Composition for treating iron-containing sulfide, application of composition and method for treating emulsified crude oil containing iron-containing sulfide solid particles

Abstract

The invention relates to the field of petrochemical engineering, and discloses a composition for treating iron-containing sulfide, application of the composition and a method for treating emulsified crude oil containing iron-containing sulfide solid particles. The composition contains a demulsifier and a bio-based wetting agent which are stored independently or stored in a mixed mode of two or more of the demulsifier and the bio-based wetting agent. Wherein the demulsifying agent is a polyether imidazoline compound; the bio-based wetting agent is sophorolipid ether; the content mass ratio of the demulsifier to the bio-based wetting agent is 1: (0.5-5); the polyether imidazoline compound is alkyl phenolic resin polyether imidazoline. The composition can effectively remove iron-containing sulfide solid particles in emulsified crude oil, and the bio-based wetting agent in the composition has better biodegradability.

Description

Technical Field

[0001] The invention relates to the field of petrochemical industry, and in particular to a composition for treating iron sulfide and an application thereof, and a method for treating emulsified crude oil containing iron sulfide solid particles. Background Art

[0002] Crude oil contains impurities that can cause corrosion, heat exchanger fouling, furnace coking, catalyst deactivation, and product quality degradation. These impurities include salts, sediment and water (BS&W), solids, and metals.

[0003] The salt in crude oil includes chloride salts of sodium, calcium, and magnesium, among which NaCl is the main salt. These chloride salts are hydrolyzed during atmospheric distillation to generate corrosive HCl, which causes corrosion at the top of the fractionation tower. Therefore, refineries need to remove salt from crude oil through the electrical desalting process.

[0004] Solids in crude oil include silt, clay, volcanic ash, drilling mud, ferrous sulfide, scale, etc. These solids lead to scaling, wear, blockage and degradation of residual oil quality. On the other hand, solid particles are wrapped by oil and accumulate at the oil-water interface, becoming natural emulsifiers that are wetted by both oil and water, hindering the aggregation of water droplets, reducing the demulsification efficiency, and forming an emulsion layer at the oil-water interface, resulting in an increase in the electrical desalting current, a decrease in desalting efficiency, and an increase in the oil content of the drainage water.

[0005] As some processed crude oil is mixed with iron-containing clear oil, dirty oil or iron-containing acidified oil produced during oil field exploitation, the iron content in crude oil increases. Crude oil containing iron sulfide solid particles will cause more serious emulsification problems, especially heavy oil containing iron sulfide solid particles. These very fine iron sulfide solid particles form a crude oil emulsion layer at the oil-water interface, which will cause current increase or tripping. In addition, the thickening of the emulsion layer will increase the oil content of the drainage. The dirty oil recovered from the oily wastewater is difficult to handle. If it is reused in the electric desalination, it will have an impact on the electric desalination and aggravate the deterioration of the electric desalination operation.

[0006] In order to solve the emulsification problem caused by iron sulfide solid particles, Xia Fujun, Wu Di et al. (Recovery and treatment technology of waste oil containing ferrous sulfide particles [J]. Petroleum Planning and Design, 2006, 17(5):4.) and Wu Di, Zhang Zhijun et al. (Synergistic treatment of waste oil containing ferrous sulfide particles using surfactants and sulfide removers [C]. The 15th National Industrial Surfactant Development Seminar and the 13th National Industrial Surfactant Development Seminar. 2004.) used waste oil demulsifiers, sulfide removers and sulfide inhibitors to treat waste oil containing FeS.

[0007] CN101050382A discloses a demulsifier for reducing the FeS particle content in electrical desalination / dehydration wastewater and its preparation method, which adopts nano water purifier, imidazoline polyether surfactant and alcohol solvent to solve the problem of high FeS content in electrical desalination wastewater.

[0008] However, since the principle of the above two methods is to disperse 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, therefore, its influence on subsequent processing cannot be eliminated.

