Combined phenol-primary polyamidoamine phenol-amine resin nonionic demulsifier and preparation method thereof

Abstract

The invention discloses a combined phenol-primary polyamidoamine phenol-amine resin nonionic demulsifier and a preparation method thereof.The preparation method comprises the steps that phenol M and primary polyamidoamine are mixed, a formaldehyde solution is dropwise added, a reaction product is diluted with methyl alcohol, and phenol M-primary polyamidoamine resin slurry is obtained; the preparation method comprises the following steps: mixing organic phenol N and formaldehyde, reacting under the catalysis of sodium hydroxide, and diluting a product with methanol to obtain phenol N phenolic resin slurry; dropwise adding the phenol N phenolic resin slurry into the phenol M-primary polyamidoamine resin slurry, reacting, refluxing to remove methanol and water to obtain combined phenol-primary polyamidoamine resin, and polymerizing the combined phenol (M-N)-primary polyamidoamine resin with epoxypropane and ethylene oxide in sequence under the catalysis of alkali metal hydroxide to generate R-PO-EO diblock demulsifier polyether. And cross-linking with a cross-linking agent to obtain the finished demulsifier. The demulsifier prepared by the invention has the characteristics of high dehydration speed and high final dehydration rate for thick oil emulsion in the Bohai Sea region, and especially can effectively reduce an emulsion layer of output crude oil for thick oil output liquid in a high-water-content exploitation period.

Description

Technical Field

[0001] The present invention belongs to the technical field of oilfield chemicals, and particularly relates to a combined phenol-primary polyamide amine phenolic resin non-ionic demulsifier and a preparation method thereof. Background Art

[0002] The Bohai Oilfield is in the high water cut development stage. With the frequent implementation of various stimulation measures and the continuous development of marginal oilfields, the properties of the produced fluids are becoming increasingly complex and changeable, and the difficulty of crude oil treatment has also increased accordingly. In addition, in offshore crude oil production, there are characteristics such as small space, short process, limited residence time, and high export requirements, which pose an urgent need for the dehydration speed, deep dehydration ability of the demulsifier, especially in overcoming the emulsifying substances in crude oil to eliminate the emulsion layer.

[0003] Traditional demulsifiers such as polyamines, alcohols, phenolic resins, and phenolic amine resins are difficult to achieve coordinated progress in rapid demulsification, deep dehydration, and emulsification reduction, and are insufficient in reducing the emulsion layer contained in some crude oils. Summary of the Invention

[0004] The present invention is proposed to solve the problems existing in the prior art, and its purpose is to provide a combined phenol-primary polyamide amine phenolic resin non-ionic demulsifier and a preparation method thereof.

[0005] The present invention is achieved through the following technical solutions:

[0006] A preparation method of a combined phenol-primary polyamide amine phenolic resin non-ionic demulsifier, comprising the following steps:

[0007] (Ⅰ) Mix phenol M with primary polyamide amine, heat up to 70°C - 80°C and keep warm for 40 min, then dropwise add formaldehyde solution at a temperature below 35°C for 1 h - 2 h. After the dropping is completed, keep warm and react at 60°C for 1 h - 2 h. Cool down to 30°C and then add methanol for dilution to obtain a phenol M-primary polyamide amine resin slurry;

[0008] (Ⅱ) Mix phenol N and formaldehyde solution, and react at 60°C - 70°C for 1.5 h under the catalysis of sodium hydroxide. Cool down to 30°C and add methanol for dilution to obtain a phenol N phenolic resin slurry;

[0009] (Ⅲ) Slowly drop the phenol N phenolic resin slurry in step (Ⅱ) into the phenol M-primary polyamide amine resin slurry in step (Ⅰ), control the dropping temperature at 60°C - 70°C. After the dropping is completed, keep warm and react for 1 h, then heat up to 120°C - 140°C and react for 1 h - 1.5 h. Reflux to separate methanol and water, and after the reaction ends, obtain a combined phenol (M-N)-primary polyamide amine phenolic resin initiator;

