CN111961498A - Multiphase step heavy oil separation process and application of product thereof - Google Patents

Multiphase step heavy oil separation process and application of product thereof Download PDF

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CN111961498A
CN111961498A CN202010814150.1A CN202010814150A CN111961498A CN 111961498 A CN111961498 A CN 111961498A CN 202010814150 A CN202010814150 A CN 202010814150A CN 111961498 A CN111961498 A CN 111961498A
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oil
separation
aromatic
heavy oil
heavy
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徐金城
彭莉
廖虎
韩照宪
翟炎波
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Shandong Yida New Material Co Ltd
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Shandong Yida New Material Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
    • C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
    • C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

The invention discloses a multiphase step heavy oil separation process and application of a product thereof, wherein the separation method comprises a first-stage reduced pressure distillation separation step, wherein low boiling point components and high boiling point components are removed according to boiling points to obtain middle-stage oil; performing secondary supercritical extraction, and separating out heavy colloid according to polarity to obtain aromatic-rich oil; and the third-stage solvent refining separation is carried out, and according to the solvent dissolution characteristic, the aliphatic hydrocarbon is separated to obtain the refined aromatic oil. According to the invention, by improving the heavy oil separation method, the raw material of the lithium battery negative electrode material meeting the production requirements can be directly produced through the heavy oil, and the graphite electrode material meeting the production requirements can be produced at the same time, so that the problems of single product, poor product quality and low yield of the existing production method are solved.