[0009] US4722781A discloses a method for treating water-insoluble FeS crude oil, that is, extracting the electro-desalting emulsified layer, returning most of it to the crude oil, and adding the other part to light diluent oil. This method may be suitable for light crude oil, but for heavy crude oil, the emulsified layer is returned to the crude oil, which will aggravate the deterioration of electro-desalting and generate more emulsified layers, forming a vicious circle.

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

[0011] US6132619A discloses a method for treating an emulsion (e.g., iron-containing sludge / emulsion), in which an iron inhibitor and a demulsifier are used to treat the iron-containing acidified oil produced during the oil production process. The iron inhibitors used are nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), etc., and their 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 adsorb at the oil-water interface and cannot enter the water phase. For crude oil with a high iron content in solid particles, the effect of using demulsifiers alone is limited. The combined use of wetting agents and demulsifiers can be used to solve this problem.

[0013] The commonly used wetting agents in industry are nonylphenol polyoxyethylene ethers, but the wetting effect of conventional wetting agents is limited, and the wetting agents themselves are toxic and will cause harm to the environment if they enter the water. Summary of the invention

[0014] The purpose of the present invention is to overcome the problems in the prior art that the treatment effect of emulsified crude oil with a high iron sulfide content is poor and the treatment method is not environmentally friendly.

[0015] In order to achieve the above object, the first aspect of the present invention provides a composition for treating iron sulfide, wherein the composition contains the following components which are stored separately or in a mixture of two or more:

[0016] Demulsifiers, bio-based wetting agents;

[0017] 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;

[0018] The polyether imidazoline compound is an alkylphenol-formaldehyde resin polyether imidazoline, which has a general structure shown in Formula I:

[0019]

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

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

[0022] A third aspect of the present invention 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 described in the first aspect in the presence of a solvent to perform an electrical desalting treatment to obtain a mixed oil;

[0024] (2) Separating the mixed oil into water to obtain a water phase and an oil phase respectively.

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

[0026] The endpoints and any values ​​of the ranges disclosed in this article are not limited to the precise ranges or values, and these ranges or values ​​should be understood to include values ​​close to these ranges or values. For numerical ranges, the endpoint values ​​of each range, the endpoint values ​​of each range and the individual point values, and the individual point values ​​can be combined with each other to obtain one or more new numerical ranges, which should be considered as specifically disclosed in this article.

[0027] In the present invention, unless otherwise stated, the pressures described are gauge pressures.

[0028] In the present invention, unless otherwise stated, the iron element refers to the iron element in the form of molecules in the form of solid particles or complexes. The iron content in the drainage, the iron content in the upper layer oil, and the iron content in the lower layer oil all refer to the content of the iron element in the form of molecules in the form of solid particles or complexes in the corresponding contents.

[0029] In the present invention, unless otherwise specified, "first", "second", "third", "fourth" and "fifth" do not represent a sequence of precedence or sequence, nor do they limit the materials or operations. They are only used to distinguish between the materials or operations. For example, the "first", "second", "third", "fourth" and "fifth" in "first reaction", "second reaction", "third reaction", "fourth reaction" and "fifth reaction" are only used to distinguish to indicate that these are not the same reaction.

[0030] As mentioned above, the first aspect of the present invention provides a composition for treating iron-containing sulfides, wherein the composition contains the following components which are stored separately or in a mixture of two or more:

[0031] Demulsifiers, bio-based wetting agents;

[0032] 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;

[0033] The polyether imidazoline compound is an alkylphenol-formaldehyde resin polyether imidazoline, which has a general structure shown in Formula I:

[0034]

[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 invention, preferably, the mass ratio of the demulsifier to the bio-based wetting agent is 1:1.25-3. The above preferred embodiment is conducive to further removing iron-containing sulfides in the emulsified crude oil and obtaining a better iron-containing sulfide removal effect.

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

[0038] (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;

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

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

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

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

[0043] According to some embodiments of the present invention, 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 to the homogeneous solution.

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

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

[0046] According to some embodiments of the present invention, preferably, 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.

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

[0048] According to some embodiments of the present invention, preferably, 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.

[0049] According to some embodiments of the present invention, preferably, 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.

