CN111410978A - Device and method for preparing petroleum coke from high-metal-content raw oil - Google Patents
Device and method for preparing petroleum coke from high-metal-content raw oil Download PDFInfo
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- CN111410978A CN111410978A CN202010300009.XA CN202010300009A CN111410978A CN 111410978 A CN111410978 A CN 111410978A CN 202010300009 A CN202010300009 A CN 202010300009A CN 111410978 A CN111410978 A CN 111410978A
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B55/00—Coking mineral oils, bitumen, tar, and the like or mixtures thereof with solid carbonaceous material
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
- C10B57/00—Other carbonising or coking processes; Features of destructive distillation processes in general
- C10B57/02—Multi-step carbonising or coking processes
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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
- C10G7/00—Distillation of hydrocarbon oils
Abstract
The invention provides a device and a method for preparing petroleum coke from high-metal-content raw oil, wherein the device comprises a primary coking unit, a secondary coking unit and a fractionating unit, wherein a top outlet of the primary coking unit is connected with an inlet of the secondary coking unit, a top outlet of the secondary coking unit is connected with an inlet of the fractionating unit, and a bottom outlet of the fractionating unit is connected with an inlet of the secondary coking unit; each stage of coking unit comprises a preheating device and a coke drum, and the outlet of the preheating device is connected with the inlet of the coke drum. According to the invention, raw oil with high metal content is used as a raw material, and decomposition and removal are carried out by utilizing the chemical characteristics of the raw oil according to the existence form of metal components in the raw oil through the arrangement of two stages of coking units, so as to prepare high-quality petroleum coke meeting the technical requirements; the device has the advantages of simple structure, low equipment cost, simple and convenient operation of the method, good adaptability to raw materials, expanded operation flexibility of production enterprises, improved economic benefit and suitability for large-scale application.
Description
Technical Field
The invention belongs to the technical field of petroleum coking, and relates to a device and a method for preparing petroleum coke from high-metal-content raw oil.
Background
Petroleum coke, as a petroleum product, including ordinary petroleum coke, acicular petroleum coke and the like, is a main raw material of an ordinary power graphite electrode for steelmaking or a prebaked anode for electrolytic aluminum, however, at present, few enterprises capable of producing petroleum coke are available, so that the cost is high, and the application of the petroleum coke in the steelmaking and electrolytic aluminum industries is limited.
At present, the main factor influencing the quality of petroleum coke is the high metal content in the raw materials of a delayed coking device, so that the metal content in the petroleum coke produced by the process cannot meet the technical requirements of high-quality petroleum coke, and the production process of the petroleum coke needs to be improved. CN 102634361A discloses a preparation method of needle petroleum coke, which comprises the steps of putting petroleum paraffin base or naphthenic base heavy raw materials into a test tube, then placing the test tube into a tubular reaction kettle, pressurizing and sealing inert gas, preheating the reaction kettle, then heating to the carbonization temperature of 430-480 ℃, discharging gas to the initial pressure at intervals, measuring the volume of the discharged gas, and carbonizing for 12-18 h at the temperature after the gas volume is less than 10-20 ml/10min to obtain needle coke with complete coke blocks; however, the raw material used in the method does not relate to the treatment of metal components, the metal content of the raw material oil used in the method is high, the quality of petroleum coke obtained is greatly influenced, the steps of the method are numerous, the operating conditions need to be finely controlled, and the method is not suitable for large-scale production and application.
CN 1315490a discloses a method for producing acicular petroleum coke from atmospheric residue, which comprises subjecting atmospheric residue and cycle oil generated in the coking process to mild heat treatment, separating the generated light fraction from coking oil gas, heating the rest heavy fraction, introducing into a coke tower, leaving the generated coke in the coke tower, and separating the coking oil gas in a fractionating tower. CN 1325938A discloses a method for producing acicular petroleum coke from sulfur-containing atmospheric residue, which comprises the steps of sequentially carrying out hydrofining, hydrodemetallization and hydrodesulfurization on the sulfur-containing atmospheric residue, separating and hydrogenating to generate oil, obtaining hydrogenated heavy distillate oil, entering the hydrogenated heavy distillate oil into a delayed coking device, and then generating the acicular coke in a coke tower. In the above patent, the former also does not mention whether the raw oil contains metal and how to treat the raw oil, and the pretreatment hydrogenation operation in the latter not only increases the equipment and operation cost, but also makes the light fraction more active and increases the difficulty of subsequent processing.
