阅读说明：本技术 一种烷基萘胺聚醚萘磺酸盐表面活性剂及其制备方法和应用 (Alkyl naphthylamine polyether naphthalene sulfonate surfactant and preparation method and application thereof ) 是由 鲍新宁 李应成 吴欣悦 孟勇 于 2020-07-06 设计创作，主要内容包括：本发明公开了一种烷基萘胺聚醚萘磺酸盐表面活性剂及其制备方法和应用,所述表面活性剂的结构式(I)所示：其中,在式(I)中,R-(2)、R～(2)独立地选自为磺酸盐、醋酸盐、H或C-(1)-C-(10)的烷基；R-(1)和R～(1)独立地选自H或C-(1)-C-(40)的烷基、且不同时为H,m1+m2＝0～80,n1+n2＝0～60,且m1、n1不同时为0,m2、n2不同时为0；Y选自磺酸盐。采用本发明的技术方案,用于提高稠油的采收率,采用胜利油田孤岛稠油进行驱替实验,提高采收率7.9％,取得了较好的技术效果。(The invention discloses an alkyl naphthylamine polyether naphthalene sulfonate surfactant, a preparation method and application thereof, wherein the surfactant has a structural formula (I): wherein, in the formula (I), R 2 、R 2 Independently selected from the group consisting of sulfonate, acetate, H, and C 1 ‑C 10 Alkyl groups of (a); r 1 And R 1 Independently selected from H or C 1 ‑C 40 The alkyl group of (1) is not H at the same time, m1+ m2 is 0-80, n1+ n2 is 0-60, m1 and n1 are not 0 at the same time, and m2 and n2 are not 0 at the same time; y is selected from sulfonate. By adopting the technical scheme of the invention, the recovery ratio of the thickened oil is improved, and the victory oil field island thickened oil is adopted for carrying out a displacement experiment, so that the recovery ratio is improved by 7.9 percent, and a better technical effect is achieved.)

1. An alkyl naphthylamine polyether naphthalene sulfonate surfactant has a structure shown in formula (I):

wherein, in the formula (I), R₂And R²Independently selected from sulfonate, acetate, H or C₁-C₁₀Alkyl of R₁And R¹Independently selected from H or C₁-C₄₀And (3) the alkyl is not H at the same time, m1+ m2 is 0-80, n1+ n2 is 0-60, m1 and n1 are not 0 at the same time, m2 and n2 are not 0 at the same time, and Y is selected from sulfonate.

2. The alkylnaphthylamine polyether naphthalenesulfonate surfactant of claim 1, wherein in formula (I), R₂、R²Independently selected from the group consisting of sulfonate, H, -CH₃or-CH₂CH₃(ii) a And/or, R₁Is selected from C₆-C₃₀Alkyl groups of (a); and/or, R¹Is selected from H or C₁-C₃₀Alkyl groups of (a); and/or m1+ m2 is 1-50, and n1+ n2 is 0-40; y is selected from ammonium sulfonate, alkali metal sulfonate or alkali earth metal sulfonate.

3. The alkylnaphthylamine polyether naphthalenesulfonate surfactant according to claim 1 or 2, characterized in that, in formula (I),

R₂、R²independently selected from the group consisting of sulfonate or H; and/or

R₁Is selected from C₈～C₁₆Alkyl groups of (a); and/or

R¹Is H; and/or

Y is selected from any one of sodium sulfonate, potassium sulfonate, calcium sulfonate or magnesium sulfonate.

4. A method for preparing the alkyl naphthylamine polyether naphthalene sulfonate surfactant as claimed in any one of claims 1 to 3, comprising the following steps:

step 1, sequentially carrying out nitration treatment and hydrogenation treatment on an alkyl naphthalene compound shown in a formula (II) to obtain an alkyl naphthylamine compound;

step 2, mixing the alkyl naphthylamine compound and an epoxy monomer for reaction, and then optionally carrying out end capping treatment by using an end capping agent to obtain alkyl naphthylamine polyether;

step 3, mixing the alkyl naphthylamine polyether with a sulfonation reagent, and reacting to obtain an alkyl naphthylamine polyether naphthalene sulfonate surfactant;

in the formula (II), R₁And R¹Independently selected from H or C₁-C₄₀And not both are H.

5. The production method according to claim 4, wherein, in step 1,

carrying out the nitration treatment in the presence of a nitration reagent and an optional auxiliary agent, wherein the nitration reagent is selected from nitric acid and/or dinitrogen pentoxide, and the auxiliary agent is selected from at least one of concentrated sulfuric acid, glacial acetic acid and acetic anhydride; and/or

The hydrotreating is carried out in the presence of a hydrogenation catalyst selected from palladium on carbon and/or raney nickel.

6. The production method according to claim 5,

the molar ratio of the nitrating reagent to the alkyl naphthalene compound shown in the formula (II) is (1-5): 1, preferably (1-3): 1; and/or the molar ratio of the auxiliary reagent to the alkyl naphthalene compound shown in the formula (II) is (0-1): 1, preferably (0.2-0.65): 1;

and/or

The dosage of the hydrogenation catalyst is 0.01 wt% -10 wt% of the alkyl nitronaphthalene, and preferably 0.5 wt% -10 wt%.

