CN114426885B - Method and device for processing residual oil - Google Patents
Method and device for processing residual oil Download PDFInfo
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- CN114426885B CN114426885B CN202011026409.2A CN202011026409A CN114426885B CN 114426885 B CN114426885 B CN 114426885B CN 202011026409 A CN202011026409 A CN 202011026409A CN 114426885 B CN114426885 B CN 114426885B
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
- C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
- C10G67/12—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including oxidation as the refining step in the absence of hydrogen
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4006—Temperature
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4012—Pressure
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/40—Characteristics of the process deviating from typical ways of processing
- C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
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- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention relates to the field of hydrocarbon oil processing, and discloses a method and a device for processing residual oil, wherein the method comprises the following steps: (1) Hydrotreating a residuum feedstock to obtain a hydrogenated residuum; (2) Introducing the hydrogenated residual oil into an oxidation desulfurization device in the presence of an oxidant to perform oxidation desulfurization reaction to obtain oxidation desulfurization generated oil; (3) Introducing the oxidative desulfurization generated oil reaching the coking temperature into a coke tower for delayed coking treatment to obtain coke and coking oil gas; (4) And separating the coking oil gas to obtain at least one of coking gasoline, coking diesel oil and coking wax oil. The method for processing residual oil provided by the invention can realize the aim of producing low-sulfur petroleum coke with low cost.
Description
Technical Field
The invention relates to the field of hydrocarbon oil processing, in particular to a method and a device for processing residual oil.
Background
Petroleum coke can be classified into low sulfur coke (sulfur < 3 wt%) and high sulfur coke (sulfur > 3 wt%) according to sulfur content.
The low sulfur coke can be divided into five types of sulfur content (sulfur is less than or equal to 0.5 wt%), 2A (sulfur is 0.5wt% -1.0 wt%), 2B (sulfur is 1.0wt% -1.5 wt%), 3A (sulfur is 1.5wt% -2.0 wt%) and 3B (sulfur is 2.0wt% -3.0 wt%) according to the different sulfur contents, wherein the No. 1 low sulfur coke is mainly used for manufacturing a graphite electrode with common power in the steelmaking industry; 2A low sulfur coke and 2B low sulfur coke are commonly used in the aluminum industry to make prebaked anodes; 3A low sulfur coke and 3B low sulfur coke are commonly used to make raw materials for carbide and carbon industries; while high sulfur coke is commonly used as a fuel in cement plants and power plants.
Pretreatment of coker feedstock to reduce its sulfur content is the most effective way to reduce the sulfur content of petroleum coke.
The sulfur content of the raw material of the coking device is reduced, and the coking device mainly comprises two modes of hydrogen and non-hydrogen.
The Chevron company Pasclagnoula refinery adopts a combined residual oil hydrodesulfurization and delayed coking process to produce low sulfur petroleum coke.
After the high-sulfur residual oil is hydrogenated by a 470 ten thousand ton/year fixed bed residual oil hydrogenation device, hydrogenated wax oil is used as FCC or hydrocracking feed, and hydrogenated slag reduction is used as delayed coking feed. After the residuum hydrogenation device is added, straight-run slag reduction in coking feed: hydrogenation residue reduction = 53%:47%, the sulfur content of the coke product is reduced from 7.3wt% to 2.5wt%, and 3B low sulfur coke can be produced, but the reaction condition of the process is more severe, and higher production cost is required.
The Flex DS process developed by Auterra corporation is a non-critical hydrogen desulfurization technique. Medium-sized tests were performed 1 month 2011 with a test apparatus throughput of 20 liters/day. The typical oil sand asphalt is used as a raw material, the sulfur content is 4.8wt percent, the total metal content is 1200ppm, and after the process treatment, the sulfur content is reduced to 2.8wt percent, and the total metal content is reduced to 500ppm. However, no subsequent report of the process has been found.
Disclosure of Invention
The invention aims to overcome the defects that the cost is high and the industrial production is not favored in the process for producing the low-sulfur petroleum coke from the residual oil raw material in the prior art.
To achieve the above object, a first aspect of the present invention provides a method of processing residuum, the method comprising:
(1) Hydrotreating a residuum feedstock to obtain a hydrogenated residuum;
(2) Introducing the hydrogenated residual oil into an oxidation desulfurization device in the presence of an oxidant to perform oxidation desulfurization reaction to obtain oxidation desulfurization generated oil;
(3) Introducing the oxidative desulfurization generated oil reaching the coking temperature into a coke tower for delayed coking treatment to obtain coke and coking oil gas;
(4) And separating the coking oil gas to obtain at least one of coking gasoline, coking diesel oil and coking wax oil.
