Multifunctional oil removal agent for oilfield sewage and preparation method of multifunctional oil removal agent

Abstract

The invention provides a multifunctional oil removal agent for oilfield sewage and a preparation method thereof, and the multifunctional oil removal agent for oilfield sewage is mainly prepared from the following raw materials in parts by mass: 1-2 parts of diethylenetriamine, 2-8 parts of epoxypropane, 5-8 parts of perfluorotriamine, 4-12 parts of 3-dodecyl-5-octyl benzyl bromide and 4-16 parts of an end-capping reagent. The multifunctional oil removal agent for oilfield sewage can efficiently treat oily sewage, and is particularly suitable for rapid and efficient treatment of produced liquid sewage.

Description

Technical Field

[0001] The present invention relates to the technical field of oil remover preparation, and particularly relates to a multifunctional oil remover for oilfield sewage and a preparation method thereof. Background Art

[0002] With the rapid development of the petroleum industry, more and more oilfield sewage is generated, and the resulting pollution is also increasing day by day. The control and treatment of water environmental pollution have gradually attracted people's attention. How to treat such sewage has gradually become a severe problem faced by petroleum enterprises. If these oily sewage are directly discharged without treatment, it will seriously pollute the environment and at the same time greatly waste water resources. To effectively utilize the produced sewage in oilfields, it is necessary to effectively treat the sewage.

[0003] At present, the conventional treatment process (natural sedimentation - coagulation sedimentation - filtration) is difficult to effectively treat the heavy oil thermal recovery sewage. Moreover, the quality of the produced sewage is complex, containing a large amount of residual alkali, surfactants, and polymers (such as polyacrylamide PAM), resulting in an increase in the viscosity of the sewage, a decrease in the particle size of the sewage oil droplets, serious emulsification of the sewage, and an increase in the difficulty of demulsification and purification of the produced liquid.

[0004] Another method for removing oil from oilfield produced sewage is to use an oil remover. Oil removers are generally divided into the following two categories. One category has diverse components and good oil removal effects, but has the disadvantages of complex preparation processes, poor salt resistance, and high costs. The other category of oil removers has a single component, relatively simple preparation methods and processes, and low requirements for water quality, but has the disadvantage of poor oil removal effects. Domestic research on rapid oil removers mainly focuses on inorganic flocculants, other modified polymers, modified quaternary ammonium salt reverse demulsifiers, and their compound products with inorganic polymers. They have a fast water clarification speed and low costs, but the oily sewage flocculated by them contains a large amount of high molecular cationic polymers. If this part of the oily sewage returns to the crude oil production system, it will inevitably lead to difficulties in crude oil dehydration. Therefore, the development of an oil remover with a fast process, high temperature resistance, and environmental protection has become an important direction in the research of oilfield chemicals.

[0005] In view of this, the present invention is specifically proposed. Summary of the Invention

[0006] The first object of the present invention is to provide a multifunctional oil remover for oilfield sewage with a simple formula, which can efficiently treat oily sewage, especially suitable for the rapid and efficient treatment of produced liquid sewage. Moreover, it has a simple production process, low costs, strong adaptability, strong salt resistance, strong high temperature resistance, and good oil removal effects. Its maximum high temperature resistance reaches 250°C, and the oil removal rate of oily sewage reaches more than 99%, which is more than 65% higher than that of existing agents.

[0007] The second object of the present invention is to provide a preparation method of the above-mentioned multifunctional oil remover for oilfield sewage. The preparation method is simple in operation, mild in operating conditions, pollution-free, without the discharge of three wastes, and safe and environmentally friendly.

[0008] In order to achieve the above objects of the present invention, the following technical solutions are specifically adopted: The present invention provides a multifunctional oil remover for oilfield sewage, which is mainly prepared from the following raw materials: by mass, 1-2 parts of diethylenetriamine, 2-8 parts of propylene oxide, 5-8 parts of perfluorotriamine, 4-12 parts of 3-dodecyl-5-octylbenzyl bromide, and 4-16 parts of a capping agent.

[0009] Preferably, as a further feasible solution, by mass, 1.2-1.8 parts of diethylenetriamine, 3-7 parts of propylene oxide, 6-7 parts of perfluorotriamine, 6-10 parts of 3-dodecyl-5-octylbenzyl bromide, and 6-14 parts of a capping agent.

[0010] Preferably, as a further feasible solution, by mass, 1.5 parts of diethylenetriamine, 6 parts of propylene oxide, 6.5 parts of perfluorotriamine, 8 parts of 3-dodecyl-5-octylbenzyl bromide, and 10 parts of a capping agent.