For the treatment of raw oil with high metal content, at present, two processes are mainly used, namely, electric desalting operation, but the metal removal effect is poor based on the existence form of metal in the oil, and secondary problems such as corrosion and the like are brought to a production device; and secondly, a residual oil hydrogenation process is added before the delayed coking process to remove metal impurities in the raw materials, but the processing cost is increased sharply and the subsequent treatment difficulty is increased, so that a new method is required to be searched for the treatment of the raw oil with high metal content to reduce the difficulty of removing metal components so as to obtain high-quality petroleum coke.
Disclosure of Invention
Aiming at the problems in the prior art, the invention aims to provide a device and a method for preparing petroleum coke from high-metal-content raw oil, wherein the device is provided with a two-stage coking unit, and the metal component in the raw oil is removed by utilizing the characteristic of the metal component, so that a high-quality petroleum coke product is prepared; the device has the advantages of simple structure, simple and convenient operation method, low equipment and operation cost and suitability for large-scale application.
In order to achieve the purpose, the invention adopts the following technical scheme:
in one aspect, the invention provides a device for preparing petroleum coke from high-metal-content raw oil, which comprises a primary coking unit, a secondary coking unit and a fractionation unit, wherein a top outlet of the primary coking unit is connected with an inlet of the secondary coking unit, a top outlet of the secondary coking unit is connected with an inlet of the fractionation unit, and a bottom outlet of the fractionation unit is connected with an inlet of the secondary coking unit; each stage of coking unit comprises a preheating device and a coke drum, wherein the outlet of the preheating device is connected with the inlet of the coke drum.
According to the invention, the device takes high-metal-content raw oil as a raw material, through the arrangement of two-stage coking units, metal components in the raw oil are firstly removed, and the raw oil is decomposed and removed by utilizing the chemical characteristics according to the existence form of the metal components in the raw oil, so that the raw oil is prevented from entering petroleum coke products, and thus high-quality petroleum coke with low metal content is prepared and obtained, and the technical requirement of the petroleum coke is met; the oil gas component of the coking unit is fractionated to obtain a plurality of distillate oil, so that the utilization value of the raw material residual oil is greatly improved; the device has simple structure, does not need to add additional devices, has lower equipment cost and reduces the production cost of petroleum coke products.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferable technical scheme of the invention, the preheating device comprises a heating furnace.
Preferably, the furnace comprises a convection section and a radiant section.
As a preferable technical scheme, the primary coking unit comprises a first preheating device and a first coke drum, the secondary coking unit comprises a second preheating device and a second coke drum, and the top outlet of the first coke drum is connected with the inlet of the second preheating device.
Preferably, the fractionation unit comprises a fractionation column, and a bottom outlet of the fractionation column is connected to an inlet of the second preheating device.
According to the invention, the coking oil gas of the primary coking unit is mixed with the circulating oil at the bottom of the fractionation unit, the coking oil gas can be subjected to primary heating by using the heat at the bottom of the fractionation unit, and the circulating oil is subjected to coking reaction again, so that the utilization rate of raw oil is improved, and the yield of petroleum coke is improved.
In another aspect, the present invention provides a method for preparing petroleum coke from high metal content raw oil, wherein the method is performed by using the above apparatus, and comprises the following steps:
(1) preheating the high-metal content raw oil, and then carrying out mild thermal cracking to obtain coke and first-stage coking oil gas;
(2) the first-stage coking oil gas obtained in the step (1) is heated again to carry out cracking and coking reaction to obtain petroleum coke and second-stage coking oil gas;
(3) and (3) fractionating the secondary coking oil gas obtained in the step (2) to obtain gas, light oil and heavy oil, and returning part of the heavy oil to the step (2) for reaction.
As a preferred technical scheme of the invention, the high metal content raw oil in the step (1) comprises any one or a combination of at least two of atmospheric residue, vacuum residue, ethylene tar, furfural extract oil or fuel oil, and typical but non-limiting examples of the combination include: the combination of the atmospheric residue oil and the vacuum residue oil, the combination of the vacuum residue oil and the ethylene tar, the combination of the atmospheric residue oil, the furfural extract oil and the fuel oil, the combination of the atmospheric residue oil, the vacuum residue oil, the ethylene tar and the furfural extract oil, and the like.
