High-end prebaked anode special petroleum coke and preparation method and application thereof

Abstract

The application belongs to the technical field of petroleum processing, and particularly 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 and ethylene tar as raw materials. The high-end prebaked anode special petroleum coke is prepared by using the ethylene tar and the vacuum residue with high metal content as main raw materials, and the raw materials are pretreated and used as coking raw materials. After the coking raw materials are heated by a heating furnace, the coking raw materials are injected into a coking tower for delayed coking, and the high-end prebaked anode special petroleum coke can be produced.

Description

TECHNICAL FIELD

[0001] The present application belongs to the technical field of petroleum processing, and particularly relates to a special petroleum coke for high-end prebaked anodes and a preparation method thereof, in particular, a delayed coking production method using Shengli vacuum residue and ethylene tar as raw materials. BACKGROUND

[0002] Metal aluminum is one of the important raw materials to ensure the sustainable development of national economy, and is widely used in various fields. It is reported that about 0.49 tons of prebaked anode is needed for producing 1 ton of electrolytic aluminum in an electrolytic aluminum enterprise. The prebaked anode is made of petroleum coke, pitch coke as aggregate and coal tar pitch as binder, and is used as anode material for prebaked aluminum electrolysis cell. Since the material has been baked and has a stable geometric shape, it is also called prebaked anode carbon block, and is also commonly known as carbon anode for aluminum electrolysis. The aluminum electrolysis cell using prebaked anode carbon block as anode is called prebaked anode electrolysis cell, which is a kind of modern large-scale aluminum electrolysis cell.

[0003] Petroleum coke is the main production raw material of prebaked anode, and the product quality directly affects the quality of prebaked anode, and the main factors affecting the quality of petroleum coke are various trace elements contained therein. For example, trace elements such as Ni and V have a relatively fast oxidation speed, which causes the prebaked anode to be severely oxidized and problems such as slagging and block dropping to occur, resulting in a decrease in the electrical conductivity of the prebaked anode, a decrease in the current effect in the aluminum electrolysis cell, and a significant increase in the demand for carbon during the production process of the prebaked anode; and trace elements such as Si and Fe mainly affect the mechanical properties and purity of the finished primary aluminum. Therefore, in order to ensure the product quality of the prebaked anode, it is necessary to treat and control these trace elements in the petroleum coke to improve the quality of the prebaked anode, improve the consumption of the anode, and be beneficial to energy saving and emission reduction of the aluminum electrolysis industry under the "double carbon" target.

[0004] Petroleum coke is generally a carbonized product obtained by deep thermal cracking reaction at high temperature through a delayed coking process. The raw material of the delayed coking device is mainly vacuum residue, and the residue is heavy residue obtained by vacuum distillation of crude oil. Therefore, the properties of the crude oil, especially the content of trace elements, are the key factors to determine the content of trace elements in the residue and petroleum coke. When the content of trace elements in the coking raw material is high, the petroleum coke produced is prone to cause unstable quality of the prebaked anode when used for producing the prebaked anode. In addition, the existence of trace elements in the petroleum coke also affects the quality of the prebaked anode. At present, the manufacturers producing high-end prebaked anode coke are mostly refineries processing high-quality crude oil.

[0005] The Ca and Ni element contents of the petroleum coke product produced by the refinery of Qilu Company using vacuum residue of the fourth atmospheric-vacuum distillation unit as raw material are relatively high, and the rest of the indexes meet the requirements. The reason is that the fourth atmospheric-vacuum distillation unit mainly processes Shengli high-sulfur and high-acid crude oil, and the Ca and Ni element contents in the crude oil are relatively high, so the Ca content in the Shengli vacuum residue is 40-50 mg·kg -1 , and the Ni content is 42-52 mg·kg -1 . Since most of the metal elements in the raw material finally enter the petroleum coke during the production of petroleum coke, and the yield of petroleum coke is about 20%, when the Shengli vacuum residue is used as the single raw material to produce petroleum coke, the Ca and Ni element contents in the petroleum coke are both more than 200 mg·kg -1 , which does not meet the index requirement of Ca≤200 mg·kg -1 and Ni≤200 mg·kg -1 provided by Suotong Development Company for high-end prebaked anode coke. Therefore, the vacuum residue of Shengli crude oil can only be used to produce ordinary prebaked anode coke, and the raw material of the 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 for producing ethylene, and has a complex composition structure, high content of unsaturated hydrocarbons such as aromatic hydrocarbons and aromatic alkenes, poor oxidation stability, easy deposition of coke under heating, high condensation degree, and poor compatibility 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 producing high-end prebaked anode coke.

