CN112439462B - Method for recycling waste hydrogenation catalyst - Google Patents
Method for recycling waste hydrogenation catalyst Download PDFInfo
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- CN112439462B CN112439462B CN201910822958.1A CN201910822958A CN112439462B CN 112439462 B CN112439462 B CN 112439462B CN 201910822958 A CN201910822958 A CN 201910822958A CN 112439462 B CN112439462 B CN 112439462B
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- B01J38/72—Regeneration or reactivation of catalysts, in general including segregation of diverse particles
Abstract
The invention relates to the field of hydrogenation catalysts, and discloses a method for recycling waste hydrogenation catalysts, which comprises the following steps: (1) Performing heat treatment and grinding on the waste hydrogenation catalyst to obtain waste agent powder; (2) Separating the waste agent powder to obtain high-density waste agent powder and low-density waste agent powder respectively; (3) The low-density waste agent powder is used for slurry bed catalytic hydrogenation reaction with or without grinding. The method of the invention is based on the density difference of the waste agent powder, can realize the separation of the powder with low metal deposition amount and the powder with high metal deposition amount, and further utilizes the regenerated powder with low metal deposition amount for slurry bed hydrogenation reaction, and can obtain good catalytic activity.
Description
Technical Field
The invention relates to the field of hydrogenation catalysts, in particular to a method for recycling waste hydrogenation catalysts.
Background
The hydrotreating technology is a main technical means for deep processing of heavy oil, and mainly adopts a fixed bed process, and mainly aims to provide high-quality raw materials for catalytic cracking (RFCC) or catalytic cracking (DCC) and other devices so as to further produce clean and light oil products.
However, the heavy oil has high content of asphaltene, metal and other impurity components, and has strong toxic action on the catalyst, so that the service life of the heavy oil hydrotreating catalyst is greatly shortened compared with that of other light oil hydrotreating catalysts, and a large amount of industrial waste agents are generated when the device is stopped. The replaced industrial waste contains a large amount of impurity elements, for example V, ni, mo, fe, S, C, which is liable to cause environmental pollution. Therefore, how to efficiently utilize spent hydrotreating catalysts has become a focus of widespread attention.
Currently, spent hydrotreating catalysts are treated primarily by landfills or metal recovery and the like. However, the metal recovery efficiency of these treatment methods is low, and the metal is easy to cause environmental pollution, and especially the acid-base cleaning is generally performed when the metal is recovered, which is more likely to cause the problem of secondary environmental pollution.
The method comprehensively considers environmental and economic factors, improves the metal recovery efficiency by utilizing the high-efficiency separation method, realizes the catalytic recycling of the high-activity waste agent powder, can furthest reduce industrial solid waste, and can reduce the production cost of the catalyst.
US7335618 discloses a process for producing a hydrotreating catalyst and recovering metals. The method comprises the steps of firstly carrying out heat treatment and grinding on the waste agent to obtain waste agent powder, then carrying out magnetic separation on the waste agent powder to obtain regenerated powder with low metal content, and finally carrying out molding, drying and roasting to obtain the regenerated catalyst. However, in this prior art, if magnetic separation of the spent agent powder is to be achieved, the spent agent must have a higher Fe content. While generally only the surface of the spent hydroprocessing protectant particles will deposit a substantial amount of Fe element, other types of spent hydroprocessing catalysts generally do not have a higher Fe element deposit. Therefore, the method is only suitable for recycling the waste protective agent with higher Fe content, has low applicability to other types of waste agents, and has complex magnetic separation process.
Disclosure of Invention
One of the objects of the present invention is to overcome the drawbacks of poor applicability of the existing technical methods for treating spent agents (spent catalysts).
The second purpose of the invention is to minimize industrial solid waste and reduce the production cost of the catalyst.
