CN107815298B - An emulsifier and its preparation method and oil-based drilling fluid - Google Patents
An emulsifier and its preparation method and oil-based drilling fluid Download PDFInfo
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- C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
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Abstract
本发明提供了一种乳化剂的制备方法，包括：将二聚酸和长链烷基单胺进行反应，得到乳化剂；所述长链烷基单胺中碳原子数为10～20。本发明提供的乳化剂的制备方法选择特定的原料采用一步法合成具有多吸附点的乳化剂，这种方法合成步骤简单、能耗低、无有机溶剂，适用于大规模工业化生产。而且这种方法制备得到的乳化剂吸附点多、乳化能力能强，适用钻井液范围宽，不仅可在常规油基钻井液中起到良好的乳化作用，而且在高温高密度的油基钻井液中也可使用，增加了高固相含量时的乳液稳定性。本发明提供的乳化剂能够使钻井液具有良好的综合性能。本发明还提供了一种乳化剂和油基钻井液。
The invention provides a preparation method of an emulsifier, which comprises: reacting a dimer acid and a long-chain alkyl monoamine to obtain an emulsifier; the number of carbon atoms in the long-chain alkyl monoamine is 10-20. The preparation method of the emulsifier provided by the invention selects specific raw materials and adopts a one-step method to synthesize the emulsifier with multiple adsorption points. This method has simple synthesis steps, low energy consumption, no organic solvent, and is suitable for large-scale industrial production. In addition, the emulsifier prepared by this method has many adsorption points, strong emulsifying ability, and is suitable for a wide range of drilling fluids. It can also be used in medium to increase emulsion stability at high solids content. The emulsifier provided by the invention can make the drilling fluid have good comprehensive performance. The present invention also provides an emulsifier and an oil-based drilling fluid.
Description
Technical Field
The invention relates to the technical field of drilling fluid, and particularly relates to an emulsifier, a preparation method thereof and an oil-based drilling fluid.
Background
The oil-based drilling fluid has been developed and matured abroad, forms a series of systems and matching technologies, and is widely applied to shale gas development wells and deep wells with complex stratumsAnd deep water drilling, etc., the domestic oil-based drilling fluid is rapidly developed in recent years, and a series of treating agents are researched and applied, so that the density of the oil-based drilling fluid is basically 2.2g/cm3The following requirements for the performance of oil-based drilling fluids are met, but if the density is further increased, the solid content of the drilling fluid system is high (such as 2.5g/cm density)3The volume fraction of the weighting material is about 55 percent), the emulsion stability is deteriorated, the problems of high plastic viscosity, large high-temperature and high-pressure filtration loss, easy sedimentation of the weighting material at high temperature and the like are caused, and the safe drilling of high-temperature complex strata is difficult to ensure.
Chinese patent 201210580265.4 discloses an oxidized polymerized fatty acid ester emulsifier for oil-based drilling fluid and a preparation method thereof, which can be used for a long time in a large range of 60: 40-95: 5 oil-water ratio and a temperature range of 150-220 ℃, but the applicable density is not more than 2.5g/cm3The drilling fluid has harsh preparation conditions, needs high temperature and high pressure (200-220 ℃ and 5-15 MPa), and is not beneficial to scale production and application; chinese patent 201410024812.X discloses a cyclic amide emulsifier for oil-based drilling fluid and a preparation method thereof, and the cyclic amide emulsifier is mainly used for the oil-based drilling fluid with the density of 2.3g/cm3In the soilless-phase oil-based drilling fluid, ethanol is used as a solvent in the preparation process, and the ethanol needs to be distilled for recycling in the later period, so that the production cost is increased.
Aiming at the problems that the traditional emulsifier for the oil-based drilling fluid is easy to degrade at high temperature and high pressure and has large maintenance dosage, Chinese patent No. 200980117528.4 discloses a polyamide emulsifier based on fatty acid/carboxylic acid and polyamine and a preparation method thereof, wherein the emulsifier can keep stable performance of the oil-based drilling fluid at high temperature and high pressure, reduce the dosage during maintenance and still have the defect of poor low-temperature fluidity. Chinese patent 201310497559.5 discloses a tripolyamide nonionic surfactant and a preparation method thereof, wherein in the preparation method of the emulsifier disclosed by the patent, thionyl chloride is adopted as an organic solvent and is recovered by distillation, and the reaction steps are complicated (3-4 steps), which are not beneficial to industrial production and use. Chinese patent 201410325690.8 discloses a water-in-oil polyamide emulsifier for drilling fluid and a synthesis method thereof, wherein N-methyl-1, 3-propane diamine is used as an intermediate, two-step reaction is still required, and the emulsifier is not suitable for being used in high-density oil-based drilling fluid.
