Viscosity-reducing agent composition, viscosity-reducing agent, viscosity-reducing agent combination liquid, and use thereof

Abstract

The present application relates to the field of heavy oil exploitation, and discloses a viscosity reducer composition, a viscosity reducer, a viscosity reducer combination liquid and application thereof, the composition comprising a polyene polyamine modified styrene maleic anhydride copolymer, a polyethanolamine modified styrene maleic anhydride copolymer, a solvent and an inorganic additive.The viscosity reducer composition can effectively reduce the viscosity of heavy oil and super heavy oil and improve the flowability.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of heavy oil recovery, in particular to a viscosity reducer composition, a viscosity reducer, a viscosity reducer composition liquid and application thereof. BACKGROUND

[0002] The quantity of colloid and asphaltene contained in the crude oil directly affects the viscosity of the crude oil. More than 60% of the crude oil in China is heavy oil containing colloid and asphaltene. The high viscosity and large density of the heavy oil make it difficult to be driven in the oil reservoir environment, and the flow resistance is too large in the transportation process. The recovery of the heavy oil faces a series of problems such as high cost and difficult recovery. The heavy oil fields discovered so far are mainly distributed in Liaohe, Xinjiang, Shengli, Henan, Dagang, Jilin and other oil fields.

[0003] In terms of chemical composition, heavy oil is mainly a mixture of various hydrocarbons and non-hydrocarbons, and the relative content of various components is different, and the physical properties are also different. Among them, the content of asphaltene and colloid in heavy oil is particularly high, and their structure is complex and the molecular weight is large. The microstructure study of asphaltene and colloid shows that the molecules of asphaltene and colloid contain a large number of hydroxyl, carboxyl or amino groups, and form strong hydrogen bond interactions between the molecules of asphaltene and colloid, and between the molecules of asphaltene and colloid. At the same time, the aromatic condensed ring planes of asphaltene molecules overlap and stack together, and are fixed by hydrogen bonds between polar groups to form asphaltene particles. The aromatic condensed ring planes of colloid molecules overlap and stack on the surface of asphaltene particles, and are fixed by hydrogen bonds to form a coating layer of asphaltene particles. These particles are connected to each other through multiple hydrogen bonds to form supramolecular aggregates, which ultimately results in the high viscosity characteristics of heavy oil.

[0004] In the process of recovery, wellbore lifting and transportation of crude oil, due to the large viscosity of the crude oil, especially when the crude oil contains a certain amount of water, the crude oil will become more and more thick with the flow of the crude oil. Because of the large viscosity of the crude oil, it is strongly adsorbed to the bottom layer and the wall during the recovery, wellbore lifting and transportation process, which not only increases the resistance of the recovery and transportation of the crude oil, but also seriously affects the recovery rate and transportation efficiency of the crude oil.

[0005] In order to reduce the viscosity of thick oil, the aggregate structure thereof must be broken. At present, the main technologies for viscosity reduction are physical or chemical methods such as mixed thin oil method, steam stimulation method, catalytic viscosity reduction method, emulsification viscosity reduction method, etc. The chemical viscosity reduction of thick oil has a history of several decades at home and abroad, and the commonly used viscosity reducers are surfactants and complex agents. In recent years, a large number of scholars are also developing and utilizing new viscosity reducers. Among them, nano new materials are also used in the viscosity reduction of thick oil. This technology utilizes the modification effect of surfactants on nano materials, so that the oil-water interface film formed by the modified surfactants is more firm and stable, the stability of the emulsion is increased, and the viscosity reduction effect on thick oil is improved. The research on the additives for viscosity reducers is also very much, and many scholars add alkali, short-chain alcohol and amine substances in the formula to improve the viscosity reduction efficiency and the stability of the formed emulsion.

[0006] With the rapid growth of China's national economy, the demand for oil is also increasing. Higher requirements are put forward for reducing the viscosity of crude oil and the resistance of crude oil production and transportation, and improving the recovery rate and transportation efficiency of crude oil. Although various types of methods for reducing the viscosity of crude oil have been developed for the production, wellbore lifting and transportation of crude oil, for example, mixed thin oil method, heating method and chemical viscosity reduction method, new viscosity reduction methods and new viscosity reducers are still needed to reduce the viscosity of crude oil and change the flowability of crude oil to facilitate the production, wellbore lifting and transportation of crude oil. SUMMARY

[0007] The purpose of the present application is to overcome the problems of high viscosity and large density of thick oil in the process of production, wellbore lifting and transportation of crude oil, which is difficult to drive in the reservoir environment and has too large flow resistance in the transportation process. A thick oil viscosity reduction composition, thick oil viscosity reduction composition and application thereof are provided. The composition has the characteristics of high viscosity reduction rate and low use concentration when used, can effectively reduce the viscosity of thick oil and improve the flowability.

[0008] In order to achieve the above purpose, the first aspect of the present application provides a viscosity reducer composition, which comprises a polyene polyamine modified styrene maleic anhydride copolymer, a polyethanolamine modified styrene maleic anhydride copolymer, a solvent and an inorganic additive.

[0009] The second aspect of the present application provides a viscosity reducer, which comprises the above viscosity reducer composition.

[0010] The third aspect of the present application provides a viscosity reducer composition liquid, which comprises water and the viscosity reducer composition.

[0011] The fourth aspect of the present application provides the application of the above viscosity reducer composition, viscosity reducer or viscosity reducer composition liquid in reducing the viscosity of thick oil.