In order to achieve the above object, the present invention provides a method for recycling a spent hydrogenation catalyst, comprising:
(1) Carrying out heat treatment and grinding on a waste hydrogenation catalyst to obtain waste catalyst powder, wherein the waste hydrogenation catalyst is obtained by hydrotreating raw oil with a fresh hydrogenation catalyst;
(2) Separating the waste agent powder to obtain high-density waste agent powder and low-density waste agent powder respectively;
(3) Grinding the low-density waste agent powder or not, and then using the low-density waste agent powder for slurry bed catalytic hydrogenation reaction;
wherein in step (2), the average relative particle density of the high-density waste agent powder and the average relative particle density of the low-density waste agent powder satisfy formula (1):
k 1 ＞k 2 (1),
in formula (1), k 2 Is 1 to 5, k 1 Less than or equal to 20, and k 1 Average particle density of high density spent agent powder/average particle density of fresh hydrogenation catalyst dry base powder, k 2 The average particle density of the low density spent catalyst powder/the average particle density of the fresh hydrogenation catalyst dry basis powder.
The method of the invention is based on the density difference of the waste agent powder, can realize the separation of the powder with low metal deposition amount and the powder with high metal deposition amount, and further can obtain good catalytic activity by using the regenerated powder with low metal deposition amount as a catalyst or a catalyst admixture for slurry bed hydrogenation reaction.
The method of the present invention can obtain regenerated catalyst powder with low metal content for reuse and waste agent with high metal content for recovery metal or landfill treatment, respectively, by separating the waste agent. Namely, the method of the invention can realize the recycling of the waste hydrotreating catalyst, reduce industrial solid waste and reduce the production cost of the catalyst.
The method can also utilize the regenerated powder of various industrial waste agents to prepare the slurry bed hydrotreating catalyst so as to furthest reduce industrial solid waste and reduce the production cost of the catalyst. Namely, the method provided by the invention can treat different types of industrial waste agents and has higher applicability.
Drawings
FIG. 1 is a schematic flow diagram of a preferred embodiment of the separation process in the method of the present invention.
Description of the reference numerals
P type feeder
F. Fluidized bed
C1 and C2 are cyclone separators
R1 and R2 are containers
V1 and V2 are valves
101. 102, 103, 104 are pipelines
Detailed Description
The endpoints and any values of the ranges disclosed herein are not limited to the precise range or value, and are understood to encompass values approaching those ranges or values. For numerical ranges, one or more new numerical ranges may be found between the endpoints of each range, between the endpoint of each range and the individual point value, and between the individual point value, in combination with each other, and are to be considered as specifically disclosed herein.
As previously described, the present invention provides a method for recycling spent hydrogenation catalyst comprising:
(1) Carrying out heat treatment and grinding on a waste hydrogenation catalyst to obtain waste catalyst powder, wherein the waste hydrogenation catalyst is obtained by hydrotreating raw oil with a fresh hydrogenation catalyst;
(2) Separating the waste agent powder to obtain high-density waste agent powder and low-density waste agent powder respectively;
(3) Grinding the low-density waste agent powder or not, and then using the low-density waste agent powder for slurry bed catalytic hydrogenation reaction;
wherein in step (2), the average relative particle density of the high-density waste agent powder and the average relative particle density of the low-density waste agent powder satisfy formula (1):
k 1 ＞k 2 (1),
in formula (1), k 2 Is 1 to 5, k 1 Less than or equal to 20, and k 1 Average particle density of high density spent agent powder/average particle density of fresh hydrogenation catalyst dry base powder, k 2 The average particle density of the low density spent catalyst powder/the average particle density of the fresh hydrogenation catalyst dry basis powder.
Preferably, the conditions of the separation in step (2) are controlled such that the low-density waste powder accounts for 10 to 80% by weight of the total waste powder, more preferably such that the low-density waste powder accounts for 20 to 60% by weight of the total waste powder.
Preferably k 1 1.5, particularly preferably k 1 ≥2。
The inventors found that controlling k 1 1.5, particularly preferably k 1 When the metal content of the waste powder is more than or equal to 2, the high-density waste powder is mainly waste powder with high metal content, the low-density waste powder is mainly waste powder with low metal content, and a remarkable metal content (average value) difference exists between the high-density waste powder and the low-density waste powder, so that good catalytic activity can be obtained when the low-density waste powder is used as regenerated catalyst powder to prepare a slurry bed hydrotreating catalyst.
