A kind of residual oil hydrogenation anti-coking and anti-scaling agent and preparation method thereof

Abstract

The invention provides a residual oil hydrogenation anti-coking scale inhibitor and a preparation method thereof, belonging to the technical field of petrochemical industry. The scale inhibitor comprises N-hydroxyphthalimide and / or N-hydroxy-1,8-naphthalimide; and di(trialkylsilyl)amine; and quinacridone derivative of quinoxaline; and an inhibitor; and tributylphosphine oxide; and poly(ethylene glycol) diacrylate; and a solvent. The scale inhibitor with high-efficiency scale inhibition effect is prepared by compounding multiple components and optimizing the proportion.

Description

Technical Field

[0001] The invention relates to the technical field of petrochemical industry, and in particular to a residual oil hydrogenation anti-coking and anti-scaling agent and a preparation method thereof. Background Art

[0002] As my country's crude oil imports continue to increase, the properties of imported crude oil are becoming heavier and inferior, with high sulfur, nitrogen and heavy metal contents, making its processing, especially the processing of its residue oil, more difficult. The hydrogenation process has the function of stabilizing unsaturated compounds in the raw materials and hydrogenating and modifying metals, sulfur, oxygen, nitrogen and halogen compounds in the clean raw materials that are harmful to the downstream processing process. In order to optimize the raw material structure of downstream process units, increase the flexibility of unit operation, meet the requirements of increasingly stringent environmental regulations, and maximize the economic benefits of refineries, residue oil hydrogenation technology has become an important means and mainstream process to achieve this goal. However, in the process of residue oil hydrogenation cleaning and modification, the free radical polymerization reaction of the residue oil initiated by heteroatoms such as oxygen, sulfur and nitrogen, the metal catalytic polymerization reaction of nickel, vanadium and other metals in the raw oil, the deposition of corrosion products and metal salts, and the dehydrogenation condensation reaction participated by colloids and asphaltene will cause serious scaling of equipment pipelines. The heaviness of the raw materials will increase the tendency of scaling and coking of the hydrogenation heat exchanger and reactor bed. The coking of the raw material heat exchanger will seriously affect the heat exchange efficiency of the raw materials, increase the load of the heating furnace, increase energy consumption, and reduce the raw material processing capacity of the device; the coking of the catalyst bed will increase the pressure drop of the bed and even block the bed, which may lead to shutdown in severe cases.

[0003] At present, there are two main methods to solve the problem of equipment coking and fouling. One is to change the operating conditions, improve the equipment, and chemically passivate the inner surface of the equipment and pipelines. The other is to add a certain amount of scale inhibitors to the crude oil to inhibit and delay the formation of coke scale on the equipment surface. The use of scale inhibitors has the advantages of not changing the process flow, not affecting normal operation, convenient and flexible filling, low capital investment, and short recovery period, making it the most economical way to solve the problem of equipment coking and fouling. However, the anti-coking and anti-scaling effect of existing scale inhibitors still needs to be improved. Summary of the invention

[0004] In view of the above problems, the present invention provides a residual oil hydrogenation anti-coking and anti-scaling agent and a preparation method thereof.

[0005] The purpose of the present invention is achieved by the following technical solutions:

[0006] A residual oil hydrogenation anti-coking and anti-scaling agent, comprising the following components:

[0007] First component: N-hydroxyphthalimide and / or N-hydroxy-1,8-naphthalimide; and

[0008] Second component: di(trialkylsilyl)amine; and

[0009] The third component: a quinacridone derivative of quinoxaline; and

[0010] The fourth component: an inhibitor; and

[0011] Fifth component: tributylphosphine oxide; and

[0012] Sixth component: poly(ethylene glycol) diacrylate; and a solvent.

[0013] Preferably, the mass ratio of the first component to the second component, the third component, the fourth component, the fifth component and the sixth component is 1:1: (0.7-1.2): (0.4-1): (0.1-0.5): (0.4-0.7).

[0014] More preferably, the mass ratio of the first component to the second component, the third component, the fourth component, the fifth component and the sixth component is 1:1:0.98:0.77:0.4:0.62.

[0015] Preferably, the di(trialkylsilyl)amine is di(trimethylsilyl)amine, di(triphenylsilyl)amine, di(dimethylphenylsilyl)amine or di(diphenylmethylsilyl)amine.

