阅读说明：本技术 一种积炭失活加氢催化剂的再生方法 (Regeneration method of carbon deposit inactivation hydrogenation catalyst ) 是由 孙进 郭蓉 周勇 李扬 杨成敏 于 2020-04-15 设计创作，主要内容包括：本发明公开了一种积炭失活加氢催化剂的再生方法,包括如下内容：(1)将积炭失活加氢催化剂进行加氢处理,得到物料M；(2)采用含有有机物X和有机物Y的溶液浸渍处理物料M；其中有机物X为硼酸酯类化合物,有机物Y为含有苯环取代基的有机物；(3)将步骤(2)得到的物料进行水蒸气接触,进行活化处理；(4)将步骤(3)得到的物料进行烧炭处理,烧炭气氛为水蒸气和空气混合气体,得到再生后的加氢催化剂。该方法能够有效恢复再生加氢催化剂的酸性质,再生后的催化剂有着良好的加氢活性。(The invention discloses a regeneration method of a carbon deposit inactivation hydrogenation catalyst, which comprises the following steps: (1) carrying out hydrogenation treatment on the carbon deposit inactivation hydrogenation catalyst to obtain a material M; (2) dipping the material M by using a solution containing an organic matter X and an organic matter Y; wherein the organic matter X is a borate compound, and the organic matter Y is an organic matter containing a benzene ring substituent; (3) carrying out steam contact on the material obtained in the step (2) and carrying out activation treatment; (4) and (4) carrying out charcoal burning treatment on the material obtained in the step (3), wherein the charcoal burning atmosphere is a mixed gas of water vapor and air, and thus obtaining the regenerated hydrogenation catalyst. The method can effectively recover the acid property of the regenerated hydrogenation catalyst, and the regenerated catalyst has good hydrogenation activity.)

1. A regeneration method of a carbon deposit inactivation hydrogenation catalyst is characterized by comprising the following steps: (1) carrying out hydrogenation treatment on the carbon deposit inactivation hydrogenation catalyst to obtain a material M; (2) dipping the material M by using a solution containing an organic matter X and an organic matter Y; wherein the organic matter X is a borate compound, and the organic matter Y is an organic matter containing a benzene ring substituent; (3) carrying out steam contact on the material obtained in the step (2) and carrying out activation treatment; (4) and (4) carrying out charcoal burning treatment on the material obtained in the step (3), wherein the charcoal burning atmosphere is a mixed gas of water vapor and air, and thus obtaining the regenerated hydrogenation catalyst.

2. The method of claim 1, wherein: the carbon deposition deactivated hydrogenation catalyst in the step (1) is a hydrogenation catalyst deactivated in various processes of hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrorefining and hydrodearomatization in petroleum refining.

3. The method of claim 1, wherein: the carbon deposition is 4-19 wt% based on the weight of the deactivated hydrogenation catalyst.

4. The method of claim 1, wherein: the hydrotreating conditions in the step (1) are as follows: the temperature is 250-500 ℃, the pressure is 1-9 MPa, and the atmosphere is H₂The reaction time is 1-4 hours.

5. The method of claim 1, wherein: the hydrotreating conditions in the step (1) are as follows: the temperature is 280-450 ℃, the pressure is 1.5-6.5 MPa, and the atmosphere is H₂The reaction time is 1-4 hours.

6. The method of claim 1, wherein: the borate compound in the step (2) is one or more of trimethyl borate, triethyl borate, tripropyl borate or tributyl borate.

7. The method of claim 1, wherein: the organic matter containing the benzene ring substituent in the step (2) is one or more of benzyl alcohol, phenethyl alcohol, anisole, phenetole, phenylpropanol, phenylbutanol, benzoic acid, phenylacetic acid or phenylpropionic acid.

8. The method of claim 1, wherein: the molar ratio of the organic matter X in the solution in the step (2) to the total active metal elements in the material M is 0.05: 1-0.15: 1; the molar ratio of the organic matter Y to the total active metal elements in the material M is 0.08: 1-0.2: 1, and the active metal is a metal in a VIII group and/or a VIB group.

9. The method of claim 1, wherein: the impregnation treatment condition in the step (2) is equal-volume impregnation.

10. The method of claim 1, wherein: the activation treatment conditions in the step (3) are as follows: the temperature is 150-400 ℃, and preferably 200-350 ℃; the activation pressure is less than 15MPa, preferably 1-10 MPa, and more preferably 1.2-8 MPa; the activation time is 1 to 10 hours, preferably 2 to 5 hours.

