Treatment of iron sulfide-containing compositions, uses thereof and methods of treating emulsified crude oil

Abstract

The present application relates to the field of petroleum chemical industry, discloses a composition for treating iron sulfide and application thereof and a method for treating emulsified crude oil containing iron sulfide solid particles.The composition contains the following components which are independently stored or mixedly stored: a demulsifier, a bio-based wetting agent; wherein the demulsifier is a polyether imidazoline compound; the bio-based wetting agent is a sophorolipid ether; the content mass ratio of the demulsifier to the bio-based wetting agent is 1:0.5-5; and the polyether imidazoline compound is an alkyl phenol formaldehyde resin polyether imidazoline.The composition can effectively remove the iron sulfide solid particles in the emulsified crude oil, and the bio-based wetting agent has better biodegradability.

Description

TECHNICAL FIELD

[0001] The present application relates to the field of petroleum chemical industry, in particular to a composition for treating iron sulfide-containing composition and application thereof and a method for treating emulsified crude oil containing iron sulfide solid particles. BACKGROUND

[0002] Impurities contained in crude oil can cause problems such as corrosion, heat exchanger fouling, heating furnace coking, catalyst deactivation and product quality deterioration. These impurities include salts, precipitates and water (BS&W), solids and metals.

[0003] The salts in crude oil include sodium, calcium and magnesium chlorides, among which NaCl is predominant. These chlorides are hydrolyzed during atmospheric distillation to generate corrosive HCl, which causes corrosion at the top of the fractionating column. Therefore, oil refineries remove the salts in crude oil through electric desalting.

[0004] The solids in crude oil include silt, clay, volcanic ash, drilling mud, ferrous sulfide and scale, etc. On the one hand, these solids cause fouling, abrasion, plugging and deterioration of residual oil quality, and on the other hand, the solid particles are wrapped by oil, accumulated at the oil-water interface, become natural emulsifiers which are both wetted by oil and water, hinder the coalescence of water droplets, reduce the demulsification efficiency, form an emulsion layer at the oil-water interface, cause the increase of electric current and the decrease of desalting efficiency, and increase the oil content in drainage.

[0005] With the incorporation of iron-containing clean oil, dirty oil or acidized oil containing iron produced during oilfield exploitation into some processed crude oil, the iron content in the crude oil increases. Crude oil containing iron sulfide solid particles can cause serious emulsification problems, especially thick oil containing iron sulfide solid particles. These very fine iron sulfide solid particles form an emulsion layer of crude oil at the oil-water interface, which can cause the increase of electric current or tripping. In addition, the thickening of the emulsion layer can cause the increase of oil content in drainage. The dirty oil recovered from the oil-containing wastewater is difficult to treat, and if reused in electric desalting, it can cause impact on electric desalting and exacerbate the deterioration of electric desalting operation.

[0006] In order to solve the emulsification problem caused by iron sulfide solid particles, Xia Fujun, Wu Di, et al. (Treatment of dirty oil containing ferrous sulfide particles [J]. Petroleum Planning and Design, 2006, 17(5): 4.) and Wu Di, Zhang Zhijun, et al. (Synergistic treatment of dirty oil containing ferrous sulfide particles with surfactants and sulfide removers [C]. The Fifteenth National Industrial Surfactants Development Seminar and the Thirteenth National Industrial Surfactants Development Seminar. 2004.) used dirty oil demulsifiers, sulfide removers and sulfide inhibitors to treat dirty oil containing FeS.

[0007] CN101050382A discloses a demulsifier for reducing the content of FeS particles in electric desalting / dewatering drainage and a preparation method thereof, which uses a nano water purifier, an imidazoline polyether surfactant and an alcohol solvent to solve the problem of high FeS content in electric desalting drainage.

[0008] However, the above two methods are based on dispersing FeS from the oil-water interface into the oil phase to reduce its influence on the emulsion layer and drainage, but FeS is not removed from the crude oil, so its influence on subsequent processing cannot be eliminated.

[0009] US4722781A discloses a method for treating water-insoluble FeS-containing crude oil, i.e. electric desalting emulsion layer is extracted, most of which is returned to the crude oil, and the other part is added to light dilution oil. This method may be suitable for light crude oil, but for heavy crude oil, the reuse of the emulsion layer to the crude oil will exacerbate the electric desalting deterioration, generating more emulsion layer and forming a vicious cycle.

[0010] US5080779A discloses a method for removing FeS from crude oil, i.e. adding a chelating agent such as oxalic acid, EDTA, etc. to the water injection. This method is suitable for crude oil with low FeS content, but when the solid particle content of iron sulfide is high, the amount of chelating agent used is quite large, and other metal ions (such as Na) may be introduced into the crude oil, or the chelating agent itself may cause corrosion problems due to its strong acidity.

[0011] US6132619A discloses a method for treating emulsion (such as iron-containing sludge / emulsion), which uses an iron inhibitor and a demulsifier to treat iron-containing acidified oil generated during the oil production process. The iron inhibitor used is nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), etc., and the actual use also has the problem of high cost.