[0012] Through the above technical solution, the present application at least obtains the following technical effects:

[0013] The product containing the viscosity reducer composition of the present application can effectively reduce the viscosity of thick oil and super-thick oil, improve the flowability, and the combination of the components in the composition makes the viscosity reducer composition have the characteristics of low use concentration and high flash point. The composition of the present application does not affect the subsequent processing of crude oil when used, the dosing process is simple and easy to operate, and can be better applied to thick oil viscosity reduction and transportation. DETAILED DESCRIPTION

[0014] The endpoints of the ranges and any values disclosed herein are not limited to the precise values recited as the exact dimensions are not critical to the present application. Any numerical value, however, can be expressed as a range to include any and all subranges therebetween. The ranges and individual points within those ranges are intended to be included herein. Any reference to a number of points is intended to include all points within the range, unless the context clearly indicates otherwise.

[0015] The first aspect of the present application provides a viscosity reducer composition, which comprises a polyene polyamine modified styrene maleic anhydride copolymer, a polyethanolamine modified styrene maleic anhydride copolymer, a solvent, and an inorganic additive.

[0016] In the present application, the product containing the viscosity reducer composition described in the present application can effectively reduce the viscosity of thick oil and super-thick oil, improve the flowability, and the main components in the composition include polyene polyamine modified styrene maleic anhydride copolymer and polyethanolamine modified styrene maleic anhydride copolymer, which belong to high molecular copolymers, so that the composition has a high flash point, increasing the safety of the composition when used. The inventors speculate that the anhydride of the styrene maleic anhydride copolymer will hydrolyze, and the use of polyene polyamine and polyethanolamine can better improve the structure, and the obtained polyene polyamine modified styrene maleic anhydride copolymer and polyethanolamine modified styrene maleic anhydride copolymer can increase the stability of the composition during use by interacting with the inorganic additive in the solvent, and the branched structure existing in the system when the composition acts on thick oil can extend into the interior of the thick oil molecules, reducing the viscosity of the thick oil.

[0017] According to the present application, the content of the polyene polyamine modified styrene maleic anhydride copolymer in the composition is not limited as long as the purpose of the present application can be achieved. In some embodiments, the content of the polyene polyamine modified styrene maleic anhydride copolymer is greater than or equal to 20 wt%, preferably 30-80 wt%, for example 30 wt%, 33 wt%, 37 wt%, 40 wt%, 45 wt%, 60 wt%, 66 wt%, 77 wt% or 80 wt%, based on the total mass of the composition.

[0018] According to the present application, the ratio of the polyene polyamine modified styrene maleic anhydride copolymer and the polyethanolamine modified styrene maleic anhydride copolymer is not particularly limited as long as the purpose of the present application can be achieved, and in some embodiments, the weight ratio of the polyene polyamine modified styrene maleic anhydride copolymer and the polyethanolamine modified styrene maleic anhydride copolymer is 100:(5-40), such as 100:5, 100:10, 100:15, 100:22, 100:25, 100:30 or 100:40. With the foregoing embodiments, the polyene polyamine modified styrene maleic anhydride copolymer and the polyethanolamine modified styrene maleic anhydride copolymer can better synergize, so that the product containing the composition of the present application has excellent viscosity reduction performance.

[0019] As long as the purpose of the present application can be achieved, in some embodiments, the polyene polyamine modified styrene maleic anhydride copolymer is provided by a polyene polyamine modified styrene maleic anhydride copolymer solution; and the polyethanolamine modified styrene maleic anhydride copolymer is provided by a polyethanolamine modified styrene maleic anhydride copolymer solution.

[0020] According to the present application, it can be understood that the polyene polyamine modified styrene maleic anhydride copolymer provided by the polyene polyamine modified styrene maleic anhydride copolymer solution is prepared by using polyene polyamine and styrene maleic anhydride copolymer as main raw materials in a copolymerization solvent reaction. If the polyene polyamine modified styrene maleic anhydride copolymer is needed to be obtained alone, a purification step such as washing and drying of the polyene polyamine modified styrene maleic anhydride copolymer solution after the copolymerization reaction is needed to remove the solvent after the copolymerization reaction. In the present application, the polyene polyamine modified styrene maleic anhydride copolymer provided by the polyene polyamine modified styrene maleic anhydride copolymer solution is directly used as one component in the composition, which not only can omit the purification step after the reaction and simplify the process flow, but also the copolymerization solvent existing in the reaction system can further act as a solvent in the composition, further increasing the compatibility of the composition system. Similarly, the polyethanolamine modified styrene maleic anhydride copolymer provided by the polyethanolamine modified styrene maleic anhydride copolymer solution is directly used as one component in the composition.

[0021] According to the present application, in some embodiments, the raw materials of the polyene polyamine modified styrene maleic anhydride copolymer solution include polyene polyamine, styrene maleic anhydride copolymer and copolymerization solvent.

[0022] According to the present application, in some preferred embodiments, the molar ratio of the polyene polyamine to the maleic anhydride in the polyene polyamine modified styrene maleic anhydride copolymer is (0.05-0.50):1, for example, 0.05:1, 0.1:1, 0.12:1, 0.15:1, 0.17:1, 0.24:1, 0.25:1, 0.30:1, 0.35:1, 0.40:1 or 0.50:1, preferably (0.1-0.25):1. And it can be understood that when the polyene polyamine is two or more than two different kinds of polyene polyamine, the molar amount is the sum of the molar amount of all polyene polyamines, and the polyene polyamine modified styrene maleic anhydride copolymer prepared by the foregoing embodiments can better interact with other components.

[0023] According to the present application, in some embodiments, the raw materials for preparing the polyene polyamine modified styrene maleic anhydride copolymer solution contain, by weight, 100 parts of styrene, 20-40 parts of maleic anhydride, 5-10 parts of polyene polyamine, 0.5-1 part of initiator, and 100 parts of copolymerization solvent.

[0024] According to the present application, in some embodiments, the method for preparing the polyene polyamine modified styrene maleic anhydride copolymer solution comprises: carrying out a first copolymerization reaction of styrene and maleic anhydride in the presence of an initiator and a copolymerization solvent to obtain a mixed solution containing a styrene maleic anhydride copolymer and a copolymerization solvent, and then adding a polyene polyamine to the mixed solution to carry out an amination reaction.

