CN114540062A - Mesophase pitch prepared from heavy oil and method thereof - Google Patents
Mesophase pitch prepared from heavy oil and method thereof Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 76
- 239000011302 mesophase pitch Substances 0.000 title claims abstract description 65
- 239000000295 fuel oil Substances 0.000 title claims abstract description 36
- 239000012071 phase Substances 0.000 claims abstract description 113
- 125000003118 aryl group Chemical group 0.000 claims abstract description 80
- 238000006243 chemical reaction Methods 0.000 claims abstract description 76
- 239000003921 oil Substances 0.000 claims abstract description 64
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 56
- 230000005526 G1 to G0 transition Effects 0.000 claims abstract description 53
- 239000002904 solvent Substances 0.000 claims abstract description 39
- 238000010828 elution Methods 0.000 claims abstract description 32
- 238000005406 washing Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 12
- 238000003763 carbonization Methods 0.000 claims abstract description 10
- 238000001179 sorption measurement Methods 0.000 claims abstract description 8
- 239000007791 liquid phase Substances 0.000 claims abstract description 7
- 239000012046 mixed solvent Substances 0.000 claims abstract description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 92
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 65
- 229910052757 nitrogen Inorganic materials 0.000 claims description 46
- 230000008569 process Effects 0.000 claims description 34
- 230000007935 neutral effect Effects 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 18
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 229910052717 sulfur Inorganic materials 0.000 claims description 18
- 239000011593 sulfur Substances 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 10
- 239000002002 slurry Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 8
- 239000011280 coal tar Substances 0.000 claims description 7
- 238000011010 flushing procedure Methods 0.000 claims description 7
- 238000004523 catalytic cracking Methods 0.000 claims description 6
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 5
- 239000005977 Ethylene Substances 0.000 claims description 5
- 239000011269 tar Substances 0.000 claims description 5
- 230000003213 activating effect Effects 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 238000005374 membrane filtration Methods 0.000 claims description 4
- 238000004517 catalytic hydrocracking Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 239000000084 colloidal system Substances 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000002994 raw material Substances 0.000 abstract description 41
- 238000002360 preparation method Methods 0.000 abstract description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 50
- 238000003756 stirring Methods 0.000 description 28
- 239000003795 chemical substances by application Substances 0.000 description 17
- 229910001220 stainless steel Inorganic materials 0.000 description 17
- 239000010935 stainless steel Substances 0.000 description 17
- 229910052593 corundum Inorganic materials 0.000 description 15
- 229910001845 yogo sapphire Inorganic materials 0.000 description 15
- 229920000049 Carbon (fiber) Polymers 0.000 description 14
- 239000004917 carbon fiber Substances 0.000 description 14
- 238000001704 evaporation Methods 0.000 description 14
- 239000000203 mixture Substances 0.000 description 14
- 238000006068 polycondensation reaction Methods 0.000 description 14
- 238000010926 purge Methods 0.000 description 14
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 9
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 9
- 238000000926 separation method Methods 0.000 description 8
- 239000010426 asphalt Substances 0.000 description 7
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 6
- 230000004048 modification Effects 0.000 description 6
- 238000012986 modification Methods 0.000 description 6
- 239000011295 pitch Substances 0.000 description 6
- 239000006228 supernatant Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 5
- 238000007865 diluting Methods 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000012528 membrane Substances 0.000 description 4
- 239000003575 carbonaceous material Substances 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000005087 graphitization Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000003208 petroleum Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- XPNGNIFUDRPBFJ-UHFFFAOYSA-N (2-methylphenyl)methanol Chemical compound CC1=CC=CC=C1CO XPNGNIFUDRPBFJ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000012752 auxiliary agent Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 238000009987 spinning Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- HIXDQWDOVZUNNA-UHFFFAOYSA-N 2-(3,4-dimethoxyphenyl)-5-hydroxy-7-methoxychromen-4-one Chemical compound C=1C(OC)=CC(O)=C(C(C=2)=O)C=1OC=2C1=CC=C(OC)C(OC)=C1 HIXDQWDOVZUNNA-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 239000004988 Nematic liquid crystal Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000005377 adsorption chromatography Methods 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 239000003849 aromatic solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- GCBSCAKBRSMFCP-UHFFFAOYSA-N benzene;methanol Chemical compound OC.OC.C1=CC=CC=C1 GCBSCAKBRSMFCP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000003749 cleanliness Effects 0.000 description 1