[0012] Since the solid particles of iron sulfide are easily wetted by the oil phase, they become emulsifiers and are adsorbed at the oil-water interface, and cannot enter the water phase. For crude oil with high solid particle iron content, the effect of simply using a demulsifier is limited, and a method of using a wetting agent and a demulsifier in combination can be used to solve the problem.

[0013] The commonly used wetting agent in industry is nonylphenol polyoxyethylene ether, but the wetting effect of the conventional wetting agent is limited, and the wetting agent itself is toxic and can harm the environment when entering water bodies. SUMMARY

[0014] The purpose of the present application is to overcome the problems of poor treatment effect and lack of environmental protection in the treatment of emulsified crude oil with high iron sulfide content in the prior art.

[0015] In order to achieve the above object, the first aspect of the present application provides a composition for treating iron sulfide-containing composition, the composition containing the following components each independently stored or stored in combination with two or more:

[0016] Demulsifier, bio-based wetting agent;

[0017] The demulsifier is a polyether imidazoline compound; the bio-based wetting agent is a sophorolipid ether; the content mass ratio of the demulsifier to the bio-based weting agent is 1:0.5-5;

[0018] The polyether imidazoline compound is an alkyl phenol formaldehyde resin polyether imidazoline, which has a general structure shown in formula I:

[0019] Formula I;

[0020] In the formula, R is nonyl or octyl; a is 2-10; x is 1-2; y is 5-8.

[0021] The second aspect of the present application provides the use of the composition of the first aspect in treating emulsified crude oil containing iron sulfide solid particles.

[0022] The third aspect of the present application provides a method for treating emulsified crude oil containing iron sulfide solid particles, the method comprising:

[0023] (1) contacting the emulsified crude oil with the composition of the first aspect in the presence of a solvent to perform electric desalting treatment to obtain a mixed oil;

[0024] (2) separating the mixed oil into water phase and oil phase.

[0025] Through the above technical solution, the composition for treating iron sulfide-containing composition provided by the present application uses a specific bio-based wetting agent in combination with a specific demulsifier in a specific ratio, which is used to treat emulsified crude oil containing iron sulfide solid particles. Not only can the composition effectively remove the iron sulfide solid particles in the emulsified crude oil, but compared with the existing conventional wetting agent, the bio-based wetting agent in the composition has better biodegradability and better environmental protection. DETAILED DESCRIPTION

[0026] The endpoints of the ranges and any values disclosed herein are not limited to the precise values stated. The endpoints of the ranges and any values are understood to be approximate values. The exact numerical values of the endpoints of the ranges and the separate points are not to be construed as being more precise than they appear to be from the context of the specification. Rounding off, rounding up or rounding down to the nearest significant figure is understood to be done only where such rounding off, rounding up or rounding down is not otherwise explicitly addressed in the specification. In this context, the term "about" means that the value concerned can vary from the value stated, by as much as 1%, 2%, 5%, 10%, 15%, 20%, 25%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or even 100%, but preferably no more than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90% or even 100%.

[0027] In the present application, the pressure is all the gauge pressure unless otherwise stated.

[0028] In the present application, the iron element refers to the molecular form of iron element existing in the form of solid particles or complex unless otherwise stated. The iron content in the drainage, the iron content in the upper oil and the iron content in the lower oil all refer to the content of the molecular form of iron element existing in the form of solid particles or complex in the corresponding content.

[0029] In the present application, “first”, “second”, “third”, “fourth” and “fifth” do not represent the order of precedence, nor do they limit the respective materials or operations, but only distinguish the respective materials or operations, for example, “first”, “second”, “third”, “fourth” and “fifth” in “first reaction”, “second reaction”, “third reaction”, “fourth reaction” and “fifth reaction” only distinguish them and do not mean the same reaction.

[0030] As described above, the first aspect of the present application provides a composition for treating iron-containing sulfides, the composition containing the following components stored independently or in combination:

[0031] Demulsifier, bio-based wetting agent;

[0032] The content mass ratio of the demulsifier to the bio-based wetting agent is 1:0.5-5.

[0033] The polyether imidazoline compound is an alkyl phenol formaldehyde resin polyether imidazoline, which has a general structure shown in formula I:

[0034] Formula I;

[0035] In the formula, R is nonyl or octyl; a is 2-10; x is 1-2; and y is 5-8.

[0036] According to some embodiments of the present application, preferably, the content mass ratio of the demulsifier to the bio-based wetting agent is 1:1.25-3. The above preferred embodiments are advantageous for further removing the iron-containing sulfides in the emulsified crude oil and obtaining better iron-containing sulfide removal effect.

[0037] According to some embodiments of the present application, preferably, the sophorolipid ether is prepared by a method comprising the following steps:

[0038] (a) contacting sophorolipid with methanol in the presence of an acidic catalyst I to perform a first reaction to obtain sophorolipid methyl ester;

[0039] (b) performing a second reaction by contacting the sophorolipid methyl ester with propylene oxide in the presence of a basic catalyst I, and performing a third reaction by contacting the obtained reaction product with ethylene oxide.