The second aspect of the invention provides a device for processing residual oil, which comprises a hydrogenation unit, an oxidation desulfurization unit, a coke tower and a separation unit which are sequentially communicated, wherein the hydrogenation unit is provided with a residual oil raw material inlet, a hydrogen inlet and a hydrogenated residual oil outlet, and the separation unit is provided with a product oil outlet.
The method for processing residual oil provided by the invention can realize the aim of producing low-sulfur petroleum coke with low cost.
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, a first aspect of the present invention provides a process for processing residuum, the process comprising:
(1) Hydrotreating a residuum feedstock to obtain a hydrogenated residuum;
(2) Introducing the hydrogenated residual oil into an oxidation desulfurization device in the presence of an oxidant to perform oxidation desulfurization reaction to obtain oxidation desulfurization generated oil;
(3) Introducing the oxidative desulfurization-resultant oil reaching the coking temperature into a coke tower for delayed coking treatment to obtain coke (hereinafter also referred to as petroleum coke) and coking oil gas;
(4) And separating the coking oil gas to obtain at least one of coking gasoline, coking diesel oil and coking wax oil.
Preferably, the method of the present invention further comprises: in step (1), the hydrogenated oil obtained after the hydrotreatment is first separated (the present invention does not particularly require a specific operation for the separation, and a person skilled in the art may perform the method according to a known method in the art, and the present invention will not be further described herein, and the person skilled in the art should not be construed as limiting the present invention), so as to obtain the hydrogenated wax oil and the hydrogenated residual oil, respectively. Preferably, the cutting point between the hydrogenated wax oil and the hydrogenated residual oil is 500-540 ℃.
Preferably, the hydrogenated wax oil according to the invention is introduced into a catalytic cracking unit for further processing.
According to a preferred embodiment, the method further comprises, before performing said step (3), introducing said oxidative desulfurization-resultant oil obtained in step (2) into a coking furnace for heating to obtain said oxidative desulfurization-resultant oil reaching a coking temperature in step (3).
The method of the present invention may further comprise deoxidizing the oxidative desulfurization-resultant oil prior to introducing the oxidative desulfurization-resultant oil into the coking furnace for heating. The specific operation of the deoxygenation treatment is not particularly critical to the present invention and may be carried out in a manner known to those skilled in the art as long as the oxygen content of <5.0wt% target is achieved, and the operation of the deoxygenation treatment is not described in detail and should not be construed as limiting the present invention.
Preferably, in step (1), the hydrotreating conditions at least satisfy: the reaction temperature is 300-430 ℃, more preferably 370-390 ℃; the reaction pressure is 3.0-22.0MPa, more preferably 11.0-14.0MPa; volume space velocity of 0.1-3.0h -1 More preferably 0.1 to 0.8h -1 The method comprises the steps of carrying out a first treatment on the surface of the Hydrogen oil volume ratio of 300-2000Nm 3 /m 3 More preferably 400-1000Nm 3 /m 3 。
Preferably, in step (1), the hydrotreating is performed in the presence of a catalyst, and the active component element contained in the catalyst is at least one selected from the group consisting of group VIB metal elements and group VIII metal elements.
Preferably, the active component element contained in the catalyst is selected from at least one of Mo, W, ni, co, fe.
Particularly preferably, the active component element contained in the catalyst is Mo and/or Ni.
Preferably, in step (1), the support contained in the catalyst is selected from Al 2 O 3 、SiO 2 And at least one of amorphous silica-alumina, more preferably Al 2 O 3 。
Particularly preferred catalysts involved in the hydrotreatment include a hydrogenation guard catalyst, a hydrodemetallization catalyst, a hydrodesulphurisation catalyst.
Preferably, in step (2), the conditions of the oxidative desulfurization reaction at least satisfy: the reaction temperature is 30-150 ℃, more preferably 80-100 ℃; the average residence time is 2 to 60min, more preferably 5 to 20min.
