Composite hydrogenation scale inhibitor and preparation method thereof
Patent Information
- Application Number
- CN202611471369.X
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2026-09-21
- Publication Date
- 2026-10-27
AI Technical Summary
其中阻聚剂是通过受阻酚类或胺类化合物分子中的活泼氢捕获活性自由基以终止链式反应，从而抑制烯烃、二烯烃等不饱和烃的聚合结垢，然而，单一阻聚剂仅能针对自由基聚合这一条路径发挥作用；分散剂通过极性基团吸附垢物微粒、长链烷基提供空间位阻来阻止垢物微粒的聚集与沉积，但分散剂无法从根本上阻止垢物的化学形成；金属钝化剂主要通过与油品中游离的金属离子发生螯合作用或在设备表面形成钝化膜以减少金属离子的溶出，从而抑制金属对聚合反应的催化，但其功能单一，无法对已生成的垢物起到清除或分散作用
本申请复合功能剂是将改性超支化聚酰胺-胺、硼酸三异辛酯和三异辛胺复合制得，其中改性超支化聚酰胺-胺是采用酰胺反应将水杨酸封端改性超支化聚酰胺-胺制得，超支化聚酰胺-胺骨架具有高度支化的三维结构，使得水杨酸芳环的大π共轭平面能够与垢物中稠环芳烃/沥青质的芳环体系通过π-π堆积相互作用，锚定稠环芳烃垢物；另外水杨酸分子中的酚羟基可通过配位作用螯合金属离子，钝化其对聚合反应的催化活性；硼酸三异辛酯中的硼原子具有空p轨道，能够与改性超支化聚酰胺-胺的酚羟基形成B-O配位键，同时硼酸三异辛酯的长支链可以提供空间位阻共同抑制改性超支化聚酰胺-胺中水杨酸芳环π-π自聚集并提升油相分散稳定性，另外，在高温下，硼酸酯可分解生成硼的氧化物，在换热器金属表面形成钝化膜，从而抑制金属离子对油品中不饱和烃类自由基聚合结焦的催化作用；三异辛胺的氮原子能够与硼酸三异辛酯中的硼原子通过B-N配位键结合，提高硼酸三异辛酯水解稳定性，稳定配位结构，三者之间通过动态配位键结合，形成稳定分散网络，共同提升复合加氢阻垢剂的阻垢性能。
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Figure CN122979003A_ABST
Abstract
Description
Technical Field
[0001] This application belongs to the field of petrochemical technology, and in particular relates to a composite hydrogenation scale inhibitor and its preparation method. Background Technology
[0002] Hydrorefining, hydrocracking, and residue hydrotreating units are core process units in the oil refining industry for upgrading oil quality and lightening heavy oil. As crude oil quality becomes increasingly heavy and degraded, the content of impurities such as gums, asphaltenes, sulfur, nitrogen, and heavy metals in the feedstock of hydrotreating units increases significantly. In actual industrial operation, polycyclic aromatic hydrocarbons, gums, and asphaltenes in the feedstock readily undergo condensation reactions upon heating. Simultaneously, the ferrous sulfide particles generated from the reaction of active hydrogen sulfide with equipment metals cross-link with these organic macromolecules and deposit on the heat exchanger tube walls. Furthermore, these particles accumulate in large quantities in the catalyst bed as they enter the reactor with the fluid, leading to a series of problems such as heat exchanger scaling, increased reactor bed pressure drop, and coking of furnace tubes. These issues severely restrict the long-term stable operation of the unit. Scale accumulation also causes a sharp increase in heat exchanger pressure differential, increased furnace heat load, and increased unit energy consumption.
