.3 is a C.sub.1-C.sub.10 alkyl, alkenyl or phenylalkyl group; more preferably, the blocking agent is selected from methyl iodide, ethyl iodide, propyl iodide, vinyl iodide, toluene iodide, acetic acid, acetic anhydride, acetyl chloride, benzoyl chloride; and the molar ratio of the blocking agent to the alkylaniline is preferably (2-2.6):1, and preferably (2.04-2.4):1.

16. The process according to claim 8, characterized in that the sulfonating agent is selected from concentrated sulfuric acid, fuming sulfuric acid and sulfur trioxide.

17. The process according to claim 8, characterized in that step 2 comprises the sub-steps of: Step 2-1, mixing the alkylaniline polyether with a sulfonating agent, and carrying out sulfonation reaction at 20-80° C. for 0.5-10 hours; Step 2-2, adjusting the pH value to 10-14, and performing hydrolysis reaction for 0.5-5 hours, to obtain the alkylaniline polyether benzenesulfonate.

18. An enhanced oil recovery agent composition, comprising the alkylaniline polyether benzenesulfonate according to claim 1 as a surfactant and water, wherein the weight ratio of the surfactant to the water is 1:(50-2000), preferably 1:(80-500).

Description

EMBODIMENTS OF THE INVENTION

[0087] While the present invention will be described in conjunction with specific Examples thereof, it is to be understood that the following Examples are presented by way of illustration only and not by way of limitation, and that numerous insubstantial modifications and adaptations of the invention may be made by those skilled in the art in light of the teachings herein.

[0088] The raw materials used in the Examples and comparative examples are, if not particularly limited, those having been disclosed in the prior art, or may be, for example, obtained as they are or prepared according to the processes disclosed in the prior art.

[0089] In the Examples and comparative examples, the dehydrated crude oil from Chengdong field of Shengli Oilfield having a viscosity of 44 mPa.Math.s was used, and a density of 0.908 g/cm.sup.−3.

Example 1

1. Synthesis of 4-octylaniline polyoxypropylene (30) polyoxyethylene (16) ether sodium disulfonate benzenesulfonate

[0090] a) 1.0 mol of octyl benzene was added into a reactor equipped with a condensing device and a stirring device, 1.5 mol of 65% concentrated nitric acid and 20 g of 98% concentrated sulfuric acid were added dropwise, for which the reaction temperature was controlled to be 30° C., and after the dropwise addition, reaction was continued for 2 hours, to obtain 0.88 mol of 4-octyl nitrobenzene.

[0091] b) 0.88 mol of 4-octyl nitrobenzene was added into the reactor, 5 g of 10% palladium on carbon was added, and the reactor was sealed. Nitrogen was introduced for replacement for 5 times, then hydrogen was introduced for replacement for 5 times, heated to 60° C., hydrogenation was started, and the system pressure was controlled to be 1-4 MPa, for reaction for 6 hours to obtain 0.85 mol of 4-octylaniline.

[0092] c) 0.85 mol of 4-octylaniline and 2.5 g of sodium hydroxide were charged into the reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85° C. under continuous feeding of nitrogen gas, and reacted for 1 hour under stirring. The vacuum system was started, dehydrated at a temperature of 90° C. under a pressure of −0.08 MPa for 1 hour, then purged with nitrogen for 4 times to remove air in the system, and the reaction temperature of the system was adjusted to 150° C., then 25.5 mol of propylene oxide and 13.6 mol of ethylene oxide were sequentially and slowly introduced, and the pressure was controlled to be ≤0.40 MPa to carry out etherification reaction. After the reaction, the system was purged with nitrogen, cooled, neutralized and dehydrated to obtain 0.84 mol of 4-octylaniline polyoxypropylene (30) polyoxyethylene (16) ether.

