WO2024060685A1 - Procédé et appareil de fabrication par lots de coke en aiguilles - Google Patents

Procédé et appareil de fabrication par lots de coke en aiguilles Download PDF

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Publication number
WO2024060685A1
WO2024060685A1 PCT/CN2023/098774 CN2023098774W WO2024060685A1 WO 2024060685 A1 WO2024060685 A1 WO 2024060685A1 CN 2023098774 W CN2023098774 W CN 2023098774W WO 2024060685 A1 WO2024060685 A1 WO 2024060685A1
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oil
reaction
manufacturing
coking
mol
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PCT/CN2023/098774
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English (en)
Chinese (zh)
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郭丹
侯栓弟
初人庆
武云
张媛媛
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中国石油化工股份有限公司
中石化（大连）石油化工研究院有限公司
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Publication of WO2024060685A1 publication Critical patent/WO2024060685A1/fr

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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

Definitions

  • the invention belongs to the technical field of petrochemical industry, and in particular relates to a method and device for manufacturing needle coke in a batch feeding manner.
  • needle coke production technology In recent years, my country's needle coke production technology has developed rapidly. In terms of production technology, unlike conventional delayed coking, needle coke production usually uses pressurization, variable temperature, and large cycle ratio operations. That is to say, within a reaction cycle, raw materials are continuously fed into the coke tower, and needle coke products are obtained by adjusting parameters such as pressure, temperature, and circulation ratio.
  • CN113004924A discloses a needle coke production process.
  • the feed oil and vacuum residual oil are mixed and then sent to the coke tower for coking reaction.
  • the circulation ratio is controlled to 0.15-0.20, and needle coke with high particle strength coefficient can be obtained.
  • CN103184057A discloses a method for producing needle coke, which includes three steps: (1) Enter the fresh raw materials into the coke tower at a relatively low temperature; (2) After the first step is completed, increase the outlet temperature of the heating furnace, and put the fresh raw materials into the coke tower. It is mixed with the coked heavy distillate oil and sent to the coke tower; (3) When the coke tower reaches the solidification coking temperature, the coked middle distillate oil generated in the first step is sent to the coke tower at a higher temperature. This method can improve the uniformity of needle coke properties in different parts of the coke tower.
  • the inventor of the present invention found that coke-generating raw materials with different aromatic carbon ratios or different polymerization abilities require different times to complete the coke-generating reaction. For this reason, needle coke with uniform product quality can be produced by making raw materials with different aromatic carbon ratios or different polymerization abilities have different residence times in the coke tower. According to the present invention, the microstructural structure of needle coke products can be improved, the generation of short fibers, small flakes and other organizational structures can be reduced, and high-quality needle coke can be obtained. The present invention was completed on the basis of these findings.
  • the present invention relates to a method for manufacturing needle coke, which includes sequentially adding n (n is an integer above 2, preferably 2-15 or 3-5) feed oils to the coking reaction at predetermined time intervals.
  • n is an integer above 2, preferably 2-15 or 3-5
  • the aromatic carbon ratio of the i-th (n-1 ⁇ i ⁇ 1) raw material oil is A (unit is mol%)
  • B aromatic carbon ratio of the i+1th raw oil
  • B ⁇ A preferably BA ⁇ 5mol% or BA ⁇ 10mol%
  • B1 is greater than A1 (preferably B1-A1 ⁇ 10mol% or B1-A1 ⁇ 20mol%).
  • the present invention relates to a needle coke manufacturing device, which includes the following units:
  • Raw material oil supply unit configured to provide n (n is an integer of 2 or more, preferably 2-15 or 3-5) raw oils, wherein the aromatic carbon of the i-th (n-1 ⁇ i ⁇ 1) raw oil is assumed The rate is A (unit is mol%), let the aromatic carbon rate of the i+1th feed oil be B (unit is mol%), let the aromatic carbon rate of the first feed oil be A1 (unit is mol%), Suppose the aromatic carbon ratio of the nth feed oil is B1 (unit is mol%), then B ⁇ A (preferably B-A ⁇ 5mol% or B-A ⁇ 10mol%), and B1 is greater than A1 (preferably B1-A1 ⁇ 10mol% or B1 -A1 ⁇ 20mol%),
  • a coking unit is configured to receive the n raw oils and cause them to undergo a coking reaction to obtain needle coke,
  • the control unit is configured to sequentially enter the n pieces of raw oil from the raw oil supply unit into the coking unit at predetermined time intervals.
  • the present invention may have one or a combination of multiple or all of the following advantages:
  • the present invention divides the coking reaction cycle into three stages, which can improve the performance of needle coke.
  • the coking feed is the first raw material (the first heavy oil), which contains a large amount of hydrogenation products, has low polymerization ability, and has a long residence time in the coke tower, which can promote the conversion of the first raw material into macromolecules; in the second In the first stage, the coking feed is the second raw material (middle distillate).
  • the coking feed is the second raw material (middle distillate).
  • the coking feed is the second raw material (middle distillate).
  • the coking feed is the third raw material (the third heavy oil).
  • the third raw material has undergone delayed coking reaction, and its aromatic carbon rate is higher. It has strong heating capacity for the system and helps to improve the properties of needle coke. Due to the different molecular structures of the three raw materials, the residence times in the coke tower are also different, which is beneficial to the uniform quality of needle coke products.