[0003] To address the aforementioned scaling problems, existing technologies primarily employ hydrogenated scale inhibitors, using a combination of components with different functions to achieve both scale prevention and removal. Polymerization inhibitors, for example, inhibit the polymerization and scaling of unsaturated hydrocarbons such as olefins and dienes by capturing active free radicals in hindered phenolic or amine compounds to terminate chain reactions. However, a single polymerization inhibitor only works along the free radical polymerization pathway. Dispersants prevent the aggregation and deposition of scale particles by adsorbing them with polar groups and by providing steric hindrance with long-chain alkyl groups, but they cannot fundamentally prevent the chemical formation of scale. Metal passivators mainly inhibit the catalysis of polymerization reactions by chelating with free metal ions in the oil or forming a passivation film on the equipment surface to reduce the dissolution of metal ions. However, their function is singular and they cannot remove or disperse existing scale. Existing hydrogenated scale inhibitors are mostly simple combinations of the above components, lacking composite functional components that integrate multiple functions into a single molecular framework. Summary of the Invention
[0004] To address the aforementioned problems and further improve the scale inhibition performance of hydrogenated scale inhibitors, this application provides a composite hydrogenated scale inhibitor and its preparation method.
[0005] This application first provides a composite hydrogenated scale inhibitor, which comprises the following components in parts by weight: 8-15 parts of polyisobutylene succinimide dispersant, 10-15 parts of antioxidant, 5-8 parts of polymerization inhibitor, 15-30 parts of composite functional agent, and 30-50 parts of solvent. The composite functional agent is prepared by mixing 8-15 parts of modified hyperbranched polyamide-amine, 5-10 parts of triisooctyl borate, and 2-5 parts of triisooctylamine. The method for preparing the modified hyperbranched polyamide-amine includes the following steps: S1, diethylenetriamine and methyl acrylate are reacted in methanol to obtain an intermediate; S2, the intermediate is reacted with diethylenetriamine in methanol to obtain a hyperbranched polyamide-amine; S3, salicylic acid and hyperbranched polyamide-amine are heated and refluxed to obtain a modified hyperbranched polyamide-amine.
[0006] Furthermore, in S1, the molar ratio of diethylenetriamine to methyl acrylate is 1:6-8.
[0007] Furthermore, in S2, the molar ratio of diethylenetriamine to the intermediate is 1:14-16.
[0008] Furthermore, in S3, the molar ratio of salicylic acid to hyperbranched polyamide-amine is 4-5:1.
[0009] Furthermore, the preparation method of the triisooctyl borate includes the following steps: boron anhydride and calcium hydride are mixed with anhydrous isooctyl alcohol under stirring, and the mixture is heated to react and purify to obtain triisooctyl borate.
[0010] Furthermore, the antioxidant is N-cyclohexyl-N-phenyl-p-phenylenediamine or diisooctyldiphenylamine.
[0011] Furthermore, the solvent is a heavy aromatic hydrocarbon or diesel oil.
[0012] Furthermore, the polymerization inhibitor is tetramethylpiperidine nitroxide radical phosphite or 4-hydroxy-TEMPO.
[0013] Furthermore, this application provides a method for preparing a composite hydrogenation scale inhibitor, comprising the following steps: weighing each component according to the proportion, adding the modified hyperbranched polyamide-amine and part of the solvent into a reaction vessel, heating and stirring until completely dissolved, then cooling to 60-70°C, adding triisooctyl borate and triisooctylamine and stirring, then adding antioxidant, polymerization inhibitor, and polyisobutylene succinimide dispersant, continuing to stir for 1-2 hours, and cooling to room temperature to obtain the product.