[0007] For example, Chinese Patent CN101608132A discloses a delayed coking production method using ethylene cracking tar as raw material, which uses ethylene cracking tar, vacuum residue and catalytic oil slurry to form a delayed coking mixed raw material, so as to reduce the sulfur content and nitrogen content of the gasoline and diesel oil of the coking device, and reduce the sulfur content and metal content of the wax oil and petroleum coke. However, this simple blending is not suitable for Shengli vacuum residue, mainly because the compatibility of the ethylene tar of Qilu with the Shengli vacuum residue is poor, and there is obvious stratification and condensation phenomenon. In addition, due to the high calcium and nickel contents of the Shengli vacuum residue, the coking raw material is not uniformly mixed, which may cause the calcium content of the petroleum coke to exceed the standard.

[0008] For example, Chinese Patent CN113122330A discloses a scheme for preparing petroleum coke using catalytic oil slurry and ethylene tar, the catalytic oil slurry is processed in stages and subjected to hydrogenation treatment, and the ethylene tar is fed into the coking device in reaction cycles. However, this method is complex and causes waste of resources when used to produce prebaked anode coke. SUMMARY

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

[0010] The second technical problem to be solved by the present application is to provide a preparation method of the prebaked anode special petroleum coke, which solves the stability problem of ethylene tar and the compatibility problem of mixing, and the use of Shengli vacuum residue and ethylene tar as delayed coking raw materials reduces the nickel content and calcium content of the delayed coking raw materials, and 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 application is to provide an application of the prebaked anode special petroleum coke.

[0012] To solve the above technical problems, the preparation method of the high-end prebaked anode special petroleum coke comprises the following steps:

[0013] (1) ethylene tar is mixed with a tar stabilizer to obtain a first mixture, which is ready for use;

[0014] (2) vacuum residue is mixed with a heavy oil compatibility solvent to obtain a second mixture, which is ready for use;

[0015] (3) the first mixture and the second mixture are mixed and subjected to delayed coking reaction, and the petroleum coke is obtained.

[0016] Specifically, 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 addition amount of the tar stabilizer based on the ethylene tar is 200-300 ppm;

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

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

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

[0022] Specifically, in the step (1), the preparation method of the high-end prebaked anode special petroleum coke further comprises the step of subjecting the first mixture 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 a step of continuously stirring the first mixture after high-speed shearing.

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

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

[0027] Specifically, in the preparation method of the high-end prebaked anode special petroleum coke, in the step (2), the heavy oil phase solvent comprises a mixture of p-alkylaniline, dodecylbenzenesulfonic acid, span-80 and 1,2-epoxypropane.

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

[0029] Preferably, the addition amount of the heavy oil phase solvent based on the vacuum residue is 200-300 ppm.

[0030] Preferably, it further comprises a step of mixing the heavy oil phase solvent with the atmospheric and vacuum diesel oil.

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

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

[0033] Specifically, in the preparation method of the high-end prebaked anode special petroleum coke, in the step (2), it further comprises a step of high-speed shearing the second mixture.

[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 continuously stirring the second mixture after high-speed shearing.

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

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

[0038] Specifically, in the preparation method of the high-end petroleum coke special for pre-baked anodes, in the step (3), in the delayed coking reaction step, the outlet temperature of the heating furnace is controlled to be 490-500℃, the operating pressure of the coke tower is 0.1-0.2 Mpa, and the generated petroleum coke is stripped from the coke tower.

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

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

[0041] The application further discloses the high-end petroleum coke special for pre-baked anodes prepared by the method.

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

[0043] The application further discloses the use of the high-end petroleum coke special for pre-baked anodes for preparing pre-baked anodes.

[0044] The high-end prebaked anode special petroleum coke provided by the application is prepared by using the vacuum residue of Shengli and ethylene tar as the main raw material of delayed coking device, and by pretreating the raw material.

