CN114958417B

CN114958417B - Application of bio-based wetting agent, composition for treating iron-containing sulfide, treatment method and application

Info

Publication number: CN114958417B
Application number: CN202110199869.3A
Authority: CN
Inventors: 王振宇; 于丽; 陆语; 张峰; 沈明欢; 苗杰
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2021-02-22
Filing date: 2021-02-22
Publication date: 2023-08-08
Anticipated expiration: 2041-02-22
Also published as: CN114958417A

Abstract

The invention relates to the field of petrochemical industry, and discloses application of a bio-based wetting agent, a composition for treating iron-containing sulfide, a treatment method and application. The composition for treating the iron-containing sulfide contains the following components which are stored independently or stored in a mixed way: a bio-based wetting agent, an oil-soluble demulsifier, and a water-soluble demulsifier; the bio-based wetting agent is at least one selected from sophorolipid methyl ester and sophorolipid carboxylic acid. When the bio-based wetting agent is used for treating emulsified crude oil containing iron sulfide, the bio-based wetting agent is easier to biodegrade than the wetting agent in the prior art, and does not bring about the problem of environmental pollution.

Description

Application of bio-based wetting agent, composition for treating iron-containing sulfide, treatment method and application

Technical Field

The invention relates to the field of petrochemical industry, in particular to application of a bio-based wetting agent, a composition for treating iron-containing sulfide, a treatment method and application.

Background

Crude oil contains impurities such as salt, sediment, water (Bs & W), solids, metals and the like, and the presence of the impurities can lead to corrosion, heat exchanger scaling, furnace coking, catalyst deactivation and product quality degradation.

Solids in crude oil include silt, clay, volcanic ash, drilling mud, ferrous sulfide, scale and the like, wherein crude oil containing iron sulfide solid particles can cause serious emulsification problems, particularly thick oil containing iron sulfide solid particles, the very fine iron sulfide solid particles form a crude oil emulsion layer at an oil-water interface, the phenomenon of current rise or tripping can be caused, in addition, thickening of the emulsion layer can cause the increase of drainage oil content, dirty oil recovered from oily wastewater is difficult to treat, impact is caused to electric desalting if the oil is recycled, and the deterioration of electric desalting operation is aggravated. Therefore, how to solve the problem of emulsification caused by solid particles of iron sulfide becomes a hot spot of researchers at home and abroad.

CN108264926a discloses a method for treating emulsified crude oil containing iron sulfide solid particles, which uses an oil-soluble demulsifier to treat emulsified crude oil, and then uses a water-soluble demulsifier to treat the emulsified crude oil, so that the iron sulfide solid particles are transferred from an oil phase to an aqueous phase.

Currently, emulsified crude oils with high iron content of iron-containing sulfide solid particles are typically treated with a combination of wetting agents and demulsifiers. The wetting agent commonly used in industry is nonylphenol polyoxyethylene ether, but the wetting effect of the wetting agent is poor, and the wetting agent is toxic, and the entering water can cause harm to the environment.

Disclosure of Invention

The invention aims to solve the problems of poor effect and environmental pollution in the prior art for treating emulsified crude oil with higher iron-containing sulfide content.

In order to achieve the above object, the first aspect of the present invention provides a use of a bio-based wetting agent selected from at least one of methyl sophorolipid and sophorolipid carboxylic acid in treating emulsified crude oil.

In a second aspect, the present invention provides a composition for treating iron-containing sulphides, the composition comprising the following components, each independently or in combination:

a bio-based wetting agent, an oil-soluble demulsifier, and a water-soluble demulsifier;

the bio-based wetting agent is selected from at least one of sophorolipid methyl ester and sophorolipid carboxylic acid;

the oil-soluble demulsifier contains alkyl ester of styrene-maleic anhydride copolymer and/or alkyl phenolic resin polyether;

the water-soluble demulsifier contains glycerol polyoxyethylene polyoxypropylene ether and/or cationic hydroxyl silicone oil;

the content of the bio-based wetting agent is 80-10000 parts by weight, and the content of the water-soluble demulsifier is 80-1500 parts by weight, relative to 100 parts by weight of the oil-soluble demulsifier.

In a third aspect the invention provides the use of a composition according to the second aspect for treating emulsified crude oil containing iron sulphide solid particles.

In a fourth aspect the invention provides a method of treating emulsified crude oil containing iron sulphide solid particles, the method comprising:

(1) Mixing the emulsified crude oil with the components in the composition according to the second aspect in the presence of a solvent to obtain a mixed oil;

(2) And (3) carrying out oil-water separation on the mixed oil to obtain an aqueous phase and an oil phase respectively.

The inventor finds that when the bio-based wetting agent disclosed by the invention is used for treating emulsified crude oil containing iron sulfide, the bio-degradation can be easier than that of the wetting agent in the prior art, and the problem of environmental pollution is avoided.

In particular, the inventor also found that the composition according to the second aspect of the invention is formed by adopting the bio-based wetting agent according to the invention and cooperatively combining components such as the oil-soluble demulsifier, the water-soluble demulsifier and the like with specific content and specific type, and the iron-containing sulfide in the emulsified crude oil can be removed more effectively by adopting each component in the composition to treat the emulsified crude oil with higher iron-containing sulfide.

Detailed Description

The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.

In the present invention, the aromatic hydrocarbon solvent I and the aromatic hydrocarbon solvent II are each independently selected from at least one of benzene, toluene and xylene, unless otherwise stated.

In the present invention, unless otherwise indicated, the pressures are gauge pressures.