- 239000011300 coal pitch Substances 0.000 description 1
- 239000011162 core material Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000010779 crude oil Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007123 defense Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000005984 hydrogenation reaction Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000000197 pyrolysis Methods 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229930195734 saturated hydrocarbon Natural products 0.000 description 1
- 238000000638 solvent extraction Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 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
-
- 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)
- Engineering & Computer Science (AREA)
- General Chemical & Material Sciences (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)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses mesophase pitch prepared from heavy oil and a method thereof, wherein the method comprises the following steps: selecting heavy oil as a raw material; deashing the raw materials to obtain clarified oil; separating clarified oil by a solid-liquid adsorption method, respectively adjusting the polarity of an alumina stationary phase and the washing strength of a mobile phase according to different raw materials, and performing gradient elution through a first mobile phase and a second mobile phase to obtain an aromatic-rich component, wherein the first mobile phase and the second mobile phase use a mixed or single solvent, preferably a mixed solvent; and (4) carrying out liquid-phase carbonization on the aromatic-rich component in a high-pressure reaction kettle to obtain the mesophase pitch. The preparation method of the invention has no strict requirements on equipment, and the finally obtained mesophase pitch has good spinnability.
Description
Technical Field
The invention relates to a preparation method of mesophase pitch, in particular to a method for preparing mesophase pitch and pitch-based carbon fiber by heavy oil ash removal, aromatic hydrocarbon enrichment and thermal polycondensation, belonging to the technical field of deep processing of petroleum.
Background
The mesophase pitch is a nematic liquid crystal substance composed of flat macromolecules or rod-shaped molecules, which is obtained by using high molecular polymers, heavy oil, petroleum, coal pitch and the like as raw materials through a thermal polycondensation and catalytic polycondensation method, has easy graphitization and can be used for preparing various novel high-quality carbon materials. The carbon materials play a great role in the fields of national defense industry, high-end science and technology, aerospace, civil industry and the like. The mesophase pitch with higher mesophase content has spinnability and enough microscopic order, and can be subjected to melt spinning process and further pre-oxidation, carbonization and graphitization to obtain pitch-based carbon fibers with high-quality mechanical properties.
Generally, mesophase pitches can be produced by direct thermal polycondensation, novel mesophase processes, catalytic modification, alkylation modification, crosslinking synthesis, and hydrogenation modification. Raw materials with different properties need to be prepared by different methods, and the appropriate preparation method is selected according to the thermal polycondensation reaction activity of the raw materials. The initial raw material structure and the preparation process of the mesophase pitch are the key for determining the anisotropic content and the liquid crystal structure of the mesophase pitch. And (4) separating the heavy oil by solid-liquid adsorption chromatography. The treated components are rich in aromatic compounds, and the heavy oil has simple source, low price and convenient treatment, thus being an ideal raw material for preparing high-quality mesophase pitch.
The carbon fiber prepared by the mesophase pitch is easy to obtain a graphitized structure and has better physical properties, and when the mesophase pitch is used for preparing the carbon fiber, the higher the content of the mesophase pitch is, the higher the modulus of the prepared carbon fiber is, and the more excellent the comprehensive properties are. In order to promote the development of military industry, pitch-based carbon fibers gradually become a research hotspot, mesophase pitch is spun to prepare carbon fibers with high orientation degree, and the carbon fibers are very easy to graphitize to form high-strength high-modulus graphitized fibers with excellent graphite structures. The pitch-based carbon fiber has the characteristics of high modulus and high strength, has the advantages of good electrical conductivity, low thermal conductivity and low thermal expansion coefficient, and can be used as a high-performance carbon material for special purposes.
