Preparation method and application of a magnetic-responsive eugenol polyether demulsifier

Abstract

The present invention relates to a preparation method and application of a magnetic-responsive eugenol polyether demulsifier. In this method, epoxy groups are anchored on the surface of Fe 3 O 4 @SiO 2 magnetic-responsive nanoparticles through a hydrolysis condensation reaction. Subsequently, a magnetic-responsive demulsifier is synthesized by grafting eugenol linear block polyether. The obtained magnetic nanoparticles grafted with eugenol block polyether can adsorb oil droplets in oily sewage and can migrate rapidly under the synergistic action of a magnetic field and gravity, ultimately achieving rapid and efficient oil-water separation. The magnetic-responsive polyether demulsifier obtained in the present invention has excellent demulsification effect, good recyclability and cyclicity, and has a very broad application prospect in the field of oil-water separation of oil-in-water emulsions (O / W emulsions).

Description

Technical Field

[0001] The present invention relates to a preparation method and application of a magnetic-responsive eugenol polyether demulsifier, belonging to the technical field of demulsifier preparation. Background Art

[0002] In the petrochemical industry, a large amount of oily sewage is generated. Its direct discharge will not only cause waste of oil resources, but also cause serious environmental pollution. Most oily wastewater exists in the form of O / W oil-in-water emulsion, and has high stability due to the presence of surface active substances, increasing the difficulty of treatment. Therefore, for the effective utilization of resources and environmental protection work, it is of great significance to quickly and efficiently separate oil and water from oily sewage.

[0003] Currently, the most commonly used chemical reagent for treating oily sewage is a flocculant. Its addition can accelerate the oil removal process, but it cannot be recycled and is prone to secondary pollution, thus limiting their application. In order to solve the problem of the recovery of the demulsifier after treating oily sewage and reduce the limitations of its application, in recent years, many scholars endow the demulsifier with magnetic responsiveness, so that it can be recovered under the action of an external magnetic field.

[0004] Chinese patent document CN105950211A discloses a method for modifying the surface of magnetic particles with chitosan. The obtained particles have good dispersibility in water and can migrate from the aqueous phase to the surface of oil droplets, and then realize the oil-water separation of O / W emulsion under the drive of a magnetic field.

[0005] Chinese patent document CN110613960A discloses a demulsifier obtained by simultaneously anchoring alkylsilane and aminosilane on the surface of Fe 3 O 4 @SiO 2 nanoparticles. The obtained product can be well dispersed in both the aqueous phase and the oil phase, and has cationic characteristics and excellent interfacial activity.

[0006] Although the above magnetic-responsive demulsifiers have good dispersibility, their demulsification effect is general, and the stability of the O / W emulsion itself is poor, which reduces the difficulty of demulsification to a certain extent.

[0007] Chinese patent document CN115124709A discloses a polyether demulsifier using decyltetradecanol as an initiator, its preparation method and application. The polyether demulsifier has the characteristics of large molecular weight, high cloud point, strong surface activity, etc.; the lipophilic group with a branched chain has strong penetration in crude oil and has a special demulsification effect on shale oil, and the separated water quality is clear and the oil-water interface is neat. Although this polyether demulsifier has a good demulsification effect, it cannot be recycled, and its residue in the aqueous phase is easy to cause secondary pollution and is not easy to be completely removed from the aqueous phase.

[0008] In summary, in current reports, there is almost no report on the efficient oil-water separation of O / W emulsions grafted with block polyethers in magnetic nanoparticles, and there is still no report on the research of synthesizing magnetic demulsifiers using eugenol linear block polyether grafted magnetic nanoparticles. Summary of the Invention

[0009] Aiming at the deficiencies of the prior art, the present invention provides a preparation method and application of a magnetic-responsive eugenol polyether demulsifier. This magnetic-responsive eugenol polyether demulsifier is a magnetic-responsive nanoparticle demulsifier with excellent interfacial activity, fast demulsification speed, high demulsification efficiency, good salt tolerance, acid and alkali resistance, has good demulsification effects on oily sewage with different oil contents, has good recyclability and recyclability, can achieve efficient and rapid oil-water separation of oil-in-water emulsions (O / W emulsions), and is suitable for treating oily sewage.