Description

Multiphase step heavy oil separation process and application of product thereof
Technical Field
The invention relates to the technical field of heavy oil separation and application, in particular to a multiphase step heavy oil separation process and application of a product thereof.
Background
The needle coke used as the electrode material is prepared by extracting materials in raw oil and performing delayed coking, and is divided into two categories according to different production raw materials, wherein one category is oil-based needle coke taking heavy oil as the production raw material; the other is coal-based needle coke which takes coal tar, pitch and important fractions thereof as raw materials. The raw oil for producing the oil-based needle coke is heavy oil and has higher viscosity and density. The heavy oil contains not only aromatic components and saturated components but also colloids and asphaltenes.
At present, the preparation of the lithium battery negative electrode material needs to remove the heavy components such as colloid, asphaltene and the like in raw oil, the processing methods are various, such as a hydrogenation method, a thermal filtration method, a high-temperature centrifugation method, a supercritical solvent extraction method and the like, the most commonly adopted method is a supercritical extraction process, the asphaltene in the raw oil is removed, aromatic-rich oil is collected, in the lower-layer substances of the supercritical extraction, besides the asphaltene, the components such as colloid, heavy aromatic components, saturated components and the like exist, and the needle coke raw material is required to have high aromatic hydrocarbon content, low colloid and asphaltene content and low heterocyclic compounds such as sulfur and nitrogen. And only light and medium aromatic components and partial saturated components are collected in the upper layer material obtained by extraction. The aromatic components cannot be completely collected, and the aromatic-rich oil subjected to supercritical extraction is directly coked under the conventional coking condition without removing light components, so that the strength of the produced needle coke is low and the structure is poor due to excessive light components.
The preparation of the graphite electrode material is usually to remove asphaltene through one-time reduced pressure distillation and furfural extraction, and then to prepare the graphite electrode material through conventional delayed coking, but the colloid content in the refined aromatic oil obtained by the process is not enough, while the electrode coke pays attention to the mechanical strength, and needs coke with certain large particles as aggregate, so that the prepared graphite electrode material has extremely strong strength and strength which cannot meet the requirements.
With the heat of fire in the electric furnace steelmaking market, the demand for high-quality needle coke will continue to increase, and mature heavy oil separation method technology and high-quality electrode raw materials are urgently needed.
Disclosure of Invention
The invention provides a multiphase step heavy oil separation process and application of the product thereof aiming at the defects. According to the invention, by improving the heavy oil separation method, the raw material of the lithium battery negative electrode material meeting the production requirement can be directly produced by using the heavy oil, and the graphite electrode material meeting the production requirement can be produced at the same time, so that the problems of single product, poor product quality and low yield of the existing production method are solved.
The invention relates to a multiphase cascade heavy oil separation process and an application technical scheme of a product thereof, wherein the multiphase cascade heavy oil separation process comprises the following steps:
(1) performing first-stage reduced pressure distillation separation, and removing low-boiling-point components and high-boiling-point components according to boiling points to obtain middle-stage oil;
(2) performing secondary supercritical extraction, and separating out heavy colloid according to polarity to obtain aromatic-rich oil;
(3) and the third-stage solvent refining separation is carried out, and according to the solvent dissolution characteristic, the aliphatic hydrocarbon is separated to obtain the refined aromatic oil.
The low boiling point component in the step (1) is a diesel oil component with the boiling point less than 400 ℃, and the high boiling point component is petroleum asphalt with the boiling point more than 500 ℃.
In the step (2), supercritical extraction adopts an extraction solvent, wherein the extraction solvent consists of butane, cyclopentane and n-pentane; the supercritical extraction temperature is 240 ℃ and 245 ℃ and the pressure is 4.6 MPa.
The mass percentage of butane in the extraction solvent is not less than 80%, the mass percentage of cyclopentane is 10-15%, and the mass percentage of n-pentane is 5-10%.
Adding the middle oil and an extraction solvent into a supercritical extraction tank, extracting heavy colloid from a lower-layer substance through a colloid stripping tower, and separating aromatic-rich oil from an upper-layer substance through a supercritical separation tower and an aromatic stripping tower in sequence; and the solvent in the supercritical separation tower is recovered through a heat exchanger and a liquid separation tank.
After the supercritical extraction in the step (2), the temperature of the recovered middle section oil is 280 plus 300 ℃, and the pressure is reduced by 0.2-0.3 MPa in the supercritical extraction tower.
In the step (3), the aromatic-rich oil and furfural are added into a furfural extraction tower, light components are separated by an aliphatic hydrocarbon separation tower to obtain aliphatic hydrocarbons, and other components are separated by an aromatic hydrocarbon refining separation tower to obtain aromatic hydrocarbon refined oil.
The furfural contains N-methyl pyrrolidone with the mass percentage of not more than 10 percent.
The aromatic hydrocarbon oil produced by the multiphase step heavy oil separation process is applied to the production of lithium battery negative electrode materials.
The blend of the refined aromatic oil and the heavy colloid produced by the multiphase step separation heavy oil process is applied to producing UHP materials.
The invention has the beneficial effects that: according to the invention, by improving the heavy oil separation method and organically combining three-stage separation of reduced pressure distillation, supercritical extraction and solvent refining, the high-quality lithium battery cathode material meeting the production requirements can be directly produced from the heavy oil, and the graphite electrode material meeting the production requirements can be produced at the same time, so that the problems of single product, poor product quality and low yield of the existing production method are solved.
Drawings
FIG. 1 is a process flow diagram of the present invention;
FIG. 2 is a flow diagram of the supercritical extraction stage process of the present invention;