11. The method of claim 1, wherein: the volume ratio of the water vapor to the air in the step (4) is 20: 80-50: 50.

12. The method of claim 1, wherein: the charcoal burning conditions in the step (4) are as follows: the charcoal burning temperature is 250-450 ℃, and preferably 280-400 ℃; the charcoal burning pressure is less than 15MPa, and preferably 1-6 MPa; the charcoal burning time is 1-10 hours, preferably 2-6 hours.

Technical Field

The invention relates to a regeneration method of a carbon deposit deactivated hydrogenation catalyst, in particular to a regeneration method of a carbon deposit deactivated hydrogenation desulfurization catalyst with a carrier with a certain acid amount.

Background

The carrier of various hydrogenation catalysts used in petroleum refining, such as hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrofining, hydrodearomatization and the like, is alumina or composite alumina with a certain acidic center. During the long-term operation of the hydrogenation catalyst, the acid center surface of the hydrogenation catalyst can cover carbon deposit under high-temperature conditions, and the activity of the catalyst is reduced. After a certain period of operation, the acidity can be restored again only by regeneration treatment.

CN102463153A introduces a regeneration and reactivation method of a carbon deposit inactivated hydrotreating catalyst, the carbon deposit inactivated catalyst comprises a VIB group metal component and a VIII group metal component, and under the action of oxygen-containing gas, the carbon deposit of the inactivated catalyst is removed, so that the carbon content in the catalyst is 0.5-2% by mass; then contacting with solution containing alkaline substance and solution of organic additive, finally obtaining catalyst with restored activity by heat treatment.

CN 106669866 a discloses a regeneration method of deactivated hydrogenation catalyst, comprising the following steps: (1) carrying out charcoal burning treatment on the inactivated hydrogenation catalyst; (2) dipping the deactivated hydrogenation catalyst after the charcoal burning in the step (1) by using a solution containing ammonium fluoroborate and 2-amino-1, 3-propanediol; (3) and (3) carrying out heat treatment on the catalyst subjected to the dipping treatment in the step (2) to deactivate the hydrogenation catalyst to regenerate the catalyst.

CN 106669710A discloses a regeneration method of a catalytic diesel hydrocracking catalyst, which comprises the following steps: (1) roasting the inactivated hydrocracking catalyst in the catalytic diesel oil hydroconversion process in an oxygen-containing atmosphere until the decarbonization rate is 40-80% to obtain a decarbonization catalyst; (2) and (2) carrying out high-temperature treatment on the decarbonization catalyst obtained in the step (1) in an inert atmosphere to obtain a regenerated hydrocracking catalyst.

CN 109926105 a provides a regeneration method of a hydrogenation catalyst, which comprises the following steps: (1) contacting a hydrogenation catalyst to be regenerated with oxygen-containing gas for charcoal burning treatment to obtain a catalyst A; (2) contacting the catalyst A with an organic compound solution, and carrying out heat treatment to obtain a catalyst B; (3) and (3) introducing hydrazine hydrate into the catalyst B, and then carrying out heat treatment to obtain a regenerated catalyst.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a regeneration method of a hydrogenation catalyst with carbon deposit inactivation.

The inventor has found that in the process of catalyst regeneration research: in the inactivated catalyst, carbon deposits with different strong and weak acid sites exist in various forms such as oil coke, amorphous carbon and graphitized carbon, a compact carbon layer is firmly combined with a carrier in the roasting process, a large amount of oxygen is needed, and the local oxygen is insufficient, so that the carbon deposits are converted into graphitized carbon from the oil coke and amorphous form in the regeneration process, the original and newly generated graphitized carbon can be removed by high-temperature roasting, generally, the roasting is carried out at 550-750 ℃ for more than 3 hours, the carbon deposits can be damaged by completely burning off the carbon deposits by high-temperature roasting, the acid property is poor, the strong acid and the weak acid in the catalyst are reduced, the total acid amount is reduced, and the L acid is reduced and increased by the B acid,

based on the reasons, the invention provides a regeneration method of a hydrogenation catalyst with carbon deposit inactivation, which comprises the following steps:

(1) carrying out hydrogenation treatment on the carbon deposit inactivation hydrogenation catalyst to obtain a material M;

(2) dipping the material M by using a solution containing an organic matter X and an organic matter Y; wherein the organic matter X is a borate compound, and the organic matter Y is an organic matter containing a benzene ring substituent;

(3) carrying out steam contact on the material obtained in the step (2) and carrying out activation treatment;

(4) and (4) carrying out charcoal burning treatment on the material obtained in the step (3), wherein the charcoal burning atmosphere is a mixed gas of water vapor and air, and thus obtaining the regenerated hydrogenation catalyst.