In conclusion, the emulsifier for the oil-based drilling fluid used in the prior art has the defects of poor temperature resistance, narrow applicable drilling fluid density range, harsh synthesis industrial conditions, complicated steps and no contribution to industrial production.
Disclosure of Invention
In view of the above, the invention aims to provide an emulsifier, a preparation method thereof and an oil-based drilling fluid.
The invention provides a preparation method of an emulsifier, which comprises the following steps:
reacting dimer acid with long-chain alkyl monoamine to obtain an emulsifier;
the number of carbon atoms in the long-chain alkyl monoamine is 10-20.
Preferably, the long-chain alkyl monoamine is one or more of octadecylamine, hexadecylamine, tetradecylamine, dodecylamine, decylamine and n-octylamine.
Preferably, the mass ratio of the dimer acid to the long-chain alkyl monoamine is (45-75): (25-55).
Preferably, the reaction temperature is 150-200 ℃.
Preferably, the reaction time is 6-16 hours.
Preferably, after the reaction is finished, cooling the obtained reaction product to 60-100 ℃ to obtain the emulsifier.
The invention provides an emulsifier prepared by the method in the technical scheme.
Preferably, the emulsifier comprises a structure according to formula I:
in the formula I, R1And R2Independently selected from alkyl with 4-8 carbon atoms;
R3is composed of
R4Is alkylene with 5-10 carbon atoms;
R5is an alkyl group having 8 to 18 carbon atoms;
R3two bonds R on the middle and left side1And R2Two bond bonds R on the right4。
Preferably, said R is1Is CH3(CH2)7-or CH3(CH2)5-；
R2Is CH3(CH2)7-、CH3(CH2)5-or CH3(CH2)CH＝CH-；
R4Is- (CH)2)7-；
R5Is CH3(CH2)nN is 7, 9, 11, 13, 15 or 17.
The invention provides an oil-based drilling fluid, which comprises an emulsifier prepared by the method in the technical scheme or the emulsifier in the technical scheme.
The preparation method of the emulsifier provided by the invention selects specific raw materials and adopts a one-step method to synthesize the emulsifier with multiple adsorption points, and the method has the advantages of simple synthesis steps, low energy consumption and no organic solvent, and is suitable for large-scale industrial production. The emulsifier prepared by the method has multiple adsorption points, strong emulsifying capacity and wide applicable drilling fluid range, not only can play a good emulsifying role in the conventional oil-based drilling fluid, but also can be used in the high-temperature and high-density oil-based drilling fluid, and the emulsion stability under the condition of high solid content is improved. The experimental result shows that when the addition amount of the emulsifier provided by the invention is 5 wt%, the oil-water ratio is 9:1, and the density is 2.5g/cm3In the oil-based drilling fluid, after aging at 180 ℃/16h, the demulsification voltage of the drilling fluid is more than 1500V, and the plastic viscosity is less than 80mPa & s, so that the drilling fluid has good comprehensive performance.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to the provided drawings without creative efforts.
FIG. 1 is an infrared spectrum of an emulsifier prepared in example 1 of the present invention.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other examples, which may be modified or appreciated by those of ordinary skill in the art based on the examples given herein, are intended to be within the scope of the present invention.
The invention provides a preparation method of an emulsifier, which comprises the following steps:
reacting dimer acid with long-chain alkyl monoamine to obtain an emulsifier;
the number of carbon atoms in the long-chain alkyl monoamine is 10-20.
In the invention, the reaction temperature is preferably 150-200 ℃, more preferably 160-190 ℃, and most preferably 170-180 ℃. In the present invention, the reaction time is preferably 6 to 16 hours, more preferably 8 to 14 hours, and most preferably 10 to 12 hours. The reaction is preferably carried out under stirring in the present invention.