7. The production method according to claim 4,

the nitration treatment described in step 1 is carried out as follows: at 0-100 ℃ for 1-10 hours, preferably at 20-70 ℃ for 2-8 hours.

Step 1 the hydrotreatment is carried out as follows: at 20-150 deg.C and under less than 5MPa, preferably at 60-100 deg.C and under 1-3 MPa.

8. The method according to claim 4, wherein in step 2, the epoxy monomer is selected from C₂～C₆Preferably from propylene oxide and/or ethylene oxide;

preferably, the reaction of step 2 is carried out in the presence of a basic catalyst, and more preferably, the basic catalyst is at least one selected from the group consisting of alkali metal, alkali metal hydroxide, alkaline earth metal hydroxide, alkali metal alkoxide, and alkali metal oxide.

9. The production method according to claim 8, wherein, in step 2,

the molar ratio of the propylene oxide to the alkyl naphthylamine compound is (0-60): 1, preferably (0-40): 1; the molar ratio of the ethylene oxide to the alkyl naphthylamine compound is (0-80): 1, preferably (1-50): 1; and/or

The dosage of the alkaline catalyst is 0.005-2 wt%, preferably 0.05-1 wt% of the alkyl naphthylamine compound; and/or

The reaction is carried out at 135-200 ℃ and 0-5 MPa.

10. The production method according to claim 4,

in step 2, the blocking agent is selected from R²-X and R₂-X, wherein X is selected from halogen, hydroxyl or acyl, preferably the capping agent is selected from at least one of halogenated hydrocarbons, organic acids, compounds containing anhydride groups and compounds containing acid halide groups; more preferably, the blocking agent is selected from at least one of methyl iodide, ethyl iodide, propyl iodide, ethylene iodide, toluene iodide, acetic acid, acetic anhydride, acetyl chloride, benzoyl chloride;

in step 3, the sulfonating agent is selected from at least one of concentrated sulfuric acid, oleum, and sulfur trioxide.

11. The production method according to any one of claims 4 to 10,

in the step 2, the molar ratio of the end capping agent to the alkyl naphthylamine compound is (2-2.6): 1, preferably (2.04-2.4): 1

In the step 3, the molar ratio of the alkyl naphthylamine polyether to the sulfonating reagent is 1 (1-8), and preferably 1 (1-5).

12. The production method according to claim 11, characterized in that, in step 3:

the reaction is carried out at 20-80 ℃ for 0.5-10 hours; and/or

Adjusting the pH value to 9-14 after the reaction, and hydrolyzing for 0.5-5 hours.

13. An oil-displacing agent composition, which comprises the alkyl naphthylamine polyether naphthalene sulfonate surfactant disclosed in any one of claims 1 to 3 or the alkyl naphthylamine polyether naphthalene sulfonate surfactant prepared by the preparation method disclosed in any one of claims 4 to 12 and water, wherein the weight ratio of the surfactant to the water is 1 (50-2000).

14. Use of the alkyl naphthylamine polyether naphthalene sulfonate surfactant according to any one of claims 1 to 3 or the oil-displacing agent composition according to claim 13 for enhanced recovery of heavy oil.

Technical Field

The invention belongs to the field of viscosity reducers, and particularly relates to a thick oil viscosity reducer as well as a preparation method and application thereof.

Background

The thick oil accounts for a large proportion of the world oil and gas resources, and the reserves of the world thick oil, the super thick oil and the natural asphalt are about 1000 multiplied by 10⁸Ton. Countries with abundant thickened oil resources include canada, venezuela, usa, the former soviet union, china, indonesia, etc. China's thick oil resources are widely distributed, and the exploitation of thick oil has great potential. The main difference between the thick oil and the common crude oil is that the viscosity of the thick oil is far higher than that of the common crude oil, and the conventional method is not suitable for thick oil exploitation. The most applied heavy oil recovery modes include steam oil recovery, hot water oil recovery, burning oil reservoirs, thinning and viscosity reduction and the like. In recent years, chemical cold recovery has received much attention.

Thickened oils generally have the following notable features: (1) the condensed ring structure colloid and asphaltene content in the thickened oil is extremely high, the content of saturated hydrocarbon and aromatic hydrocarbon is low, the hydrocarbon content is generally less than 60%, and simultaneously, a large amount of sulfur-containing heterocyclic derivatives and nitrogen-containing heterocyclic derivatives exist, and the relative density and viscosity of the thickened oil are correspondingly increased along with the increase of heavy components and impurity components. (2) The temperature has obvious influence on the viscosity of the thick oil, the viscosity of the thick oil is sharply reduced along with a certain value of the temperature rise, and the fluidity is greatly enhanced. (3) The heavy oil contains many heterocyclic hydrocarbon derivatives containing oxygen, sulfur, nitrogen, phosphorus and other heteroatoms and part of rare metals. (4) Thickened oils have complex rheological properties. The different rheological behavior with increasing temperature, the non-newtonian fluid gradually changes into a newtonian fluid. For heavy oil reservoirs, conventional methods are difficult to recover, and therefore, special technological measures such as thermal oil recovery, chemical oil recovery, biological oil recovery, combination methods and the like are adopted.