[0014] Compared with the prior art, this application has the following beneficial effects: This application describes a composite functional agent prepared by combining modified hyperbranched polyamide-amine, triisooctyl borate, and triisooctylamine. The modified hyperbranched polyamide-amine is prepared by end-capping salicylic acid with a salicylic acid via an amide reaction. The hyperbranched polyamide-amine skeleton has a highly branched three-dimensional structure, allowing the large π-conjugated plane of the salicylic acid aromatic ring to interact with the aromatic ring system of fused-ring aromatic hydrocarbons / asphaltite in the scale through π-π stacking interactions, thus anchoring the fused-ring aromatic hydrocarbon scale. Furthermore, the phenolic hydroxyl groups in the salicylic acid molecule can chelate metal ions through coordination, passivating their catalytic activity in the polymerization reaction. The boron atoms in triisooctyl borate have empty p orbitals, which can interact with the phenolic hydroxyl groups of the modified hyperbranched polyamide-amine. The BO coordination bonds are formed by the radicals, and the long branched chains of triisooctyl borate can provide steric hindrance to jointly inhibit the π-π self-aggregation of salicylic acid aromatic rings in the modified hyperbranched polyamide-amine and improve the dispersion stability of the oil phase. In addition, at high temperatures, the borate ester can decompose to generate boron oxides, forming a passivation film on the metal surface of the heat exchanger, thereby inhibiting the catalytic effect of metal ions on the free radical polymerization and coking of unsaturated hydrocarbons in the oil. The nitrogen atom of triisooctylamine can combine with the boron atom in triisooctyl borate through BN coordination bonds, improving the hydrolytic stability of triisooctyl borate and stabilizing the coordination structure. The three are combined through dynamic coordination bonds to form a stable dispersion network, which together improves the scale inhibition performance of the composite hydrogenation scale inhibitor. Attached Figure Description
[0015] Figure 1 The image shows the infrared spectrum of the modified hyperbranched polyamide-amine from Example 2.
[0016] Figure 2 The scale inhibition rate is shown in the graphs for different amounts of scale inhibitor added in Examples 1-3 and Comparative Examples 1-2. Detailed Implementation
[0017] To make the inventive objectives, technical solutions, and beneficial effects of this application clearer, the following detailed description is provided in conjunction with embodiments. Obviously, the described embodiments are only a portion of the embodiments of this application, and not all of them. All other embodiments obtained by those skilled in the art based on the embodiments of this application without inventive effort are within the scope of protection of this application.
[0018] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the application. The term "and / or" as used herein includes any and all combinations of one or more of the associated listed items.
[0019] When using “including,” “having,” and “contains” as described herein, the intention is to cover non-exclusive inclusion, unless an explicit qualifying term such as “only” is used, in which case another component may be added.
[0020] In this application, "at least one" means one or more, such as one, two, or more. "Multiple" or "several" means at least two, such as two, three, etc., and "multi-layered" means at least two layers, such as two layers, three layers, etc., unless otherwise explicitly specified. In the description of this application, "several" means at least one, such as one, two, etc., unless otherwise explicitly specified.
[0021] When a numerical range is disclosed herein, the range is considered continuous and includes the minimum and maximum values of the range, as well as every value between the minimum and maximum values. Furthermore, when the range refers to integers, it includes every integer between the minimum and maximum values of the range. Additionally, when multiple ranges are provided to describe a feature or characteristic, the ranges may be combined. In other words, unless otherwise specified, all ranges disclosed herein should be understood to include any and all subranges to which they are incorporated.
[0022] Unless otherwise specified, all steps in this application may be performed sequentially or randomly. For example, the method comprising steps (a) and (b) indicates that the method may include steps (a) and (b) performed sequentially, or it may include steps (b) and (a) performed sequentially. For example, the mention that the method may also include step (c) indicates that step (c) may be added to the method in any order; for example, the method may include steps (a), (b), and (c), or it may include steps (a), (c), and (b), or it may include steps (c), (a), and (b), etc. Unless otherwise stated, singular terms may include plural forms and should not be construed as having a quantity of one.
[0023] The present application will be further illustrated by the following examples, but these examples do not limit the scope of the present application.
[0024] When numerical ranges are given in the embodiments, it should be understood that, unless otherwise stated in this application, both endpoints of each numerical range and any value between the two endpoints may be selected. Unless otherwise defined, all technical and scientific terms used in this application have the same meaning as commonly understood by one of ordinary skill in the art. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. All reagents or instruments whose manufacturers are not specified are conventional products that can be purchased commercially. In addition to the specific methods, equipment, and materials used in the embodiments, based on the knowledge of the prior art possessed by one of ordinary skill in the art and the description in this application, any prior art methods, equipment, and materials similar to or equivalent to those described, used, or made by the methods, equipment, and materials in the embodiments of this application may be used to implement this application.