[0050] According to some embodiments of the present invention, the polyether imidazoline compound is an alkylphenol-formaldehyde resin polyether imidazoline having a general structure shown in Formula I:

[0051]

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

[0053] Preferably, the polyether imidazoline compound is nonylphenolic resin polyether imidazoline, that is, R is nonyl in Formula I. The above preferred embodiment is conducive to further removing iron-containing sulfides in emulsified crude oil and obtaining a better iron-containing sulfide removal effect.

[0054] According to some embodiments of the present invention, the polyether imidazoline compound can be commercially available or prepared by itself.

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

[0056] (S1) contacting an alkylphenol-formaldehyde 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 invention, preferably, in step (S1), the alkylphenol-formaldehyde resin polyether has a general structure shown in Formula II:

[0059]

[0060] Wherein, R, a, x, and y are defined and selected as above and will not be described in detail here;

[0061] Preferably, the alkylphenol-formaldehyde resin polyether is nonylphenol-formaldehyde resin polyether.

[0062] According to some embodiments of the present invention, the alkylphenol-formaldehyde resin polyether can be commercially available or prepared by itself.

[0063] According to a preferred embodiment of the present invention, the alkylphenol-formaldehyde resin polyether is prepared by a method comprising the following steps:

[0064] 1) Under an inert atmosphere, an alkylphenol-formaldehyde resin and a base I are contacted with propylene oxide to react to obtain an intermediate product; wherein:

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

[0066] The reaction conditions include: temperature of 125-135°C, pressure of 0.1-0.5MPa, and time of 15min-2h;

[0067] 2) under an inert atmosphere, contacting the intermediate product and base II with ethylene oxide to react to obtain an alkylphenol-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 of 115-125° C., pressure of 0.1-0.5 MPa, and time of 15 min-2 h.

[0070] Preferably, in step 1), the alkylphenol-formaldehyde resin can be obtained commercially or prepared by itself. The preparation method thereof may include:

[0071] In the presence of a catalyst, alkylphenol and formaldehyde are subjected to a condensation reaction. The catalyst may be an acid or a base. The specific reaction conditions are well known to those skilled in the art and will not be described in detail herein.

[0072] Preferably, in step 1), the degree of polymerization of the alkylphenol-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 invention, preferably, the weight average molecular weight of the alkylphenol-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 invention, preferably, in step (S1), the mass ratio of the alkylphenol-formaldehyde resin polyether to the succinic anhydride is 90-150:8, preferably 100-120:8, and more preferably 100-110:8.

[0075] According to some embodiments of the present invention, 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° C., preferably 105-115° C.; time of 1-8 h, preferably 2-6 h.

[0078] According to some embodiments of the present invention, 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 invention, 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 contacting step comprises: first mixing the carboxylated polyether with diethylenetriamine at a temperature of 140-160°C, preferably 145-155°C, and then heating to 230-250°C, preferably 235-245°C, until no water is generated.

[0083] According to some embodiments of the present invention, the composition uses a specific demulsifier and a specific bio-based wetting agent in a specific mass ratio, which can release solid iron sulfide particles from the emulsion layer, transfer them from the oil phase to the water phase, aggregate and grow, and sink to the bottom of the water phase, and then remove the iron sulfide in the emulsified crude oil through subsequent separation of the water phase and the oil phase.

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

[0085] The composition provided by the invention can be used for demulsification and dehydration of crude oil in the process of oil mining and transportation, and can also be used for electrical desalination of crude oil in refineries.

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

[0087] A third aspect of the present invention 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 described in the first aspect in the presence of a solvent to perform an electrical desalting treatment to obtain a mixed oil;

[0089] (2) Separating the mixed oil into water to obtain a water phase and an oil phase respectively.

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

[0091] According to some embodiments of the present invention, preferably, in step (1), the amount of the demulsifier used 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 invention, preferably, in step (1), the amount of the bio-based wetting agent used is 50-1000 μg, preferably 100-500 μg, relative to 1 g of the emulsified crude oil.

[0093] The use of the raw material dosage in the above preferred embodiment 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 invention, preferably, in step (1), the solvent is water, for example, deionized water.

