Comb-type polyester ether demulsifier using polyamino polyether as initiator and preparation method thereof

Abstract

The present invention discloses a comb-type polyester ether demulsifier with polyamino polyether as an initiator and a preparation method thereof. A new polyester ether structure demulsifier derived from the polyamino polyether is used, that is, a polyamino polyether with a certain degree of polymerization is used as an initiator, and a ring-opening polymerization reaction is carried out with ethylene carbonate under the action of a catalyst to obtain a comb-type polyester ether demulsifier with polyamino polyether as an initiator. The demulsifier product synthesized by this technology is developed in the spirit of improving the disadvantages of the original patented product, simplifying the process flow, optimizing product performance, reducing manufacturing costs, and improving operational safety. The present invention uses ethylene carbonate as a raw material. Compared with the polyether demulsifier produced with ethylene oxide and propylene oxide as raw materials, the raw material price is reduced by more than 20%, and the production cost has a more competitive advantage in the market. The product performance can fully meet the technical requirements for the demulsification and dehydration link in the oil field production process.

Description

Technical Field

[0001] The invention belongs to the field of preparing demulsifiers by chemical methods, and particularly relates to a comb-type polyester ether demulsifier using polyamino polyether as an initiator and a preparation method thereof. Background Art

[0002] Publication number CN104774646A, the prior art of comb-type polyether demulsifier and preparation method with polyamino polyether as initiator, is to synthesize polyamino polyether into polyamino polyether lipophilic head first, and then synthesize demulsifier, which is prepared by two-step method, and the method has the following problems: first, the preparation process is cumbersome, and second, ethylene oxide and propylene oxide are used in the preparation process, and ethylene oxide and propylene oxide are flammable and explosive, toxic and carcinogenic, and difficult to transport, and have regional problems. On the other hand, ethylene carbonate is not only a polar organic solvent with excellent performance, but also has the advantages of high boiling point, high flash point, low volatility and low toxicity, and is a potential green organic chemical basic raw material. China is the world's largest ethylene carbonate production area, accounting for more than 50% of the market share. With the continuous innovation of China's synthetic ethylene carbonate technology, the production capacity is on the rise, making ethylene carbonate cheaper and easier to obtain, thereby promoting the development and market promotion of downstream products with significant raw material cost advantages. The comb-shaped polyester ether demulsifier of the present invention uses ethylene carbonate as a raw material. Compared with polyether demulsifiers produced using ethylene oxide and propylene oxide as raw materials, the raw material price is reduced by more than 20%, and the production cost has a greater market competitive advantage. Summary of the invention

[0003] The present invention aims to overcome the deficiencies of the prior art and provides a comb-type polyester ether demulsifier using polyamino polyether as an initiator and a preparation method thereof. The invention uses a novel polyester ether structure demulsifier derived from the polyamino polyether, that is, polyamino polyether with a certain polymerization degree as an initiator, and reacts with ethylene carbonate under the action of a catalyst to undergo a ring-opening polymerization reaction to obtain a comb-type polyester ether demulsifier using polyamino polyether as an initiator.

[0004] The present invention discloses a comb-type polyester ether demulsifier using polyamino polyether as an initiator, and its structural formula is as follows:

[0005]

[0006] In the above structural formula: a and b are the polymerization degrees of the polyamino polyether initiator, a and b are positive integers greater than or equal to 1, and 5≤(a+b)≤50;

[0007] In the above structural formula: m is the polymerization degree of carbonate groups in the product molecule, n is the polymerization degree of ethoxy groups in the molecule, and both values ​​are positive integers greater than or equal to 1, and 5≤(m+n)≤250.