FIG. 3 is a process flow diagram of the solvent refining stage of the present invention;
FIG. 4 is a flow chart of a conventional process.
Detailed Description
For better understanding of the present invention, the technical solution of the present invention will be described in detail with specific examples, but the present invention is not limited thereto. The process conditions used in the following examples are conventional ones unless otherwise specified.
Example 1
Raw materials: heavy oil FCC slurry oil (catalytic cracking slurry oil)
A multiphase cascade heavy oil separation process comprises the following steps:
(1) performing first-stage reduced pressure distillation separation, and removing low-boiling-point components and high-boiling-point components according to boiling points to obtain middle-stage oil; the low-boiling point component is a diesel oil component with a boiling point less than 400 ℃, and the high-boiling point component is petroleum asphalt with a boiling point greater than 500 ℃.
(2) Performing secondary supercritical extraction, and separating out heavy colloid according to polarity to obtain aromatic-rich oil; adding the middle-stage oil and an extraction solvent into a supercritical extraction tank, extracting heavy colloid from a lower-layer substance through a colloid stripping tower, and separating aromatic-rich oil from an upper-layer substance through a supercritical separation tower and an aromatic hydrocarbon stripping tower in sequence; and the solvent in the supercritical separation tower is recovered through a heat exchanger and a liquid separation tank.
The supercritical extraction adopts an extraction solvent, and the extraction solvent consists of butane, cyclopentane and n-pentane; the supercritical extraction temperature is 240 ℃ and 245 ℃ and the pressure is 4.6 MPa. The mass percentage of the n-butane, the mass percentage of the isobutane, the mass percentage of the cyclopentane and the mass percentage of the n-pentane in the extraction solvent are 45%, 35%, 15% and 5%, respectively. After the supercritical extraction, the temperature of the recovered middle section oil is 280 plus 300 ℃, and the pressure is reduced by 0.2-0.3 MPa in the supercritical extraction tower.
(3) And (3) refining and separating the solvent in the third stage, adding the aromatic-rich oil and furfural into a furfural extraction tower, separating light components by an aliphatic hydrocarbon separation tower to obtain aliphatic hydrocarbons, and separating other components by an aromatic hydrocarbon refining separation tower to obtain aromatic hydrocarbon refined. The furfural contains 8% of N-methyl pyrrolidone by mass.
The material composition ratio at each stage is shown in table 1:
TABLE 1
Figure BDA0002632068780000041
Example 2
Raw material heavy oil: FCC slurry oil (catalytic cracking slurry oil) + vacuum residuum + ethylene tar
A multiphase cascade heavy oil separation process comprises the following steps:
(1) performing first-stage reduced pressure distillation separation, and removing low-boiling-point components and high-boiling-point components according to boiling points to obtain middle-stage oil; the low-boiling point component is a diesel oil component with a boiling point less than 400 ℃, and the high-boiling point component is petroleum asphalt with a boiling point greater than 500 ℃.
(2) Performing secondary supercritical extraction, and separating out heavy colloid according to polarity to obtain aromatic-rich oil; adding the middle-stage oil and an extraction solvent into a supercritical extraction tank, extracting heavy colloid from a lower-layer substance through a colloid stripping tower, and separating aromatic-rich oil from an upper-layer substance through a supercritical separation tower and an aromatic hydrocarbon stripping tower in sequence; the solvent in the supercritical separation tower is recovered through a heat exchanger and a liquid separating tank;
the supercritical extraction adopts an extraction solvent, and the extraction solvent consists of butane, cyclopentane and n-pentane; the temperature of the supercritical extraction is 240 ℃ to 245 ℃, and the pressure is 4.6 MPa. The mass percentage of the n-butane, the mass percentage of the isobutane, the mass percentage of the cyclopentane and the mass percentage of the n-pentane in the extraction solvent are respectively 55%, 30%, 10% and 5%. After the supercritical extraction, the temperature of the recovered middle section oil is 280 plus 300 ℃, and the pressure is reduced by 0.2-0.3 MPa in the supercritical extraction tower.
(3) And (3) refining and separating the solvent in the third stage, adding the aromatic-rich oil and furfural into a furfural extraction tower, separating light components by an aliphatic hydrocarbon separation tower to obtain aliphatic hydrocarbons, and separating other components by an aromatic hydrocarbon refining separation tower to obtain aromatic hydrocarbon refined. The furfural contains 6% of N-methyl pyrrolidone by mass.
The material composition ratio at each stage is shown in table 2:
TABLE 2
Figure BDA0002632068780000051
Figure BDA0002632068780000061
Comparative example 1
The conventional negative electrode needle coke treatment process comprises the following steps: supercritical extraction + conventional delayed coking 1.
The material composition ratio at each stage is shown in table 3:
TABLE 3
Figure BDA0002632068780000062
Comparative example 2
The technological process is shown in attached figure 4 of the specification, and the conventional electrode needle coke treatment process comprises the following steps: vacuum distillation, furfural extraction and conventional delayed coking 2.
The material composition ratio at each stage is shown in table 4:
TABLE 4
Figure BDA0002632068780000063
Figure BDA0002632068780000071
Examples of the experiments
Preparing a lithium battery negative electrode material by conventional delayed coking from the refined aromatic oil produced in the example 1 and the example 2 and the aromatic-rich oil produced in the comparative example 1; the comparative example is the preparation of lithium battery negative electrode material by conventional delayed coking using aromatic-rich oil produced by means of conventional supercritical extraction (as described in the background section of the specification). The prepared lithium battery negative electrode material pair is shown in table 5:
TABLE 5
Degree of graphitization Gram capacity mAh/g First effect% Compacted density g/cm3
Example 1 95.57％ 359 92.56 1.69
Example 2 95.80％ 361 92.67 1.71
Comparative example 1 94.76％ 356 91.45 1.65
Note: the gram capacities described in the table are first discharge gram capacities.
Example 4
Preparing a graphite electrode material by conventional delayed coking with the refined aromatic oil and the heavy colloid produced in the examples 1 and 2; comparative example 2 is a graphite electrode material prepared by conventional delayed coking using a refined aromatic oil produced by a conventional manner. The prepared graphite electrode material pair is shown in table 6:
TABLE 6
Figure BDA0002632068780000072
Figure BDA0002632068780000081
The data are obtained by industrial full-electric production.

