CN112745944B

CN112745944B - Hydrocarbon oil processing method for producing anode coke product and common petroleum coke product

Info

Publication number: CN112745944B
Application number: CN201911048111.9A
Authority: CN
Inventors: 王翠红; 申海平; 王红; 廖志新; 刘自宾; 佘玉成; 范启明
Original assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Current assignee: Sinopec Research Institute of Petroleum Processing; China Petroleum and Chemical Corp
Priority date: 2019-10-30
Filing date: 2019-10-30
Publication date: 2022-09-27
Anticipated expiration: 2039-10-30
Also published as: CN112745944A

Abstract

The invention relates to the field of hydrocarbon oil processing, and discloses a hydrocarbon oil processing method for producing an anode coke product and a common petroleum coke product, which comprises the following steps: introducing vacuum residue into a first separator to perform countercurrent contact with a solvent contained in the first separator to respectively obtain a first overhead material flow and a first kettle material flow; introducing the first overhead stream into a second separator for countercurrent contact with a solvent contained therein to obtain a second overhead stream and a second bottoms stream, respectively; carrying out hydrotreating on the second tower bottom material flow to obtain a hydrogenated material flow; carrying out delayed coking treatment on the hydrogenated material flow to obtain an anode coke product; and introducing the first tower bottom material flow and the second tower top material flow into a coking unit after solvent removal treatment so as to obtain a petroleum coke product. The method realizes the high-efficiency utilization of the hydrocarbon oil, improves the utilization rate and the utilization value of the hydrocarbon oil to the maximum extent, and the produced anode coke has higher quality.

Description

Hydrocarbon oil processing method capable of producing anode coke product and common petroleum coke product

Technical Field

The invention relates to the field of hydrocarbon oil processing, in particular to a hydrocarbon oil processing method for producing an anode coke product and a common petroleum coke product.

Background

With the rapid development of the electrolytic aluminum industry, the demand for prebaked anode coke for aluminum has increased greatly, and the prebaked anode coke for aluminum industry has gradually become a new investment growth point.

Generally, when the sulfur content of petroleum coke is lower, the consumption of the anode is reduced along with the increase of the sulfur content, because the sulfur increases the coking rate of asphalt and reduces the void ratio of asphalt coking; meanwhile, sulfur is combined with metal impurities, so that the catalytic action of the metal impurities is reduced, but if the sulfur content is too high, the thermal brittleness of the carbon anode is increased, the sulfur is mainly converted into gas phase in the form of oxides in the electrolytic process, the electrolytic environment is seriously influenced, the environmental protection pressure is high, and in addition, an iron sulfide film can be generated on an anode rod to increase the voltage drop.

Thus, in producing anode coke feedstock, a low asphaltene, low sulfur, low metals content, lower saturates content feedstock should be selected.

With the continuous development of the oil refining industry, the processing capacity of crude oil is improved year by year, and the heavy and inferior degrees of the crude oil are gradually increased, so that the properties of residual oil are increasingly poor, which is shown in that the contents of metal, carbon residue, asphaltene, sulfur and nitrogen are increasingly high, the properties of raw materials for producing anode coke are increasingly poor, and the difficulty in producing qualified anode coke products is increasingly high.

The existing anode coke (paste) production process usually adopts medium-temperature asphalt or/and high-temperature asphalt as raw materials.

However, when the anode paste produced by using the medium-temperature asphalt as the raw material is used, the smoke generated due to high volatile content is large, and the environment is polluted; when high-temperature asphalt is adopted as a raw material, because the high-temperature asphalt has high sulfur content, high metal content and high carbon residue value, shot coke is easily generated during coke formation, and SO is discharged during use of the generated coke _x Affecting the environment.

CN1349955A discloses a method for producing clean anode coke, which comprises the steps of uniformly mixing raw material petroleum coke and medium-temperature asphalt, removing impurities by using an electromagnetic separator, crushing, forming, roasting at 1000-1300 ℃ for 12-24 h, and cooling the mature anode coke by a cooling tower to obtain a clean anode coke product; the electromagnetic separator has a separating effect only on free metal impurities and has no separating effect on metal compounds, sulfur and the like.

