CN110272756B - Preparation method of mesophase pitch precursor - Google Patents
Preparation method of mesophase pitch precursor Download PDFInfo
- Publication number
- CN110272756B CN110272756B CN201910519734.3A CN201910519734A CN110272756B CN 110272756 B CN110272756 B CN 110272756B CN 201910519734 A CN201910519734 A CN 201910519734A CN 110272756 B CN110272756 B CN 110272756B
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- China
- Prior art keywords
- additive
- asphalt
- catalytic cracking
- mesophase pitch
- precursor
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 20
- 239000002243 precursor Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 6
- 239000002002 slurry Substances 0.000 claims abstract description 31
- 238000004523 catalytic cracking Methods 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 25
- 239000010426 asphalt Substances 0.000 claims abstract description 15
- 239000000654 additive Substances 0.000 claims abstract description 14
- 230000000996 additive effect Effects 0.000 claims abstract description 14
- 238000004821 distillation Methods 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 5
- 239000011949 solid catalyst Substances 0.000 claims abstract description 4
- 238000006482 condensation reaction Methods 0.000 claims abstract description 3
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 3
- 230000006911 nucleation Effects 0.000 claims abstract description 3
- 238000010899 nucleation Methods 0.000 claims abstract description 3
- 239000003208 petroleum Substances 0.000 claims description 2
- 239000011337 anisotropic pitch Substances 0.000 abstract description 2
- 239000003575 carbonaceous material Substances 0.000 abstract description 2
- 125000005842 heteroatom Chemical group 0.000 abstract description 2
- 238000005504 petroleum refining Methods 0.000 abstract description 2
- 239000011295 pitch Substances 0.000 abstract description 2
- 239000007795 chemical reaction product Substances 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 25
- 238000000926 separation method Methods 0.000 description 10
- 238000004062 sedimentation Methods 0.000 description 7
- 239000000843 powder Substances 0.000 description 6
- 239000003054 catalyst Substances 0.000 description 5
- 239000002994 raw material Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- -1 alkylbenzene sulfonate Chemical class 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 2
- 239000000084 colloidal system Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 229920002503 polyoxyethylene-polyoxypropylene Polymers 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000080 wetting agent Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000006057 Non-nutritive feed additive Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 150000008051 alkyl sulfates Chemical class 0.000 description 1
- 150000008052 alkyl sulfonates Chemical class 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 238000011001 backwashing Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000007833 carbon precursor Substances 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 239000010763 heavy fuel oil Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10C—WORKING-UP PITCH, ASPHALT, BITUMEN, TAR; PYROLIGNEOUS ACID
- C10C3/00—Working-up pitch, asphalt, bitumen
- C10C3/02—Working-up pitch, asphalt, bitumen by chemical means reaction
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Working-Up Tar And Pitch (AREA)
Abstract
A preparation method of a mesophase pitch precursor belongs to the field of petroleum refining and deep processing, and is characterized in that an additive is added into catalytic cracking oil slurry, then the catalytic cracking oil slurry is subjected to heat treatment for 2-10 hours at the temperature of 420-450 ℃, organic molecules in the additive take solid catalyst particles and metal ions as cores to perform heterogeneous nucleation and condensation reaction to form anisotropic pitch globules with the slip path of more than 560 ℃, fractions at the temperature of 420-520 ℃ are intercepted through reduced pressure distillation, and purified pitch with the softening point of 80-85 ℃ and the ash content of less than 0.0015 wt% is obtained. The purified asphalt obtained by the invention can be used as a precursor of mesophase asphalt and a carbon material, and the additive used in the treatment process is a rear-end product, so that the introduction of heteroatoms can be effectively controlled, and the molecular characteristics of the mesophase asphalt precursor are ensured.
Description
Technical Field
The invention relates to a preparation method of a mesophase pitch precursor, belonging to the field of petroleum refining deep processing.
Background
The catalytic cracking slurry oil is unconverted hydrocarbon with boiling point more than 350 ℃ in the catalytic cracking process, is rich in colloid and asphaltene, has the characteristics of high viscosity and high density, is usually rich in solid catalyst powder, and has high ash content, generally ranging from 0.2 to 0.9 wt%. On one hand, the catalytic cracking slurry oil is mainly used as a blending component of heavy fuel oil, a hydrocracking raw material and a rubber and plastic processing aid; on the other hand, the catalytic cracking slurry oil can be used for producing carbon materials and precursors thereof after catalyst powder is removed, for example, the catalytic cracking slurry oil adopted by the American Cyanite company for preparing high-quality mesophase pitch, and the ash content of the mesophase pitch is controlled to be 0.0025%.