In recent years, chemical processes have received increasing attention. The main difficulties in heavy oil recovery are high crude oil viscosity, poor crude oil fluidity and high crude oil viscosity, which cause poor efficiency in the displacement process of general displacement fluid (such as hot water). The method comprises the steps of injecting a surfactant, wherein the surfactant has oleophilic (hydrophobic) and hydrophilic (oleophobic) properties, so that when the surfactant is dissolved in water, molecules are mainly distributed on an oil-water interface, the interfacial tension between crude oil and formation water can be reduced, and the crude oil is easy to flow; the reduction of the oil-water interfacial tension means the reduction of the adhesion work, i.e. the crude oil is easily eluted from the surface of the formation; the crude oil is emulsified to form an oil-in-water emulsion under the action of the surfactant, so that the viscosity of the crude oil can be reduced; the oil displacement effect of the surfactant is also shown in the effects of reversing the wettability of the oleophilic rock surface, emulsifying crude oil, improving the surface charge density, merging oil drops and the like, so that the surfactant is regarded as important in chemical cold recovery of thick oil.

Disclosure of Invention

The invention provides a novel alkyl naphthylamine polyether naphthalene sulfonate oil displacement surfactant, which aims to solve the technical problem that the oil displacement effect of the surfactant in a heavy oil reservoir is poor in the prior production technology. The alkyl naphthylamine polyether naphthalene sulfonate oil-displacing surfactant can effectively reduce the viscosity of the thick oil, and has high interfacial activity, so that the recovery ratio of the thick oil can be improved.

One of the purposes of the invention is to provide an alkyl naphthylamine polyether naphthalene sulfonate surfactant, which has a structure shown in a formula (I):

wherein, in the formula (I), R₂、R²Independently selected from the group consisting of sulfonate, acetate, H, and C₁-C₁₀Alkyl of R₁And R¹Independently selected from H or C₁-C₄₀And (3) the alkyl is not H at the same time, m1+ m2 is 0-80, n1+ n2 is 0-60, m1 and n1 are not 0 at the same time, m2 and n2 are not 0 at the same time, and Y is selected from sulfonate.

In a preferred embodiment, in formula (I), R₂、R²Independently selected from sulfonate, H, -CH₃or-CH₂CH₃(ii) a And/or, R₁Is selected from C₆-C₃₀Alkyl groups of (a); and/or, R¹Is selected from H or C₁-C₃₀Alkyl groups of (a); and/or m1+ m2 is 1-50, and n1+ n2 is 0-40; y is selected from ammonium sulfonate, alkali metal sulfonate or alkali earth metal sulfonate.

When R is₂、R²Independently selected from sulfonate salts, it may be ammonium sulfonate salts, alkali metal sulfonate salts or alkaline earth metal sulfonate salts.

In a preferred embodiment, in formula (I), R₂、R²Independently selected from sulfonate or H.

In a preferred embodiment, in formula (I), R₁Is selected from C₈～C₁₆Alkyl group of (1).

In a preferred embodiment, in formula (I), R¹Is H.

In a preferred embodiment, in formula (I), M is selected from any one of sodium sulfonate, potassium sulfonate, calcium sulfonate, or magnesium sulfonate.

The alkyl naphthylamine polyether naphthalene sulfonate oil-displacing surfactant disclosed by the invention has good surface and interface activities and good salt resistance, can form low interface tension on an oil-water interface, is used for chemical flooding enhanced oil recovery, and has wide application prospects and practical significance.

The invention also aims to provide a preparation method of the alkyl naphthylamine polyether naphthalene sulfonate surfactant, which comprises the following steps:

step 1, sequentially carrying out nitration treatment and hydrogenation treatment on an alkyl naphthalene compound shown in a formula (II) to obtain an alkyl naphthylamine compound;

step 2, mixing the alkyl naphthylamine compound and an epoxy monomer for reaction, and then optionally carrying out end capping treatment by using an end capping agent to obtain alkyl naphthylamine polyether;

step 3, mixing the alkyl naphthylamine polyether with a sulfonation reagent, and reacting to obtain an alkyl naphthylamine polyether naphthalene sulfonate surfactant;

in the formula (II), R₁And R¹Independently selected from H or C₁-C₄₀And not both are H.

In a preferred embodiment, in step 1, the nitration treatment is carried out in the presence of a nitrating agent selected from nitric acid and/or dinitrogen pentoxide and optionally an auxiliary agent selected from at least one of concentrated sulfuric acid, glacial acetic acid, acetic anhydride.

In a further preferred embodiment, the molar ratio of the nitrating agent to the alkylnaphthalene compound represented by the formula (II) is (1-5): 1, preferably (1-3): 1.

In a further preferred embodiment, the molar ratio of the auxiliary agent to the alkylnaphthalene compound represented by the formula (II) is (0-1): 1, preferably (0.2-0.65): 1.

In a still further preferred embodiment, the nitration treatment of step 1 is carried out as follows: at 0-100 ℃ for 1-10 hours, preferably at 20-70 ℃ for 2-8 hours.

In a preferred embodiment, in step 1, the hydrotreating is carried out in the presence of a hydrogenation catalyst selected from palladium on carbon and/or raney nickel.

In a further preferred embodiment, the hydrogenation catalyst is used in an amount of 0.01 to 10 wt%, preferably 0.5 to 10 wt% of the alkylnitronaphthalene.