[0016] Preferably, the method for preparing the quinacridone derivative of quinoxaline comprises the following steps:

[0017] (1) Weigh 2,3-diamino-7-bromo-9,9'-dialkylfluorene and dissolve it in toluene solvent, add anhydrous ferric chloride as a catalyst, raise the temperature to 40-50°C, slowly dropwise add the toluene solution of α-dicarbonyl compound under stirring conditions, and after the dropwise addition is completed, stir and react at 70-80°C for 1-2h, separate water with a water separator during the reaction, separate the precipitate after the reaction is completed, wash the solution with deionized water, dry it, and evaporate the solvent under reduced pressure to obtain a quinoxaline product;

[0018] Wherein, the mass ratio of the 2,3-diamino-7-bromo-9,9'-dialkylfluorene to the ferric chloride and the α-dicarbonyl compound is 10:(2.5-3):(8.5-10);

[0019] (2) weighing quinacridone and dissolving it in anhydrous tetrahydrofuran solvent, adding sodium hydride and tetrabutylammonium bromide, heating and reflux for 1-2 hours, adding the quinoxaline product under a protective atmosphere, continuing to reflux for 4-6 hours, adding methanol after the reaction is completed to terminate the reaction, concentrating under reduced pressure and purifying with a chromatographic column to remove unreacted reactants, and obtaining the quinacridone derivative of quinoxaline;

[0020] Wherein, the mass ratio of the quinacridone to the sodium hydride, the tetrabutylammonium bromide to the quinoxaline product is (1-1.2): (0.7-0.75): (1.3-1.5): 10.

[0021] Preferably, the α-dicarbonyl compound is 2,3-butanedione, 3,4-hexanedione, 4,5-octanedione or diphenylethanedione.

[0022] Preferably, the polymerization inhibitor is hydroquinone, vanillin, 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol or 2,2,6,6-tetramethylpiperidin-1-oxyphenol;

[0023] Among them, vanillin is mainly obtained by conversion and has an inhibitory effect on 2-methoxy-4-methylphenol.

[0024] Preferably, the solvent is heavy aromatic hydrocarbons, gasoline, diesel, kerosene or solvent oil.

[0025] Another aspect of the present invention is to provide a method for preparing the residual oil hydrogenation anti-coking and anti-scaling agent, which specifically comprises the following steps:

[0026] S1. Weigh each component according to the ratio and set aside;

[0027] S2. Under normal pressure, mix the components, raise the temperature to 50-70°C and mix and stir for 1-2 hours, and adjust the kinematic viscosity of the solvent to no more than 50 mm 2 / s, obtained.

[0028] The method of using the residual oil hydrogenation anti-coking and anti-scaling agent is to inject it into the crude oil buffer tank through a mixer by a scale inhibitor filling pump, and enter the heat exchange system after sufficient mixing, and adopt a continuous filling method, and the filling amount is 100-200 mg / kg (based on solute) of the feed amount.

[0029] The beneficial effects of the present invention are:

[0030] Aiming at the problem that the anti-coking and scale inhibitors in the prior art have a low inhibitory effect on the formation of coking scale, the present invention prepares a scale inhibitor with a high-efficiency scale inhibition effect by formulating multiple components and optimizing the ratio. Specifically, the mixed system with redox composed of N-hydroxydicarboximide and di(trialkylsilyl)amine plays a role in free radical capture, reducing polymerization and coking in the free radical pathway; the quinacridone derivative of quinoxaline has good amphiphilicity and a large conjugated structure, has a good deactivation effect on metals such as nickel and vanadium, reduces metal or salt deposition caused by metal catalysis, and catalyzes dehydrogenation condensation, thereby improving the scale inhibition performance; the poly(ethylene glycol) diacrylate, as a weak Lewis base, can promote the passivation effect of the metal and improve the dispersibility of the composition system; the scale inhibitor of the present invention is a composite composition including the effects of polymerization inhibition, oxidation resistance, dispersion and metal deactivation, has good cleaning dispersibility, oxidation resistance and passivation, can hinder free radical reaction, terminate chain reaction, resist corrosion and passivate metal functions, and has no adverse effect on hydrogenation reaction. Implementation