According to a preferred embodiment, in step (2), the weight ratio of the amount of the oxidizing agent to the residual oil feedstock in step (1) is between 0.1 and 10:100, more preferably 0.5-5:100.
preferably, in the step (2), the oxidizing agent is at least one selected from concentrated nitric acid, hydrogen peroxide, tert-butyl peroxide and dibenzoyl peroxide; particularly preferably, in step (2), the oxidizing agent is hydrogen peroxide.
Preferably, in step (3), the condition of the delayed coking process at least satisfies: the reaction temperature is 400-550 ℃, more preferably 450-500 ℃; the reaction pressure is 0 to 0.3MPa, more preferably 0.1 to 0.2MPa; the circulation ratio is 0 to 1.0, more preferably 0.3 to 0.7.
Preferably, in step (1), the residuum feedstock is selected from at least one of an atmospheric residuum with or without light oil, a vacuum residuum with or without light oil.
Preferably, the light oil is selected from at least one of a catalytic cracking heavy cycle oil, a catalytic cracking clarified oil, and a solvent deasphalted oil.
As described above, the second aspect of the present invention provides an apparatus for processing residuum, comprising a hydrogenation unit, an oxidative desulfurization unit, a coke drum, and a separation unit, which are sequentially connected, wherein the hydrogenation unit is provided with a residuum raw material inlet, a hydrogen inlet, a hydrogenated residuum outlet, and the separation unit is provided with a product oil outlet.
Preferably, a coking heating furnace is further arranged between the oxidation desulfurization unit and the coke tower, and the coking heating furnace is respectively communicated with the oxidation desulfurization unit and the coke tower.
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 were commercially available and analytically pure.
The cut point between the hydrogenated wax oil and the hydrogenated residuum in the following examples is 530 ℃; the cutting point between the coking gasoline and the coking diesel oil is 200 ℃, and the cutting point between the coking diesel oil and the coking wax oil is 350 ℃.
The hydrotreating in the following examples was carried out in a medium fixed bed reactor with packed catalysts of a hydrogenation protecting catalyst C1, a hydrodemetallization catalyst C2, a hydrodemetallization catalyst C3 and a hydrodesulphurisation catalyst C4 in a packed volume ratio of c1:c2:c3:c4=6:32:32:30; the catalyst was purchased from medium petrochemical long-term catalyst company. Wherein the commodity brand of the catalyst C1 is RG-30B; catalyst C2 is commercially available under the trade designation RDM-201; catalyst C3 is commercially available under the trade designation RDM-202; catalyst C4 is commercially available under the trade designation RDM-53.
The properties of the residuum feedstock used in the examples below are set forth in table 1.
TABLE 1
Example 1
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 370 ℃, the reaction pressure is 11.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, and feeding the obtained hydrogenated residual oil (sulfur content is 1.2 wt%) into an oxidation desulfurization device to make oxidation desulfurization reaction under the following reaction conditions: the reaction temperature is 80 ℃; the reaction pressure is normal pressure, and the average residence time is 5min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Example 2
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: reaction temperature 370 ℃, reaction pressure 11.0MPa, and bodyVolume space velocity 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, and feeding the obtained hydrogenated residual oil (sulfur content is 1.2 wt%) into an oxidation desulfurization device to make oxidation desulfurization reaction under the following reaction conditions: the reaction temperature is 85 ℃; the reaction pressure is normal pressure, and the average residence time is 5min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Example 3
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 370 ℃, the reaction pressure is 11.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, and feeding the obtained hydrogenated residual oil (sulfur content is 1.2 wt%) into an oxidation desulfurization device to make oxidation desulfurization reaction under the following reaction conditions: the reaction temperature is 90 ℃; the reaction pressure is normal pressure, and the average residence time is 5min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Example 4
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 370 ℃, the reaction pressure is 11.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, and feeding the obtained hydrogenated residual oil (sulfur content is 1.2 wt%) into an oxidation desulfurization device to make oxidation desulfurization reaction under the following reaction conditions: the reaction temperature is 85 ℃; the reaction pressure is normal pressure, the average residence time is 10min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Example 5
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 370 ℃, the reaction pressure is 11.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, and feeding the obtained hydrogenated residual oil (sulfur content is 1.2 wt%) into an oxidation desulfurization device to make oxidation desulfurization reaction under the following reaction conditions: the reaction temperature is 85 ℃; the reaction pressure is normal pressure, and the average residence time is 15min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Example 6
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 370 ℃, the reaction pressure is 12.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, and feeding the obtained hydrogenated residual oil (sulfur content is 1.0 wt%) into an oxidation desulfurization device to make oxidation desulfurization reaction under the following reaction conditions: the reaction temperature is 85 ℃; the reaction pressure is normal pressure, and the average residence time is 10min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The petroleum coke produced is left in the cokeIn the carbon tower, the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Example 7