[0093] d) 0.84 mol of 4-octylaniline polyoxypropylene (30) polyoxyethylene (16) ether synthesized in step c) was added into the reactor equipped with a condensing device, a dripping device and a stirring device, 3.0 mol of 20% fuming sulfuric acid was added dropwise, during which the reaction temperature was controlled to be 50° C., and after the dropwise addition, the reaction was continued for 1 hour, washed with water, extracted to remove the redundant acid, then sodium hydroxide was added into the organic phase to adjust the pH value to be 9, so as to obtain 0.78 mol of 4-octylaniline polyoxypropylene (30) polyoxyethylene (16) ether sodium disulfonate sodium benzenesulfonate.

2. Evaluation of Surfactant Properties

[0094] Formulation of Oil Displacement Agent

[0095] The oil displacement agent obtained by mixing 1 part by weight of the surfactant above and 399 parts by weight of seawater was used for interfacial tension evaluation and oil-flooding experiments. The compositions of the seawater used in all Examples and comparative examples of the present invention were shown in Table 1. The compositions of the oil displacement agents were shown in Table 2 for comparison.

[0096] Evaluation of Interfacial Tension:

[0097] The interfacial tension between the oil displacement agent and the dehydrated crude oil from Chengdong field of Shengli Oilfield was measured by using a TX-500C rotary drop interfacial tension tester produced by Texas university, USA at 80° C. and 4500 rpm, and the results were shown in Table 3.

Example 2

1. Synthesis of 4-dodecylaniline polyoxyethylene (6) ether sodium dicarboxylate benzenesulfonate

[0098] a) 1.0 mol of dodecyl benzene was added into a reactor equipped with a condensing device and a stirring device, 1.05 mol of 65% nitric acid and 50 g of 98% concentrated sulfuric acid were added dropwise, for which the reaction temperature was controlled to be 20° C., and after the dropwise addition, reaction was continued for 1 hour, to obtain 0.90 mol of 4-dodecyl nitrobenzene.

[0099] b) 0.90 mol of 4-dodecyl nitrobenzene was added into the high-pressure reactor, 5.1 g of 10% palladium on carbon was added, and the reactor was sealed. Nitrogen was introduced for replacement for 5 times, then hydrogen was introduced for replacement for 5 times, heated to 60° C., hydrogenation was started, and the system pressure was controlled to be 1-4 MPa, for reaction for 6 hours to obtain 0.86 mol of 4-dodecylaniline.

[0100] c) 0.86 mol of 4-dodecylaniline and 2.5 g sodium hydroxide were charged into the reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85° C. under continuous feeding of nitrogen gas, and reacted for 1 hour under stirring. The vacuum system was started, dehydrated at a temperature of 90° C. under a pressure of −0.08 MPa for 1 hour, then purged with nitrogen for 4 times to remove air in the system, and the reaction temperature of the system was adjusted to 150° C., then 5.16 mol ethylene oxide was added slowly, and the pressure was controlled to be ≤0.40 MPa to carry out etherification reaction. After the reaction, the system was purged with nitrogen, cooled, neutralized and dehydrated to obtain 0.81 mol of 4-dodecylaniline polyoxyethylene (6) ether.

[0101] The dodecylaniline polyoxyethylene (6) ether obtained was dissolved into a benzene solvent, sodium hydroxide was added according to a proportion of 1:3, alkalified for 1 hour at 60° C., and a carboxylation reagent sodium chloroacetate was added according to a proportion of 1:2.5, and reacted for 8 hours to obtain 0.75 mol of 4-dodecylaniline polyoxyethylene (6) ether sodium dicarboxylate.

[0102] d) 0.75 mol of 4-dodecylaniline polyoxyethylene (6) ether sodium dicarboxylate synthesized in step c) was added into the reactor equipped with a condensing device, a dripping device and a stirring device, 3.0 mol of 20% fuming sulfuric acid was added dropwise, during which the reaction temperature was controlled to be 50° C., and after the dropwise addition, the reaction was continued for 1 hour, then sodium hydroxide was added to adjust the pH value to be 13, and a hydrolytic reaction was conducted for 2 hours, so as to obtain 0.70 mol of 4-dodecylaniline polyoxyethylene (6) ether sodium dicarboxylate sodium benzenesulfonate.