  • the heavy component (first heavy oil) obtained by separation of the catalytic oil slurry obtained after hydrogenation is first subjected to a cracking reaction, and the aromatic hydrocarbons undergo side chain scission reactions and are converted into products with a small amount of short side chains.
  • the aromatic hydrocarbon structure of the chain is then cut into fractions, and the tricyclic and tetracyclic aromatic hydrocarbon fractions are used as raw materials for preparing needle coke.
  • the aromatic hydrocarbons in the catalytic oil slurry are fully utilized, and the aromatic hydrocarbons are converted into tricyclic and tetracyclic aromatic hydrocarbons suitable for preparing needle coke to the greatest extent, thereby improving Needle coke yield.
  • the entire fraction of the catalytic oil slurry is subjected to hydrogenation. After the five-ring and above aromatic hydrocarbons contained in the catalytic slurry undergo hydrogenation, fractionation, and cracking reactions in sequence, this part of the five-ring and above aromatic hydrocarbons will be converted into bands after the hydrogenation reaction. Tetracyclic aromatic hydrocarbons with saturated side chains may even be converted into tricyclic aromatic hydrocarbons with saturated side chains.
  • the catalytic oil slurry is generally fractionated and then a suitable fraction is selected for hydrogenation, or a suitable fraction is selected after hydrogenation as a raw material for needle coke production.
  • this part of the catalytic oil slurry contains aromatic hydrocarbons with five or more rings. It is used rationally and cannot be used as raw material for the production of needle coke.
  • the method of the invention can convert the five-ring and above aromatic hydrocarbons in the catalytic oil slurry into needle coke raw materials, improve the effective utilization efficiency of the catalytic oil slurry, increase the needle coke raw materials and needle coke yield, and improve The economic value of catalytic oil slurry is improved.
  • the bicyclic aromatic hydrocarbons and part of the tricyclic aromatic hydrocarbons contained in the first light oil can also be converted into tricyclic and tetracyclic aromatic hydrocarbons through condensation reactions, and also become high-quality raw materials for needle coke.
  • the needle coke manufacturing method of the present invention can reduce the thermal load of the coking device.
  • the cracking reaction of aromatic hydrocarbon side chains is an endothermic reaction.
  • the escape of the generated small molecules will also take away a large amount of heat, resulting in a low system temperature.
  • a separate cracking reaction system is provided in the catalytic oil slurry treatment method and treatment system of the present invention.
  • the side-chain breaking reaction of the hydrogenated catalytic oil slurry is transferred to the cracking reactor at appropriate temperature and pressure. , residence time conditions, obtaining aromatic hydrocarbon raw materials with short side chains. Moreover, injecting steam into the cracking reactor can quickly bring the small molecules generated by cracking out of the reactor to avoid staying in the cracking reactor and causing secondary condensation reactions.
  • the needle coke manufacturing method of the present invention can expand the needle coke Source of raw materials, the first auxiliary feed oil is introduced and mixed with the first heavy oil, a molecular structure optimization reaction occurs in the cracking reaction system, and the saturated hydrocarbons and aromatic hydrocarbon side chains in the first auxiliary feed oil are removed in the cracking reaction system; and/or the third auxiliary feed oil is introduced
  • the second auxiliary raw material oil is blended with the cracked products to improve the aromatic hydrocarbon composition of the needle coke raw material.
  • Figure 1 is a schematic diagram of a needle coke manufacturing method and production system according to an embodiment of the present invention.
  • Figure 2 is a schematic diagram of the catalytic oil slurry treatment method in the comparative example.
  • spatially relative terms such as “below”, “below”, “lower”, “upper”, “upper”, etc., may be used to describe an element or feature The relationship to another element or feature in the drawing. It will be understood that the spatially relative terms are intended to encompass different orientations of the item in use or operation in addition to the orientation depicted in the figures. For example, if the object in the figures is turned over, elements described as “below” or “beneath” other elements or features would then be oriented “above” the elements or features. Therefore, the exemplary term “below” may include both lower and upper directions. Objects can also have other orientations (for example, rotated 90 degree or other orientation) and the spatially relative terms used herein should be interpreted accordingly.
  • first”, “second”, etc. are used to distinguish two different elements or parts, and are not used to limit a specific position or relative relationship. In other words, in some embodiments, the terms “first”, “second”, etc. may also be interchanged with each other.
  • catalytic slurry refers to the heavy distillate produced by catalytic cracking reactions.
  • polarizing microstructure (coarse fibers, fine fibers, short fibers, large flakes, small flakes, mosaic) is determined by the YB/T 077 method.
  • the ash content of the oil is measured by the GB/T 508 method
  • the sulfur content is measured by the SH/T 0689 method
  • the aromatic carbon rate is measured by the SH/T 0793 method
  • the aromatic hydrocarbon content is measured by the SH/T 0659 method.
  • the ash content of coke is determined by the GB/T 1429 method and the sulfur content is determined by the GB/T 24526 method
  • the present invention relates to a method for manufacturing needle coke.
  • the needle coke manufacturing method is performed in a needle coke manufacturing device described below. For this reason, if there is no detailed description in the manufacturing method section, you can directly refer to the relevant content described below for the manufacturing device.
