Petroleum coke special for high-end prebaked anode as well as preparation method and application of petroleum coke

Abstract

The invention belongs to the technical field of petroleum processing, particularly relates to petroleum coke special for a high-end prebaked anode and a preparation method of the petroleum coke, and particularly relates to a delayed coking production method adopting Shengli vacuum residue and ethylene tar as raw materials. According to the petroleum coke special for the high-end prebaked anode, ethylene tar and vacuum residue with the high metal content serve as main raw materials, the raw materials are pretreated to serve as coking raw materials, the coking raw materials are heated through a heating furnace and then injected into a coke tower for delayed coking, and the petroleum coke special for the high-end prebaked anode can be produced.

Description

Technical Field

[0001] The invention belongs to the technical field of petroleum processing, and specifically relates to a high-end prebaked anode special petroleum coke and a preparation method thereof, in particular to a delayed coking production method using Shengli vacuum residue oil and ethylene tar as raw materials. Background Art

[0002] As one of the important raw materials to ensure the sustainable development of the national economy, aluminum metal is widely used in various fields. It is reported that electrolytic aluminum enterprises need about 0.49 tons of prebaked anodes to produce 1 ton of electrolytic aluminum. Prebaked anodes are made of petroleum coke and asphalt coke as aggregates and coal tar as binder, and are used as anode materials for prebaked aluminum electrolytic cells. Because the material has been baked and has a stable geometric shape, it is also called prebaked anode carbon block, and is customarily called carbon anode for aluminum electrolysis. The aluminum electrolytic cell using prebaked anode carbon blocks as anodes is called prebaked anode electrolytic cell, or prebaked cell for short. This is a modern large-scale aluminum electrolytic cell.

[0003] As the main raw material for the production of prebaked anodes, the product quality of petroleum coke directly affects the quality of prebaked anodes, and the main factors affecting the quality of petroleum coke are the various trace elements it contains. For example, trace elements such as Ni and V oxidize quickly, causing serious oxidation of prebaked anodes, and problems such as slag and block falling, resulting in reduced conductivity and weakened current effect in aluminum electrolysis cells. During the production of prebaked anodes, the demand for carbon increases significantly; while trace elements such as Si and Fe mainly affect the mechanical properties and purity of finished raw aluminum. Therefore, in order to ensure the product quality of prebaked anodes, it is necessary to process and control these trace elements in petroleum coke to improve the quality of prebaked anodes and improve the consumption of anodes, which is conducive to energy conservation and emission reduction under the "dual carbon" goal of the aluminum electrolysis industry.

[0004] Petroleum coke is generally a carbonized product obtained by deep thermal cracking reaction at high temperature through delayed coking process. The raw material of delayed coking unit is vacuum residue oil as the main raw material, and residue oil is heavy residue oil obtained by vacuum distillation of crude oil. Therefore, various physical properties in crude oil, especially the content of trace elements, are the key factors determining the content of trace elements in residue oil and petroleum coke. When the content of trace elements in coking raw materials is high, the quality of prebaked anodes is easily unstable when the produced petroleum coke is used to produce prebaked anodes. In addition, the presence of trace elements in petroleum coke will also affect the quality of prebaked anodes. At present, most manufacturers of high-end prebaked anode coke are refineries that process high-quality crude oil.

[0005] Qilu Company's refinery uses the vacuum residue oil from the fourth atmospheric and vacuum unit as raw material to produce petroleum coke. The petroleum coke products produced have high Ca and Ni content, and the other indicators meet the requirements. The reason for this is that the fourth atmospheric and vacuum unit mainly processes Shengli high-sulfur and high-acid crude oil, which contains high Ca and Ni content, resulting in high Ca and Ni content in Shengli vacuum residue oil. The Ca content of Shengli vacuum residue oil is 40-50 mg kg -1 、Ni content: 42-52mg·kg -1 In the process of producing petroleum coke, most of the metal elements in the raw materials eventually enter the petroleum coke, and the yield of petroleum coke is about 20%. Therefore, when Shengli vacuum residue is used as the single raw material to produce petroleum coke, the content of Ca and Ni in the petroleum coke exceeds 200 mg kg. -1 , does not meet the high-end pre-baked anode coke Ca≤200mg·kg provided by Sotong Development Company -1 、Ni≤200mg·kg -1 Therefore, the vacuum residue oil of Shengli crude oil can only produce ordinary prebaked anode coke, and the raw materials of delayed coking unit must be adjusted to produce high-end prebaked anode coke.