In the present invention, unless otherwise specified, the iron element refers to an iron element in a molecular form existing in a solid particle or a complex state. The iron content of the drain water, the iron content of the upper oil and the iron content of the lower oil refer to the content of iron elements in molecular forms existing in a solid particle or a complex state in the corresponding content.

In the present invention, the basic catalyst II, the basic catalyst III and the basic catalyst IV are each independently selected from sodium hydroxide and/or potassium hydroxide, unless otherwise stated.

As previously mentioned, a first aspect of the present invention provides the use of a bio-based wetting agent selected from at least one of methyl sophorolipid, sophorolipid carboxylic acid in the treatment of emulsified crude oil.

Preferably, the content of iron element in the emulsified crude oil is 100-200ppm.

As previously described, the second aspect of the present invention provides a composition for treating iron-containing sulfides, the composition comprising the following components, each independently or in admixture:

Preferably, the bio-based wetting agent is contained in an amount of 500 to 1800 parts by weight and the water-soluble demulsifier is contained in an amount of 200 to 500 parts by weight with respect to 100 parts by weight of the oil-soluble demulsifier.

According to a particularly preferred embodiment, the sophorolipid methyl ester is prepared by a process comprising the steps of: in the presence of an acidic catalyst I, sophorolipid and methanol are subjected to a contact reaction I.

Preferably, the acidic catalyst I is selected from sulfuric acid having a concentration of 70wt% or more. Illustratively, the acidic catalyst I is selected from sulfuric acid having a concentration of 70 wt%.

Preferably, the amount of the acidic catalyst I, the sophorolipid and the methanol is 1 in mass ratio: 10-30:30-80.

Preferably, the conditions of the contact reaction I include: the temperature is 30-50deg.C, and the time is 0.5-5h.

According to a particularly preferred embodiment, the sophorolipid carboxylic acid is prepared by a process comprising the steps of: in the presence of a basic catalyst I, sophorolipids, water and ethanol are subjected to a contact reaction II.

Preferably, the basic catalyst I is KOH.

Preferably, the using amount mass ratio of the sophorolipid, the water and the ethanol is 1:1-3:3-5, wherein the dosage mass ratio of the sophorolipid to the alkaline catalyst I is 15-25:1.

preferably, at least the conditions of the contact reaction II are: the time is 1-4h.

Preferably, the reaction temperature of the contact reaction II is such that reflux of the reaction system can occur.

According to a particularly preferred embodiment, the oil-soluble demulsifier is present in an amount of from 0.2 to 2 by mass: 1 and an alkyl phenol-formaldehyde resin polyether.

More preferably, in the oil-soluble demulsifier, the content mass ratio of the alkyl ester of the styrene-maleic anhydride copolymer to the alkyl phenolic resin polyether is 0.5-1.5:1. in this preferred case, significantly more of the iron-containing sulfide solid particles in the emulsified crude oil can be washed into the aqueous phase, significantly increasing the iron content of the drainage.

According to a particularly preferred embodiment, the alkyl ester of a styrene-maleic anhydride copolymer is prepared by a process comprising the steps of:

(a) In the presence of an initiator, carrying out copolymerization reaction on a styrene monomer and a maleic anhydride monomer to obtain a styrene-maleic anhydride copolymer;

(b) In the presence of an acid catalyst II, the styrene-maleic anhydride copolymer and fatty alcohol with 12-30 carbon atoms are subjected to esterification reaction.

In the present invention, the step (a) and the step (b) may be performed in an aromatic hydrocarbon solvent I, and the aromatic hydrocarbon solvents I may be the same or different. Preferably, the aromatic hydrocarbon solvent I of step (a) and step (b) are the same.

Preferably, in step (a), the initiator is selected from at least one of Benzoyl Peroxide (BPO), azobisisobutyronitrile.

Preferably, in step (a), the initiator is used in an amount of 0.1 to 1wt%, preferably 0.3 to 0.8wt% based on the total weight of the monomers.

Preferably, in step (a), the molar ratio of the styrene monomer to the maleic anhydride monomer is in the range of 0.8 to 1.5:1, preferably 0.9-1.1:1.

the desired molecular weight of the styrene-maleic anhydride copolymer can be obtained in the course of the copolymerization described in step (a) of the present invention, for example, using a molecular weight regulator, such as, for example, dodecyl mercaptan.

Preferably, in step (a), the weight average molecular weight of the styrene-maleic anhydride copolymer is 500-20000, preferably 1000-10000.

Preferably, in step (a), the conditions of the copolymerization reaction include: the temperature is 80-90 ℃ and the time is 1-8h.

Preferably, in step (b), the fatty alcohol has a carbon number of 16-20.

Preferably, in step (b), the acidic catalyst II is selected from at least one of sulfuric acid, phosphoric acid and p-toluenesulfonic acid.

Preferably, in step (b), the esterification reaction conditions include at least: reflux temperature, time is 0.5-10h.

According to a particularly preferred embodiment, the alkylphenol polyether is one in which the alkyl chain is C ₃ -C ₁₀ The alkoxide of the alkylphenol resin of (2), preferably having C as the alkyl chain ₅ -C ₇ Alkoxide of alkyl phenol resin.

Preferably, the alkyl phenolic polyether is prepared by a process comprising the steps of: in the presence of an alkaline catalyst II, the alkyl phenolic resin is subjected to synthetic reaction with propylene oxide and ethylene oxide in sequence.

Preferably, the molar ratio of the alkyl phenolic resin to the epoxy propane to the epoxy ethane is 1:5-20:1-10, preferably 1:7-15:3-6.

Preferably, the weight average molecular weight of the alkylphenol resin is 500-10000, preferably 1000-5000.