[0025] Example 1 The composite hydrogenation scale inhibitor in this embodiment comprises the following components by weight: 80g of polyisobutylene succinimide dispersant, 100g of antioxidant, 50g of polymerization inhibitor, 150g of composite functional agent, and 300g of solvent; the composite functional agent is prepared by mixing 80g of modified hyperbranched polyamide-amine, 50g of triisooctyl borate, and 20g of triisooctylamine; the antioxidant is N-cyclohexyl-N-phenyl-p-phenylenediamine; the solvent is heavy aromatic hydrocarbon; and the polymerization inhibitor is tetramethylpiperidine nitroxide free radical triphosphite.
[0026] The preparation method of the composite hydrogenated scale inhibitor in this embodiment is as follows: Weigh each component according to the proportion, add the modified hyperbranched polyamide-amine and part of the solvent into the reaction vessel, heat to 90°C and stir until completely dissolved, then cool to 60°C, add triisooctyl borate and triisooctylamine and stir for 30 min, then add antioxidant, polymerization inhibitor and polyisobutylene succinimide dispersant, continue stirring for 1 h, and cool to room temperature to obtain the product.
[0027] The preparation method of the modified hyperbranched polyamide-amine in this embodiment is as follows: S1. Weigh a mixed solution of 2 mol diethylenetriamine and 20 mol methanol and add it to a four-necked flask. Equip the reflux condenser, magnetic stirrer and constant pressure dropping funnel. Stir the mixture evenly under the protection of ice water bath and nitrogen. Add 12 mol methyl acrylate dropwise over 2 hours. Heat to 30℃ and react continuously for 24 hours. After the reaction is completed, remove excess methanol and methyl acrylate by rotary evaporation to obtain the intermediate.
[0028] S2, weigh 2 mol of intermediate and 20 mol of methanol, mix thoroughly and add 0.14 mol of diethylenetriamine dropwise over 2 hours, react at 25°C for 24 hours, and after the reaction is complete, perform rotary distillation to remove excess methanol and diethylenetriamine to obtain hyperbranched polyamide-amine.
[0029] S3. 0.4 mol of salicylic acid and 0.1 mol of hyperbranched polyamide-amine were placed in a three-necked flask, and an appropriate amount of toluene was added as a solvent. The mixture was heated to 110 °C and refluxed for 4 h. The mixture was then filtered and the solvent was evaporated to obtain the modified hyperbranched polyamide-amine.
[0030] The preparation method of triisooctyl borate in this embodiment is as follows: In a well-ventilated fume hood, 0.125 mol of boric anhydride and 0.485 mol of calcium hydride were added to a thoroughly dried three-necked round-bottom flask. A reflux condenser with a calcium chloride drying tube and a constant-pressure dropping funnel were set up. Under stirring, 0.98 mol of anhydrous isooctanol was slowly added dropwise through the constant-pressure dropping funnel. After the isooctanol was added, the mixture was slowly heated. After the hydrogen release from the system slowed down, the reaction mixture was heated to 85°C and stirred for 8 hours. After the reaction was completed, the reflux apparatus was changed to a vacuum distillation apparatus to distill off the volatile products. The crude product was further purified by distillation to obtain triisooctyl borate.
[0031] Example 2 The composite hydrogenated scale inhibitor in this embodiment comprises the following components by weight: 120g of polyisobutylene succinimide dispersant, 125g of antioxidant, 65g of polymerization inhibitor, 200g of composite functional agent, and 400g of solvent; the composite functional agent is prepared by mixing 110g of modified hyperbranched polyamide-amine, 70g of triisooctyl borate, and 20g of triisooctylamine; the antioxidant is diisooctyl diphenylamine; the solvent is heavy aromatic hydrocarbon; and the polymerization inhibitor is 4-hydroxy-TEMPO.
[0032] The preparation method of the composite hydrogenated scale inhibitor in this embodiment is as follows: Weigh each component according to the proportion, add the modified hyperbranched polyamide-amine and part of the solvent into the reaction vessel, heat to 90°C and stir until completely dissolved, then cool to 65°C, add triisooctyl borate and triisooctylamine and stir for 30 min, then add antioxidant, polymerization inhibitor and polyisobutylene succinimide dispersant, continue stirring for 1.5 h, and cool to room temperature to obtain the final product.