[0006] Ethylene tar is a by-product of high-temperature condensation in the process of steam cracking to produce ethylene. It has a complex composition structure, high content of unsaturated hydrocarbons such as aromatics and aromatic alkenes, poor oxidation stability, easy deposition and coking when heated, high degree of condensation, and poor solubility with other heavy oil components. However, ethylene tar has the characteristics of low content of trace elements and is a good potential raw material for the production of high-end prebaked anode coke.

[0007] For example, Chinese patent CN101608132A discloses a delayed coking production method using ethylene cracking tar as raw material, wherein the delayed coking mixed raw material is composed of ethylene cracking tar, vacuum residue oil and catalytic oil slurry, which reduces the sulfur content and nitrogen content of gasoline and diesel in the coking unit, and reduces the sulfur content and metal content of wax oil and petroleum coke. However, this simple blending is not suitable for Shengli vacuum residue oil, mainly because the ethylene tar of Qilu and Shengli vacuum residue oil have poor compatibility, and there are obvious stratification and agglomeration phenomena, and because the calcium and nickel content of Shengli vacuum residue is high, the coking raw materials are mixed unevenly, which will cause the calcium content of petroleum coke to exceed the standard.

[0008] Another example is the scheme of using catalytic oil slurry and ethylene tar to prepare petroleum coke, disclosed in Chinese patent CN113122330A, in which the catalytic oil slurry fraction is processed in stages and hydrogenated, and the ethylene tar is fed into the coking device in reaction cycles. However, this method is complex and wastes resources when used to produce prebaked anode coke. Summary of the invention

[0009] Therefore, the technical problem to be solved by the present invention is to provide a high-end pre-baked anode special petroleum coke produced by using Shengli vacuum residue oil and ethylene tar as raw materials, and the produced petroleum coke fully meets the requirements of high-end pre-baked anode petroleum coke;

[0010] The second technical problem to be solved by the present invention is to provide a method for preparing the above-mentioned prebaked anode special petroleum coke, which solves the stability problem of ethylene tar and the miscibility problem of mixing. Shengli vacuum residue oil and ethylene tar are used as delayed coking raw materials, which reduces the nickel content and calcium content of the delayed coking raw materials. The produced petroleum coke fully meets the requirements of high-end prebaked anode petroleum coke.

[0011] The third technical problem to be solved by the present invention is to provide the application of the above-mentioned prebaked anode-specific petroleum coke.

[0012] In order to solve the above technical problems, a method for preparing high-end prebaked anode-specific petroleum coke according to the present invention comprises the following steps:

[0013] (1) adding ethylene tar to a tar stabilizer to obtain a first mixed material for later use;

[0014] (2) taking vacuum residue oil and adding heavy oil phase solvent to mix, to obtain a second mixed material, which is reserved for use;

[0015] (3) The first mixed material and the second mixed material are mixed and subjected to a delayed coking reaction to obtain the product.

[0016] Specifically, in the method for preparing the high-end prebaked anode special petroleum coke, in the step (1), the tar stabilizer comprises a mixture of dodecylbenzenesulfonic acid, p-alkylphenol and N,N-dimethylamide;

[0017] Preferably, the mass ratio of dodecylbenzenesulfonic acid, p-alkylphenol and N,N-dimethylamide is 2-4:1-2:1-2;

[0018] Preferably, the tar stabilizer is added in an amount of 200-300 ppm based on the ethylene tar;

[0019] Preferably, the method further comprises the step of mixing the tar stabilizer with ethylene diesel;

[0020] Preferably, the mass ratio of the tar stabilizer to the ethylene diesel is 1-2:1-2;

[0021] Preferably, the mass ratio of the tar stabilizer to the ethylene diesel is 1:1.

[0022] Specifically, the method for preparing high-end prebaked anode-specific petroleum coke, in the step (1), further comprises the step of subjecting the first mixed material to high-speed shearing treatment;

[0023] Preferably, the shearing speed of the high-speed shearing step is 3000-5000 r / min;

[0024] Preferably, the step (1) further comprises the step of continuing to stir the first mixed material after high-speed shearing;

[0025] Preferably, the stirring rate of the stirring step is 200-300 r / min, the stirring time is 60-90 min, and the stirring constant temperature is 60-70°C.

[0026] Specifically, in the method for preparing high-end prebaked anode-specific petroleum coke, in step (1), the metal content of the ethylene tar is: Ca content: 0.3-3.0 mg·kg -1 、Fe content: 6-10mg·kg -1 、Na content: 4-8mg·kg -1 、Ni content: 2-6mg·kg -1 、Si content: 4-8mg·kg -1 、V content: 3-7mg·kg -1 .