[0040] According to some embodiments of the present application, preferably, in step (a), the acidic catalyst I is sulfuric acid; preferably, the sulfuric acid is provided in the form of a 70wt% or above aqueous solution of sulfuric acid. Exemplarily, in step (a), the sulfuric acid is provided in the form of a 70wt% aqueous solution of sulfuric acid.

[0041] According to some embodiments of the present application, preferably, in step (a), the acidic catalyst I is used in a mass ratio of 0.5-2.5:50, preferably 1-2:50, with respect to the sophorolipid.

[0042] According to some embodiments of the present application, preferably, in step (a), the sophorolipid is used in a ratio of 1g:3.5-5mL with respect to the methanol.

[0043] According to some embodiments of the present application, preferably, in step (a), the contacting step comprises: first mixing the sophorolipid with the methanol to obtain a homogeneous solution, and then adding the acidic catalyst I into the homogeneous solution.

[0044] According to some embodiments of the present application, preferably, in step (a), the first reaction is performed under conditions including: a temperature of 30-50°C, and a time of 1-5h.

[0045] According to some embodiments of the present application, preferably, in step (b), the basic catalyst I is KOH.

[0046] According to some embodiments of the present application, preferably, in step (b), the basic catalyst I, the sophorolipid methyl ester, the propylene oxide and the ethylene oxide are used in a mass ratio of 1:100-400:100-200:450-550.

[0047] According to some embodiments of the present application, preferably, in step (b), the second reaction and the third reaction are performed under an inert atmosphere.

[0048] According to some embodiments of the present application, preferably, in step (b), the second reaction is performed under conditions including: a temperature of 100-140°C, a time of 0.5-5h, and a pressure of 0.1-0.4MPa.

[0049] According to some embodiments of the present application, preferably, in step (b), the third reaction is performed under conditions including: a temperature of 100-140°C, a time of 0.5-5h, and a pressure of 0.1-0.4MPa.

[0050] According to some embodiments of the present application, the polyether imidazoline compound is an alkyl phenol resin polyether imidazoline, which has a general structure shown in Formula I:

[0051] Formula I;

[0052] In the formula, R is a nonyl group or an octyl group, preferably a nonyl group; a is 2-10, preferably 4-6; x is 1-2; and y is 5-8.

[0053] Preferably, the polyether imidazoline compound is a nonyl phenol resin polyether imidazoline, i.e., R in Formula I is a nonyl group. With the above preferred embodiment, it is beneficial to further remove iron-containing sulfides in the emulsified crude oil, and a better iron-containing sulfide removal effect is obtained.

[0054] According to some embodiments of the present application, the polyether imidazoline compound can be obtained by commercial purchase or self-preparation.

[0055] According to some embodiments of the present application, preferably, the polyether imidazoline compound is prepared by a method comprising the following steps:

[0056] (S1) contacting an alkyl phenol resin polyether with succinic anhydride to perform a fourth reaction, to obtain a carboxylated polyether;

[0057] (S2) contacting the carboxylated polyether with diethylenetriamine to perform a fifth reaction.

[0058] According to some embodiments of the present application, preferably, in step (S1), the alkyl phenol resin polyether has a general structure shown in Formula II:

[0059] Formula II;

[0060] In the formula, R, a, x, and y are defined and selected as described above, and will not be repeated here.

[0061] Preferably, the alkyl phenol resin polyether is a nonyl phenol resin polyether.

[0062] According to some embodiments of the present application, the alkyl phenol resin polyether can be obtained by commercial purchase or self-preparation.

[0063] According to a preferred embodiment of the present application, the alkyl phenol resin polyether is prepared by a method comprising the following steps:

[0064] 1) contacting an alkyl phenol resin and a base I with propylene oxide under an inert atmosphere to perform a reaction, to obtain an intermediate product; wherein:

[0065] The base I is sodium hydroxide and / or potassium hydroxide; the mass ratio of the alkyl phenol-formaldehyde resin, the base I and the propylene oxide is 50-240:1:35-200;

[0066] The reaction conditions include: temperature is 125-135℃, pressure is 0.1-0.5 MPa, time is 15 min-2h;

[0067] 2) under inert atmosphere, the intermediate product and base II are contacted with ethylene oxide to react to obtain an alkyl phenol-formaldehyde resin polyether; wherein:

[0068] The base II is sodium hydroxide and / or potassium hydroxide; the mass ratio of the intermediate product, the base II and the ethylene oxide is 100:1-2:10-30;

[0069] The reaction conditions include: temperature is 115-125℃, pressure is 0.1-0.5 MPa, time is 15 min-2h.

[0070] Preferably, in step 1), the alkyl phenol-formaldehyde resin can be obtained by commercial purchase or self-preparation. The preparation method can include:

[0071] In the presence of a catalyst, the alkyl phenol and formaldehyde are subjected to condensation reaction, the catalyst can be an acid or a base, and the specific reaction conditions are well known to those skilled in the art, which will not be repeated here.