[0045] The preparation method of the high-end prebaked anode special petroleum coke provided by the application uses the vacuum residue of Shengli and ethylene tar as the raw material of delayed coking device, and by pretreating the raw material, the ethylene tar and tar stabilizer are first mixed at high speed, then the mixture is put into the ethylene tar storage tank for further mixing, then the ethylene tar, vacuum residue and heavy oil phase solvent are mixed at high speed, and then the mixture is put into the mixed raw material storage tank for further mixing, so that the problem of poor miscibility of the ethylene tar and the vacuum residue is solved, and the uniformity of the metal element distribution of the coking raw material and the petroleum coke product is ensured.

[0046] The preparation method of the high-end prebaked anode special petroleum coke provided by the application uses the vacuum residue of Shengli and ethylene tar as the raw material of delayed coking device, and by pretreating the raw material, the ethylene tar and tar stabilizer are first mixed at high speed, then the mixture is put into the ethylene tar storage tank for further mixing, then the ethylene tar, vacuum residue and heavy oil phase solvent are mixed at high speed, and then the mixture is put into the mixed raw material storage tank for further mixing, so that the problem of poor miscibility of the ethylene tar and the vacuum residue is solved, and the uniformity of the metal element distribution of the coking raw material and the petroleum coke product is ensured.

[0047] The preparation method of the high-end prebaked anode special petroleum coke provided by the application uses the vacuum residue of Shengli and ethylene tar as the raw material of delayed coking device, and by pretreating the raw material, the ethylene tar and tar stabilizer are first mixed at high speed, then the mixture is put into the ethylene tar storage tank for further mixing, then the ethylene tar, vacuum residue and heavy oil phase solvent are mixed at high speed, and then the mixture is put into the mixed raw material storage tank for further mixing, so that the problem of poor miscibility of the ethylene tar and the vacuum residue is solved, and the uniformity of the metal element distribution of the coking raw material and the petroleum coke product is ensured.

[0048] The preparation method of the high-end prebaked anode special petroleum coke provided by the application fully utilizes the low-nickel and low-calcium advantages of ethylene tar, reduces the calcium content and nickel content of the coking raw material, and the produced petroleum coke meets the index of high-end prebaked anode special petroleum coke, and realizes the low-value high-use of ethylene tar.

[0049] The high-end prebaked anode special petroleum coke of the application, the produced petroleum coke is special petroleum coke meeting the requirements of high-end prebaked anode, the element content of the petroleum coke is: Ca≦200mg·kg -1 , Fe≦200mg·kg -1 , Na≦100mg·kg -1 , Ni≦200mg·kg -1 , Si≦200mg·kg -1 , V≦200mg·kg -1 , the sulfur content is ≦4%, and the performance can meet the performance requirements of high-end prebaked anode. BRIEF DESCRIPTION OF DRAWINGS

[0050] In order to make the content of the application more easily understood, the application will be further described in detail below according to the specific embodiments of the application and in combination with the drawings, wherein,

[0051] Figure 1 The process flow chart of the processing test device for preparing the petroleum coke of the application;

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

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

[0054] As shown in the device flow chart, Figure 1 the process for producing the high-end prebaked anode special petroleum coke of the application is processed based on the device. As shown in the flow, Figure 1 , the tar stabilizer and ethylene diesel oil are mixed according to 1:1, then are combined with ethylene tar in a pipeline, enter the ethylene tar storage tank 1 through the high-speed shearing machine 6 of 4000 revolutions / minute, are stirred and stabilized in the ethylene tar storage tank 1 for 60-90min, and are output from the ethylene tar through a pipeline. The heavy oil phase solvent and atmospheric and vacuum diesel oil are mixed according to 1:1, then are combined with the preheated Shengli residue and the stabilized ethylene tar in a pipeline, enter the mixed raw material storage tank 2 through the high-speed shearing machine 6 of 4000 revolutions / minute, are stirred and mixed in the tank for 120-180min, the pretreated mixed raw material oil enters the heating furnace 3 through a pipeline, is heated to 490-500℃, then enters the coking tower 4 through a pipeline, the generated petroleum coke is shovelled out from the bottom of the coking tower, and the generated oil gas enters the fractionating tower 5.

[0055] The schemes in the following embodiments 1-5 and comparative examples 1-3 of the application are based on the above Figure 1The device shown processes, produces and evaluates petroleum coke.