2. Evaluation of Surfactant Properties

[0103] The property evaluation method was the same as in Example 1 except for the different composition of the oil displacement agent. For comparison, the compositions of the oil displacement agents were shown in Table 2, and the evaluation results were shown in Table 3.

Example 3

1. Synthesis of 2-dodecyl-4-octylaniline polyoxypropylene (4) polyoxyethylene (8) ether benzenesulfonate

[0104] a) 1.0 mol of dodecyl octylbenzene was added into a reactor equipped with a condensing device and a stirring device, 1.2 mol of 65% nitric acid and 50 g of 98% concentrated sulfuric acid were added dropwise, for which the reaction temperature was controlled to be 20° C., and after the dropwise addition, reaction was continued for 1 hour, to obtain 0.91 mol of 2-dodecyl-4-octyl nitrobenzene.

[0105] b) 0.95 mol of 2-dodecyl-4-octyl nitrobenzene was added into the high-pressure reactor, 5 g of 10% palladium on carbon was added, and the reactor was sealed. Nitrogen was introduced for replacement for 5 times, then hydrogen was introduced for replacement for 5 times, heated to 60° C., hydrogenation was started, and the system pressure was controlled to be 1-4 MPa, for reaction for 6 hours to obtain 0.89 mol of 2-dodecyl-4-octylaniline.

[0106] c) 0.89 mol of 2-dodecyl-4-octylaniline and 2.5 g sodium hydroxide were charged into the reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85° C. under continuous feeding of nitrogen gas, and reacted for 1 hour under stirring. The vacuum system was started, dehydrated at a temperature of 90° C. under a pressure of −0.08 MPa for 1 hour, then purged with nitrogen for 4 times to remove air in the system, and the reaction temperature of the system was adjusted to 150° C., then 3.56 mol of propylene oxide and 7.12 mol of ethylene oxide were sequentially and slowly introduced, and the pressure was controlled to be ≤0.40 MPa to carry out etherification reaction. After the reaction, the system was purged with nitrogen, cooled, neutralized and dehydrated to obtain 0.85 mol of 2-dodecyl-4-octylaniline polyoxypropylene (4) polyoxyethylene (8) ether.

[0107] d) 0.85 mol 2-dodecyl-4-octylaniline polyoxypropylene (4) polyoxyethylene (8) ether synthesized in step c) was added into the reactor equipped with a condensing device, a dripping device and a stirring device, 2.8 mol SO.sub.3 was added dropwise, during which the reaction temperature was controlled to be 50° C., reacted for 2 hours, 10% aqueous sodium hydroxide was added dropwise to adjust the pH value of the system to be 12, and hydrolyzed at 80° C. for 2 hours, so as to obtain 0.74 mol 2-dodecyl-4-octylaniline polyoxypropylene (4) polyoxyethylene (8) ether sodium benzenesulfonate.

2. Evaluation of Surfactant Properties

[0108] The property evaluation method was the same as in Example 1 except for the different composition of the oil displacement agent. For comparison, the compositions of the oil displacement agents were shown in Table 2, and the evaluation results were shown in Table 3.

Example 4

1. Synthesis of 4-triacontylaniline polyoxypropylene (6) polyoxyethylene ether (20) benzenesulfonate

[0109] a) 1.0 mol of triacontyl benzene was added into a reactor equipped with a condensing device and a stirring device, 1.1 mol of 65% nitric acid and 50 g of 98% concentrated sulfuric acid were added dropwise, for which the reaction temperature was controlled to be 20° C., and after the dropwise addition, reaction was continued for 1 hour, to obtain 0.86 mol of 4-triacontyl nitrobenzene.

[0110] b) 0.86 mol of 4-triacontyl nitrobenzene was added into the high-pressure reactor, 5 g of 10% palladium on carbon was added, and the reactor was sealed. Nitrogen was introduced for replacement for 5 times, then hydrogen was introduced for replacement for 5 times, heated to 60° C., hydrogenation was started, and the system pressure was controlled to be 1-4 MPa, for reaction for 6 hours to obtain 0.82 mol of 4-triacontylaniline.