[0010] To achieve the above-mentioned invention purpose, the present invention adopts the following technical solutions:

[0011] A preparation method of a magnetic-responsive eugenol polyether demulsifier, comprising the following steps:

[0012] (1) Eugenol reacts with propylene oxide in the presence of a catalyst to prepare an epoxy propane block of eugenol polyether;

[0013] (2) The epoxy propane block of eugenol polyether reacts with ethylene oxide to prepare eugenol linear block polyether;

[0014] (3) Fe 3 O 4 nanoparticles are added to a mixed solution of H 2 O, ethanol and ammonia water, and react with tetraethyl orthosilicate to prepare Fe 3 O 4 @SiO 2 ;

[0015] (4) The Fe 3 O 4 @SiO 2 obtained in step (3) reacts with 3-glycidoxypropyltrimethoxysilane (GOPTS) to prepare Fe 3 O 4 @SiO 2 -Epoxy;

[0016] (5) The eugenol linear block polyether obtained in step (2) reacts with the Fe 3 O 4 @SiO 2 -Epo obtained in step (4) to obtain a magnetic-responsive eugenol polyether demulsifier.

[0017] Preferably according to the present invention, in step (1), the reaction is carried out at a pressure of 0.10 to 0.50 MPa and a temperature of 110 to 140 °C for 4 to 24 hours.

[0018] Preferably according to the present invention, in step (1), the reaction is carried out under the conditions of 0.30 MPa and 125 °C for 8 hours.

[0019] Preferably according to the present invention, in step (1), the catalyst is selected from alkali metal alkoxides, hydroxides, amides, organometallic compounds, alkaline earth metal oxides, phosphazene-based organic base compounds or coordination bimetallic compounds.

[0020] Preferably according to the present invention, in step (1), the catalyst is a hydroxide.

[0021] Most preferably, in step (1), the catalyst is potassium hydroxide.

[0022] Preferably according to the present invention, in step (1), the mass ratio of eugenol to propylene oxide is 1:10 to 1:50; preferably, the mass ratio of eugenol to propylene oxide is 1:20 to 1:40.

[0023] Preferably according to the present invention, in step (1), the mass ratio of the catalyst to propylene oxide is 1:(400 - 600).

[0024] Preferably according to the present invention, in step (2), the reaction is carried out at a pressure of 0.10 to 0.50 MPa and a temperature of 100 to 140 °C for 2 to 24 hours.

[0025] Preferably according to the present invention, in step (2), the reaction is carried out under the conditions of 0.3 MPa and 110 °C for 6 hours.

[0026] Preferably according to the present invention, in step (2), the mass ratio of ethylene oxide to the propylene oxide block of eugenol polyether is 1:1 to 1:5; preferably, the mass ratio of ethylene oxide to the propylene oxide block of eugenol polyether is 1:1 to 1:3.

[0027] Preferably according to the present invention, in step (3), the mass of tetraethyl orthosilicate is 40% - 90% of the mass of Fe 3 O 4 nanoparticles; preferably, the mass of tetraethyl orthosilicate is 45% of the mass of Fe 3 O 4 nanoparticles.

[0028] Preferably according to the present invention, in step (3), the volume ratio of H 2 O to ethanol is 1:1 to 1:3, and the amount of ammonia water used is such that pH = 9 - 12.

[0029] Most preferably, the amount of ammonia water is such that pH = 10.

[0030] According to the preference of the present invention, in step (3), the mass ratio of Fe 3 O 4 nanoparticles to the mixed solution is 1:10 to 1:20.

[0031] According to the preference of the present invention, in step (4), the mass of GOPTS is 45% to 65% of the mass of Fe 3 O 4 @SiO 2 ; preferably, the mass of the GOPTS is 45% of the mass of Fe 3 O 4 @SiO 2 .

[0032] According to the preference of the present invention, in step (4), the reaction is carried out at a temperature of 140 to 160 °C for 6 to 15 hours.

[0033] According to the preference of the present invention, step (4) is the epoxidation of GOPTS to Fe 3 O 4 @SiO 2 , and the obtained product is denoted as Fe 3 O 4 @SiO 2 -Epoxy.

[0034] According to the preference of the present invention, in step (5), the mass of the eugenol linear block polyether is 5% to 10% of the mass of Fe 3 O 4 @SiO 2 -Epoxy; preferably, the mass of the eugenol linear block polyether is 10% of the mass of Fe 3 O 4 @SiO 2 -Epo.