[0008] The preparation method of a comb-type polyester ether demulsifier using polyamino polyether as an initiator of the present invention comprises the following steps:

[0009] Put the initiator polyamino polyether, ethylene carbonate and catalyst potassium hydroxide into the reactor, heat up to 70-80℃ under closed conditions, start stirring; fully replace the reactor with nitrogen, replace the air in the reaction system, and press the reactor pressure to 0.09-0.1Mpa with nitrogen; continue to heat to 120-150℃, during which the pressure is controlled between 0.2-0.4Mpa, if it exceeds 0.4Mpa, properly vent and release the pressure to ensure the safety and normal progress of the reaction; maintain the reaction time for 9-12 hours, and in the later stage of the reaction, take samples to measure the hydroxyl value of the product. When the hydroxyl value of the product is ≥500mgKOH / g, continue the aging reaction for 1 hour. After the reaction is completed, cool water is introduced into the reactor coil, the temperature drops to below 40℃, and the reactor is depressurized to normal pressure to take out the product, so as to obtain a comb-type polyester ether demulsifier product with polyamino polyether as the initiator.

[0010] The molar ratio of the initiator polyamino polyether to ethylene carbonate is 1:5-250, and the added amount of the catalyst potassium hydroxide is 1-3‰ of the total mass of the polyamino polyether and ethylene carbonate.

[0011] The present invention is based on the fact that during the ring-opening polymerization of ethylene carbonate, a certain degree of CO2 removal reaction will occur to generate a polymer with a polyester (2-hydroxyethyl carbonate) / polyether (2-hydroxyethyl ether) block structure, which is similar to the polyoxypropylene / polyoxyethylene block polyether structure in polyether demulsifiers and has the characteristics of hydrophilic and lipophilic groups of polyether demulsifiers in structure.

[0012] The present invention uses ethylene carbonate as a raw material to replace propylene oxide and ethylene oxide in the prior art. From a process point of view, the two-step reaction is simplified to a one-step reaction, making the production process simpler and the operation process safer and more environmentally friendly. At the same time, it also avoids the problems of ethylene oxide and propylene oxide being flammable and explosive, toxic and carcinogenic, difficult to transport, and regional. Thus, the optimization and upgrading of the prior art products is achieved. The comb-type polyester ether demulsifier product synthesized by this patent has a wide adaptability to various crude oil emulsions, and can fully meet the requirements of the water content of the oil phase and the oil content of the water phase in the demulsification and dehydration link in the oil field production process, and has a very important application prospect in the oil and gas gathering and transportation process. Implementation

[0013] The technology of the present invention belongs to a comb-type polyester ether demulsifier using polyamino polyether as an initiator and a preparation method thereof, which is prepared by the following steps:

[0014] 1. Synthesis of initiator polyamino polyether:

[0015] The synthesis process of polyamino polyether is based on the authorized patent "CN 201510193464.3 "Comb-type polyether demulsifier using polyamino polyether as initiator and preparation method thereof". The specific preparation process is as follows:

[0016] 1.1 Synthesis of chlorinated polyether

[0017] 1.1.1 Add precisely weighed ethylene glycol and catalyst boron trifluoride-ether complex to a dry reactor, and start stirring;

[0018] 1.1.2 Control the reaction temperature to 50°C, add measured epichlorohydrin dropwise, and control the addition time to 4 to 5 hours;

[0019] 1.1.3 After the addition is completed, the reaction temperature is controlled at 50°C and the reaction is continued for 2 hours. Then the temperature of the reactor is raised to 90°C and the reaction is continued for 1 hour.

[0020] 1.1.4 After the reaction is completed, at a temperature of 90°C in the reactor, unreacted epichlorohydrin and catalyst are extracted under negative pressure, and the chlorinated polyether is released for standby use by cooling;

[0021] In the reaction process described in 1.1.5, the amount of the catalyst boron trifluoride-ether complex added is 3-5‰ of the total mass of ethylene glycol and epichlorohydrin;

[0022] In the reaction process described in 1.1.6, the molar ratio of ethylene glycol to epichlorohydrin is 1:5 to 50. Preferably, the molar ratio of ethylene glycol to epichlorohydrin is 1:20, 1:30, and 1:40, and chlorinated polyethers CPE20, CPE30, and CPE40 with different polymerization degrees are prepared according to these ratios.

[0023] 1.2 Synthesis of polyamino polyether

[0024] 1.2.1 Add the accurately weighed chloropolyether (CPE) prepared in the previous step, 40% commercial concentration monomethylamine solution, solvent ethanol, and phase transfer catalyst tetra-n-butylammonium bromide into the autoclave in sequence;

[0025] 1.2.2 Close the autoclave and start stirring. Control the autoclave temperature to 90-100℃ and continue the reaction for 4 hours. The pressure should not exceed 0.3MPa.