[0111] c) 0.82 mol of 4-triacontylaniline and 2.5 g sodium hydroxide were charged into the reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85° C. under continuous feeding of nitrogen gas, and reacted for 1 hour under stirring. The vacuum system was started, dehydrated at a temperature of 90° C. under a pressure of −0.08 MPa for 1 hour, then purged with nitrogen for 4 times to remove air in the system, and the reaction temperature of the system was adjusted to 150° C., then 4.92 mol of propylene oxide and 16.4 mol of ethylene oxide were sequentially and slowly introduced, and the pressure was controlled to be ≤0.40 MPa to carry out etherification reaction. After the reaction, the system was purged with nitrogen, cooled, neutralized and dehydrated to obtain 0.78 mol of 4-triacontylaniline polyoxypropylene (6) polyoxyethylene (20) ether.

[0112] d) 0.78 mol of 4-triacontylaniline polyoxypropylene (6) polyoxyethylene (20) ether synthesized in step c) was added into the reactor equipped with a condensing device, a dripping device and a stirring device, 4.0 mol of 98% sulfuric acid was added dropwise, during which the reaction temperature was controlled to be 50° C., and after the dropwise addition, the reaction was continued for 1 hour, then sodium hydroxide was added to adjust the pH value to be 13, and a hydrolytic reaction was conducted for 2 hours, so as to obtain 0.72 mol 4-triacontylaniline polyoxypropylene (6) polyoxyethylene (20) ether sodium disulfonate sodium benzenesulfonate.

2. Evaluation of Surfactant Properties

[0113] The property evaluation method was the same as in Example 1 except for the different composition of the oil displacement agent. For comparison, the compositions of the oil displacement agents were shown in Table 2, and the evaluation results were shown in Table 3.

Example 5

1. Synthesis of 4-cetylaniline polyoxyethylene (8) dimethyl ether benzenesulfonate

[0114] a) 1.0 mol of cetylbenzene was added into a reactor equipped with a condensing device and a stirring device, 1.2 mol of 65% nitric acid and 30 g of 98% concentrated sulfuric acid were added dropwise, for which the reaction temperature was controlled to be 20° C., and after the dropwise addition, reaction was continued for 1 hour, to obtain 0.87 mol of 4-cetyl nitrobenzene.

[0115] b) 0.87 mol of 4-cetyl nitrobenzene was added into the high-pressure reactor, 5.5 g of 10% palladium on carbon was added, and the reactor was sealed. Nitrogen was introduced for replacement for 5 times, then hydrogen was introduced for replacement for 5 times, heated to 60° C., hydrogenation was started, and the system pressure was controlled to be 1-4 MPa, for reaction for 6 hours to obtain 0.85 mol of 4-cetylaniline.

[0116] c) 0.85 mol of 4-cetylaniline and 2.5 g sodium hydroxide were charged into the reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85° C. under continuous feeding of nitrogen gas, and reacted for 1 hour under stirring. The vacuum system was started, dehydrated at a temperature of 90° C. under vacuum for 1 hour, then purged with nitrogen for 4 times to remove air in the system, and the reaction temperature of the system was adjusted to 150° C., then 6.8 mol ethylene oxide was added slowly, and the pressure was controlled to be ≤0.40 MPa to carry out etherification reaction. After the reaction, the system was purged with nitrogen, 2.4 mol of iodomethane was added, and reacted at 90° C. for 1 hour, cooled, neutralized and dehydrated to obtain 0.82 mol of 4-cetylaniline polyoxyethylene (8) dimethyl ether.

[0117] d) 0.82 mol of 4-cetylaniline polyoxyethylene (8) dimethyl ether synthesized in step c) was added into the reactor equipped with a condensing device, a dripping device and a stirring device, 1.2 mol SO.sub.3 was added, during which the reaction temperature was controlled to be 50° C., reacted for 1 hour, then sodium hydroxide was added to adjust the pH value to be 12, and a hydrolytic reaction was conducted for 2 hours, so as to obtain 0.74 mol of 4-cetylaniline polyoxyethylene (8) dimethyl ether sodium benzenesulfonate.