Chinese patent CN108795467A discloses a method for preparing mesophase pitch by extracting, separating and thermal polycondensation of FCC clarified oil, which is a method for preparing spinnable mesophase pitch by taking fraction with a boiling point lower than 540 ℃ in naphthenic FCC clarified oil as a raw material, and performing extraction, separation and pretreatment and then thermal polycondensation. Firstly, the impurities such as catalyst and the like in the raw materials are removed by a reduced pressure distillation process, then the partial saturated hydrocarbon in the raw materials is removed by a solvent extraction process, and then the mesophase pitch is prepared by a thermal polycondensation process, so that the anisotropic content in the product can be improved, the molecular structure of the mesophase is improved, and the spinning performance is improved. However, in the extraction separation process, for other raw material modification processes, the requirement of an extracting agent on equipment is high, and the extracting agent is difficult to completely remove.
Chinese patent CN107384462A discloses a method for preparing mesophase pitch by two-stage hydro-upgrading-thermal polycondensation of FCC slurry oil, which comprises the steps of using naphthenic base crude oil catalytic cracking slurry oil to cut out mesophase fraction through reduced pressure distillation as a raw material, adjusting the structural composition of the raw material and an intermediate product through a two-stage hydro-upgrading method, achieving the purpose of keeping the molecular structure composition of a system uniform, and further generating the mesophase pitch with high anisotropic structure content, low softening point and good spinning performance. However, the hydro-upgrading process is complex, the requirement on equipment is high, the system is difficult to completely separate and recover the byproducts, the cost is high, and industrialization is difficult to realize.
Chinese patent CN108728147A discloses a method for preparing mesophase pitch and carbon fibers by carrying out rapid pyrolysis pretreatment-catalytic polycondensation on heavy oil. The method has simple process flow, no corrosion of the catalyst to equipment and low requirement on the equipment. The prepared mesophase pitch has low softening point, high mesophase content, a large-area streamline optical anisotropic structure and high spinnability, and the high-modulus and high-strength pitch-based carbon fiber can be obtained after the protofilaments are subjected to preoxidation, carbonization and graphitization treatment, but the method has high cost and is not easy to industrialize.
Chinese patent CN108611113A discloses a method for preparing mesophase pitch and carbon fiber by deep oxidation-catalytic polycondensation, which adopts an air blowing method to carry out deep oxidation crosslinking modification on raw materials, and then uses ZrO2The catalyst is subjected to thermal polycondensation to obtain mesophase pitch, and further the carbon fiber with excellent performance is obtained. However, in this method ZrO2Is easy to remain in the mesophase pitch product, and can influence the further improvement of the quality of the subsequent carbon fiber.
Disclosure of Invention
In order to solve the problems, the invention provides mesophase pitch prepared from heavy oil and a method thereof.
To achieve the above object, the process for preparing mesophase pitch from heavy oil of the present invention comprises the steps of:
step (1): deashing heavy oil serving as a raw material to obtain clarified oil;
step (2): separating the clarified oil obtained in the step (1) by adopting a solid-liquid adsorption method, respectively adjusting the polarity of an alumina stationary phase and the washing strengths of a first mobile phase and a second mobile phase according to the difference of components in heavy oil, and performing step elution through the first mobile phase and the second mobile phase to obtain an aromatic-rich component;
and (3): and (3) carrying out liquid-phase carbonization reaction on the aromatic-rich component obtained in the step (2) in a high-pressure reaction kettle to obtain the mesophase pitch.
The type of the heavy oil as the raw material is not particularly limited in the present invention, and any heavy oil may be used, and the recommended heavy oil as the raw material includes, but is not limited to, medium and low temperature coal tar, high temperature coal tar, atmospheric residue, vacuum residue, catalytic cracking slurry oil, hydrocracking tail oil, ethylene tar heavy oil, and fractions thereof, and catalytic cracking slurry oil or ethylene tar is preferable.
The kind of the deliming treatment process is not particularly limited in the present invention, and the recommended deliming treatment processes are aid sedimentation deliming, filtration deliming, electrostatic deliming, and inorganic membrane filtration deliming is preferable.
The ash content of the clarified oil obtained in the deashing treatment process of the invention can reach the required index of the product, and the ash content is preferably less than or equal to 100 ppm.