[0026] 1.2.3 After the reaction is completed, cool the autoclave to 20-30°C while stirring;

[0027] 1.2.4 Open the autoclave and add accurately weighed 40% sodium hydroxide aqueous solution into the autoclave;

[0028] 1.2.5 Close the high-pressure reactor and start stirring. Heat the reactor to 80-90°C and react for 3 hours.

[0029] 1.2.6 Keep the temperature of the autoclave rising continuously, and evaporate the solvent ethanol and water under negative pressure, with the final temperature not exceeding 120℃;

[0030] 1.2.7 After the negative pressure distillation is completed, cooling water is introduced into the autoclave to cool it down to 20-30°C, and then anhydrous ethanol is added into the autoclave, and after stirring evenly, the reaction product polyamino polyether (MAP) ethanol solution is released;

[0031] 1.2.8 Filter the above ethanol solution through a filter press to remove the inorganic salt, evaporate the ethanol from the liquid part, and the remaining product is the reaction product polyamino polyether (MAP).

[0032] In the reaction process of the present invention, polyamino polyethers MAP20, MAP30 and MAP40 with different polymerization degrees are prepared according to chlorinated polyethers CPE20, CPE30 and CPE40 with different polymerization degrees.

[0033] The molar ratio of chlorinated polyether to monomethylamine is:

[0034] Polyamino polyether MAP20: Chlorinated polyether CPE20 / monomethylamine=1 / 20

[0035] Polyamino polyether MAP20: Chlorinated polyether CPE30 / monomethylamine=1 / 30

[0036] Polyamino polyether MAP20: Chlorinated polyether CPE40 / monomethylamine=1 / 40

[0037] For other conditions of the synthesis process of polyamino polyether, please refer to the requirements of the patent "CN201510193464.3 "Comb-type polyether demulsifier using polyamino polyether as initiator and preparation method" of Daqing Fujie Chemical Co., Ltd.

[0038] 2. Synthesis of comb-type polyester ether demulsifier with polyamino polyether as initiator:

[0039] 2.1 Add the prepared polyamino polyether initiator (MAP), ethylene carbonate and catalyst potassium hydroxide into the reactor, and close the reactor;

[0040] 2.2 The reactor is heated to 70-80°C and stirring is started; nitrogen is introduced to replace the air in the reactor, and the pressure of the reactor is pressed to 0.09-0.1Mpa with nitrogen;

[0041] 2.3 Continue to heat up, control the temperature at 120-150℃, the pressure at 0.2-0.4Mpa, and maintain the reaction for 9-12 hours; if the pressure of the reactor exceeds 0.4Mpa, open the reactor to vent and control the reaction pressure within the required range;

[0042] 2.4 When the reaction time reaches 9 hours, take out a proper amount of product every 1 hour to measure the hydroxyl value until the hydroxyl value of the product is ≥500mgKOH / g, and continue to maintain the reactor temperature at 150℃ for aging reaction for 1 hour. After the aging is completed, the reaction is considered to be completed;

[0043] 2.5 After the reaction is completed, cooling water is introduced into the reactor coil to reduce the temperature to below 40°C, and the reactor is depressurized to normal pressure to take out the product, thus obtaining a comb-type polyester ether demulsifier product with polyamino polyether as the initiator;

[0044] In the above reaction process, different series of comb-type polyester ether demulsifiers are prepared by using polyamino polyethers MAP20, MAP30 and MAP40 with different polymerization degrees as initiators and ethylene carbonate, wherein the molar ratio of polyamino polyether to ethylene carbonate is generally determined according to the number of amino groups in the polyamino polyethers with different polymerization degrees.