According to a particularly preferred embodiment, the alkylphenol polyether is prepared by a process comprising the steps of: in the presence of an aromatic hydrocarbon solvent II and a basic catalyst II, carrying out a contact reaction III on alkyl phenolic resin and propylene oxide, and then carrying out a contact reaction IV on the obtained reaction product and ethylene oxide.

Preferably, the basic catalyst II is used in an amount of 0.3 to 2% by weight and the aromatic hydrocarbon solvent II is used in an amount of 5 to 10% by weight, based on the total weight of the alkylphenol resin, propylene oxide and ethylene oxide.

Preferably, the conditions of the contact reaction III include: the temperature is 130+/-5 ℃, the pressure is 0.1-0.5MPa, and the time is 15-120 min.

Preferably, the conditions of the contact reaction IV include: the temperature is 110+/-5 ℃, the pressure is 0.1-0.5MPa, and the time is 15-120 min.

The source of the alkyl phenol resin is not particularly limited, and the alkyl phenol resin can be commercially available or prepared by itself. Preferably, the alkyl phenol-formaldehyde resin is prepared by a process comprising the steps of: the alkylphenol and formaldehyde are subjected to a condensation reaction in the presence of a catalyst, which may be an acid or a base, and specific reaction conditions are well known to those skilled in the art and will not be described in detail herein, and those skilled in the art should not be construed as limiting the present invention.

The kind of the alkylphenol is not particularly limited in the present invention, and the alkylphenol may be, for example, tert-butylphenol or nonylphenol.

Preferably, the water-soluble demulsifier is prepared from the following components in percentage by mass of 2-10:1 and cationic hydroxy silicone oil.

Preferably, the content mass ratio of the glycerol polyoxyethylene polyoxypropylene ether to the cationic hydroxyl silicone oil is 3-7:1. the inventors have found that in this preferred case the process of the present invention is able to wash significantly more of the iron-containing sulphide solid particles in the emulsified crude oil into the aqueous phase, thereby significantly increasing the iron content of the drainage.

In the method of the invention, the glycerol polyoxyethylene polyoxypropylene ether can be obtained commercially or prepared by itself. According to a particularly preferred embodiment, the glycerol polyoxyethylene polyoxypropylene ether is prepared by a process comprising the steps of: in the presence of a basic catalyst III, glycerol and propylene oxide are subjected to a contact reaction V, and then the obtained intermediate product is subjected to a contact reaction VI with ethylene oxide.

Preferably, propylene oxide is used in an amount of 20 to 90mol and ethylene oxide is used in an amount of 10 to 70mol relative to 1mol of glycerol. More preferably, propylene oxide is used in an amount of 50 to 70mol and ethylene oxide is used in an amount of 20 to 50mol with respect to 1mol of glycerol.

Preferably, the basic catalyst III is used in an amount of 0.3 to 2% by weight, based on the total weight of glycerol and propylene oxide.

Preferably, the conditions of the contact reaction V include: the temperature is 135+ -5deg.C, the pressure is 0.1-0.5MPa, and the time is 15min-120min.

Preferably, the conditions of the contact reaction VI include: the temperature is 125+/-5 ℃, the pressure is 0.1-0.5MPa, and the time is 15-120 min.

In the process of the present invention, the cationic hydroxy silicone oils may be obtained commercially or may be prepared by themselves. According to another particularly preferred embodiment, the cationic hydroxy silicone oil is prepared by a process comprising the steps of: adding a cationic emulsifier and an alkaline catalyst IV into a reaction container to dissolve the cationic emulsifier and the alkaline catalyst IV in water; dropwise adding small molecular siloxane with the weight average molecular weight not higher than 500 into a reaction container under the stirring condition, heating to 50-100 ℃, and reacting at the temperature of 50-100 ℃ for 2-12h; and cooling the reactant, adding glacial acetic acid, and neutralizing to neutrality to obtain the micro blue light semitransparent cationic hydroxyl silicone oil emulsion.

Preferably, the cationic emulsifier is a cationic biquaternary surfactant, further preferably at least one of N, N-di (tetradecyldimethyl) -3-oxa-1, 5-pentanediammonium dibromide, N-di (hexadecyldimethyl) -3-oxa-1, 5-pentanediammonium dibromide, N-di (decayldimethyl) -3-oxa-1, 5-pentanediammonium dibromide.

Preferably, the cationic emulsifier is used in an amount of 1 to 10wt% based on the total weight of the cationic hydroxy silicone oil emulsion.

Preferably, the amount of the alkaline catalyst IV is 0.08-0.8wt% of the total weight of the cationic hydroxyl silicone oil emulsion.

Preferably, the small molecule siloxane is octamethyl cyclotetrasiloxane.

Preferably, the octamethyl cyclotetrasiloxane is used in an amount of 20 to 40wt% based on the total weight of the cationic hydroxyl silicone oil emulsion.

As previously mentioned, a third aspect of the invention provides the use of a composition according to the second aspect for treating emulsified crude oil containing solid particles of iron sulphide.

As previously described, a fourth aspect of the present invention provides a method of treating emulsified crude oil containing iron sulphide solid particles, the method comprising:

Preferably, in step (1), the step of mixing the emulsified crude oil with the components of the composition of the second aspect comprises: in the presence of a solvent I, mixing the emulsified crude oil, a bio-based wetting agent and an oil-soluble demulsifier, and then performing first-stage electric desalting treatment to obtain a material I; and then mixing the material I and a water-soluble demulsifier in the presence of a solvent II, and then carrying out second-stage electric desalting treatment.

Preferably, the bio-based wetting agent is used in an amount of 50-1000. Mu.g, the oil-soluble demulsifier is used in an amount of 10-60. Mu.g, and the water-soluble demulsifier is used in an amount of 50-150. Mu.g, relative to 1g of emulsified crude oil.