[0033] The preparation method of the modified hyperbranched polyamide-amine in this embodiment is as follows: S1. Weigh a mixed solution of 2 mol diethylenetriamine and 20 mol methanol and add it to a four-necked flask. Equip the reflux condenser, magnetic stirrer and constant pressure dropping funnel. Stir the mixture evenly under the protection of ice water bath and nitrogen. Add 16 mol methyl acrylate dropwise over 2 hours. Heat the mixture to 30°C and react continuously for 24 hours. After the reaction is completed, remove excess methanol and methyl acrylate by rotary evaporation to obtain the intermediate.
[0034] S2, weigh 2 mol of intermediate and 20 mol of methanol, mix thoroughly and add 0.125 mol of diethylenetriamine dropwise over 2 hours, react at 25°C for 24 hours, and after the reaction is complete, perform rotary distillation to remove excess methanol and diethylenetriamine to obtain hyperbranched polyamide-amine.
[0035] S3. 0.5 mol of salicylic acid and 0.1 mol of hyperbranched polyamide-amine were placed in a three-necked flask, and an appropriate amount of toluene was added as a solvent. The mixture was heated to 110 °C and refluxed for 4 h. The mixture was then filtered and the solvent was evaporated to obtain the modified hyperbranched polyamide-amine.
[0036] The preparation method of triisooctyl borate in this embodiment is as follows: In a well-ventilated fume hood, 0.125 mol of boric anhydride and 0.485 mol of calcium hydride were added to a thoroughly dried three-necked round-bottom flask. A reflux condenser with a calcium chloride drying tube and a constant-pressure dropping funnel were set up. Under stirring, 0.98 mol of anhydrous isooctanol was slowly added dropwise through the constant-pressure dropping funnel. After the isooctanol was added, the mixture was slowly heated. After the hydrogen release from the system slowed down, the reaction mixture was heated to 85°C and stirred for 8 hours. After the reaction was completed, the reflux apparatus was changed to a vacuum distillation apparatus to distill off the volatile products. The crude product was further purified by distillation to obtain triisooctyl borate.
[0037] Example 3 The composite hydrogenation scale inhibitor in this embodiment comprises the following components by weight: 150g of polyisobutylene succinimide dispersant, 150g of antioxidant, 80g of polymerization inhibitor, 300g of composite functional agent, and 500g of solvent; the composite functional agent is prepared by mixing 150g of modified hyperbranched polyamide-amine, 100g of triisooctyl borate, and 50g of triisooctylamine; the antioxidant is diisooctyl diphenylamine; the solvent is diesel oil; and the polymerization inhibitor is 4-hydroxy-TEMPO.
[0038] The preparation method of the composite hydrogenated scale inhibitor in this embodiment is as follows: Weigh each component according to the proportion, add the modified hyperbranched polyamide-amine and part of the solvent into the reaction vessel, heat to 90°C and stir until completely dissolved, then cool to 70°C, add triisooctyl borate and triisooctylamine and stir for 30 min, then add antioxidant, polymerization inhibitor and polyisobutylene succinimide dispersant, continue stirring for 2 h, and cool to room temperature to obtain the product.
[0039] The preparation method of the modified hyperbranched polyamide-amine in this embodiment is as follows: S1. Weigh a mixed solution of 2 mol diethylenetriamine and 20 mol methanol and add it to a four-necked flask. Equip the reflux condenser, magnetic stirrer and constant pressure dropping funnel. Stir the mixture evenly under the protection of ice water bath and nitrogen. Add 14 mol methyl acrylate dropwise over 2 hours. Heat to 30℃ and react continuously for 24 hours. After the reaction is completed, remove excess methanol and methyl acrylate by rotary evaporation to obtain the intermediate.
[0040] S2, weigh 2 mol of intermediate and 20 mol of methanol, mix thoroughly and add 0.13 mol of diethylenetriamine dropwise over 2 hours, react at 25°C for 24 hours, and after the reaction is complete, perform rotary distillation to remove excess methanol and diethylenetriamine to obtain hyperbranched polyamide-amine.
