A polymer, a method for preparing the same and an application thereof

Abstract

The application provides a polymer, a preparation method and application thereof. A structural schematic diagram of the polymer is shown in formula I: wherein a ratio of x:y:z is 1:1:1; M + is at least one selected from Fe 3+ , Co 2+ , Ni 2+ , Cu 2+ , Zn 2+ , Ag + ; R is Na + and / or K + . The polymer can be used as a catalyst for heavy oil modification. When the polymer is added in an amount of 0.1% of the mass of Tahe heavy oil (the original viscosity at 50 DEG C is 3540 mPa.s), the viscosity reduction rate of the Tahe heavy oil is 88.36% to 91.21% and the coking inhibition rate is 61.89% to 88.5% after the Tahe heavy oil is catalytically modified at 380 DEG C for 30 min.

Description

Technical Field

[0001] This invention belongs to the field of heavy oil catalytic upgrading technology, and particularly relates to a polymer, its preparation method and application. Background Technology

[0002] Petroleum is the material foundation of human social and economic development and a major driving force for leaps in productivity, often referred to as the "lifeblood of industry." With the continuous development of the global economy, the world's demand for petroleum is increasing, while the dwindling resources of petroleum oil are forcing people to focus their attention on heavy oil.

[0003] my country possesses abundant heavy oil resources, mainly concentrated in the Shengli Oilfield, Karamay Oilfield, and the Tahe and Lungu Oilfields in the Tarim Basin. Currently, heavy oil reservoirs are entering the later stages of exploitation, and the problems of high energy consumption, high pollution, and high costs are becoming increasingly serious, necessitating technological upgrades to improve development methods. Catalytic reforming of heavy and extra-heavy oils is currently a hot topic. Catalytic reforming of heavy oil involves injecting a reforming catalyst into the reservoir, causing it to react with the heavy oil, achieving irreversible viscosity reduction and efficient extraction.

[0004] Currently, commonly used heavy oil reforming catalysts include oil-soluble catalysts, water-soluble catalysts, ionic liquid catalysts, nano-metal catalysts, and solid catalysts. Among them, oil-soluble catalysts are the most widely used heavy oil reforming catalysts due to their advantages such as high dispersibility, inexpensive and readily available raw materials, and the elimination of the need for separation in subsequent processing. However, conventional oil-soluble catalysts in existing technologies have low viscosity reduction efficiency for heavy oil, making it difficult to solve various complex engineering problems. Summary of the Invention

[0005] The first aspect of this invention provides a polymer, the structure of which is shown in Formula I:

[0006]

[0007] Where the ratio of x:y:z is 1:1:1; M + Selected from Fe 3+ Co 2+ Ni 2+ Cu 2+ Zn 2+ Ag + At least one of them; R is Na + and / or K + ;

[0008] Preferably, R is Na + .

[0009] The structural diagrams provided in this invention only represent the types of structural units of the polymer and the quantitative relationships between various structural units, and do not represent specific polymer structures.

[0010] In the structural schematic provided by this invention, M + The "+" in the text only indicates M + It is a transition metal ion, but does not mean M. + Specifically refers to transition metal ions with a +1 valence; M + This invention merely indicates that the structural schematic provided in this invention contains transition metal ions, and does not imply that the transition metal ions M in the structural schematic are present. + The ratio of -COO- to -COO- is fixed at 1:1.

[0011] According to one specific embodiment of the present invention, the polymer has a weight-average molecular weight of 2,000 to 10,000.

[0012] A second aspect of the present invention provides a method for preparing a polymer as described in the first aspect of the present invention, comprising the following steps:

[0013] 1) Maleic anhydride, 1-octadecene, and p-styrene sulfonate are subjected to a first reaction in the presence of an initiator to obtain an intermediate product;

[0014] 2) The transition metal salt and the intermediate product are subjected to a second reaction to obtain the polymer.

[0015] According to one specific embodiment of the present invention, the molar ratio of maleic anhydride, 1-octadecene and p-styrene sulfonate is 1:1:1.

