Vacuum residue deacidification agent and vacuum residue deacidification method

Abstract

The invention discloses a vacuum residue deacidification agent and a vacuum residue deacidification method, and relates to the field of petroleum processing. The method comprises the following steps: preheating vacuum residue, adding a deacidification agent (50-80 parts by weight of organic amine, 20-40 parts by weight of a solvent, 5-30 parts by weight of an auxiliary agent and 2-10 parts by weight of a condensing agent), stirring by using a shearing machine to uniformly disperse the deacidification agent, and finally carrying out constant-temperature operation. According to the invention, naphthenic acid in residual oil is directly converted into amide or naphthenic acid ammonium salt by utilizing a mechanism that carboxyl is activated by a condensing agent and then amidation reaction is carried out with organic amine, so that an emulsification phenomenon is avoided, and emission of three wastes is reduced. The deacidification agent is not easy to separate out at low temperature, the deacidification performance is stable, and the deacidification operation is more convenient. In the deacidification process, unreacted deacidification agent components and reacted deacidification products can be removed from residual oil under the action of the auxiliaries, the separation procedure is avoided, and deacidification operation is more convenient. The deacidification reaction is fast, the deacidification effect is good, and the production cost is low.

Description

Technical Field

[0001] The invention relates to the technical field of petroleum processing, and in particular to a vacuum residue deacidification agent and a vacuum residue deacidification method. Background Art

[0002] In recent years, due to the gradual reduction of crude oil resources worldwide and the invention and use of new mining technologies, crude oil has been developing towards high sulfur, high acidity and heavy quality. High acidity crude oil (acidity greater than 1mgKOH·g -1 ) has been increasing at a rate of almost 0.3%, and improving the processing capacity of high-acid crude oil has become an inevitable choice for oil refining companies.

[0003] Acidic compounds in petroleum generally refer to cyclohexane acid and other inorganic acids, organic acids, mercaptans and other components, while cyclohexane acid and other organic acids are collectively referred to as petroleum acid. The total amount of cyclohexane acid in petroleum acid can account for 90% or even higher proportion of the petroleum acid composition. In the process of crude oil processing, due to the corrosiveness of petroleum acid, it will not only cause serious corrosion of the heating furnace, atmospheric and vacuum distillation tower and equipment pipelines in the atmospheric and vacuum refining unit, but also cause the catalyst bed of the hydrocracking reactor to be blocked, resulting in an increase in the bed pressure drop, which seriously endangers the long-term operation of the hydrocracking unit. In addition, the cyclohexane acid contained in high-acid crude oil is mainly concentrated in the distillate oil, so the acid value of the distillate oil is usually high, which will seriously affect the normal processing and use performance of the oil. Therefore, it is very important to deacidify high-acid crude oil and distillate oil.

[0004] The Chinese patent with publication number CN1810757A discloses a method for removing and recovering cyclohexane acid from oil products. The method is to select one of imidazole derivatives or a 5% to 60% alcohol solution thereof as a deacidifying agent, and mix and react with the oil products at a ratio of 1:1 to 1:15 under the condition of 20 to 90°C. The cyclohexane acid in the oil products will react with the imidazole derivatives to generate ionic liquids. After the reaction is completed, the oil phase with reduced acid value and the ionic liquid phase are separated quickly and efficiently by utilizing the large difference in polarity between the ionic liquid and the oil products. However, this method has low removal efficiency for cyclohexane acid. The energy consumption of distilling the organic solvent phase enriched with cyclohexane acid under reduced pressure at a temperature of 190°C is high, and it is difficult to carry out large-scale industrial production. Moreover, the reaction is carried out under the condition of 20 to 90°C. The heavy fraction oil in the present invention cannot be fully dissolved with the deacidifying agent at this temperature, and the expected deacidifying effect cannot be achieved.

[0005] Chinese patent publication number CN1847366A discloses a method for removing cyclohexane acid from crude oil or distillate oil. The method comprises adding at least one ionic liquid and / or auxiliary compound to the crude oil or distillate oil, mixing and reacting at 20-80°C, standing and separating to obtain deacidified crude oil or distillate oil. However, the reaction is carried out at 20-80°C. The heavy component distillate oil in the present invention has poor fluidity at this temperature and cannot be fully dissolved in the deacidifying agent, and the expected deacidification effect cannot be achieved. Summary of the invention

[0006] The purpose of the present invention is to provide a vacuum residue deacidification agent and a vacuum residue deacidification method to solve the problems existing in the prior art.