At present, no proper process is available for treating vacuum residue with poor property to enable the vacuum residue to be used as a raw material for producing high-quality anode coke, and the fixed bed residue can remove sulfur and metals in the vacuum residue by hydrogenation, but the economic efficiency is poor in consideration of the construction cost of a hydrogenation device, the hydrogen consumption and the service cycle of a catalyst. In addition, the vacuum residue is hydrogenated and then used as coking feed, the saturation degree of the feed of a coking device is greatly increased, and the properties of volatile carbon-containing substances, the pile ratio, the moldability and the like of the produced anode coke are difficult to meet the quality requirement of the anode coke.

Disclosure of Invention

The invention aims to overcome the problems in the prior art and provide a hydrocarbon oil processing method for producing an anode coke product and a common petroleum coke product at the same time, so as to achieve the purpose of separating a high-quality anode coke raw material from hydrocarbon oil to produce high-quality anode coke.

In order to achieve the above object, the present invention provides a hydrocarbon oil processing method for producing both an anode coke product and a common petroleum coke product, the method comprising:

(1) introducing vacuum residue into a first separator to perform countercurrent contact with a solvent contained in the first separator to respectively obtain a first overhead material flow and a first kettle material flow, wherein the sulfur content of the vacuum residue is not lower than 3 wt%;

(2) introducing the first overhead stream into a second separator for countercurrent contact with a solvent contained therein to obtain a second overhead stream and a second bottoms stream, respectively;

(3) carrying out hydrotreating on the second tower bottom material flow to obtain a hydrogenated material flow;

(41) carrying out delayed coking treatment on the hydrogenated material flow to obtain an anode coke product;

(42) and (3) carrying out solvent removal treatment on the first tower bottom material flow and the second tower top material flow, and introducing the treated materials into a coking device to obtain a sulfur-containing petroleum coke product with the sulfur content of more than or equal to 4 wt%.

The invention adopts the vacuum residue oil as the raw material for producing the anode coke, and can avoid the situation of competing for the raw material (the oil slurry is a high-quality raw material for producing the needle coke after pretreatment) with the production of the needle coke (the price of the needle coke is higher than that of the anode coke), thereby producing more products with high added values on the basis of ensuring the original high added value products of enterprises.

The method ensures that the anode coke generated by the obtained anode coke raw material through the delayed coking reaction has high volatilization temperature and lower content of volatile components, and the anode coke can keep good environment in the using process; in addition, the method of the invention separates and removes the components which are difficult to coke and the components which are easy to generate shot coke, so that the efficiency of generating the anode coke is high and the quality of the anode coke is good.

In addition, the rest components obtained by the method can be used as raw materials for producing petroleum coke, and products such as coking gasoline and coking gasoline can be obtained, so that the added value of the products is improved, and zero delivery of heavy oil is realized.

Drawings

FIG. 1 is a flow chart of a hydrocarbon oil processing process for producing both anode coke products and ordinary petroleum coke products in accordance with a preferred embodiment of the present invention.

Description of the reference numerals

1. Vacuum residue 2, first solvent 3 and first separator

4. A second separator 5, a first overhead stream 6, a second overhead stream

7. First tower cauldron commodity circulation 8, separator 9, coking tower

10. Second tower bottom material flow 11, hydrotreater 12 and coking material flow

13. Delayed coking unit 14, second solvent

Detailed Description

The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.

As described above, the present invention provides a hydrocarbon oil processing method for producing both an anode coke product and a common petroleum coke product, the method comprising:

(42) and (3) carrying out solvent removal treatment on the first tower bottom material flow and the second tower top material flow, and introducing the treated materials into a coking device to obtain a sulfur-containing petroleum coke product with the sulfur content of more than or equal to 4 weight percent.

Preferably, the solvent contained in the first separator and the second separator is the same or different, and each is independently selected from at least one of propane, butane, pentane.

Preferably, the operating conditions in the first separator comprise: the temperature at the top of the tower is 30-240 ℃, the temperature at the bottom of the tower is 20-230 ℃, the operating pressure is 2.0-10.0 MPa, and the weight ratio of the solvent to the oil is 1.0-5.0: 1. More preferably, the operating conditions in the first separator include: the temperature at the top of the tower is 45-220 ℃, the temperature at the bottom of the tower is 35-210 ℃, the operating pressure is 3.5-8.0 MPa, and the weight ratio of the solvent to the oil is 1.5-4.0: 1.