In a preferred embodiment, the hydrotreating of step 1 is carried out as follows: at 20-150 deg.C and under less than 5MPa, preferably at 60-120 deg.C and under 1-3 MPa.

In a preferred embodiment, in step 2, the epoxy monomer is selected from C₂～C₆Preferably from propylene oxide and/or ethylene oxide.

In a further preferred embodiment, in step 2, the molar ratio of the propylene oxide to the alkyl naphthylamine compound is (0-60): 1, preferably (0-40): 1; the molar ratio of the ethylene oxide to the alkyl naphthylamine compound is (0-80): 1, and preferably (1-50): 1.

In a preferred embodiment, the reaction described in step 2 is carried out in the presence of a basic catalyst.

In a further preferred embodiment, the basic catalyst is selected from at least one of alkali metals, alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal alcoholates, alkali metal oxides, preferably from alkali metal hydroxides and/or alkaline earth metal hydroxides.

In a still further preferred embodiment, the basic catalyst is used in an amount of 0.005 to 2 wt%, preferably 0.05 to 1 wt% of the alkyl naphthylamine compound.

In a preferred embodiment, in step 2, the reaction is carried out at 135 to 200 ℃ and 0 to 5 MPa.

In a further preferred embodiment, in step 2, the reaction is carried out at 140 to 180 ℃ and 0 to 3 MPa.

In a preferred embodiment, in step 2, the capping agent is selected from R²-X and R₂-X, wherein X is selected from halogen, hydroxy or acyl.

In a further preferred embodiment, in step 2, the end-capping agent is selected from at least one of a halogenated hydrocarbon, an organic acid, an acid anhydride group-containing compound, and an acid halide group-containing compound; more preferably, the blocking agent is selected from at least one of methyl iodide, ethyl iodide, propyl iodide, ethylene iodide, toluene iodide, acetic acid, acetic anhydride, acetyl chloride, and benzoyl chloride.

In a further preferred embodiment, the molar ratio of the blocking agent to the alkyl naphthylamine compound is (2-2.6): 1, preferably (2.04-2.4): 1.

In a preferred embodiment, in step 2, the unreacted alkyl naphthylamine compound and epoxy monomer in the reaction system are removed before the end-capping treatment.

In a further preferred embodiment, in step 2, the removal treatment is carried out at 80 to 110 ℃, preferably at 80 to 110 ℃ under vacuum or under nitrogen bubbling.

In a preferred embodiment, in step 3, the sulfonating agent is selected from at least one of concentrated sulfuric acid, oleum, and sulfur trioxide.

In a further preferred embodiment, in the step 3, the molar ratio of the alkyl naphthylamine polyether to the sulfonating agent is 1 (1-8), preferably 1 (1-5).

In a preferred embodiment, in step 3, the reaction is carried out at 20 to 80 ℃ for 0.5 to 10 hours, preferably at 30 to 60 ℃ for 1 to 4 hours.

In a further preferred embodiment, the pH is adjusted to 9 to 14 after the reaction in step 3, and the hydrolysis is carried out for 0.5 to 5 hours.

The third purpose of the invention is to provide an oil displacement agent composition, which comprises the alkyl naphthylamine polyether naphthalene sulfonate surfactant for the first purpose of the invention or the alkyl naphthylamine polyether naphthalene sulfonate surfactant obtained by the preparation method for the second purpose of the invention and water, wherein the weight ratio of the surfactant to the water is 1 (50-2000), and preferably 1 (80-500).

In a preferred embodiment, the water is selected from one or more of mineralized water with a total mineralization degree ranging from 0 to 80000mg/L, oilfield injection water, formation water, seawater, rainwater and river water, and is preferably mineralized water and/or oilfield injection water with a total mineralization degree ranging from 1000 to 50000 mg/L.

Among them, for the reasons of construction convenience and water resource saving, the oilfield injection water is more preferable, for example, the victory oilfield injection water adopted in the embodiment of the present invention, and the composition is shown in table 1. In order to increase the oil displacement effect, the oil displacement agent of the invention can also comprise additives commonly used in the field, such as at least one of polyacrylamide, small molecular alcohols, DMSO, diethanolamine, CTAC and the like.

The fourth purpose of the invention is to provide the application of the alkyl naphthylamine polyether naphthalene sulfonate surfactant of one purpose of the invention or the oil displacement agent composition of the third purpose of the invention in improving the recovery ratio of thick oil.

In a preferred embodiment, the method for enhanced oil recovery using the surfactant or the composition comprises: and injecting the oil displacement agent composition into a thick oil stratum to displace thick oil.

Compared with the prior art, the invention has the following beneficial effects:

(1) the alkyl naphthylamine polyether naphthalene sulfonate anionic nonionic sulfonate surfactant has a naphthalene ring in the structure, has high interfacial activity and strong action capacity with thickened oil, and can form microemulsion with the thickened oil, so that the viscosity of the thickened oil is effectively reduced, and the recovery ratio of the thickened oil is improved.

(2) The technical scheme of the invention is adopted for improving the recovery ratio of the thickened oil, and victory oil field island thickened oil (the viscosity of the thickened oil is 11356mPa.s, and the density is 0.985 g/cm)³) And the displacement experiment is carried out, the recovery ratio is improved by 7.9 percent, and a better technical effect is obtained.

Detailed Description

While the present invention will be described in detail with reference to the following examples, it should be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the present invention.