Preferably, the bio-based wetting agent is used in an amount of 100-500. Mu.g, the oil-soluble demulsifier is used in an amount of 20-40. Mu.g, and the water-soluble demulsifier is used in an amount of 70-120. Mu.g, relative to 1g of emulsified crude oil. The inventors have found that with this preferred embodiment, more of the iron-containing sulfide solid particles in the emulsified crude oil can be washed into the aqueous phase, thereby increasing the iron content of the drainage.

Preferably, the solvent I and the solvent II are both water.

Preferably, the dosage mass ratio of the emulsified crude oil to the solvent I is 3-20:1, preferably 6-15:1.

preferably, the dosage mass ratio of the emulsified crude oil to the solvent II is 3-20:1, preferably 6-15:1.

preferably, the conditions of the first stage electro-desalting treatment include: the temperature is 60-140 ℃, the electric field intensity is 100-300V/cm, and the time is 0.5-3h. More preferably, the conditions of the first stage electro-desalting treatment include: the temperature is 90-120 ℃, the electric field strength is 150-250V/cm, and the time is 1-2h.

Preferably, the conditions of the second stage electrical desalting treatment include: the temperature is 60-140 ℃, the electric field intensity is 100-300V/cm, and the time is 0.5-3h. More preferably, the conditions of the second stage electro-desalting treatment include: the temperature is 90-120 ℃, the electric field strength is 150-250V/cm, and the time is 1-2h.

Preferably, the emulsified crude oil has a density of not more than 960g/cm at 20 DEG C ³ Viscosity at 80deg.C is not higher than 150mm ² /s。

It should be noted that "I", "II", "III", "IV", "V", "VI" in the contact reaction I, the contact reaction II, the contact reaction III, the contact reaction IV, the contact reaction V, the contact reaction VI, and the like in the present invention are used only to indicate that six contact reactions are involved, not the same contact reaction, but this does not represent a sequence unless otherwise specified.

The invention will be described in detail below by way of examples. In the following examples, all of the raw materials used were commercial products unless otherwise specified.

Sophorolipids: lactone, available from Shandong Qilu Biotechnology group Co., ltd;

styrene: purchased from enokava reagent company;

maleic anhydride: purchased from enokava reagent company;

molecular weight regulator: dodecyl mercaptan, available from enoKai reagent company;

fatty alcohol: stearyl alcohol, available from enoKai reagent company;

fatty alcohol: cetyl alcohol, available from enoKai reagent company;

alkyl phenol resin: tertiary butyl phenol aldehyde resin, having a weight average molecular weight of 4000, available from san Laiket, shanghai;

alkyl phenol resin: a nonylphenol-formaldehyde resin having a weight average molecular weight of 3000, available from san Laikete, shanghai;

cationic emulsifier: n, N-di (tetradecyldimethyl) -3-oxa-1, 5-pentanediammonium dibromide, available from enokava reagent company;

cationic emulsifier: n, N-di (hexadecyldimethyl) -3-oxa-1, 5-pentanediammonium dibromide, available from enokava reagent company;

propylene oxide: purchased from enokava reagent company;

ethylene oxide: purchased from enokava reagent company;

70wt% sulfuric acid: purchased from enokava reagent company;

oil-soluble demulsifier: POI2420, available from Jihua Liaoyuan chemical company of limited responsibility;

a water-soluble demulsifier: SP169, purchased from Jihua Liaoyuan chemical industry Co., ltd;

nonylphenol polyoxyethylene ether: the brand is NP7, purchased from Jiangsu sea Ann petrochemical plant;

SEM-EDS analysis: and (5) adopting a scanning electron microscope thermogravimetric instrument for analysis.

Without the contrary, in the following example:

the properties of the oil blend composed of crude oil and iron-containing sulfide clean tank oil are shown in Table 1.

TABLE 1

Project
		Density (20 ℃), g/cm ³	960.0
Viscosity (80 ℃ C.) mm ² .s ^-1	136.7
		w(Fe)，μg/g	150.8

The emulsified crude oil was washed with xylene, and mechanical impurities were filtered out and analyzed by SEM-EDS, the relative content of each element in the mechanical impurities being shown in table 2. As can be seen from table 2, the mechanical impurities are mainly solid particles of iron sulphide.

TABLE 2

Mechanical impurity element species	Impurity content/wt%
		w(Na)	0.20
w(Mg)	0.43
		w(S)	1.49
w(Ca)	0.78
		w(Fe)	4.19

In each of the examples and comparative examples, the iron content of the wastewater, the iron content of the upper layer oil, and the iron content of the lower layer oil were measured by plasma inductively coupled emission spectrometry (ICP).

Preparation example 1

This preparation is used to illustrate the preparation of stearyl styrene-maleic anhydride copolymer.

To a three-necked flask, 9.8g of maleic anhydride and 60ml of toluene were added, and dissolved at 60℃and then 10.3g of styrene and 0.2g of dodecylmercaptan were added, and at 85℃40ml of toluene solution in which 0.24g of BPO was dissolved was added dropwise, and after reaction for 6 hours, filtration was carried out, and the product was dried under vacuum at 80℃for 4 hours to obtain a styrene-maleic anhydride copolymer (SMA) having a weight average molecular weight of 5000.

100ml of toluene, 8.6g of stearyl alcohol, 0.5g of p-toluenesulfonic acid and SMA (0.032 mol) prepared by the method are added into a three-port bottle, after reflux reaction is carried out for 1h, a water separator is arranged, and reflux water separation is carried out for 6h, thus obtaining styrene-maleic anhydride copolymer stearyl ester A1.