[0072] Preferably, in step 1), the polydispersity of the alkyl phenol-formaldehyde resin is 2-10, preferably 4-6; the weight average molecular weight is 440-2200 g / mol, preferably 880-1320 g / mol.

[0073] According to some embodiments of the present application, preferably, the weight average molecular weight of the alkyl phenol-formaldehyde resin polyether is 440-2200 g / mol, preferably 880-1320 g / mol; the hydroxyl value is 25.5-127 mgKOH / g, preferably 42.4-63.6 mgKOH / g.

[0074] According to some embodiments of the present application, preferably, in step (S1), the mass ratio of the alkyl phenol-formaldehyde resin polyether and the succinic anhydride is 90-150:8, preferably 100-120:8, more preferably 100-110:8.

[0075] According to some embodiments of the present application, in step (S1), the fourth reaction is a carboxylation reaction. The equation of the fourth reaction is as follows:

[0076]

[0077] Preferably, the conditions of the fourth reaction include: temperature of 100-120℃, preferably 105-115℃; time of 1-8h, preferably 2-6h.

[0078] According to some embodiments of the present application, preferably, in step (S2), the mass ratio of the carboxylated polyether to the diethylenetriamine is 11-15:1, preferably 12-14:1.

[0079] According to some embodiments of the present application, in step (S2), the fifth reaction includes an amidation reaction and a cyclization reaction. The equation of the fifth reaction includes:

[0080]

[0081]

[0082] Preferably, in step (S2), the step of contacting includes: first mixing the carboxylated polyether and diethylenetriamine at a temperature of 140-160℃, preferably 145-155℃, and then heating to 230-250℃, preferably to 235-245℃, until no water is generated.

[0083] According to some embodiments of the present application, the composition can release the iron sulfide solid particles from the emulsified layer, transfer from the oil phase to the water phase, and coalesce and grow, and sink to the bottom of the water phase, and then realize the removal of the iron sulfide in the emulsified crude oil through the subsequent separation of the water phase and the oil phase, by using a specific demulsifier and a specific bio-based wetting agent in a specific mass ratio.

[0084] According to some embodiments of the present application, the inert atmosphere is provided by at least one inert gas selected from nitrogen, argon, neon and helium.

[0085] The composition provided by the present application can be used for crude oil demulsification and dehydration in the process of oil exploitation and collection, and can also be used for electric desalting of crude oil in a refinery.

[0086] The second aspect of the present application provides the use of the composition of the first aspect in treating emulsified crude oil containing iron sulfide solid particles.

[0087] The third aspect of the present application provides a method for treating emulsified crude oil containing iron sulfide solid particles, the method comprising:

[0088] (1) contacting the emulsified crude oil with the composition of the first aspect in the presence of a solvent to perform electric desalting treatment, to obtain a mixed oil;

[0089] (2) performing oil-water separation on the mixed oil to obtain a water phase and an oil phase, respectively.

[0090] According to some embodiments of the present application, the method can convert the oil-wetted iron sulfide solid particles into water-wetted ones by using the specific bio-based wetting agent in the composition provided by the present application in combination with the specific demulsifier in a specific ratio, and then wash them into the water phase by subsequent electro-desalting treatment.

[0091] According to some embodiments of the present application, preferably, in step (1), the amount of the demulsifier is 50-1000 μg, preferably 80-450 μg, relative to 1 g of the emulsified crude oil.

[0092] According to some embodiments of the present application, preferably, in step (1), the amount of the bio-based wetting agent is 50-1000 μg, preferably 100-500 μg, relative to 1 g of the emulsified crude oil.

[0093] The use of the raw material amount in the preferred embodiments described above is conducive to further removing the iron-containing sulfides in the emulsified crude oil, and obtaining a better iron-containing sulfide removal effect.

[0094] According to some embodiments of the present application, preferably, in step (1), the solvent is water, for example, deionized water.

[0095] According to some embodiments of the present application, preferably, in step (1), the mass ratio of the emulsified crude oil to the solvent is 3-20:1, preferably 5-10:1.

[0096] According to some embodiments of the present application, preferably, in step (1), the conditions of the electro-desalting treatment include: a temperature of 90-140℃, preferably 90-120℃; an electric field strength of 100-300 V / cm, preferably 150-250 V / cm; and a time of 0.5-3 h, preferably 1-2 h.

[0097] The use of the conditions in the preferred embodiments described above is conducive to further removing the iron-containing sulfides in the emulsified crude oil, and obtaining a better iron-containing sulfide removal effect.

[0098] According to some embodiments of the present application, preferably, the content of the iron element in the emulsified crude oil is 205-300 μg, relative to 1 g of the emulsified crude oil.

[0099] According to some embodiments of the present application, preferably, the 20℃ density of the emulsified crude oil is not higher than 950 kg / cm 3 , and the 80℃ viscosity is not higher than 390 mm 2 / s.