[0035] A magnetic-responsive eugenol polyether demulsifier prepared by the above method has the following structure:

[0036]

[0037] Wherein: the mass ratio of the eugenol initiator to the n block is 1:10 to 1:50; the mass ratio of the m block to the n block is 1:1 to 1:5.

[0038] The application of the above magnetic-responsive eugenol polyether demulsifier is used for rapid oil-water separation of oil-in-water emulsions.

[0039] According to the preference of the present invention, the specific application method is as follows:

[0040] Add the above magnetic-responsive eugenol polyether demulsifier to the oily sewage, mix evenly, and let it stand for stratification under the action of a magnetic field; the dosage of the magnetic-responsive eugenol polyether demulsifier is 100 - 300 mg·L -1 .

[0041] Technical features and advantages of the present invention:

[0042] 1. The magnetic-responsive eugenol polyether demulsifier of the present invention has strong interfacial activity, fast demulsification speed, high demulsification efficiency, good salt tolerance and acid and alkali resistance, and has good demulsification effects on oily sewage with different oil contents, which can solve the problems of large dosage, poor effect and non-recovery of conventional demulsifiers in the process of oil exploitation.

[0043] 2. The magnetic-responsive eugenol polyether demulsifier of the present invention is aimed at oily sewage with an oil content of 20,000 mg·L -1 and a salinity of 10,249. When the addition amount of the demulsifier of the present invention is 200 mg·L -1 , the oil removal rate reaches more than 90% within 10 minutes.

[0044] 3. The magnetic-responsive eugenol polyether demulsifier of the present invention has a good recycling effect. After using a magnet to recycle and demulsify 5 times, the oil removal rate can still be maintained above 85%. Description of the Drawings

[0045] Figure 1 is the schematic diagram of the preparation of the magnetic-responsive eugenol polyether demulsifier in the present invention.

[0046] Figure 2 is the infrared spectrum of the magnetic-responsive eugenol polyether demulsifier prepared in Example 3-1 of the present invention. Detailed Embodiments

[0047] According to the following embodiments, the present invention can be better understood. However, those skilled in the art can easily understand that the content described in the embodiments is only used to illustrate the present invention, and should not and will not limit the present invention described in detail in the claims.

[0048] Example 1-1

[0049] Preparation of eugenol linear block polyether:

[0050] 1) Add 10.0 g of eugenol and 0.5 g of potassium hydroxide as a catalyst into a high-pressure reactor. Connect the high-pressure reactor to a vacuum pump and evacuate it to -0.1 MPa. Turn on the mechanical stirring paddle and adjust the rotation speed to 50 rpm. Heat up to 125 °C, slowly introduce propylene oxide to keep the pressure at 0.3 MPa, maintain the reaction temperature at 130 °C, introduce propylene oxide with a mass 20 times that of the eugenol feed amount, react for 8 hours until the pressure drops to -0.1 MPa, lower the temperature to 50 °C, and discharge to obtain 210.0 g of the propylene oxide block intermediate product C1# of eugenol block polyether.

[0051] 2) Add 100.0 g of the propylene oxide block intermediate product C1# of eugenol block polyether into a high-pressure reactor. Connect the high-pressure reactor to a vacuum pump and evacuate it to -0.1 MPa. Turn on the mechanical stirring paddle and adjust the rotation speed to 50 rpm. Heat up to 110 °C, slowly introduce ethylene oxide to keep the pressure at 0.3 MPa, maintain the reaction temperature at 110 °C, introduce 100.0 g of ethylene oxide, react for 6 hours until the pressure drops to -0.1 MPa, lower the temperature to 50 °C and discharge to obtain 200.0 g of the eugenol block polyether product CE1#.

[0052] Example 1-2

[0053] Preparation of linear block polyether of eugenol:

[0054] 1) The propylene oxide block intermediate product C1# of eugenol block polyether is synthesized according to the method in Example 1.

[0055] 2) Add 100.0 g of the propylene oxide block intermediate product C1# of eugenol block polyether into a high-pressure reactor. Connect the high-pressure reactor to a vacuum pump and evacuate it to -0.1 MPa. Turn on the mechanical stirring paddle and adjust the rotation speed to 50 rpm. Heat up to 110 °C, slowly introduce ethylene oxide to keep the pressure at 0.3 MPa, maintain the reaction temperature at 110 °C, introduce 50.0 g of ethylene oxide, react for 6 hours until the pressure drops to -0.1 MPa, lower the temperature to 50 °C and discharge to obtain 150.0 g of the eugenol block polyether product CE2#.