2. Evaluation of Surfactant Properties

[0118] The property evaluation method was the same as in Example 1 except for the different composition of the oil displacement agent. For comparison, the compositions of the oil displacement agents were shown in Table 2, and the evaluation results were shown in Table 3.

Example 6

1. Synthesis of 4-octylaniline polyoxybutylene (2) polyoxypropylene (2) polyoxyethylene (4) ether benzenesulfonate

[0119] a) 1.0 mol of octyl benzene was added into a reactor equipped with a condensing device and a stirring device, 1.5 mol of 65% concentrated nitric acid and 20 g of 98% concentrated sulfuric acid were added dropwise, for which the reaction temperature was controlled to be 30° C., and after the dropwise addition, reaction was continued for 2 hours, to obtain 0.87 mol of 4-octyl nitrobenzene.

[0120] b) 0.87 mol of 4-octyl nitrobenzene was added into the high-pressure reactor, 5 g of 10% palladium on carbon was added, and the reactor was sealed. Nitrogen was introduced for replacement for 5 times, then hydrogen was introduced for replacement for 5 times, heated to 60° C., hydrogenation was started, and the system pressure was controlled to be 1-4 MPa, for reaction for 6 hours to obtain 0.84 mol of 4-octylaniline.

[0121] c) 0.84 mol of 4-octylaniline and 2.5 g of sodium hydroxide were charged into the reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85° C. under continuous feeding of nitrogen gas, and reacted for 1 hour under stirring. The vacuum system was started, dehydrated at a temperature of 90° C. under a pressure of −0.08 MPa for 1 hour, then purged with nitrogen for 4 times to remove air in the system, and the reaction temperature of the system was adjusted to 150° C., then 1.68 mol of butylene oxide, 1.68 mol of propylene oxide and 3.36 mol of ethylene oxide were sequentially and slowly introduced, and the pressure was controlled to be ≤0.40 MPa to carry out etherification reaction. After the reaction, the system was purged with nitrogen, cooled, neutralized and dehydrated to obtain 0.82 mol of 4-octylaniline polyoxybutylene (2) polyoxypropylene (2) polyoxyethylene (4) ether.

[0122] d) 0.82 mol 4-octylaniline polyoxybutylene (2) polyoxypropylene (2) polyoxyethylene (4) ether synthesized in step c) was added into the reactor equipped with a condensing device, a dripping device and a stirring device, 3.5 mol of 20% fuming sulfuric acid was added dropwise, during which the reaction temperature was controlled to be 50° C., and after the dropwise addition, reaction was continued for 1 hour, 10% aqueous sodium hydroxide was added dropwise to adjust the pH value of the system to be 12, and hydrolyzed at 80° C. for 2 hours, so as to obtain 0.73 mol of 4-octylaniline polyoxybutylene (2) polyoxypropylene (2) polyoxyethylene (4) ether sodium benzenesulfonate.

2. Evaluation of Surfactant Properties

[0123] The property evaluation method was the same as in Example 1 except for the different composition of the oil displacement agent. For comparison, the compositions of the oil displacement agents were shown in Table 2, and the evaluation results were shown in Table 3.

Example 7

1. Synthesis of 4-octylaniline polyoxybutylene (2) polyoxypropylene (2) polyoxyethylene (4) ether-3,5-sodium disulfonate

[0124] a) 1.0 mol of octyl benzene was added into a reactor equipped with a condensing device and a stirring device, 5 mol of fuming nitric acid was added dropwise, for which the reaction temperature was controlled to be 50° C., and after the dropwise addition, reaction was continued for 4 hours, to obtain 0.85 mol of 4-octyl nitrobenzene.

[0125] b) 0.85 mol of 4-octyl nitrobenzene was added into the reactor, 5 g of 10% palladium on carbon was added, and the reactor was sealed. Nitrogen was introduced for replacement for 5 times, then hydrogen was introduced for replacement for 5 times, heated to 60° C., hydrogenation was started, and the system pressure was controlled to be 1-4 MPa, for reaction for 6 hours to obtain 0.82 mol of 4-octylaniline.