[0056] Example 1

[0057] The preparation method of the petroleum coke comprises the following steps:

[0058] (1) The tar stabilizer (2 parts by weight of dodecyl benzene sulfonic acid, 1 part by weight of p-alkyl phenol, and 1 part by weight of N, N-dimethylamide) is mixed with ethylene diesel oil at a ratio of 1:1, and then is combined with ethylene tar and is sent into an ethylene tar storage tank through a high-speed shearing machine; wherein, the addition amount of the tar stabilizer based on the ethylene tar is 200 ppm, the stirring rate of the ethylene tar storage tank is controlled to be 250 r / min, the stirring stabilization time is controlled to be 90 min, and the constant temperature is controlled to be 70 DEG C;

[0059] (2) The heavy oil phase solvent (2 parts by weight of p-alkyl aniline, 2 parts by weight of dodecyl benzene sulfonic acid, 1 part by weight of span-80, and 1 part by weight of 1, 2-epoxypropane) is mixed with atmospheric and vacuum diesel oil at a ratio of 1:1, and then is combined with ethylene tar and Shengli vacuum residue and is sent to a mixed raw material tank through a high-speed shearing machine; wherein, the weight fraction of the Shengli vacuum residue is 70 parts, the weight fraction of the ethylene tar is 30 parts, and the addition amount of the heavy oil phase solvent based on the vacuum residue is 300 ppm; the mixed raw material storage tank is provided with a stirrer, the stirring rate is controlled to be 250 r / min, the stirring stabilization time is controlled to be 180 min, and the constant temperature is controlled to be 80 DEG C;

[0060] (3) The pretreated coking mixed raw material is sent into a heating furnace, the outlet temperature of the heating furnace is 495 DEG C, the mixed raw material is sent from the heating furnace into a coke tower, the reaction pressure of the coke tower is 0.16 MPa, the generated petroleum coke is shovelled out from the bottom of the coke tower, the petroleum coke is collected from the upper part and the lower part of the coke tower respectively, and element analysis is performed, and the results are shown in the following table 1.

[0061] Example 2

[0062] The preparation method of the petroleum coke comprises the following steps:

[0063] (1) The tar stabilizer is mixed with ethylene diesel oil at a ratio of 1:1, and then is combined with ethylene tar and is sent into an ethylene tar storage tank through a high-speed shearing machine; the addition amount of the tar stabilizer based on the ethylene tar is 240 ppm, the weight fractions of the components of the tar stabilizer are as follows: 3 parts of dodecyl benzene sulfonic acid, 2 parts of p-alkyl phenol, and 2 parts of N, N-dimethylamide; the stirring rate of the ethylene tar storage tank is controlled to be 250 r / min, the stirring stabilization time is controlled to be 70 min, and the constant temperature is controlled to be 65 DEG C;

[0064] (2) Take heavy oil phase solvent and atmospheric-vacuum diesel oil 1:1 mixed with ethylene tar, Shengli vacuum residue, and then send to the mixed raw material tank through a high-speed shearing machine; wherein, the weight fraction of Shengli vacuum residue is 60 parts, the weight fraction of ethylene tar is 40 parts, the addition amount of heavy oil phase solvent based on the vacuum residue is 260 ppm, and the weight fraction of heavy oil phase solvent composition is: 4 parts of p-alkyl aniline, 3 parts of dodecyl benzene sulfonic acid, 2 parts of span-80, and 2 parts of 1,2-epoxypropane; the mixed raw material storage tank is provided with a stirrer, the stirring rate is 250 r / min, the stirring stabilization time is 160 min, and the constant temperature is 90℃;

[0065] (3) The pretreated coking mixed raw material enters the heating furnace, and the outlet temperature of the heating furnace is 500℃. The mixed raw material enters the coke tower from the heating furnace, the reaction pressure of the coke tower is 0.16 MPa, 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 respectively and subjected to element analysis, and the results are shown in Table 1 below.