[0007] The technical solution adopted by the present invention to solve the technical problem is as follows:

[0008] The vacuum residue deacidifying agent provided by the invention consists of the following components in parts by weight: 50-80 parts of organic amine, 20-40 parts of solvent, 5-30 parts of auxiliary agent and 2-10 parts of condensing agent.

[0009] As a preferred embodiment, the organic amine is monoethanolamine, diethanolamine, triethanolamine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, propanolamine, isopropanolamine, butanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyisobutylene succinimide or hyperbranched polyethyleneimine.

[0010] As a preferred embodiment, the solvent is white oil, isopropyl alcohol, distilled water or kerosene.

[0011] As a preferred embodiment, the auxiliary agent is tetraethylammonium hydroxide.

[0012] As a preferred embodiment, the condensing agent is N,N-carbonyldiimidazole, dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide or 1-hydroxybenzotriazole.

[0013] The invention provides a vacuum residue deacidification method, comprising the following steps: preheating the vacuum residue, adding a deacidification agent, stirring with a shearing machine to make the deacidification agent dispersed evenly, and finally performing a constant temperature operation.

[0014] As a preferred embodiment, the preheating temperature is 70°C-90°C.

[0015] As a preferred embodiment, the amount of the deacidifying agent added to the vacuum residue is 100ppm-2500ppm.

[0016] As a preferred embodiment, the rotation speed during stirring is 1250 r / min-1750 r / min, and the time is 4 min-6 min.

[0017] As a preferred embodiment, the temperature during constant temperature is 90°C-350°C, and the time is 20h-28h.

[0018] The beneficial effects of the present invention are:

[0019] Based on many years of research, the present invention has developed a new green deacidification agent formula and deacidification method with organic amine as the core component. Compared with the prior art, the present invention has the following advantages:

[0020] (1) The present invention utilizes the mechanism that the condensing agent activates the carboxyl group and then undergoes an amidation reaction with an organic amine to directly convert the cyclopentane acid in the residual oil into amide or cyclopentane acid ammonium salt, thereby avoiding the occurrence of emulsification and reducing the discharge of three wastes.

[0021] (2) The deacidifying agent of the present invention is liquid at room temperature and is not easy to precipitate at low temperature, thereby improving the solubility of the deacidifying agent in crude oil and residual oil. The deacidifying agent can be directly added for use and is not easy to precipitate even in a low temperature environment in winter. The deacidifying performance is stable and the deacidifying operation is more convenient.

[0022] (3) During the deacidification process, the unreacted deacidification agent components and the deacidification products after the reaction are removed from the residual oil through the action of the auxiliary agent, thus avoiding an additional separation process and making the deacidification operation more convenient.

[0023] (4) During the deacidification process, when the constant temperature is increased from 100°C to 350°C, the deacidification rate is increased from 60% to 81%, the deacidification reaction is faster, and the deacidification effect is good.

[0024] (5) The vacuum residue deacidification method of the present invention has low equipment investment cost and low production cost in actual industrial production. DETAILED DESCRIPTION

[0025] The vacuum residue deacidifying agent provided by the invention consists of the following components in parts by weight: 50-80 parts of organic amine, 20-40 parts of solvent, 5-30 parts of auxiliary agent and 2-10 parts of condensing agent.

[0026] Preferably, the vacuum residue deacidification agent provided by the present invention is composed of the following components in parts by weight: 60-70 parts of organic amine, 25-30 parts of solvent, 5-10 parts of auxiliary agent, and 3-5 parts of condensation agent.

[0027] Preferably, the organic amine is monoethanolamine, diethanolamine, triethanolamine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, propanolamine, isopropanolamine, butanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyisobutylene succinimide or hyperbranched polyethyleneimine, but is not limited thereto.

[0028] More preferably, the organic amine is triethanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine or hyperbranched polyethyleneimine.

[0029] Most preferably, the organic amine is triethylenetetramine.

[0030] Preferably, the solvent is white oil, isopropyl alcohol, distilled water or kerosene, but is not limited thereto.

[0031] More preferably, the solvent is isopropanol.

[0032] Preferably, the auxiliary agent is tetraethylammonium hydroxide, but is not limited thereto.

[0033] Preferably, the condensing agent is N,N-carbonyldiimidazole, dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide (EDCI) or 1-hydroxybenzotriazole.