[0031] The present invention is further described in conjunction with the following examples. Example 1

[0032] A residual oil hydrogenation anti-coking and anti-scaling agent, comprising the following components:

[0033] First component: N-hydroxyphthalimide; and

[0034] Second component: bis(triphenylsilyl)amine; and

[0035] The third component: a quinacridone derivative of quinoxaline; and

[0036] Fourth component: hydroquinone; and

[0037] Fifth component: tributylphosphine oxide; and

[0038] The sixth component: poly(ethylene glycol) diacrylate (PEG200DA); and solvent diesel;

[0039] Wherein, the mass ratio of the first component to the second component, the third component, the fourth component, the fifth component and the sixth component is 1:1:0.98:0.77:0.4:0.62;

[0040] The preparation method of the quinacridone derivative of quinoxaline comprises the following steps:

[0041] (1) Weigh 2,3-diamino-7-bromo-9,9'-dialkylfluorene and dissolve it in toluene solvent, add anhydrous ferric chloride as a catalyst, heat to 45°C, slowly dropwise add diphenylethylenedione toluene solution under stirring, and after the dropwise addition is completed, stir and react at 70°C for 1.5 hours. During the reaction, water is separated by a water separator. After the reaction is completed, the precipitate is separated, and the solution is washed with deionized water. After drying, the solvent is evaporated under reduced pressure to obtain a quinoxaline product;

[0042] Wherein, the mass ratio of the 2,3-diamino-7-bromo-9,9'-dialkylfluorene to the ferric chloride and the diphenylethanedione is 10:2.7:8.8;

[0043] (2) weighing quinacridone and dissolving it in anhydrous tetrahydrofuran solvent, adding sodium hydride and tetrabutylammonium bromide, heating and reflux for 2 hours, adding the quinoxaline product under a protective atmosphere, continuing to reflux for 5 hours, adding methanol after the reaction is completed to terminate the reaction, concentrating under reduced pressure, and purifying through a chromatographic column (silica gel, 500 mesh, eluting with chloroform) to remove unreacted reactants, thereby obtaining the quinacridone derivative of quinoxaline;

[0044] Wherein, the mass ratio of the quinacridone to the sodium hydride, the tetrabutylammonium bromide to the quinoxaline product is 1.1:0.72:1.35:10;

[0045] The preparation method of the residual oil hydrogenation anti-coking and anti-scaling agent specifically comprises the following steps:

[0046] S1. Weigh each component according to the ratio and set aside;

[0047] S2. Mix all components under normal pressure, raise the temperature to 60℃ and mix and stir for 1.5h, and adjust the kinematic viscosity to no more than 50mm with solvent diesel. 2 / s, obtained. Example 2

[0048] A residual oil hydrogenation anti-coking and anti-scaling agent, comprising the following components:

[0049] First component: N-hydroxyphthalimide; and

[0050] Second component: bis(triphenylsilyl)amine; and

[0051] The third component: a quinoxaline derivative; and

[0052] Fourth component: hydroquinone; and

[0053] Fifth component: tributylphosphine oxide; and

[0054] The sixth component: poly(ethylene glycol) diacrylate (PEG200DA); and solvent diesel;

[0055] Wherein, the mass ratio of the first component to the second component, the third component, the fourth component, the fifth component and the sixth component is 1:1:0.98:0.77:0.4:0.62;

[0056] The preparation method of the quinoxaline derivative comprises the following steps:

[0057] (1) Weigh 2,3-diamino-7-bromo-9,9'-dialkylfluorene and dissolve it in toluene solvent, add anhydrous ferric chloride as a catalyst, raise the temperature to 45°C, slowly dropwise add a toluene solution of diphenylethylenedione under stirring, and after the dropwise addition is completed, stir and react at 70°C for 1.5 hours. During the reaction, water is separated by a water separator. After the reaction is completed, the precipitate is separated, and the solution is washed with deionized water. After drying, the solvent is evaporated under reduced pressure to obtain a quinoxaline derivative;

[0058] Wherein, the mass ratio of the 2,3-diamino-7-bromo-9,9'-dialkylfluorene to the ferric chloride and the diphenylethanedione is 10:2.7:8.8;