Preparation example 2

This preparation example is used to illustrate the preparation of sixteen styrene-maleic anhydride copolymers.

The procedure of preparation 1 was followed except that 8.6g of stearyl alcohol in preparation 1 was replaced with 7.7g of cetyl alcohol, to obtain styrene-maleic anhydride copolymer cetyl ester A2.

Preparation example 3

This preparation example is used to illustrate the preparation of the alkylphenol polyether.

70.5g of tertiary butyl phenol aldehyde resin with weight average molecular weight of 4000 and 1.1g of potassium hydroxide are added into an autoclave, 17.6g of dimethylbenzene is added, air is replaced by nitrogen, stirring and heating are carried out to 130 ℃, 114.8g of propylene oxide is continuously added at the temperature of 130 ℃ and 0.3MPa, and after the addition is finished, the reaction is continued for 0.5h and cooling is carried out; then, 87.1g of ethylene oxide is continuously added at the temperature of 110 ℃ and the pressure of 0.3MPa, and after the addition is finished, the reaction is continued for 0.5h, and the material is cooled and discharged to obtain the alkyl phenolic resin polyether B1.

Preparation example 4

The procedure of preparation 3 was followed except that the alkylphenol resin was a nonylphenol resin having a weight average molecular weight of 3000, to obtain alkylphenol polyether B2.

Preparation example 5

This preparation example is for explaining the preparation method of glycerol polyoxyethylene polyoxypropylene ether.

Adding 3.7g of glycerol and 1.74g of potassium hydroxide into an autoclave, purging with nitrogen, removing air, vacuumizing, starting stirring, heating to 130 ℃, dropwise adding 170.5g of propylene oxide at the temperature of 135 ℃ under the pressure of 0.3MPa, continuing to react for 0.5h after the dropwise adding is finished, cooling, and discharging to obtain an intermediate product;

100g of intermediate product and 1.86g of potassium hydroxide are added into a high-pressure reaction kettle, nitrogen is used for purging and vacuumizing, stirring is started and the temperature is raised to 120 ℃, 49.6g of ethylene oxide is dropwise added under the conditions of the pressure of 0.3MPa and the reaction temperature of 125 ℃, after the dropwise addition is finished, the reaction is continued for 0.5h, and the glycerol polyoxyethylene polyoxypropylene ether C1 is obtained after cooling and discharging.

Preparation example 6

Adding 3.7g of glycerol and 2g of potassium hydroxide into an autoclave, purging with nitrogen, removing air, vacuumizing, starting stirring, heating to 130 ℃, dropwise adding 197.6g of propylene oxide at the temperature of 135 ℃ under the pressure of 0.3MPa, continuing to react for 0.5h after the dropwise adding is finished, cooling, and discharging to obtain an intermediate product;

100g of intermediate product and 1.32g of potassium hydroxide are added into a high-pressure reaction kettle, nitrogen is used for purging and vacuumizing, stirring is started and the temperature is raised to 120 ℃, 31.6g of ethylene oxide is dropwise added under the conditions of the pressure of 0.3MPa and the reaction temperature of 125 ℃, after the dropwise addition is finished, the reaction is continued for 0.5h, and the glycerol polyoxyethylene polyoxypropylene ether C2 is obtained after cooling and discharging.

Preparation example 7

The preparation example is used for explaining the preparation method of the cationic hydroxyl silicone oil.

Into a four-neck flask equipped with a reflux condenser, a dropping funnel, a stirrer and a thermometer, 0.5g of cationic emulsifier N, N-di (tetradecyldimethyl) -3-oxa-1, 5-glutarimide, 0.04g of catalyst potassium hydroxide and 34.46g of distilled water are added and stirred until the cationic emulsifier and the catalyst are completely dissolved in the water;

then under the condition of stirring, dropwise adding 15g of octamethyl cyclotetrasiloxane into a four-neck flask, gradually heating to 50 ℃, preserving heat and reacting for 2 hours, cooling the reactant after the reaction is stopped, adding glacial acetic acid and neutralizing to be neutral, thus obtaining the semitransparent cation hydroxyl silicone oil emulsion D1 with slight blue light.

Preparation example 8

2g of cationic emulsifier N, N-di (hexadecyldimethyl) -3-oxa-1, 5-glutarimide, 0.16g of catalyst potassium hydroxide and 37.84g of distilled water are added into a four-neck flask provided with a reflux condenser, a dropping funnel, a stirrer and a thermometer, and stirred until the cationic emulsifier and the catalyst are completely dissolved in the water;

then under the condition of stirring, dropwise adding 10g of octamethyl cyclotetrasiloxane into a four-neck flask, gradually heating to 75 ℃, preserving heat and reacting for 6 hours, cooling the reactant after the reaction is stopped, adding glacial acetic acid and neutralizing to be neutral, thus obtaining the semitransparent cation hydroxyl silicone oil emulsion D2 with slight blue light.

Preparation example 9

This preparation example is used for explaining the preparation method of sophorolipid methyl ester.

50g of sophorolipid is added into 190ml of methanol, stirred into a homogeneous solution, the temperature is controlled to be 40+/-2 ℃, 1.5ml of 70wt% sulfuric acid is added dropwise, and the mixture is reacted for 1.5 hours at 40 ℃ after the dropwise addition is finished, so that sophorolipid methyl ester E1 is obtained.

Preparation example 10

The procedure of preparation 9 was followed except that 50g of sophorolipid in preparation 9 was replaced with 40g of sophorolipid to obtain sophorolipid methyl ester E2.