[0041] S3. 0.45 mol of salicylic acid and 0.1 mol of hyperbranched polyamide-amine were placed in a three-necked flask, and an appropriate amount of toluene was added as a solvent. The mixture was heated to 110 °C and refluxed for 4 h. The mixture was then filtered and the solvent was evaporated to obtain the modified hyperbranched polyamide-amine.
[0042] The preparation method of triisooctyl borate in this embodiment is as follows: In a well-ventilated fume hood, 0.125 mol of boric anhydride and 0.485 mol of calcium hydride were added to a thoroughly dried three-necked round-bottom flask. A reflux condenser with a calcium chloride drying tube and a constant-pressure dropping funnel were set up. Under stirring, 0.98 mol of anhydrous isooctanol was slowly added dropwise through the constant-pressure dropping funnel. After the isooctanol was added, the mixture was slowly heated. After the hydrogen release from the system slowed down, the reaction mixture was heated to 85°C and stirred for 8 hours. After the reaction was completed, the reflux apparatus was changed to a vacuum distillation apparatus to distill off the volatile products. The crude product was further purified by distillation to obtain triisooctyl borate.
[0043] Comparative Example 1 The composite hydrogenated scale inhibitor in this comparative example comprises the following components by weight: 120g of polyisobutylene succinimide dispersant, 125g of antioxidant, 65g of polymerization inhibitor, 200g of composite functional agent, and 400g of solvent; the composite functional agent is hyperbranched polyamide-amine; the antioxidant is diisooctyl diphenylamine; the solvent is heavy aromatic hydrocarbon; and the polymerization inhibitor is 4-hydroxy-TEMPO.
[0044] The preparation method of the composite hydrogenated scale inhibitor in this comparative example is as follows: weigh each component according to the proportion, add hyperbranched polyamide-amine and part of the solvent into the reaction vessel, heat to 90℃ and stir until completely dissolved, then cool to 65℃, add antioxidant, polymerization inhibitor and polyisobutylene succinimide dispersant, continue stirring for 1.5h, and cool to room temperature to obtain the product.
[0045] The preparation method of the hyperbranched polyamide-amine in this comparative example is as follows: S1. Weigh a mixed solution of 2 mol diethylenetriamine and 20 mol methanol and add it to a four-necked flask. Equip the reflux condenser, magnetic stirrer and constant pressure dropping funnel. Stir the mixture evenly under the protection of ice water bath and nitrogen. Add 16 mol methyl acrylate dropwise over 2 hours. Heat the mixture to 30°C and react continuously for 24 hours. After the reaction is completed, remove excess methanol and methyl acrylate by rotary evaporation to obtain the intermediate.
[0046] S2, weigh 2 mol of intermediate and 20 mol of methanol, mix thoroughly and add 0.125 mol of diethylenetriamine dropwise over 2 hours, react at 25°C for 24 hours, and after the reaction is complete, perform rotary distillation to remove excess methanol and diethylenetriamine to obtain hyperbranched polyamide-amine.
[0047] Comparative Example 2 The composite hydrogenated scale inhibitor in this comparative example comprises the following components by weight: 120g of polyisobutylene succinimide dispersant, 125g of antioxidant, 65g of polymerization inhibitor, 150g of composite functional agent, and 400g of solvent; the composite functional agent is prepared by mixing 110g of modified hyperbranched polyamide-amine with 40g of triisooctylamine; the antioxidant is diisooctyl diphenylamine; the solvent is heavy aromatic hydrocarbon; and the polymerization inhibitor is 4-hydroxy-TEMPO.
[0048] The preparation method of the composite hydrogenated scale inhibitor in this comparative example is as follows: weigh each component according to the proportion, add the modified hyperbranched polyamide-amine and part of the solvent into the reaction vessel, heat to 90℃ and stir until completely dissolved, then cool to 65℃, add triisooctylamine and stir for 30 min, then add antioxidant, polymerization inhibitor and polyisobutylene succinimide dispersant, continue stirring for 1.5 h, and cool to room temperature to obtain the product.
