CN112646073B - Oil-soluble thick oil viscosity reducer and preparation method thereof - Google Patents
Oil-soluble thick oil viscosity reducer and preparation method thereof Download PDFInfo
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
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Abstract
The invention discloses an oil-soluble thick oil viscosity reducer and a preparation method thereof, wherein the oil-soluble thick oil viscosity reducer is obtained by reacting four monomers, namely 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and stearyl methacrylate, and the molar ratio of the four monomers is as follows: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride, stearyl methacrylate, 1, (2-4), (1-3) and (9-11). The oil-soluble viscosity reducer for thickened oil is a novel viscosity reducer containing F, has better effect on colloid and asphaltene, has more obvious viscosity reducing effect, simple preparation process, mild condition and good oil solubility compared with the prior art, and can be mixed with toluene for use.
Description
Technical Field
The invention relates to the field of oilfield chemical additives, in particular to an oil-soluble thick oil viscosity reducer and a preparation method thereof.
Background
According to statistics, the heavy oil accounts for a large proportion of the whole petroleum resources, and the heavy oil reserves found all over the world are about 1000 multiplied by 108t. The Chinese heavy oil has abundant and widely distributed reserves, and has huge reserves in Liaoning, Henan, Shandong and Xinjiang. The estimated heavy oil resource in China is about 300 multiplied by 108t. However, the heavy oil has high density, high viscosity, poor fluidity, etc., and its exploitation and transportation have great difficulty.
Different viscosity reduction modes are selected according to different characteristics of the produced thick oil in different regions, and the currently common viscosity reduction modes in China mainly comprise: heating to reduce viscosity, blending and diluting to reduce viscosity, hydrothermally cracking to reduce viscosity and reducing viscosity of microorganisms. The heating viscosity reduction has the characteristics of wide adaptability, simple and convenient operation and the like and is commonly adopted, but the method has huge energy loss, and pipe condensation can be generated due to the increase of the viscosity of the thick oil when the heating is stopped, so that accidents are caused and dangers are generated; the thin oil blending method is simple and easy to implement, has obvious effect, but has larger demand for thin oil, and increases the refining cost; the hydrothermal cracking method can change the content of each component in the thickened oil, the oil product is essentially improved, but the energy consumption is huge, and the heavy metal in the thickened oil is easy to reduce the activity of the catalyst, so that the effect is reduced; the microbial viscosity reduction method utilizes the interaction of microbes and metabolites with the thick oil, does not pollute the environment, but has higher requirements on the environment by the microbes, otherwise, the microbes are difficult to survive. Therefore, the selection of a viscosity reduction method with simple filling process and effectiveness is very important for reducing the cost and increasing the production amount.
In addition, in the composition of the thick oil in China, the high content of colloid and asphaltene is the main reason of the high viscosity of the thick oil. The accumulation of colloids and asphaltenes in the thickened oil can increase the viscosity of the thickened oil, and if the colloids and the asphaltenes can be effectively dispersed in the oil, the viscosity of the thickened oil can be remarkably reduced. The oil-soluble viscosity reducer has oil solubility, so that the viscosity reducer can be directly added into thick oil without affecting the quality of the oil, and a small amount of the viscosity reducer can successfully reduce the viscosity. However, at present, the research on the oil-soluble viscosity reducer is less, most of the research is limited to laboratory research and field test stages, and the problems of insufficient oil solubility, insignificant viscosity reduction effect and poor universality exist.
Disclosure of Invention
In view of the above, the invention provides an oil-soluble viscosity reducer for thick oil and a preparation method thereof, and the viscosity reducer has good oil solubility, obvious viscosity reduction effect, good universality and simple preparation method.
In order to achieve the above object, the present invention firstly provides an oil-soluble viscosity reducer for thick oil, which is obtained by reacting four monomers, namely 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and stearyl methacrylate, wherein the molar ratio of the four monomers is as follows: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride, stearyl methacrylate, 1, (2-4), (1-3) and (9-11).
Preferably, the molar ratio of the four monomers is: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride, stearyl methacrylate, 1:3:2: 10.
The invention also provides a preparation method of the oil-soluble thick oil viscosity reducer, which comprises the following steps: mixing, dissolving and heating 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and stearyl methacrylate according to the molar ratio to initiate reaction, thereby obtaining the oil-soluble thick oil viscosity reducer.
Preferably, the molar ratio is: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride, stearyl methacrylate, 1:3:2: 10.
Preferably, the solvent selected in the dissolving process is toluene, and the mass of the toluene is 90-110% of the mass sum of the four monomers.
Preferably, the heating temperature of the heating process is 60-80 ℃.