[0025] According to the present application, it can be understood that the above is only one embodiment for preparing the polyene polyamine modified styrene maleic anhydride copolymer solution, but the present application is not limited thereto, for example, a commercially available styrene maleic anhydride copolymer can also be subjected to an amination reaction with a polyene polyamine in a solvent.

[0026] According to the present application, the conditions for the amination reaction are not limited as long as the purpose of the present application can be achieved, and in some embodiments, the conditions for the amination reaction comprise: a reaction temperature of 105-130°C, for example, 105°C, 110°C, 115°C, 120°C or 125°C, preferably 110-125°C; and in some embodiments, the conditions for the amination reaction comprise: a reaction time of 1-10h, for example, 1h, 3h, 4h, 4h, 5h, 7h, 8h or 10h, preferably 3-8h.

[0027] According to the present application, it can be understood that the first copolymerization reaction is mainly to enable styrene and maleic anhydride to copolymerize to obtain a product containing styrene maleic anhydride, and the conditions for the first copolymerization reaction are not limited as long as the purpose of the present application can be achieved, and in some embodiments, the method for preparing the polyene polyamine modified styrene maleic anhydride copolymer solution comprises:

[0028] (1) In the reaction kettle, add the copolymerization solvent, maleic anhydride, initiator, stir until completely dissolved, then pass nitrogen and keep nitrogen atmosphere until the reaction is completed;

[0029] (2) Heat to 60-62℃;

[0030] (3) Start dropping styrene with peristaltic pump, control the dropping of styrene within 1.5 hours, during the dropping process, control the temperature within 60-65℃; if the temperature rises to 65℃, stop dropping and cool down to 60-65℃; if the temperature drops below 60℃, do heating treatment to keep the temperature within 60-65℃;

[0031] (4) After the dropping of styrene is completed, adjust the temperature to 64-65℃, keep for 2 hours to get the mixed solution containing styrene maleic anhydride copolymer and copolymerization solvent;

[0032] (5) Add polyene polyamine to the mixed solution for amination reaction.

[0033] According to the present application, in some embodiments, the raw materials of the polyethanolamine modified styrene maleic anhydride copolymer solution include polyethanolamine, styrene maleic anhydride copolymer and copolymerization solvent.

[0034] According to the present application, in some embodiments, the molar ratio of polyethanolamine to maleic anhydride in the polyethanolamine modified styrene maleic anhydride copolymer is (0.05-0.50):1, for example 0.05:1, 0.1:1,.23:1, 0.25:1, 0.35:1, 0.40:1 or 0.50:1, preferably (0.10-0.25):1. With the foregoing embodiments, the prepared polyethanolamine modified styrene maleic anhydride copolymer can better interact with other components.

[0035] According to the present application, in some embodiments, the raw materials of the polyethanolamine modified styrene maleic anhydride copolymer solution contain, by weight, 100 parts of styrene, 20-40 parts of maleic anhydride, 5-10 parts of polyethanolamine, 0.5-1 part of initiator and 100 parts of copolymerization solvent.

[0036] According to the present application, the preparation method of the polyethanolamine modified styrene maleic anhydride copolymer solution is not limited as long as the purpose of the present application can be achieved, and in some embodiments, the preparation method of the polyethanolamine modified styrene maleic anhydride copolymer solution includes: in the presence of initiator and copolymerization solvent, styrene and maleic anhydride are subjected to second copolymerization reaction to obtain mixed solvent containing styrene maleic anhydride copolymer and copolymerization solvent, and then polyethanolamine is added to the mixed solvent for esterification reaction.

[0037] According to the present application, the conditions of the esterification reaction are not particularly limited as long as the object of the present application can be achieved, and in some embodiments, the conditions of the esterification reaction include: the reaction temperature is 105-130℃, such as 105℃, 110℃, 120℃, 125℃ or 130℃, preferably 110-125℃; in some embodiments, the reaction time is 1-10h, such as 1h, 3h, 4h, 5h, 7h, 8h or 10h.

[0038] In the present application, the mixed solution containing styrene maleic anhydride copolymer and copolymerization solvent obtained by the first copolymerization reaction can be the same as or different from the mixed solution containing styrene maleic anhydride copolymer and copolymerization solvent obtained by the second copolymerization reaction, i.e., the first copolymerization reaction conditions can be the same or different, and in some embodiments, the preparation method of the polyalcohol amine modified styrene maleic anhydride copolymer solution comprises:

[0039] S1 adding copolymerization solvent, maleic anhydride and initiator into a reaction kettle, stirring until completely dissolved, then purging with nitrogen and maintaining a nitrogen atmosphere until the reaction is completely finished;

[0040] S2 heating to 60-62℃;

[0041] S3 starting to add styrene by peristaltic pump, controlling the addition to be completed within 1.5 hours, and controlling the temperature to be within 60-65℃ during the addition; if the temperature rises to 65℃, stop adding and cool to within 60-65℃; if the temperature drops below 60℃, heat to maintain the temperature within 60-65℃;

[0042] S4 after the addition of styrene is completed, adjusting the temperature to 64-65℃ and maintaining the temperature for 2 hours to obtain a mixed solution containing styrene maleic anhydride copolymer and copolymerization solvent;

[0043] S5 adding polyalcohol amine to the mixed solution to perform esterification reaction.

[0044] According to the present application, the types of initiator and copolymerization solvent used in the first copolymerization reaction and the second copolymerization reaction are not limited as long as the object of the present application can be achieved, and in the present application, azobisisobutyronitrile is used as the initiator and N,N-dimethylformamide is used as the copolymerization solvent as an exemplary description of the present application, but the present application is not limited thereto.