[0010] (Ⅳ) Put the combined phenol (M-N)-polyamide amine phenolic resin initiator obtained in step (Ⅲ) into a high-pressure reactor. Start stirring and heat up to 100 °C, then add the catalyst. Conduct vacuum treatment at 100 °C - 110 °C for 20 min - 30 min. Replace the nitrogen in the reactor three times. Control the temperature at 130 °C - 140 °C and slowly add propylene oxide. After the reaction with propylene oxide ends, conduct vacuum for 15 min. Control the temperature at 120 °C - 130 °C and react with added ethylene oxide. After the reaction with ethylene oxide ends, cool down and discharge to obtain the demulsifier polyether;

[0011] (Ⅴ) Mix the demulsifier polyether obtained in step (Ⅳ) with a solvent, and slowly dropwise add a crosslinking agent thereto at 75 °C - 85 °C. After the dropwise addition is completed, keep the temperature for reaction for 1.5 h - 2.5 h to obtain the demulsifier.

[0012] A preparation method of a combined phenol-primary polyamide amine phenolic resin non-ionic demulsifier, comprising the following steps:

[0013] (Ⅰ) Mix phenol M with primary polyamide amine, heat up to 70 °C - 80 °C and keep the temperature for 40 min. Then, dropwise add a formaldehyde solution at a temperature below 35 °C, with the dropping time being 1 h - 2 h. After the dropwise addition is completed, keep the temperature at 60 °C for reaction for 1 h - 2 h. Cool down to 30 °C and then add methanol for dilution to obtain a phenol M-primary polyamide amine resin slurry;

[0014] (Ⅱ) Mix phenol N and a formaldehyde solution, and react at 60 °C - 70 °C for 1.5 h under the catalysis of sodium hydroxide. Cool down to 30 °C and add methanol for dilution to obtain a phenol N phenolic resin slurry;

[0015] (Ⅲ) Slowly dropwise add the phenol N phenolic resin slurry obtained in step (Ⅱ) into the phenol M-primary polyamide amine resin slurry obtained in step (Ⅰ), control the dropping temperature at 60 °C - 70 °C. After the dropwise addition is completed, keep the temperature for reaction for 1 h, then heat up to 120 °C - 140 °C and react for 1 h - 1.5 h. Reflux to separate methanol and water. After the reaction ends, obtain the combined phenol (M-N)-primary polyamide amine phenolic resin initiator;

[0016] (Ⅳ) Put the combined phenol (M-N)-polyamide amine phenolic resin initiator obtained in step (Ⅲ) into a high-pressure reactor. Start stirring and heat up to 100 °C, then add the catalyst. Conduct vacuum treatment at 100 °C - 110 °C for 20 min - 30 min. Replace the nitrogen in the reactor three times. Control the temperature at 130 °C - 140 °C and slowly add propylene oxide. After the reaction with propylene oxide ends, conduct vacuum for 15 min. Control the temperature at 120 °C - 130 °C and react with added ethylene oxide. After the reaction with ethylene oxide ends, cool down and discharge to obtain the demulsifier polyether;

[0017] (Ⅴ) Mix the demulsifier polyether obtained in step (Ⅳ) with a solvent, then add acrylic acid, an initiator, and an esterification catalyst, keep the temperature at 70 °C to 80 °C for a heat preservation reaction for 1.5 h, reflux and dehydrate at 150 °C for 1.5 h, and obtain a demulsifier after cooling.

[0018] In the above technical solution, the phenol M in step (Ⅰ) and the phenol N in step (Ⅱ) are independently selected from bisphenol A, phenol, tert-butylphenol, and nonylphenol, and phenol M and phenol N are different.

[0019] In the above technical solution, the primary polyamidoamine in step (Ⅰ) is an amine-terminated zero-grade polyamidoamine; the preparation method of the amine-terminated zero-grade polyamidoamine is: (ⅰ) Ethylenediamine and methyl acrylate are subjected to an addition reaction according to a molar ratio of 1:4; (ⅱ) The product of step (ⅰ) and ethylenediamine are subjected to a transesterification reaction according to a molar ratio of 1:4, and finally a primary polyamidoamine with a terminal amine group is obtained, which is also called a 0-grade polyamidoamine with a terminal amine group in the industry.