Preferably, the initiator for initiating the reaction is benzoyl peroxide, and the mass of the benzoyl peroxide is 1% -2% of the sum of the four monomers.
Preferably, the time for initiating the reaction is 5h-7h, and the heating is stopped after the reaction is finished.
The invention also provides application of the oil-soluble thick oil viscosity reducer, and the oil-soluble thick oil viscosity reducer is used for reducing the thick oil with the viscosity of 24300-34100mPa & s.
More preferably, the viscosity is 32600 mPas.
The invention has the beneficial effects that:
1. the F ions in the selected 2, 2, 3, 3-tetrafluoropropyl methacrylate can form hydrogen bonds with colloid and asphaltene, styrene provides benzene rings and can generate pi-pi electron conjugation with the colloid and the asphaltene, maleic anhydride adds a space structure to the viscosity reducer, octadecyl methacrylate provides a long carbon chain, and the oil solubility of the viscosity reducer is improved.
2. The molar ratio of the four monomers is as follows: in the case of 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and stearyl methacrylate which are 1:3:2:10, the viscosity reduction rate of the thick oil can be as high as 65.34%, so that the viscosity of the thick oil is reduced from 32600 mPas to 11300 mPas.
3. The preparation process of the oil-soluble thick oil viscosity reducer is simple, the conditions are mild, and the synthesized viscosity reducer has good oil solubility and can be mixed with toluene for use.
4. The heating temperature selected in the preparation method of the oil-soluble thick oil viscosity reducer is 60-80 ℃, the time for initiating the reaction is 5-7 h, the method is a selection combining the characteristics of four monomers, the monomers can be better polymerized into a preset compound at the temperature and the time, and the viscosity reduction efficiency of the synthesized viscosity reducer is increased.
5. The viscosity reduction rate of 24300-34100mPa & s thick oil is about 50%, which shows that the viscosity reducer has good universality, is suitable for thick oil with various compositions, and particularly has the highest viscosity reduction rate of 65.34% for thick oil with viscosity of 32600mPa & s, and has excellent viscosity reduction effect.
Drawings
FIG. 1 is an infrared spectrum of the oil-soluble viscosity reducer for thick oil of the present invention.
Detailed Description
In order that those skilled in the art will better understand the technical solutions of the present invention, the present invention will be further described in detail with reference to the following embodiments.
The invention firstly provides an oil-soluble thick oil viscosity reducer which is obtained by reacting four monomers, namely 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and stearyl methacrylate, wherein the molar ratio of the four monomers is as follows: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride, stearyl methacrylate, 1, (2-4), (1-3) and (9-11). The F ions in the selected 2, 2, 3, 3-tetrafluoropropyl methacrylate can form hydrogen bonds with colloid and asphaltene, styrene provides benzene rings and can generate pi-pi electron conjugation with the colloid and the asphaltene, maleic anhydride adds a space structure to the viscosity reducer, octadecyl methacrylate provides a long carbon chain, the oil solubility of the viscosity reducer is increased, and a better viscosity reduction effect is achieved.
Preferably, the molar ratio of the four monomers is: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride, stearyl methacrylate, 1:3:2: 10. Under the condition of the proportion, functional groups in the monomers play a good synergistic effect, so that the viscosity reducing effect of the viscosity reducer is good.
The invention also provides a preparation method of the oil-soluble thick oil viscosity reducer, which comprises the following steps: mixing, dissolving and heating 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and stearyl methacrylate according to the molar ratio to initiate reaction, thereby obtaining the oil-soluble thick oil viscosity reducer.
Preferably, the molar ratio is: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride, stearyl methacrylate, 1:3:2: 10.
Preferably, the solvent selected in the dissolving process is toluene, and the mass of the toluene is 90-110% of the mass sum of the four monomers. Compared with other solvents, the solvent has low toxicity and does not influence the reaction.
Preferably, the heating temperature of the heating process is 60-80 ℃.
Preferably, the initiator for initiating the reaction is benzoyl peroxide, and the mass of the benzoyl peroxide is 1% -2% of the sum of the four monomers.
Preferably, the time for initiating the reaction is 5h-7h, and the heating is stopped after the reaction is finished.
The temperature and the time are selected by combining the characteristics of the four monomers, and the monomers can be better polymerized into preset compounds at the temperature and the time, so that the viscosity reduction efficiency of the synthetic viscosity reducer is increased.
The invention also provides application of the oil-soluble thick oil viscosity reducer, and the oil-soluble thick oil viscosity reducer is used for reducing the thick oil with the viscosity of 24300-34100mPa & s.
The foregoing is a detailed description of the invention and the following is an example of the invention.
Example 1
The molar ratio of the reaction monomers is: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and octadecyl methacrylate are 1:2:1: 9.