[0049] The preparation method of the modified hyperbranched polyamide-amine in this comparative example is as follows: S1. Weigh a mixed solution of 2 mol diethylenetriamine and 20 mol methanol and add it to a four-necked flask. Equip the reflux condenser, magnetic stirrer and constant pressure dropping funnel. Stir the mixture evenly under the protection of ice water bath and nitrogen. Add 16 mol methyl acrylate dropwise over 2 hours. Heat the mixture to 30°C and react continuously for 24 hours. After the reaction is completed, remove excess methanol and methyl acrylate by rotary evaporation to obtain the intermediate.
[0050] S2, weigh 2 mol of intermediate and 20 mol of methanol, mix thoroughly and add 0.125 mol of diethylenetriamine dropwise over 2 hours, react at 25°C for 24 hours, and after the reaction is complete, perform rotary distillation to remove excess methanol and diethylenetriamine to obtain hyperbranched polyamide-amine.
[0051] S3. 0.5 mol of salicylic acid and 0.1 mol of hyperbranched polyamide-amine were placed in a three-necked flask, and an appropriate amount of toluene was added as a solvent. The mixture was heated to 110 °C and refluxed for 4 h. The mixture was then filtered and the solvent was evaporated to obtain the modified hyperbranched polyamide-amine.
[0052] Performance testing Scale inhibition performance: Weigh 350g of oil sample into a pressure vessel, add different amounts of composite hydrogenated scale inhibitor, shake well, place the weighed test piece in, heat to a certain temperature, and maintain the temperature for 3 hours. Simultaneously, a blank group without composite hydrogenated scale inhibitor was completed. Scale inhibition rate = (W0 - W1) / W0 × 100%, where W0 is the scale weight without scale inhibitor and W1 is the scale weight with scale inhibitor.
[0053] Catalyst bed pressure drop test: A self-made micro high-pressure hydrogenation reaction experimental device was used. Crude oil and composite hydrogenation scale inhibitor were mixed with high-pressure hydrogen from the pipeline network through the feed pump and the dosing pump, respectively, and then entered the reactor. The reactor was heated and reacted under the action of the catalyst. The average bed pressure drop of the first 5 hours before dosing was used as the blank value. Then, 0.1% composite hydrogenation scale inhibitor was injected and the change of bed pressure drop was observed.
[0054] Dispersion performance: Add 1g of composite hydrogenated scale inhibitor, 9g of sludge and 10g of base oil to a beaker, heat and stir at 150℃ for 1.5h, take a drop of the above test oil while it is hot and drop it onto filter paper, put it in an oven at 80℃ for 2h, and measure the ratio of diffusion ring to oil ring (SDT).
[0055] Analyze Examples 1-3 and Comparative Examples 1-2, in conjunction with Table 1 and Figures 1-2 It can be seen that the synergistic effect of salicylic acid-terminated hyperbranched polyamide-amine, triisooctyl borate, and triisooctylamine can effectively improve the scale inhibition and dispersion performance and pressure drop control capability of the composite hydrogenated scale inhibitor.
[0056] Table 1. Performance test results of the composite hydrogenation scale inhibitors in Examples 1-3 and Comparative Examples 1-2 Analysis Table 1 and Figure 2 Compared to Examples 1-3, the composite hydrogenation scale inhibitor prepared in Comparative Example 1 only used unmodified hyperbranched polyamide-amine, without adding triisooctyl borate and triisooctylamine. Lacking the π-π stacking anchoring points of the salicylic acid aromatic ring, it could not effectively adsorb fused-ring aromatic hydrocarbon scale. Furthermore, lacking the boron oxide passivation film generated by the decomposition of borate esters at high temperatures, it was difficult to effectively inhibit catalytic coking on the metal surface. Consequently, the scale inhibition rate of Comparative Example 1 decreased significantly at all addition levels, and the dispersion value also decreased significantly. The composite hydrogenation scale inhibitor prepared in Comparative Example 2, compared to Examples 1-3, only added modified hyperbranched polyamide-amine and triisooctylamine, without adding triisooctyl borate. Lacking the inhibitory effect of BO coordination bonds on the π-π self-aggregation of the salicylic acid aromatic ring, the modified hyperbranched polyamide-amine experienced decreased dispersibility in the oil phase due to self-aggregation. Consequently, the scale inhibition rate, dispersion performance, and pressure drop control ability of Comparative Example 2 decreased.