In the method, the carbon deposition deactivated hydrogenation catalyst in the step (1) can be a hydrogenation catalyst deactivated in various process procedures such as hydrodesulfurization, hydrodenitrogenation, hydrodemetallization, hydrofining, hydrodearomatization and the like in petroleum refining, and the carbon deposition amount is generally 4-19 wt% based on the weight of the deactivated hydrogenation catalyst; the active metal component of the catalyst is typically a group VIB and/or group VIII metal, typically Mo and/or W and typically Co and/or Ni. The catalyst is generally one or more of alumina, silica, amorphous silica-alumina, titania, zirconia, boria or silica-alumina phosphate and the like, so that the catalyst has a certain acid center.

In the method of the invention, the hydrogenation conditions in the step (1) are as follows: the temperature is 250-500 ℃, preferably 280-450 ℃, the pressure is more than 0.6MPa, preferably 1.5-6.5 MPa, and the atmosphere is H₂The reaction time is 1-4 hours.

In the method of the present invention, the borate compound in step (2) is one or more of trimethyl borate, triethyl borate, tripropyl borate and tributyl borate, preferably trimethyl borate and/or triethyl borate. The organic matter containing the benzene ring substituent is one or more of benzyl alcohol, phenethyl alcohol, anisole, phenetole, phenylpropanol, phenylbutanol, benzoic acid, phenylacetic acid or phenylpropionic acid, and preferably one or more of benzyl alcohol, phenethyl alcohol, anisole, phenetole, benzoic acid or phenylacetic acid.

In the method, the molar ratio of the organic matter X in the solution in the step (2) to the total active metal elements in the material M is 0.05: 1-0.15: 1; the molar ratio of the organic matter Y to the total active metal elements in the material M is 0.08: 1-0.2: 1, and the active metal is generally a metal in a VIII group and/or a VIB group.

In the method of the present invention, the impregnation treatment condition in the step (2) is equal-volume impregnation.

In the method of the present invention, the activation treatment conditions in step (3) are: the temperature is 150-400 ℃, and preferably 200-350 ℃; the activation pressure is less than 15MPa, preferably 1-10 MPa, and more preferably 1.2-8 MPa; the activation time is 1 to 10 hours, preferably 2 to 5 hours.

In the method, the volume ratio of the water vapor to the air in the step (4) is 20: 80-50: 50.

In the method, the charcoal burning conditions in the step (4) are as follows: the charcoal burning temperature is 250-450 ℃, and preferably 280-400 ℃; the charcoal burning pressure is less than 15MPa, and preferably 1-6 MPa; the charcoal burning time is 1-10 hours, preferably 2-6 hours.

Compared with the prior art, the regeneration method of the carbon deposition inactivation hydrogenation catalyst can recover more than 91% of the total acid content of the catalyst, and basically achieves the acid distribution of a fresh catalyst. In the regeneration process, the reaction path of converting oil coke and amorphous carbon deposits into graphitized carbon is terminated through the hydrotreatment of the oil coke and the amorphous carbon deposits, and the subsequent organic matter impregnation step, the activation step and the carbon burning step by steam and air are matched, so that the carbon deposits are well removed, and the surface acidity of the catalyst is recovered.

Detailed Description

The following examples further illustrate the present invention and the effects thereof, but are not intended to limit the present invention.

Taking industrial deactivated CoMo/Al₂O₃The hydrogenation catalyst comprises 4.8wt% of Co element in terms of oxide and 19.5wt% of molybdenum element in terms of oxide. The following examples and comparative examples each used the deactivated catalyst to conduct a regeneration experiment and an evaluation of activity recovery.