In the invention, the dimer acid is a mixture with complex components, wherein the dimer acid is dicarboxylic acid which is prepared by taking unsaturated fatty acid of natural oil as a raw material and catalytically polymerizing two or more molecular oleic acids, and comprises monomer acid, dimer fatty acid and trimer fatty acid, wherein the dimer fatty acid is the main component of the dimer fatty acid, and the molecular formula of the dimer fatty acid is C36H64O4. In the invention, the mass content of the monomer acid in the dimer acid is preferably 2-22%, more preferably 5-18%, more preferably 8-16%,most preferably 10 to 14%. In the present invention, the content of the dimer fatty acid in the dimer acid is preferably 78 to 98%, more preferably 82 to 95%, more preferably 84 to 92%, and most preferably 86 to 90% by mass. In the present invention, the mass content of the trimeric fatty acid in the dimer acid is preferably 0 to 12%, more preferably 2 to 10%, more preferably 3 to 8%, and most preferably 4 to 6%. The source of the dimer acid is not particularly limited, and the dimer acid known to those skilled in the art can be used, and can be purchased from the market, for example, the dimer acid provided by rainbow chemical industry, ltd, Chongqing can be used.
In the invention, the number of carbon atoms in the long-chain alkyl monoamine is 10-20, and one or more of octadecylamine, hexadecylamine, tetradecylamine, dodecylamine, decylamine and n-octylamine are preferable.
In the invention, the mass ratio of the dimer acid to the long-chain alkyl monoamine is preferably (45-75): (25-55), more preferably (50-70): (30-60), most preferably (55-65): (35-45).
The acid value of the emulsifier prepared by the method provided by the invention is preferably 5-15 mg KOH/g, more preferably 8-12 mg KOH/g, and most preferably 10mg KOH/g. The amine value of the emulsifier prepared by the method provided by the invention is preferably 2-50 mg KOH/g, more preferably 5-45 mg KOH/g, more preferably 10-40 mg KOH/g, more preferably 15-35 mg KOH/g, and most preferably 20-30 mg KOH/g.
In the present invention, the reaction is considered to be completed 1 to 2 hours after no water drops are formed in the reaction process. In the invention, after the reaction is finished, the obtained reaction product is preferably cooled to 60-100 ℃ to obtain the emulsifier. The method provided by the invention can obtain the emulsifier with liquid or solid powder appearance according to different adopted raw materials and cooling time, and is beneficial to packaging, storage and field use.
The invention provides an emulsifier prepared by the method in the technical scheme. In the present invention, the emulsifier is the same as the emulsifier prepared by the method of the above technical scheme, and details are not repeated herein. In the present invention, the emulsifier preferably comprises a structure represented by formula I:
in the formula I, R1And R2Independently selected from alkyl with 4-8 carbon atoms;
R3is composed of
R4Is alkylene with 5-10 carbon atoms;
R5is an alkyl group having 8 to 18 carbon atoms;
R3two bonds R on the middle and left side1And R2Two bond bonds R on the right4。
In the present invention, R3And R1、R2And R4The connection structure of (2) may be:
wherein x is 4-8, y is 4-8, and z is 5-10.
In the present invention, said R1Preferably CH3(CH2)7-or CH3(CH2)5-；R2Preferably CH3(CH2)7-、CH3(CH2)5-or CH3(CH2)CH＝CH-；R4Is preferably- (CH)2)7-；R5Preferably CH3(CH2)nN is 7, 9, 11, 13, 15 or 17.
The invention provides an oil-based drilling fluid which comprises the emulsifier in the technical scheme. The present invention is not particularly limited to the components of the oil-based drilling fluid other than the emulsifier, and the components of the oil-based drilling fluid known to those skilled in the art may be used. In the present invention, the oil-based drilling fluid preferably comprises: base oil, organic soil, emulsifier, alkalinity regulator, calcium chloride water solution, filtrate reducer and barite.