PREPARATION EXAMPLE 11

This preparation example is used to illustrate the preparation method of sophorolipid carboxylic acid.

100g of sophorolipid was placed in a 1000ml round bottom flask, 200ml of water and 500ml of ethanol were added, and stirred to be homogeneous, 5.5g of KOH was added, and the mixture was refluxed for 2 hours, to obtain sophorolipid carboxylic acid F1.

Preparation example 12

According to the method of preparation 11, except that 110g of sophorolipid was used instead of 100g of sophorolipid in preparation 11, sophorolipid carboxylic acid F2 was obtained.

Example 1

60g of emulsified crude oil is taken, 6000 mug of biological base wetting agent, 10g of deionized water and 2400 mug of oil-soluble demulsifier are added into the emulsified crude oil after the emulsified crude oil is preheated at 85 ℃, the emulsified crude oil is mixed by a mixer, and demulsification and water separation are carried out for 1h under the condition of adding 180V/cm of electric field at 90 ℃; 10g of deionized water and 7200 mu g of water-soluble demulsifier are added into the obtained oil phase, the mixture is mixed by a mixer, and demulsification and water separation are carried out for 2 hours under the condition of adding 180V/cm of an electric field at 90 ℃. Wherein the bio-based wetting agent is E1, the oil-soluble demulsifier is A1+B1, and the content mass ratio of A1 to B1 is 1.5:1, a step of; the water-soluble demulsifier is C1+D1, and the content mass ratio of C1 to D1 is 7:1.

and (3) extracting the water phase, adding enough acid to dissolve metal in the water phase, filtering, and measuring the iron content in the filtrate, namely the iron content in the drainage.

Taking 45g of upper layer oil as upper layer oil and 15g of lower layer oil as lower layer oil, and measuring the iron content in the upper layer oil and the lower layer oil respectively.

The test results for each parameter are shown in Table 3.

Example 2

According to the method of example 1, except that 60g of emulsified crude oil was taken, 18000. Mu.g of bio-based wetting agent, 4g of deionized water and 1200. Mu.g of oil-soluble demulsifier were added thereto after preheating at 85℃and mixed by a mixer, and demulsified and water-separated for 1.5 hours under the condition of adding an electric field of 250V/cm at 120 ℃; 4g of deionized water and 4500 mu g of water-soluble demulsifier are added into the obtained oil phase, the mixture is mixed by a mixer, and demulsification and water separation are carried out for 1h under the condition of adding an electric field of 250V/cm at 120 ℃. Wherein the bio-based wetting agent is F2, the oil-soluble demulsifier is A2+B2, and the content mass ratio of A2 to B2 is 0.5:1, a step of; the water-soluble demulsifier is C2+D2, and the content mass ratio of C2 to D2 is 3:1.

the test results for each parameter are shown in Table 3.

Example 3

According to the method of example 1, except that 60g of emulsified crude oil was taken, 12000. Mu.g of bio-based wetting agent, 6g of deionized water and 1800. Mu.g of oil-soluble demulsifier were added thereto after preheating at 85℃and mixed by a mixer, and demulsified and water-separated for 2 hours under the condition of adding 200V/cm of electric field at 100 ℃; 6g deionized water and 6000 mu g water-soluble demulsifier are added into the obtained oil phase, the mixture is mixed by a mixer, and demulsification and water separation are carried out for 1.5 hours under the condition of adding an electric field of 200V/cm at 100 ℃. Wherein the bio-based wetting agent is F1, the oil-soluble demulsifier is A1+B1, and the content mass ratio of A1 to B1 is 1:1, a step of; the water-soluble demulsifier is C1+D1, and the content mass ratio of C1 to D1 is 5:1.

the test results for each parameter are shown in Table 3.

Example 4

The procedure of example 3 was followed except that the bio-based wetting agent was of the type E2.

The test results for each parameter are shown in Table 3.

Example 5

The procedure of example 3 was followed, except that the amount of biobased wetting agent used was 3000. Mu.g.

The test results for each parameter are shown in Table 3.

Example 6

The procedure of example 3 was followed except that the amount of bio-based wetting agent used was 48000. Mu.g.

The test results for each parameter are shown in Table 3.

Example 7

The procedure of example 3 was followed except that the oil-soluble demulsifier was all A1 in kind.

The test results for each parameter are shown in Table 3.

Example 8

The procedure of example 3 was followed, except that the oil-soluble demulsifier (a1+b1) in example 3 was replaced with an oil-soluble demulsifier POI2420 of equal mass.

The test results for each parameter are shown in Table 3.

Example 9

The procedure of example 3 was followed except that the oil-soluble demulsifier was used in an amount of 3600. Mu.g.

The test results for each parameter are shown in Table 3.

Example 10

The procedure of example 3 was followed except that the water-soluble demulsifier was all C1.

The test results for each parameter are shown in Table 3.

Example 11

The procedure of example 3 was followed, except that the water-soluble demulsifier (C1+D1) was replaced with the water-soluble demulsifier SP 169.

The test results for each parameter are shown in Table 3.

Example 12

The procedure of example 3 was followed, except that the amount of the water-soluble demulsifier used was 3000. Mu.g.

The test results for each parameter are shown in Table 3.

Example 13

According to the method of example 3, except that 60g of emulsified crude oil was taken, 12000. Mu.g of bio-based wetting agent (F1) and 6g of deionized water were added thereto after preheating at 85℃and mixed by a mixer, and demulsified and split for 2 hours under the condition of applying an electric field of 200V/cm at 100 ℃; adding 6g deionized water and 6000 mug water-soluble demulsifier (C1+D1, the content mass ratio of C1 to D1 is 5:1) into the obtained oil phase, mixing by a mixer, demulsifying and water-separating for 1.5 hours under the condition of adding an electric field of 200V/cm at 100 ℃, and then measuring each parameter.