  • the needle coke manufacturing method includes the step of sequentially adding (feeding) n raw oils to the coking reaction at predetermined time intervals.
  • the feeding sequence of these raw oils is very critical to achieving the expected technical effects of the present invention and cannot be adjusted at will.
  • the feeding can be carried out in a batch or continuous manner, preferably in a continuous manner.
  • the so-called predetermined time interval refers to an original After the feed oil is fed for a period of time, another feed oil is fed. The difference between the feeding timings of the two is the time interval.
  • the time when one feed oil starts to be fed is the time when the feed of other feed oils (if any) stops.
  • the n feed oils are preferably added to the coking reaction separately at different timings, with basically no overlapping feeds.
  • the present invention has no particular limitation on the specific value of the predetermined time interval, as long as the time interval can effectively separate the feeding timings of the n raw oils, however, it is preferred. Details below.
  • n is an integer of 2 or more, preferably 2-15 or 3-5.
  • the aromatic carbon ratio of the i-th (n-1 ⁇ i ⁇ 1) raw material oil be A (unit is mol%)
  • the aromatic carbon ratio of the i+1th raw material oil be B. (unit is mol%)
  • B ⁇ A Preferably, B-A ⁇ 5 mol% or B-A ⁇ 10 mol%. If B is less than A, especially if B-A ⁇ 5 mol%, then the aromatic carbon ratios of the two are similar, and the cracking/polymerization capabilities are likely to be similar.
  • B1 is greater than A1 .
  • the aromatic carbon ratio of the first feed oil is 40 mol%-80 mol% (preferably 55 mol%-75 mol%).
  • the aromatic carbon ratio of the m-th raw oil is 60 mol%-90 mol% (preferably 70 mol%-85 mol%).
  • m is any integer greater than 1 and less than n.
  • the aromatic carbon ratio of the n-th feed oil is greater than 75 mol% (preferably 80 mol%-95 mol%).
  • the sulfur content of the i-th (n-1 ⁇ i ⁇ 1) raw oil is no more than 0.45wt% (preferably no more than 0.37wt%), and the ash content is no more than 0.05wt% (preferably Not more than 0.01wt%), the 5% distillation temperature is 330°C-430°C (preferably 360°C-400°C), and the 95% distillation temperature is 470°C-530°C (preferably 485°C-510°C).
  • the sulfur content of the nth raw oil is no more than 0.55wt% (preferably no more than 0.5wt%), the ash content is no more than 0.05wt% (preferably no more than 0.01wt%), and 5%
  • the distillation temperature is 280°C-380°C (preferably 310°C-360°C), and the 95% distillation temperature is not greater than 480°C.
  • the predetermined time interval divides the coking reaction into n reaction sections.
  • the feed oil corresponding to the reaction section is added continuously or intermittently from the beginning to the end of the reaction time of the reaction section.
  • the predetermined time interval divides the coking reaction into n reaction sections.
  • the reaction time of the first reaction section be T1 (unit is hour)
  • the reaction time of the mth (m is any integer greater than 1 and less than n) reaction section be Tm (unit is hour)
  • Tn unit is hour
  • T1/T 5%-40% (preferably 10%-25%)
  • Tm/T 15%-85% (preferably 25%) -70%)
  • Tn/T 15%-80% (preferably 25%-55%).
  • the first feed oil is the hydrogenation product of catalytic oil slurry
  • the nth feed oil is the heavy part of coked oil gas
  • the other feed oils are Either of the oils is a cracked product of the hydrogenation product of the catalytic oil slurry.
  • n 3.
  • the number of raw material oils is three, namely the first raw material oil, the second raw material oil and the third raw material oil.
  • the reaction cycle T of the coking reaction is divided into three reaction sections, namely the first reaction section, the second reaction section and the third reaction section, wherein in the first reaction section In the section, the first feed oil is added to the coking reaction, in the second reaction section, the second feed oil is added to the coking reaction, in the third reaction section In the section, the third raw material oil is added to the coking reaction.
  • the method for manufacturing the first raw oil includes: purifying the catalytic oil slurry to obtain the purified oil slurry and entering it into a hydrogenation treatment system, and performing a hydrogenation reaction under the action of hydrogen gas and a hydrogenation catalyst;
  • the hydrogenation reaction product is separated to obtain a gas phase stream and a liquid phase stream.
  • the liquid phase stream enters the first separation system to obtain a first light oil and a first heavy oil, wherein the first heavy oil is used as the first raw oil.
  • the ash content of the catalytic oil slurry is generally higher than 0.01wt%, and the sulfur content is generally higher than 0.5wt%, and some are higher than 0.8wt%. For this reason, if the ash and sulfur content in the catalytic oil slurry cannot meet the raw material requirements for needle coke, it needs to be processed.
  • the ash content of the purified oil slurry is ⁇ 0.008wt%, preferably the ash content is ⁇ 0.005wt%.
  • the purification treatment is generally a desolidification treatment.
  • the desolidification treatment can adopt any one or more of filtration, centrifugal sedimentation, and flocculation sedimentation treatment methods, and filtration is preferably used.
  • the core equipment of the filtration process is a filter.
  • the filter element can be one or more combinations of a sintered metal powder filter element, a metal mesh filter element, a ceramic membrane filter element, etc., and a ceramic membrane filter element is preferably used. .