In the present invention, the base oil is preferably diesel oil or white oil, more preferably 0#Diesel oil or 5#White oil. In the invention, the mass content of the base oil in the oil-based drilling fluid is preferably 15-75%, more preferably 20-70%, more preferably 30-60%, and most preferably 40-50%. The invention has no special limitation on the type and source of the organic soil, and the organic soil for the oil-based drilling fluid, which is well known to a person skilled in the art, can be adopted, for example, the organic soil product provided by Zhejiang Fenghong New Material GmbH. In the invention, the mass content of the organic soil in the oil-based drilling fluid is preferably 2-3%, and more preferably 2.5%. In the present invention, the emulsifier is the emulsifier described in the above technical scheme, and is not described herein again. In the invention, the mass content of the emulsifier in the oil-based drilling fluid is preferably 4.5-5.5%, and more preferably 5%. The alkalinity regulator is not particularly limited in the invention in terms of the type and source, and may be those known to those skilled in the art, and is preferably calcium oxide, such as calcium oxide product provided by Wenxing building materials chemical plant in Tangyin county, Henan province. In the invention, the mass content of the alkalinity regulator in the oil-based drilling fluid is preferably 2.5-3.5%, and more preferably 3%. In the present invention, the mass concentration of the calcium chloride aqueous solution is preferably 15 to 25%, more preferably 18 to 22%, and most preferably 20%. In the invention, the mass content of the calcium chloride aqueous solution in the oil-based drilling fluid is preferably 0-10%, more preferably 1-9%, more preferably 2-8%, more preferably 3-7%, and most preferably 4-6%. The type and source of the fluid loss additive are not particularly limited, and the fluid loss additive for the oil-based drilling fluid, which is well known to those skilled in the art, can be used. In the invention, the quality of the filtrate reducer in the oil-based drilling fluidThe content is preferably 3.5 to 4.5%, more preferably 4%. The invention has no special limitation on the type and source of the barite, and the barite for the oil-based drilling fluid, which is well known to a person skilled in the art, can be adopted, for example, the barite provided by Hongxin mining industry, Inc., which is prefectural in Hubei province and city. In the invention, the mass content of the barite in the oil-based drilling fluid is preferably 50-80%, more preferably 55-75%, and most preferably 60-70%.
The preparation method of the oil-based drilling fluid is not particularly limited, and the base oil, the organic soil, the emulsifier, the alkalinity regulator, the calcium chloride aqueous solution, the filtrate reducer and the barite are uniformly mixed. In the invention, the preparation method of the oil-based drilling fluid is preferably as follows:
adding organic soil into base oil to carry out first stirring to obtain a first stirring product;
adding an emulsifier into the first stirring product to carry out second stirring to obtain a second stirring product;
adding an alkalinity regulator into the second stirring product to carry out third stirring to obtain a third stirring product;
adding a calcium chloride aqueous solution into the third stirring product to carry out fourth stirring to obtain a fourth stirring product;
adding a filtrate reducer into the fourth stirred product to carry out fifth stirring to obtain a fifth stirred product;
and adding barite into the fifth stirring product to carry out sixth stirring, so as to obtain the oil-based drilling fluid.
In the present invention, the speed of the first stirring, the second stirring, the third stirring, the fourth stirring, the fifth stirring and the sixth stirring is preferably selected independently from 8000 to 12000rpm, more preferably 9000 to 11000rpm, and most preferably 10000 rpm. In the present invention, the time of the first stirring, the second stirring, the third stirring, the fourth stirring and the fifth stirring is preferably independently selected from 4 to 6 minutes, more preferably 4.5 to 5.5 minutes, and most preferably 5 minutes. In the present invention, the sixth stirring time is preferably 15 to 25 minutes, more preferably 18 to 22 minutes, and most preferably 20 minutes.
The acid value of the emulsifier was tested as follows:
weighing 0.2-1.0 g of emulsifier and placing the emulsifier in a 150mL conical flask; adding 100mL of 95% ethanol, and shaking for dissolution; after the emulsifier is completely dissolved, adding 4-5 drops of phenolphthalein indicator; titration is carried out with 0.1mol/LKOH standard solution until reddish color appears for 30s without disappearance, and the number of ml of alkaline solution consumed is recorded.
The acid value Y of the emulsifier (KOH/(mg/g) was calculated as follows:
in the formula:
c is the concentration of potassium hydroxide solution, mol/L;
v is the volume of the potassium hydroxide solution consumed by titration, mL;
56.1 is the molar mass of potassium hydroxide [ M (KOH) ], g/mol;
w is the mass of emulsifier, g.
The amine number of the emulsifiers was tested as follows:
weighing 0.2-1.0 g of emulsifier, and placing in a 150mL conical flask; adding 50mL of 95% ethanol, heating in a hot water bath until the emulsifier is completely dissolved; adding 3 drops of bromophenol blue indicator solution (10 g/L); titrating with hydrochloric acid standard solution [ c (HCl) ═ 0.1mol/L ] while the solution is hot until the solution turns from blue to yellow, and keeping the solution for 30s without fading to obtain the end point.