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 370 ℃, the reaction pressure is 13.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, and feeding the obtained hydrogenated residual oil (sulfur content is 0.7wt%) into an oxidation desulfurization device to make oxidation desulfurization reaction under the following reaction conditions: the reaction temperature is 85 ℃; the reaction pressure is normal pressure, and the average residence time is 10min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Example 8
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 370 ℃, the reaction pressure is 14.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, and feeding the obtained hydrogenated residual oil (sulfur content is 0.68 wt%) into an oxidation desulfurization device to make oxidation desulfurization reaction under the following reaction conditions: the reaction temperature is 85 ℃; the reaction pressure is normal pressure, and the average residence time is 10min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Example 9
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 380 ℃, the reaction pressure is 13.0MPa, and the volume is emptySpeed is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, and feeding the obtained hydrogenated residual oil (sulfur content is 0.48 wt%) into an oxidation desulfurization device to make oxidation desulfurization reaction under the following reaction conditions: the reaction temperature is 85 ℃; the reaction pressure is normal pressure, and the average residence time is 10min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Example 10
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 390 ℃, the reaction pressure is 13.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, and feeding the obtained hydrogenated residual oil (sulfur content is 0.46 wt%) into an oxidation desulfurization device to make oxidation desulfurization reaction under the following reaction conditions: the reaction temperature is 85 ℃; the reaction pressure is normal pressure, and the average residence time is 10min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Comparative example 1
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 380 ℃, the reaction pressure is 13.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, feeding the obtained hydrogenated residual oil (sulfur content is 0.48 wt%) into a coking heating furnace, heating to coking temperature, feeding into a coke tower for reaction, and the reaction conditions in the coke tower are as follows: the reaction temperature is 490 DEG CThe pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Comparative example 2
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 390 ℃, the reaction pressure is 13.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, feeding the obtained hydrogenated residual oil (sulfur content is 0.46 wt%) into a coking heating furnace, heating to coking temperature, feeding into a coke tower for reaction, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Comparative example 3
Hydrotreating residual oil raw materials, wherein the hydrotreating conditions are as follows: the reaction temperature is 390 ℃, the reaction pressure is 14.0MPa, and the volume space velocity is 0.2h -1 Hydrogen oil volume ratio 600Nm 3 /m 3 . Separating to obtain hydrogenated wax oil and hydrogenated residual oil, feeding the obtained hydrogenated residual oil (sulfur content is 0.44 wt%) into a coking heating furnace, heating to coking temperature, feeding into a coke tower for reaction, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
Comparative example 4
Residual oil raw materials enter an oxidation desulfurization device to carry out oxidation desulfurization reaction, and the reaction conditions are as follows: the reaction temperature is 85 ℃; the reaction pressure is normal pressure, and the average residence time is 10min; the mass ratio of the oxidant (hydrogen peroxide) to the residual oil raw material is 3.0:100. the obtained oxidative desulfurization generated oil enters a coking heating furnace, and enters a coke tower for reaction after being heated to the coking temperature, wherein the reaction conditions in the coke tower are as follows: the reaction temperature is 490 ℃, the reaction pressure is 0.15MPa, and the circulation ratio is 0.5. The generated petroleum coke is left in the coke tower, and the coking oil gas is separated to obtain coking gas, coking gasoline, coking diesel oil and coking wax oil.
The sulfur content of petroleum coke prepared in examples 1-10 and comparative examples 1-4 and the cost accounting results of the preparation process are shown in Table 2.
TABLE 2
| Examples numbering | Sulfur content of petroleum coke, wt% | Cost per ton of oil |
| Example 1 | 1.5 | 240 |
| Example 2 | 1.2 | 245 |
| Example 3 | 1.2 | 250 |
| Example 4 | 1.0 | 250 |
| Example 5 | 1.0 | 260 |
| Example 6 | 0.8 | 260 |
| Example 7 | 0.6 | 270 |
| Example 8 | 0.59 | 280 |
| Example 9 | 0.40 | 320 |
| Example 10 | 0.39 | 360 |
| Comparative example 1 | 3.6 | 270 |
| Comparative example 2 | 3.2 | 310 |
| Comparative example 3 | 2.8 | 330 |
| Comparative example 4 | 5.6 | 50 |
As can be seen from the data in Table 2, the sulfur content of the petroleum coke prepared by the process of the present invention is less than 1.5wt%, and the sulfur contents of the petroleum coke obtained in example 9 and example 10 are 0.40wt% and 0.39wt%, respectively, which meet the standard of No. 1 low sulfur coke, while the sulfur content of the petroleum coke obtained in comparative example 3 is 2.8wt%, which meets the standard of low sulfur coke.