[0059] The preparation method of the residual oil hydrogenation anti-coking and anti-scaling agent specifically comprises the following steps:

[0060] S1. Weigh each component according to the ratio and set aside;

[0061] S2. Mix all components under normal pressure, raise the temperature to 60℃ and mix and stir for 1.5h, and adjust the kinematic viscosity to no more than 50mm with solvent diesel. 2 / s, obtained. Example 3

[0062] A residual oil hydrogenation anti-coking and anti-scaling agent, comprising the following components:

[0063] First component: a quinacridone derivative of quinoxaline; and

[0064] Second component: hydroquinone; and

[0065] The third component: tributylphosphine oxide; and

[0066] The fourth component: poly(ethylene glycol) diacrylate (PEG200DA); and solvent diesel;

[0067] Among them, the mass ratio of the first component, the second component, the third component and the fourth component is 0.98:0.77:0.4:0.62;

[0068] The preparation method of the quinacridone derivative of quinoxaline comprises the following steps:

[0069] (1) Weigh 2,3-diamino-7-bromo-9,9'-dialkylfluorene and dissolve it in toluene solvent, add anhydrous ferric chloride as a catalyst, heat to 45°C, slowly dropwise add diphenylethylenedione toluene solution under stirring, and after the dropwise addition is completed, stir and react at 70°C for 1.5 hours. During the reaction, water is separated by a water separator. After the reaction is completed, the precipitate is separated, and the solution is washed with deionized water. After drying, the solvent is evaporated under reduced pressure to obtain a quinoxaline product;

[0070] Wherein, the mass ratio of the 2,3-diamino-7-bromo-9,9'-dialkylfluorene to the ferric chloride and the diphenylethanedione is 10:2.7:8.8;

[0071] (2) weighing quinacridone and dissolving it in anhydrous tetrahydrofuran solvent, adding sodium hydride and tetrabutylammonium bromide, heating and reflux for 2 hours, adding the quinoxaline product under a protective atmosphere, continuing to reflux for 5 hours, adding methanol after the reaction is completed to terminate the reaction, concentrating under reduced pressure, and purifying through a chromatographic column (silica gel, 500 mesh, eluting with chloroform) to remove unreacted reactants, thereby obtaining the quinacridone derivative of quinoxaline;

[0072] Wherein, the mass ratio of the quinacridone to the sodium hydride, the tetrabutylammonium bromide to the quinoxaline product is 1.1:0.72:1.35:10;

[0073] The preparation method of the residual oil hydrogenation anti-coking and anti-scaling agent specifically comprises the following steps:

[0074] S1. Weigh each component according to the ratio and set aside;

[0075] S2. Mix all components under normal pressure, raise the temperature to 60℃ and mix and stir for 1.5h, and adjust the kinematic viscosity to no more than 50mm with solvent diesel. 2 / s, obtained. Example 4

[0076] A residual oil hydrogenation anti-coking and anti-scaling agent, comprising the following components:

[0077] First component: N-hydroxyphthalimide; and

[0078] Second component: bis(triphenylsilyl)amine; and

[0079] The third component: hydroquinone; and

[0080] Fourth component: tributylphosphine oxide; and

[0081] The fifth component: poly(ethylene glycol) diacrylate (PEG200DA); and solvent diesel;

[0082] Wherein, the mass ratio of the first component to the second component, the third component, the fourth component and the fifth component is 1:1:0.77:0.4:0.62;

[0083] The preparation method of the residual oil hydrogenation anti-coking and anti-scaling agent specifically comprises the following steps:

[0084] S1. Weigh each component according to the ratio and set aside;

[0085] S2. Mix all components under normal pressure, raise the temperature to 60℃ and mix and stir for 1.5h, and adjust the kinematic viscosity to no more than 50mm with solvent diesel. 2 / s, obtained.

[0086] Evaluation of scale inhibition performance:

[0087] 100 mL of blank hydrocracking crude oil was added to a 500 mL high-pressure reactor, which was sealed. The hydrocracking crude oil was replaced with nitrogen for at least 3 times, and the anti-coking and anti-scaling agent was added at 350°C. After 6 hours, it was extracted and dried with heptane, and the anti-scaling effect of the anti-scaling agent was investigated based on the amount of insoluble matter.