[0045] According to the present application, the content of the inorganic additive in the composition is not limited as long as the object of the present application can be achieved, and in some embodiments, the content of the inorganic additive is 0.5-10wt%, for example, 0.5wt%, 0.7wt%, 1wt%, 2wt%, 3wt%, 4wt%, 5wt%, 8wt% or 10wt%, based on the total mass of the composition. With the foregoing embodiments, the viscosity of the heavy oil can be reduced better when the composition of the present application is used, and the inventors speculate that in the system of the present application, the inorganic additive and other components in the system can interact with each other to change the crystallization behavior of the wax in the heavy oil, as well as the aggregation mode of the colloid and asphaltene, thereby improving the flowability of the heavy oil at low temperature.

[0046] According to the present application, in some embodiments, the particle size of the inorganic additive is 3-10μm, preferably 3-8μm.

[0047] According to the present application, in some embodiments, the flake size of the inorganic additive is 1-15nm, further preferably 1-10nm. With the foregoing embodiments, the viscosity reduction rate of the viscosity reduction composition can be further improved.

[0048] According to the present application, the type of the inorganic additive is not limited as long as the object of the present application can be achieved, and in some embodiments, the inorganic additive includes an inorganic additive containing hydroxyl. The existing composition containing the inorganic additive containing hydroxyl can cause the agglomeration of the inorganic additive due to the effect of the hydroxyl in the system, thereby reducing the performance of the composition, while the foregoing embodiments of the present application can increase the viscosity reduction when the composition is used, and the inventors speculate that the branched structure of the polyene polyamine modified styrene maleic anhydride copolymer and the polyethylene amine modified styrene maleic anhydride copolymer in the present application can make the inorganic additive containing hydroxyl better dispersed in the system, and at the same time, the inorganic additive can better interact with the polyene polyamine modified styrene maleic anhydride copolymer and the polyethylene amine modified styrene maleic anhydride copolymer to increase the wettability and permeability of the composition to the heavy oil when the composition is used.

[0049] According to the present application, in some embodiments, the inorganic additive containing hydroxyl is selected from one or more of white carbon black, hydrotalcite, montmorillonite, kaolin, talc powder, graphene oxide and cellulose, preferably graphene oxide. With the foregoing embodiments, it can produce a better structure effect, and interact with other components in the composition to better change the crystallization behavior of the wax in the heavy oil, as well as the aggregation mode of the colloid and asphaltene, thereby improving the flowability of the heavy oil at low temperature.

[0050] According to the present application, in some embodiments, the general formula of the polyene polyamine is H2N(CH2CH2NH) nH, n is an integer from 1 to 6, for example, 1, 2, 3, 4, 5, 6 or 7, preferably an integer from 2 to 4. By using the foregoing embodiment, the polyene polyamine modified styrene maleic anhydride copolymer can better interact with the polyethylene amine modified styrene maleic anhydride copolymer, so that the composition can exhibit excellent viscosity reduction effect.

[0051] According to the present application, it can be understood that when n is 2, the polyene polyamine is diethylene triamine; when n is 3, the polyene polyamine is triethylene tetramine; and when n is 4, the polyene polyamine is tetraethylene pentamine. Different types of polyene polyamines can be used alone or in combination.

[0052] According to the present application, in some embodiments, the polyethylene amine includes diethanolamine and / or triethanolamine, preferably diethanolamine. By using the foregoing embodiment, the viscosity reduction effect of the composition in use can be further increased, and the inventor speculates that the polyethylene amine modified styrene maleic anhydride copolymer and the polyene polyamine modified styrene maleic anhydride copolymer can better interact to increase the wetting and impregnation of the composition, and increase the dispersibility and solubility of the composition in thick oil.

[0053] According to the present application, it can be understood that the main purpose of the solvent is to mix the components in the composition uniformly, and the amount of the solvent is not limited. When the amount of other components in the composition is added, the solvent can be supplemented to 100 wt%.

[0054] According to the present application, as long as the purpose of the present application can be achieved, the type of the solvent is not limited, and in some embodiments, the solvent includes a fatty hydrocarbon solvent and / or a terpene solvent, preferably a terpene solvent.

[0055] According to the present application, in some embodiments, the terpene solvent is selected from one or more of α-pinene, β-pinene and limonene.

[0056] In the present application, limonene is used as an exemplary embodiment to illustrate the advantages of the present application, but the present application is not limited thereto.

[0057] The second aspect of the present application provides a viscosity reducer, which includes the above-mentioned viscosity reducer composition, and preferably, the weight content of the composition is 80-100%.

[0058] According to the present application, it can be understood that the viscosity reducer is prepared from the components in the above-mentioned viscosity reducer composition and optionally other components, and the preparation method is not limited. As long as the components in the viscosity reducer composition are mixed uniformly, the viscosity reducer can be obtained, and the present application will not be described in detail.

[0059] In the present application, the viscosity reducer in the viscosity reducer composition of the present application can effectively reduce the viscosity of thick oil and super-thick oil and improve the flowability.

[0060] The third aspect of the present application provides a viscosity reducer composition, which comprises water and the viscosity reducer composition.

[0061] According to the present application, the weight ratio of water to the viscosity reducer composition is not limited as long as the purpose of the present application can be achieved. In some embodiments, the weight content of the composition in the composition solution is 0.5-10%, preferably 2-5%.

[0062] In the present application, the viscosity reducer composition solution comprising water and the viscosity reducer composition can effectively reduce the viscosity of thick oil when used. The inventors speculate that when the viscosity reducer composition is used, the polyene polyamine modified styrene maleic anhydride copolymer and the polyethylene amine modified styrene maleic anhydride copolymer in the composition can form an oil-in-water structure with each other, and the inorganic additive makes the oil-in-water structure more stable, which better reduces the resistance of thick oil flowing in the pore or pipeline, thereby achieving excellent effect of reducing the viscosity of thick oil.