In the invention, the raw oil is mainly selected from raw materials capable of preparing low-sulfur petroleum coke, and various residual oils obtained in the petroleum refining process can be selected in the range, so that waste is changed into valuable, and the full utilization of residual oil components is realized.
Preferably, the metal content in the feed oil is 200 to 1000ppm, for example 200ppm, 300ppm, 400ppm, 500ppm, 600ppm, 700ppm, 800ppm, 900ppm or 1000ppm, but not limited to the recited values, and other values not recited in the above range are also applicable.
Preferably, the metal components in the feedstock oil include vanadium, iron, calcium, nickel and sodium.
In the invention, the metal content in the raw oil reaches the value, and if the raw oil is not removed first, the quality of petroleum coke products is greatly influenced; meanwhile, due to the composition characteristics of the raw oil, the metal component mainly exists in the form of organic metal salt compounds, such as naphthenate, fatty acid salt, phenolate and the like, so that the metal removal is carried out in a mode suitable for removing the organic metal salt.
Preferably, the raw oil takes steam as a conveying gas.
In the invention, because the raw oil is generally in a liquid state and is viscous and not easy to flow quickly in a pipeline, the gas is adopted as the conveying gas to be conveyed under the driving action of the conveying gas, and the steam is convenient to recover and low in energy consumption, and can also be used as the steam injection of a device and a pipeline simultaneously to avoid the influence on material conveying caused by coke formation in the pipeline.
As the preferable technical scheme of the invention, the preheating in the step (1) is carried out in a first preheating device, and the heating furnace selected by the invention comprises a convection section and a radiation section, namely, the raw oil sequentially flows through the convection section and the radiation section to be heated.
Preferably, the preheated raw oil in step (1) has a temperature of 420 to 480 ℃, for example, 420 ℃, 430 ℃, 440 ℃, 450 ℃, 460 ℃, 470 ℃ or 480 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, said mild thermal cracking of step (1) is conducted in a first coke drum.
Preferably, the reaction pressure in the first coke drum is 0.2 to 1.0MPa, for example, 0.2MPa, 0.3MPa, 0.4MPa, 0.5MPa, 0.6MPa, 0.8MPa, or 1.0MPa, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
Preferably, the residence time in the first coke drum is 0.1 to 12 hours, such as 0.1 hour, 0.5 hour, 1 hour, 2 hours, 4 hours, 6 hours, 8 hours, 10 hours, or 12 hours, but is not limited to the recited values, and other values not recited in this range are equally applicable.
In the invention, proper reaction temperature and pressure are selected according to the composition and the property of the raw oil, and then the reaction residence time is determined; because the primary coking oil gas generated in the first coke tower needs to enter the secondary coking unit by means of self-pressure, the required pressure needs to be higher, but the pressure is not too high to influence the reaction in the first coke tower, so that the yield of the coke is too high.
Preferably, water or steam is injected into the raw oil during the preheating in step (1), and the injection amount is 0 to 20 wt% of the mass of the raw oil, for example, 0, 2 wt%, 5 wt%, 8 wt%, 10 wt%, 13 wt%, 16 wt%, or 20 wt%, but is not limited to the above-mentioned values, and other values not listed in the above-mentioned range are also applicable.
According to the reaction parameters, the device and the pipeline can be injected with water or steam to reduce coke formation in the pipeline and the furnace tube and avoid influencing normal operation.
As a preferred technical scheme of the invention, after the mild thermal cracking in the step (1), the metal components in the raw oil are enriched in the coke product.
Preferably, the content of each metal in the first-stage coker oil gas in step (1) is not more than 50ppm, such as 50ppm, 45ppm, 40ppm, 35ppm, 30ppm, 25ppm, 20ppm, 15ppm or 10ppm, but is not limited to the recited values, and other unrecited values in the range of values are also applicable.
Preferably, the coke yield of step (1) is 1% to 5%, such as 5%, 4.5%, 4%, 3.5%, 3%, 2.5%, 2%, 1.5%, or 1%, but not limited to the recited values, and other values not recited within the range are equally applicable.
According to the invention, through mild thermal cracking in the primary coke tower, the chemical characteristics of metal impurities such as naphthenate and metal porphyrin compounds are utilized, the metal impurities are decomposed in a heat treatment mode, most of the impurities are decomposed into a form of sulfide or oxide, the existing form is more stable, and metal-containing components are enriched in byproduct coke under the process condition; therefore, the yield of the coke also influences the production of subsequent products, and if the yield of the coke is too high, the yield of the first-stage coking oil gas is reduced, and further the yield of high-quality petroleum coke is reduced, so that resource waste is caused, and economic benefits are influenced; if the coke yield is too low, the metal components are not completely removed and cannot be sufficiently introduced into the coke.