[0095] According to some embodiments of the present invention, 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 invention, preferably, in step (1), the conditions of the electrical desalination treatment include: temperature of 90-140°C, preferably 90-120°C; electric field strength of 100-300V / cm, preferably 150-250V / cm; time of 0.5-3h, preferably 1-2h.

[0097] Adopting the conditions of the above preferred implementation mode is conducive to further removing the iron-containing sulfide in the emulsified crude oil and obtaining a better iron-containing sulfide removal effect.

[0098] According to some embodiments of the present invention, preferably, the content of iron 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 invention, preferably, the density of the emulsified crude oil at 20°C is not higher than 950 kg / cm 3 , 80℃ viscosity is not higher than 390mm 2 / s.

[0100] The method provided by the present invention can also remove other metal elements in the emulsified crude oil, for example, such as calcium or sodium. Since the main concern in the field is the iron content in the emulsified crude oil, the present invention mainly involves the treatment of the iron element in the emulsified crude oil.

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

[0102] In the following examples and comparative examples, unless otherwise specified, all raw materials used are commercially available.

[0103] Sophorolipids: lactone type, purchased from Shandong Qilu Biotechnology Group Co., Ltd.;

[0104] Methanol: purchased from Inotech Reagent Company;

[0105] Propylene oxide: purchased from Inotech Reagent Company;

[0106] Ethylene oxide: purchased from Inotech Reagent Company;

[0107] 70 wt% sulfuric acid aqueous solution: purchased from Inokane Reagent Company;

[0108] The nonylphenol-formaldehyde resin polyether is prepared by a method comprising the following steps:

[0109] 1) Preparation of nonyl phenolic resin

[0110]

[0111] 100 g of nonylphenol (molecular weight 220) was added into a three-necked flask, immersed in a 75° C. constant temperature water bath, a certain amount of concentrated hydrochloric acid (37 wt %) was added to make the solution pH 3-5, 38.9 g of formaldehyde (35 wt %) (molecular weight 30) was added dropwise with stirring, the formaldehyde addition speed was controlled to be 1 drop / s, and the addition was completed within 1 h, the polymerization temperature did not exceed 80° C., the supernatant was removed from the product, and the product was washed with water to obtain a nonylphenol-formaldehyde resin (whose weight average molecular weight was 970 g / mol and degree of polymerization was 4);

[0112] 2) Preparation of nonylphenolic resin polyether

[0113]

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

[0115] 100 g of the intermediate product and 1.86 g of potassium hydroxide were added to a high-pressure reactor, purged with nitrogen and evacuated, stirring was started and the temperature was raised to 120°C, and then 19 g of ethylene oxide was added dropwise at a pressure of 0.3 MPa and a temperature of 125°C. After the addition was completed, the reaction was continued for 0.5 h, and the material was cooled and discharged to obtain nonylphenolformaldehyde resin polyether (whose weight average molecular weight was 1244 g / mol and hydroxyl value was 45 mgKOH / g).

[0116] Nonylphenol polyoxyethylene ether: brand NP7, purchased from Jiangsu Haian Petrochemical Plant;

[0117] SEM-EDS analysis: The analysis was performed using a scanning electron microscope thermogravimetric instrument.

[0118] Emulsified crude oil is a mixture of crude oil and clear tank oil containing iron sulfide. Its properties are shown in Table 1.

[0119] Table 1

[0120] project Emulsified crude oil <![CDATA[Density (20 °C), kg / cm 3 > 942.7 <![CDATA[Viscosity (80 °C), mm 2 / s]]> 385.3 w(Fe), μg / g 208 w(colloid),% 10.6 w(asphaltene), % 14.8 w(ash content), % 0.051 Acid value, mgKOH / g 0.13 ρ(salt), mgNaCl / kg 32

[0121] The emulsified crude oil was diluted with xylene, and after filtering out 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] Element types of mechanical impurities Impurity content / wt% w(Na) 0.20 w(Mg) 0.43 w(S) 1.49 w(Ca) 0.78 w(Fe) 4.19

[0124] In each of the embodiments and comparative examples, the iron content in the drainage, the iron content in the upper layer oil, and the iron content in the lower layer oil were determined by plasma inductively coupled emission spectroscopy (ICP).