[0063] According to the present application, the preparation method of the viscosity reducer composition solution is not particularly limited, and only water and the viscosity reducer composition need to be mixed uniformly, i.e., each component in the viscosity reducer composition is mixed with water uniformly. The mixing can be mixing each component in the viscosity reducer composition and then adding water to mix uniformly, or adding water to mix during the mixing of each component in the viscosity reducer composition.

[0064] According to the present application, the mixing conditions are not limited during the preparation of the viscosity reducer composition solution. In order to increase the mixing efficiency, the mixing can be carried out under the conditions of stirring, ultrasonic or shearing. The present application does not make too much description on the preparation method of the viscosity reducer composition solution.

[0065] The fourth aspect of the present application provides the use of the above-mentioned viscosity reducer composition, viscosity reducer or viscosity reducer composition solution in reducing the viscosity of thick oil.

[0066] In the present application, the application conditions of the viscosity reducer composition and / or the viscosity reducer composition solution are not limited. Those skilled in the art can add the product containing the viscosity reducer composition or the viscosity reducer composition solution to thick oil for mixing according to the need. In order to increase the mixing effect, the mixing can be carried out under the conditions of a certain temperature and stirring, preferably at a speed of 40-120 r / min and at 30-60°C.

[0067] The present application will be described in detail by the following examples.

[0068] The test method of the viscosity of thick oil in the following examples and comparative examples is as follows:

[0069] ①Take 50 mL thick oil, add 10 mL (20%) viscosity reducer combination solution;

[0070] ②In 50℃ water bath for 3 min, stirring at 80 r / min for 30 seconds;

[0071] ③Use HAAKE MARS III rheometer to test the viscosity at 50℃.

[0072] Example 1

[0073] Polyene polyamine modified styrene maleic anhydride copolymer solution

[0074] Raw materials are: by weight,

[0075]

[0076] Preparation method:

[0077] (1) In the reaction kettle, add solvent, maleic anhydride, initiator, stir until completely dissolved, then pass nitrogen and keep nitrogen atmosphere until the reaction is completely finished;

[0078] (2) Heating to 60-62℃;

[0079] (3) The peristaltic pump starts to add styrene, and the styrene is added in 1.5 hours, and the temperature is controlled within 60-65℃ during the adding process; If the temperature rises to 65℃, stop adding and cool down to 60-65℃; If the temperature is reduced to 60℃ or below, heat treatment is done to keep the temperature within 60-65℃;

[0080] (4) After the completion of styrene addition, adjust the temperature to 64-65℃, and keep warm for 2 hours to get a mixed solvent containing styrene maleic anhydride copolymer and copolymer solvent;

[0081] (5) Add diethylene triamine to the mixed solvent, and after adding, heat to 120℃, and after 5 hours of reaction, get polyene polyamine modified styrene maleic anhydride copolymer solution;

[0082] Polyethylene amine modified styrene maleic anhydride copolymer solution

[0083] Raw materials are:

[0084]

[0085] Preparation method:

[0086] (1) In the reaction kettle, add solvent, maleic anhydride, initiator, stir until completely dissolved, then pass nitrogen and keep nitrogen atmosphere until the reaction is completely finished;

[0087] (2) Heating to 60-62℃;

[0088] (3) Start the peristaltic pump to drop the styrene, control the dropping of the styrene within 1.5 hours, and control the temperature within 60-65°C during the dropping process; if the temperature rises to 65°C, stop the dropping and reduce the temperature to within 60-65°C; if the temperature reduces to below 60°C, perform heating treatment to maintain the temperature within 60-65°C;

[0089] (4) After the dropping of the styrene is completed, adjust the temperature to 64-65°C, and maintain the temperature for 2 hours to obtain a mixed solvent containing the styrene-maleic anhydride copolymer and the copolymerization solvent;

[0090] (5) Add diethanolamine to the mixed solvent, and after the addition is completed, increase the temperature to 120°C; after 5 hours of reaction, a diethanolamine modified styrene-maleic anhydride copolymer solution is obtained;

[0091] Viscosity reducer

[0092] By weight, 100 parts of the prepared polyene polyamine modified styrene-maleic anhydride copolymer solution, 10 parts of the prepared diethanolamine modified styrene-maleic anhydride copolymer solution, 20 parts of limonene, and 1 part of graphene oxide (particle size 8 μm, flake diameter thickness 1-10 nm) are uniformly mixed to obtain a viscosity reducer.

[0093] Viscosity reducer combination solution

[0094] Using water and the viscosity reducer to uniformly mix, a viscosity reducer combination solution with a mass concentration of 3% of the viscosity reducer is prepared.

[0095] The viscosity results of the thickened oil are shown in Table 1.

[0096] Example 2

[0097] According to the method of Example 1, except that:

[0098] The raw materials of the diethanolamine modified styrene-maleic anhydride copolymer solution are:

[0099]

[0100] Viscosity reducer

[0101] By weight, 100 parts of the prepared polyene polyamine modified styrene-maleic anhydride copolymer solution, 20 parts of the prepared diethanolamine modified styrene-maleic anhydride copolymer solution, 26 parts of limonene, and 3.5 parts of graphene oxide (8-10 μm, flake diameter thickness 1-10 nm) are uniformly mixed to obtain a viscosity reducer.

[0102] The rest is the same as Example 1.

[0103] The viscosity results of the thickened oil are shown in Table 1.

[0104] Example 3

[0105] The method of Example 1 was followed, except that:

[0106] The raw materials for the polyethylene polyamine modified styrene maleic anhydride copolymer solution were:

[0107]

[0108] Viscosity reducer

[0109] The polyethylene polyamine modified styrene maleic anhydride copolymer solution prepared was 100 parts, the polyethylene polyamine modified styrene maleic anhydride copolymer solution prepared was 30 parts, limonene was 30 parts, and graphene oxide (3 μm, flake diameter thickness 1-10 nm) was 5 parts by weight, and they were mixed uniformly to obtain a viscosity reducer.