As the preferable technical scheme of the invention, the first-stage coking oil gas in the step (2) enters a second preheating device for heating.
In the invention, the coking oil gas of the primary coking unit is mixed with the circulating oil at the bottom of the fractionating unit, and the heat of the circulating oil at the bottom of the fractionating unit can be utilized to carry out primary heating.
Preferably, the outlet temperature after heating by the second preheating device is 490 to 520 ℃, for example 490 ℃, 495 ℃, 500 ℃, 505 ℃, 510 ℃, 515 ℃ or 520 ℃, but is not limited to the recited values, and other values not recited in the range of the values are also applicable.
Preferably, the cracking and coking reaction of step (2) is carried out in a second coke drum.
Preferably, the reaction pressure in the second coke drum is 0.1 to 0.2MPa, for example, 0.1MPa, 0.12MPa, 0.14MPa, 0.16MPa, 0.18MPa or 0.2MPa, but is not limited to the recited values, and other values not recited in the numerical range are also applicable.
According to the method, the proper reaction temperature is selected according to the composition and the property of the first-stage coking oil gas, the coking of a furnace tube is avoided, the pressure is adjusted according to the index requirement of the petroleum coke in the second-stage coke tower, so that the indexes of volatile matters and the like of the petroleum coke meet the standard requirement, and the yield of high-quality petroleum coke is adjusted.
Preferably, the residence time in the second coke drum is 16 to 24 hours, such as 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, or 24 hours, but not limited to the recited values, and other values not recited in this range are equally applicable.
Preferably, water or steam is injected into the feed during the reheating in step (2), and the injected amount is 0 to 20 wt% of the feed, such as 0, 2 wt%, 5 wt%, 8 wt%, 10 wt%, 13 wt%, 16 wt% or 20 wt%, but not limited to the recited values, and other unrecited values in the range of values are also applicable.
Preferably, the recycle ratio of the second coke drum is 0.1 to 1.0, such as 0.1, 0.2, 0.3, 0.4, 0.5, 0.6, 0.8, or 1.0, but not limited to the recited values, and other values not recited within this range are equally applicable.
In the invention, the material entering the second preheating device comprises two parts, wherein one part is first-stage coking oil gas, the other part is bottom fraction returning of the fractionating unit, the circulation ratio is the ratio of the latter to the former, and the retention time and the circulation ratio are adjusted according to the properties of the raw materials and relevant process parameters to obtain high-quality petroleum coke meeting the requirements; the mode of water injection or steam injection is adopted to reduce the coke formation in the pipeline and the furnace tube so as to avoid influencing the normal operation.
Preferably, the petroleum coke of step (2) is agglomerated in a second coke drum.
As a preferred embodiment of the present invention, the fractionation in the step (3) is carried out in a fractionating column.
Preferably, the light oil of step (3) comprises gasoline and diesel.
Preferably, the heavy oil in the step (3) comprises wax oil and bottom circulating oil, the circulating oil is mixed with the primary coking oil gas to perform the reaction in the step (2), and the circulating oil is subjected to coking reaction again, so that the utilization rate of the raw oil is improved, and the petroleum coke yield is improved.
According to the invention, raw oil can also obtain mixed oil-gas components besides petroleum coke, different fractions are obtained by separating different positions of a fractionating tower through the fractionation operation by utilizing different boiling points of the raw oil, and the raw oil is sequentially gas, gasoline, diesel oil, wax oil and bottom circulating oil from top to bottom, wherein the bottom circulating oil mainly comprises heavy wax oil.
On the other hand, the invention also provides the petroleum coke prepared by the method, and the performance of the petroleum coke meets the requirements of the petroleum coke industry standard NB/SH/T0527-2015 petroleum coke (green coke), and is not lower than the performance of the ordinary petroleum coke No. 1 required by the standard.