[0056] Example 1-3

[0057] Preparation of linear block polyether of eugenol:

[0058] 1) The propylene oxide block intermediate product C1# of eugenol block polyether is synthesized according to the method in Example 1.

[0059] 2) Add 100.0 g of the propylene oxide block intermediate C1# of eugenol block polyether to the autoclave. Connect the autoclave to a vacuum pump and evacuate to -0.1 MPa. Start the mechanical stirrer and adjust the rotation speed to 50 rpm. Heat up to 110 °C. Slowly introduce ethylene oxide to keep the pressure at 0.3 MPa. Maintain the reaction temperature at 110 °C. Introduce 33.3 g of ethylene oxide and react for 6 hours until the pressure drops to -0.1 MPa. Lower the temperature to 50 °C and discharge to obtain 133.3 g of eugenol block polyether product CE3#.

[0060] Examples 1 - 4

[0061] Preparation of linear block polyether of eugenol:

[0062] 1) Add 10.0 g of eugenol and 0.5 g of catalyst potassium hydroxide to the autoclave. Connect the autoclave to a vacuum pump and evacuate to -0.1 MPa. Start the mechanical stirrer and adjust the rotation speed to 50 rpm. Heat up to 125 °C. Slowly introduce propylene oxide to keep the pressure at 0.3 MPa. Maintain the reaction temperature at 130 °C. Introduce propylene oxide with a mass 30 times that of the eugenol feed and react for 8 hours until the pressure drops to -0.1 MPa. Lower the temperature to 50 °C and discharge to obtain 310.0 g of the propylene oxide block intermediate C2# of eugenol block polyether.

[0063] 2) Add 100.0 g of the propylene oxide block intermediate C2# of eugenol block polyether to the autoclave. Connect the autoclave to a vacuum pump and evacuate to -0.1 MPa. Start the mechanical stirrer and adjust the rotation speed to 50 rpm. Heat up to 110 °C. Slowly introduce ethylene oxide to keep the pressure at 0.3 MPa. Maintain the reaction temperature at 110 °C. Introduce 100.0 g of ethylene oxide and react for 6 hours until the pressure drops to -0.1 MPa. Lower the temperature to 50 °C and discharge to obtain 200.0 g of eugenol block polyether product CE4#.

[0064] Examples 1 - 5

[0065] Preparation of linear block polyether of eugenol:

[0066] 1) Add 10.0 g of eugenol and 0.5 g of catalyst potassium hydroxide to the autoclave. Connect the autoclave to a vacuum pump and evacuate to -0.1 MPa. Start the mechanical stirrer and adjust the rotation speed to 50 rpm. Heat up to 125 °C. Slowly introduce propylene oxide to keep the pressure at 0.3 MPa. Maintain the reaction temperature at 130 °C. Introduce propylene oxide with a mass 40 times that of the eugenol feed and react for 8 hours until the pressure drops to -0.1 MPa. Lower the temperature to 50 °C and discharge to obtain 410.0 g of the propylene oxide block intermediate C3# of eugenol block polyether.

[0067] 2) Add 100.0 g of the propylene oxide block intermediate C3# of eugenol block polyether to the autoclave. Connect the autoclave to a vacuum pump and evacuate to -0.1 MPa. Turn on the mechanical stirrer and adjust the rotation speed to 50 rpm. Heat up to 110 °C. Slowly introduce ethylene oxide to keep the pressure at 0.3 MPa. Maintain the reaction temperature at 110 °C and introduce 100.0 g of ethylene oxide. React for 6 hours until the pressure drops to -0.1 MPa. Lower the temperature to 50 °C and discharge to obtain 200.0 g of the eugenol block polyether product CE5#.

[0068] Example 2

[0069] Fe 3 O 4 @SiO 2 Preparation of -Epoxy:

[0070] 1) Add 10.0 g of Fe 3 O 4 nanoparticles to the reactor. Add 20 mL of deionized water and 80 mL of ethanol. Use ammonia water to adjust the pH to 10.0. Turn on the mechanical stirrer at room temperature and adjust the rotation speed to 400 rpm. Slowly dropwise add 4.5 g of tetraethyl orthosilicate. React for 6 hours. Collect the solid product with a magnet and wash it 3 times with deionized water and ethanol respectively. Dry it in vacuum at 50 °C for 4 hours to obtain 12.5 g of Fe 3 O 4 @SiO 2 magnetic nanoparticle intermediate C4#.