Claims (10)

1. A multi-phase cascade heavy oil separation process is characterized by comprising the following steps:
(1) performing first-stage reduced pressure distillation separation, and removing low-boiling-point components and high-boiling-point components according to boiling points to obtain middle-stage oil;
(2) performing secondary supercritical extraction, and separating out heavy colloid according to polarity to obtain aromatic-rich oil;
(3) and the third-stage solvent refining separation is carried out, and according to the solvent dissolution characteristic, the aliphatic hydrocarbon is separated to obtain the refined aromatic oil.
2. The multiphase step separation heavy oil process of claim 1, wherein the low boiling point component in step (1) is a diesel component with a boiling point of less than 400 ℃, and the high boiling point component is petroleum asphalt with a boiling point of more than 500 ℃.
3. The multiphase step separation heavy oil process of claim 1, wherein in the step (2), supercritical extraction adopts an extraction solvent, and the extraction solvent is composed of butane, cyclopentane and n-pentane; the supercritical extraction temperature is 240 ℃ and 245 ℃ and the pressure is 4.6 MPa.
4. The process of claim 3, wherein the extraction solvent comprises not less than 80% by mass of butane, 10-15% by mass of cyclopentane, and 5-10% by mass of n-pentane.
5. The multiphase step separation heavy oil process according to claim 1, wherein the step (2) is specifically that the middle oil and the extraction solvent are added into a supercritical extraction tank, the lower layer substance is extracted into heavy colloid through a colloid stripping tower, and the upper layer substance is separated into aromatic-rich oil through a supercritical separation tower and an aromatic stripping tower in sequence; and the solvent in the supercritical separation tower is recovered through a heat exchanger and a liquid separation tank.
6. The process of claim 1, wherein the temperature of the recovered middle oil is 280-300 ℃ and the pressure is reduced by 0.2-0.3 MPa in the supercritical extraction tower after the supercritical extraction in the step (2).
7. The multiphase step separation heavy oil process according to claim 1, wherein in the step (3), the aromatic-rich oil and furfural are added into a furfural extraction tower, light components are separated by an aliphatic hydrocarbon separation tower to obtain aliphatic hydrocarbons, and other components are separated by an aromatic hydrocarbon separation tower to obtain aromatic hydrocarbon oil.
8. The multiphase step separation heavy oil process of claim 7, wherein the furfural contains N-methyl pyrrolidone in an amount of not more than 10% by mass.
9. The application of the aromatic hydrocarbon oil produced by the multiphase step separation heavy oil process according to claim 1 in the production of lithium battery negative electrode materials.
10. The use of the blend of aromatic hydrocarbon oil and heavy gum produced by the multiphase step separation heavy oil process of claim 1 in the production of UHP materials.
CN202010814150.1A 2020-08-13 2020-08-13 Multiphase step heavy oil separation process and application of product thereof Pending CN111961498A (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108893140A (en) * 2018-06-05 2018-11-27 山东益大新材料有限公司 A method of branded oil system needle-shape coke raw material is produced by solvent separation and Extraction
CN109679674A (en) * 2019-01-07 2019-04-26 李刚 A kind of needle-shape coke raw material pretreating process
CN110283612A (en) * 2019-07-12 2019-09-27 山东滨化滨阳燃化有限公司 A kind of production method of the ripe coke of oil system needle coke

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108893140A (en) * 2018-06-05 2018-11-27 山东益大新材料有限公司 A method of branded oil system needle-shape coke raw material is produced by solvent separation and Extraction
CN109679674A (en) * 2019-01-07 2019-04-26 李刚 A kind of needle-shape coke raw material pretreating process
CN110283612A (en) * 2019-07-12 2019-09-27 山东滨化滨阳燃化有限公司 A kind of production method of the ripe coke of oil system needle coke

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