Compared with the prior art, the invention has the following beneficial effects:
(1) according to the invention, raw oil with high metal content is used as a raw material, and decomposition and removal are carried out by utilizing the chemical characteristics of the raw oil according to the existence form of metal components in the raw oil through the arrangement of two-stage coking units, so that the raw oil is prevented from entering petroleum coke products, and high-quality petroleum coke meeting the technical requirements is prepared;
(2) the oil gas component obtained by two-stage coking is fractionated to obtain various distillate oil, so that the utilization value of the raw material residual oil is greatly improved;
(3) the device has the advantages of simple structure, simple and convenient operation method, low equipment and operation cost, reduction of the production cost of petroleum coke products and suitability for large-scale application.
Drawings
FIG. 1 is a schematic structural diagram of an apparatus for preparing petroleum coke from a high metal content feedstock oil according to example 1 of the present invention;
wherein, 1-the first preheating device, 2-the first coke tower, 3-the second preheating device, 4-the second coke tower, and 5-the fractionating tower.
Detailed Description
In order to better illustrate the present invention and facilitate the understanding of the technical solutions of the present invention, the present invention is further described in detail below. However, the following examples are only simple examples of the present invention and do not represent or limit the scope of the present invention, which is defined by the claims.
The invention provides a device and a method for preparing petroleum coke from high-metal-content raw oil, wherein the device comprises a primary coking unit, a secondary coking unit and a fractionation unit, wherein a top outlet of the primary coking unit is connected with an inlet of the secondary coking unit, a top outlet of the secondary coking unit is connected with an inlet of the fractionation unit, and a bottom outlet of the fractionation unit is connected with an inlet of the secondary coking unit; each stage of coking unit comprises a preheating device and a coke drum, wherein the outlet of the preheating device is connected with the inlet of the coke drum.
The method comprises the following steps:
(1) preheating the high-metal content raw oil, and then carrying out mild thermal cracking to obtain coke and first-stage coking oil gas;
(2) the first-stage coking oil gas obtained in the step (1) is heated again to carry out cracking and coking reaction to obtain petroleum coke and second-stage coking oil gas;
(3) and (3) fractionating the secondary coking oil gas obtained in the step (2) to obtain gas, light oil and heavy oil, and returning part of the heavy oil to the step (2) for reaction.
The following are typical but non-limiting examples of the invention:
example 1:
the embodiment provides a device for preparing petroleum coke from high-metal-content raw oil, the structural schematic diagram of the device is shown in figure 1, and the device comprises a primary coking unit, a secondary coking unit and a fractionation unit, wherein a top outlet of the primary coking unit is connected with an inlet of the secondary coking unit, a top outlet of the secondary coking unit is connected with an inlet of the fractionation unit, and a bottom outlet of the fractionation unit is connected with an inlet of the secondary coking unit;
each stage of coking unit comprises a preheating device and a coke drum, wherein the outlet of the preheating device is connected with the inlet of the coke drum.
The primary coking unit comprises a first preheating device 1 and a first coke drum 2, the secondary coking unit comprises a second preheating device 3 and a second coke drum 4, and the top outlet of the first coke drum 2 is connected with the inlet of the second preheating device 3.
The preheating device comprises a heating furnace, and the heating furnace comprises a convection section and a radiation section.
The fractionating unit comprises a fractionating tower 5, and the bottom outlet of the fractionating tower 5 is connected with the inlet of the second preheating device 3.
Example 2:
this example provides a method for preparing petroleum coke from high metal content feedstock oil, using the apparatus of example 1, comprising the steps of:
(1) preheating an atmospheric residue raw material with the metal content of 513.4ppm to 420 ℃, allowing the raw material to enter a first coke tower 2 for mild thermal cracking, wherein the reaction pressure in the first coke tower 2 is 0.5MPa, the retention time is 12 hours, coke and first-stage coking oil gas are obtained, and the metal components are enriched in the coke;
(2) heating the primary coking oil gas obtained in the step (1) to 490 ℃ in a second heating furnace, allowing the primary coking oil gas to enter a second coke tower 4 for cracking and coking reaction, wherein the reaction pressure in the second coke tower 4 is 0.1MPa, the retention time is 24h, and the circulation ratio is 0.1, so as to obtain high-quality petroleum coke and secondary coking oil gas;
(3) and (3) fractionating the secondary coking oil gas obtained in the step (2) to obtain gas, gasoline, diesel oil, wax oil and bottom circulating oil, and returning the circulating oil to the step (2) to be mixed with the primary coking oil gas for reaction.