[0027] Specifically, in the method for preparing high-end prebaked anode-specific petroleum coke, in the step (2), the heavy oil phase solvent comprises a mixture of p-alkylaniline, dodecylbenzenesulfonic acid, span-80 and 1,2-propylene oxide;

[0028] Preferably, the mass ratio of p-alkylaniline, dodecylbenzenesulfonic acid, span-80 and 1,2-propylene oxide is 2-4:1-3:1-3:1-3;

[0029] Preferably, the heavy oil phase solvent is added in an amount of 200-300 ppm based on the vacuum residue;

[0030] Preferably, the step of mixing the heavy oil phase solvent with atmospheric and vacuum diesel is also included;

[0031] Preferably, the mass ratio of the heavy oil phase solvent to the atmospheric and vacuum diesel is 1-2:1-2;

[0032] Preferably, the mass ratio of the heavy oil phase solvent to the atmospheric and vacuum diesel is 1:1.

[0033] Specifically, the method for preparing high-end prebaked anode-specific petroleum coke, in the step (2), further comprises the step of subjecting the second mixed material to high-speed shearing treatment;

[0034] Preferably, the shearing speed of the high-speed shearing step is 3000-5000 r / min;

[0035] Preferably, the step (2) further comprises the step of continuing to stir the second mixed material after high-speed shearing;

[0036] Preferably, the stirring step has a stirring rate of 200-300 r / min, a stirring time of 120-180 min, and a stirring temperature of 80-90°C.

[0037] Specifically, in the method for preparing high-end prebaked anode special petroleum coke, in the step (2), the metal content of the vacuum residue is: Ca content: 40-50 mg·kg -1 、Fe content: 7-10mg·kg -1 、Na content: 2-4mg·kg -1 、Ni content: 42-52mg·kg -1 、Si content: 0.2-0.5mg·kg -1 、V content: 20-30mg·kg -1 .

[0038] Specifically, in the method for preparing high-end prebaked anode special petroleum coke, in the step (3), in the delayed coking reaction step, the outlet temperature of the heating furnace is controlled to be 490-500°C, the operating pressure of the coke drum is controlled to be 0.1-0.2Mpa, and the generated petroleum coke is stripped from the coke drum;

[0039] Preferably, in the delayed coking reaction step, the mass ratio of the vacuum residue oil to the ethylene tar is 60-90:20-50;

[0040] Preferably, the mass content of the ethylene tar in the mixed coking feedstock is ≥22%.

[0041] The invention also discloses high-end pre-baked anode-specific petroleum coke prepared by the method;

[0042] Preferably, the element content of the petroleum coke is: Ca≦200 mg·kg -1 , Fe≦200mg·kg -1 , Na≦100mg·kg -1 , Ni ≤ 200 mg kg -1 , Si ≤ 200 mg kg -1 , V ≤ 200 mg kg -1 , sulfur content ≤4%.

[0043] The invention also discloses the use of the high-end pre-baked anode special petroleum coke in preparing pre-baked anodes.

[0044] The high-end pre-baked anode special petroleum coke of the present invention uses ethylene tar and vacuum residue oil with high metal content as main raw materials, and the raw materials are pre-treated as coking raw materials. After the coking raw materials are heated in a heating furnace, they are injected into a coke tower for delayed coking, so as to produce high-end pre-baked anode special petroleum coke.

[0045] The method for preparing high-end prebaked anode special petroleum coke of the present invention uses Shengli vacuum residue oil and ethylene tar as raw materials for a delayed coking device, and pretreats the raw materials. First, the ethylene tar and the tar stabilizer are sheared at high speed, and then enter the ethylene tar storage tank for further mixing. Then, the ethylene tar, vacuum residue oil and heavy oil phase solvent are sheared at high speed, and then transported to the mixed raw material storage tank for further mixing. The problem of poor compatibility when ethylene tar and vacuum residue oil are mixed is solved, and the uniformity of the distribution of metal elements in the coking raw materials and petroleum coke products is ensured. The produced petroleum coke meets the requirements of high-end prebaked anode special coke, solves the problem that Shengli residue oil has a high metal content and cannot produce high-end prebaked anode coke, and at the same time realizes the comprehensive utilization of ethylene tar and improves added value.

[0046] The preparation method of high-end prebaked anode special petroleum coke of the present invention adopts Shengli vacuum residue oil and ethylene tar as delayed coking mixed raw materials. Compared with simply mixing the two raw materials, ethylene tar stabilizer and heavy oil mixed phase solvent are added in the raw material processing process. The tar stabilizer is first added to the ethylene tar, which ensures the stability of the properties of the ethylene tar and promotes the role of the heavy oil mixed phase solvent, so as to promote the full and uniform mixing of Shengli vacuum residue oil and ethylene tar, thereby ensuring the stable and uniform properties of the product petroleum coke.