  • the hydrogenation reaction is carried out in a hydrotreating system.
  • the hydrotreating system includes a reaction unit and a separation unit.
  • the reaction unit is equipped with at least one hydrogenation reactor.
  • the hydrogenation reactor can be selected from an ebullating bed reactor, a suspended bed reactor, and a slurry bed reactor. , one or several combinations of fixed bed reactors, preferably fixed bed reactors;
  • the separation unit includes a hot high-pressure separator, a cold high-pressure separator, a hot low-pressure separator, a cold low-pressure separator, and may also include a stripping tower , fractionation tower and other equipment.
  • the hydrogenation catalyst can be prepared using existing methods in the field, or using existing commercial catalysts, such as the FZC series hydrogenation catalysts developed by Sinopec Dalian Petrochemical Research Institute.
  • Hydrogenation catalysts generally use alumina as a carrier, and the active components are oxides of Group VIB and/or Group VIII metals, such as one or several combinations of Mo, W, Co, Ni and other metal oxides.
  • reaction temperature is 310°C-450°C, preferably 340°C-390°C
  • reaction pressure is 2MPa-20MPa, preferably 4MPa-8MPa
  • hydrogen-to-oil volume ratio is 100-2500, preferably 800-1800
  • liquid hourly volume space velocity is 0.1h -1 -2.0h -1 , preferably 0.6h -1 -1.2h -1 .
  • the liquid phase stream is a liquid phase stream from which non-condensable vapor is separated, preferably a liquid phase stream from which non-condensable vapor and naphtha fractions are separated.
  • the sulfur content in the liquid phase stream is ⁇ 0.4wt%, preferably the sulfur content is ⁇ 0.35wt%.
  • the 5% distillation temperature of the first heavy oil is 330°C-420°C, preferably 360°C-400°C.
  • the 95% distillation temperature of the first light oil is 310°C-420°C, preferably 340°C-400°C.
  • the first light oil discharge device is either sent to the condensation reaction system for treatment, or part of the first light oil discharge device is sent to the condensation reaction system for treatment.
  • the operating conditions of the condensation reaction system are: reaction temperature is 350°C-530°C, preferably 380°C-450°C, reaction pressure is 0.01MPa-5MPa, preferably 1MPa-3MPa, residence time It is 0.1h-15h, preferably 0.5h-6h.
  • the condensation reaction system is equipped with at least one fixed bed reactor, and the reactor includes at least one feed port and one discharge port.
  • the reaction time of the first reaction section accounts for 5%-40% of the reaction period T, preferably 10%-25%. That is, in the first stage, the coking system feeds the first feed oil, and its feeding time accounts for 5% to 40% of the reaction cycle, preferably 10% to 25%.
  • the reaction time of the second reaction section accounts for 15%-85% of the reaction period T, preferably 25%-70%. That is, in the second stage, the coking system feeds the second feed oil, and its feeding time accounts for 15% to 85% of the reaction cycle, preferably 25% to 70%.
  • the coking system feed is the third feed oil, and its feeding time accounts for the remaining part of the reaction cycle.
  • the reaction cycle of the coking reaction is 24-92 hours (preferably 36-60 hours).
  • the manufacturing method of the second feed oil includes: the first feed oil (such as the first heavy oil) enters a cracking reaction system, and a cracking reaction occurs in the presence of a carrier gas, The obtained cracked product enters the second separation system, and after separation, a second light oil, a middle distillate oil and a second heavy oil are obtained, wherein the middle distillate oil is used as the second feed oil.
  • the first feed oil such as the first heavy oil
  • a cracking reaction occurs in the presence of a carrier gas
  • the obtained cracked product enters the second separation system, and after separation, a second light oil, a middle distillate oil and a second heavy oil are obtained, wherein the middle distillate oil is used as the second feed oil.
  • the cracking reaction is carried out in a cracking reaction system.
  • the cracking reaction system is provided with at least one reactor, and the reactor type can be one or several combinations of a tubular reactor, a tower reactor, a tank reactor, and a tower reactor is preferred.
  • the reactor includes at least two feed ports and one discharge port, one feed port is used to feed the first heavy oil, and the other feed port is used to feed the carrier gas.
  • the carrier gas may be one or more of water vapor, nitrogen, and an inert gas (which may be helium, neon, argon, etc.), preferably water vapor.
  • an inert gas which may be helium, neon, argon, etc.
  • the operating conditions of the cracking reaction are as follows: the reaction temperature is 380°C-520°C, preferably 420°C-490°C, the reaction pressure is 0.1MPa-5MPa, preferably 0.2MPa-1.0MPa, the residence time is 0.01h-30h, preferably 0.1h-3h, and the oil-gas mass ratio is 100:0.1-100:20, preferably 100:1-100:8.
  • the 5% distillation temperature of the middle distillate oil is 340°C-430°C, preferably 360°C-400°C, and the 95% distillation temperature is 470°C-530°C, preferably 485°C-510°C.
  • the sulfur content is ⁇ 0.43wt%, preferably ⁇ 0.37wt%
  • the ash content is ⁇ 0.006wt%, preferably ⁇ 0.004wt%.
  • the 95% distillation temperature of the second light oil is 330°C-430°C, preferably 350°C-400°C, or the 5% distillation temperature of the second heavy oil is 470°C-540°C, preferably 485°C. °C-520°C.