[0020] In the above technical solution, the molar ratio of phenol M, formaldehyde, and primary polyamidoamine in step (Ⅰ) is 1:(1 - 2.6):(1.5 - 3); the mass content of phenol M and primary polyamidoamine in the phenol M-primary polyamidoamine resin slurry after dilution with methanol is 50% of the mass content of phenol M and primary polyamidoamine in the solution before dilution.

[0021] In the above technical solution, phenol N and formaldehyde solution in step (Ⅱ) are mixed according to a molar ratio of phenol N to formaldehyde of 1:(1 - 2.5); the added mass of sodium hydroxide in step (Ⅱ) is 1% of the mass of phenol N; the mass concentration of the formaldehyde solution in step (Ⅱ) is 37%; the mass content of phenol N in the phenol N-phenol formaldehyde resin slurry after dilution with methanol is 50% of the mass content of phenol N in the solution before dilution.

[0022] In the above technical solution, the mass ratio of the phenol N-phenol formaldehyde resin slurry in step (Ⅱ) to the phenol M-primary polyamidoamine resin slurry in step (Ⅰ) in step (Ⅲ) is (10 - 40):100.

[0023] In the above technical solution, the mass ratio of the combined phenol (M-N)-polyamidoamine phenol amine resin initiator, propylene oxide, and ethylene oxide in step (Ⅳ) to the product in step (Ⅲ) is 1:(80 - 260):(15 - 130); the catalyst in step (Ⅳ) is an alkali metal hydroxide; the catalyst accounts for 0.3% - 0.5% of the total mass of the combined phenol (M-N)-polyamidoamine phenol amine resin initiator, propylene oxide, and ethylene oxide.

[0024] In the above technical solution, the crosslinking agent in step (Ⅴ) is toluene diisocyanate; the solvent is xylene; the mass ratio of the demulsifier polyether, solvent and crosslinking agent in step (Ⅴ) is 100:(115 - 200):(3 - 7).

[0025] In the above technical solution, the solvent in step (Ⅴ) is xylene; the initiator in step (Ⅴ) is benzoyl peroxide; the esterification catalyst in step (Ⅴ) is p-toluenesulfonic acid; the mass ratio of the demulsifier polyether, solvent and acrylic acid in step (Ⅴ) is 100:(100 - 140):(5 - 15); the added mass of the initiator is 0.25% - 2.25% of the mass of the demulsifier polyether; the added mass of the esterification catalyst is 1% - 2.5% of the mass of the demulsifier polyether.

[0026] A combined phenol-primary polyamide amine phenolic resin non-ionic demulsifier is prepared by the aforementioned method.

[0027] The beneficial effects of the present invention are as follows:

[0028] The present invention provides a combined phenol-primary polyamide amine phenolic resin non-ionic demulsifier and its preparation method. After synthesizing a new initiator using phenol M, phenol N, formaldehyde solution and primary polyamide amine, it is polymerized with propylene oxide and ethylene oxide to form a block demulsifier polyether, and a non-ionic demulsifier is obtained after chain extension with a crosslinking agent. The prepared polyether demulsifier has good demulsification performance and emulsification reduction ability for Bohai heavy oil emulsion, and is especially suitable for the treatment of heavy oil production fluid in the high water cut production period. The demulsifier has been applied in multiple oil fields in the Bohai region, and has obvious effect on the rapid and deep demulsification of heavy oil production fluid in the high water cut production period; the preparation method is simple and easy to industrialize. Description of the Drawings

[0029] Figure 1 It is a photo of the indoor dehydration experiment of the demulsifier prepared in Examples 1 - 4 of the present invention (taken after the experiment readings ended, corresponding to Table 1);

[0030] Figure 2 It is a graph of the water content of the crude oil in the lower cabin of the electro-dehydrator after the application of the demulsifier product prepared in Example 1 of the present invention (the blue curve is the demulsifier product BH-236 prepared in Example 1, and the yellow curve is a certain demulsifier product BH-171 originally used in the oil field).

[0031] For those of ordinary skill in the art, without creative efforts, other relevant drawings can be obtained based on the above drawings. Detailed Embodiments

[0032] To enable those skilled in the art to better understand the technical solution of the present invention, the technical solution of the present invention will be further described below in conjunction with the accompanying drawings of the specification and through specific embodiments.