In the step (2) of the present invention, the waste powder obtained in the step (1) is preferably subjected to sieving before being separated, the purpose of the sieving being to keep the waste powders of different densities in the same or close particle size range.
Preferably, in step (2), the step of separating the waste agent powder is selected from at least one of modes a, b and c:
mode a: introducing the waste agent powder into a fluidized bed for particle classification;
mode b: introducing the waste agent powder into a sedimentation separator for separation;
mode c: and carrying out solvent flotation on the waste agent powder.
For the separation of the present invention, the present invention illustratively provides a preferred separation scheme (scheme a) in combination with the separation scheme illustrated in fig. 1:
the feeder P delivers the spent powder via line 101 to the fluidized bed F, into which a gas, e.g. air, is introduced via line 102 for fluidization, typically controlling the fluidization velocity of the powder particles to be 5-50 mm/s, and valve V1 is opened to let the powder particles enter cyclone C1 via line 103, after separation by cyclone C1, into vessel R1 for storage. Since the fluidization velocity of the particles is also different due to the difference of the particle densities, the fluidization velocity is controlled so that the low-density powder particles slowly enter the container R1, so that the powder particles stored in the container R1 are mostly low-density waste agent powder, and the regenerated powder in the container R1 is controlled to account for the mass percentage of the fluidized bed feed. Illustratively, when separating the spent catalyst powder of hydrodemetallization catalyst RDM-2, the spent catalyst regeneration powder of hydrodemetallization catalyst RDM-2 (i.e. the powder particles stored in vessel R1) generally represents 10-50%, preferably 20-40% by mass of the total feed to the fluidized bed; in separating the spent catalyst powder of the hydrodesulfurization catalyst RMS-1, the spent catalyst regenerated powder of the hydrodesulfurization catalyst RMS-1 (i.e., the powder particles stored in the vessel R1) generally accounts for 30 to 80% by mass, preferably 30 to 60% by mass of the total feed to the fluidized bed. When the mass percentage of the regenerated powder in the container R1 accounting for the feeding of the fluidized bed reaches the control index, the valve V2 is opened to enable the powder particles to enter the cyclone separator C2 through the pipeline 104, and the powder particles enter the container R2 for storage after being separated through the cyclone separator C2. The powder particles stored in the container R2 are mostly high-density waste agent powder. According to the method, most of the low-density powder particles stored in the container R1 are regenerated powder with low metal content, wherein the low-density powder with small particle size can be directly used as slurry bed heavy oil hydrotreating catalyst or doping material of slurry bed heavy oil hydrotreating catalyst; the low-density powder with large particle size needs to be ground again, and the ground powder can be used as slurry bed heavy oil hydrotreating catalyst or the admixture of slurry bed heavy oil hydrotreating catalyst. In addition, according to the method of the present invention, the powder particles stored in the container R2 may be subjected to landfill or recovery metal treatment.
Preferably, in step (1), the grinding conditions are controlled so that the average particle size of the waste powder is 150 μm or less, for example, 100 to 150 μm or less.
Preferably, in step (1), the conditions of the heat treatment include: the spent hydrogenation catalyst is calcined at 300 to 800 ℃ for 1 to 20 hours, more preferably the temperature of the heat treatment is 400 to 600 ℃. Because the waste hydrogenation catalyst contains a certain amount of carbon and sulfur, the roasting process is the process of burning the carbon and the sulfur, and therefore, the temperature rising speed and the roasting temperature can be controlled according to the conventional method in the field when the roasting temperature rises, so as to achieve the purposes of preventing the temperature from flying and keeping the crystal forms of the carrier and the active center stable.
Preferably, in step (3), the low-density waste powder obtained with or without grinding has an average particle diameter of 50 to 200 μm.
More preferably, in step (3), water and/or an organic solvent or the like may be added during the milling to assist the milling to prepare a reclaimed powder of a lower particle diameter.