[0088] The calculation method of scale inhibition rate is: scale inhibition rate A% = (W0-W1) / W0*100%, where W0 is the mass of insoluble matter produced without adding scale inhibitor; W1 is the mass of insoluble matter produced by adding scale inhibitor; the experiment was repeated 3 times, and the results are as follows:

[0089]

[0090] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention, rather than to limit the scope of protection of the present invention. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solution of the present invention can be modified or replaced by equivalents without departing from the essence and scope of the technical solution of the present invention.

Claims

1. A residual oil hydrogenation anti-coking and anti-scaling agent, characterized in that: Includes the following components: First component: N-hydroxyphthalimide and / or N-hydroxy-1,8-naphthalimide; and Second component: di(trialkylsilyl)amine; and The third component: a quinacridone derivative of quinoxaline; and The fourth component: an inhibitor; and Fifth component: tributylphosphine oxide; and Sixth component: poly(ethylene glycol) diacrylate; and solvent; The mass ratio of the first component to the second component, the third component, the fourth component, the fifth component and the sixth component is 1:1:(0.7-1.2):(0.4-1):(0.1-0.5):(0.4-0.7); The preparation method of the quinacridone derivative of quinoxaline comprises the following steps: (1) Weigh 2,3-diamino-7-bromo-9,9'-dialkylfluorene and dissolve it in toluene solvent, add anhydrous ferric chloride as a catalyst, raise the temperature to 40-50°C, slowly dropwise add the toluene solution of α-dicarbonyl compound under stirring conditions, and after the dropwise addition is completed, stir and react at 70-80°C for 1-2h, separate water with a water separator during the reaction, separate the precipitate after the reaction is completed, wash the solution with deionized water, dry it, and evaporate the solvent under reduced pressure to obtain a quinoxaline product; Wherein, the mass ratio of the 2,3-diamino-7-bromo-9,9'-dialkylfluorene to the ferric chloride and the α-dicarbonyl compound is 10:(2.5-3):(8.5-10); (2) weighing quinacridone and dissolving it in anhydrous tetrahydrofuran solvent, adding sodium hydride and tetrabutylammonium bromide, heating and reflux for 1-2 hours, adding the quinoxaline product under a protective atmosphere, continuing to reflux for 4-6 hours, adding methanol after the reaction is completed to terminate the reaction, concentrating under reduced pressure and purifying with a chromatographic column to remove unreacted reactants, and obtaining the quinacridone derivative of quinoxaline; Wherein, the mass ratio of the quinacridone to the sodium hydride, the tetrabutylammonium bromide to the quinoxaline product is (1-1.2): (0.7-0.75): (1.3-1.5): 10; The α-dicarbonyl compound is 2,3-butanedione, 3,4-hexanedione, 4,5-octanedione or diphenylethanedione.

2. A residual oil hydrogenation anti-coking and anti-scaling agent according to claim 1, characterized in that: The mass ratio of the first component to the second component, the third component, the fourth component, the fifth component and the sixth component is 1:1:0.98:0.77:0.4:0.

62.

3. A residual oil hydrogenation anti-coking and anti-scaling agent according to claim 1, characterized in that: The di(trialkylsilyl)amine is di(trimethylsilyl)amine, di(triphenylsilyl)amine, di(dimethylphenylsilyl)amine or di(diphenylmethylsilyl)amine.

4. A residual oil hydrogenation anti-coking and anti-scaling agent according to claim 1, characterized in that: The polymerization inhibitor is hydroquinone, vanillin, 4-methoxyphenol, 2,6-di-tert-butyl-4-methylphenol or 2,2,6,6-tetramethylpiperidin-1-oxyphenol.

5. A residual oil hydrogenation anti-coking and anti-scaling agent according to claim 1, characterized in that: The solvent is heavy aromatic hydrocarbons, gasoline, diesel or kerosene.

6. The method for preparing a residual oil hydrogenation anti-coking and anti-scaling agent according to any one of claims 1 to 5, characterized in that: The following steps are involved: S1. Weigh each component in proportion and set aside; S2. Mix the components under normal pressure, raise the temperature to 50-70°C and mix and stir for 1-2 hours, and adjust the kinematic viscosity of the solvent to no more than 50 mm 2 / s, obtained.

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