The raw materials used in the examples and comparative examples are disclosed in the prior art if not particularly limited, and may be, for example, directly purchased or prepared according to the preparation methods disclosed in the prior art.

In the examples and comparative examples, thickened oil is dehydrated by victory oil field island, the viscosity of the thickened oil is 11356mPa.s, and the density is 0.985g/cm^-3。

[ example 1 ]

1. Synthesis of decyl naphthylamine polyoxypropylene (10) polyoxyethylene (15) ether naphthalene sulfonate

a) Adding 1.0mol of decyl naphthalene into a reactor provided with a condensing device and a stirring device, dropwise adding 2.0mol of 65% concentrated nitric acid, controlling the reaction temperature to 65 ℃, and continuously reacting for 4 hours after the dropwise adding is finished to obtain 0.91mol of decyl nitronaphthalene;

b) adding 0.91mol of decyl nitronaphthalene into a high-pressure reaction kettle, adding 22g of Raney nickel catalyst, and sealing the reaction kettle. Filling nitrogen for replacement for 5 times, then introducing hydrogen for replacement for 5 times, heating to 80 ℃, starting hydrogenation, controlling the system pressure not to exceed 4MPa, and reacting for 6 hours to obtain 0.87mol of decyl naphthylamine;

c) into a reactor equipped with a condensing device, a stirring device and a gas disperser, 0.87mol of decylnaphthylamine and 2.5g of sodium hydroxide were charged, and the mixture was heated to 85 ℃ with introduction of nitrogen gas, and stirred for 1 hour. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging for 4 times by using nitrogen to remove air in the system, adjusting the reaction temperature of the system to 145 ℃, sequentially and slowly introducing 8.70mol of propylene oxide and 13.05mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa to carry out etherification reaction; after the reaction, the system was purged with nitrogen, cooled, neutralized and dehydrated to obtain 0.85mol of decylnaphthylamine polyoxypropylene (10) polyoxyethylene (15) ether.

d) And c) adding 0.85mol of decyl naphthylamine polyoxypropylene (10) polyoxyethylene (15) ether synthesized in the step c) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 3.4mol of 50% fuming sulfuric acid, controlling the reaction temperature to be 65 ℃, continuing to react for 1 hour after dripping is finished, washing with water, extracting to remove redundant acid, adding sodium hydroxide into an organic phase to adjust the pH to 9, and obtaining 0.79mol of decyl naphthylamine polyoxypropylene (10) polyoxyethylene (15) ether sodium naphthalenesulfonate.

2. Evaluation of surfactant Properties

Preparing an oil displacement agent:

the oil displacement agent obtained by mixing 1 part by weight of the surfactant and 600 parts by weight of injection water of a victory oil field island is used for thick oil viscosity reduction effect evaluation, interfacial tension evaluation and oil displacement experiments. Wherein the compositions of the injection water of the victory oil field island used in all the examples and comparative examples of the present invention are shown in table 1. The compositions of the oil displacing agents are listed in table 2 for comparison.

And (3) evaluating the viscosity reduction effect of the thickened oil:

adopting a Brookfield viscometer DV-III according to the method of QSH 10201519-2013 general technical conditions of the thick oil viscosity reducer. The thickened oil is dehydrated by adopting victory oil field isolated island, the viscosity of the thickened oil is 11356mPa & s, and the density is 0.985g/cm³. The viscosity reduction rate of the prepared oil displacement agent on the dehydrated thickened oil of the victory oil field island is measured, and the result is listed in table 3.

And (3) evaluating interfacial tension:

the interfacial tension between the oil displacement agent and the victory oil field dehydrated thickened oil is measured by a TX-500C rotary drop interfacial tensiometer produced by American Texas university at 80 ℃ and the rotating speed of 4500 r/min, and the result is shown in Table 3.

[ example 2 ]

1. Synthesis of dodecyl naphthylamine polyoxyethylene (5) ether naphthalene sulfonate

a) Adding 1.0mol of dodecyl naphthalene into a reactor provided with a condensing device and a stirring device, dropwise adding 1.3mol of 65% nitric acid and 45g of 98% concentrated sulfuric acid, controlling the reaction temperature to be 30 ℃, and continuously reacting for 1 hour after the dropwise adding is finished to obtain 0.91mol of dodecyl nitronaphthalene;

b) adding 0.91mol of dodecyl nitronaphthalene into a high-pressure reaction kettle, adding 20g of Raney nickel catalyst, and sealing the reaction kettle. Filling nitrogen for replacement for 5 times, then introducing hydrogen for replacement for 5 times, heating to 80 ℃, starting hydrogenation, controlling the system pressure not to exceed 4MPa, and reacting for 6 hours to obtain 0.88mol of dodecyl naphthylamine;

c) 0.88mol of dodecylnaphthylamine and 3.0g of sodium hydroxide were charged into a reactor equipped with a condensing apparatus, a stirring apparatus and a gas disperser, and the mixture was stirred and reacted for 1 hour while heating to 80 ℃ under nitrogen. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging for 4 times by using nitrogen to remove air in the system, adjusting the reaction temperature of the system to 160 ℃, slowly introducing 4.4mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa to carry out etherification reaction; after the reaction is finished, vacuumizing is carried out for 30 minutes at the temperature of 90 ℃, then a nitrogen purging system is used, 2.1 mol of methyl iodide is added, the reaction is carried out for 1 hour at the temperature of 90 ℃, and neutralization and dehydration are carried out after cooling, so that 0.84mol of dodecyl naphthylamine polyoxyethylene (5) ether is obtained.