[0126] c) 0.82 mol of 4-octylaniline and 2.5 g of sodium hydroxide were charged into the reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85° C. under continuous feeding of nitrogen gas, and reacted for 1 hour under stirring. The vacuum system was started, dehydrated at a temperature of 90° C. under a pressure of −0.08 MPa for 1 hour, then purged with nitrogen for 4 times to remove air in the system, and the reaction temperature of the system was adjusted to 150° C., then 1.86 mol of butylene oxide, 1.86 mol of propylene oxide and 3.72 mol of ethylene oxide were sequentially and slowly introduced, and the pressure was controlled to be ≤0.40 MPa to carry out etherification reaction. After the reaction, the system was purged with nitrogen, cooled, neutralized and dehydrated to obtain 0.81 mol of 4-octylaniline polyoxybutylene (2) polyoxypropylene (2) polyoxyethylene (4) ether.

[0127] d) 0.81 mol 4-octylaniline polyoxybutylene (2) polyoxypropylene (2) polyoxyethylene (4) ether synthesized in step c) was added into the reactor equipped with a condensing device, a dripping device and a stirring device, 3.0 mol of SO.sub.3 was added, during which the reaction temperature was controlled to be 60° C., reacted for 2 hours, then 10% aqueous sodium hydroxide was added dropwise to adjust the pH value of the system to be 12, and hydrolyzed at 80° C. for 2 hours, so as to obtain 0.75 mol of 4-octylaniline polyoxybutylene (2) polyoxypropylene (2) polyoxyethylene (4) ether-3,5-sodium disulfonate.

2. Evaluation of Surfactant Properties

[0128] The property evaluation method was the same as in Example 1 except for the different composition of the oil displacement agent. For comparison, the compositions of the oil displacement agents were shown in Table 2, and the evaluation results were shown in Table 3.

Example 8

[0129] According to the test of the physically simulated oil-flooding effect of the complex oil-flooding system in the SY/T6424-2000 complex oil-flooding system performance test method, dehydrated crude oil from Chengdong field of Shengli Oilfield wa used for a simulated oil-flooding experiment on a rock core with a length of 30 cm, a diameter of 2.5 cm and a permeability of 1.5 m.sup.2 at a temperature of 80° C. Firstly, seawater was used to carry out water flooding until the water content was 98%, and after the water flooding was finished, 0.3 pv (core pore volume) of the oil flooding agent was injected, then water flooding was carried out until the water content was 98%, and the improved crude oil recovery ratio was calculated.

[0130] Oil-flooding experiments and evaluations were carried out on the oil-flooding agents prepared in Example 2 and Example 5 according to the above methods, and the results showed respectively 10.1% and 12.8% of enhanced oil recovery.

Comparative Example 1

[0131] The evaluation method was the same as Example 2 except that sodium petroleum sulfonate (Daqing refinery) was used instead of the dodecylanline polyoxyethylene (6) ether sodium benzenesulfonate surfactant in Example 1, and the others were the same, and it was determined that an interfacial tension of 0.024 mN/m was formed between the composition and dehydrated crude oil from Chengdong field of Shengli Oilfield.

[0132] Oil-flooding same as Example 6 was carried out, and a yield of the crude oil was measured to be enhanced by 3.8%.

Comparative Example 2

[0133] C.sub.16-18 alkylbenzenesulfonate was synthesized according to the method of Example 1 in patent CN 200410096431.9, evaluation method was the same as Example 1, and it was determined that an interfacial tension of 0.012 mN/m was formed between the composition and dehydrated crude oil from Chengdong field of Shengli Oilfield.

[0134] Oil-flooding same as Example 6 was carried out, and a yield of the crude oil was measured to be enhanced by 4.5%.

Comparative Example 3

[0135] It was same as in Example 5, except that the starting material for the etherification reaction was different, where aniline was used.