[0071] 2) Add 10.0 g of the Fe 3 O 4 @SiO 2 magnetic nanoparticle intermediate C4# to the reactor. Add 200 mL of toluene. Turn on the mechanical stirrer at 90 °C and adjust the rotation speed to 400 rpm. Slowly dropwise add 4.5 g of GOPTS. React for 4 hours. Collect the solid product with a magnet and wash it 3 times with ethanol. Dry it in vacuum at 100 °C for 4 hours to obtain 10.5 g of Fe 3 O 4 @SiO 2 -Epoxy magnetic nanoparticle intermediate C5#.

[0072] Example 3-1

[0073] Preparation of the magnetic-responsive eugenol polyether demulsifier:

[0074] Add the Fe 3 O 4 @SiO 2- 10.0 g of the epoxy magnetic nanoparticle intermediate C5# was added to 150 mL of toluene. The mechanical stirring paddle was started at 120 °C and the rotation speed was adjusted to 400 rpm to fully disperse the Fe 3 O 4 @SiO 2 - Epo magnetic nanoparticles for 30 min. 1.0 g of the eugenol block polyether product CE1# was added to the reaction system and reacted for 4 h. After the reaction, the solid product was collected with a magnet, washed 3 times with ethanol, and vacuum dried at 100 °C for 4 h to obtain the magnetic-responsive eugenol polyether demulsifier CEM#1.

[0075] Example 3-2

[0076] Preparation of magnetic-responsive eugenol polyether demulsifier:

[0077] 10.0 g of the Fe 3 O 4 @SiO 2 - Epo magnetic nanoparticle intermediate C5# was added to 150 mL of toluene. The mechanical stirring paddle was started at 120 °C and the rotation speed was adjusted to 400 rpm to fully disperse the Fe 3 O 4 @SiO 2 - Epo magnetic nanoparticles for 30 min. 1.0 g of the eugenol block polyether product CE2# was added to the reaction system and reacted for 4 h. After the reaction, the solid product was collected with a magnet, washed 3 times with ethanol, and vacuum dried at 100 °C for 4 h to obtain the magnetic-responsive eugenol polyether demulsifier CEM#2.

[0078] Example 3-3

[0079] Preparation of magnetic-responsive eugenol polyether demulsifier:

[0080] 10.0 g of the Fe 3 O 4 @SiO 2 - Epo magnetic nanoparticle intermediate C5# was added to 150 mL of toluene. The mechanical stirring paddle was started at 120 °C and the rotation speed was adjusted to 400 rpm to fully disperse the Fe 3 O 4 @SiO 2 - Epo magnetic nanoparticles for 30 min. 1.0 g of the eugenol block polyether product CE3# was added to the reaction system and reacted for 4 h. After the reaction, the solid product was collected with a magnet, washed 3 times with ethanol, and vacuum dried at 100 °C for 4 h to obtain the magnetic-responsive eugenol polyether demulsifier CEM#3.

[0081] Example 3-4

[0082] Preparation of Magnetic Responsive Eugenol Polyether Demulsifier:

[0083] Add Fe into the reactor 3 O 4 @SiO 2 -Epo magnetic nanoparticle intermediate product C5# (10.0 g), add 150 mL of toluene, start the mechanical stirring paddle at 120 °C and adjust the rotation speed to 400 rpm to fully disperse the Fe 3 O 4 @SiO 2 -Epo magnetic nanoparticles for 30 min. Add 1.0 g of eugenol block polyether product CE4# to the reaction system and react for 4 hours. After the reaction, collect the solid product with a magnet, wash it 3 times with ethanol, and dry it under vacuum at 100 °C for 4 hours to obtain the magnetic responsive eugenol polyether demulsifier CEM#4.