d) And c) adding 0.84mol of the dodecylnaphthylamine polyoxyethylene (5) ether synthesized in the step c) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 1.5mol of 50% fuming sulfuric acid, controlling the reaction temperature to be 50 ℃, continuing to react for 2 hours after the dripping is finished, then adding sodium hydroxide to adjust the pH value to be 13, and carrying out hydrolysis reaction for 2 hours to obtain 0.78mol of the dodecylnaphthylamine polyoxyethylene (5) ether sodium naphthalenesulfonate.

2. Evaluation of surfactant Properties

The performance evaluation method was the same as in example 1 except that the oil-displacing agent composition was different. The compositions of the oil-displacing agents are shown in Table 2 for comparison, and the evaluation results are shown in Table 3.

[ example 3 ]

1. Synthesis of dodecyl octyl naphthylamine polyoxypropylene (4) polyoxyethylene (9) ether naphthalene sulfonate

a) Adding 1.0mol of dodecyl octyl naphthalene into a reactor provided with a condensing device and a stirring device, dropwise adding 1.5mol of 65% nitric acid and 50g of 98% concentrated sulfuric acid, controlling the reaction temperature to be 40 ℃, and continuously reacting for 2 hours after the dropwise adding is finished to obtain 0.95mol of dodecyl octyl nitronaphthalene;

b) adding 0.95mol of dodecyl octyl nitronaphthalene into a high-pressure reaction kettle, adding 30g of Raney nickel catalyst, and sealing the reaction kettle. Filling nitrogen for replacement for 5 times, then introducing hydrogen for replacement for 5 times, heating to 50 ℃, starting hydrogenation, controlling the system pressure not to exceed 4MPa, and reacting for 6 hours to obtain 0.92mol of dodecyl octyl naphthylamine;

c) 0.92mol of dodecyloctylnaphthylamine and 4.0g of sodium hydroxide were charged into a reactor equipped with a condensing device, a stirring device and a gas disperser, and the mixture was stirred and reacted for 1 hour while heating to 85 ℃ under nitrogen. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging for 4 times by using nitrogen to remove air in the system, adjusting the reaction temperature of the system to 135 ℃, sequentially and slowly introducing 3.68mol of propylene oxide and 8.28mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa to carry out etherification reaction; after the reaction is finished, the nitrogen is used for purging the system, and after cooling, neutralization and dehydration are carried out, thus obtaining 0.85mol of dodecyl octyl naphthylamine polyoxypropylene (4) polyoxyethylene (9) ether.

d) And c) adding 0.85mol of dodecyl octyl naphthylamine polyoxypropylene (4) polyoxyethylene (9) ether synthesized in the step c) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 3.0mol of 50% fuming sulfuric acid, controlling the reaction temperature to be 50 ℃, continuing to react for 2 hours after finishing dripping, adding sodium hydroxide to adjust the pH value to be 10, and performing hydrolysis reaction for 2 hours to obtain 0.79mol of dodecyl octyl naphthylamine polyoxypropylene (4) polyoxyethylene (9) ether sodium naphthalenesulfonate.

2. Evaluation of surfactant Properties

The performance evaluation method was the same as in example 1 except that the oil-displacing agent composition was different. The compositions of the oil-displacing agents are shown in Table 2 for comparison, and the evaluation results are shown in Table 3.

[ example 4 ]

1. Synthesis of triacontyl naphthylamine polyoxypropylene (8) polyoxyethylene ether (28) naphthalene sulfonate

a) Adding 1.0mol of triacontyl naphthalene into a reactor provided with a condensing device and a stirring device, dropwise adding 1.5mol of 65% nitric acid and 60g of 98% concentrated sulfuric acid, controlling the reaction temperature to be 30 ℃, and continuously reacting for 4 hours after the dropwise adding is finished to obtain 0.96mol of triacontyl nitronaphthalene;

b) 0.96mol of triacontyl nitronaphthalene is added into a high-pressure reaction kettle, 5g of 10 percent palladium carbon is added, and the reaction kettle is sealed. Filling nitrogen for replacement for 5 times, then introducing hydrogen for replacement for 5 times, heating to 100 ℃, starting hydrogenation, controlling the system pressure to be not more than 4MPa, and reacting for 6 hours to obtain 0.92mol of triacontyl naphthylamine;

c) 0.92mol of triacontylnaphthylamine and 3.5g of sodium hydroxide were charged into a reactor equipped with a condensing device, a stirring device and a gas disperser, and the mixture was stirred and reacted for 1 hour while heating to 85 ℃ under nitrogen. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging for 4 times by using nitrogen to remove air in the system, adjusting the reaction temperature of the system to 140 ℃, sequentially and slowly introducing 7.36mol of propylene oxide and 25.76mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa to carry out etherification reaction; after the reaction is finished, the system is purged by nitrogen, and after cooling, neutralization and dehydration are carried out, thus obtaining 0.89mol of triacontyl naphthylamine polyoxypropylene (8) polyoxyethylene (28) ether.

d) And c) adding 0.89mol of the triacontyl naphthylamine polyoxypropylene (8) polyoxyethylene (28) ether synthesized in the step c) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 4.0mol of 98% sulfuric acid, controlling the reaction temperature to be 65 ℃, continuing to react for 4 hours after dripping is finished, adding sodium hydroxide to adjust the pH value to be 12, and performing hydrolysis reaction for 2 hours to obtain 0.75mol of the triacontyl naphthylamine polyoxypropylene (8) polyoxyethylene (28) ether sodium naphthalenesulfonate.