[0100] The method provided by the application can also remove other metal elements in the emulsified crude oil, for example, calcium elements or sodium elements. Since the field mainly focuses on the content of iron elements in the emulsified crude oil, the application mainly relates to the treatment of iron elements in the emulsified crude oil.

[0101] The application will be described in detail below through examples.

[0102] In the following examples and comparative examples, various raw materials used without special instructions are commercially available. Among them:

[0103] Sophorolipid: lactone type, purchased from Shandong Qilu Biological Technology Group Co., Ltd.;

[0104] Methanol: purchased from Inokai Reagent Co., Ltd.;

[0105] Propylene oxide: purchased from Inokai Reagent Co., Ltd.;

[0106] Ethylene oxide: purchased from Inokai Reagent Co., Ltd.;

[0107] 70wt% sulfuric acid aqueous solution: purchased from Inokai Reagent Co., Ltd.;

[0108] Nonyl phenolic resin polyether is prepared by a method comprising the following steps:

[0109] 1) Preparation of nonyl phenolic resin

[0110]

[0111] 100g of nonyl phenol (molecular weight 220) was added to a three-necked flask, immersed in a constant temperature water bath of 75℃, a certain amount of concentrated hydrochloric acid (37wt%) was added to make the solution pH 3-5, and 38.9g of formaldehyde (35wt%) (molecular weight 30) was added dropwise under stirring. The dropping speed of formaldehyde was controlled at 1 drop / s, and the polymerization reaction temperature was not more than 80℃. The product was removed from the upper clear liquid, washed with water, and nonyl phenolic resin (with a weight average molecular weight of 970 g / mol and a polymerization degree of 4) was obtained;

[0112] 2) Preparation of nonyl phenolic resin polyether

[0113]

[0114] 110g of the obtained nonyl phenolic resin and 1.1g of potassium hydroxide were added to an autoclave, purged with nitrogen to exclude air, vacuumized, and stirred to heat to 130℃. Then 132g of propylene oxide (molar ratio 6) was added dropwise at 0.3MPa and 135℃. After the dropwise addition was completed, the reaction was continued for 0.5h, and the temperature was lowered to obtain an intermediate product;

[0115] 100 g of the obtained intermediate product and 1.86 g of potassium hydroxide were added into a high-pressure reaction kettle, purged with nitrogen and vacuumized, stirring was started and the temperature was raised to 120℃, then 19 g of ethylene oxide was added dropwise at a pressure of 0.3 MPa and a temperature of 125℃, after the addition was completed, the reaction was continued for 0.5 h, and the product was discharged after cooling, to obtain a nonyl phenolic resin polyether (with a weight average molecular weight of 1244 g / mol and a hydroxyl value of 45 mgKOH / g).

[0116] Nonylphenol polyoxyethylene ether: NP7 brand, purchased from Jiangsu Hai'an Petrochemical Factory;

[0117] SEM-EDS analysis: analyzed by a scanning electron microscope thermogravimetric instrument.

[0118] The emulsified crude oil is a mixed oil composed of crude oil and tank bottom oil containing iron sulfide, and its properties are shown in Table 1.

[0119] Table 1

[0120]

[0121] The emulsified crude oil was diluted with xylene, and after filtering out the mechanical impurities, SEM-EDS analysis was performed, and the analysis results are shown in Table 2. As can be seen from Table 2, the mechanical impurities are mainly solid particles of iron sulfide.

[0122] Table 2

[0123]

[0124] In each of the examples and comparative examples, the inductively coupled plasma atomic emission spectrometry (ICP) was used to determine the iron content in the drainage, the upper layer oil, and the lower layer oil.

[0125] The following preparation examples are used to illustrate the sophorolipid ether and the preparation method thereof

[0126] Preparation Example A1

[0127] (a) contacting 50 g of sophorolipid with methanol in the presence of an acidic catalyst I to perform a first reaction to obtain sophorolipid methyl ester; wherein:

[0128] The acidic catalyst I is sulfuric acid, which is provided in the form of a 70wt% sulfuric acid aqueous solution;

[0129] The mass ratio of the amount of use of the acidic catalyst I to the sophorolipid is 1.5:50; and the amount ratio of the sophorolipid to the methanol is 1 g:3.8 mL;

[0130] The step of contacting specifically is: first mixing the sophorolipid with the methanol to obtain a homogeneous solution, and then adding the acidic catalyst I into the homogeneous solution;

[0131] The first reaction is carried out at a temperature of 40℃ for 1.5h;

[0132] (b) contacting 50g of the methyl sophorolipid ester with propylene oxide in the presence of the basic catalyst I to carry out a second reaction, and contacting the obtained reaction product with ethylene oxide to carry out a third reaction, to obtain a sophorolipid ether AZ1; wherein:

[0133] The basic catalyst I is KOH; the mass ratio of the basic catalyst I, the methyl sophorolipid ester, the propylene oxide and the ethylene oxide is 1:200:168:512;

[0134] The second reaction and the third reaction are carried out under an inert atmosphere provided by nitrogen;

[0135] The second reaction is carried out at a temperature of 130℃ for 1h under a pressure of 0.3MPa;

[0136] The third reaction is carried out at a temperature of 120℃ for 1h under a pressure of 0.3MPa.