[0084] Examples 3 - 5

[0085] Preparation of Magnetic Responsive Eugenol Polyether Demulsifier:

[0086] Add Fe into the reactor 3 O 4 @SiO 2 -Epo magnetic nanoparticle intermediate product C5# (10.0 g), add 150 mL of toluene, start the mechanical stirring paddle at 120 °C and adjust the rotation speed to 400 rpm to fully disperse the Fe 3 O 4 @SiO 2 -Epo magnetic nanoparticles for 30 min. Add 1.0 g of eugenol block polyether product CE5# to the reaction system and react for 4 hours. After the reaction, collect the solid product with a magnet, wash it 3 times with ethanol, and dry it under vacuum at 100 °C for 4 hours to obtain the magnetic responsive eugenol polyether demulsifier CEM#5.

[0087] Performance Detection:

[0088] 1. According to SY / T 5797 - 93 (Evaluation Method for the Use Performance of Demulsifiers for Oil-in-Water Emulsions), apply a magnetic field at the bottom simultaneously and test the oil removal rate of each demulsifier. The addition amount of each demulsifier is 200 mg·L -1 . The experimental results are shown in Table 1 below.

[0089] Table 1. Demulsification Performance of Magnetic Responsive Eugenol Polyether Demulsifier

[0090] Demulsifier Number Oil Removal Rate in 5 Minutes (%) Oil Removal Rate in 10 Minutes (%) CE1# 7.8 12.4 CE2# 26.9 29.8 CE3# 10.4 13.5 CE4# 4.4 5.3 CE5# 9.6 13.0 CEM1# 51.3 78.9 CEM2# 65.4 91.4 CEM3# 56.8 75.4 CEM4# 43.7 65.0 CEM5# 60.8 72.1

[0091] As can be seen from Table 1, the demulsification effect of eugenol linear block polyethers (CE1# - CE5#) on oily sewage is poor. Among them, the demulsification effect of CE2# is slightly better, but the oil removal rate is less than 30%. After grafting eugenol linear block polyethers onto magnetic nanoparticles, the demulsification effect is significantly improved: not only is the demulsification rate accelerated, but also the oil removal rate increases. This shows that the magnetic-responsive eugenol polyether demulsifier can accelerate the demulsification process by means of the synergistic effect of magnetic field and gravity, which plays a crucial role in the demulsification effect of the magnetic-responsive eugenol polyether demulsifier.

[0092] Combined with the examples, further analysis of the data in the table shows that for the magnetic-responsive eugenol polyether demulsifier CEM#2, its demulsification rate and oil removal rate perform best. That is, when the mass ratio of eugenol initiator to m block is 1:20 and the mass ratio of m block to n block is 1:1, the demulsification effect of the magnetic-responsive eugenol polyether demulsifier synthesized by grafting the eugenol block polyether product CE2# is the best.

[0093] 2. The cyclic demulsification performance of each magnetic-responsive eugenol polyether demulsifier was tested, and the test results are shown in Table 2.

[0094] Test method: After the demulsification process is completed, use a magnet to collect the solid, and wash it 3 times each with ethanol and petroleum ether, then dry it in vacuum at 50°C for 2 h, weigh it and reuse it. Repeat the process 5 times.

[0095] Table 2. Cyclic demulsification performance of magnetic-responsive eugenol polyether demulsifier

[0096] Demulsifier Number Oil Removal Rate (%) Recovery Rate (%) Number of Cycles CEM1# 70.8 98.6 5 times CEM2# 86.4 96.4 5 times CEM3# 68.1 95.7 5 times CEM4# 59.7 97.8 5 times CEM5# 63.3 97.1 5 times

[0097] As can be seen from Table 2, after 5 cycles, the oil removal rate of the magnetic-responsive eugenol polyether demulsifier slightly decreases, but the oil removal rate of CEM#2 is still above 85%. This shows that the magnetic-responsive eugenol polyether demulsifier has good recyclability. After 5 cycles, its recovery rate can be maintained above 95%, indicating that the magnetic-responsive eugenol polyether demulsifier has good recoverability.

[0098] Combined with the examples, further analysis of the data in the table shows that for the magnetic-responsive eugenol polyether demulsifier CEM#2, its demulsification rate and oil removal rate perform best. That is, when the mass ratio of eugenol initiator to m block is 1:20 and the mass ratio of m block to n block is 1:1, the demulsification effect of the magnetic-responsive eugenol polyether demulsifier synthesized by grafting the eugenol block polyether product CE2# is the best.

[0099] 3. The salt tolerance performance of each magnetic-responsive eugenol polyether demulsifier was tested, and the test results are shown in Table 3.