In the separation by the solid-liquid adsorption method, the polarity of the alumina stationary phase is adjusted by activating gamma neutral alumina at the temperature of 450-500 ℃ for 2-6h, cooling to 20-30 ℃, and then adding 1.5-6.0 wt.% of deionized water to adjust the polarity of the alumina, wherein the recommended adding proportion is 2-4 wt.%. Because the polarity of the alumina after high-temperature activation is too strong, the components cannot be removed from the stationary phase when the alumina is directly used or the addition amount of water is too small, and the yield of the aromatic-rich components is greatly reduced, the addition amount of water needs to be adjusted, the polarity of the alumina needs to be controlled, and the yield is improved as much as possible while the quality of the aromatic-rich components is ensured. In addition, if the addition amount of the deionized water is too high, the mobile phase and the stationary phase are mutually repelled, and the purpose of solid-liquid separation is difficult to achieve.
The mobile phase in the separation by the solid-liquid adsorption method of the present invention is not particularly limited, the first mobile phase and the second mobile phase are mixed solvents or single solvents, but it is necessary to ensure that a difference in washing strength exists between the first mobile phase and the second mobile phase, when the first mobile phase and the second mobile phase are mixed solvents, the first mobile phase and the second mobile phase comprise a low-washing-strength solvent and a high-washing-strength solvent, the volume content of the low-washing-strength solvent in the first mobile phase is 10% to 100%, the volume content of the low-washing-strength solvent in the second mobile phase is 0% to 90%, more preferably the volume content of the low-washing-strength solvent in the first mobile phase is 20% to 80%, the volume content of the low-washing-strength solvent in the second mobile phase is 10% to 70%, and it is ensured that the washing strength of the second mobile phase is higher than that of the first mobile phase, benzene and/or toluene is preferably selected as the low-washing-strength solvent, preferably benzene; methanol and/or ethanol as high wash strength solvent, preferably ethanol.
The purpose of cascade flushing can be achieved by using pure solvents as the first mobile phase and the second mobile phase, but because the flushing intensity of the pure solvents cannot be adjusted, the difference of the flushing intensity of the first mobile phase and the second mobile phase is adjusted by using mixed solvents aiming at different components, so that the purpose of effectively separating the aromatic-rich components is achieved. In addition, since solvents such as C7 and petroleum ether are difficult to dissolve aromatic components, it is recommended to use aromatic solvents such as benzene and toluene to improve the solubility.
The aromatic-rich component obtained in the solid-liquid adsorption separation process has the properties that the nitrogen content is less than 0.5%, the sulfur content is less than 0.5%, the C/H atomic ratio is greater than 0.88, the saturation content is less than 5%, the aroma content is 80-90%, the colloid content is 5-15%, and the asphaltene content is less than 1%.
For mesophase pitch raw materials, as the saturated components and the asphaltenes rapidly generate free radicals at the reaction temperature, the reaction speed is too high, so that the content of the mesophase pitch raw materials needs to be low enough to ensure that the mesophase structure has sufficient conversion and fusion time, and further a large-scale optical anisotropic structure is formed.
In the carbonization process, the reaction temperature of the liquid-phase carbonization reaction process of benzene is preferably 380-450 ℃, the reaction pressure is 1-5 MPa, and the reaction time is 3-14 h. The liquid phase carbonization reaction mainly takes place of thermal cracking reaction and thermal polycondensation reaction, the overflow of micromolecule hydrocarbon can be inhibited by adjusting pressure, the viscosity of a reaction system is reduced, the fluidity of the product is ensured, and then the high yield of the product can be better ensured and the microcrystalline arrangement can be oriented. The temperature is regulated to promote the deep thermal decomposition reaction and thermal polycondensation reaction of the reaction molecules, the reaction molecules are oriented orderly, the cleanliness and the orientation degree are gradually increased along with the reaction, and the crystal can be developed and oriented by sufficient reaction time.
Compared with the existing preparation method, the invention has the following beneficial effects:
(1) all the raw materials related by the invention have no corrosivity, low price, good economical efficiency and no harsh requirements on equipment.
(2) The invention uses a solid-liquid separation method, and adjusts the polarity of the stationary phase and the washing strength of the mobile phase according to the properties of the raw materials to obtain high-quality aromatic-rich components with low saturation component content, low asphaltene content and high aromatic component content as the raw materials for further preparing the mesophase pitch.
(3) The softening point of the mesophase pitch prepared by the method is as low as 220-350 ℃, the content of the mesophase pitch is as high as 95%, and the mesophase pitch has good spinnability.