[0137] Preparation Example A2

[0138] According to the method of Preparation Example A1, except that in step (a), the amount of sophorolipid is 40g; wherein the mass ratio of the acid catalyst I to sophorolipid is 1.5:50; the amount ratio of sophorolipid to methanol is 1g:4.75mL; and the rest are the same, to obtain a sophorolipid ether AZ2.

[0139] Preparation Example A3

[0140] According to the method of Preparation Example A1, except that in step (a), the amount of sophorolipid is 60g; wherein the mass ratio of the acid catalyst I to sophorolipid is 1.5:50; the amount ratio of sophorolipid to methanol is 1g:3.17mL; and the rest are the same, to obtain a sophorolipid ether AZ3.

[0141] The following preparation examples are used to illustrate the polyether imidazoline compound and the preparation method thereof

[0142] Preparation Example B1

[0143] (S1) contacting 100g of the alkyl phenol formaldehyde resin polyether with succinic anhydride to carry out a fourth reaction, to obtain a carboxylated polyether; wherein:

[0144] The alkyl phenol formaldehyde resin polyether is a nonyl phenol formaldehyde resin polyether;

[0145] The mass ratio of the alkyl phenol formaldehyde resin polyether to succinic anhydride is 100:8;

[0146] The fourth reaction is a carboxylation reaction; the conditions for the fourth reaction are: temperature 110° C., time 6 hours; wherein, after the reaction is carried out for 1 hour, the acid value is measured every 0.5 hours until the acid value no longer changes;

[0147] (S2) contacting 108 g of the carboxylated polyether with diethylenetriamine to carry out a fifth reaction to obtain nonylphenolic resin polyether imidazoline BZ1; wherein:

[0148] The mass ratio of carboxylated polyether to diethylenetriamine is 108:8.3;

[0149] The fifth reaction includes an amidation reaction and a cyclization reaction; the contact steps are: first, diethylenetriamine is added dropwise to the carboxylated polyether at a temperature of 150°C to mix, the generated water is continuously condensed and separated to an acid value equilibrium, and then the temperature is raised to 240°C until no water is generated, and the reaction is stopped.

[0150] Preparation Example B2

[0151] The method of Preparation Example B1 was followed, except that:

[0152] In step (S1), the alkylphenol-formaldehyde resin polyether is nonylphenol-formaldehyde resin polyether;

[0153] The mass ratio of alkylphenol-formaldehyde resin polyether to succinic anhydride is 110:8;

[0154] The conditions for the fourth reaction are: temperature 120°C, time 4h;

[0155] In step (S2), the mass ratio of carboxylated polyether to diethylenetriamine is 13.9:1;

[0156] The contacting steps are: first, at a temperature of 140° C., diethylenetriamine is added dropwise to the carboxylated polyether to mix, the generated water is continuously condensed and separated until the acid value is balanced, and then the temperature is raised to 250° C. until no water is generated, and the reaction is stopped;

[0157] The rest are the same, and nonylphenolic resin polyether imidazoline BZ2 is obtained.

[0158] The following examples are used to illustrate the composition for treating iron sulfide and the method for treating emulsified crude oil containing iron sulfide solid particles.

[0159] Example 1

[0160] (1) In the presence of a solvent, 60 g of emulsified crude oil is contacted with a demulsifier and a bio-based wetting agent for electro-desalting to obtain a mixed oil; wherein:

[0161] The solvent is deionized water; the demulsifier is nonylphenolic resin polyether imidazoline BZ1; the bio-based wetting agent is sophorolipid ether AZ1;

[0162] The amount of demulsifier is 80 μg relative to 1 g of emulsified crude oil; the amount of bio-based wetting agent is 100 μg relative to 1 g of emulsified crude oil; the mass ratio of emulsified crude oil to solvent is 5:1;

[0163] Before the contact is performed, the emulsified crude oil is preheated to 85℃;

[0164] The conditions of the electric desalting treatment are: the temperature is 90℃; the electric field strength is 180 V / cm; and the time is 1 h;

[0165] (2) The mixed oil is subjected to oil-water separation to obtain a water phase and an oil phase, respectively;

[0166] The water phase is extracted, a sufficient amount of acid is added to dissolve the metal in the water phase, filtration is performed, and then the iron content in the filtrate is determined, which is the iron content in the drainage;

[0167] 45 g of the upper layer oil is taken as the upper layer oil, and 15 g of the lower layer oil is taken as the lower layer oil, and the iron content of the upper layer oil and the lower layer oil is determined, respectively. The determination results are shown in Table 3.

[0168] Example 2

[0169] According to the method of Example 1, except that in step (1), the demulsifier is nonyl phenolic resin polyether imidazoline BZ1; the bio-based wetting agent is sophorolipid ether AZ2; the rest are the same, and the determination results are shown in Table 3.