[0125] The following preparation examples are used to illustrate sophorolipid ethers and their preparation methods

[0126] Preparation Example A1

[0127] (a) in the presence of an acidic catalyst I, 50 g of sophorolipid is contacted with methanol for 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 sulfuric acid aqueous solution with a mass fraction of 70 wt%;

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

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

[0131] The conditions for the first reaction were: temperature 40°C, time 1.5 h;

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

[0133] The alkaline catalyst I is KOH; the mass ratio of the alkaline catalyst I, sophorolipid methyl ester, propylene oxide and 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 conditions of the second reaction were: temperature 130°C, time 1h, pressure 0.3MPa;

[0136] The conditions of the third reaction are: temperature of 120° C., time of 1 h, and pressure of 0.3 MPa.

[0137] Preparation Example A2

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

[0139] Preparation Example A3

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

[0141] The following preparation examples are used to illustrate polyether imidazoline compounds and their preparation methods.

[0142] Preparation Example B1

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

[0144] The alkylphenol-formaldehyde resin polyether is nonylphenol-formaldehyde resin polyether;

[0145] The mass ratio of alkylphenol-formaldehyde resin polyether to succinic anhydride is 100:8;

[0146] The fourth reaction is a carboxylation reaction; the conditions of 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 above carboxylated polyether with diethylenetriamine to carry out a fifth reaction to obtain a 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 contacting steps are: first, at a temperature of 150° C., diethylenetriamine is added dropwise to the carboxylated polyether 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 of 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] Relative to 1g of emulsified crude oil, the amount of demulsifier used is 80μg; relative to 1g of emulsified crude oil, the amount of bio-based wetting agent used is 100μg; the mass ratio of emulsified crude oil to solvent is 5:1;

[0163] Before contact, the emulsified crude oil was preheated to 85°C;

[0164] The conditions for the electrical desalination treatment were: temperature 90°C; electric field strength 180V / cm; time 1h;

[0165] (2) separating the mixed oil into water to obtain a water phase and an oil phase respectively;

[0166] The water phase is drawn off, sufficient acid is added to dissolve the metal in the water phase, filtered, and the iron content of the filtrate is determined, which is the iron content in the drainage water;

[0167] 45 g of the upper layer oil was taken as the upper layer oil, and 15 g of the lower layer oil was taken as the lower layer oil, and the iron content of the upper layer oil and the iron content of the lower layer oil were measured respectively. The measurement results are shown in Table 3.

[0168] Example 2

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

[0170] Example 3

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

[0172] Example 4

[0173] The method of Example 1 is different from that of Example 1:

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

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

[0176] The conditions for the electrical desalination treatment are: temperature 120°C; electric field strength 220V / cm; time 2h;

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

[0178] Comparative Example 1

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

[0180] Comparative Example 2

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

[0182] Comparative Example 3

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

[0184] Comparative Example 4

[0185] The method of Example 3 was followed, except that no demulsifier was used and only a bio-based wetting agent was used; the rest was the same, and the measurement results are shown in Table 3.

[0186] Table 3

[0187]

[0188]

[0189] It can be seen from the above results that the use of the composition provided by the present invention to treat emulsified crude oil with a high content of iron sulfide solid particles can significantly increase the iron content in the drainage, and the treatment effect is good.

[0190] Test Case

[0191] The biodegradability of the bio-based wetting agent prepared in the present invention and the nonylphenol polyoxyethylene ether used in the comparative example were tested, and the ratio (B / C) of biological oxygen demand (BOD) to chemical oxygen demand (CODcr) was used to represent the biodegradability. The test results are shown in Table 4. Among them:

[0192] BOD is tested using the determination method of standard HJ505-2009 "Five-day biochemical oxygen demand of water quality";

[0193] CODcr is tested using standard HJ828-2017 "Determination of Chemical Oxygen Demand in Water - Dichromate Method".