In addition, the comparative example is significantly higher in production cost than the example. Therefore, the process of the invention can realize low-cost production of high-value low-sulfur petroleum coke.
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 (15)
1. A method of processing residuum, the method comprising:
(1) Hydrotreating a residuum feedstock to obtain a hydrogenated residuum;
(2) Introducing the hydrogenated residual oil into an oxidation desulfurization device in the presence of an oxidant to perform oxidation desulfurization reaction to obtain oxidation desulfurization generated oil;
(3) Introducing the oxidative desulfurization generated oil reaching the coking temperature into a coke tower for delayed coking treatment to obtain coke and coking oil gas;
(4) Separating the coking oil gas to obtain at least one of coking gasoline, coking diesel oil and coking wax oil;
in step (1), the hydrotreating conditions at least satisfy: the reaction temperature is 370-390 ℃, the reaction pressure is 11.0-14.0MPa, and the volume space velocity is 0.1-0.8h -1 Hydrogen oil volume ratio of 400-1000Nm 3 /m 3 ；
In the step (2), the conditions of the oxidative desulfurization reaction at least satisfy: the reaction temperature is 80-100 ℃; the average residence time is 5-20min.
2. The method for processing residuum as claimed in claim 1 further comprising, prior to said step (3), introducing said oxidatively desulfurized resulting oil from step (2) into a coking furnace for heating to obtain said oxidatively desulfurized resulting oil that reaches a coking temperature of step (3).
3. The method for processing residuum as claimed in claim 1 or 2, wherein in step (1), the hydrotreating is performed in the presence of a catalyst containing an active component element selected from at least one of group VIB metal elements, group VIII metal elements.
4. The method for processing residuum as claimed in claim 3 wherein the active component element contained in the catalyst is selected from at least one of Mo, W, ni, co, fe.
5. The method for processing residuum as claimed in claim 3 wherein the active component element contained in the catalyst is Mo and/or Ni.
6. A method of processing residuum as claimed in claim 3 wherein in step (1) the support contained in the catalyst is selected from the group consisting of Al 2 O 3 、SiO 2 And at least one of amorphous silica-alumina.
7. The method for processing residuum as claimed in claim 6 wherein in step (1), the carrier contained in the catalyst is Al 2 O 3 。
8. The process for processing resid of claim 1 or 2, wherein in step (2) the weight ratio of the oxidant to the resid feed in step (1) is from 0.1 to 10:100.
9. the process for processing resid of claim 1 or 2, wherein in step (2) the weight ratio of the oxidant to the resid feed in step (1) is in the range of 0.5 to 5:100.
10. the method of processing residuum as claimed in claim 1 or 2, wherein in step (2), the oxidizing agent is selected from at least one of concentrated nitric acid, hydrogen peroxide, t-butyl peroxide, dibenzoyl peroxide.
11. The method of processing residuum as claimed in claim 1 or 2 wherein in step (2) the oxidizing agent is hydrogen peroxide.
12. The method of processing residuum as claimed in claim 1 or 2 wherein in step (3) the condition of the delayed coking treatment is at least: the reaction temperature is 400-550 ℃, the reaction pressure is 0-0.3MPa, and the circulation ratio is 0-1.0.
13. The method of processing residuum as claimed in claim 1 or 2 wherein in step (3) the condition of the delayed coking treatment is at least: the reaction temperature is 450-500 ℃; the reaction pressure is 0.1-0.2MPa; the circulation ratio is 0.3-0.7.
14. The method for processing residuum according to claim 1 or 2, wherein in step (1), the residuum feedstock is selected from at least one of an atmospheric residuum with or without light oil, a vacuum residuum with or without light oil.
15. The method of processing residuum of claim 14 wherein the light oil is selected from at least one of a catalytically cracked heavy cycle oil, a catalytically cracked clarified oil, and a solvent deasphalted oil.
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