[0011] In the multifunctional oil remover for oilfield sewage of the present invention, the capping agent is at least one of benzene, toluene, and dimethyl sulfoxide.

[0012] The multifunctional oil remover for oilfield sewage of the present invention is different from the conventional oil removers with single components and complex preparation processes. It not only achieves a good oil removal effect by mutually matching various substances, but also has a relatively simple preparation method.

[0013] In the above formula, attention needs to be paid to the dosage relationship between various substances. The dosage of each substance needs to be controlled within a reasonable range, because if the dosage of any component is too large, it will cover up the effects of other components. Although the stability is improved, the oil removal effect will be affected. Therefore, in addition to paying attention to the specific combination between formulas, attention also needs to be paid to the compatibility relationship between dosages.

[0014] The present invention also provides a preparation method of a water-soluble high-efficiency oil remover, which includes the following steps: After adding diethylenetriamine, propylene oxide, and a capping agent, react for 0.5-4 h, and then add perfluorotriamine, a catalyst, and 3-dodecyl-5-octylbenzyl bromide.

[0015] Preferably, as a further feasible solution, during the reaction for 0.5-4 h after adding diethylenetriamine, propylene oxide, and a capping agent, the temperature is 10-30 °C.

[0016] Preferably, as a further feasible solution, after adding perfluorotriamine, stir at a speed of 250-350 rpm for 5-10 min in an environment of 40-60 °C, and then add other substances.

[0017] Preferably, as a further feasible solution, after adding 3-dodecyl-5-octylbenzyl bromide, stir at a speed of 450-500 rpm for 8-12 h in an environment of 80-85 °C.

[0018] Preferably, as a further feasible solution, after adding 3-dodecyl-5-octylbenzyl bromide and stirring for 8-12 h, the following steps are further included: heat to above 130 °C, under a pressure of less than 1 MPa, heat for more than 8 h, wash 3-4 times with sodium hydroxide with a mass concentration of 10-15%, dry and dilute its mass concentration to less than 40%, and let it stand for 24-48 h.

[0019] By defining each operating parameter in the preparation method, the quality of the prepared multifunctional oil remover is improved. The oil remover has good stability, high temperature resistance, environmental protection, and the oil removal rate is also significantly improved. Detailed implementation mode

[0020] The following will describe the implementation scheme of the present invention in detail in combination with examples. However, those skilled in the art will understand that the following examples are only used to illustrate the present invention and should not be regarded as limiting the scope of the present invention. For those not specified in the examples, they are carried out according to the conventional conditions or the conditions recommended by the manufacturer. Those reagents or instruments not specified in the manufacturer are all conventional products that can be obtained through commercial purchase.

[0021] Example 1 The specific preparation process of the multifunctional oil remover for oilfield sewage is operated according to the following steps: (1) Put 1 kg of diethylenetriamine, 8 kg of propylene oxide, and 4 kg of capping agent into the reaction kettle, introduce nitrogen into it, and slowly drop the mixed solution of methyl acrylate and ethanol, and react at 10-30 °C for 0.5-4 h.

[0022] (2) Put the above mixed solution into the stirring kettle, and add 8 kg of perfluorotriamine to it, and stir at a speed of 250-350 rpm for 5-10 min in an environment of 40-60 °C.

[0023] After the stirring is completed, slowly drop the catalyst dimethyl sulfate. After the dropping is completed, cool to room temperature.

[0024] (4) 4 kg of 3-dodecyl-5-octylbenzyl bromide was dropped into the above-mentioned mixed solution, and the mixture was stirred at a speed of 450 - 500 rpm for 8 - 12 h in an environment of 80 - 85 °C, then cooled to 50 - 60 °C and reacted for 2 - 2.5 h.

[0025] (5) The mixed solution was heated to 130 °C, ensuring that the pressure inside the reaction kettle was less than or equal to 1 MPa, and heated for 8 h to evaporate the ethanol inside. After evaporation, it was washed three times with 10% sodium hydroxide by mass concentration.

[0026] (6) The washed mixed solution was dried and its mass concentration was diluted to 40%. After standing for 24 - 48 h, the multifunctional oil remover could be obtained.

[0027] (7) Packaged, tested, and sold as a product.

[0028] Example 2 The specific preparation process of the multifunctional oil remover for oilfield sewage was operated according to the following steps: (1) 2 kg of diethylenetriamine, 2 kg of propylene oxide, and 16 kg of capping agent were put into the reaction kettle, and nitrogen was introduced into it. A mixed solution of methyl acrylate and ethanol was slowly dropped, and the reaction was carried out at 10 - 30 °C for 0.5 - 4 h.