  • the first feed oil and the first auxiliary feed oil enter the cracking reaction system together.
  • the ash content in the first auxiliary raw material oil is no more than 0.02wt%, preferably no more than 0.01wt%
  • the sulfur content is no more than 0.4wt%, preferably the sulfur content is no more than 0.35wt%, tricyclic and tricyclic
  • the above aromatic hydrocarbon content is not less than 40wt%
  • the aromatic carbon rate is not less than 40mol%, preferably 55mol%-80mol%
  • the distillation range is 300°C-550°C, preferably 330°C-510°C.
  • the first auxiliary raw material oil is one or more selected from the group consisting of catalytic oil slurry, ethylene tar, vacuum wax oil, coking wax oil, deasphalted oil, and hydrogenated oil.
  • the mass ratio of the first auxiliary raw material oil to the first raw material oil is 0:100-50:100, preferably 5:100-20:100.
  • the cracked product enters the second separation system together with the second auxiliary feed oil.
  • the ash content in the second auxiliary raw material oil is no more than 0.02wt%, preferably no more than 0.01wt%
  • the sulfur content is no more than 0.4wt%, preferably the sulfur content is no more than 0.35wt%
  • the aromatic hydrocarbon content is 50wt%. -95wt%, preferably 65wt%-90wt%, in which the content of tricyclic and above aromatic hydrocarbons is not less than 40wt%, and the aromatic carbon rate is not less than 50mol%, preferably not less than 75mol%.
  • the second auxiliary raw material oil is one or more selected from the group consisting of catalytic oil slurry, ethylene tar, vacuum wax oil, coking wax oil, and deasphalted oil.
  • the mass ratio of the second auxiliary raw material oil to the cracked product is 0:100-100:10, preferably 5:100-20:100.
  • the cracked product and the product obtained by the condensation reaction of the first light oil enter the second separation system for separation.
  • the mass ratio of the cracked product and the product obtained by the condensation reaction of the first light oil is 100:0-100:20, preferably 100:0-100:5.
  • the method for manufacturing the third feedstock oil includes: the coked oil gas generated by the coking reaction enters the third separation system, and after separation, coked gas, third light oil and gas are obtained. oil and a third heavy oil, wherein the third heavy oil is used as the third raw material oil.
  • the 5% distillation temperature of the third heavy oil is 280°C-380°C, preferably 310°C-360°C.
  • the 95% distillation temperature of the third light oil is 270°C-380°C, preferably 300°C-360°C.
  • the operating conditions of the coking reaction are: the heating furnace outlet temperature is 420°C-560°C, preferably 440°C-530°C, and the heating rate is 0.5°C/h-30°C/h, preferably 3 °C/h-7°C/h; the coke tower top pressure is 0.01MPa-2.5MPa, preferably 0.2MPa-1.3MPa.
  • the coking reaction can be a constant pressure operation or a variable pressure operation. If voltage transformation operation is adopted, the voltage transformation rate is 0.1MPa/h-5MPa/h.
  • the reaction period of the coking reaction is generally 24h-92h, preferably 36h-60h.
  • the coking reaction is carried out in a coking system.
  • the coking system generally includes at least one heating furnace and two coke towers.
  • the coke drums always keep at least one in the reaction stage and at least one in the purge and decoking stages.
  • the reaction conditions of the coking system are: the heating furnace outlet temperature is 420°C-560°C, preferably 440°C-530°C, and the heating rate is 0.5°C/h-30°C/h, preferably 3°C/h-7°C/h;
  • the top pressure of the coke tower is 0.01MPa-2.5MPa, preferably 0.2MPa-1.3MPa. It can be operated at constant pressure or with variable pressure.
  • the pressure variable rate is 0.1MPa/h-5MPa/h;
  • the reaction period is 10h-72h, preferably 32h-54h; the needle coke generated by the reaction is deposited at the bottom of the tower, and the coked oil and gas generated is discharged from the top of the tower.
  • the aforementioned condensation reaction is performed in a condensation reaction system.
  • the reaction conditions of the condensation reaction system are: reaction temperature is 350°C-530°C, preferably 380°C-450°C, reaction pressure is 0.01MPa-5MPa, preferably 1MPa-3MPa, and residence time is 0.1h-15h , preferably 0.5h-6h.
  • the condensation reaction system is provided with at least one fixed bed reactor, and the reactor includes at least one feed port and one discharge port.
  • the condensation reaction can be carried out under the action of a condensation catalyst.
  • the condensation catalyst includes a carrier and an active component, wherein the carrier is one of kaolin, montmorillonite, alumina, and silicon-containing alumina.
  • the active component is at least one of the oxides of Group IVB and/or Group VIB metals, such as zirconium, tungsten, molybdenum and other metal oxides.
  • the active component content is 0.1wt%-50wt%, preferably 5wt%-25wt%.
  • the shape of the condensation catalyst can be one of spherical, cylindrical, clover, four-leaf clover, Raschig ring, etc., or a combination of several.
  • the present invention also relates to a needle coke manufacturing device.
  • the needle coke manufacturing device is specially used to implement the needle coke manufacturing method mentioned above. For this reason, there is no detailed description in the manufacturing device section, and you can directly refer to the relevant content described in the full text regarding the manufacturing method.