The spent hydrogenation catalyst of the present invention may be a different type of spent hydrotreating catalyst, and the catalyst types are typically catalysts having these functions, such as a hydrogenation protecting catalyst, a hydrodemetallization catalyst, a hydrogenation transition catalyst, a hydrodesulfurization catalyst, a hydrodenitrogenation catalyst, and a hydrodecarbonization catalyst. Therefore, preferably, the fresh hydrogenation catalyst of the present invention is at least one selected from the group consisting of a hydrogenation protecting catalyst, a hydrodemetallization catalyst, a hydrogenation transition catalyst, a hydrodesulfurization catalyst, a hydrodenitrogenation catalyst and a hydrodecarbonization catalyst, and the spent hydrogenation catalyst is a catalyst obtained by hydrotreating a raw oil with the fresh hydrogenation catalyst.
The waste hydrogenation catalyst of the invention is a catalyst which takes inorganic oxide (such as alumina) as a carrier, takes oxide of metal of VIB group and/or VIII group (such as oxide of one or more of Mo, W, co and Ni) as an active component and selectively adds various auxiliary agents (such as one or more of P, si, F and B). The inorganic oxide is preferably a mesoporous inorganic oxide. In particular, it is preferable that the fresh hydrogenation catalyst contains a support and an active component, and optionally contains an auxiliary component, the support is an inorganic oxide, the active component is at least one of group VIB and group VIII metal elements, and the auxiliary component is at least one of P, si, F, and B.
In the present invention, the fresh hydrogenation catalyst is, for example, a heavy and residual oil hydrogenation protecting catalyst, a hydrodemetallization catalyst, a hydrogenation transition catalyst, a hydrodesulphurisation catalyst, a hydrodenitrogenation catalyst and a hydrodecarbonization catalyst of the RG, RDM, RMS, RSN and RSC series developed by the institute of petrochemical science.
According to a preferred embodiment, the fresh hydrogenation catalyst is a hydrodemetallization catalyst, k 2 1 to 2.
According to another preferred embodiment, the fresh hydrogenation catalyst is a hydrodesulphurisation catalyst, k 2 1 to 1.5.
According to a preferred embodiment, in step (3), the low density spent agent powder obtained with or without grinding is used directly as slurry bed hydroprocessing catalyst and/or as admixture for slurry bed hydroprocessing catalyst.
Preferably, the feedstock oil is selected from one or a combination of two or more of a wax oil fraction, a deasphalted oil, an atmospheric residue, a vacuum residue, and an oil obtained by pyrolysis of at least one of coal, petroleum sand, oil shale, and asphalt.
Preferably, in the step (3), when the low-density spent agent powder obtained with or without grinding is used as a spent agent regeneration powder for slurry bed catalytic hydrogenation, the spent agent regeneration powder accounts for 10 to 100 mass% of the total feed of the slurry bed.
According to the method, the separation of the low-metal deposition powder and the high-metal deposition powder is realized based on the density difference of the waste agent powder, so that the high residual catalytic activity of the low-metal deposition regenerated powder is fully utilized for slurry bed heavy oil hydrotreatment, and a good catalytic effect is obtained. The recycled powder of the method accounts for 10-80% of the mass of the waste agent, and compared with the prior art, the method can save the production cost of the catalyst by 20-50%, and maximally reduce the industrial solid waste. Meanwhile, the method is also beneficial to improving the recovery efficiency of waste metals.
The waste agent raw material used for slurry bed heavy oil hydrotreatment is regenerated powder with certain catalytic activity and low metal deposition amount. The process operation condition is kept unchanged, and the hydrodesulfurization rate and/or hydrodemetallization rate of the regenerated powder with low metal deposition amount under the condition of a certain reaction temperature is generally 10-90% of that of the new agent based on the hydrodesulfurization rate and/or hydrodemetallization rate of the fresh hydrotreating catalyst under the condition of the reaction temperature.
Unless otherwise indicated, the pressures described herein are gauge pressures.
The invention will be described in detail below by way of examples. In the following examples, unless otherwise specified, all materials used are commercially available.
In the following examples, the spent agent used was the stripper after shutdown of the refinery residuum hydrotreater. The fresh catalysts used for starting the residual oil hydrogenation device are all developed by the institute of petrochemical industry and are all catalysts produced by the catalyst Kaolin company of China petrochemical industry Co.