[0034] More preferably, the condensing agent is N,N-carbonyldiimidazole.

[0035] The present invention also provides a method for deacidifying vacuum residue oil, which specifically comprises the following steps: preheating the vacuum residue oil at 70°C-90°C, adding a deacidifying agent, wherein the amount of the deacidifying agent added to the vacuum residue oil is 100ppm-2500ppm, subsequently stirring the vacuum residue oil at 1250r / min-1750r / min for 4min-6min using a shearing machine to fully and evenly disperse the deacidifying agent, and finally maintaining a constant temperature at 90°C-350°C for 20h-28h, thereby completing the deacidification of the vacuum residue oil.

[0036] Preferably, the preheating temperature is 80°C.

[0037] Preferably, the amount of the deacidifying agent added to the vacuum residue is 500ppm-1000ppm.

[0038] More preferably, the amount of the deacidifying agent added to the vacuum residue is 1000 ppm.

[0039] Preferably, the stirring speed is 1500 r / min and the stirring time is 5 min.

[0040] Preferably, the temperature during constant temperature is 300° C. and the time is 24 hours.

[0041] The following will be combined with the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative work are within the scope of protection of the present invention.

[0042] Example 1 Vacuum residue deacidification method

[0043] According to the formula in Table 1, 50 parts of triethylenetetramine, 20 parts of isopropanol, 20 parts of tetraethylammonium hydroxide and 10 parts of N,N-carbonyldiimidazole were weighed into a beaker and stirred until dissolved to obtain vacuum residue deacidification agent A1.

[0044] Weigh 100g of vacuum residue oil for testing, preheat at 80℃, add vacuum residue oil deacidification agent A1 at an addition amount of 500μg / g, then stir at 1500r / min for 5min using a shearing machine to fully disperse the vacuum residue oil deacidification agent A1 in the vacuum residue oil, then add the vacuum residue oil into a 100mL test tube, put the test tube into a 90℃ water bath, keep the temperature constant for 24h, and take out part of the vacuum residue oil from the middle and upper layers for acid value test after the constant temperature is completed. The results are shown in Table 1.

[0045] Example 2 Vacuum residue deacidification method

[0046] According to the formula in Table 1, 55 parts of triethylenetetramine, 25 parts of isopropanol, 5 parts of tetraethylammonium hydroxide and 10 parts of N,N-carbonyldiimidazole were weighed and put into a beaker, and stirred until dissolved to obtain vacuum residue deacidification agent A2. The vacuum residue deacidification method is the same as that in Example 1. The results are shown in Table 1.

[0047] Example 3 Vacuum residue deacidification method

[0048] According to the formula in Table 1, 60 parts of triethylenetetramine, 30 parts of isopropanol, 6 parts of tetraethylammonium hydroxide and 4 parts of N,N-carbonyldiimidazole were weighed and put into a beaker, and stirred until dissolved to obtain vacuum residue deacidification agent A3. The vacuum residue deacidification method is the same as that in Example 1. The results are shown in Table 1.

[0049] Example 4 Vacuum residue deacidification method

[0050] According to the formula in Table 1, 65 parts of triethylenetetramine, 35 parts of isopropanol, 7 parts of tetraethylammonium hydroxide and 3 parts of N,N-carbonyldiimidazole were weighed and put into a beaker, and stirred until dissolved to obtain vacuum residue deacidification agent A4. The vacuum residue deacidification method is the same as that in Example 1. The results are shown in Table 1.

[0051] Example 5 Vacuum residue deacidification method

[0052] According to the formula in Table 1, 68 parts of triethylenetetramine, 20 parts of isopropanol, 9 parts of tetraethylammonium hydroxide and 3 parts of N,N-carbonyldiimidazole were weighed and put into a beaker, and stirred until dissolved to obtain vacuum residue deacidification agent A5. The vacuum residue deacidification method is the same as that in Example 1. The results are shown in Table 1.

[0053] Table 1

[0054]

[0055]

[0056] It can be seen from Table 1 that when the constant temperature is 90° C. and the constant temperature time is 24 h, the deacidification rates of the vacuum residue deacidification agents with different components and proportions obtained in Examples 1-5 are between 40% and 55%.