Detailed Description
In order to make the method for preparing mesophase pitch by using heavy oil according to the present invention clearer, the following will further describe the technical scheme of the present invention with reference to the specific embodiments:
example 1:
the catalytic cracking slurry oil is used as a raw material, and the inorganic membrane is used for filtering to obtain clarified oil, wherein the yield of the clarified oil is 90 wt.%, the ash removal rate is 95%, and the ash content is 30 ppm.
Activating gamma-neutral alumina at 490 ℃ for 6h, cooling to 20 ℃, adding 1.5 wt.% of deionized water, mixing uniformly, and adding into a chromatographic column. Diluting the clarified oil with a small amount of benzene, and adding the diluted clarified oil into a chromatographic column, wherein the volume ratio of the clarified oil to the benzene is 8: 2, using the benzene-ethanol as a mobile phase to wash the stationary phase; the volume ratio of 2: 8, using benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 60 wt.%.
The basic properties of the aromatic-rich component were 0.40% nitrogen, 0.47% sulfur, 1.03 atomic ratio of C/H, 4.2% saturates, 86.6% aromatics, 12.8% gums, and 0.4% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 440 ℃, the reaction pressure is 2MPa, the stirring speed is 400r/min, and the constant-temperature reaction is carried out for 8 hours, so that the intermediate phase asphalt with the anisotropic content of 98 percent and the softening point of 230 ℃ is obtained.
Example 2:
the catalytic cracking slurry oil is used as a raw material, and the inorganic membrane is used for filtering to obtain clarified oil, wherein the yield of the clarified oil is 90 wt.%, the ash removal rate is 95%, and the ash content is 30 ppm.
The stationary phase in the column is gamma neutral alumina, activated for 6 hours at 490 ℃, cooled to 20 ℃, added with 1.5 wt.% deionized water, mixed evenly, and then added into the chromatographic column. Diluting the clarified oil with a small amount of benzene, adding into a chromatographic column, and washing the stationary phase with n-heptane as a mobile phase; toluene is continuously used as a mobile phase to wash the stationary phase, and the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) taking the elution phase, and evaporating the solvent to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 53 wt.%.
The basic properties of the aromatic-rich component were 0.43% nitrogen, 0.49% sulfur, 1.03 atomic ratio of C/H, 15.1% saturates, 71% aromatics, 11.7% gums, and 2.2% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 440 ℃, the reaction pressure is 2MPa, the stirring speed is 400r/min, and the constant-temperature reaction is carried out for 8 hours, so that the intermediate phase asphalt with the anisotropic content of 90 percent and the softening point of 210 ℃ is obtained.
Example 3:
the method comprises the steps of taking medium-low temperature coal tar as a raw material, adding 1 wt.% of marketized settling aid, uniformly mixing, standing at 90 ℃ for settling for 24 hours, and taking supernatant oil on the upper layer, wherein the yield of the supernatant oil is 90 wt.%, the ash removal rate is 90%, and the ash content is 90 ppm.
The stationary phase in the column is gamma neutral alumina, activated for 6 hours at 450 ℃, cooled to 20 ℃, added with 1.5 wt.% deionized water, mixed evenly, and then added into the chromatographic column. Diluting the clarified oil with a small amount of benzene, and adding the diluted clarified oil into a chromatographic column, wherein the volume ratio of the clarified oil to the benzene is 10: 0 benzene-ethanol is used as a mobile phase to wash the stationary phase; the volume ratio of the mixture is continuously used as 9: 1, using benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 50 wt.%.
The basic properties of the aromatic-rich component were 0.40% nitrogen, 0.47% sulfur, 1.03 atomic ratio of C/H, 4.2% saturates, 86.6% aromatics, 12.8% gums, and 0.4% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 380 ℃, the reaction pressure is 5MPa, the stirring speed is 400r/min, and the constant-temperature reaction is carried out for 3 hours to obtain the mesophase pitch with the anisotropic content of 98 percent and the softening point of 220 ℃.
Example 4:
the high-temperature coal tar is used as a raw material, a commercial filter (the material of a filter element is usually stainless steel powder or porous metal sintered by a wire mesh, and the filtering pore diameter is 0.2-20 mu m) is used, and high-temperature filtration, removal and deashing are carried out at 100 ℃. The yield of clarified oil was 92 wt.%, the ash removal rate was 93%, and the ash was 85 ppm.