In the following examples, the waste agents of the hydrodemetallization catalyst RDM-2 and the hydrodesulphurization catalyst RMS-1 are collected as raw materials and screened to obtain corresponding hydrodemetallization regeneration powder and hydrodesulphurization regeneration powder.
Without particular explanation, the process flows in the following examples are as follows:
(1) Collecting and heat-treating industrial waste agent (roasting for 3 hours at 600 ℃), grinding, and removing C, S and other impurity elements in the waste agent to obtain waste agent powder, wherein the waste agent powder has a particle size of 100-150 mu m accounting for 80% by weight of all waste agent powder obtained after grinding;
(2) Separating the waste agent powder by the process flow shown in fig. 1 to obtain high-density waste agent powder (namely high-metal content powder which can be subjected to landfill or metal recovery treatment, wherein the metal recovery treatment can obtain Ni, V, co, W, mo and other metals) and low-density waste agent powder respectively;
(3) And (3) carrying out secondary grinding on the low-density waste agent powder to obtain regenerated powder, so that the regenerated powder is used as a slurry bed heavy oil hydrotreating catalyst or an admixture of the slurry bed heavy oil hydrotreating catalyst.
Example 1
Grinding the waste agent in the step (1), and taking waste agent powder with the particle size of 100-150 mu m;
for hydrodemetallization catalyst RDM-2: separating the waste powder according to the step (2), wherein the low-density waste powder (waste regenerated powder) is 20% by mass of the total feed of the fluidized bed, in which case k 1 ＝2.3，k 2 =1.2, the resulting spent catalyst regeneration powder can be used as a slurry bed heavy oil hydroprocessing catalyst. The hydrotreatment experiment of the slurry bed of the residual oil is carried out on a small autoclave with the volume of 1L, and the raw material is a residual oil raw material R. The reaction conditions are as follows: the reaction temperature is 395 ℃; the reaction pressure (gauge pressure) is 14MPa; the reaction time is 12 hours; the residual oil addition amount is 300g; the addition amount of the regenerated powder was 30g. The resulting hydrogenated residuum product is HR.
For hydrodesulfurization catalyst RMS-1: separating the waste powder according to the step (2), wherein the low-density waste powder (waste regenerated powder) is 40% by mass of the total feed of the fluidized bed, in which case k 1 ＝1.7，k 2 =1.2, the resulting spent catalyst regeneration powder can be used as a slurry bed heavy oil hydroprocessing catalyst. Specifically, the obtained waste agent regenerated powder is used as a slurry bed heavy oil hydrotreating catalyst. The hydrotreatment experiment of the slurry bed of the residue oil is carried out on a small autoclave with the volume of 1L, the raw materials are the hydrogenated residue oil HR obtained by the above, and the reaction conditions are as follows: the reaction temperature is 395 ℃; the reaction pressure is 14MPa; the reaction time is 12 hours; the addition amount of the raw materials is 200g; the addition amount of the regenerated powder was 20g. The resulting hydrogenated residuum product is HHR.
The residue R, hydrogenated residue HR and hydrogenated residue HHR were analyzed separately, and the analysis properties obtained are shown in table 1.
Table 1: properties of residuum R, hydrogenated residuum HR, and hydrogenated residuum HHR in example 1
| Residuum R | Hydrogenated residuum HR | Hydrogenated residuum HHR | |
| Kangshi carbon residue, weight percent | 12.7 | 7.01 | 4.09 |
| Sulfur, wt% | 3.68 | 2.00 | 0.58 |
| Nitrogen, weight% | 0.39 | 0.34 | 0.20 |
| Metals (Nickel and vanadium), μg/ |
101 | 16.9 | 8.08 |
As can be seen from Table 1, the obtained hydrogenated residue HR had an S content of 2.00wt.%, an N content of 0.34wt.%, a carbon residue content of 7.01wt.%, and a heavy metal (Ni+V) content of 16.9. Mu.g/g. The obtained hydrogenated residue HHR had an S content of 0.58wt.%, an N content of 0.20wt.%, a carbon residue content of 4.09wt.%, and a heavy metal (Ni+V) content of 8.08. Mu.g/g. The obtained hydrogenated residual oil HHR basically meets the feeding quality requirement of a catalytic cracking device.