[0047] In the preparation method of the high-end prebaked anode special petroleum coke of the present invention, during the pretreatment of the raw materials, the ethylene tar stabilizer and the heavy oil phase solvent are not simply added. Since the viscosity of ethylene tar and vacuum residue oil is relatively large, direct addition will result in the inability of the additive to fully diffuse. The present invention is to mix the ethylene tar stabilizer with coking diesel, and then shear it with ethylene tar at high speed by virtue of the good compatibility between ethylene diesel and ethylene tar, to ensure that the ethylene tar stabilizer is fully mixed with ethylene tar, inhibit the polymerization of colloids and asphaltene in the tar, and achieve the stability of the tar properties. The heavy oil phase solvent is first mixed with atmospheric and vacuum diesel, and by virtue of the good compatibility between atmospheric and vacuum residue oil, it is then mixed with ethylene tar and vacuum residue oil for high-speed shearing, so that the Shengli vacuum residue oil and ethylene tar are fully mixed and uniform.

[0048] The method for preparing high-end prebaked anode special petroleum coke of the present invention makes full use of the low nickel and low calcium advantages of ethylene tar, reduces the calcium content and nickel content of the coking raw materials, and the produced petroleum coke meets the indicators of high-end prebaked anode special petroleum coke, realizing low-value and high-use of ethylene tar.

[0049] The petroleum coke produced by the present invention is a special petroleum coke that meets the requirements of high-end prebaked anodes, and the content of each element in the petroleum coke is: Ca≦200mg·kg -1 , Fe≦200mg·kg -1 , Na≦100mg·kg -1 , Ni ≤ 200 mg kg -1 , Si ≤ 200 mg kg -1 , V ≤ 200 mg kg -1 , sulfur content ≤ 4%, and its performance can meet the performance requirements of high-end prebaked anodes. BRIEF DESCRIPTION OF THE DRAWINGS

[0050] In order to make the content of the present invention more clearly understood, the present invention is further described in detail below according to specific embodiments of the present invention in conjunction with the accompanying drawings, wherein:

[0051] Figure 1 The present invention is a flow chart of a processing test device for preparing the petroleum coke;

[0052] The reference numerals in the figure are as follows: 1-ethylene tar storage tank, 2-mixed raw material storage tank, 3-heating furnace, 4-coke tower, 5-distillation tower, 6-high-speed shearing machine. DETAILED DESCRIPTION

[0053] In order to make the purpose, technical solution and advantages of the embodiments of the present invention more clear, the technical solution in the embodiments of the present invention will be clearly and completely described below in combination with the embodiments of the present invention.

[0054] like Figure 1 The process of producing high-end pre-baked anode special petroleum coke according to the present invention is based on the device flow chart shown in FIG. Figure 1 In the process shown, the tar stabilizer is mixed with ethylene diesel in a ratio of 1:1, and then merged with ethylene tar in a pipeline, and then enters the ethylene tar storage tank 1 through a 4000 rpm high-speed shearing machine 6, and is stirred and stabilized in the ethylene tar storage tank 1 for 60-90 minutes, and then outputted from the ethylene tar through a pipeline. Another heavy oil phase solvent is mixed with atmospheric and vacuum diesel in a ratio of 1:1, and then merged with the preheated Shengli slag and stabilized ethylene tar in a pipeline, and then enters the mixed raw material storage tank 2 through a 4000 rpm high-speed shearing machine 6, and is stirred and mixed in the tank for 120-180 minutes. The pretreated mixed raw material oil enters the heating furnace 3 through a pipeline, and after being heated to 490-500°C, enters the coke tower 4 through a pipeline, and the generated petroleum coke is shoveled out from the bottom of the coke tower, and the generated oil and gas enter the fractionation tower 5.

[0055] The following embodiments 1-5 and comparative examples 1-3 of the present invention are based on the above Figure 1The device shown is used for processing, production and evaluation of petroleum coke.