The test results for each parameter are shown in Table 3.

Comparative example 1

According to the method of example 3, except that 60g of emulsified crude oil is taken without adding a bio-based wetting agent, 6g of deionized water and 1800 mu g of oil-soluble demulsifier (A1+B1, the content mass ratio of A1 to B1 is 1:1) are added into the emulsified crude oil after preheating at 85 ℃, and the emulsified crude oil is mixed by a mixer, demulsified and water-separated for 2 hours under the condition of adding an electric field of 200V/cm at 100 ℃; adding 6g deionized water and 6000 mug water-soluble demulsifier (C1+D1, the content mass ratio of C1 to D1 is 5:1) into the obtained oil phase, mixing by a mixer, demulsifying and water-separating for 1.5 hours under the condition of adding an electric field of 200V/cm at 100 ℃, and then measuring each parameter.

The test results for each parameter are shown in Table 3.

Comparative example 2

The procedure of example 3 was followed except that nonylphenol polyoxyethylene ether was used in place of the biobased wetting agent.

The test results for each parameter are shown in Table 3.

Comparative example 3

The procedure of example 3 was followed except that 60g of emulsified crude oil was taken, preheated at 85℃and 6g of deionized water and 1800. Mu.g of an oil-soluble demulsifier (A1+B1, content mass ratio of A1 to B1: 1) were added thereto, mixed by a mixer, demulsified and water-separated at 100℃with an electric field of 200V/cm for 2 hours, and then the measurement of each parameter was carried out.

The test results for each parameter are shown in Table 3.

Comparative example 4

The procedure of example 3 was followed except that 60g of emulsified crude oil was taken, preheated at 85℃and 6g of deionized water and 6000. Mu.g of a water-soluble demulsifier (C1+D1, content mass ratio of C1 to D1: 5:1) were added thereto, and the mixture was mixed by a mixer, and demulsified and water-separated at 100℃and 200V/cm by applying an electric field for 1.5 hours, followed by measurement of each parameter.

The test results for each parameter are shown in Table 3.

TABLE 3 Table 3

As can be seen from Table 3, the bio-based wetting agent disclosed by the invention is adopted to cooperatively match specific contents of components such as specific types of oil-soluble demulsifiers and water-soluble demulsifiers to form a composition for treating iron-containing sulfides, and the components in the composition are adopted to treat emulsified crude oil with higher iron-containing sulfides, so that the iron content of drainage can be obviously improved.

Test case

The biodegradability test was carried out on the bio-based wetting agent prepared by the present invention and the nonylphenol polyoxyethylene ether prepared by the comparative example, respectively, and the biodegradability was represented by the ratio (B/C) of biological oxygen consumption (BOD) to chemical oxygen consumption (CODcr), and the specific test results are shown in Table 4.

Wherein BOD is detected by adopting a measuring method of a standard HJ505-2009 'five-day Biochemical oxygen demand of water quality';

CODcr was detected using the standard HJ828-2017 bichromate method for determination of chemical oxygen demand of Water quality.

TABLE 4 Table 4

	B/C
		E1	0.28
E2	0.28
		F1	0.31
F2	0.30
		Polyoxyethylene nonylphenol ether	0

As can be seen from Table 4, the bio-based wetting agent used in the present invention has better biodegradability than the conventional wetting agent, and does not cause environmental pollution.

The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.

Claims

1. Use of a bio-based wetting agent for treating emulsified crude oil, characterized in that the bio-based wetting agent is selected from at least one of methyl sophorolipid, sophorolipid carboxylic acid;

wherein, the sophorolipid methyl ester is prepared by a method comprising the following steps: in the presence of an acid catalyst I, sophorolipid and methanol are subjected to a contact reaction I;

the sophorolipid carboxylic acid is prepared by a method comprising the following steps: in the presence of a basic catalyst I, sophorolipids, water and ethanol are subjected to a contact reaction II.

2. Use according to claim 1, wherein the content of elemental iron in the emulsified crude oil is 100-200ppm.

3. A composition for treating iron-containing sulfides, comprising the following components, each independently or in combination:

the content of the bio-based wetting agent is 80-10000 parts by weight relative to 100 parts by weight of the oil-soluble demulsifier, and the content of the water-soluble demulsifier is 80-1500 parts by weight;

4. The composition of claim 3, wherein the bio-based wetting agent is contained in an amount of 500 to 1800 parts by weight and the water-soluble demulsifier is contained in an amount of 200 to 500 parts by weight with respect to 100 parts by weight of the oil-soluble demulsifier.

5. The composition according to claim 3 or 4, wherein the acidic catalyst I is selected from sulfuric acid having a concentration of 70wt% or more.

6. The composition according to claim 3 or 4, wherein the acidic catalyst I, the sophorolipid and the methanol are used in a mass ratio of 1:10-30:30-80.

7. The composition of claim 3 or 4, wherein the conditions of contact reaction I comprise: the temperature is 30-50deg.C, and the time is 0.5-5h.

8. The composition according to claim 3 or 4, wherein the basic catalyst I is KOH.

9. The composition according to claim 3 or 4, wherein the sophorolipids, the water and the ethanol are used in a mass ratio of 1:1-3:3-5, wherein the dosage mass ratio of the sophorolipid to the alkaline catalyst I is 15-25:1.

10. the composition of claim 3 or 4, wherein at least the conditions of contact reaction II are: the time is 1-4h.

11. The composition according to claim 3 or 4, wherein the oil-soluble demulsifier is present in an amount of from 0.2 to 2 by mass: 1 and an alkyl phenol-formaldehyde resin polyether.