The amine value Z (mgKOH/g) of the emulsifier is calculated according to the following formula:
in the formula:
c is the actual concentration of the hydrochloric acid standard solution, mol/L;
v is the volume of hydrochloric acid standard solution consumed by titration, mL;
56.1 is the molar mass of potassium hydroxide [ M (KOH) ], g/mol;
m0for emulsificationMass of the agent, g.
The oil-based drilling fluid is prepared according to the following method:
adding 3 wt% of organic soil (purchased from Zhejiang Fenghong New Material Co., Ltd.) into 200-300 mL of 0# diesel oil, stirring at 10000rpm for 5min, then adding 5 wt% of emulsifier, continuing to stir for 5min, adding 3 wt% of calcium oxide (purchased from Wenxing building materials chemical plant in Tangyin county of Henan province), stirring for 5min, adding 20% of calcium chloride aqueous solution (the dosage of the calcium chloride aqueous solution is that the volume ratio of oil to water in the oil-based drilling fluid is 80: 20, 85: 15, 90: 10 or all oil), continuing to stir for 5min, adding 4 wt% of oxidized asphalt (purchased from seventh chemical industry Co., Ltd., New county of Henan province), further stirring for 5min, adding 50-80 wt% of barite (provided by Hongxin mining industry development responsibility Co., Ltd., prefecture, Hubei province), and finally stirring for 20min to obtain the oil-based drilling fluid.
The prepared oil-based drilling fluid is filled into an aging tank, is placed in a roller furnace with the temperature of 80-180 ℃ to roll for 16h, and then the comprehensive performance of the drilling fluid is measured at the temperature of 60 ℃, wherein the measuring method is as follows GB/T16783.2-2012 "petroleum and natural gas industry drilling fluid field test part 2: oil-based drilling fluids ].
The test result shows that the apparent viscosity of the oil-based drilling fluid prepared by the emulsifier provided by the invention is 45-98 mPa & s, the plastic viscosity is 36-79 mPa & s, the dynamic shear force is 9-17 Pa, the initial and final shear is 3.5-6.5/4.5-8, the API fluid loss is 0.4-1.6 mL, the demulsification voltage is 800-2050V, and the density is 1.6-2.5 g & cm & lt/EN & gt-3And the aging temperature is 80-180 ℃.
The dimer acid used in the following examples of the present invention was obtained from rainbow chemical company, llc, of ansqing, octadecylamine was obtained from grease chemical company, llc, of siexamine, tetradecylamine, dodecylamine, decylamine, and octylamine were obtained from henbang chemical technology company, llc, su.
Example 1
Adding 199.08g of dimer acid and 125.66g of octadecylamine into a 500mL four-neck flask provided with a thermometer, a condenser and a stirrer, slowly heating to 180 ℃, reacting for 8 hours, collecting 11.20g of water, cooling to 80 ℃, pouring out the product, cooling to obtain a reddish brown solid at normal temperature, and crushing by using a crusher to obtain a powdery product, namely the emulsifier.
The acid value and the amine value of the emulsifier prepared in the embodiment 1 of the present invention were measured according to the method described in the above technical scheme, and the test result shows that the acid value of the emulsifier prepared in the embodiment 1 of the present invention is 9.54mg KOH/g, and the amine value is 7.02mg KOH/g.
The emulsifier prepared in example 1 of the present invention was subjected to infrared spectroscopic examination, and the examination result is shown in FIG. 1, in which 3301.7cm-1The peak of absorption of stretching vibration of imide is 2918.96cm-1And 2850.90cm-1Is hydrophobic long chain medium-CH in emulsifier2Vibration absorption Peak of-1638.54 cm-1Is a characteristic absorption peak of-C ═ O, 1549.01cm-1、1376.63cm-1And 721.25cm-1Are respectively-CO-NH-, -CH3And an aromatic ring substitution absorption peak, wherein the aromatic ring is contained in the dimer acid typical isomer, so that the raw materials can be judged to react to obtain an emulsifier product with an expected structure.