[0033] Example 1

[0034] A preparation method of a combined phenol-primary polyamide amine phenolic resin non-ionic demulsifier includes the following steps:

[0035] (Ⅰ) Add 46 g of bisphenol A and 217 g of primary polyamide amine into a three-necked flask. Insert a thermometer and a dropping funnel into the three-necked flask, heat up to 75 °C, keep warm for 40 min, then cool down to 30 °C. Add 33 g of formaldehyde solution with a mass fraction of 37% into the dropping funnel, and cover the piston. Control the reaction temperature not higher than 35 °C and slowly dropwise add the formaldehyde solution for 60 min. After the formaldehyde solution is completely dropped, heat up to 65 °C, keep warm and react for 1.5 h, then cool down to 30 °C and add 249 g of methanol and stir evenly for standby;

[0036] (Ⅱ) Add 44 g of nonylphenol, 25 g of formaldehyde solution with a mass fraction of 37%, and 0.66 g of sodium hydroxide into a three-necked flask. Insert a thermometer into the three-necked flask, heat up to 70 °C, keep warm and react for 60 min, then cool down to 30 °C and add 26 g of methanol and stir evenly for standby;

[0037] (Ⅲ) Add the solution obtained in step (Ⅰ) into a three-necked flask. Insert a thermometer, a dropping funnel, and a condensation reflux device into the three-necked flask. Control the reaction temperature at 65 °C and slowly dropwise add 95.66 g of the solution prepared in step (Ⅱ). The dropping time is 60 min. After the dropping is completed, keep warm and react for 1 h, then heat up to 140 °C, reflux to separate methanol and water in the system. After the separation is completed, keep warm and react for 1 h, then cool down to obtain an initiator;

[0038] (Ⅳ) Put 10 g of the initiator in step (Ⅲ) into a high-pressure reactor, start stirring, heat up to 100 °C and add potassium hydroxide. Evacuate at 110 °C for 20 min, then replace with nitrogen three times. Control the temperature at 136 °C and slowly dropwise add 1500 g of propylene oxide; After the reaction of propylene oxide is completed, evacuate for 15 min, then control the temperature at 125 °C and slowly dropwise add 380 g of ethylene oxide for reaction. After the reaction of ethylene oxide is completed, cool down and discharge to obtain a demulsifier polyether;

[0039] (Ⅴ) Add 150 g of the demulsifier polyether obtained from the above reaction and 236 g of xylene into a three-necked flask. Insert a thermometer and a dropping funnel into the three-necked flask. Control the reaction temperature at 80 °C and slowly dropwise add 8 g of toluene diisocyanate. After the dropping is completed, keep warm and react for 2 h to obtain a demulsifier monomer, denoted as FR.

[0040] Example 2

[0041] A preparation method of a combined phenol-primary polyamide amine phenolic resin non-ionic demulsifier, comprising the following steps:

[0042] (Ⅰ) Add 46 g of bisphenol A and 217 g of primary polyamide amine into a three-necked flask. Insert a thermometer and a dropping funnel into the three-necked flask. Heat up to 75 °C, keep warm for 40 min, then cool down to 30 °C. Add 33 g of formaldehyde solution with a mass fraction of 37% into the dropping funnel, cover the piston, and slowly add the formaldehyde solution while controlling the reaction temperature not higher than 35 °C. The dropping time is 40 min to 90 min. After the formaldehyde solution is completely added, heat up to 70 °C, keep the reaction warm for 1.5 h, and then cool down to 30 °C. Add 270 g of methanol and stir evenly for standby;

[0043] (Ⅱ) Add 30 g of tert-butylphenol, 25 g of formaldehyde solution with a mass fraction of 37%, and 0.5 g of sodium hydroxide into a three-necked flask. Insert a thermometer into the three-necked flask, heat up to 70 °C, keep the reaction warm for 60 min, then cool down to 30 °C, add 12 g of methanol and stir evenly for standby;