Example 2
Grinding the waste agent in the step (1), and taking waste agent powder with the particle size of 100-150 mu m;
for hydrodemetallization catalyst RDM-2: separating the waste powder according to the step (2), wherein the low-density waste powder (waste regenerated powder) is 40% by mass of the total feed of the fluidized bed, in which case k 1 ＝2.5，k 2 =1.3, the resulting spent catalyst regeneration powder can be used as a slurry bed heavy oil hydroprocessing catalyst. The hydrotreatment experiment of the slurry bed of the residual oil is carried out on a small autoclave with the volume of 1L, and the raw material is a residual oil raw material R. The reaction conditions are as follows: the reaction temperature is 395 ℃; the reaction pressure is 14MPa; the reaction time is 12 hours; the residual oil addition amount is 300g; the addition amount of the regenerated powder was 30g. The resulting hydrogenated residuum product is HR.
For hydrodesulfurization catalyst RMS-1: separating the waste powder according to the step (2), wherein the low-density waste powder (waste regenerated powder) is 60% by mass of the total feed of the fluidized bed, in which case k 1 ＝1.8，k 2 =1.3, the resulting spent catalyst regeneration powder can be used as a slurry bed heavy oil hydroprocessing catalyst. The hydrotreatment experiment of the slurry bed of the residuum was carried out on a small autoclave having a volume of 1L, starting from the hydrogenated residuum HR obtained in the previous example, under the following reaction conditions: the reaction temperature is 395 ℃; the reaction pressure is 14MPa; the reaction time is 12 hours; the addition amount of the raw materials is 200g; the addition amount of the regenerated powder was 20g. The resulting hydrogenated residuum product is HHR.
The residue R, hydrogenated residue HR and hydrogenated residue HHR of this example were analyzed separately, and the analysis properties obtained are shown in table 2.
Table 2: properties of residuum R, hydrogenated residuum HR, and hydrogenated residuum HHR in example 2
As can be seen from table 2, the hydrogenated residue HR obtained in this example had an S content of 2.48wt.%, an N content of 0.36wt.%, a carbon residue content of 8.62wt.%, and a heavy metal (ni+v) content of 34.03 μg/g. The obtained hydrogenated residue HHR had an S content of 0.78wt.%, an N content of 0.22wt.%, a carbon residue content of 5.03wt.%, and a heavy metal (Ni+V) content of 19.68. Mu.g/g. The obtained hydrogenated residual oil HHR basically meets the feeding quality requirement of a catalytic cracking device.
Since the spent agent regeneration powders of hydrodemetallization catalyst RDM-2 and hydrodesulphurisation catalyst RMS-1 respectively account for the mass percent of the total feed to the fluidised bed during said separation, the purity of the low metal content powder in the regeneration powder of example 2 is lower than that of the low metal content powder in the regeneration powder of example 1, compared to the mass percent in example 1. Thus, the hydrogenated residuum HR obtained in example 2 has a higher impurity content than the hydrogenated residuum HR obtained in example 1, while the hydrogenated residuum HHR obtained in example 2 has a higher impurity content than the hydrogenated residuum HHR obtained in example 1.
Example 3
Grinding the waste agent in the step (1), and taking waste agent powder with the particle size of 100-150 mu m;
for hydrodemetallization catalyst RDM-2: separating the waste powder according to the step (2), wherein the low-density waste powder (waste regenerated powder) is 70% by mass of the total feed of the fluidized bed, in which case k 1 ＝3.0，k 2 =1.6, the resulting spent catalyst regeneration powder can be used as a slurry bed heavy oil hydroprocessing catalyst. The hydrotreatment experiment of the slurry bed of the residual oil is carried out on a small autoclave with the volume of 1L, and the raw material is a residual oil raw material R. The reaction conditions are as follows: the reaction temperature is 395 ℃; the reaction pressure was 14MPa, a; the reaction time is 12 hours; the residual oil addition amount is 300g; the addition amount of the regenerated powder was 30g. The resulting hydrogenated residuum product is HR.