According to the method of the technical scheme, the oil-based drilling fluid is prepared by using the demulsifier prepared in the embodiment 1 of the invention. According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the embodiment 1 of the invention under different oil-water volume ratios are tested. The test results are shown in table 1, and table 1 shows the performance test results of the oil-based drilling fluids prepared in the examples and comparative examples of the present invention.
Comparative example 1
The oil-based drilling fluid is prepared according to the method in the embodiment 1, and different from the embodiment 1, the emulsifier in the Chinese patent 201410575264.X is adopted to replace the emulsifier in the embodiment 1, and the preparation method of the emulsifier provided in the patent comprises the following steps:
firstly, 600 parts of tall oil acid, 80 parts of tetraethylenepentamine and 50 parts of dimethylbenzene are sequentially added into a stainless steel reaction kettle, and the mixture is heated to 170 ℃ under the condition of continuous stirring and reacts for 4 hours. After the reaction is finished, the reaction kettle is heated to 250 ℃ for reaction for 6 hours. After the reaction is finished, cooling to 80 ℃, adding 200 parts of white oil, uniformly stirring, and discharging to obtain a finished product.
According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the comparative example 1 are tested under different oil-water volume ratios. The results are shown in Table 1.
Example 2
Adding 188.11g of dimer acid and 11.89g of dodecylamine into a 500mL four-neck flask provided with a thermometer, a condenser and a stirrer, slowly heating to 160 ℃, reacting for 12 hours, collecting 12.07g of water, cooling to 60 ℃, pouring out the product, cooling to obtain a reddish brown solid at normal temperature, and crushing by using a crusher to obtain a powdery product, namely the emulsifier.
The acid value and the amine value of the emulsifier prepared in the embodiment 1 of the present invention were measured according to the method described in the above technical scheme, and the test result shows that the acid value of the emulsifier prepared in the embodiment 2 of the present invention is 18.56mg KOH/g, and the amine value is 2.38mg KOH/g.
The emulsifier prepared in the embodiment 2 of the invention is subjected to infrared spectrum detection, and the raw materials can be judged to react according to the detection result, so that the emulsifier product with an expected structure is obtained.
According to the method of the technical scheme, the oil-based drilling fluid is prepared by using the demulsifier prepared in the embodiment 2 of the invention. According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the embodiment 2 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Comparative example 2
An oil-based drilling fluid was prepared as described in example 2, except that the emulsifier of comparative example 1 was used in place of the emulsifier of example 2.
According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the comparative example 2 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Example 3
In a 500mL four-neck flask equipped with a thermometer, a condenser and a stirrer, 199.08g of dimer acid and 100.92g of dodecylamine are added, the temperature is slowly raised to 150 ℃, the reaction is carried out for 16 hours, 12.75g of water is collected, the temperature is reduced to 60 ℃, the product is poured out and cooled, and the product is a reddish brown viscous liquid at normal temperature, namely the emulsifier.
The acid value and the amine value of the emulsifier prepared in the embodiment 3 of the present invention are tested according to the method described in the above technical scheme, and the test result shows that the acid value of the emulsifier prepared in the embodiment 3 of the present invention is 35.33mg KOH/g, and the amine value is 25.05mg KOH/g.
The emulsifier prepared in the embodiment 3 of the invention is subjected to infrared spectrum detection, and the raw materials can be judged to react according to the detection result, so that the emulsifier product with an expected structure is obtained.
According to the method of the technical scheme, the oil-based drilling fluid is prepared by using the demulsifier prepared in the embodiment 3 of the invention. According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the embodiment 3 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Comparative example 3
An oil-based drilling fluid was prepared as described in example 3, except that the emulsifier of comparative example 1 was used in place of the emulsifier of example 3.
According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the comparative example 3 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Example 4
In a 500mL four-neck flask provided with a thermometer, a condenser and a stirrer, 176.36g of dimer acid and 123.64g of decylamine are added, the temperature is slowly raised to 170 ℃, the reaction lasts for 10 hours, 11.30g of water is collected, the temperature is reduced to 80 ℃, the product is poured out and cooled, and then the product is a reddish brown viscous liquid at normal temperature, namely the emulsifier.
The acid value and the amine value of the emulsifier prepared in the embodiment 4 of the present invention were measured according to the method described in the above technical scheme, and the test result shows that the acid value of the emulsifier prepared in the embodiment 4 of the present invention is 10.36mg KOH/g, and the amine value is 34.50mg KOH/g.