The research of China on mesophase pitch has a history of more than forty years, catalytic cracking oil slurry is used as a raw material, and the ash content in the catalytic cracking oil slurry is removed by adopting a filtration method, a natural sedimentation method, an auxiliary agent sedimentation method, an electrostatic separation method, a centrifugal separation method and the like, so that the effect is not ideal. The natural sedimentation method, for example, is the method used at the earliest, but since the particle size of the catalyst powder is in the range of 0 to 80 μm, in which particle sizes of 20 μm or less account for considerable specific gravity, the sedimentation rate is slow. In addition, the slurry viscosity is high, and the colloid and the asphaltene hinder the sedimentation of the catalyst powder, so that the sedimentation effect is not ideal even if the temperature is raised. The filtration method, the electrostatic separation method and the centrifugal separation method have high requirements on equipment. The filter device requires the filter holes to be small in size and thus easily clogged, requiring frequent backwashing. The electrostatic separation apparatus cannot achieve a desired effect due to the oil-coated surface of some parts, which is inevitably generated during the process. Centrifugal separation methods are not valuable and practical for industrial applications because of the difficulty in handling large batches of slurry.
At present, domestic petrochemical enterprises or individuals realize reduction of ash content in catalytic cracking slurry oil to different degrees by one or a combination of several methods. If the ash content in the catalytic cracking slurry oil is reduced to 0.006-0.01% by a filtering mode adopted by the Zhongpetrochemical ChangLing refining division company, and if the slurry oil is used as a raw material and a mesophase pitch precursor is prepared by a conventional process, the ash content of the precursor is increased to 0.02-0.03%, and the ash content of the mesophase pitch precursor is further prepared to 0.04-0.06%.
Patent CN 101205472B discloses a composition for removing catalyst powder from catalytic cracking slurry oil and a removing method thereof, wherein one or more of a wetting agent selected from alkylphenol ethoxylates, alkylsulfonate, alkylsulfate, alkylbenzene sulfonate and alkylphenol polyoxyethylene sulfate, and one or more of a demulsifier selected from alkoxylated alkylphenol formaldehyde resin, polyol polyoxyethylene polyoxypropylene block copolymer, polyethylene, polyamine polyoxyethylene polyoxypropylene block copolymer and a compound thereof are used, the ash content of the slurry oil is reduced to 0.0227% by a standing sedimentation method, the ash content is higher, and the addition of the wetting agent and the demulsifier in the slurry oil can destroy the generation of mesophase pitch, which is not beneficial to the high-quality production of mesophase pitch.
Patent CN201310456765.1 discloses a purification apparatus and a purification method for purifying catalytic cracking slurry oil, which adopts a combined manner of technologies such as standing settling, centrifugal separation, two-stage electrostatic separation, etc. to reduce the ash content of the catalytic cracking slurry oil to 0.0008%, if the slurry oil is used to prepare mesophase pitch precursor, the ash content of the precursor can be controlled to 0.0016%, however, the method disclosed in patent CN201310456765.1 needs technologies such as standing settling, centrifugal separation, two-stage electrostatic separation, etc., the process is complicated, the investment of equipment and supporting engineering is huge, and industrial production and lower cost control are difficult to realize.
Disclosure of Invention
The invention aims to solve the problems of insufficient degree and high cost of catalyst powder in catalytic cracking slurry oil removal in the prior art, and provides a method for treating catalytic cracking slurry oil with high purity and low cost and preparing a mesophase pitch precursor, which comprises the following steps:
(1) a preparation method of a mesophase pitch precursor comprises the steps of adding an additive into catalytic cracking slurry oil, then carrying out heat treatment on the catalytic cracking slurry oil for 2-10 hours at the temperature of 420-450 ℃, enabling organic molecules in the additive to take solid catalyst particles and metal ions as cores to carry out heterogeneous nucleation and condensation reaction to form anisotropic pitch pellets with the slip path being larger than 560 ℃, and intercepting fractions at the temperature of 420-520 ℃ through reduced pressure distillation to obtain purified pitch. The mass ratio of the additive to the catalytic cracking slurry oil is 0.5-3: 100.
(2) The additive is isotropic petroleum asphalt with the softening point of 150-220 ℃.
(3) The mass content of the anisotropic asphalt generated in the heat treatment process is controlled to be 0.5-5%.
(4) The purified asphalt has a softening point of 80-85 ℃ and ash content of less than 0.0015%.