In the operating conditions of the first separator, the solvent-to-oil weight ratio refers to the weight ratio of solvent to vacuum residue.

Preferably, the operating conditions in the second separator comprise: the temperature of the top of the tower is 45-260 ℃, the temperature of the bottom of the tower is 35-250 ℃, the operating pressure is 2.0-10.0 MPa, and the weight ratio of the solvent to the oil is 0.5-4.5: 1.

Preferably, the operating conditions in the second separator comprise: the temperature at the top of the tower is 50-240 ℃, the temperature at the bottom of the tower is 40-230 ℃, the operating pressure is 3.5-8.0 MPa, and the weight ratio of the solvent to the oil is 1.5-3.0: 1.

In the operating conditions of the second separator, the weight ratio in the solvent-oil refers to the weight ratio of solvent to first overhead stream.

Preferably, in step (3), the hydrotreating is carried out in the presence of a hydrogenation protection catalyst and a hydrofinishing catalyst, the conditions of the hydrotreating comprising: the reaction temperature is 300-420 ℃, the hydrogen partial pressure is 2-12 MPa, and the volume space velocity is 0.2h ^-1 -1.5 ^-1 Hydrogen to oil volume ratio of 200Nm ³ /m ³ -900 Nm ³ /m ³ 。

Illustratively, the hydrogenation protection catalyst is in a Raschig ring shape and comprises an alumina carrier and molybdenum and/or tungsten and nickel and/or cobalt loaded on the alumina carrier, wherein the content of the molybdenum and/or tungsten is 1-10 wt% and the content of the nickel and/or cobalt is 0.5-3 wt% based on the total weight of the hydrogenation protection agent and calculated by oxides; the alumina is preferably gamma-alumina, and the pore volume of the hydrogenation protection catalyst is not less than 0.5 ml/g.

Preferably, the hydrofining catalyst contains a carrier and an active metal element loaded on the carrier, wherein the active metal element is at least one of molybdenum, tungsten, nickel and cobalt, and the carrier is alumina or a combination of alumina and silica.

More preferably, in the hydrofinishing catalyst, the active metal element is a combination of molybdenum and/or tungsten as component a and nickel and/or cobalt as component B.

Particularly preferably, the content of the component A is 8 to 20% by weight and the content of the component B is 0.3 to 8% by weight, based on the total weight of the hydrofining catalyst and based on the oxide of the active metal element.

Particularly preferably, in the hydrofinishing catalyst, the pore volume of the carrier is distributed such that the pore volume of 60 to 100 angstroms in diameter accounts for 75 to 98% of the total pore volume, and more preferably the pore volume of the hydrofinishing catalyst is not less than 0.4 ml/g.

The loading volume ratio of the hydrogenation protection catalyst and the hydrogenation refining catalyst is not particularly limited in the present invention, and those skilled in the art can load the hydrogenation protection catalyst and the hydrogenation refining catalyst by using the loading ratio conventionally used in the art.

Preferably, in step (41), the delayed coking process is carried out in a delayed coking unit, the operating conditions in the delayed coking unit comprising: the outlet temperature of the heating furnace is controlled to be 480-520 ℃, the pressure of the coke tower is 0.1-0.5 MPa, and the circulation ratio is 0.5-1.6.

In the method of the present invention, the anode coke product obtained in the step (4) can be obtained as well as, for example, coker dry gas, coker gasoline, coker diesel oil, coker gas oil, and the like.

Preferably, in step (42), the coking process is carried out in a coking unit, the operating conditions in the coking unit comprising: the outlet temperature of the heating furnace is controlled to be 485-515 ℃, the pressure of the coke tower is 0.1-0.45 MPa, and the circulation ratio is 0.8-1.4.

Preferably, the solvent removal treatment in step (42) is carried out in a manner that includes introducing the first bottoms stream and the second overhead stream into a separation unit for solvent removal. Preferably, the solvent removal treatment is carried out under conditions including flash evaporation to recover most of the solvent, followed by steam stripping to recover the remaining small portion of the solvent.

Preferably, the vacuum resid also has at least one of the following characteristics:

(a) a carbon residue value of not less than 15% by weight;

(b) the total content of Ni and V is not less than 100 ug/g.

Unless otherwise specified, all pressures described herein are expressed as gauge pressure.