[0016] According to one specific embodiment of the present invention, the ratio of the total amount of maleic anhydride, 1-octadecene and p-styrene sulfonate to the amount of transition metal salt is 1:(0.3 to 1).

[0017] According to one specific embodiment of the present invention, the total mass of the maleic anhydride, 1-octadecene and p-styrene sulfonate is 100%, and the amount of the initiator is 0.5 wt%.

[0018] According to a specific embodiment of the present invention, the p-styrene sulfonate is sodium p-styrene sulfonate and / or potassium p-styrene sulfonate; and / or

[0019] The initiator is a persulfate; and / or

[0020] The transition metal salt is selected from at least one of ferric chloride, cobalt nitrate, nickel nitrate, copper chloride, zinc nitrate, and silver nitrate;

[0021] Preferably, the p-styrene sulfonate is sodium p-styrene sulfonate; and / or

[0022] The persulfate is ammonium persulfate and / or potassium persulfate; and / or

[0023] The nickel nitrate in question is nickel nitrate hexahydrate.

[0024] According to a specific embodiment of the present invention, in step 2), the transition metal salt is first dissolved in a solvent to obtain a transition metal salt solution, and then the transition metal salt solution and the intermediate product are mixed before the second reaction is carried out; and / or

[0025] The reaction product obtained from the second reaction is separated to obtain the polymer;

[0026] Preferably, the solvent is water;

[0027] Preferably, in the transition metal salt solution, the mass fraction of the transition metal salt is 10 to 30 wt%;

[0028] Preferably, the reaction product obtained from the second reaction is separated by anhydrous ethanol precipitation.

[0029] According to a specific embodiment of the present invention, the conditions for the first reaction are: reacting at 90°C for 4 hours; and / or

[0030] The reaction conditions for the second reaction are 2 to 4 hours at 90°C.

[0031] Application of the polymer according to the first aspect of the present invention or the polymer prepared by the method according to the second aspect of the present invention in the catalytic upgrading of heavy oil;

[0032] Preferably, the viscosity of the heavy oil at 50°C is not less than 3540 mPa·s.

[0033] The beneficial effects of this invention are:

[0034] To address the low viscosity reduction efficiency of conventional oil-soluble catalysts in heavy oil, which hinders the solution of various complex engineering problems, this invention provides a polymer, its preparation method, and its applications. The polymer is obtained by reacting maleic anhydride, 1-octadecene, and p-styrene sulfonate under the action of an initiator, followed by a further reaction with a transition metal salt, thus serving as a heavy oil reforming catalyst. The polymer can be used as an oil-soluble viscosity reducer at low temperatures, requires a small dosage, has widely available raw materials, and a simple and easy-to-implement preparation process. It exhibits good viscosity reduction and reforming effects on heavy oil: when the polymer is added at 0.1 wt% of the Tarim River heavy oil mass, the viscosity reduction rate is 88.36% to 91.21%. The polymer has a short catalytic reforming reaction time for heavy oil, completing the catalytic reforming of heavy oil in 30 minutes at 380°C, and can effectively inhibit asphaltene coking during the heavy oil reforming process: when the polymer is added at 0.1 wt% of the Tarim River heavy oil mass, the coking inhibition rate is 61.89% to 88.5%. Detailed Implementation

[0035] The present invention will be further described below with reference to the embodiments. However, the embodiments of the present invention are merely illustrative examples and should not be construed as limiting the present invention under any circumstances.

[0036] Example 1

[0037] 1) Mix 98.1g maleic anhydride, 252.5g 1-octadecene, and 206.2g sodium p-styrene sulfonate (corresponding to a molar ratio of 1:1:1), then add 2.784g ammonium persulfate, and react at 90℃ for 4h to obtain the intermediate product;

[0038] 2) First, 162.2 g (corresponding to 1 mol) of ferric chloride was dissolved in water to obtain a ferric chloride aqueous solution with a ferric chloride mass fraction of 10 wt%. Then, this ferric chloride aqueous solution was mixed with the intermediate product and reacted at 90 °C for 2 h until the reaction was complete. The polymer with the structural diagram of Formula I was obtained by precipitation with anhydrous ethanol. The corresponding weight-average molecular weight was 3500, where the ratio of x, y, and z was 1:1:1, and M... + For Fe 3+ , R is Na + .