[0056] Example 1

[0057] The method for preparing petroleum coke of the present invention comprises the following steps:

[0058] (1) taking a tar stabilizer (2 parts by weight of dodecylbenzenesulfonic acid, 1 part by weight of p-alkylphenol, and 1 part by weight of N,N-dimethylamide) and mixing it with ethylene diesel in a ratio of 1:1, and then mixing it with ethylene tar and entering an ethylene tar storage tank through a high-speed shearing machine; wherein, the amount of the tar stabilizer added based on ethylene tar is 200 ppm, and the stirring rate of the ethylene tar storage tank is controlled to be 250 r / min, the stirring stabilization time is 90 min, and the constant temperature is 70°C;

[0059] (2) taking a heavy oil phase solvent (2 parts by weight of p-alkylaniline, 2 parts by weight of dodecylbenzenesulfonic acid, 1 part by weight of span-80, and 1 part by weight of 1,2-propylene oxide) and mixing it with atmospheric and vacuum diesel in a ratio of 1:1, and then combining it with ethylene tar and Shengli vacuum residue oil and sending it to a mixed raw material tank through a high-speed shearing machine; wherein, the weight portion of Shengli vacuum residue oil is 70 parts, the weight portion of ethylene tar is 30 parts, and the addition amount of the heavy oil phase solvent based on the vacuum residue oil is 300ppm; the mixed raw material storage tank is equipped with a stirrer, a stirring speed of 250r / min, a stirring stabilization time of 180min, and a constant temperature of 80°C;

[0060] (3) The pretreated coking mixed raw material is introduced into a heating furnace, the outlet temperature of the heating furnace is 495°C, the mixed raw material is introduced into a coke drum from the heating furnace, the reaction pressure of the coke drum is 0.16 MPa, the generated petroleum coke is shoveled out from the bottom of the coke drum, and the petroleum coke is collected from the upper and lower parts of the coke drum for elemental analysis. The results are shown in Table 1 below.

[0061] Example 2

[0062] The method for preparing petroleum coke of the present invention comprises the following steps:

[0063] (1) After mixing tar stabilizer with ethylene diesel in a ratio of 1:1, the mixture is combined with ethylene tar and sent into an ethylene tar storage tank through a high-speed shearing machine; the amount of tar stabilizer added based on ethylene tar is 240 ppm, and its weight parts are: 3 parts of dodecylbenzenesulfonic acid, 2 parts of p-alkylphenol, and 2 parts of N,N-dimethylamide; the stirring speed of the ethylene tar storage tank is controlled to be 250 r / min, the stirring stabilization time is 70 min, and the constant temperature is 65°C;

[0064] (2) After mixing the heavy oil phase solvent with atmospheric and vacuum diesel in a ratio of 1:1, the mixture is combined with ethylene tar and Shengli vacuum residue and sent to a mixed raw material tank via a high-speed shearing machine; wherein the weight portion of Shengli vacuum residue is 60 parts, the weight portion of ethylene tar is 40 parts, the addition amount of the heavy oil phase solvent based on the vacuum residue is 260ppm, and the weight portions of the heavy oil phase solvent composition are: 4 parts of p-alkylaniline, 3 parts of dodecylbenzenesulfonic acid, 2 parts of span-80, and 2 parts of 1,2-propylene oxide; the mixed raw material storage tank is equipped with a stirrer, a stirring rate of 250r / min, a stirring stabilization time of 160min, and a constant temperature of 90°C;

[0065] (3) The pretreated coking mixed raw material enters the heating furnace, and the outlet temperature of the heating furnace is 500°C. The mixed raw material enters the coke drum from the heating furnace, and the reaction pressure of the coke drum is 0.16MPa. The generated petroleum coke is shoveled out from the bottom of the coke drum, and the petroleum coke is collected from the upper and lower parts of the coke drum and elemental analysis is performed. The results are shown in Table 1 below.

[0066] Example 3

[0067] The method for preparing petroleum coke of the present invention comprises the following steps:

[0068] (1) Take a tar stabilizer and ethylene diesel in a ratio of 1:1, mix them with ethylene tar, and then enter the ethylene tar storage tank through a high-speed shearing machine; the amount of tar stabilizer added based on ethylene tar is 300ppm, and its weight parts are: 2 parts of dodecylbenzenesulfonic acid, 2 parts of p-alkylphenol, and 2 parts of N,N-dimethylamide. The stirring rate of the ethylene tar storage tank is 250r / min, the stirring stabilization time is 60min, and the constant temperature is 60℃;

[0069] (2) After mixing the heavy oil phase solvent with atmospheric and vacuum diesel in a ratio of 1:1, the mixture is combined with ethylene tar and Shengli vacuum residue and sent to a mixed raw material tank via a high-speed shearing machine; wherein the weight portion of Shengli vacuum residue is 90 parts, the weight portion of ethylene tar is 30 parts, and the addition amount of the heavy oil phase solvent based on the vacuum residue is 200ppm, and the weight portions of the heavy oil phase solvent composition are: 4 parts of p-alkylaniline, 1 part of dodecylbenzenesulfonic acid, 1 part of span-80, and 1 part of 1,2-propylene oxide; the mixed raw material storage tank is equipped with a stirrer, a stirring rate of 250r / min, a stirring stabilization time of 120min, and a constant temperature of 90°C;

[0070] (3) The pretreated coking mixed raw material enters the heating furnace, and the outlet temperature of the heating furnace is 490°C. The mixed raw material enters the coke drum from the heating furnace, and the reaction pressure of the coke drum is 0.16MPa. The generated petroleum coke is shoveled out from the bottom of the coke drum, and the petroleum coke is collected from the upper and lower parts of the coke drum and elemental analysis is performed. The results are shown in Table 1 below.