[0110] The rest was the same as Example 1.

[0111] The viscosity results of the thick oil are shown in Table 1.

[0112] Example 4

[0113] The method of Example 1 was followed, except that:

[0114] The raw materials for the polyethylene polyamine modified styrene maleic anhydride copolymer solution were:

[0115]

[0116] The preparation method was the same as Example 1, and triethylene tetramine was used instead of diethylene triamine during preparation;

[0117] Viscosity reducer

[0118] The polyethylene polyamine modified styrene maleic anhydride copolymer solution prepared was 100 parts, the polyethylene polyamine modified styrene maleic anhydride copolymer solution prepared was 30 parts, limonene was 30 parts, and graphene oxide (3 μm, flake diameter thickness 1-10 nm) was 5 parts by weight, and they were mixed uniformly to obtain a viscosity reducer.

[0119] The rest was the same as Example 1.

[0120] The viscosity results of the thick oil are shown in Table 1.

[0121] Example 5

[0122] The method of Example 1 was followed, except that:

[0123] The raw materials for the polyethylene polyamine modified styrene maleic anhydride copolymer solution were:

[0124]

[0125] The preparation method is the same as in Example 1, except that diethylenetriamine is replaced with triethylenetetramine during preparation;

[0126] The raw materials for the polyethanolamine-modified styrene-maleic anhydride copolymer are:

[0127]

[0128] Viscosity reducer

[0129] By weight, 100 parts of the prepared polyene-polyamine modified styrene-maleic anhydride copolymer, 22 parts of the prepared polyethanolamine modified styrene-maleic anhydride copolymer, 25 parts of limonene, and 2.5 parts of graphene oxide (8-10 μm, sheet diameter and thickness 1-5 nm) are mixed evenly to obtain a viscosity reducer.

[0130] The rest is the same as in Example 1.

[0131] The viscosity results of the heavy oil are shown in Table 1.

[0132] Example 6

[0133] The method is the same as in Example 1, except that:

[0134] The raw materials for the polyene-polyamine modified styrene-maleic anhydride copolymer are:

[0135]

[0136] The preparation method is the same as in Example 1, except that diethylenetriamine is replaced with triethylenetetramine during preparation;

[0137] The raw materials for the polyethanolamine-modified styrene-maleic anhydride copolymer are:

[0138]

[0139] Viscosity reducer

[0140] By weight, 100 parts of the prepared polyene-polyamine modified styrene-maleic anhydride copolymer, 10 parts of the prepared polyethanolamine modified styrene-maleic anhydride copolymer, 20 parts of limonene, and 1 part of graphene oxide (8-10 μm, sheet diameter and thickness 1-5 nm) are mixed evenly to obtain a viscosity reducer.

[0141] The rest is the same as in Example 1.

[0142] The viscosity results of the heavy oil are shown in Table 1.

[0143] Example 7

[0144] The method is the same as in Example 1, except that:

[0145] The raw materials for the polyene-polyamine modified styrene-maleic anhydride copolymer are:

[0146]

[0147] The preparation method is the same as that in Example 1, and tetraethylenepentamine is used instead of diethylenetriamine in the preparation;

[0148] Viscosity reducer

[0149] The prepared polyamine modified styrene maleic anhydride copolymer solution 100 parts, the prepared polyamine modified styrene maleic anhydride copolymer solution 20 parts, limonene 25 parts, graphene oxide (8-10 μm, sheet diameter thickness 1-5 nm) 1.5 parts are mixed uniformly to obtain a viscosity reducer;

[0150] The rest is the same as in Example 1.

[0151] The viscosity results of the heavy oil are shown in Table 1.

[0152] Example 8

[0153] According to the method of Example 1, except that:

[0154] The raw materials of the polyamine modified styrene maleic anhydride copolymer solution are:

[0155]

[0156] The preparation method is the same as that in Example 1, and tetraethylenepentamine is used instead of diethylenetriamine in the preparation;

[0157] The raw materials of the polyamine modified styrene maleic anhydride copolymer solution are:

[0158]

[0159]

[0160] Viscosity reducer

[0161] The prepared polyamine modified styrene maleic anhydride copolymer solution 100 parts, the prepared polyamine modified styrene maleic anhydride copolymer solution 20 parts, limonene 25 parts, graphene oxide (8-10 μm, sheet diameter thickness 1-5 nm) 1.5 parts are mixed uniformly to obtain a viscosity reducer;

[0162] The rest is the same as in Example 1.

[0163] The viscosity results of the heavy oil are shown in Table 1.

[0164] Example 9

[0165] According to the method of Example 1, except that:

[0166] The raw materials of the polyamine modified styrene maleic anhydride copolymer solution are as follows:

[0167]

[0168] The preparation method is the same as that in Example 1, and tetraethylenepentamine is used to replace diethylenetriamine during preparation;

[0169] The raw materials of the polyamine modified styrene maleic anhydride copolymer solution are as follows:

[0170]

[0171]

[0172] Viscosity reducer

[0173] The prepared polyamine modified styrene maleic anhydride copolymer solution 100 parts, the prepared polyamine modified styrene maleic anhydride copolymer solution 30 parts, limonene 30 parts, graphene oxide (3 μm, sheet diameter thickness 1-10 nm) 5 parts are mixed uniformly to obtain a viscosity reducer;

[0174] The rest is the same as in Example 1.

[0175] The viscosity results of the thickened oil are shown in Table 1.

[0176] Example 10

[0177] According to the method of Example 1, except that:

[0178] Viscosity reducer

[0179] The prepared polyamine modified styrene maleic anhydride copolymer solution 100 parts, the prepared polyamine modified styrene maleic anhydride copolymer solution 10 parts, limonene 30 parts, white carbon black (particle size 20-60 nm) 5 parts are mixed uniformly to obtain a viscosity reducer;

[0180] The rest is the same as in Example 1.