  • the needle coke manufacturing device includes the following units:
  • Raw material oil supply unit configured to provide n (n is an integer of 2 or more) raw material oils, wherein the aromatic carbon rate of the i-th (n-1 ⁇ i ⁇ 1) raw material oil is A (unit is mol%) , let the aromatic carbon ratio of the i+1th feed oil be B (unit is mol%), let the aromatic carbon ratio of the first feed oil be A1 (unit is mol%), let the aromatic carbon ratio of the nth feed oil be The rate is B1 (unit is mol%), then B ⁇ A, and B1 is greater than A1,
  • the coking unit is configured to receive the n feed oils and cause them to undergo a coking reaction to obtain needle coke,
  • the control unit is configured to sequentially enter the n pieces of raw oil from the raw oil supply unit into the coking unit at predetermined time intervals.
  • B-A ⁇ 5 mol% or B-A ⁇ 10 mol% it is preferred that B-A ⁇ 5 mol% or B-A ⁇ 10 mol%.
  • B1-A1 ⁇ 10 mol% or B1-A1 ⁇ 20 mol% it is preferred that B1-A1 ⁇ 10 mol% or B1-A1 ⁇ 20 mol%.
  • a purification treatment system which is used to receive and purify catalytic oil slurry, and obtain purified oil slurry after treatment;
  • a hydrogenation treatment system which is used to receive hydrogen and purified oil slurry from the purification treatment system, perform a hydrogenation reaction under the action of a hydrogenation catalyst, and obtain a gas phase stream and a liquid phase stream after the hydrogenation reaction product is separated;
  • a first separation system which is used to receive the liquid phase stream from the hydrotreating system and obtain the first light oil and the first heavy oil after separation;
  • a cracking reaction system which is used to receive the first heavy oil from the first separation system and the optional first auxiliary feed oil, and perform the reaction in the presence of carrier gas;
  • a second separation system which is used to receive the reaction effluent from the cracking reaction system and optional second auxiliary feed oil, and obtain the second light oil, middle distillate oil and second heavy oil after separation;
  • Coking unit which is used to receive the first heavy oil (the first feed oil) from the first separation system, the middle distillate oil (the second feed oil) from the second separation system and the third heavy oil from the third separation system. Oil (the third raw material oil), after the reaction, coked oil gas and needle coke are obtained;
  • a third separation system configured to receive the coked oil gas obtained after the reaction from the coking unit, After separation, coked gas, third light oil and third heavy oil are obtained.
  • the manufacturing device further includes a condensation reaction system for receiving the first light oil from the first separation system.
  • the first light oil enters the condensation reaction system, and under the action of the condensation catalyst
  • the condensation reaction is carried out under the conditions, and the reaction effluent obtained by the condensation reaction enters the second fractionation unit and is separated together with the cracking reaction effluent.
  • the first separation system can be one or a combination of a stripping tower, a flash tower, a fractionation tower, etc., preferably a fractionation tower.
  • the condensation reaction system is provided with at least one fixed bed reactor, and the reactor includes at least one feed port and one discharge port.
  • the purification treatment system adopts any one or more of a filter device, a centrifugal sedimentation device, a flocculation sedimentation device, etc., preferably a filter device; a filter device
  • the core equipment is the filter.
  • the filter element can be one or several combinations of sintered metal powder filter element, metal mesh filter element, ceramic membrane filter element, etc. Ceramic membrane filter element is preferred.
  • the hydrotreating system in the needle coke manufacturing device, includes a reaction unit and a separation unit.
  • the reaction unit is provided with at least one hydrogenation reactor.
  • the hydrogenation reactor can be selected from: One or several combinations of ebullating bed reactors, suspended bed reactors, slurry bed reactors, fixed bed reactors, etc., preferably fixed bed reactors;
  • the separation unit includes a hot high-pressure separator, a cold high-pressure separator, a thermal Low-pressure separators, cold low-pressure separators, and can also include equipment such as stripping towers and fractionating towers.
  • the first separation system in the needle coke manufacturing device, can be one or a combination of a stripping tower, a flash tower, a fractionation tower, etc., preferably a fractionation tower.
  • the cracking reaction system is provided with at least one reactor, and the reactor can be at least one of a tubular reactor, a tower reactor, and a tank reactor.
  • the reactor includes at least two feed ports and one discharge port, one feed port is used to feed the first heavy oil, and the other feed port is used to feed the carrier gas.
  • the second separation system may be one or several combinations of a stripping tower, a flash tower, a fractionation tower, etc., preferably fractionation tower.
  • the coking system includes Contains at least one heating furnace, two coke towers, and a fractionation tower.
  • the coke drums always keep at least one in the reaction stage and at least one in the purge and decoking stages.
  • the specific process of the needle coke manufacturing method provided by the present invention is as follows: the catalytic oil slurry 1 first enters the purification treatment system 2 for desolidification and purification treatment, and the purified oil slurry 9 obtained after the treatment is mixed with hydrogen 11 and enters the processing system.
  • the hydrogenation treatment system 3 reacts under the action of a hydrogenation catalyst.
  • the hydrogenation reaction product 10 enters the hydrogenation separation unit 4 for separation. After separation, a gas phase stream 12 and a liquid phase stream 13 are obtained.