[0136] 0.1 mol of aniline and 2.5 g sodium hydroxide were charged into the reactor equipped with a condensing device, a stirring device and a gas disperser, heated to 85° C. under continuous feeding of nitrogen gas, and reacted for 1 hour under stirring. The vacuum system was started, dehydrated at a temperature of 90° C. under vacuum for 1 hour, then purged with nitrogen for 4 times to remove air in the system, and the reaction temperature of the system was adjusted to 150° C., then 7.20 mol ethylene oxide was added slowly, and the pressure was controlled to be ≤0.40 MPa to carry out etherification reaction. After the reaction, the system was purged with nitrogen, 2.4 mol of iodomethane was added, and reacted at 90° C. for 1 hour, cooled, neutralized and dehydrated to obtain aniline polyoxyethylene (8) cetyl ether.

[0137] The aniline polyoxyethylene (8) cetyl ether was added into the reactor equipped with a condensing device, a dripping device and a stirring device, 3.0 mol of 50% fuming sulfuric acid was added, during which the reaction temperature was controlled to be 55° C., and after the dropwise addition, the reaction was continued for 1 hour, then sodium hydroxide was added to adjust the pH value to be 10, and a hydrolytic reaction was conducted for 2 hours, so as to obtain aniline polyoxyethylene (8) cetyl ether sodium benzenesulfonate.

[0138] Oil-flooding same as Example 6 was carried out, and a yield of the crude oil was measured to be enhanced by 5.3%.

Comparative Example 4

[0139] The process of Example 5 was repeated, except that amylbenzene was used replacing cetyl benzene, while other conditions remained unchanged.

[0140] Oil-flooding same as Example 6 was carried out, and a yield of the crude oil was measured to be enhanced by 3.2%.

TABLE-US-00001 TABLE 1 Sea Water 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 10369 1196 425 18215 1011 162 0 31378

TABLE-US-00002 TABLE 2 compositions of the oil displacement agents of Examples 1-5 Surfactant Seawater, Parts by Parts by Examples Structural parameters weight weight 1 R.sub.1 = C.sub.8, R.sub.2 = H, R.sub.3 = —SO.sub.3Na, n = 1, x.sub.1 + x.sub.2 = 30, 1 399 y.sub.1 + y.sub.2 = 16, z.sub.1 + z.sub.2 = 0, M = Na 2 R.sub.1 = C.sub.12, R.sub.2 = H, R.sub.3 = —CH.sub.2COONa, n = 1, 1 199 x.sub.1 + x.sub.2 = 0, y.sub.1 + y.sub.2 = 6, z.sub.1 + z.sub.2 = 0, M = Na 3 R.sub.1 = C.sub.12, R.sub.2 = C.sub.8, R.sub.3 = H, n = 1, x.sub.1 + x.sub.2 = 4, y.sub.1 + y.sub.2 = 8, 1 500 z.sub.1 + z.sub.2 = 0, M = Na 4 R.sub.1 = C.sub.30, R.sub.2 = H, R.sub.3 = —SO.sub.3Na, n = 1, x.sub.1 + x.sub.2 = 6, 1 80 y.sub.1 + y.sub.2 = 20, z.sub.1 + z.sub.2 = 0, M = Na 5 R.sub.1 = C.sub.16, R.sub.2 = H, R.sub.3 = —CH.sub.3, n = 1, x.sub.1 + x.sub.2 = 0, 1 200 y.sub.1 + y.sub.2 = 8, z.sub.1 + z.sub.2 = 0, M = Na 6 R.sub.1 = C.sub.8, R.sub.2 = H, R.sub.3 = H, n = 1, x.sub.1 + x.sub.2 = 2, y.sub.1 + y.sub.2 = 4, 1 200 z.sub.1 + z.sub.2 = 2, M = Na 7 R.sub.1 = C.sub.8, R.sub.2 = —SO.sub.3Na, R.sub.3 = H, n = 1, x.sub.1 + x.sub.2 = 2, 1 200 y.sub.1 + y.sub.2 = 4, z.sub.1 + z.sub.2 = 2, M = Na

TABLE-US-00003 TABLE 3 interfacial tension properties of the oil displacement agents of Examples 1-5 Examples Interfacial tension (mN/m) 1 0.0078 2 0.0035 3 0.0084 4 0.0063 5 0.00011 6 0.0023 7 0.012