[0071] Example 4

[0072] The method for preparing petroleum coke of the present invention comprises the following steps:

[0073] (1) After the tar stabilizer is mixed with ethylene diesel in a ratio of 1:1, it is combined with ethylene tar and sent into the ethylene tar storage tank through a high-speed shearing machine. The amount of tar stabilizer added based on ethylene tar is 220ppm, and the weight proportion of the composition is: 4 parts of dodecylbenzenesulfonic acid, 2 parts of p-alkylphenol, and 1 part of N,N-dimethylamide. The stirring rate of the ethylene tar storage tank is 250r / min, the stirring stabilization time is 70min, and the constant temperature is 65℃.

[0074] (2) After the heavy oil phase solvent is mixed with atmospheric and vacuum diesel in a ratio of 1:1, it is combined with ethylene tar and Shengli vacuum residue and sent to the mixed raw material tank through a high-speed shearing machine. The weight proportion of Shengli vacuum residue is 80 parts, the weight proportion of ethylene tar is 40 parts, the addition amount of heavy oil phase solvent based on the vacuum residue is 240ppm, and the weight proportion of heavy oil phase solvent composition is: 2 parts of p-alkylaniline, 3 parts of dodecylbenzenesulfonic acid, 3 parts of span-80, and 3 parts of 1,2-propylene oxide. The mixed raw material storage tank is equipped with a stirrer, a stirring rate of 250r / min, a stirring stabilization time of 140min, and a constant temperature of 85°C.

[0075] (3) The pretreated coking mixed raw material enters the heating furnace, and the outlet temperature of the heating furnace is 495°C. The mixed raw material enters the coke drum from the heating furnace, and the reaction pressure of the coke drum is 0.16MPa. The generated petroleum coke is shoveled out from the bottom of the coke drum. The petroleum coke is collected from the upper and lower parts of the coke drum and elemental analysis is performed. The results are shown in Table 1 below.

[0076] Example 5

[0077] The method for preparing petroleum coke of the present invention comprises the following steps:

[0078] (1) Take a tar stabilizer and ethylene diesel in a ratio of 1:1, mix them with ethylene tar, and then enter the ethylene tar storage tank through a high-speed shearing machine; the amount of tar stabilizer added based on ethylene tar is 240ppm, and its weight parts are: 3 parts of dodecylbenzenesulfonic acid, 1 part of p-alkylphenol, and 1 part of N,N-dimethylamide. The stirring speed of the ethylene tar storage tank is 250r / min, the stirring stabilization time is 80min, and the constant temperature is 70℃;

[0079] (2) After mixing the heavy oil phase solvent with atmospheric and vacuum diesel in a ratio of 1:1, the mixture is combined with ethylene tar and Shengli vacuum residue and sent to a mixed raw material tank via a high-speed shearing machine; wherein the weight portion of Shengli vacuum residue is 80 parts, the weight portion of ethylene tar is 23 parts, the addition amount of the heavy oil phase solvent based on the vacuum residue is 280ppm, and the weight portions of the heavy oil phase solvent composition are: 2 parts of p-alkylaniline, 3 parts of dodecylbenzenesulfonic acid, 1 part of span-80, and 3 parts of 1,2-propylene oxide; the mixed raw material storage tank is equipped with a stirrer, a stirring rate of 250r / min, a stirring stabilization time of 180min, and a constant temperature of 90°C;

[0080] (3) The pretreated coking mixed raw material enters the heating furnace, and the outlet temperature of the heating furnace is 495°C. The mixed raw material enters the coke drum from the heating furnace, and the reaction pressure of the coke drum is 0.16MPa. The generated petroleum coke is shoveled out from the bottom of the coke drum. The petroleum coke is collected from the upper and lower parts of the coke drum and elemental analysis is performed. The results are shown in Table 1 below.

[0081] Comparative Example 1

[0082] The preparation method of petroleum coke described in this comparative example is to directly use Shengli vacuum residue oil as raw material, which enters the heating furnace through a pipeline. The outlet temperature of the heating furnace is 495°C. The raw material enters the coke tower from the heating furnace. The reaction pressure of the coke tower is 0.16MPa. The generated petroleum coke is shoveled out from the bottom of the coke tower, and the petroleum coke is collected from the upper and lower parts of the coke tower and elemental analysis is performed. The results are shown in Table 1 below.