  • the liquid phase stream 13 enters the first separation system 5, and after separation, the first light oil 14 and the first heavy oil 15 are obtained; the first light oil 14 can be directly discharged from the device, or enter the condensation reaction system 7 for condensation reaction, and the condensation reaction product 16 is sent to the second separation system 6; in the first stage of the coking reaction, the first heavy oil 15 enters the coking system 22A/22B as the first raw material 25. In the remaining stages of the coking reaction, the first heavy oil 15 and any first auxiliary raw material oil 27 Entering the cracking reaction system 8, the cracking reaction is carried out in the presence of the carrier gas 17. The reaction effluent 18 obtained by the cracking reaction and any second auxiliary raw material oil 26 enter the second separation system 6.
  • the second light oil 19 and the intermediate The distillate oil 20 and the second heavy oil 21, of which the second light oil 19 is discharged from the device, or enters the purification treatment system 2 as a diluent to be mixed with the catalytic oil slurry 1 for purification treatment; the second heavy oil 21 is discharged from the device.
  • the middle distillate oil 20 enters the coking system 22A/22B as the second raw material for producing needle coke.
  • the coked oil gas 23 and the needle coke product 24 are obtained, of which the coked oil gas 23 enters the third separation system 30 , after separation, coked gas 28, third light oil 29 and third heavy oil 30 are obtained.
  • the third heavy oil 30 enters the coking system 22A/22B as the third raw material for producing needle coke.
  • the raw material properties of the catalytic oil slurry, first auxiliary raw material oil, and second auxiliary raw material oil used in the examples and comparative examples of the present invention are shown in Table 1.
  • the hydrogenation catalyst used is FZC-34BT hydrogenation catalyst developed by Sinopec Dalian Petrochemical Research Institute.
  • the purification treatment system uses filters and the carrier gas uses water vapor.
  • the catalytic oil slurry enters the hydrogenation system after purification treatment, and the hydrogenation reaction products are separated to obtain
  • the liquid phase stream is sent to the first separation system, and the first light oil and the first heavy oil are separated.
  • Part of the first heavy oil is used as the first raw material oil and sent to the coke tower in the first stage of the coking reaction; part of the first heavy oil enters
  • the cracking reaction effluent enters the second separation system to separate the second light oil, middle distillate oil and second heavy oil.
  • the middle distillate oil is used as the second feed oil and is sent to the coke tower in the second stage of the coking reaction.
  • the needle coke generated by the coking reaction is deposited at the bottom of the tower, and the coked oil and gas are sent to the third separation system to separate the coked gas, the third light oil and the third heavy oil, of which the third heavy oil is used as the third raw material oil.
  • the third stage of the coking reaction is sent to the coke tower.
  • the hydrogenation reaction, cracking reaction, and coking reaction conditions are listed in Table 2, and the feed properties of the three-stage coking system are listed in Table 3.
  • the needle coke yield based on catalytic oil slurry is listed in Table 4.
  • Embodiment 2 The difference between Embodiment 2 and Embodiment 1 is that: the first feed oil is sent to the coke tower during the entire coking reaction cycle, the second feed oil is sent to the coke tower during the second stage of the coking reaction, and the third feed oil is sent to the coke tower during the coking reaction. The third stage of the reaction is sent to the coke tower.
  • the hydrogenation reaction, cracking reaction, and coking reaction conditions are listed in Table 2, and the feed properties of the three-stage coking system are listed in Table 6.
  • the needle coke yield based on catalytic oil slurry is listed in Table 4.
  • Embodiment 3 is the same as that of Embodiment 1, except for some operating parameters.
  • the hydrogenation reaction, cracking reaction, and coking reaction conditions are listed in Table 2, and the feed properties of the three-stage coking system are listed in Table 7.
  • the needle coke yield based on catalytic oil slurry is listed in Table 4.
  • Embodiment 4 is the same as that of Embodiment 1, except for some operating parameters.
  • the hydrogenation reaction, cracking reaction, and coking reaction conditions are listed in Table 2, and the feed properties of the three-stage coking system are listed in Table 8.
  • the needle coke yields based on catalytic oil slurry are listed in Table 4.
  • Example 5 The process of Example 5 is basically the same as that of Example 4, except that the first light oil enters the condensation reaction system.
  • the condensation reaction conditions are: reaction temperature is 405°C, reaction pressure is 1.2MPa, residence time is 2.5h; the condensation catalyst is : Using alumina as carrier, 8wt% ZrO2-3.5wt% MoO2 as active components, clover structure.
  • the condensation reaction product enters the second separation system, and the mass ratio of cracking product to condensation product is 100:9.
  • the hydrogenation reaction, cracking reaction, and coking reaction conditions are listed in Table 2, and the feed properties of the three-stage coking system are listed in Table 9.
  • the needle coke yield based on catalytic oil slurry is listed in Table 4.
  • Example 6 The process of Example 6 is basically the same as that of Example 1, except that the first auxiliary raw material and the first heavy oil enter the cracking reaction system at a mass ratio of 7:100.
  • the hydrogenation reaction, cracking reaction, and coking reaction conditions are listed in Table 2, and the feed properties of the three-stage coking system are listed in Table 10.
  • the needle coke yield based on the catalytic oil slurry and the first auxiliary raw material is listed in Table 4.