[0066] Example 3

[0067] The preparation method of the petroleum coke provided by the application comprises the following steps:

[0068] (1) Take the tar stabilizer and ethylene diesel oil 1:1 mixed with ethylene tar, and then send to the ethylene tar storage tank through a high-speed shearing machine; the addition amount of the tar stabilizer based on the ethylene tar is 300 ppm, and the weight fraction of the composition is: 2 parts of dodecyl benzene sulfonic acid, 2 parts of p-alkyl phenol, and 2 parts of N,N-dimethylamide. The stirring rate of the ethylene tar storage tank is 250 r / min, the stirring stabilization time is 60 min, and the constant temperature is 60℃;

[0069] (2) Take heavy oil phase solvent and atmospheric-vacuum diesel oil 1:1 mixed with ethylene tar, Shengli vacuum residue, and then send to the mixed raw material tank through a high-speed shearing machine; wherein, the weight fraction of Shengli vacuum residue is 90 parts, the weight fraction of ethylene tar is 30 parts, and the addition amount of heavy oil phase solvent based on the vacuum residue is 200 ppm, and the weight fraction of heavy oil phase solvent composition is: 4 parts of p-alkyl aniline, 1 part of dodecyl benzene sulfonic acid, 1 part of span-80, and 1 part of 1,2-epoxypropane; the mixed raw material storage tank is provided with a stirrer, the stirring rate is 250 r / min, the stirring stabilization time is 120 min, and the constant temperature is 90℃;

[0070] (3) The pretreated coking mixed raw material enters the heating furnace, and the outlet temperature of the heating furnace is 490℃. The mixed raw material enters the coke tower from the heating furnace, the reaction pressure of the coke tower is 0.16 MPa, 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 respectively and subjected to element analysis, and the results are shown in Table 1 below.

[0071] Example 4

[0072] The preparation method of the petroleum coke comprises the following steps:

[0073] (1) The tar stabilizer is mixed with ethylene diesel oil at a ratio of 1:1, and then is mixed with ethylene tar through a high-speed shearing machine to enter an ethylene tar storage tank. The addition amount of the tar stabilizer based on the ethylene tar is 220 ppm, and the weight fractions of the components are as follows: 4 parts of dodecyl benzene sulfonic acid, 2 parts of p-alkyl phenol 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 70 min, and the constant temperature is 65 DEG C.

[0074] (2) The heavy oil phase solvent is mixed with atmospheric and vacuum diesel oil at a ratio of 1:1, and then is mixed with ethylene tar and Shengli vacuum residue through a high-speed shearing machine to be sent to a mixed raw material tank. The weight fraction of the Shengli vacuum residue is 80 parts, the weight fraction of the ethylene tar is 40 parts, the addition amount of the heavy oil phase solvent based on the vacuum residue is 240 ppm, and the weight fractions of the components of the heavy oil phase solvent are as follows: 2 parts of p-alkyl aniline, 3 parts of dodecyl benzene sulfonic acid, 3 parts of span-80 and 3 parts of 1, 2-epoxypropane. The mixed raw material storage tank is provided with a stirrer, the stirring rate is 250 r / min, the stirring stabilization time is 140 min, and the constant temperature is 85 DEG C.

[0075] (3) The pretreated coking mixed raw material enters a heating furnace, and the outlet temperature of the heating furnace is 495 DEG C. The mixed raw material enters a coke tower from the heating furnace, the reaction pressure of the coke tower is 0.16 MPa, the generated petroleum coke is shovelled out from the bottom of the coke tower, and the petroleum coke is collected from the upper part and the lower part of the coke tower respectively and is subjected to element analysis. The results are shown in Table 1.

[0076] Example 5

[0077] The preparation method of the petroleum coke comprises the following steps:

[0078] (1) The tar stabilizer is mixed with ethylene diesel oil at a ratio of 1:1, and then is mixed with ethylene tar through a high-speed shearing machine to enter an ethylene tar storage tank. The addition amount of the tar stabilizer based on the ethylene tar is 220 ppm, and the weight fractions of the components are as follows: 4 parts of dodecyl benzene sulfonic acid, 2 parts of p-alkyl phenol 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 70 min, and the constant temperature is 65 DEG C.

[0079] (2) The heavy oil phase solvent is mixed with the atmospheric and vacuum diesel oil at a ratio of 1:1, then mixed with the ethylene tar and the Shengli vacuum residue, and sent to the mixed raw material tank by a high-speed shearing machine. The weight fraction of the Shengli vacuum residue is 80 parts, the weight fraction of the ethylene tar is 23 parts, the addition amount of the heavy oil phase solvent based on the vacuum residue is 280 ppm, and the weight fraction of the heavy oil phase solvent is as follows: 2 parts of p-alkyl aniline, 3 parts of dodecyl benzene sulfonic acid, 1 part of span-80, and 3 parts of 1,2-epoxypropane. The mixed raw material storage tank is provided with a stirrer, the stirring rate is 250 r / min, the stirring stabilization time is 180 min, and the constant temperature is 90°C.