[0181] The viscosity results of the thickened oil are shown in Table 1.

[0182] Example 11

[0183] According to the method of Example 1, except that:

[0184] Viscosity reducer

[0185] The prepared polyamine modified styrene maleic anhydride copolymer solution 100 parts, the prepared polyamine modified styrene maleic anhydride copolymer solution 10 parts, limonene 30 parts, hydrotalcite (particle size 5-15 μm) 5 parts are mixed uniformly to obtain a viscosity reducer;

[0186] The rest is the same as example 1.

[0187] The viscosity results of the heavy oil are shown in Table 1.

[0188] Example 12

[0189] According to the method of example 1, except that:

[0190] Using ethylenediamine instead of diethylenetriamine;

[0191] The raw materials of the polyene polyamine modified styrene maleic anhydride copolymer solution are:

[0192]

[0193] The rest is the same as example 1.

[0194] The viscosity results of the heavy oil are shown in Table 1.

[0195] Example 13

[0196] According to the method of example 1, except that:

[0197] Using pentaethylenehexamine instead of diethylenetriamine;

[0198] The raw materials of the polyene polyamine modified styrene maleic anhydride copolymer solution are:

[0199]

[0200] The rest is the same as example 1.

[0201] The viscosity results of the heavy oil are shown in Table 1.

[0202] Comparative example 1

[0203] According to the method of example 1, except that:

[0204] Viscosity reducer

[0205] According to parts by weight, respectively, the prepared polyene polyamine modified styrene maleic anhydride copolymer solution 105 parts, the prepared polyethylene amine modified styrene maleic anhydride copolymer solution 10 parts, limonene 20 parts are mixed uniformly to obtain a viscosity reducer;

[0206] The rest is the same as example 1.

[0207] The viscosity results of the heavy oil are shown in Table 1.

[0208] Comparative example 2

[0209] The polyethylene amine modified styrene maleic anhydride copolymer solution in the viscosity reducer is replaced by the polyene polyamine modified styrene maleic anhydride copolymer solution;

[0210] That is, by weight, respectively, take the preparation of polyene polyamine modified styrene maleic anhydride copolymer 110 parts, 20 parts of limonene, graphene oxide (8-10 μm, sheet diameter thickness 1-5 nm) 1 parts mixed uniformly to reduce viscosity agent;

[0211] The rest is the same as example 1.

[0212] The viscosity results of the heavy oil are shown in Table 1.

[0213] Comparative example 3

[0214] The polyene polyamine modified styrene maleic anhydride copolymer in the viscosity reducer is replaced by a polyethanolamine modified styrene maleic anhydride copolymer;

[0215] That is, by weight, respectively, take the preparation of polyethanolamine modified styrene maleic anhydride copolymer 110 parts, 20 parts of limonene, graphene oxide (8-10 μm, sheet diameter thickness 1-5 nm) 1 parts mixed uniformly to reduce viscosity agent;

[0216] The rest is the same as example 1.

[0217] The viscosity results of the heavy oil are shown in Table 1.

[0218] Comparative example 4

[0219] The polyethanolamine modified styrene maleic anhydride copolymer is replaced by a monoethanolamine modified styrene maleic anhydride copolymer;

[0220] The raw materials are:

[0221]

[0222] Preparation method:

[0223] (1) In the reaction kettle, add solvent, maleic anhydride, initiator, stir until completely dissolved, then pass nitrogen and keep nitrogen atmosphere until the reaction is completely finished;

[0224] (2) Heat to 60-62℃;

[0225] (3) The peristaltic pump starts to add styrene, and the styrene is added in 1.5 hours. During the addition process, the temperature is controlled within 60-65℃; if the temperature rises to 65℃, stop adding and cool down to 60-65℃; if the temperature drops below 60℃, do heating treatment to keep the temperature within 60-65℃;

[0226] (4) After the addition of styrene is completed, adjust the temperature to 64-65℃, and keep warm for 2 hours;

[0227] (5) Add monoethanolamine, and after adding, heat to 120℃ and react for 5 hours;

[0228] (6) the single ethanol amine modified styrene maleic anhydride copolymer;

[0229] viscosity reducer

[0230] The prepared polyene polyamine modified styrene maleic anhydride copolymer 100 parts, the prepared single ethanol amine modified styrene maleic anhydride copolymer 10 parts, limonene 20 parts, graphene oxide (8-10 μm, flake thickness 1-5 nm) 1 part are mixed uniformly to obtain a viscosity reducer;

[0231] The rest is the same as example 1.

[0232] The viscosity results of the thick oil are shown in Table 1.

[0233] Table 1

[0234]

[0235] From the results in Table 1, it can be seen that the viscosity reducer composition of examples 1-13 of the viscosity reducer composition of the present application can effectively reduce the viscosity of thick oil and super thick oil and improve the flowability at a low dosage.

[0236] The above describes the preferred embodiments of the present application, but the present application is not limited thereto. Within the technical concept of the present application, various simple modifications can be made to the technical solutions of the present application, including the combination of various technical features in any other suitable manner. These simple modifications and combinations should also be considered as disclosed by the present application and fall within the protection scope of the present application.