2. Evaluation of surfactant Properties

The performance evaluation method was the same as in example 1 except that the oil-displacing agent composition was different. The compositions of the oil-displacing agents are shown in Table 2 for comparison, and the evaluation results are shown in Table 3.

[ example 5 ]

1. Synthesis of dodecyl octyl naphthylamine polyoxypropylene (4) polyoxyethylene (9) ether naphthalene sulfonate

a) Adding 1.0mol of dodecyl octyl naphthalene into a reactor provided with a condensing device and a stirring device, dropwise adding 1.3mol of 65% nitric acid and 20g of 98% concentrated sulfuric acid, controlling the reaction temperature to be 50 ℃, and continuously reacting for 1 hour after the dropwise adding is finished to obtain 0.91mol of dodecyl octyl nitronaphthalene;

b) 0.91mol of dodecyl octyl nitronaphthalene is added into a high-pressure reaction kettle, 5.3g of 10 percent palladium carbon is added, and the reaction kettle is sealed. Filling nitrogen for replacement for 5 times, then introducing hydrogen for replacement for 5 times, heating to 90 ℃, starting hydrogenation, controlling the system pressure to be not more than 4MPa, and reacting for 8 hours to obtain 0.88mol of dodecyl octyl naphthylamine;

c) 0.88mol of dodecyloctylnaphthylamine and 4.0g of sodium hydroxide were charged into a reactor equipped with a condensing device, a stirring device and a gas disperser, and the mixture was stirred and reacted for 1 hour while heating to 85 ℃ under nitrogen. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 90 ℃, then purging for 4 times by using nitrogen to remove air in the system, adjusting the reaction temperature of the system to 145 ℃, sequentially and slowly introducing 3.52mol of propylene oxide and 7.92mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa to carry out etherification reaction; after the reaction is finished, the nitrogen is used for purging the system, and after cooling, neutralization and dehydration are carried out, thus obtaining 0.86mol of dodecyl octyl naphthylamine polyoxypropylene (4) polyoxyethylene (9) ether.

d) And c) adding 0.86mol of dodecyl octyl naphthylamine polyoxypropylene (4) polyoxyethylene (9) ether synthesized in the step c) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 4.0mol of 20% fuming sulfuric acid, controlling the reaction temperature to be 50 ℃, continuing to react for 1 hour after finishing dripping, adding sodium hydroxide to adjust the pH value to be 10, and performing hydrolysis reaction for 2 hours to obtain 0.81mol of dodecyl octyl naphthylamine polyoxypropylene (4) polyoxyethylene (9) ether sodium naphthalenesulfonate.

2. Evaluation of oil-displacing agent Performance

The performance evaluation method was the same as in example 1 except that the oil-displacing agent composition was different. The compositions of the oil-displacing agents are shown in Table 2 for comparison, and the evaluation results are shown in Table 3.

[ example 6 ]

1. Synthesis of decyl naphthylamine polyoxypropylene (40) polyoxyethylene (10) ether naphthalene sulfonate

a) Adding 1.0mol of decyl naphthalene into a reactor provided with a condensing device and a stirring device, dropwise adding 3.0mol of dinitrogen pentoxide, controlling the reaction temperature to be 70 ℃, and continuously reacting for 8 hours after dropwise adding is finished to obtain 0.90mol of decyl nitronaphthalene;

b) adding 0.90mol of decyl nitronaphthalene into a high-pressure reaction kettle, adding 14g of palladium carbon catalyst, and sealing the reaction kettle. Filling nitrogen for replacement for 5 times, then introducing hydrogen for replacement for 5 times, heating to 60 ℃, starting hydrogenation, controlling the system pressure not to exceed 4MPa, and reacting for 8 hours to obtain 0.86mol of decyl naphthylamine;

c) into a reactor equipped with a condensing device, a stirring device and a gas disperser, 0.86mol of decylnaphthylamine and 0.24g of sodium methoxide were charged, and the mixture was heated to 75 ℃ with introduction of nitrogen gas, and stirred and reacted for 1 hour. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 85 ℃, then purging for 4 times by using nitrogen to remove air in the system, adjusting the reaction temperature of the system to 180 ℃, sequentially and slowly introducing 34.4mol of propylene oxide and 8.6mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa to carry out etherification reaction; after the reaction, the system was purged with nitrogen, cooled, neutralized and dehydrated to obtain 0.84mol of decylnaphthylamine polyoxypropylene (40) polyoxyethylene (10) ether.

d) And c) adding 0.84mol of decyl naphthylamine polyoxypropylene (40) polyoxyethylene (10) ether synthesized in the step c) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 1.68mol of fuming sulfuric acid, controlling the reaction temperature to be 80 ℃, continuing to react for 0.5 hour after finishing dripping, washing with water, extracting to remove redundant acid, adding sodium hydroxide into an organic phase to adjust the pH to 13, and performing hydrolysis reaction for 0.5 hour to obtain 0.79mol of decyl naphthylamine polyoxypropylene (40) polyoxyethylene (10) ether sodium naphthalenesulfonate.