[0080] (3) The pretreated coking mixed raw material enters the heating furnace, the outlet temperature of the heating furnace is 495°C. The mixed raw material enters the coke tower from the heating furnace, the reaction pressure of the coke tower is 0.16 MPa, 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 respectively and subjected to element analysis. The results are shown in Table 1 below.

[0081] Comparative Example 1

[0082] The preparation method of the petroleum coke in the present comparative example is as follows: the Shengli vacuum residue is directly used as the raw material, 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 0.16 MPa, 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 respectively and subjected to element analysis. The results are shown in Table 1 below.

[0083] Comparative Example 2

[0084] The preparation method of the petroleum coke in the present comparative example includes the following steps:

[0085] (1) 300 ppm of a tar stabilizer is added to the ethylene tar, the weight fraction of the tar stabilizer is as follows: 4 parts of dodecyl benzene sulfonic acid, 2 parts of p-alkyl phenol, and 1 part of N,N-dimethylformamide. 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 the mixed raw material tank through a pipeline, at the same time, the Shengli vacuum residue and the heavy oil phase solvent are added into the mixed raw material tank. The weight fraction of the Shengli vacuum residue is 90 parts, the weight fraction of the ethylene tar is 30 parts, the addition amount of the heavy oil phase solvent is 300 ppm, and the weight fraction of the heavy oil phase solvent is as follows: 4 parts of p-alkyl aniline, 3 parts of dodecyl benzene sulfonic acid, 3 parts of span-80, and 3 parts of 1,2-epoxypropane. The stirring rate of the mixed raw material storage tank is 250 r / min, the stirring stabilization time is 180 min, 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 DEG C. The mixed raw material enters the coke tower from the heating furnace, the reaction pressure of the coke tower is 0.16 MPa, the generated petroleum coke is shovelled out from the bottom of the coke tower, and the petroleum coke is collected from the upper part and the lower part of the coke tower respectively and subjected to element analysis, and the results are shown in Table 1 below.

[0088] Comparative Example 3

[0089] The petroleum coke production method of the present comparative example comprises the following steps:

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

[0091] (2) The weight fraction of the Shengli vacuum residue is 80 parts, the weight fraction of the ethylene tar is 23 parts, and the mixed raw material is input into the mixing raw material storage tank for stirring, the stirring rate is 250 r / min, the stirring stabilization time is 180 min, and the constant temperature is 90 DEG C;

[0092] (3) The pretreated coking mixed raw material enters the heating furnace, and the outlet temperature of the heating furnace is 493 DEG C. The mixed raw material enters the coke tower from the heating furnace, the reaction pressure of the coke tower is 0.16 MPa, the generated petroleum coke is shovelled out from the bottom of the coke tower, and the petroleum coke is collected from the upper part and the lower part of the coke tower respectively and subjected to element analysis, and 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 material and the petroleum coke product under different test conditions are shown in Table 1.

[0094] Table 1: Analysis results of the properties of the coking raw material and the product

[0095]

[0096]

[0097] As can be seen from Table 1, the element content of the petroleum coke collected from the upper part and the lower part of the coke tower in examples 1-5 is close, and the product properties are uniform. By comparison with the high-end prebaked anode coke indicators provided by SOTON Development Company in Table 1, the Ca content of the petroleum coke in examples 1-5 is ≦200 mg·kg -1 , and the Ni content is ≦200 mg·kg -1 , which meets the requirements of high-end prebaked anode coke. In comparative example 1, when the petroleum coke is produced by using Shengli vacuum residue as a single raw material, the Ca content of the upper petroleum coke is 225.2 mg·kg -1 , the Ni content is 248.3 mg·kg -1 , and the Ca content of the lower petroleum coke is 227.4 mg·kg -1, Ni content is 252.2mg·kg -1 , Ca, Ni content does not meet the high-end prebaked anode coke requirement. In Comparative Example 2 and Comparative Example 3, the petroleum coke products collected from the upper and lower parts of the coke tower differ greatly, thus it can be known that the ethylene tar and Shengli vacuum residue are simply mixed, or the tar stabilizer and heavy oil phase solvent are simply added, and the properties of the produced petroleum coke are not uniform.