[0083] Comparative Example 2

[0084] The method for preparing petroleum coke described in this comparative example comprises the following steps:

[0085] (1) Add 300 ppm of tar stabilizer to ethylene tar, the weight proportion of the tar stabilizer is: 4 parts of dodecylbenzenesulfonic acid, 2 parts of p-alkylphenol, and 1 part of N,N-dimethylamide; the stirring rate of the ethylene tar storage tank is 250 r / min, the stirring stabilization time is 90 min, and the constant temperature is 70°C;

[0086] (2) The stabilized ethylene tar is transported to a mixed raw material tank via a pipeline, and at the same time, Shengli vacuum residue and heavy oil phase solvent are added into the mixed raw material tank; wherein the weight portion of Shengli vacuum residue is 90 parts, the weight portion of ethylene tar is 30 parts, the amount of heavy oil phase solvent added is 300ppm, and the weight portion of the heavy oil phase solvent composition is: 4 parts of p-alkylaniline, 3 parts of dodecylbenzenesulfonic acid, 3 parts of span-80, and 3 parts of 1,2-propylene oxide; the mixed raw material storage tank is stirred at a rate of 250r / min, the stirring stabilization time is 180min, and the constant temperature is 90°C;

[0087] (3) The pretreated coking mixed raw material enters the heating furnace, and the outlet temperature of the heating furnace is 500°C. The mixed raw material enters the coke drum from the heating furnace, and the reaction pressure of the coke drum is 0.16MPa. The generated petroleum coke is shoveled out from the bottom of the coke drum, and the petroleum coke is collected from the upper and lower parts of the coke drum and elemental analysis is performed. The results are shown in Table 1 below.

[0088] Comparative Example 3

[0089] The method for preparing petroleum coke described in this comparative example comprises the following steps:

[0090] (1) Ethylene tar is added into an ethylene tar storage tank, and the stirring rate in the storage tank is 250 r / min, the stirring stabilization time is 90 min, and the constant temperature is 70°C;

[0091] (2) 80 parts by weight of Shengli slag and 23 parts by weight of ethylene tar were input into a mixed raw material storage tank for stirring at a stirring rate of 250 r / min, a stirring stabilization time of 180 min, and a constant temperature of 90°C;

[0092] (3) The pretreated coking mixed raw material enters the heating furnace, and the outlet temperature of the heating furnace is 493°C. The mixed raw material enters the coke drum from the heating furnace, and the reaction pressure of the coke drum is 0.16MPa. The generated petroleum coke is shoveled out from the bottom of the coke drum, and the petroleum coke is collected from the upper and lower parts of the coke drum and elemental analysis is performed. The results are shown in Table 1 below.

[0093] In the above Examples 1-5 and Comparative Examples 1-3, the properties of the coking raw materials and petroleum coke products under different test conditions are shown in Table 1.

[0094] Table 1 Analysis results of coking raw materials and product properties

[0095]

[0096]

[0097] As can be seen from Table 1, the petroleum coke produced by the method of the present invention has similar element contents in the petroleum coke collected from the upper and lower parts of the coke tower in Examples 1-5, indicating that the product properties are uniform. By comparing with the high-end prebaked anode coke indicators provided by Sotong Development Company in Table 1, the Ca content of the petroleum coke in Examples 1-5 is ≤200 mg·kg -1 、Ni content ≤ 200mg·kg -1 , all meet the requirements of high-end prebaked anode coke. In Comparative Example 1, when Shengli vacuum residue was used as a single raw material to produce petroleum coke, the Ca content of the upper petroleum coke was 225.2 mg·kg -1 , Ni content is 248.3 mg·kg -1 , the Ca content of the lower petroleum coke is 227.4 mg kg -1, Ni content is 252.2 mg·kg -1 , Ca and Ni contents do not meet the requirements of high-end prebaked anode coke. In Comparative Examples 2 and 3, the properties of the petroleum coke products collected from the upper and lower parts of the coke tower are quite different. It can be seen that the properties of the petroleum coke produced by simply mixing ethylene tar and Shengli vacuum residue oil, or simply adding tar stabilizer and heavy oil phase solvent are not uniform.

[0098] The embodiments of the present invention are described in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core idea. At the same time, for those skilled in the art, according to the idea of ​​the present invention, there will be changes in the specific implementation methods and application scope. In summary, the content of this specification should not be understood as limiting the present invention.