Example 3:
this example provides a method for preparing petroleum coke from high metal content feedstock oil, using the apparatus of example 1, comprising the steps of:
(1) preheating a vacuum residue raw material with the metal content of 745.1ppm to 450 ℃, allowing the raw material to enter a first coke tower 2 for mild thermal cracking, wherein the reaction pressure in the first coke tower 2 is 0.2MPa, the retention time is 3h, the water injection amount accounts for 5 wt% of the raw material oil mass, coke and first-stage coking oil gas are obtained, and the metal components are enriched in the coke;
(2) heating the primary coking oil gas obtained in the step (1) to 505 ℃ in a second heating furnace, allowing the primary coking oil gas to enter a second coke tower 4 for cracking and coke formation reaction, wherein the reaction pressure in the second coke tower 4 is 0.15MPa, the retention time is 18h, the circulation ratio is 0.5, and the water injection amount accounts for 10 wt% of the feeding amount, so that high-quality petroleum coke and secondary coking oil gas are obtained;
(3) and (3) fractionating the secondary coking oil gas obtained in the step (2) to obtain gas, gasoline, diesel oil, wax oil and bottom circulating oil, and returning the circulating oil to the step (2) to be mixed with the primary coking oil gas for reaction.
Example 4:
this example provides a method for preparing petroleum coke from high metal content feedstock oil, using the apparatus of example 1, comprising the steps of:
(1) preheating ethylene tar raw oil with metal content of 683.2ppm to 480 ℃, allowing the ethylene tar raw oil to enter a first coke tower 2 for mild thermal cracking, wherein the reaction pressure in the first coke tower 2 is 1.0MPa, the retention time is 0.2h, the water injection amount accounts for 20 wt% of the raw oil mass, coke and first-stage coking oil gas are obtained, and the metal components are enriched in the coke;
(2) heating the primary coking oil gas obtained in the step (1) to 520 ℃ in a second heating furnace, allowing the primary coking oil gas to enter a second coke tower 4 for cracking and coking reaction, wherein the reaction pressure in the second coke tower 4 is 0.2MPa, the retention time is 16h, the circulation ratio is 0.5, and the water injection amount accounts for 20 wt% of the feeding amount, so that high-quality petroleum coke and secondary coking oil gas are obtained;
(3) and (3) fractionating the secondary coking oil gas obtained in the step (2) to obtain gas, gasoline, diesel oil, wax oil and bottom circulating oil, and returning the circulating oil to the step (2) to be mixed with the primary coking oil gas for reaction.
Example 5:
this example provides a method for preparing petroleum coke from high metal content feedstock oil, using the apparatus of example 1, comprising the steps of:
(1) preheating vacuum residue oil raw oil with the metal content of 265.3ppm to 440 ℃, allowing the vacuum residue oil raw oil to enter a first coke tower 2 for mild thermal cracking, wherein the reaction pressure in the first coke tower 2 is 0.35MPa, the retention time is 6h, the water injection amount accounts for 10 wt% of the raw oil mass, coke and first-stage coking oil gas are obtained, and the metal components are enriched in the coke;
(2) heating the primary coking oil gas obtained in the step (1) to 500 ℃ in a second heating furnace, allowing the primary coking oil gas to enter a second coke tower 4 for cracking and coking reaction, wherein the reaction pressure in the second coke tower 4 is 0.12MPa, the retention time is 18h, the circulation ratio is 0.8, and the water injection amount accounts for 15 wt% of the feeding amount, so that high-quality petroleum coke and secondary coking oil gas are obtained;
(3) and (3) fractionating the secondary coking oil gas obtained in the step (2) to obtain gas, gasoline, diesel oil, wax oil and bottom circulating oil, and returning the circulating oil to the step (2) to be mixed with the primary coking oil gas for reaction.
Example 6:
this example provides a method for preparing petroleum coke from high metal content feedstock oil, using the apparatus of example 1, comprising the steps of:
(1) preheating raw vacuum residue oil with metal content of 955.1ppm to 460 ℃, allowing the raw vacuum residue oil to enter a first coke tower 2 for mild thermal cracking, wherein the reaction pressure in the first coke tower 2 is 0.7MPa, the retention time is 9h, the water injection amount accounts for 15 wt% of the raw oil mass, coke and first-stage coking oil gas are obtained, and the metal components are enriched in the coke;
(2) heating the primary coking oil gas obtained in the step (1) to 510 ℃ in a second heating furnace, allowing the primary coking oil gas to enter a second coke tower 4 for cracking and coking reaction, wherein the reaction pressure in the second coke tower 4 is 0.16MPa, the retention time is 22h, the circulation ratio is 0.3, and the water injection amount accounts for 9 wt% of the feeding amount, so that high-quality petroleum coke and secondary coking oil gas are obtained;
(3) and (3) fractionating the secondary coking oil gas obtained in the step (2) to obtain gas, gasoline, diesel oil, wax oil and bottom circulating oil, and returning the circulating oil to the step (2) to be mixed with the primary coking oil gas for reaction.