[0098] The above has carried out the detailed introduction to the embodiment of the application, the principle and implementation mode of the application have been described in this paper by applying specific examples, the above embodiment is only used to help understanding the method of the application and its core idea; at the same time, for the general technical personnel in the art, according to the idea of the application, the specific implementation mode and application range will have changes, and the above is described, the content of the specification should not be understood as the limitation of the application.

Claims

1. A method for preparing high-end prebaked anode-specific petroleum coke, characterized in that, Includes the following steps: (1) Take ethylene tar and add tar stabilizer to mix to obtain the first mixture, which is then set aside. (2) Take vacuum residue and add it to the heavy oil phase solvent to mix, and obtain a second mixture for later use; (3) The first mixture and the second mixture are mixed and subjected to delayed coking reaction to obtain high-end prebaked anode special petroleum coke; The tar stabilizer comprises a mixture of dodecylbenzenesulfonic acid, p-alkylphenol, and N,N-dimethylamide; Step (1) further includes the step of mixing the tar stabilizer with ethylene diesel oil; Step (1) further includes a step of subjecting the first mixture to high-speed shearing. In step (2), the heavy oil phase solvent includes a mixture of p-alkylaniline, dodecylbenzenesulfonic acid, Span-80 and 1,2-epoxypropane; Step (2) further includes the step of mixing the heavy oil solvent with atmospheric and vacuum diesel oil; Step (2) further includes a step of subjecting the second mixture to high-speed shearing.

2. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 1, characterized in that, The mass ratio of dodecylbenzenesulfonic acid, p-alkylphenol and N,N-dimethylamide is 2-4:1-2:1-2; The tar stabilizer is based on an addition amount of 200-300 ppm of ethylene tar; The mass ratio of the tar stabilizer to the ethylene diesel oil is 1-2:1-2.

3. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 2, characterized in that, The mass ratio of the tar stabilizer to the ethylene diesel is 1:

1.

4. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 2, characterized in that, The shearing speed in the high-speed shearing step is 3000-5000 r / min; Step (1) further includes the step of continuing to stir the first mixture after high-speed shearing; The stirring rate of the stirring step is 200-300 r / min, the stirring time is 60-90 min, and the stirring temperature is 60-70℃.

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

6. The method for preparing high-end prebaked anode-specific petroleum coke according to any one of claims 1-4, characterized in that, The mass ratio of p-alkylaniline, dodecylbenzenesulfonic acid, Span-80 and 1,2-epoxypropane is 2-4:1-3:1-3:1-3; The heavy oil phase solvent is 200-300 ppm based on the amount of vacuum residue added; The mass ratio of the heavy oil solvent to the atmospheric and vacuum diesel oil is 1-2:1-2.

7. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 6, characterized in that, The mass ratio of the heavy oil solvent to the atmospheric and vacuum diesel oil is 1:

1.

8. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 6, characterized in that, The shearing speed in the high-speed shearing step is 3000-5000 r / min; Step (2) further includes the step of continuing to stir the second mixture after high-speed shearing; 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℃.

9. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 8, characterized in that, In step (2), the metal content of the vacuum residue is: Ca content: 40-50 mg·kg -1 Fe content: 7-10 mg / kg -1 Sodium content: 2-4 mg / kg -1 Ni content: 42-52 mg / kg -1 Si content: 0.2-0.5 mg·kg -1 Vitamin C content: 20-30 mg / kg -1 .

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

11. The method for preparing high-end prebaked anode-specific petroleum coke according to claim 1, characterized in that, The elemental content of the high-end prebaked anode-specific petroleum coke is: Ca≦200mg·kg -1 Fe≦200mg·kg -1 Na≦100mg·kg -1 Ni≦200mg·kg -1 Si≦200mg·kg -1 V≦200mg·kg -1 Sulfur content ≤ 4%.

12. The high-end prebaked anode-specific petroleum coke obtained by the preparation method of any one of claims 1-11 is used for the preparation of prebaked anodes.

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