12. The composition according to claim 3 or 4, wherein in the oil-soluble demulsifier, the content mass ratio of the alkyl ester of the styrene-maleic anhydride copolymer to the alkylphenol polyether is 0.5 to 1.5:1.

13. the composition of claim 3 or 4, wherein the alkyl ester of styrene-maleic anhydride copolymer is prepared by a process comprising the steps of:

14. The composition of claim 13, wherein the fatty alcohol has a carbon number of 16-20.

15. The composition of claim 13 or 14, wherein the styrene monomer and the maleic anhydride monomer are used in a molar ratio of 0.8-1.5:1.

16. the composition of claim 13 or 14, wherein the styrene monomer and the maleic anhydride monomer are used in a molar ratio of 0.9-1.1:1.

17. the composition according to claim 3 or 4, wherein the weight average molecular weight of the styrene-maleic anhydride copolymer is 500-20000.

18. The composition of claim 3 or 4, wherein the styrene-maleic anhydride copolymer has a weight average molecular weight of 1000-10000.

19. The composition of claim 3 or 4 wherein the alkylphenol polyether is an alkyl chain of C ₃ -C ₁₀ An alkoxide of an alkylphenol resin.

20. The composition of claim 3 or 4, wherein the alkylphenol polyether is one having an alkyl chain of C ₅ -C ₇ Alkoxide of alkyl phenol resin.

21. The composition of claim 3 or 4, wherein the alkylphenol polyether is prepared by a process comprising the steps of: in the presence of an alkaline catalyst II, the alkyl phenolic resin is subjected to synthetic reaction with propylene oxide and ethylene oxide in sequence.

22. The composition of claim 21, wherein the alkyl phenol formaldehyde resin, the propylene oxide, and the ethylene oxide are used in a molar ratio of 1:5-20:1-10.

23. The composition of claim 21 or 22, wherein the alkyl phenol-formaldehyde resin, the propylene oxide, the ethylene oxide are used in a molar ratio of 1:7-15:3-6.

24. The composition of claim 21 or 22, wherein the alkylphenol resin has a weight average molecular weight of 500-10000.

25. The composition of claim 21 or 22, wherein the alkylphenol resin has a weight average molecular weight of 1000-5000.

26. The composition according to claim 3 or 4, wherein the water-soluble demulsifier is present in an amount of from 2 to 10 by mass: 1 and cationic hydroxy silicone oil.

27. The composition according to claim 26, wherein the content mass ratio of the glycerol polyoxyethylene polyoxypropylene ether to the cationic hydroxyl silicone oil is 3-7:1.

28. use of a composition according to any one of claims 3 to 27 for treating emulsified crude oil containing iron sulphide solid particles.

29. A method of treating emulsified crude oil containing iron sulfide solid particles, the method comprising:

(1) Mixing the emulsified crude oil with the components of the composition of any one of claims 3-27 in the presence of a solvent to obtain a mixed oil;

30. The method of claim 29, wherein in step (1), the step of mixing the emulsified crude oil with the components of the composition of any one of claims 3-27 comprises: in the presence of a solvent I, mixing the emulsified crude oil, a bio-based wetting agent and an oil-soluble demulsifier, and then performing first-stage electric desalting treatment to obtain a material I; and then mixing the material I and a water-soluble demulsifier in the presence of a solvent II, and then carrying out second-stage electric desalting treatment.

31. The method according to claim 29 or 30, wherein in step (1), the bio-based wetting agent is used in an amount of 50-1000 μg, the oil-soluble demulsifier is used in an amount of 10-60 μg, and the water-soluble demulsifier is used in an amount of 50-150 μg relative to 1g of emulsified crude oil.

32. The method according to claim 29 or 30, wherein in step (1), the bio-based wetting agent is used in an amount of 100 to 500 μg, the oil-soluble demulsifier is used in an amount of 20 to 40 μg, and the water-soluble demulsifier is used in an amount of 70 to 120 μg relative to 1g of emulsified crude oil.

33. The method of claim 30, wherein the solvent I and the solvent II are both water.

34. The method of claim 30, wherein the emulsified crude oil and the solvent I are used in a mass ratio of 3-20:1.

35. the method of claim 30, wherein the emulsified crude oil and the solvent I are used in a mass ratio of 6-15:1.

36. the method of claim 30, wherein the emulsified crude oil and the solvent II are used in a mass ratio of 3-20:1.

37. the method of claim 30, wherein the emulsified crude oil and the solvent II are used in a mass ratio of 6-15:1.

38. the method of claim 30, wherein the conditions of the first stage electro-desalting treatment comprise: the temperature is 60-140 ℃, the electric field intensity is 100-300V/cm, and the time is 0.5-3h.

39. The method of claim 30, wherein the conditions of the first stage electro-desalting treatment comprise: the temperature is 90-120 ℃, the electric field strength is 150-250V/cm, and the time is 1-2h.

40. The method of claim 30, wherein the conditions of the second stage electro-desalting treatment comprise: the temperature is 60-140 ℃, the electric field intensity is 100-300V/cm, and the time is 0.5-3h.

41. The method of claim 30, wherein the conditions of the second stage electro-desalting treatment comprise: the temperature is 90-120 ℃, the electric field strength is 150-250V/cm, and the time is 1-2h.

42. The method according to claim 29 or 30, wherein the content of iron element in the emulsified crude oil is 100-200ppm.

43. The method of claim 29 or 30, wherein the emulsified crude oil has a density of not greater than 960g/cm at 20 °c ³ Viscosity at 80deg.C is not higher than 150mm ² /s。