According to the method of the technical scheme, the oil-based drilling fluid is prepared by using the demulsifier prepared in the embodiment 4 of the invention. According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the embodiment 4 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Comparative example 4
An oil-based drilling fluid was prepared as described in example 4, except that the emulsifier of comparative example 1 was used in place of the emulsifier of example 4.
According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the comparative example 4 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Example 5
Adding 356.12g of dimer acid and 243.88g of tetradecylamine into a 1000mL four-neck flask provided with a thermometer, a condenser and a stirrer, slowly heating to 180 ℃, reacting for 8 hours, collecting 22.85g of water, cooling to 90 ℃, pouring out the product, cooling, and obtaining a reddish brown solid at normal temperature, namely the emulsifier.
The acid value and the amine value of the emulsifier prepared in example 5 of the present invention were measured according to the method described in the above technical scheme, and the test result shows that the acid value of the emulsifier prepared in example 5 of the present invention is 45.46mg KOH/g, and the amine value is 24.22mg KOH/g.
According to the method of the technical scheme, the oil-based drilling fluid is prepared by using the demulsifier prepared in the embodiment 5 of the invention. According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the embodiment 5 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Comparative example 5
An oil-based drilling fluid was prepared as described in example 5, except that the emulsifier of comparative example 1 was used in place of the emulsifier of example 5.
According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the comparative example 5 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Example 6
Adding 308.16g of dimer acid and 291.84g of hexadecylamine into a 1000mL four-neck flask provided with a thermometer, a condenser and a stirrer, slowly heating to 180 ℃, reacting for 8 hours, collecting 19.77g of water, cooling to 80 ℃, pouring out a product, cooling to obtain a reddish brown solid at normal temperature, and crushing by using a crusher to obtain a powdery product, namely the emulsifier.
The acid value and the amine value of the emulsifier prepared in the embodiment 6 of the present invention were measured according to the method described in the above technical scheme, and the test result shows that the acid value of the emulsifier prepared in the embodiment 6 of the present invention is 12.50mg KOH/g, and the amine value is 23.41mg KOH/g.
According to the method of the technical scheme, the oil-based drilling fluid is prepared by using the demulsifier prepared in the embodiment 6 of the invention. According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the embodiment 6 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Comparative example 6
An oil-based drilling fluid was prepared as described in example 6, except that the emulsifier of comparative example 1 was used in place of the emulsifier of example 6.
According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the comparative example 6 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Example 7
Adding 347.43g of dimer acid, 102.32g of octadecylamine and 152.24g of hexadecylamine into a 1000mL four-neck flask provided with a thermometer, a condenser and a stirrer, slowly heating to 170 ℃, reacting for 10 hours, collecting 22.30g of water, cooling to 60 ℃, pouring out the product, cooling to obtain a reddish brown solid at normal temperature, and crushing by a crusher to obtain a powdery product, namely the emulsifier.
The acid value and the amine value of the emulsifier prepared in example 7 of the present invention were measured according to the method described in the above technical scheme, and the test result shows that the acid value of the emulsifier prepared in example 7 of the present invention is 28.43mg KOH/g, and the amine value is 25.71mg KOH/g.
According to the method of the technical scheme, the oil-based drilling fluid is prepared by using the demulsifier prepared in the embodiment 7 of the invention. According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the embodiment 7 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Example 8
In a 1000mL four-neck flask equipped with a thermometer, a condenser and a stirrer, 422.34g of dimer acid, 72.66g of decylamine and 105.0g of n-octylamine are added, the temperature is slowly raised to 150 ℃, the reaction is carried out for 14 hours, 27.10g of water is collected, the temperature is lowered to 70 ℃, the product is poured out and cooled, and the product is a reddish brown viscous liquid at normal temperature, namely the emulsifier.
The acid value and the amine value of the emulsifier prepared in the embodiment 8 of the present invention were measured according to the method described in the above technical scheme, and the test result shows that the acid value of the emulsifier prepared in the embodiment 8 of the present invention is 38.62mg KOH/g, and the amine value is 40.53mg KOH/g.
According to the method of the technical scheme, the oil-based drilling fluid is prepared by using the demulsifier prepared in the embodiment 8 of the invention. According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the embodiment 8 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Comparative example 8
An oil-based drilling fluid was prepared as described in example 8, except that the emulsifier of comparative example 1 was used in place of the emulsifier of example 8.