Claims

1. A viscosity-reducing composition, characterized in that, The composition includes polyene-polyamine modified styrene-maleic anhydride copolymer, polyethanolamine modified styrene-maleic anhydride copolymer, solvent, and inorganic additives; The content of the polyene-polyamine modified styrene-maleic anhydride copolymer is greater than or equal to 20 wt% based on the total mass of the composition. The mass ratio of the polyene-polyamine modified styrene-maleic anhydride copolymer to the polyethanolamine modified styrene-maleic anhydride copolymer is 100:(5-40). The polyene-polyamine modified styrene-maleic anhydride copolymer is provided by a polyene-polyamine modified styrene-maleic anhydride copolymerizing liquid; the polyethanolamine modified styrene-maleic anhydride copolymer is provided by a polyethanolamine modified styrene-maleic anhydride copolymerizing liquid; The inorganic additive is 0.5-10 wt% based on the total mass of the composition. The inorganic additives include hydroxyl-containing inorganic additives; the hydroxyl-containing inorganic additives are selected from one or more of silica, hydrotalcite, montmorillonite, kaolin, talc, graphene oxide and cellulose. The particle size of the inorganic additive is 3-10µm; The inorganic additive has a flake diameter and thickness of 1-15 nm; The solvents include aliphatic hydrocarbon solvents and / or terpene solvents.

2. The composition according to claim 1, wherein, The content of the polyene-polyamine modified styrene-maleic anhydride copolymer is 30-80 wt% based on the total mass of the composition; and / or The raw materials for the polyene-polyamine modified styrene-maleic anhydride copolymer include polyene-polyamine, styrene-maleic anhydride copolymer, and copolymer solution.

3. The composition according to claim 2, wherein, In the polyene-polyamine modified styrene-maleic anhydride copolymer, the molar ratio of polyene-polyamine to maleic anhydride in the styrene-maleic anhydride copolymer is (0.05-0.50):1; The raw materials of the polyene-polyamine modified styrene-maleic anhydride copolymer liquid contain, by weight, 100 parts styrene, 20-40 parts maleic anhydride, 5-10 parts polyene-polyamine, 0.5-1 parts initiator, and 100 parts copolymer solvent.

4. The composition according to claim 3, wherein, In the polyene-polyamine modified styrene-maleic anhydride copolymer, the molar ratio of polyene-polyamine to maleic anhydride in the styrene-maleic anhydride copolymer is (0.10-0.25):

1.

5. The composition according to claim 1, wherein, The preparation method of the polyene-polyamine modified styrene-maleic anhydride copolymer liquid includes: in the presence of an initiator and a copolymerizing solvent, styrene and maleic anhydride undergo a first copolymerization reaction to obtain a mixed solution containing styrene-maleic anhydride copolymer and copolymerizing solvent, and then polyene-polyamine is added to the mixed solution to carry out an amination reaction.

6. The composition according to claim 5, wherein, The conditions for the amination reaction include: The reaction temperature is 105-130℃; and / or The reaction time is 1-10 hours.

7. The composition according to claim 6, wherein, The conditions for the amination reaction include: The reaction temperature is 110-125℃; and / or The reaction time is 3-8 hours.

8. The composition according to claim 1, wherein, The raw materials for the polyethanolamine-modified styrene-maleic anhydride copolymer include polyethanolamine, styrene-maleic anhydride copolymer, and copolymer solvent.

9. The composition according to claim 8, wherein, In the polyethanolamine-modified styrene-maleic anhydride copolymer, the molar ratio of polyethanolamine to maleic anhydride in the styrene-maleic anhydride copolymer is (0.05-0.50):1; The raw materials of the polyethanolamine-modified styrene-maleic anhydride copolymer liquid contain, by weight, 100 parts styrene, 20-40 parts maleic anhydride, 5-10 parts polyethanolamine, 0.5-1 parts initiator, and 100 parts copolymer solvent.

10. The composition according to claim 9, wherein, In the polyethanolamine-modified styrene-maleic anhydride copolymer, the molar ratio of polyethanolamine to maleic anhydride in the styrene-maleic anhydride copolymer is (0.10-0.25):

1.

11. The composition according to claim 1, wherein, The preparation method of the polyethanolamine-modified styrene-maleic anhydride copolymer liquid includes: in the presence of an initiator and a copolymerizing solvent, styrene and maleic anhydride undergo a second copolymerization reaction to obtain a mixed solvent containing styrene-maleic anhydride copolymer and copolymerizing solvent, and then polyethanolamine is added to the mixed solvent to carry out an esterification reaction.

12. The composition according to claim 11, wherein, The conditions for the esterification reaction include: The reaction temperature is 105-130℃; and / or The reaction time is 1-10 hours.

13. The composition according to claim 12, wherein, The conditions for the esterification reaction include: The reaction temperature is 110-125℃; and / or The reaction time is 3-8 hours.

14. The composition according to claim 1, wherein, The inorganic additive has a particle size of 3-8µm, and / or The inorganic additive has a flake diameter and thickness of 1-10 nm; The hydroxyl-containing inorganic additive is selected from graphene oxide.

15. The composition according to claim 1, wherein, The general formula for the polyene polyamine is H2N(CH2CH2NH). n H, where n is an integer from 1 to 6 in the general formula; and / or The polyethanolamines include diethanolamine and / or triethanolamine; The solvent includes terpene solvents.

16. The composition according to claim 15, wherein, The general formula for the polyene polyamine is H2N(CH2CH2NH). n H, where n is an integer from 2 to 4 in the general formula; and / or The polyethanolamine is diethanolamine; The terpene solvent is selected from one or more of α-pinene, β-pinene, and limonene.

17. A viscosity reducer, characterized in that, The viscosity reducer comprises the composition according to any one of claims 1-16.

18. The viscosity reducer according to claim 17, wherein, The composition has a weight content of 80-100%.

19. A viscosity-reducing liquid mixture, characterized in that, The combined liquid comprises water and the composition according to any one of claims 1-16.

20. The viscosity-reducing liquid composition according to claim 19, wherein, The weight content of the composition in the combined solution is 0.5-10%.

21. The viscosity-reducing liquid composition according to claim 20, wherein, The weight content of the composition in the combined solution is 2-5%.

22. The use of the viscosity reducing composition according to any one of claims 1-16, the viscosity reducing agent according to claim 17 or 18, or the viscosity reducing agent combination liquid according to any one of claims 19-21 in reducing the viscosity of heavy oil.

Images