[0045] MAP20 Series:

[0046] The initiator polyamino polyether MAP20 is preferably used in four ratios of 1:20, 1:40, 1:60, and 1:80, and the obtained MAP20 series comb-type polyester ether demulsifier products are as follows:

[0047]

[0048] MAP30 Series:

[0049] Among them, the initiator polyamino polyether MAP30 is preferably used in four ratios of 1:30, 1:60, 1:90, and 1:120, and the obtained MAP30 series comb-type polyester ether demulsifier products are as follows:

[0050]

[0051] MAP40 Series:

[0052] The preferred ratios of the initiator polyamino polyether MAP40 are 1:40, 1:80, 1:120, and 1:160, and the obtained MAP40 series comb-type polyester ether demulsifier products are as follows:

[0053]

[0054] The polymer flooding produced fluid of the Xing 13-1 Joint Station of the Fifth Oil Production Plant of Daqing Oilfield was used as the test medium (wherein the oil content was 55%, the water content was 45%, the surfactant content was 58 mg / L, and the polymer content was 776 mg / L) to carry out a bottle test dehydration experiment on the above-mentioned synthetic sample to illustrate the effect of the present invention. The experimental conditions are as follows:

[0055] Test temperature: 50℃;

[0056] Experimental equipment: formula bottle, constant temperature water bath, micro-injector, oil-water content determination device and common instruments;

[0057] Emulsification conditions: Emulsification was shaken on a shaker for 30 minutes.

[0058] Demulsifier dosage: 30mg / L;

[0059] After emulsification and shaking, the formula bottle containing the test medium is immediately placed in a 50°C water bath. After static dehydration for 60 minutes, the upper oil phase is extracted for water content determination using the standard GB / T8929 "Determination of Water Content of Crude Oil - Distillation Method"; the lower water phase is extracted for water-oil determination using the standard SY / T0530 "Determination of Oil Content in Oilfield Wastewater - Spectrophotometric Method".

[0060] The experimental data are shown in the table:

[0061]

[0062] Based on the above experimental data, MAP39 and MAP48 models were selected as superior products for further experiments. The purpose was to compare the performance with the superior products MAP (199) 151 and MAP (299) 310 in the patent (CN 201510193464.3). The synthesis process of MAP (199) 151 and MAP (299) 310 is detailed in the patent "CN 201510193464.3 "Comb-type polyether demulsifier using polyamino polyether as initiator and preparation method thereof". The experimental data are shown in the table:

[0063]

[0064] Through the analysis of the demulsification and dehydration effects of the samples of the above invention examples, it can be seen that the product synthesized by the technology of the present invention is better than the patent "CN 201510193464.3 "Comb-type polyether demulsifier and preparation method using polyamino polyether as initiator" in terms of oil phase water content and water phase oil content data than the original patented product. In summary, it can be explained that the technology of the present invention completely realizes the optimization and upgrading of the structure of the original patented product, and the performance fully meets the technical requirements for the demulsification and dehydration link in the oil field production process.

Claims

1. A comb-type polyester ether demulsifier using polyamino polyether as an initiator, the structural formula of which is as follows: ， In the above structural formula: a, b are the polymerization degrees of the polyamino polyether initiator, a, b are positive integers greater than or equal to 1, and 5≤(a+b)≤50, In the above structural formula: m is the degree of polymerization of the carbonate group in the product molecule, n is the degree of polymerization of the ethoxy group in the molecule, and the values ​​are both positive integers greater than or equal to 1, and 5≤(m+n)≤250; The preparation method of the comb-type polyester ether demulsifier comprises the following steps: Putting the initiator polyamino polyether, ethylene carbonate and the catalyst potassium hydroxide into a reactor, heating to 70-80°C under closed conditions, and starting stirring; fully replacing the reactor with nitrogen, and pressing the reactor pressure to 0.09-0.1Mpa with nitrogen; continuing to heat to 120-150°C, during which the pressure is controlled between 0.2-0.4Mpa, maintaining the reaction time for 9-12 hours, and when the hydroxyl value of the product is ≥500mgKOH / g, continuing the aging reaction for 1 hour, after the reaction is completed, introducing cooling water into the reactor coil, the temperature drops to below 40°C, and the reactor is depressurized to normal pressure to take out the product, so as to obtain a comb-type polyester ether demulsifier product with polyamino polyether as the initiator; The molar ratio of the initiator polyamino polyether to ethylene carbonate is 1:5-250, and the added amount of the catalyst potassium hydroxide is 1-3‰ of the total mass of the polyamino polyether and ethylene carbonate.

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