[0170] Example 3

[0171] According to the method of Example 1, except that in step (1), the demulsifier is nonyl phenolic resin polyether imidazoline BZ1; the bio-based wetting agent is sophorolipid ether AZ3; the rest are the same, and the determination results are shown in Table 3.

[0172] Example 4

[0173] According to the method of Example 1, except that:

[0174] In step (1), the demulsifier is nonyl phenolic resin polyether imidazoline BZ2 obtained from Preparation Example B2; the bio-based wetting agent is sophorolipid ether AZ1;

[0175] The amount of demulsifier is 80 μg relative to 1 g of emulsified crude oil; the amount of bio-based wetting agent is 100 μg relative to 1 g of emulsified crude oil; the mass ratio of emulsified crude oil to solvent is 8:1;

[0176] The conditions of the electric desalting treatment are: the temperature is 120℃; the electric field strength is 220 V / cm; and the time is 2 h;

[0177] The rest are the same, and the determination results are shown in Table 3.

[0178] Comparative Example 1

[0179] According to the method of Example 1, except that in step (1), no bio-based wetting agent was used, only demulsifier was used; the rest were the same, and the test results are shown in Table 3.

[0180] Comparative Example 2

[0181] According to the method of Example 3, except that in step (1), an equal amount of nonylphenol polyoxyethylene ether was used to replace the bio-based wetting agent; the rest were the same, and the test results are shown in Table 3.

[0182] Comparative Example 3

[0183] According to the method of Example 3, except that in step (1), no bio-based wetting agent was used, only demulsifier was used; the rest were the same, and the test results are shown in Table 3.

[0184] Comparative Example 4

[0185] According to the method of Example 3, except that no demulsifier was used, only bio-based wetting agent was used; the rest were the same, and the test results are shown in Table 3.

[0186] Table 3

[0187]

[0188] From the above results, it can be seen that using the composition provided by the present application to treat emulsified crude oil with high content of iron sulfide solid particles can significantly increase the iron content in the drainage, and the treatment effect is good.

[0189] Test Example

[0190] The bio-based wetting agent prepared by the present application and the nonylphenol polyoxyethylene ether used in the comparative examples were tested for biodegradability, and the ratio of biological oxygen consumption (BOD) to chemical oxygen consumption (CODcr) (B / C) was used to represent the biodegradability. The test results are shown in Table 4. Among them:

[0191] BOD was detected by the determination method of standard HJ505-2009 “Water Quality Five-Day Biochemical Oxygen Demand”;

[0192] CODcr was detected by standard HJ828-2017 “Determination of Chemical Oxygen Demand of Water Quality – Dichromate Method”.

[0193] Table 4

[0194]

[0195] It can be seen from the above results that, compared with the existing conventional wetting agent, the bio-based wetting agent adopted by the application has better biodegradability and better environmental protection.

[0196] The preferred embodiments of the application are described in detail above, but the application is not limited thereto. Within the technical concept of the application, various simple modifications can be made to the technical solutions of the application, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be considered as disclosed by the application and fall within the protection scope of the application.

Claims

1. A composition for treating iron sulfides, characterized in that: The composition contains the following components which are stored independently or in combination: a demulsifier, a bio-based wetting agent; Wherein, the demulsifier is a polyether imidazoline compound; the bio-based wetting agent is a sophorolipid ether; the mass ratio of the demulsifier to the bio-based wetting agent is 1:0.5-5; The polyether imidazoline compound is an alkylphenol-formaldehyde resin polyether imidazoline, which has the general structure shown in Formula I: Formula I; In the formula, R is nonyl or octyl; a is 2-10; x is 1-2; and y is 5-8.

2. The composition according to claim 1, wherein The mass ratio of the demulsifier to the bio-based wetting agent is 1:1.25-3.

3. The composition according to claim 1 or 2, wherein The sophorolipid ether is prepared by a method comprising the following steps: (a) contacting a sophorolipid with methanol in the presence of an acidic catalyst I to carry out a first reaction to obtain sophorolipid methyl ester; (b) contacting the sophorolipid methyl ester with propylene oxide in the presence of a basic catalyst I to perform a second reaction, and contacting the resulting reaction product with ethylene oxide to perform a third reaction.

4. The composition according to claim 3, wherein In step (a), the acidic catalyst I is sulfuric acid.

5. The composition according to claim 4, wherein In step (a), the sulfuric acid is provided in the form of a sulfuric acid aqueous solution with a mass fraction of 70 wt % or more.

6. The composition according to claim 4, wherein In step (a), the mass ratio of the acidic catalyst I to the sophorolipid is 0.5-2.5:

50.

7. The composition according to claim 4, wherein In step (a), the mass ratio of the acidic catalyst I to the sophorolipid is 1-2:

50.

8. The composition according to claim 3, wherein In step (a), the ratio of the sophorolipid to the methanol is 1 g: 3.5-5 mL.

9. The composition according to claim 3, wherein In step (a), the conditions of the first reaction include: temperature of 30-50° C. and time of 1-5 h.