The following provides a preferred embodiment of the method for processing inferior residual oil according to the present invention with reference to the accompanying drawings.

As shown in fig. 1, a vacuum residue 1 and a first solvent 2 enter the first separator 3 from the middle upper part and the middle lower part of the first separator 3 respectively, the vacuum residue 1 and the first solvent 2 are in countercurrent contact in the first separator 3, a first overhead stream 5 extracted from the top of the first separator 3 enters from the middle upper part of the second separator 4, a second solvent 14 enters from the middle lower part of the second separator 4 and is in countercurrent contact in the second separator, a second bottom stream 10 extracted from the bottom of the second separator 4 enters a hydrotreater 11 for hydrotreatment to obtain an anode coke feed stream, and the anode coke feed stream is introduced into a delayed coking device 13 to obtain a delayed coking product containing anode coke; the first tower bottom material flow 7 extracted from the bottom of the first separator 3 and the second tower top material flow 6 extracted from the top of the second separator 4 respectively or together enter a separation device 8 to separate the solvent to obtain a coking material flow 12, and the extracted coking material flow 12 enters a coking tower 9 to obtain a coking product containing petroleum coke.

The present invention will be described in detail below by way of examples. In the following examples, various raw materials used below were all commercially available without specific description. The properties of the vacuum resid feed used below are shown in table 1.

The hydrogenation protection catalyst RG-30B and the hydrogenation refining catalyst RMS-30 are commercial agents produced by ChangLing catalyst division of China petrochemical catalyst, Inc.

The following examples, without specific reference thereto, were carried out using the process flow shown in fig. 1, and the detailed flow of each example is not described in detail below, and those skilled in the art should not be construed as limiting the present invention.

Example 1

The first solvent and the second solvent used in this example are the same and are both n-butane, and the first solvent and the second solvent are from the same solvent storage unit and are controlled only by different pipelines with valves.

The hydrotreater of this example was a fixed bed reactor.

The specific reaction conditions referred to in the above examples are shown in Table 2;

the compositions and properties of the coker feed stream and the second column bottoms stream are shown in table 3;

the components and properties of the anode coke raw material (i.e. the hydrogenated stream obtained by hydrotreating the second column bottom stream) are shown in table 4;

the composition of the resulting delayed coking product and the properties of the anode coke are shown in table 5;

the composition of the resulting coker product and the properties of the petroleum coke are shown in table 6.

Example 2

This example was carried out using the same process flow as example 1, except that some of the specific parameters involved in the flow were different from example 1, and the specific parameters and results are shown in the following table.

Comparative example 1

Vacuum residue is processed according to the method of example 1, except that the vacuum residue feedstock is not passed through the first separator, the second separator and the hydrotreatment of the present invention, but is directly fed as a feedstock for preparing anode coke to the same delayed coking unit as in example 1 for delayed coking treatment to obtain a delayed coking product containing anode coke.

The specific reaction conditions involved in this comparative example are shown in Table 2, and the composition of the delayed coking product and the properties of the anode coke are shown in Table 5.

Comparative example 2

Vacuum residue was processed as in example 1, except that the vacuum residue feedstock was not subjected to the separation treatment in the first and second separators of the present invention, but was directly subjected to a hydrotreatment unit (same as in example 1) identical to that of example 1 to be subjected to hydrotreatment, and then the resultant hydrogenated stream was introduced into a delayed coking unit identical to that of example 1 to be subjected to delayed coking treatment, thereby obtaining a delayed coking product containing anode coke.

The specific reaction conditions involved in this comparative example are shown in Table 2, the composition and properties of the anode coke feed stream are shown in Table 4, and the composition of the resulting delayed coking product and the properties of the anode coke are shown in Table 5.

TABLE 1

TABLE 2

TABLE 3

TABLE 4

TABLE 5

TABLE 6

From the results, the qualified anode coke product can be obtained by processing the vacuum residue by adopting the method, the performance index of the anode coke product is superior to that of the comparative example 1 which directly uses the vacuum residue as the raw material for preparing the anode coke, and the coke breeze amount, the sulfur content, the ash content, the volatile matter and the solid carbon index of the anode coke obtained by the comparative example 1 can not meet the requirements.