[0039] Example 2

[0040] 1) Mix 9.81g maleic anhydride, 25.25g 1-octadecene, and 20.62g sodium p-styrene sulfonate (corresponding to a molar ratio of 1:1:1), then add 0.2784g ammonium persulfate, and react at 90℃ for 4h to obtain the intermediate product;

[0041] 2) First, 18.2843 g (corresponding to 0.1 mol) of cobalt nitrate was dissolved in water to obtain a cobalt nitrate aqueous solution with a cobalt nitrate mass fraction of 15 wt%. Then, this cobalt nitrate aqueous solution was mixed with the intermediate product and reacted at 90 °C for 4 h until the reaction was complete. The polymer with the structural diagram of Formula I was obtained by precipitation with anhydrous ethanol. The corresponding weight-average molecular weight was 5600, where the ratio of x, y, and z was 1:1:1, and M... + For Co 2+ , R is Na + .

[0042] Example 3

[0043] 1) Mix 98.1g maleic anhydride, 252.5g 1-octadecene, and 206.2g sodium p-styrene sulfonate (corresponding to a molar ratio of 1:1:1), then add 2.784g ammonium persulfate, and react at 90℃ for 4h to obtain the intermediate product;

[0044] 2) First, 290.81 g (corresponding to 1 mol) of nickel nitrate hexahydrate was dissolved in water to obtain a nickel nitrate aqueous solution with a nickel nitrate mass fraction of 20 wt%. Then, this nickel nitrate aqueous solution was mixed with the intermediate product and reacted at 90 °C for 4 h until the reaction was complete. The polymer with the structural diagram of Formula I was obtained by precipitation with anhydrous ethanol. The corresponding weight-average molecular weight was 7500, where the ratio of x, y, and z was 1:1:1, and M... + For Ni 2+ , R is Na + .

[0045] Example 4

[0046] 1) Mix 98.1g maleic anhydride, 252.5g 1-octadecene, and 206.2g sodium p-styrene sulfonate (corresponding to a molar ratio of 1:1:1), then add 2.784g ammonium persulfate, and react at 90℃ for 4h to obtain the intermediate product;

[0047] 2) First, dissolve 135g (corresponding to 1mol) of copper chloride in water to obtain a copper chloride aqueous solution with a copper chloride mass fraction of 10wt%. Then, mix this copper chloride aqueous solution with the intermediate product and react at 90℃ for 4 hours until the reaction is complete. Separate the polymer with the structure shown in Formula I by anhydrous ethanol precipitation. The corresponding weight-average molecular weight is 4630, where the ratio of x, y, and z is 1:1:1, and M... + Cu 2+ , R is Na + .

[0048] Example 5

[0049] 1) Mix 98.1g maleic anhydride, 252.5g 1-octadecene, and 206.2g sodium p-styrene sulfonate (corresponding to a molar ratio of 1:1:1), then add 2.784g ammonium persulfate, and react at 90℃ for 4h to obtain the intermediate product;

[0050] 2) First, 189.4 g (corresponding to 1 mol) of zinc nitrate was dissolved in water to obtain a zinc nitrate aqueous solution with a zinc nitrate mass fraction of 30 wt%. Then, this zinc nitrate aqueous solution was mixed with the intermediate product and reacted at 90 °C for 2 h until the reaction was complete. The polymer with the structural diagram of Formula I was obtained by precipitation with anhydrous ethanol. The corresponding weight-average molecular weight was 8650, where the ratio of x, y, and z was 1:1:1, and M... + Zn 2+ , R is Na + .