(5) The heat treatment equipment adopts a kettle type reactor or a tubular reactor.
The invention has the following advantages:
the ash content of the obtained asphalt is 0.03-0.04% by conventional distillation of the oil slurry, the ash content of the purified asphalt obtained by adopting the method is less than 0.0015%, and the ash removal efficiency is improved by 95%.
The additive used in the treatment process is a product at the rear end, so that the introduction of heteroatoms can be effectively controlled, and the molecular characteristics of the mesophase pitch precursor are ensured.
The selected equipment is a common kettle type reactor, a tubular reactor and conventional distillation equipment, so that the investment cost is low and the industrialization is convenient.
Detailed Description
The method comprises the steps of adopting catalytic cracking slurry oil with ash content of 0.01% as a raw material, reacting in a 100-liter reaction kettle at reaction temperatures of 420, 435 and 450 ℃ for 2, 5 and 10 hours respectively according to the mass ratio of 0.5-1.5: 100 of an additive to the catalytic cracking slurry oil, and carrying out reduced pressure distillation on the obtained product to obtain fractions at the temperature of 420-520 ℃, so as to obtain the purified asphalt with the properties shown in Table 1.
The treatment process with the mass ratio of the additive to the catalytic cracking slurry oil of 1.5:100, the reaction temperature of 435 ℃ and the reaction time of 10 hours is the preferred scheme of the mesophase pitch precursor.
TABLE 1 clean asphalt treatment protocol and Properties
Claims (5)
1. A preparation method of a mesophase pitch precursor is characterized by comprising the following steps: adding an additive into the catalytic cracking oil slurry, then carrying out heat treatment on the catalytic cracking oil slurry at the temperature of 420-450 ℃ for 2-10 hours, wherein organic molecules in the additive take solid catalyst particles and metal ions as cores to carry out heterogeneous nucleation and condensation reaction to form anisotropic asphalt globules with the distillation range of more than 560 ℃, and intercepting fractions at the temperature of 420-520 ℃ through reduced pressure distillation to obtain purified asphalt; the mass ratio of the additive to the catalytic cracking slurry oil is 0.5-3: 100.
2. The method for preparing a mesophase pitch precursor according to claim 1, wherein: the additive is isotropic petroleum asphalt with the softening point of 150-220 ℃.
3. The method for preparing a mesophase pitch precursor according to claim 1, wherein: the mass content of the anisotropic asphalt generated in the heat treatment process is controlled to be 0.5-5% of the total amount.
4. The method for preparing a mesophase pitch precursor according to claim 1, wherein: the purified asphalt has a softening point of 80-85 ℃ and ash content of less than 0.0015 wt%.
5. The method of claim 1, wherein the heat treatment is carried out using a tank reactor or a tubular reactor.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910519734.3A CN110272756B (en) | 2019-06-17 | 2019-06-17 | Preparation method of mesophase pitch precursor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910519734.3A CN110272756B (en) | 2019-06-17 | 2019-06-17 | Preparation method of mesophase pitch precursor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110272756A CN110272756A (en) | 2019-09-24 |
| CN110272756B true CN110272756B (en) | 2021-02-12 |
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| CN114106863B (en) * | 2022-01-27 | 2022-04-15 | 克拉玛依市先进能源技术创新有限公司 | Spinning mesophase pitch and preparation method thereof |
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| CN108192650B (en) * | 2018-01-04 | 2021-07-02 | 北京化工大学 | Preparation method of ultralow-ash asphalt |
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| CN110272756A (en) | 2019-09-24 |
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Address after: Room 2202, building F1, Lugu Yuyuan, No.27 Wenxuan Road, high tech Development Zone, Changsha City, Hunan Province Patentee after: Hunan Dongying Carbon Materials Technology Co.,Ltd. Address before: Room 2202, building F1, Lugu Yuyuan, No.27 Wenxuan Road, high tech Development Zone, Changsha City, Hunan Province Patentee before: HUNAN DONGYING CARBON MATERIAL TECHNOLOGY CO.,LTD. |
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Address after: 410000, No. 467 Xianjiahu West Road, Lugu Street, Xiangjiang New District, Changsha City, Hunan Province Patentee after: Hunan Dongying Carbon Materials Technology Co.,Ltd. Country or region after: China Address before: Room 2202, building F1, Lugu Yuyuan, No.27 Wenxuan Road, high tech Development Zone, Changsha City, Hunan Province Patentee before: Hunan Dongying Carbon Materials Technology Co.,Ltd. Country or region before: China |