Example 1

100g of the deactivated catalyst is placed in a closed reaction furnace, hydrogen is introduced, and the hydrogenation conditions are as follows: the temperature is 300 ℃, the pressure is 5MPa, and the time is 3 hours. The treated catalyst is soaked in an ethanol solution containing trimethyl borate and benzoic acid in equal volume. The molar ratio of trimethyl borate to the total metals of the fresh catalyst in the impregnation solution was 0.1, and the molar ratio of benzoic acid to the total metals was 0.13. Placing the impregnated catalyst in a closed reaction furnace, and introducing water vapor for activation treatment, wherein the activation treatment conditions are as follows: the temperature is 220 ℃, the pressure is 2.5MPa, and the time is 4 hours. And finally, introducing 30: 70, carrying out charcoal burning treatment on the mixed gas of water vapor and air, wherein the charcoal burning treatment conditions are as follows: the temperature is 350 ℃, the pressure is 5MPa, the duration is 3 hours, and the regenerated catalyst is obtained, and the number is RF-1.

Example 2

100g of the deactivated catalyst is placed in a closed reaction furnace, hydrogen is introduced, and the hydrogenation conditions are as follows: the temperature is 340 ℃, the pressure is 3MPa, and the time duration is 2.5 hours. The treated catalyst is soaked in an ethanol solution containing triethyl borate and phenethyl alcohol in equal volume. The molar ratio of triethyl borate to the total metals of the fresh catalyst in the impregnation solution was 0.08, and the molar ratio of phenethyl alcohol to the total metals was 0.16. Placing the impregnated catalyst in a closed reaction furnace, and introducing water vapor for activation treatment, wherein the activation treatment conditions are as follows: the temperature is 330 ℃, the pressure is 6MPa, and the time is 2 hours. And finally introducing 45: 55, carrying out charcoal burning treatment on the steam/air mixed gas, wherein the charcoal burning treatment conditions are as follows: the temperature is 380 ℃, the pressure is 2MPa, the duration is 5 hours, and the regenerated catalyst with the number of RF-2 is obtained.

Example 3

100g of the deactivated catalyst is placed in a closed reaction furnace, hydrogen is introduced, and the hydrogenation conditions are as follows: the temperature is 420 ℃, the pressure is 1.8MPa, and the time is 2 hours. The treated catalyst is soaked in an ethanol solution containing trimethyl borate and phenetole in equal volume. The molar ratio of trimethyl borate to the total metals of the fresh catalyst in the impregnation solution was 0.13, and the molar ratio of phenetole to the total metals was 0.1. Placing the impregnated catalyst in a closed reaction furnace, and introducing water vapor for activation treatment, wherein the activation treatment conditions are as follows: the temperature is 270 ℃, the pressure is 4MPa, and the time duration is 3 hours. And finally introducing 40: 60, carrying out charcoal burning treatment on the mixed gas of water vapor and air, wherein the charcoal burning treatment conditions are as follows: the temperature is 310 ℃, the pressure is 4MPa, the duration is 5 hours, and the regenerated catalyst with the number of RF-3 is obtained.

Comparative example 1

Following the procedure described in example 1, but with the removal of the hydrogenation step, the calcined carbon was activated with steam after direct impregnation with trimethyl borate and benzoic acid to give a regenerated catalyst, code DRF-1.

Comparative example 2

Following the procedure described in example 1, but eliminating the impregnation of trimethyl borate and benzoic acid, the regenerated catalyst, code DRF-2, was obtained.

Comparative example 3

Following the procedure described in example 1, but eliminating the steam activation step, the regenerated catalyst, code DRF-3, was obtained.

Comparative example 4

The regenerated catalyst, designated DRF-4, was obtained by following the procedure described in example 1, but by passing pure air instead in the charcoal burning step.

Comparative example 5

According to a conventional method for regenerating the catalyst, 100g of the deactivated catalyst is placed in a closed reaction furnace, air is directly introduced to burn carbon at the temperature of 600 ℃ for 5 hours, and the regenerated catalyst is obtained, and is numbered DRF-5.

The properties of the fresh agent and the spent agent and the regenerants in the examples and the comparative examples are shown in Table 1.

TABLE 1 physicochemical Properties of the regenerant and the spent catalyst with the regenerated catalysts of the examples and comparative examples

The regenerated catalysts of the above examples and comparative examples were subjected to activity evaluation tests in a 10mL hydrogenation reaction apparatus, and the properties of the raw materials used are shown in Table 2, and the evaluation conditions and results are shown in Table 3, wherein the percentages in the tables are percentages by mass.

TABLE 2 Properties of the feed oils

TABLE 3 evaluation conditions and results