The preparation process comprises the following steps: 0.2g of 2, 2, 3, 3-tetrafluoropropyl methacrylate, 0.22g of styrene, 0.1g of maleic anhydride and 3.05g of octadecyl methacrylate are added into a three-neck flask provided with a spherical condenser, a thermometer and a magnetic stirrer, 1.57g of toluene is added as a solvent, the mixture is heated and stirred in an oil bath kettle to the temperature of 60 ℃, 0.714g of benzoyl peroxide is dissolved in 2g of toluene, the mixture is dropwise added into the three-neck flask to initiate reaction, after the reaction is carried out for 5 hours, the heating is stopped, the reaction solution is subjected to rotary evaporation under the vacuum condition, the toluene solvent is removed, and the oil-soluble thick oil viscosity reducer is prepared.
Example 2
The molar ratio of the reaction monomers is: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and octadecyl methacrylate are 1:4:3: 11.
The preparation process comprises the following steps: 0.2g of 2, 2, 3, 3-tetrafluoropropyl methacrylate, 0.44g of styrene, 0.3g of maleic anhydride and 3.72g of octadecyl methacrylate are added into a three-neck flask provided with a spherical condenser, a thermometer and a magnetic stirrer, 2.66g of toluene is added as a solvent, the mixture is heated and stirred in an oil bath kettle to the temperature of 60 ℃, 0.0932g of benzoyl peroxide is dissolved in 2g of toluene, the mixture is dropwise added into the three-neck flask to initiate reaction, after the reaction is carried out for 5 hours, the heating is stopped, the reaction solution is subjected to rotary evaporation under the vacuum condition, the solvent toluene is removed, and the oil-soluble thick oil viscosity reducer is prepared.
Example 3
The molar ratio of the reaction monomers is: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and octadecyl methacrylate are 1:3:2: 10.
The preparation process comprises the following steps: a three-necked flask equipped with a bulb-shaped condenser, a thermometer and a magnetic stirrer was charged with 0.2g of 2, 2, 3, 3-tetrafluoropropyl methacrylate, 0.33g of styrene, 0.2g of maleic anhydride and 3.38g of stearyl methacrylate, and then 2.08g of toluene was added as a solvent. Heating and stirring the mixture in an oil bath kettle until the temperature is 60 ℃, dissolving 0.0822g of benzoyl peroxide in 2g of toluene, dropwise adding the mixture into a three-neck flask to initiate reaction, stopping heating after the reaction is carried out for 5 hours, carrying out rotary evaporation on the reaction solution under a vacuum condition, removing the solvent toluene, and obtaining the oil-soluble thick oil viscosity reducer.
Example 4
The only difference from example 3 is that the heating temperature is 70 ℃ and the reaction time is 6 h.
Example 5
The only difference from example 3 is that the heating temperature is 80 ℃ and the reaction time is 7 h.
Example 6
The viscosity reducers obtained in examples 1 to 5 were evaluated by pouring 100mL of thick oil into a 100mL tall glass beaker, keeping the temperature at 50 ℃ for 1h, and measuring the viscosity of the thick oil with an NDJ-8S digital display viscometer, which is recorded as eta, according to SY/T0520-0Dissolving 0.05g of viscosity reducer in 1g of toluene, adding the solution into a thick oil cup after the viscosity reducer is completely dissolved, uniformly stirring, heating the thick oil cup in a 50 ℃ water bath kettle at a very high temperature for 2 hours, stirring every 15-20 min during the period, measuring the viscosity, and marking as eta1. Finally, according to the formula v ═ eta [ (. eta.) ]0-η1)/η0]The viscosity reduction rate is calculated by multiplying 100 percent, and the viscosity reduction result of the thickened oil is shown in the table 1.
TABLE 1 viscosity reduction Performance test of viscosity reducer on thickened oil
As can be seen from Table 1, examples 1-3 changed the ratio of four monomers, wherein the viscosity reduction ratio of example 3 was the most significant, indicating that the molar ratio of the reactive monomers of the present invention was: the viscosity reducing effect of the 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and octadecyl methacrylate is the best as the functional groups in the monomers have better synergistic effect in the proportion, so that the viscosity reducing effect of the viscosity reducer is better. The comparison of examples 3-5 shows that both the reaction temperature and the reaction time have an influence on the viscosity reduction efficiency, which indicates that the heating temperature is 60 ℃, the initiation reaction time is 5 hours, and the viscosity reduction effect is most remarkable, because the high temperature causes the monomers to generate the implosion phenomenon, the molecular weight of the product is smaller, so that the viscosity reducer does not react to become the target product, and the viscosity reduction effect is poor; the reaction time is too long, so that the molecular structure is further increased, the molecular weight is continuously increased, and the viscosity reduction rate is poor because the excessive molecular weight is not beneficial to the reduction of the viscosity of the thick oil.