[0194] Table 4

[0195] project B / C Sophorolipid ether AZ1 0.31 Sophorolipid ether AZ2 0.31 Sophorolipid ether AZ3 0.31 Nonylphenol polyoxyethylene ether (NP7) 0

[0196] It can be seen from the above results that, compared with the existing conventional wetting agents, the bio-based wetting agent used in the present invention has better biodegradability and better environmental protection.

[0197] The preferred embodiments of the present invention are described in detail above, but the present invention is not limited thereto. Within the technical concept of the present invention, the technical solution of the present invention can be subjected to a variety of simple modifications, including the combination of various technical features in any other suitable manner, and these simple modifications and combinations should also be regarded as the contents disclosed by the present invention and belong to the protection scope of the present invention.

Claims

1. A composition for treating iron sulfide, characterized in that: The composition contains the following components which are stored separately 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 a general structure shown in 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 for a second reaction, and contacting the resulting reaction product with ethylene oxide for a third reaction.

4. The composition according to claim 3, wherein In step (a), the acidic catalyst I is sulfuric acid; the sulfuric acid is provided in the form of a sulfuric acid aqueous solution with a mass fraction of 70 wt % or more; Preferably, in step (a), the mass ratio of the acidic catalyst I to the sophorolipid is 0.5-2.5:50, preferably 1-2:50; Preferably, in step (a), the ratio of the sophorolipid to the methanol is 1 g: 3.5-5 mL; Preferably, in step (a), the conditions of the first reaction include: temperature of 30-50° C., and time of 1-5 h.

5. The composition according to claim 3 or 4, wherein In step (b), the alkaline catalyst I is KOH; Preferably, 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; Preferably, in step (b), the second reaction and the third reaction are carried out under an inert atmosphere; Preferably, in step (b), the conditions of the second reaction include: temperature of 100-140°C, time of 0.5-5h, and pressure of 0.1-0.4MPa; Preferably, 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.

6. The composition according to any one of claims 1 to 5, wherein In Formula I, R is nonyl; a is 4-6; Preferably, 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.

7. The composition according to claim 6, wherein In step (S1), the mass ratio of the alkylphenol-formaldehyde resin polyether to the succinic anhydride is 90-150:8, preferably 100-120:8, more preferably 100-110:8; Preferably, the fourth reaction is a carboxylation reaction; the conditions of the fourth reaction include: a temperature of 100-120° C., preferably 105-115° C.; and a time of 1-8 h, preferably 2-6 h.

8. The composition according to claim 6 or 7, wherein In step (S2), the mass ratio of the carboxylated polyether to the diethylenetriamine is 11-15:1, preferably 12-14:1; Preferably, in step (S2), the fifth reaction includes an amidation reaction and a cyclization reaction; the contacting step includes: first mixing the carboxylated polyether with diethylenetriamine at a temperature of 140-160°C, preferably 145-155°C, and then heating to 230-250°C, preferably 235-245°C.

9. Use of the composition according to any one of claims 1 to 8 in treating emulsified crude oil containing iron sulfide solid particles.

10. 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 8 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 respectively.

11. The method according to claim 10, wherein: 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; Preferably, in step (1), the amount of the bio-based wetting agent used is 50-1000 μg, preferably 100-500 μg, relative to 1 g of the emulsified crude oil; Preferably, in step (1), the solvent is water; Preferably, in step (1), the mass ratio of the emulsified crude oil to the solvent is 3-20:1, preferably 5-10:

1.

12. The method according to claim 10 or 11, wherein: In step (1), the conditions of the electrical desalination treatment include: temperature of 90-140°C, preferably 90-120°C; electric field strength of 100-300V / cm, preferably 150-250V / cm; time of 0.5-3h, preferably 1-2h.

13. The method according to any one of claims 10 to 12, wherein: The content of iron in the emulsified crude oil is 205-300 μg relative to 1 g of the emulsified crude oil; Preferably, the density of the emulsified crude oil at 20°C is not higher than 950 kg / cm 3 , 80℃ viscosity is not higher than 390mm 2 / s.

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