  • Example 7 The process of Example 7 is basically the same as that of Example 1, except that the second auxiliary raw material and the cracked product enter the cracking reaction system at a mass ratio of 9:100.
  • the hydrogenation reaction, cracking reaction, and coking reaction conditions are listed in Table 2, and the feed properties of the three-stage coking system are listed in Table 11.
  • the needle coke yields based on catalytic oil slurry and the second auxiliary raw material are listed in Table 4.
  • Comparative Example 1 The specific process of Comparative Example 1 is shown in Figure 2. After purification, the catalytic oil slurry enters the vacuum distillation device to separate the first middle distillate oil; the first middle distillate oil is sent to the hydrogenation treatment system, and the hydrogenation reaction The liquid phase stream obtained by product separation is sent to the hydrogenation separation system, and the second middle distillate oil is separated; the second middle distillate oil is sent to the coke tower as the first feed oil, and the needle coke generated by the reaction is deposited in the tower At the bottom, the coked oil gas is sent to the coking separation system, and the separated coked heavy oil is used as the second raw material oil. The second raw oil and the first raw oil are returned to the coke tower at a mass ratio of 1:1.
  • the hydrogenation reaction and coking reaction conditions are listed in Table 12, and the feed properties of the coking system are listed in Table 13.
  • the needle coke yield based on catalytic oil slurry is listed in Table 14.
  • the catalytic oil slurry enters the hydrogenation system after purification.
  • the liquid phase stream obtained by separation of the hydrogenation reaction product is sent to the first separation system to separate the first light oil and the first heavy oil.
  • Part of the first heavy oil is used as the first A feed oil;
  • part of the first heavy oil enters the cracking reaction system, and the cracking reaction effluent enters the second separation system, and the second light oil, middle distillate oil and second heavy oil are separated, with the middle distillate oil being the second feed oil; coking
  • the coked oil gas generated by the reaction is sent to the third separation system, and the coked gas, the third light oil and the third heavy oil are separated, of which the third heavy oil is used as the third raw material oil.
  • the first feed oil, the second feed oil, and the third feed oil are sent to the coke tower in a mass ratio of 2:4:4, and the needle coke generated by the coking reaction is deposited at the bottom of the tower.
  • the hydrogenation reaction, cracking reaction, and coking reaction conditions are listed in Table 12, and the feed properties of the coking system are listed in Table 16.
  • the needle coke yield based on catalytic oil slurry is listed in Table 14.
  • the acquisition method of the three raw oils is the same as that of Comparative Example 2, but the coke drum feeding stage is different, the difference is: the third raw oil is sent to the coke drum in the first stage of the coking reaction, the second raw oil is sent to the coke drum in the second stage of the coking reaction, and the first raw oil is sent to the coke drum in the third stage of the coking reaction.
  • the conditions of the hydrogenation reaction, cracking reaction, and coking reaction are listed in Table 12, and the properties of the coking system feed are listed in Table 17.
  • the needle coke yield based on catalytic oil slurry is listed in Table 14.
  • the proportion of crude fiber and fine fiber in the embodiment reaches more than 60%.
  • the proportion of crude fiber and fine fiber in the comparative example is less than 55%.

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  • Materials Engineering (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé et un appareil pour la fabrication par lots de coke en aiguilles. La présente invention permet de fabriquer du coke en aiguille ayant une qualité de produit uniforme. Le procédé de fabrication de coke en aiguille selon la présente invention comprend l'étape consistant à ajouter séquentiellement n huiles brutes à une réaction de cokéfaction à un intervalle de temps prédéfini, le rapport carbone aromatique d'une ième huile brute étant réglé pour être A (en % en moles), le rapport carbone aromatique d'une huile brute i +1 étant réglé pour être B (en % en moles), le rapport carbone aromatique d'une première huile brute étant réglé pour être A1 (en % en moles), et le rapport carbone aromatique d'une nième huile brute étant réglé pour être B1 (en % en moles), B ≥ A et B1 étant supérieur à A1.
PCT/CN2023/098774 2022-09-20 2023-06-07 Procédé et appareil de fabrication par lots de coke en aiguilles WO2024060685A1 (fr)

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CN202211146194.7A CN117778039A (zh) 2022-09-20 2022-09-20 一种批次进料方式制造针状焦的方法和装置

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140072761A (ko) * 2012-11-30 2014-06-13 세메스 주식회사 기판 처리 설비 및 방법
CN107987880A (zh) * 2016-10-26 2018-05-04 中国石油化工股份有限公司 一种制备针状焦原料的方法和设备
CN112745916A (zh) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 一种制备针状焦原料的方法和设备
CN114479906A (zh) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 一种制备优质石油焦的方法

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20140072761A (ko) * 2012-11-30 2014-06-13 세메스 주식회사 기판 처리 설비 및 방법
CN107987880A (zh) * 2016-10-26 2018-05-04 中国石油化工股份有限公司 一种制备针状焦原料的方法和设备
CN112745916A (zh) * 2019-10-31 2021-05-04 中国石油化工股份有限公司 一种制备针状焦原料的方法和设备
CN114479906A (zh) * 2020-10-27 2022-05-13 中国石油化工股份有限公司 一种制备优质石油焦的方法

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