Comparative example 1:
this comparative example provides an apparatus and process for making petroleum coke from a high metal content feedstock oil, with reference to the apparatus of example 1, except that: the apparatus does not include a primary coking unit.
The process was carried out using the apparatus of this comparative example, with reference to the process of example 3, with the only difference that: does not comprise the step (1), and directly prepares petroleum coke from raw oil.
In the above examples, the properties of the feedstock oils used in examples 2 to 6 are shown in Table 1; the metal content of the first-stage coker gas oil obtained in step (1) of examples 2 to 6 was measured, and the results are shown in table 2; the properties of the petroleum cokes obtained in examples 2 to 6 and comparative example 1 were analyzed, and the results are shown in table 3.
TABLE 1 Properties of the feed oils described in examples 2-6
Table 2 metals content in first stage coker gas oils as described in examples 2-6
TABLE 3 Properties of Petroleum cokes obtained in examples 2-6 and comparative example 1
As can be seen from the comparison of the contents of metal elements such as vanadium, iron, calcium, nickel, sodium and the like in the first-stage coking oil gas in the table 2 with the contents of corresponding elements in the raw oil in the table 1, the content of metal in the raw oil is obviously reduced through mild thermal cracking reaction, and the content of each metal element in the first-stage coking oil gas can be reduced to below 30 ppm; as can be seen from the analysis of the properties of the petroleum coke in the example in table 3, each index of the petroleum coke satisfies the quality requirement of No. 1 petroleum coke, and particularly, the index of the content of metal elements is obviously superior to the requirement of No. 1 petroleum coke, and the petroleum coke has the characteristics of high-quality petroleum coke; the content index of the metal elements in the comparative example 1 obviously does not meet the quality requirement of No. 1 petroleum coke, and the performance is poorer.
It can be seen from the above examples and comparative examples that the invention takes high metal content raw oil as raw material, through the arrangement of two-stage coking units, according to the existence form of metal components in the raw oil, the chemical properties are utilized to decompose and remove, thereby preventing the raw oil from entering into petroleum coke products, and thus preparing high quality petroleum coke meeting technical requirements; the device has the advantages of simple structure, low equipment and operation cost, simple and convenient operation of the method, good adaptability to raw materials, expanded operation flexibility of production enterprises, improved economic benefit and suitability for large-scale application.
The applicant states that the present invention is illustrated by the detailed apparatus and method of the present invention through the above embodiments, but the present invention is not limited to the above detailed apparatus and method, i.e. it is not meant to imply that the present invention must be implemented by the above detailed apparatus and method. It will be apparent to those skilled in the art that any modifications to the present invention, equivalents of the means for substitution and addition of means for carrying out the invention, selection of specific means, etc., are within the scope and disclosure of the invention.
Claims (10)
1. The device for preparing the petroleum coke from the high-metal-content raw oil is characterized by comprising a primary coking unit, a secondary coking unit and a fractionation unit, wherein a top outlet of the primary coking unit is connected with an inlet of the secondary coking unit, a top outlet of the secondary coking unit is connected with an inlet of the fractionation unit, and a bottom outlet of the fractionation unit is connected with an inlet of the secondary coking unit; each stage of coking unit comprises a preheating device and a coke drum, wherein the outlet of the preheating device is connected with the inlet of the coke drum.
2. The apparatus of claim 1, wherein the preheating means comprises a furnace;
preferably, the furnace comprises a convection section and a radiant section.
3. The apparatus of claim 1 or 2, wherein the primary coking unit comprises a first preheater and a first coke drum, the secondary coking unit comprises a second preheater and a second coke drum, and the top outlet of the first coke drum is connected to the inlet of the second preheater;
preferably, the fractionation unit comprises a fractionation column, and a bottom outlet of the fractionation column is connected to an inlet of the second preheating device.