[0100] Table 3. Salt tolerance performance test of magnetic-responsive eugenol polyether demulsifier

[0101]

[0102]

[0103] As can be seen from Table 3, the magnetic-responsive eugenol polyether demulsifier has good demulsification effects at different salinities. The oil removal rate is hardly affected by the salinity and remains stable at about 91%, indicating that the magnetic-responsive eugenol polyether demulsifier CEM#2 has good salt tolerance.

[0104] The above embodiments are the preferred embodiments of the present invention. However, the embodiments of the present invention are not limited to the above embodiments. Any other substitutions, modifications, combinations, changes, simplifications, etc. made without departing from the spirit and principle of the present invention shall be equivalent replacement methods and are all included in the protection scope of the present invention.

Claims

1. A preparation method of a magnetic-responsive eugenol polyether demulsifier, comprising the following steps: (1) Eugenol reacts with propylene oxide in the presence of a catalyst to prepare a propylene oxide block of eugenol polyether; (2) The propylene oxide block of eugenol polyether reacts with ethylene oxide to prepare a linear block polyether of eugenol; (3)Fe 3 O 4 nanoparticles were added to the mixed solution of H 2 O, ethanol and ammonia water, and reacted with tetraethyl orthosilicate to prepare Fe 3 O 4 @SiO 2 ; (4) The Fe obtained in step (3) 3 O 4 @SiO 2 reacts with 3-glycidoxypropyltrimethoxysilane (GOPTS) to prepare Fe 3 O 4 @SiO 2 -Epo; (5) The eugenol linear block polyether obtained in step (2) reacts with Fe 3 O 4 @SiO 2 -Epo to obtain a magnetic-responsive eugenol polyether demulsifier.

2. According to the preparation method described in claim 1, wherein, in step (1), the reaction is carried out at a pressure of 0.10 - 0.50 MPa and a temperature of 110 - 140 °C for 4 - 24 hours.

3. According to the preparation method described in claim 1, wherein, in step (1), the catalyst is selected from alkoxides, hydroxides, amides, organometallic compounds of alkali metals, alkaline earth metal oxides, phosphazene-based organic base compounds or coordination bimetallic compounds.

4. According to the preparation method described in claim 1, wherein, the mass ratio of eugenol to propylene oxide is 1:10 - 1:50, and the mass ratio of the catalyst to propylene oxide is 1:(400 - 600).

5. According to the preparation method described in claim 1, wherein, in step (2), the reaction is carried out at a pressure of 0.10 - 0.50 MPa and a temperature of 100 - 140 °C for 2 - 24 hours.

6. According to the preparation method described in claim 1, wherein, in step (2), the mass ratio of ethylene oxide to the propylene oxide block of eugenol polyether is 1:1 - 1:

3.

7. According to the preparation method described in claim 1, wherein, In step (3), the mass of tetraethyl orthosilicate is 40% - 90% of the mass of Fe 3 O 4 nanoparticles; the volume ratio of H 2 O to ethanol is 1:1 - 1:3, and the amount of ammonia water is such that pH = 9 - 12. The mass ratio of Fe 3 O 4 nanoparticles to the mixed solution is 1:10 - 1:

20.

8. According to the preparation method described in claim 1, wherein, In step (4), the mass of GOPTS is 45% - 65% of the mass of Fe 3 O 4 @SiO 2 ; in step (4), the reaction is carried out at a temperature of 140 - 160 °C for 6 - 15 hours, and in step (5), the mass of the eugenol linear block polyether is 5% - 10% of the mass of Fe 3 O 4 @SiO 2 -Epo.

9. A magnetic-responsive eugenol polyether demulsifier prepared by using the method described in any one of claims 1 - 8 has the following structure: Wherein: The mass ratio of the eugenol initiator to the m block is 1:10 - 1:50; the mass ratio of the n block to the m block is 1:1 - 1:

5.

10. The application of the magnetic-responsive eugenol polyether demulsifier described in claim 9 is used for rapid oil-water separation of oil-in-water emulsions; The specific application method is as follows: Add the above magnetic-responsive eugenol polyether demulsifier to the oily sewage, mix evenly, and let it stand for stratification under the action of a magnetic field; the dosage of the magnetic-responsive eugenol polyether demulsifier is 100~300mg·L -1 .

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