[0057] Example 6 Vacuum residue deacidification method

[0058] Weigh 100g of vacuum residue oil (Sichang vacuum residue) for testing, preheat at 80°C, add vacuum residue oil deacidification agent A4 obtained in Example 4 at an addition amount of 500μg / g, then stir at 1500r / min for 5min using a shearing machine to fully disperse the vacuum residue oil deacidification agent A4 in the vacuum residue oil, then add the vacuum residue oil into a 100mL test tube, put the test tube into a 90°C water bath, keep the temperature constant for 24h, and take out part of the vacuum residue oil from the middle and upper layers after the constant temperature is completed for acid value test. The results are shown in Table 2.

[0059] Example 7 Vacuum residue deacidification method

[0060] The same as Example 6, except that the addition amount of the vacuum residue deacidifying agent A4 obtained in Example 4 is 1000 μg / g. The results are shown in Table 2.

[0061] Example 8 Vacuum residue deacidification method

[0062] The same as Example 6, except that the addition amount of the vacuum residue deacidification agent A4 obtained in Example 4 is 1500 μg / g. The results are shown in Table 2.

[0063] Example 9 Vacuum residue deacidification method

[0064] The same as Example 6, except that the addition amount of the vacuum residue deacidification agent A4 obtained in Example 4 is 2000 μg / g. The results are shown in Table 2.

[0065] Example 10 Vacuum residue deacidification method

[0066] The same as Example 6, except that the addition amount of the vacuum residue deacidification agent A4 obtained in Example 4 is 2500 μg / g. The results are shown in Table 2.

[0067] Table 2

[0068]

[0069]

[0070] As shown in Table 2, when the amount of the deacidifying agent added is increased from 500 μg / g to 2500 μg / g, the deacidification rate is increased from 55% to 67%. Taking into account the production cost problem in actual industrial production, the preferred amount of the deacidifying agent added is 500 μg / g-1000 μg / g, and the most preferred amount of the deacidifying agent added is 1000 μg / g.

[0071] Example 11 Vacuum residue deacidification method

[0072] Weigh 100g of vacuum residue oil (four normal vacuum residue oil) for testing, preheat at 80°C, add vacuum residue oil deacidification agent A4 obtained in Example 4 at an addition amount of 1000μg / g, then stir at 1500r / min for 5min using a shearing machine to fully disperse the vacuum residue oil deacidification agent A4 in the vacuum residue oil, then add the vacuum residue oil into a 100mL test tube, put the test tube into a 100°C oven, keep the temperature constant for 24h, and take out part of the vacuum residue oil from the middle and upper layers after the constant temperature is completed for acid value test. The results are shown in Table 3.

[0073] Example 12 Vacuum residue deacidification method

[0074] Same as Example 11, except that the test tube was placed in an oven at 150°C. The results are shown in Table 3.

[0075] Example 13 Vacuum residue deacidification method

[0076] Same as Example 11, except that the test tube was placed in an oven at 200°C. The results are shown in Table 3.

[0077] Example 14 Vacuum residue deacidification method

[0078] Same as Example 11, except that the test tube was placed in an oven at 250°C. The results are shown in Table 3.

[0079] Example 15 Vacuum residue deacidification method

[0080] Same as Example 11, except that the test tube was placed in an oven at 300°C. The results are shown in Table 3.

[0081] Example 16 Vacuum residue deacidification method

[0082] Same as Example 11, except that the test tube was placed in an oven at 350°C. The results are shown in Table 3.

[0083] Table 3

[0084]

[0085]

[0086] As shown in Table 3, when the constant temperature is increased from 100°C to 350°C, the deacidification rate is increased from 60% to 81%. Considering that the oil temperature of the residual oil after heat exchange in the residual oil hydrotreating unit process in actual industrial production is between 280°C and 330°C, the preferred deacidification constant temperature is 300°C.

[0087] The above experiments show that increasing the deacidification temperature is beneficial to the deacidification of the residual oil. This is because the higher the temperature, the smaller the viscosity of the residual oil, which is more conducive to the full contact between the deacidifying agent and the residual oil, and is conducive to the uniform dispersion of the deacidifying agent in the residual oil.

[0088] In order to investigate the deacidification effect of the deacidifying agent in different distillate oils, the atmospheric and vacuum reduction line 1, line 2, line 3, line 4 and slag were selected as the deacidification investigation objects, and the following deacidification comparative test of different distillate oils in the atmospheric and vacuum reduction unit was carried out.