4. A method for producing petroleum coke using the apparatus of any one of claims 1-3, wherein the method comprises the steps of:
(1) preheating the high-metal content raw oil, and then carrying out mild thermal cracking to obtain coke and first-stage coking oil gas;
(2) the first-stage coking oil gas obtained in the step (1) is heated again to carry out cracking and coking reaction to obtain petroleum coke and second-stage coking oil gas;
(3) and (3) fractionating the secondary coking oil gas obtained in the step (2) to obtain gas, light oil and heavy oil, and returning part of the heavy oil to the step (2) for reaction.
5. The method according to claim 4, wherein the high metal content raw oil of step (1) comprises any one of or a combination of at least two of atmospheric residue, vacuum residue, ethylene tar, furfural extract oil or fuel oil;
preferably, the metal content in the high-metal-content raw oil is 200-1000 ppm;
preferably, the metal components in the raw oil comprise vanadium, iron, calcium, nickel and sodium;
preferably, the raw oil takes steam as a conveying gas.
6. The method according to claim 4 or 5, wherein said preheating of step (1) is performed in a first preheating device;
preferably, the temperature of the preheated raw oil in the step (1) is 420-480 ℃;
preferably, said mild thermal cracking of step (1) is conducted in a first coke drum;
preferably, the reaction pressure in the first coke tower is 0.2-1.0 MPa;
preferably, the residence time in the first coke tower is 0.1-12 h;
preferably, water or steam is injected into the raw oil during preheating in the step (1), and the injection amount accounts for 0-20 wt% of the mass of the raw oil.
7. The process of any of claims 4-6, wherein after said mild thermal cracking of step (1), the metal components in the feedstock oil are enriched in the coke product;
preferably, the content of each metal in the first-stage coking oil gas in the step (1) is not more than 50 ppm;
preferably, the yield of the coke in the step (1) is 1-5%.
8. The method of any one of claims 4-7, wherein the primary coker hydrocarbon of step (2) is heated in a second preheater;
preferably, the outlet temperature of the second preheating device after heating is 490-520 ℃;
preferably, the cracking and coking reaction of step (2) is carried out in a second coke drum;
preferably, the reaction pressure in the second coke tower is 0.1-0.2 MPa;
preferably, the residence time in the second coke tower is 16-24 h;
preferably, water or steam is injected into the feeding material when the heating in the step (2) is carried out again, wherein the injection amount accounts for 0-20 wt% of the feeding amount;
preferably, the circulation ratio of the second coke drum is 0.1-1.0;
preferably, the petroleum coke of step (2) is agglomerated in a second coke drum.
9. The process of any of claims 4-8, wherein said fractionating of step (3) is performed in a fractionation column;
preferably, the light oil of step (3) comprises gasoline and diesel;
preferably, the heavy oil in the step (3) comprises wax oil and bottom cycle oil, and the cycle oil is mixed with the first-stage coking oil gas to perform the reaction in the step (2).
10. A petroleum coke produced by the process of any one of claims 4 to 9.
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| US4481101A (en) * | 1981-01-13 | 1984-11-06 | Mobil Oil Corporation | Production of low-metal and low-sulfur coke from high-metal and high-sulfur resids |
| CN1297979A (en) * | 1999-12-01 | 2001-06-06 | 中国石油化工集团公司 | Method of producing acicular petroleum coke from residual oil |
| CN101724420A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Production method of needle coke raw material |
| CN101987966A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for removing nickel and vanadium from residual oil |
| CN104804764A (en) * | 2014-01-26 | 2015-07-29 | 中石化洛阳工程有限公司 | Delayed coking method |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4481101A (en) * | 1981-01-13 | 1984-11-06 | Mobil Oil Corporation | Production of low-metal and low-sulfur coke from high-metal and high-sulfur resids |
| CN1297979A (en) * | 1999-12-01 | 2001-06-06 | 中国石油化工集团公司 | Method of producing acicular petroleum coke from residual oil |
| CN101724420A (en) * | 2008-10-28 | 2010-06-09 | 中国石油化工股份有限公司 | Production method of needle coke raw material |
| CN101987966A (en) * | 2009-07-30 | 2011-03-23 | 中国石油化工股份有限公司石油化工科学研究院 | Method for removing nickel and vanadium from residual oil |
| CN104804764A (en) * | 2014-01-26 | 2015-07-29 | 中石化洛阳工程有限公司 | Delayed coking method |
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Application publication date: 20200714 |