According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the comparative example 8 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Example 9
Adding 326.62g of dimer acid, 105.20g of hexadecylamine, 85.15g of tetradecylamine and 83.03g of dodecylamine into a 1000mL four-neck flask provided with a thermometer, a condenser and a stirrer, slowly heating to 200 ℃, reacting for 6h, collecting 21.0g of water, cooling to 85 ℃, pouring out a product, cooling to obtain a reddish brown solid at normal temperature, and crushing by using a crusher to obtain a powdery product, namely the emulsifier.
The acid value and the amine value of the emulsifier prepared in the embodiment 9 of the present invention were measured according to the method described in the above technical scheme, and the test result shows that the acid value of the emulsifier prepared in the embodiment 9 of the present invention is 7.62mg KOH/g, and the amine value is 11.75mg KOH/g.
According to the method of the technical scheme, the oil-based drilling fluid is prepared by using the demulsifier prepared in the embodiment 9 of the invention. According to the method of the technical scheme, the apparent viscosity, the plastic viscosity, the dynamic shear force, the initial and final shear, the API (American Petroleum institute) fluid loss, the demulsification voltage, the density and the aging temperature of the oil-based drilling fluid prepared in the embodiment 9 of the invention under different oil-water volume ratios are tested. The results are shown in Table 1.
Table 1 results of performance test of oil-based drilling fluids prepared in examples of the present invention and comparative examples
In Table 1, AV is the apparent viscosity, PV is the plastic viscosity, YP is the dynamic shear force, Q10s/Q10minFor initial and final cutting, FLAPIAPI filtration loss and ES demulsification voltage.
The embodiments show that the drilling fluid prepared by the multi-adsorption-point emulsifier prepared by the method provided by the invention has better comprehensive properties than the existing emulsifier, especially has the advantages of low plastic viscosity and water loss and high demulsification voltage in high-temperature and high-density oil-based drilling fluid, and is beneficial to safe and rapid drilling of complex strata such as high-temperature, high-pressure, strong-water-sensitivity and the like. When the addition of the demulsifier provided by the invention is 5%, the oil-water ratio is 9:1, and the density is 2.5g/cm3The demulsifying voltage of the oil-based drilling fluid is more than 1500V and the plastic viscosity is less than 80mPa & s after the oil-based drilling fluid is aged at 180 ℃/16 h.
While only the preferred embodiments of the present invention have been shown and described, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention.
Claims (5)
1. An oil-based drilling fluid comprising an emulsifier;
the preparation method of the emulsifier comprises the following steps:
reacting dimer acid with long-chain alkyl monoamine to obtain an emulsifier;
the number of carbon atoms in the long-chain alkyl monoamine is 10-20;
the dimer acid contains monomer acid, dimer fatty acid and trimer fatty acid;
the mass content of the emulsifier in the oil-based drilling fluid is 4.5-5.5%;
the mass ratio of the dimer acid to the long-chain alkyl monoamine is (45-75): (25-55);
the reaction temperature is 150-200 ℃;
the reaction time is 6-16 hours.
2. The oil-base drilling fluid of claim 1, wherein the long-chain alkyl monoamine is one or more of octadecylamine, hexadecylamine, tetradecylamine, dodecylamine, and decylamine.
3. The oil-based drilling fluid according to claim 1, wherein the temperature of the obtained reaction product is reduced to 60-100 ℃ after the reaction is completed, so as to obtain the emulsifier.
4. The oil-based drilling fluid of claim 1, wherein the emulsifier comprises a structure according to formula I:
in the formula I, R1And R2Independently selected from alkyl with 4-8 carbon atoms;
R3is composed of
R4Is alkylene with 5-10 carbon atoms;
R5is alkyl with 10-18 carbon atoms;
R3two bonds R on the middle and left side1And R2Two bond bonds R on the right4。
5. The method of claim 4An oil-based drilling fluid, wherein R is1Is CH3(CH2)7-or CH3(CH2)5-；
R2Is CH3(CH2)7-、CH3(CH2)5-or CH3(CH2)CH＝CH-；
R4Is- (CH)2)7-；
R5Is CH3(CH2)nN is 9, 11, 13, 15 or 17.
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