10. The composition according to claim 3, wherein In step (b), the alkaline catalyst I is KOH.

11. The composition according to claim 10, wherein In step (b), the mass ratio of the basic catalyst I, the sophorolipid methyl ester, the propylene oxide and the ethylene oxide is 1:100-400:100-200:450-550.

12. The composition according to claim 3, wherein In step (b), the second reaction and the third reaction are carried out under an inert atmosphere.

13. The composition according to claim 3, wherein In step (b), the conditions of the second reaction include: temperature of 100-140° C., time of 0.5-5 h, and pressure of 0.1-0.4 MPa.

14. The composition according to claim 3, wherein In step (b), the conditions of the third reaction include: temperature of 100-140° C., time of 0.5-5 h, and pressure of 0.1-0.4 MPa.

15. The composition according to claim 1 or 2, wherein In formula I, R is nonyl; a is 4-6.

16. The composition according to claim 1 or 2, wherein The polyether imidazoline compound is prepared by a method comprising the following steps: (S1) contacting an alkylphenol-formaldehyde resin polyether with succinic anhydride to perform a fourth reaction to obtain a carboxylated polyether; (S2) contacting the carboxylated polyether with diethylenetriamine to perform a fifth reaction.

17. The composition according to claim 16, wherein In step (S1), the mass ratio of the alkylphenol-formaldehyde resin polyether to the succinic anhydride is 90-150:

8.

18. The composition according to claim 16, wherein In step (S1), the mass ratio of the alkylphenol-formaldehyde resin polyether to the succinic anhydride is 100-120:

8.

19. The composition according to claim 16, wherein In step (S1), the mass ratio of the alkylphenol-formaldehyde resin polyether to the succinic anhydride is 100-110:

8.

20. The composition according to claim 16, wherein In step (S1), the fourth reaction is a carboxylation reaction.

21. The composition according to claim 16, wherein In step (S1), the conditions of the fourth reaction include: temperature of 100-120° C.; time of 1-8 h.

22. The composition according to claim 16, wherein In step (S1), the conditions of the fourth reaction include: temperature of 105-115° C.; time of 2-6 hours.

23. The composition according to claim 16, wherein In step (S2), the mass ratio of the carboxylated polyether to the diethylenetriamine is 11-15:

1.

24. The composition according to claim 16, wherein In step (S2), the mass ratio of the carboxylated polyether to the diethylenetriamine is 12-14:

1.

25. The composition according to claim 16, wherein In step (S2), the fifth reaction includes an amidation reaction and a cyclization reaction.

26. The composition according to claim 16, wherein In step (S2), the contacting step includes: first mixing the carboxylated polyether and diethylenetriamine at a temperature of 140-160°C, and then heating the mixture to 230-250°C.

27. The composition according to claim 16, wherein In step (S2), the contacting step includes: first mixing the carboxylated polyether and diethylenetriamine at a temperature of 145-155°C, and then heating the mixture to 235-245°C.

28. Use of the composition according to any one of claims 1 to 27 in treating emulsified crude oil containing iron sulfide solid particles.

29. A method for treating emulsified crude oil containing iron sulfide solid particles, characterized in that: The method comprises: (1) contacting the emulsified crude oil with the composition according to any one of claims 1 to 27 in the presence of a solvent to perform an electrical desalting treatment to obtain a mixed oil; (2) Separating the mixed oil into water to obtain a water phase and an oil phase.

30. The method according to claim 29, wherein In step (1), the amount of the demulsifier used is 50-1000 μg relative to 1 g of the emulsified crude oil.

31. The method according to claim 29, wherein In step (1), the amount of the demulsifier used is 80-450 μg relative to 1 g of the emulsified crude oil.

32. The method of claim 29, wherein: In step (1), the amount of the bio-based wetting agent used is 50-1000 μg relative to 1 g of the emulsified crude oil.

33. The method of claim 29, wherein: In step (1), the amount of the bio-based wetting agent used is 100-500 μg relative to 1 g of the emulsified crude oil.

34. The method of claim 29, wherein: In step (1), the solvent is water.

35. The method of claim 29, wherein: In step (1), the mass ratio of the emulsified crude oil to the solvent is 3-20:

1.

36. The method of claim 29, wherein: In step (1), the mass ratio of the emulsified crude oil to the solvent is 5-10:

1.

37. The method according to any one of claims 29 to 36, wherein: In step (1), the conditions of the electrical desalination treatment include: temperature of 90-140° C.; electric field strength of 100-300 V / cm; and time of 0.5-3 h.

38. The method according to any one of claims 29 to 36, wherein: In step (1), the conditions of the electrical desalination treatment include: temperature of 90-120°C; electric field strength of 150-250 V / cm; and time of 1-2 hours.

39. The method according to any one of claims 29 to 36, wherein: The content of iron in the emulsified crude oil is 205-300 μg relative to 1 g of the emulsified crude oil.

40. The method according to any one of claims 29 to 36, wherein: The density of the emulsified crude oil at 20°C is not higher than 950 kg / cm 3 , viscosity at 80℃ is not higher than 390 mm 2 / s.

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