[0029] (2) The above-mentioned mixed solution was put into the stirring kettle, and 5 kg of perfluorotriamine was added to it. It was stirred at a speed of 250 - 350 rpm in an environment of 40 - 60 °C for 5 - 10 min.

[0030] (3) After stirring, dimethyl sulfate as a catalyst was slowly dropped. After dropping, it was cooled to room temperature.

[0031] (4) 12 kg of 3-dodecyl-5-octylbenzyl bromide was dropped into the above-mentioned mixed solution, and the mixture was stirred at a speed of 450 - 500 rpm for 8 - 12 h in an environment of 80 - 85 °C, then cooled to 50 - 60 °C and reacted for 2 - 2.5 h.

[0032] (5) The mixed solution was heated to 130 °C, ensuring that the pressure inside the reaction kettle was less than or equal to 1 MPa, and heated for 8 h to evaporate the ethanol inside. After evaporation, it was washed three times with 10% sodium hydroxide by mass concentration.

[0033] (6) The washed mixed solution was dried and its mass concentration was diluted to 40%. After standing for 24 - 48 h, the multifunctional oil remover could be obtained.

[0034] (7) Packaged, tested, and sold as a product.

[0035] Example 3 The specific preparation process of the multifunctional oil remover for oilfield sewage is operated according to the following steps: (1) Put 1.2 kg of diethylenetriamine, 7 kg of propylene oxide, and 6 kg of capping agent into the reaction kettle, introduce nitrogen into it, and slowly dropwise add the mixed solution of methyl acrylate and ethanol, and react at 10 - 30 °C for 0.5 - 4 h.

[0036] (2) Put the above mixed solution into the stirring kettle, and add 7 kg of perfluorotriamine into it, and stir at a speed of 250 - 350 rpm in an environment of 40 - 60 °C for 5 - 10 min.

[0037] (3) After stirring, slowly dropwise add the catalyst dimethyl sulfate. After the addition is completed, cool to room temperature.

[0038] (4) Drop 6 kg of 3-dodecyl-5-octylbenzyl bromide into the above mixed solution, stir at a speed of 450 - 500 rpm in an environment of 80 - 85 °C for 8 - 12 h, then cool to 50 - 60 °C and react for 2 - 2.5 h.

[0039] (5) Heat the mixed solution to 140 °C, ensure that the pressure inside the reaction kettle is less than or equal to 1 MPa, heat for 8 h, evaporate the ethanol inside it, and after the evaporation is completed, wash it three times with sodium hydroxide with a mass concentration of 12%.

[0040] (6) Dry the washed mixed solution and dilute its mass concentration to 35%. After standing for 24 - 48 h, the multifunctional oil remover can be obtained.

[0041] (7) Package, detect, and form products for sale.

[0042] Example 4 The specific preparation process of the multifunctional oil remover for oilfield sewage is operated according to the following steps: (1) Put 1.8 kg of diethylenetriamine, 3 kg of propylene oxide, and 14 kg of capping agent into the reaction kettle, introduce nitrogen into it, and slowly dropwise add the mixed solution of methyl acrylate and ethanol, and react at 10 - 30 °C for 0.5 - 4 h.

[0043] (2) Put the above mixed solution into the stirring kettle, and add 6 kg of perfluorotriamine into it, and stir at a speed of 250 - 350 rpm in an environment of 40 - 60 °C for 5 - 10 min.

[0044] (3) After stirring, slowly dropwise add the catalyst dimethyl sulfate. After the addition is completed, cool to room temperature.

[0045] (4) 10 kg of 3-dodecyl-5-octylbenzyl bromide was dropped into the above-mentioned mixed solution, and the mixture was stirred at a speed of 450-500 rpm in an environment of 80-85 °C for 8-12 h, and then cooled to 50-60 °C and reacted for 2-2.5 h.

[0046] (5) The mixed solution was heated to 150 °C, ensuring that the pressure inside the reaction kettle was less than or equal to 1 MPa, heated for 8 h, the ethanol inside was evaporated, and after evaporation, it was washed three times with sodium hydroxide with a mass concentration of 15%.

[0047] (6) The washed mixed solution was dried and its mass concentration was diluted to 30%. After standing for 24-48 h, the multifunctional oil remover could be obtained.

[0048] (7) Packaging, testing, and forming products for sale.