[0051] Example 6

[0052] 1) Mix 98.1g maleic anhydride, 252.5g 1-octadecene, and 206.2g sodium p-styrene sulfonate (corresponding to a molar ratio of 1:1:1), then add 2.784g ammonium persulfate, and react at 90℃ for 4h to obtain the intermediate product;

[0053] 2) First, 169.87 g (corresponding to 1 mol) of silver nitrate was dissolved in water to obtain a silver nitrate aqueous solution with a silver nitrate mass fraction of 25 wt%. Then, this silver nitrate aqueous solution was mixed with the intermediate product and reacted at 90 °C for 4 h until the reaction was complete. The polymer with the structural diagram of Formula I was obtained by precipitation with anhydrous ethanol. The corresponding weight-average molecular weight was 9503, where the ratio of x, y, and z was 1:1:1, and M... + For Ag + , R is Na + .

[0054] Experimental Evaluation

[0055] 1. Evaluation of the catalytic upgrading performance of polymers on heavy oil

[0056] The polymers prepared in Examples 1 to 6 were used to catalytically upgrade Tarim River heavy oil with an initial viscosity of 3540 mPa·s at 50°C. The viscosity, coking rate, and coking inhibition rate of the upgraded oil were measured to evaluate the performance of the polymers in catalytic upgrading of heavy oil. The specific methods are as follows:

[0057] i. Weigh out 6 portions of Tarim heavy oil, each weighing 100g, with an original viscosity of 3540mPa.s at 50℃, and set aside for later use;

[0058] ii. Add 0.1g of the polymer prepared in Examples 1 to 6 to 6 portions of Tarim River heavy oil, each with a mass of 100g, and react at 380°C for 30min to obtain modified oils A to F.

[0059] iii. Viscosity determination of modified oil

[0060] The viscosity of modified oils A to F at 50℃ was measured using an NDJ-5S digital display viscometer, as shown in Table 1.

[0061] Table 1. Evaluation of the catalytic upgrading performance of polymers on heavy oil: viscosity of the upgraded oil

[0062] Tarim River Heavy Oil / 3540 / Example 1 A 311 91.21 Example 2 B 382 89.21 Example 3 C 396 88.81 Example 4 D 405 88.56 Example 5 E 390 88.98 Example 6 F 412 88.36

[0063] The data in Table 1 show that when the polymers prepared in Examples 1 to 6 were added at 0.1 wt% of the Tarim River heavy oil mass, the viscosity reduction rate of the Tarim River heavy oil ranged from 88.36% to 91.21%. Among them, the polymer containing ferric ions prepared in Example 1 had the best viscosity reduction effect on the Tarim River heavy oil, with a viscosity reduction rate of 91.21%. This indicates that the polymers prepared in Examples 1 to 6 have a good viscosity reduction effect on the Tarim River heavy oil.

[0064] iv. Determination of coking rate and polymer coking inhibition rate of modified oil

[0065] The formula for calculating the coke rejection rate in this experiment is as follows:

[0066] Coking rate = (m 焦炭 / m 塔河稠油 )×100% formula (1)

[0067] In the formula, m 焦炭 The mass of coke is expressed in grams.

[0068] m 塔河稠油 Let be the initial mass of Tarim River heavy oil, in g.

[0069] 1) Determination of coking rate of modified oils A to F:

[0070] Centrifuge the modified oils A to F obtained in step ii, collect the lower layer of coke particles, wash them with ethanol, dry them at 80°C, weigh them, and calculate the coking rate according to formula (1).

[0071] 2) Determination of coking rate in blank control group: Tahe heavy oil was used as blank control: 100g of Tahe heavy oil with an original viscosity of 3540mPa.s at 50℃ was heated at 380℃ for 30min, centrifuged, the lower layer of coke particles was collected, washed with ethanol, dried at 80℃ and weighed, and the coking rate was calculated according to formula (1).