[0044] (Ⅲ) Add the solution obtained in step (Ⅰ) into a three-necked flask. Insert a thermometer, a dropping funnel, and a condensing reflux device into the three-necked flask. Control the reaction temperature at 65 °C, and slowly add 105 g of the solution prepared in step (Ⅱ). The dropping time is 60 min. After the dropping is completed, keep the reaction warm for 1 h, heat up to 150 °C, reflux to separate methanol and water in the system. After the separation is completed, keep the reaction warm for 1 h, and cool down to obtain a new initiator;

[0045] (Ⅳ) Put 10 g of the initiator in step (Ⅲ) into a high-pressure reactor, start stirring, heat up to 100 °C, add potassium hydroxide, evacuate at 110 °C, vacuum process for 20 min, control the temperature at 136 °C, and slowly add 1200 g of propylene oxide; after the reaction of propylene oxide is completed, evacuate for 15 min, then control the temperature at 125 °C, and slowly add 305 g of ethylene oxide for reaction. After the reaction of ethylene oxide is completed, cool down and discharge to obtain the demulsifier polyether;

[0046] (Ⅴ) Add 150 g of the demulsifier polyether obtained from the above reaction and 236 g of xylene into a three-necked flask. Insert a thermometer and a dropping funnel into the three-necked flask. Control the reaction temperature at 80 °C and slowly add 8 g of toluene diisocyanate. After the dropping is completed, keep the reaction warm for 2 h to obtain the demulsifier monomer, denoted as FTP.

[0047] Example 3

[0048] A preparation method of a combined phenol-primary polyamide amine phenolic resin non-ionic demulsifier, comprising the following steps:

[0049] (Ⅰ) Add 46 g of bisphenol A and 217 g of primary polyamidoamine to a three-necked flask. Insert a thermometer and a dropping funnel into the three-necked flask. Heat up to 75 °C, keep warm for 40 min, then cool down to 30 °C. Add 33 g of formaldehyde solution with a mass fraction of 37% to the dropping funnel, cover the piston, and slowly add the formaldehyde solution while controlling the reaction temperature not higher than 35 °C. The dropping time is 40 min to 90 min. After the formaldehyde solution is completely added, heat up to 70 °C, keep the reaction warm for 1.5 h, then cool down to 30 °C and add 249 g of methanol and stir evenly for standby;

[0050] (Ⅱ) Add 37.6 g of phenol, 40 g of formaldehyde solution with a mass fraction of 37%, and 0.4 g of sodium hydroxide to a three-necked flask. Insert a thermometer into the three-necked flask, heat up to 70 °C, keep the reaction warm for 60 min, then cool down to 30 °C and add 10 g of methanol and stir evenly for standby;

[0051] (Ⅲ) Add the solution obtained in step (Ⅰ) to a three-necked flask. Insert a thermometer, a dropping funnel, and a condensing reflux device into the three-necked flask. Control the reaction temperature at 65 °C and slowly add 88 g of the solution prepared in step (Ⅱ). The dropping time is 60 min. After the dropping is completed, keep the reaction warm for 1 h, then heat up to 150 °C to reflux and separate methanol and water in the system. After the separation is completed, keep the reaction warm for 1 h, then cool down to obtain a novel initiator;

[0052] (Ⅳ) Put 10 g of the initiator in step (Ⅲ) into a high-pressure reactor. Start stirring, heat up to 100 °C and add potassium hydroxide. Evacuate at 110 °C for 20 min. Control the temperature at 136 °C and slowly add 1200 g of propylene oxide; after the reaction of propylene oxide is completed, evacuate for 15 min, then control the temperature at 125 °C and slowly add 305 g of ethylene oxide for reaction. After the reaction of ethylene oxide is completed, cool down and discharge to obtain a demulsifier polyether;

[0053] (Ⅴ) Add 150 g of the demulsifier polyether obtained from the above reaction and 236 g of xylene to a three-necked flask. Insert a thermometer and a dropping funnel into the three-necked flask. Control the reaction temperature at 80 °C and slowly add 8 g of toluene diisocyanate. After the dropping is completed, keep the reaction warm for 2 h to obtain a demulsifier monomer, denoted as FP.