[0057] analyze Figure 1It can be observed that the modified hyperbranched polyamide-amine has a lower 3370 cm⁻¹ and a lower 3290 cm⁻¹ compared to the hyperbranched polyamide-amine. -1 The primary amine characteristic peak disappears at 3236 cm⁻¹. -1 Characteristic peaks of phenolic hydroxyl groups appear at 1660 and 1580 cm⁻¹. -1 The amide characteristic peak at 750 cm⁻¹ is significantly enhanced. -1 The presence of a characteristic peak of the CH bending vibration outside the aromatic ring of salicylic acid at the location confirms the successful synthesis of the modified hyperbranched polyamide-amine.
[0058] Although this application has been described in detail with reference to the foregoing embodiments, those skilled in the art can still modify the technical solutions described in the foregoing embodiments or make equivalent substitutions for some of the technical features. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this application should be included within the protection scope of this application.
Claims
1. A composite hydrogenated scale inhibitor, characterized in that, The product comprises the following components by weight: 8-15 parts of polyisobutylene succinimide dispersant, 10-15 parts of antioxidant, 5-8 parts of polymerization inhibitor, 15-30 parts of composite functional agent, and 30-50 parts of solvent. The composite functional agent is prepared by mixing 8-15 parts of modified hyperbranched polyamide-amine, 5-10 parts of triisooctyl borate, and 2-5 parts of triisooctylamine. The method for preparing the modified hyperbranched polyamide-amine includes the following steps: S1, reacting diethylenetriamine with methyl acrylate in methanol to obtain an intermediate; S2, reacting the intermediate with diethylenetriamine in methanol to obtain a hyperbranched polyamide-amine; S3, reacting salicylic acid with the hyperbranched polyamide-amine under reflux to obtain the modified hyperbranched polyamide-amine.
2. The composite hydrogenation scale inhibitor according to claim 1, characterized in that, In S1, the molar ratio of diethylenetriamine to methyl acrylate is 1:6-8.
3. The composite hydrogenation scale inhibitor according to claim 1, characterized in that, In S2, the molar ratio of diethylenetriamine to the intermediate is 1:14-16.
4. The composite hydrogenation scale inhibitor according to claim 1, characterized in that, In S3, the molar ratio of salicylic acid to hyperbranched polyamide-amine is 4-5:
1.
5. The composite hydrogenation scale inhibitor according to claim 1, characterized in that, The preparation method of the triisooctyl borate includes the following steps: boron anhydride and calcium hydride are mixed with anhydrous isooctyl alcohol under stirring, and the mixture is heated to react and purify to obtain triisooctyl borate.
6. The composite hydrogenation scale inhibitor according to claim 1, characterized in that, The antioxidant is N-cyclohexyl-N-phenyl-p-phenylenediamine or diisooctyldiphenylamine.
7. The composite hydrogenation scale inhibitor according to claim 1, characterized in that, The solvent is a heavy aromatic hydrocarbon or diesel oil.
8. The composite hydrogenation scale inhibitor according to claim 1, characterized in that, The polymerization inhibitor is tetramethylpiperidine nitroxide radical phosphite or 4-hydroxy-TEMPO.
9. A method for preparing a composite hydrogenation scale inhibitor as described in any one of claims 1-8, characterized in that, The process includes the following steps: weigh each component according to the proportion, add the modified hyperbranched polyamide-amine and part of the solvent to the reaction vessel, heat and stir until completely dissolved, then cool to 60-70℃, add triisooctyl borate and triisooctylamine and stir, then add antioxidant, polymerization inhibitor and polyisobutylene succinimide dispersant, continue stirring for 1-2 hours, and cool to room temperature to obtain the final product.