The residue R and hydrogenated residue HR of this example were each analyzed, and the analysis properties obtained are shown in table 3.
Table 3: properties of residuum R and hydrogenated residuum HR in example 3
As can be seen from Table 3, the hydrogenated residue HR obtained in this example had a S content of 2.79wt.%, a N content of 0.37wt.%, a carbon residue content of 9.65wt.%, and a heavy metal (Ni+V) content of 48.97. Mu.g/g. Compared with the property of the hydrogenated residual oil HR in the example 2, the hydrogenated residual oil HR in the example has higher S content, N content, carbon residue content and heavy metal (Ni+V) content. Since the spent catalyst regeneration powder of hydrodemetallization catalyst RDM-2 was in the separation process as a mass percentage of the total feed to the fluidized bed, respectively, the mass percentage was high relative to that in example 2.
Comparative example 1
The parameter control of this comparative example was similar to that of example 1, except that:
in the comparative example, the hydrodemetallization catalyst RDM-2 waste agent is taken as a raw material to be ground, waste agent powder with the particle size of 100-150 mu m is taken, and the waste agent powder is directly taken as a catalyst for slurry bed heavy oil hydrotreatment without fluidized bed separation.
Then, a slurry bed hydrotreatment experiment of the oil was performed on a small autoclave having a volume of 1L. The feedstock was a residuum feedstock R of the same kind as in example 1, the reaction conditions being: the reaction temperature is 405 ℃; the reaction pressure is 14MPa; the reaction time is 12 hours; the residual oil addition amount is 300g; the addition amount of the regenerated powder was 30g. The resulting hydrogenated residuum product is HR.
In the comparative example, the hydrodesulfurization catalyst RMS-1 waste agent is ground as a raw material, waste agent powder with the particle size of 100-150 mu m is taken, and the waste agent powder is directly used as a catalyst for slurry bed heavy oil hydrotreating without fluidized bed separation. Then, a slurry bed hydrotreatment experiment of the oil was performed on a small autoclave having a volume of 1L. The raw materials are hydrogenated residual oil HR of the comparative example, and the reaction conditions are as follows: the reaction temperature is 405 ℃; the reaction pressure is 14MPa; the reaction time is 12 hours; the residual oil adding amount is 200g; the addition amount of the regenerated powder was 20g. The hydrogenated residuum product obtained in this comparative example is HHR.
The remainder was the same as in example 1.
The residue R, hydrogenated residue HR and hydrogenated residue HHR were each analyzed and the resulting analytical properties are shown in Table 4.
Table 4: properties of residuum R, hydrogenated residuum HR, and hydrogenated residuum HHR in comparative example 1
| Residuum R | Hydrogenated residuum HR | Hydrogenated residuum HHR | |
| Kangshi carbon residue, weight percent | 12.7 | 10.97 | 6.53 |
| S, weight percent | 3.68 | 3.19 | 1.08 |
| N, wt% | 0.39 | 0.38 | 0.26 |
| Metals (Nickel and vanadium), μg/ |
101 | 70.88 | 46.10 |
As can be seen from Table 4, the hydrogenated residual oil obtained in this comparative example had an S content of 3.19wt.%, an N content of 0.38wt.%, a carbon residue content of 10.97wt.%, and a heavy metal (Ni+V) content of 70.88. Mu.g/g. The hydrogenated residual oil HHR obtained in this comparative example had a S content of 1.08wt.%, an N content of 0.26wt.%, a carbon residue content of 6.53wt.%, and a heavy metal (Ni+V) content of 46.10. Mu.g/g. The hydrogenated residual oil HHR obtained in the comparative example can not meet the feeding quality requirement of a catalytic cracking device.
From the above results, it is clear that when the method of the present invention is applied to treat residuum, the obtained hydrogenated residuum basically meets the feed quality requirement of the catalytic cracking device.
The preferred embodiments of the present invention have been described in detail above, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, a number of simple variants of the technical solution of the invention are possible, including combinations of the individual technical features in any other suitable way, which simple variants and combinations should likewise be regarded as being disclosed by the invention, all falling within the scope of protection of the invention.