[0054] Example 4

[0055] A preparation method of a combined phenol-primary polyamidoamine phenolic resin non-ionic demulsifier, comprising the following steps:

[0056] (Ⅰ) Add 23.5 g of phenol and 259 g of primary polyamidoamine to a three-necked flask. Insert a thermometer and a dropping funnel into the three-necked flask. Heat up to 75 °C, keep warm for 40 min, then cool down to 30 °C. Add 41 g of formaldehyde solution with a mass fraction of 37% to the dropping funnel, cover the piston, and slowly add the formaldehyde solution while controlling the reaction temperature not higher than 35 °C. The dropping time is 40 min to 90 min. After the formaldehyde solution is added dropwise, heat up to 65 °C, keep the reaction warm for 1.5 h, then cool down to 30 °C and add 242 g of methanol and stir evenly for standby;

[0057] (Ⅱ) Add 66 g of nonylphenol, 37 g of formaldehyde solution with a mass fraction of 37%, and 1 g of sodium hydroxide to a three-necked flask. Insert a thermometer into the three-necked flask, heat up to 70 °C, keep the reaction warm for 60 min, then cool down to 30 °C and add 29 g of methanol and stir evenly for standby;

[0058] (Ⅲ) Add the solution obtained in step (Ⅰ) to a three-necked flask. Insert a thermometer, a dropping funnel, and a condensation reflux device into the three-necked flask. Control the reaction temperature at 65 °C and slowly add 132 g of the solution prepared in step (Ⅱ). The dropping time is 60 min. After the dropping is completed, keep the reaction warm for 1 h, then heat up to 140 °C to reflux and separate methanol and water in the system. After the separation is completed, keep the reaction warm for 1 h, and then cool down to obtain a new initiator;

[0059] (Ⅳ) Put 10 g of the initiator in step (Ⅲ) into a high-pressure reactor, start stirring, heat up to 100 °C and add potassium hydroxide. Evacuate at 110 °C for 20 min. Control the temperature at 136 °C and slowly add 1200 g of propylene oxide; after the reaction of propylene oxide is completed, evacuate for 15 min, then control the temperature at 125 °C and slowly add 305 g of ethylene oxide for reaction. After the reaction of ethylene oxide is completed, cool down and discharge to obtain a demulsifier polyether;

[0060] (Ⅴ) Add 150 g of the demulsifier polyether obtained from the above reaction and 236 g of xylene to a three-necked flask. Insert a thermometer and a dropping funnel into the three-necked flask. Control the reaction temperature at 80 °C and slowly add 8 g of toluene diisocyanate. After the dropping is completed, keep the reaction warm for 2 h to obtain a demulsifier monomer, denoted as PR.

[0061] Perform performance tests on the demulsifiers prepared in Examples 1 to 4:

[0062] For the viscous oil produced liquid from a certain oilfield in the Bohai Sea, at the on-site temperature (78 °C), refer to the petroleum and natural gas industry standard SY / T 5281-2000 "Testing Method for the Performance of Crude Oil Demulsifier (Bottle Test Method)", see Table 1, Figure 1 .

[0063] Table 1

[0064]

[0065]

[0066] It can be proved by the above results that the novel combined phenol-primary polyamidoamine non-ionic demulsifier obtained in this embodiment has the characteristics of fast and thorough demulsification speed.

[0067] After the combined phenol-primary polyamidoamine phenolic amine resin type non-ionic demulsifier is applied to the field after production scale-up (BH-236), it can significantly reduce the BS&W of the crude oil exported from the oil tanker, and the water content of the exported crude oil remains at a low level, as shown in Figure 2 .

[0068] Principle of the present invention:

[0069] The gums, asphaltenes and unknown solid particles contained in the heavy oil produced liquid during the high water cut production period have a great impact on the emulsification of crude oil. The aromatic ring structure is the main component of asphaltenes and gums. The increase of the aromatic ring structure and the introduction of the polyamidoamine branched structure in the demulsifier molecule can make the demulsifier molecule have better compatibility with gums, asphaltenes and inorganic solid particles, thus playing a positive role in the rapid demulsification and reduction of emulsification of high water cut heavy oil. This demulsifier has the characteristics of fast dehydration speed and high final dehydration rate for the heavy oil emulsion in the Bohai Sea area, and can effectively reduce the emulsion layer of the exported crude oil especially for the heavy oil produced liquid during the high water cut production period.