Example 7
The viscosity reducer obtained in example 3 was evaluated for the effect of thick oil with different viscosities, by pouring 100mL of thick oil into a 100mL tall-leg beaker, keeping the temperature at 50 ℃ for 1h, and measuring the viscosity of the thick oil with an NDJ-8S digital display viscometer, which is recorded as eta, according to SY/T0520-2008 & lt & gt, equilibrium method of rotational viscometer for measuring crude oil viscosity, in accordance with Petroleum industry Standard SY/T0520-20080Dissolving 0.05g of viscosity reducer in 1g of toluene, adding the solution into a thick oil cup after the viscosity reducer is completely dissolved, uniformly stirring, heating the thick oil cup in a 50 ℃ water bath kettle at a very high temperature for 2 hours, stirring every 15-20 min during the period, measuring the viscosity, and marking as eta1. Finally, according to the formula v ═ eta [ (. eta.) ]0-η1)/η0]Calculating the viscosity reduction rate by multiplying 100 percent, and the viscosity reduction results for different thickened oils are shown in table 2.
TABLE 2 viscosity reduction Performance test of viscosity reducers on thickened oils of different viscosities
As can be seen from Table 2, the viscosity reduction rate of the invention for thick oil with the viscosity of 32600 mPas can reach 65.34% at most, and the viscosity reduction effect is excellent. Meanwhile, the viscosity reducing rate of the viscosity reducer to the thickened oil with the other two viscosities is about 50%, which shows that the viscosity reducer has good universality and is suitable for various thickened oils with different compositions.
Example 8
Infrared spectroscopic examination of the synthesized viscosity reducer of example 3 using a WQF-520 infrared spectrometer is shown in FIG. 1. As can be seen from the figure, the wavelength is 3450cm-1And 1720cm-1Is a peak on the ester group (-C ═ O), and has a wavelength of 2923cm-1And 2854cm-1The absorption peaks of (A) are each methyl (-CH)3) And methylene (-CH)2) The characteristic peak of (1) the wavelength of 1300-1635cm-1The region (A) is a characteristic peak of a benzene ring, and the wavelength is 1166cm-1Is a characteristic peak of fluorine, 730cm-1is-CH2And (3) judging that the target viscosity reducer is successfully synthesized because the figure has no obvious characteristic peak of olefin.
The above is only a preferred embodiment of the present invention, and it should be noted that the above preferred embodiment should not be considered as limiting the present invention, and the protection scope of the present invention should be subject to the scope defined by the claims. It will be apparent to those skilled in the art that various modifications and adaptations can be made without departing from the spirit and scope of the invention, and these modifications and adaptations should be considered within the scope of the invention.
Claims (9)
1. The oil-soluble thick oil viscosity reducer is characterized by being obtained by reacting four monomers, namely 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and stearyl methacrylate, wherein the molar ratio of the four monomers is as follows: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride, stearyl methacrylate, 1, (2-4), (1-3) and (9-11).
2. The viscosity reducer for thick oil soluble according to claim 1, wherein the molar ratio of the four monomers is: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride, stearyl methacrylate, 1:3:2: 10.
3. A preparation method of an oil-soluble thick oil viscosity reducer is characterized by comprising the following steps: the oil-soluble viscosity reducer for thick oil is prepared by mixing, dissolving and heating 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride and stearyl methacrylate according to the molar ratio of claim 1, and initiating the reaction.
4. The method for preparing the oil-soluble thick oil viscosity reducer according to claim 3, wherein the molar ratio is: 2, 2, 3, 3-tetrafluoropropyl methacrylate, styrene, maleic anhydride, stearyl methacrylate, 1:3:2: 10.
5. The preparation method of the oil-soluble thick oil viscosity reducer according to claim 3, wherein the solvent selected in the dissolving process is toluene, and the mass of the toluene is 90-110% of the sum of the four monomers.
6. The method for preparing the viscosity reducer for thick oil soluble according to claim 3, wherein the heating temperature in the heating process is 60-80 ℃.
7. The preparation method of the oil-soluble thick oil viscosity reducer according to claim 3, wherein the initiator for initiating the reaction is benzoyl peroxide, and the mass of the benzoyl peroxide is 1% -2% of the sum of the four monomers.
8. The method for preparing the viscosity reducer for thick oil soluble according to claim 3, wherein the reaction is initiated for 5-7 hours, and heating is stopped after the reaction is completed.
9. The use of the oil-soluble viscosity reducer for thick oil according to claim 1, wherein the viscosity reducer for thick oil is used for reducing thick oil with viscosity of 24300-34100 mPa-s.
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