Claims

1. A method for preparing high-end prebaked anode special petroleum coke, characterized in that: The steps include: (1) adding ethylene tar to a tar stabilizer to obtain a first mixed material for later use; (2) taking vacuum residue oil and adding heavy oil phase solvent to mix, to obtain a second mixed material, which is reserved for use; (3) The first mixed material and the second mixed material are mixed and subjected to a delayed coking reaction to obtain the product.

2. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 1, characterized in that: In the step (1), the tar stabilizer comprises a mixture of dodecylbenzenesulfonic acid, p-alkylphenol and N,N-dimethylamide; Preferably, the mass ratio of dodecylbenzenesulfonic acid, p-alkylphenol and N,N-dimethylamide is 2-4:1-2:1-2; Preferably, the tar stabilizer is added in an amount of 200-300 ppm based on ethylene tar; Preferably, the method further comprises the step of mixing the tar stabilizer with ethylene diesel; Preferably, the mass ratio of the tar stabilizer to the ethylene diesel is 1-2:1-2; Preferably, the mass ratio of the tar stabilizer to the ethylene diesel is 1:

1.

3. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 2, characterized in that: The step (1) further comprises the step of subjecting the first mixture to a high-speed shearing treatment; Preferably, the shearing speed of the high-speed shearing step is 3000-5000 r / min; Preferably, the step (1) further comprises the step of continuing to stir the first mixed material after high-speed shearing; Preferably, the stirring rate of the stirring step is 200-300 r / min, the stirring time is 60-90 min, and the stirring constant temperature is 60-70°C.

4. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 2 or 3, characterized in that: In the step (1), the metal content of the ethylene tar is: Ca content: 0.3-3.0 mg·kg -1 、Fe content: 6-10mg·kg -1 、Na content: 4-8mg·kg -1 、Ni content: 2-6mg·kg -1 、Si content: 4-8mg·kg -1 、V content: 3-7mg·kg -1 .

5. The method for preparing high-end prebaked anode-specific petroleum coke according to any one of claims 1 to 4, characterized in that: In the step (2), the heavy oil phase solvent comprises a mixture of p-alkylaniline, dodecylbenzenesulfonic acid, span-80 and 1,2-propylene oxide; Preferably, the mass ratio of p-alkylaniline, dodecylbenzenesulfonic acid, span-80 and 1,2-propylene oxide is 2-4:1-3:1-3:1-3; Preferably, the heavy oil phase solvent is added in an amount of 200-300 ppm based on the vacuum residue; Preferably, the step of mixing the heavy oil phase solvent with atmospheric and vacuum diesel is also included; Preferably, the mass ratio of the heavy oil phase solvent to the atmospheric and vacuum diesel is 1-2:1-2; Preferably, the mass ratio of the heavy oil phase solvent to the atmospheric and vacuum diesel is 1:

1.

6. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 5, characterized in that: The step (2) further includes the step of subjecting the second mixture to a high-speed shearing treatment; Preferably, the shearing speed of the high-speed shearing step is 3000-5000 r / min; Preferably, the step (2) further comprises the step of continuing to stir the second mixed material after high-speed shearing; Preferably, the stirring step has a stirring rate of 200-300 r / min, a stirring time of 120-180 min, and a stirring temperature of 80-90°C.

7. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 5 or 6, characterized in that: In the step (2), the metal content of the vacuum residue is: Ca content: 40-50 mg·kg -1 、Fe content: 7-10mg·kg -1 、Na content: 2-4mg·kg -1 、Ni content: 42-52mg·kg -1 、Si content: 0.2-0.5mg·kg -1 、V content: 20-30mg·kg -1 .

8. The method for preparing high-end prebaked anode-specific petroleum coke according to any one of claims 1 to 7, characterized in that: In the step (3), in the delayed coking reaction step, the outlet temperature of the heating furnace is controlled to be 490-500° C., the operating pressure of the coke drum is controlled to be 0.1-0.2 MPa, and the generated petroleum coke is stripped from the coke drum; Preferably, in the delayed coking reaction step, the mass ratio of the vacuum residue oil to the ethylene tar is 60-90:20-50; Preferably, the mass content of the ethylene tar in the mixed coking feedstock is ≥22%.

9. High-end prebaked anode-specific petroleum coke prepared by the method according to any one of claims 1 to 8; Preferably, the element content of the petroleum coke is: Ca≦200 mg·kg -1 ,Fe≦200mg·kg -1 , Na≦100mg·kg -1 , Ni ≤ 200 mg kg -1 , Si ≤ 200 mg kg -1 , V ≤ 200 mg kg -1 , sulfur content ≤4%.

10. Use of the high-end prebaked anode special petroleum coke according to claim 9 for preparing prebaked anodes.

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