[0072] Based on the above methods, the coking rates of Tarim River heavy oil, modified oils A to F obtained by catalytic modification experiments of Tarim River heavy oil using polymers prepared in Examples 1 to 6, and the coking inhibition rate of polymers prepared in Examples 1 to 6 as heavy oil modification catalysts were measured. The specific results are shown in Table 2.

[0073] Table 2. Evaluation of the catalytic upgrading performance of polymers on heavy oil: coking rate and coking inhibition rate during the catalytic upgrading process of heavy oil.

[0074] Tarim River Heavy Oil / 20.52 / Example 1 A 2.36 88.50 Example 2 B 3.62 82.36 Example 3 C 5.46 73.39 Example 4 D 7.55 63.21 Example 5 E 5.22 74.56 Example 6 F 7.82 61.89

[0075] As can be seen from the data in Table 2, as a blank control, the coking rate of Tarim River heavy oil without polymer catalytic modification prepared in this invention was relatively high, specifically 20.52%. In contrast, the coking rate of the modified oil obtained after polymer catalytic modification prepared in Examples 1 to 6 was only 2.36% to 7.82%, which was significantly lower than the coking rate of the blank control group. The coking inhibition rate reached 61.89% to 88.5%, proving that the polymer prepared in Examples 1 to 6, as a heavy oil modification catalyst, has a good coking inhibition effect on heavy oil.

[0076] The data in Tables 1 and 2 demonstrate that the polymers prepared in Examples 1 to 6 can achieve catalytic reforming effects on Tarim River heavy oil with a viscosity reduction rate of 88.36% to 91.21% and a coking inhibition rate of 61.89% to 88.5%. This proves that the polymers prepared in Examples 1 to 6 have good viscosity reduction and coking inhibition performance as heavy oil reforming catalysts, and have excellent catalytic reforming performance.

[0077] While the present invention has been described with reference to specific embodiments, those skilled in the art will understand that various changes can be made without departing from the true spirit and scope of the invention. Furthermore, numerous modifications can be made to the subject, spirit, and scope of the invention to suit specific situations, materials, material compositions, and methods. All such modifications are included within the scope of the claims of the present invention.

Claims

1. A method for preparing a polymer, comprising the following steps: 1) Maleic anhydride, 1-octadecene, and p-styrene sulfonate undergo a first reaction in the presence of an initiator to yield an intermediate product; wherein, The molar ratio of maleic anhydride, 1-octadecene, and p-styrene sulfonate is 1:1:1; 2) The transition metal salt and the intermediate product undergo a second reaction to obtain the polymer; The ratio of the total amount of maleic anhydride, 1-octadecene, and p-styrene sulfonate to the amount of the transition metal salt is 1:(0.3 to 1).

2. The method according to claim 1, characterized in that, The total mass of the maleic anhydride, 1-octadecene, and p-styrene sulfonate is 100%, and the amount of the initiator is 0.5 wt%.

3. The method according to claim 1 or 2, characterized in that, The p-styrene sulfonate is sodium p-styrene sulfonate and / or potassium p-styrene sulfonate; and / or The initiator is a persulfate; and / or The transition metal salt is selected from at least one of ferric chloride, cobalt nitrate, nickel nitrate, copper chloride, zinc nitrate, and silver nitrate.

4. The method according to claim 3, characterized in that, The p-styrene sulfonate is sodium p-styrene sulfonate.

5. The method according to claim 1 or 2, characterized in that, In step 2), the transition metal salt is first dissolved in a solvent to obtain a transition metal salt solution, and then the transition metal salt solution and the intermediate product are mixed before the second reaction is carried out; and / or The polymer is obtained by separating the reaction product from the second reaction. The solvent is water.

6. The method according to claim 1 or 2, characterized in that, The conditions for the first reaction were a reaction at 90°C for 4 hours; and / or The reaction conditions for the second reaction are 2 to 4 hours at 90°C.

7. The application of the polymer prepared by the method according to any one of claims 1 to 6 in the catalytic upgrading of heavy oil.

8. The application according to claim 7, characterized in that, The viscosity of the heavy oil at 50°C is not less than 3540 mPa·s.

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