[0070] The novel demulsifier developed in the present invention shows good uniform progress in key aspects such as rapid dehydration, deep demulsification and reduction of emulsification by increasing the aromatic nucleus number of the initiator molecule and coordinating the degree of branching of the molecule. The demulsifier polyether prepared by the novel initiator improves the performance of the demulsifier.

[0071] The applicant declares that the above description is only the specific implementation manner of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily thought of within the technical scope disclosed by the present invention fall within the protection scope and the disclosure scope of the present invention.

Claims

1. A method for preparing a combined phenol-primary polyamide-amine phenolamine resin nonionic demulsifier, characterized in that: The following steps are involved: (I) mixing phenol M and primary polyamide amine, heating to 70°C to 80°C for 40 minutes, then adding formaldehyde solution dropwise at a temperature below 35°C for 1 to 2 hours, and then reacting at 60°C for 1 to 2 hours, cooling to 30°C, adding methanol for dilution, and obtaining phenol M-primary polyamide amine resin slurry; (II) mixing phenol N and formaldehyde solution, reacting at 60°C to 70°C for 1.5 hours under the catalysis of sodium hydroxide, cooling to 30°C, adding methanol to dilute, and obtaining phenol N phenolic resin slurry; (III) slowly adding the phenol N novolac resin slurry of step (II) to the phenol M-primary polyamide amine resin slurry of step (I), the dropping temperature is controlled at 60°C to 70°C, and the reaction is kept warm for 1 hour after the dropwise addition is completed, and then the temperature is raised to 120°C to 140°C, and the reaction is carried out for 1 hour to 1.5 hours, and methanol and water are separated by reflux. After the reaction is completed, a combined phenol (MN)-primary polyamide amine phenol amine resin starter is obtained; (IV) putting the product combination of phenol (MN)-polyamide amine phenol amine resin initiator of step (III) into a high-pressure reactor, starting stirring, heating to 100°C, adding a catalyst, vacuumizing at 100°C-110°C for 20min-30min, nitrogen replacing the reactor 3 times, controlling the temperature at 130°C-140°C, slowly adding propylene oxide, and after the reaction with propylene oxide is completed, vacuumizing for 15min, controlling the temperature at 120°C-130°C and reacting with ethylene oxide, cooling and discharging to obtain a demulsifier polyether; (V) The demulsifier polyether obtained in step (IV) is mixed with a solvent, and a cross-linking agent is slowly added dropwise at 75° C. to 85° C. After the addition is completed, the mixture is heated and reacted for 1.5 h to 2.5 h to obtain a demulsifier.

2. A method for preparing a combined phenol-primary polyamide-amine phenolamine resin nonionic demulsifier, characterized in that: The following steps are involved: (I) mixing phenol M and primary polyamide amine, heating to 70°C to 80°C for 40 minutes, then adding formaldehyde solution dropwise at a temperature below 35°C for 1 to 2 hours, and then reacting at 60°C for 1 to 2 hours, cooling to 30°C, adding methanol for dilution, and obtaining phenol M-primary polyamide amine resin slurry; (II) mixing phenol N and formaldehyde solution, reacting at 60°C to 70°C for 1.5 hours under the catalysis of sodium hydroxide, cooling to 30°C, adding methanol to dilute, and obtaining phenol N phenolic resin slurry; (III) slowly adding the phenol N novolac resin slurry of step (II) to the phenol M-primary polyamide amine resin slurry of step (I), the dropping temperature is controlled at 60°C to 70°C, and the reaction is kept warm for 1 hour after the dropwise addition is completed, and then the temperature is raised to 120°C to 140°C, and the reaction is carried out for 1 hour to 1.5 hours, and methanol and water are separated by reflux. After the reaction is completed, a combined phenol (MN)-primary polyamide amine phenol amine resin starter is obtained; (IV) putting the product combination of phenol (MN)-polyamide amine phenol amine resin initiator of step (III) into a high-pressure reactor, starting stirring, heating to 100°C, adding a catalyst, vacuumizing at 100°C-110°C for 20min-30min, nitrogen replacing the reactor 3 times, controlling the temperature at 130°C-140°C, slowly adding propylene oxide, and after the reaction with propylene oxide is completed, vacuumizing for 15min, controlling the temperature at 120°C-130°C and reacting with ethylene oxide, cooling and discharging to obtain a demulsifier polyether after the reaction with ethylene oxide is completed; (V) The demulsifier polyether obtained in step (IV) is mixed with a solvent, and acrylic acid, an initiator and an esterification catalyst are added, and the mixture is reacted at 70° C. to 80° C. for 1.5 h, and refluxed at 150° C. for dehydration for 1.5 h, and the demulsifier is obtained after cooling.