[0089] Comparative Example 17

[0090] Weigh 100g of vacuum residue oil (normal vacuum minus first-line distillate oil) for testing, preheat at 80°C, add vacuum residue oil deacidification agent A4 obtained in Example 4 at an addition amount of 1000μg / g, then stir at 1500r / min for 5min using a shearing machine to fully disperse the vacuum residue oil deacidification agent A4 in the vacuum residue oil, then add the vacuum residue oil into a 100mL test tube, put the test tube into a 300°C oven, keep the temperature constant for 24h, and take out part of the vacuum residue oil from the middle and upper layers after the constant temperature is completed for acid value test. The results are shown in Table 4.

[0091] Comparative Example 18

[0092] The same as comparative example 17, except that the vacuum residue oil used in the test is atmospheric vacuum distillate second-line oil. The results are shown in Table 4.

[0093] Comparative Example 19

[0094] The same as comparative example 17, except that the vacuum residue oil used in the test is atmospheric vacuum minus three-line distillate oil. The results are shown in Table 4.

[0095] Comparative Example 20

[0096] The same as comparative example 17, except that the vacuum residue oil used in the test is atmospheric vacuum minus fourth-line distillate oil. The results are shown in Table 4.

[0097] Comparative Example 21

[0098] The same as comparative example 17, except that the vacuum residue oil used in the test is atmospheric vacuum residue line distillate oil. The results are shown in Table 4.

[0099] Table 4

[0100]

[0101] As shown in Table 4, after adding 1000 μg / g of the deacidifying agent, the acid values ​​of the distillates of the first-line, second-line, third-line, fourth-line and slag-line all decreased to varying degrees, and the deacidification rate was 73%-85%. This shows that the deacidifying agent for vacuum residue oil and the deacidifying method for vacuum residue oil according to the present invention improve the deacidification effect of different distillates.

[0102] The present invention discloses a vacuum residue deacidification agent and a vacuum residue deacidification method. Those skilled in the art can refer to the content of this article and appropriately improve the process parameters to achieve the above. It should be particularly noted that all similar replacements and modifications are obvious to those skilled in the art and are considered to be included in the present invention. The products of the present invention have been described through preferred embodiments, and relevant personnel can obviously modify or appropriately change and combine the products described herein without departing from the content, spirit and scope of the present invention to implement and apply the technology of the present invention.

Claims

1. A vacuum residue deacidification agent, characterized in that: The composition comprises the following components in parts by weight: 50-80 parts of organic amine, 20-40 parts of solvent, 5-30 parts of auxiliary agent and 2-10 parts of condensing agent.

2. A vacuum residue deacidification agent according to claim 1, characterized in that: The organic amine is monoethanolamine, diethanolamine, triethanolamine, methylamine, ethylamine, propylamine, isopropylamine, butylamine, propanolamine, isopropanolamine, butanolamine, ethylenediamine, diethylenetriamine, triethylenetetramine, polyisobutylene succinimide or hyperbranched polyethyleneimine.

3. A vacuum residue deacidification agent according to claim 1, characterized in that: The solvent is white oil, isopropyl alcohol, distilled water or kerosene.

4. A vacuum residue deacidification agent according to claim 1, characterized in that: The auxiliary agent is tetraethylammonium hydroxide.

5. A vacuum residue deacidification agent according to claim 1, characterized in that: The condensation agent is N,N-carbonyldiimidazole, dicyclohexylcarbodiimide, 4-dimethylaminopyridine, 1-(3-dimethylaminopropyl)-3-ethylcarbodiimide or 1-hydroxybenzotriazole.

6. A method for deacidification of vacuum residue, characterized in that: The method is implemented by using a vacuum residue deacidifying agent as described in any one of claims 1 to 5, and comprises the following steps: preheating the vacuum residue, adding the deacidifying agent, stirring with a shearing machine to make the deacidifying agent evenly dispersed, and finally performing a constant temperature operation.

7. A vacuum residue deacidification method according to claim 6, characterized in that: The temperature during preheating is 70℃-90℃.

8. The method for deacidifying vacuum residue according to claim 6, characterized in that: The amount of the deacidifying agent added to the vacuum residue is 100ppm-2500ppm.

9. The method for deacidifying vacuum residue according to claim 6, characterized in that: The speed during stirring is 1250r / min-1750r / min, and the time is 4min-6min.

10. The method for deacidifying vacuum residue according to claim 6, characterized in that: The temperature during constant temperature is 90℃-350℃, and the time is 20h-28h.

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