[0049] Example 5 The specific operation steps were the same as those in Example 4, except that the raw materials were proportioned according to the following mass percentages: 1.5 kg of diethylenetriamine, 6 kg of propylene oxide, 10 kg of capping agent, 6.5 kg of perfluorotriamine, and 8 kg of 3-dodecyl-5-octylbenzyl bromide.

[0050] Comparative Example 1 The specific operation steps were the same as those in Example 5, except that 3-dodecyl-5-octylbenzyl bromide was not added.

[0051] Comparative Example 2 The specific operation steps were the same as those in Example 5, except that the perfluorotriamine was 2 kg.

[0052] Experimental Example 1 The specific treatment effects of the multifunctional oil removers for oilfield sewage in Examples 1-5 and Comparative Examples 1-2 were evaluated, and the specific results are shown in Table 1 below: For the oilfield sewage in the factory, the oil removers prepared in the above examples and comparative examples of the present invention were added, and after stirring for oil removal for 5 h, the oil removal effect was evaluated. The specific results are as follows.

[0053] Table 1 Experimental Results

[0054] As can be seen from the results in Table 1 above, the degreasing agent of the present invention is synthesized under mild conditions, with a wide range of raw material sources, a simple and feasible synthesis process, strong adaptability, low dosage, no waste discharge during the production process, and can meet the needs of environmental protection and oilfield development; it has strong temperature resistance, reaching 250 °C; it has the characteristics of high degreasing efficiency, with a degreasing rate of oil-containing sewage reaching over 99%, an increase of over 65% compared with existing agents, meeting the requirements of oil removal pretreatment for oil-containing sewage; it can reduce the viscosity of sewage, has good salt resistance, reaching 2.5×10 4 mg / L, and does not contain inorganic flocculation components; the product is easy to obtain, convenient for transportation and storage.

[0055] Although the present invention has been illustrated and described with specific embodiments, it should be realized that many other changes and modifications can be made without departing from the spirit and scope of the present invention. Therefore, this means that all such changes and modifications within the scope of the present invention are included in the appended claims.

Claims

1. A multifunctional oil remover for oilfield wastewater, characterized in that: The invention is mainly prepared from the following raw materials: by weight, 1-2 parts of diethylenetriamine, 2-8 parts of propylene oxide, 5-8 parts of perfluorotriamine, 4-12 parts of 3-dodecyl-5-octylbenzyl bromide and 4-16 parts of end-capping agent.

2. The multifunctional oil remover for oilfield wastewater according to claim 1, characterized in that: Calculated by mass, diethylenetriamine is 1.2-1.8 parts, propylene oxide is 3-7 parts, perfluorotriamine is 6-7 parts, 3-dodecyl-5-octylbenzyl bromide is 6-10 parts, and end-capping agent is 6-14 parts.

3. The multifunctional oil remover for oilfield wastewater according to claim 1, characterized in that: In parts by mass, there are 1.5 parts of diethylenetriamine, 6 parts of propylene oxide, 6.5 parts of perfluorotriamine, 8 parts of 3-dodecyl-5-octylbenzyl bromide, and 10 parts of a capping agent.

4. The multifunctional oil remover for oilfield wastewater according to any one of claims 1 to 3, characterized in that: The end-capping agent is at least one of benzene, toluene and dimethyl sulfoxide.

5. The method for preparing the multifunctional oil removal agent for oilfield wastewater according to any one of claims 1 to 4, characterized in that: The steps include: After adding diethylenetriamine, propylene oxide and end-capping agent, react for 0.5-4h and then add perfluorotriamine, catalyst and 3-dodecyl-5-octylbenzyl bromide.

6. The preparation method according to claim 5, characterized in that: After adding diethylenetriamine, propylene oxide and end-capping agent, the reaction is carried out for 0.5-4 hours at a temperature of 10-30°C.

7. The preparation method according to claim 5, characterized in that: After adding the perfluorotriamine, stir at 250-350 rpm for 5-10 minutes at 40-60°C, and then add other substances.

8. The preparation method according to claim 5, characterized in that: After the addition of 3-dodecyl-5-octylbenzyl bromide, the mixture was stirred at 450-500 rpm for 8-12 h at 80-85°C.

9. The preparation method according to claim 8, characterized in that: After adding 3-dodecyl-5-octyl benzyl bromide and stirring for 8-12 hours, the following steps are also included: heating to above 130°C, heating for more than 8 hours under a pressure of less than 1MPa, washing 3-4 times with sodium hydroxide having a mass concentration of 10-15%, drying and diluting its mass concentration to less than 40%, and standing for 24-48 hours.

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