3. The preparation method of the combination phenol-primary polyamide-amine phenolamine resin nonionic demulsifier according to claim 1 or 2, characterized in that: The phenol M in step (I) and the phenol N in step (II) are independently selected from bisphenol A, phenol, tert-butylphenol and nonylphenol, and the phenol M and the phenol N are different; the primary polyamidoamine in step (I) is an amino-terminated zero-order polyamidoamine.

4. The method for preparing a nonionic demulsifier of a combination phenol-primary polyamide-amine phenolamine resin according to claim 1 or 2, characterized in that: In the step (I), the molecular ratio of phenol M, formaldehyde and primary polyamide amine is 1:(1-2.6):(1.5-3); the mass content of phenol M and primary polyamide amine in the phenol M-primary polyamide amine resin slurry after dilution with methanol is 50% of the mass content of phenol M and primary polyamide amine in the solution before dilution.

5. The method for preparing the nonionic demulsifier of the combined phenol-primary polyamide-amine phenolamine resin according to claim 1 or 2, characterized in that: In the step (II), phenol N and formaldehyde solution are mixed according to a molecular ratio of phenol N to formaldehyde of 1: (1-2.5); the mass of sodium hydroxide added in the step (II) is 1% of the mass of phenol N; the mass concentration of the formaldehyde solution in the step (II) is 37%; the mass content of phenol N in the phenol N novolac resin slurry after dilution with methanol is 50% of the mass content of phenol N in the solution before dilution.

6. The method for preparing the nonionic demulsifier of the combined phenol-primary polyamide-amine phenolamine resin according to claim 1 or 2, characterized in that: In the step (III), the mass ratio of the phenol N novolac resin slurry of step (II) to the phenol M-primary polyamide amine resin slurry of step (I) is (10-40):

100.

7. The method for preparing the nonionic demulsifier of the combined phenol-primary polyamide-amine phenolamine resin according to claim 1 or 2, characterized in that: In the step (IV), the mass ratio of the product of step (III) combined phenol (MN)-polyamide amine phenol amine resin initiator, propylene oxide and ethylene oxide is 1: (80-260): (15-130); the catalyst in the step (IV) is an alkali metal hydroxide; the catalyst accounts for 0.3% to 0.5% of the total mass of the combined phenol (MN)-polyamide amine phenol amine resin initiator, propylene oxide and ethylene oxide.

8. The method for preparing the combined phenol-primary polyamide-amine phenolamine resin nonionic demulsifier according to claim 1, characterized in that: The cross-linking agent in the step (V) is toluene diisocyanate; the solvent is xylene; the mass ratio of the demulsifier polyether, the solvent and the cross-linking agent in the step (V) is 100: (115-200): (3-7).

9. The method for preparing the combined phenol-primary polyamide-amine phenolamine resin nonionic demulsifier according to claim 2, characterized in that: The solvent in step (V) is xylene; the initiator in step (V) is benzoyl peroxide; the esterification catalyst in step (V) is p-toluenesulfonic acid; the mass ratio of the demulsifier polyether, the solvent and the acrylic acid in step (V) is 100:(100-140):(5-15); the added mass of the initiator is 0.25%-2.25% of the mass of the demulsifier polyether; the added mass of the esterification catalyst is 1%-2.5% of the mass of the demulsifier polyether.

10. A combined phenol-primary polyamide-amine phenol-amine resin nonionic demulsifier, characterized in that: Prepared by the method of claim 1 or 2.

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