[ example 7 ]

1. Synthesis of decyl naphthylamine polyoxypropylene (20) polyoxyethylene (50) ether naphthalene sulfonate

a) Adding 1.0mol of decyl naphthalene into a reactor provided with a condensing device and a stirring device, dropwise adding 1.2mol of 65% concentrated nitric acid, controlling the reaction temperature to be 100 ℃, and continuously reacting for 2 hours after the dropwise adding is finished to obtain 0.92mol of decyl nitronaphthalene;

b) adding 0.92mol of decyl nitronaphthalene into a high-pressure reaction kettle, adding 28.9g of Raney nickel catalyst, and sealing the reaction kettle. Filling nitrogen for replacement for 5 times, then introducing hydrogen for replacement for 5 times, heating to 120 ℃, starting hydrogenation, controlling the system pressure not to exceed 4MPa, and reacting for 4 hours to obtain 0.89mol of decyl naphthylamine;

c) into a reactor equipped with a condensing device, a stirring device and a gas disperser, 0.89mol of decylnaphthylamine and 0.13g of potassium hydroxide were charged, and the mixture was heated to 90 ℃ with introduction of nitrogen gas, and stirred for 1 hour. Starting a vacuum system, vacuumizing and dehydrating for 1 hour at the temperature of 95 ℃, then purging for 4 times by using nitrogen to remove air in the system, adjusting the reaction temperature of the system to 150 ℃, sequentially and slowly introducing 17.8mol of propylene oxide and 44.5mol of ethylene oxide, and controlling the pressure to be less than or equal to 0.40MPa to carry out etherification reaction; after the reaction, the system was purged with nitrogen, cooled, neutralized and dehydrated to obtain 0.87mol of decylnaphthylamine polyoxypropylene (20) polyoxyethylene (50) ether.

d) And c) adding 0.87mol of decyl naphthylamine polyoxypropylene (20) polyoxyethylene (50) ether synthesized in the step c) into a reaction kettle provided with a condensing device, a dripping device and a stirring device, dripping 4.35mol of concentrated sulfuric acid, controlling the reaction temperature to be 40 ℃, continuing to react for 4 hours after dripping is finished, washing with water, extracting to remove redundant acid, adding sodium hydroxide into an organic phase to adjust the pH value to 10, and performing hydrolysis reaction for 5 hours to obtain 0.79mol of decyl naphthylamine polyoxypropylene (20) polyoxyethylene (50) ether sodium naphthalenesulfonate.

[ example 8 ]

According to the test of the physical simulation oil displacement effect of the complex oil displacement system in the SY/T6424-2000 complex oil displacement system performance test method, the length is 30cm, the diameter is 2.5cm, and the permeability is 1.5m at the temperature of 80 DEG C²And performing a simulated oil displacement experiment on the core. Firstly, injecting water into a victory oil field island to carry out water drive until the water content is 98%, after the water drive is finished, transferring the oil displacement agent with the volume of 0.3pv (core pore volume), then, carrying out water drive until the water content is 98%, and calculating to improve the recovery ratio of the thickened oil.

The oil displacement agents prepared in example 3 and example 5 were evaluated in an oil displacement experiment according to the above methods, and as a result, the recovery ratio of the heavy oil was increased by 6.5% and 9.5%, respectively.

[ COMPARATIVE EXAMPLE 1 ]

A sodium methylnaphthalenesulfonate and sodium carbonate oil-displacing agent composition was formulated according to the method of example 2 in patent 02159682.4, and it was found that an interfacial tension of 0.95mN/m was formed between this composition and the victory oil field dewatering thickened oil.

The prepared composition is subjected to oil displacement by the method as in example 8, and the recovery ratio of the thickened oil is improved by 1.56 percent.

[ COMPARATIVE EXAMPLE 2 ]

Sodium dodecylnaphthalene disulfonate was synthesized according to the method of example 1 in patent 201310234746.4, and an oil displacement agent composition was prepared according to the proportion of example 1, and it was found that an interfacial tension of 2.56mN/m was formed between the composition and the dehydrated viscous oil of the victory oil field.

The prepared composition is subjected to oil displacement by the method as in example 8, and the thickened oil recovery rate is measured to be improved by 0.86%.

[ COMPARATIVE EXAMPLE 3 ]

The procedure of example 3 was repeated except that: directly carrying out steps c) to d) using 4-decyloxy aniline in place of decylnaphthylamine, under the same conditions as in steps c) to d) of [ example 1 ]. The oil-displacing agent composition was formulated in the proportions of example 1 and it was found that an interfacial tension of 0.025mN/m was formed between the composition and the victory oil field dehydrated thickened oil.

The prepared composition is subjected to oil displacement by the method as in example 8, and the thickened oil recovery rate is measured to be improved by 3.9%.

TABLE 1 victory oilfield injection water

Table 2 examples 1-5 oil-displacing agent compositions

Table 3 examples 1-5 oil displacing agent interfacial tension properties