Claims (12)
1. A method for recycling spent hydrogenation catalyst, the method comprising:
(1) Carrying out heat treatment and grinding on a waste hydrogenation catalyst to obtain waste catalyst powder, wherein the waste hydrogenation catalyst is obtained by hydrotreating raw oil with a fresh hydrogenation catalyst; the fresh hydrogenation catalyst is a hydrodemetallization catalyst or a hydrodesulphurization catalyst;
(2) Separating the spent agent powder, the separating comprising:
introducing the waste agent powder into a fluidized bed for particle classification, controlling the fluidization speed of powder particles to be 5-50 mm/s, and enabling the powder particles to enter a cyclone separator (C1) for separation to obtain low-density waste agent powder; wherein, when the fresh hydrogenation catalyst is a hydrodemetallization catalyst, the low-density waste agent powder accounts for 10-50% of the total feed of the fluidized bed by mass percent; when the fresh hydrogenation catalyst is a hydrodesulfurization catalyst, the low-density waste agent powder accounts for 30-80% of the total feed of the fluidized bed by mass percent;
when the mass percentage of the low-density waste agent powder accounting for the total feeding of the fluidized bed reaches a control index, enabling the powder particles to enter a cyclone separator (C2) for separation to obtain high-density waste agent powder;
(3) Grinding the low-density waste agent powder or not, and then using the low-density waste agent powder for slurry bed catalytic hydrogenation reaction;
wherein in step (2), the average relative particle density of the high-density waste agent powder and the average relative particle density of the low-density waste agent powder satisfy formula (1):
k 1 ＞k 2 (1),
in formula (1), k 2 K is 1-5 and is more than or equal to 1.5 1 Less than or equal to 20, and k 1 Average particle density of high density spent agent powder/average particle density of fresh hydrogenation catalyst dry base powder, k 2 The average particle density of the low density spent catalyst powder/the average particle density of the fresh hydrogenation catalyst dry basis powder.
2. The method of claim 1, wherein the conditions of the separation in step (2) are controlled such that the low density waste powder accounts for 10 to 80% by weight of the total waste powder.
3. The method of claim 2, wherein the conditions of the separation in step (2) are controlled such that the low density waste powder accounts for 20 to 60% by weight of the total waste powder.
4. A method according to any one of claims 1-3, wherein k 1 ≥2。
5. A method according to any one of claims 1 to 3, wherein in step (1), the grinding conditions are controlled so that the average particle diameter of the waste powder is 150 μm or less.
6. A method according to any one of claims 1 to 3, wherein in step (1), the conditions of the heat treatment comprise: roasting the waste hydrogenation catalyst for 1-20 hours at the temperature of 300-800 ℃.
7. A method according to any one of claims 1 to 3, wherein in step (3), the low density waste powder obtained with or without grinding has an average particle size of 50 to 200 μm.
8. The process of claim 1, wherein the fresh hydrogenation catalyst is a hydrodemetallization catalyst, k 2 1 to 2.
9. The process of claim 1, wherein the fresh hydrogenation catalyst is a hydrodesulfurization catalyst, k 2 1 to 1.5.
10. A process according to any one of claims 1 to 3, wherein in step (3) the low density spent catalyst powder obtained with or without milling is used directly as slurry bed hydroprocessing catalyst and/or as an admixture for slurry bed hydroprocessing catalyst.
11. The method of claim 1, wherein the feedstock oil is selected from one or a combination of two or more of a wax oil fraction, a deasphalted oil, an atmospheric residue, a vacuum residue, an oil obtained by pyrolysis of at least one of coal, petroleum sand, oil shale, and bitumen.
12. The method according to claim 1, wherein in step (3), when the low-density spent agent powder obtained with or without grinding is used as a spent agent regeneration powder for slurry bed catalytic hydrogenation reaction, the spent agent regeneration powder accounts for 10 to 100% by mass of the total feed of the slurry bed.
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| US7026262B1 (en) * | 2002-09-17 | 2006-04-11 | Uop Llc | Apparatus and process for regenerating catalyst |
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