As can be seen by comparing the example 1 with the comparative example 2, the performance index of the anode coke obtained by the invention is better, and the indexes of coke breeze amount, sulfur content, ash content, volatile matter and solid carbon of the anode coke obtained by the comparative example 2 can not meet the requirements.

From the results, the total content of the coking gasoline and the coking diesel oil in the coking product obtained by coking the raw material suitable for producing the anode coke and the raw material of the petroleum coke obtained by separating the vacuum residue by adopting the method of the invention is more than 46 percent, and the content of the petroleum coke is more than 33 percent.

The preferred embodiments of the present invention have been described above in detail, but the present invention is not limited thereto. Within the scope of the technical idea of the invention, many simple modifications can be made to the technical solution of the invention, including various technical features being combined in any other suitable way, and these simple modifications and combinations should also be regarded as the disclosure of the invention, and all fall within the scope of the invention.

Claims

1. A hydrocarbon oil processing method for producing anode coke products and common petroleum coke products is characterized by comprising the following steps:

(1) introducing vacuum residue into a first separator to perform countercurrent contact with a solvent contained in the vacuum residue, so as to respectively obtain a first tower top material flow and a first tower bottom material flow, wherein the sulfur content of the vacuum residue is not lower than 3 wt%;

(42) the first tower bottom material flow and the second tower top material flow are subjected to solvent removal treatment and then introduced into a coking device to obtain a sulfur-containing petroleum coke product with the sulfur content being more than or equal to 4 weight percent;

wherein the solvent contained in the first separator and the second separator is the same or different and is independently selected from at least one of propane, butane and pentane;

the operating conditions in the first separator include: the temperature at the top of the tower is 30-240 ℃, the temperature at the bottom of the tower is 20-230 ℃, the operating pressure is 2.0-10.0 MPa, and the weight ratio of the solvent to the oil is 1.0-5.0: 1;

the operating conditions in the second separator include: the temperature at the top of the tower is 45-260 ℃, the temperature at the bottom of the tower is 35-250 ℃, the operating pressure is 2.0-10.0 MPa, and the weight ratio of the solvent to the oil is 0.5-4.5: 1.

2. The method of claim 1, wherein the operating conditions in the first separator comprise: the temperature of the top of the tower is 45-220 ℃, the temperature of the bottom of the tower is 35-210 ℃, the operating pressure is 3.5-8.0 MPa, and the weight ratio of the solvent to the oil is 1.5-4.0: 1.

3. The method of claim 1, wherein the operating conditions in the second separator comprise: the temperature at the top of the tower is 50-240 ℃, the temperature at the bottom of the tower is 40-230 ℃, the operating pressure is 3.5-8.0 MPa, and the weight ratio of the solvent to the oil is 1.5-3.0: 1.

4. The process of any one of claims 1-3, wherein in step (3), the hydrotreating is carried out in the presence of a hydrogenation protection catalyst and a hydrofinishing catalyst, the conditions of the hydrotreating comprising: the reaction temperature is 300-420 ℃, the hydrogen partial pressure is 2-12 MPa, and the volume space velocity is 0.2h ^-1 -1.5h ^-1 Hydrogen to oil volume ratio of 200Nm ³ /m ³ -900 Nm ³ /m ³ 。

5. The process according to claim 4, wherein the hydrorefining catalyst comprises a carrier and an active metal element selected from at least one of molybdenum, tungsten, nickel and cobalt supported on the carrier, and the carrier is alumina or a combination of alumina and silica.

6. The method of claim 5, wherein the active metal element is a combination of molybdenum and/or tungsten as component A and nickel and/or cobalt as component B.

7. The process according to claim 6, wherein the content of the component A is 8 to 20% by weight and the content of the component B is 0.3 to 8% by weight based on the total weight of the hydrofinishing catalyst and the oxide of the active metal element.

8. The method of any one of claims 1-3, wherein in step (41), the delayed coking process is carried out in a delayed coking plant, the operating conditions in the delayed coking plant comprising: the outlet temperature of the heating furnace is controlled to be 480-520 ℃, the pressure of the coke tower is 0.1-0.5 MPa, and the circulation ratio is 0.5-1.6.

9. A process according to any one of claims 1 to 3, wherein the vacuum resid further has at least one of the following characteristics:

(a) a carbon residue value of not less than 15% by weight;

(b) the total content of Ni and V is not less than 100 ug/g.