The stationary phase in the column is gamma neutral alumina, the gamma neutral alumina is activated for 5.5 hours at 460 ℃, is cooled to 20 ℃, is added with 5.5 wt.% deionized water and is mixed evenly, and then is added into the chromatographic column. Diluting the clarified oil with a small amount of benzene, and adding the diluted clarified oil into a chromatographic column, wherein the volume ratio of the clarified oil to the liquid is 9: 1, using benzene-ethanol as a mobile phase to wash a stationary phase; the volume ratio of the continuous use is 8: 2, using the benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. Taking and elutingThe solvent is removed by phase evaporation to obtain the aromatic-rich component, and the yield of the aromatic-rich component is 49 wt.%.
The basic properties of the aromatic-rich component were 0.43% nitrogen, 0.37% sulfur, 1.05 atomic ratio of C/H, 4.4% saturates, 85.3% aromatics, 9.5% gums, and 0.8% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the flow rate of the nitrogen is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 390 ℃, the reaction pressure is 4.5MPa, the stirring speed is 400r/min, and the constant temperature reaction is carried out for 4 hours, so that the anisotropic content of the mesophase pitch is 96 percent, and the softening point is 240 ℃.
Example 5:
the method takes atmospheric residue as a raw material, and uses an inorganic membrane for filtering and removing ash, wherein the yield of clarified oil is 86 wt.%, the removal rate of ash is 91%, and the ash content is 92 ppm.
The stationary phase in the column is gamma neutral alumina, the gamma neutral alumina is activated for 5 hours at 470 ℃, the gamma neutral alumina is cooled to 20 ℃, then 2.5 wt.% of deionized water is added and mixed evenly, and then the mixture is added into a chromatographic column. The clarified oil was diluted with a small amount of benzene and loaded onto a chromatographic column. The volume ratio used was 8: 2, using the benzene-ethanol as a mobile phase to wash the stationary phase; continuing to use the mixture with the volume ratio of 7: 3, using the benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 46 wt.%.
The basic properties of the aromatic-rich component were 0.30% nitrogen, 0.46% sulfur, 1.09 atomic ratio of C/H, 4.9% saturates, 86.6% aromatics, 7.8% gums, and 0.6% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 400 ℃, the reaction pressure is 4MPa, the stirring speed is 400r/min, and the constant temperature reaction is carried out for 5 hours, so that the intermediate phase asphalt with the anisotropic content of 95% and the softening point of 259 ℃ is obtained.
Example 6:
vacuum residue was used as a raw material, and electrostatic deashing was used, wherein the yield of clarified oil was 89 wt.%, the ash removal rate was 91%, and the ash content was 87 ppm.
The stationary phase in the column is gamma neutral alumina, activated for 4.5h at 480 ℃, cooled to 20 ℃, added with 3 wt.% deionized water, mixed evenly, and then added into the chromatographic column. The clarified oil was diluted with a small amount of benzene and loaded onto a chromatographic column. The volume ratio of 7: 3, using the benzene-ethanol as a mobile phase to wash the stationary phase; the volume ratio of the mixture is continuously used as 6: 4, using benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) taking the elution phase, and evaporating the solvent to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 47 wt.%.
The basic properties of the aromatic-rich component were 0.45% nitrogen, 0.39% sulfur, 1.09 atomic ratio of C/H, 4.3% saturates, 87.3% aromatics, 8% gums, and 0.4% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 410 ℃, the reaction pressure is 3.5MPa, the stirring speed is 400r/min, and the constant temperature reaction is carried out for 6 hours, so that the mesophase pitch with the anisotropic content of 97 percent and the softening point of 282 ℃ is obtained.
Example 7:
FCC oil slurry is used as a raw material, 1 wt% of a commercial sedimentation auxiliary agent is added, the mixture is uniformly mixed and then is statically sedimentated for 24 hours at 90 ℃, and supernatant oil is taken, wherein the yield of the supernatant oil is 83 wt%, the ash removal rate is 90%, and the ash content is 99 ppm.
The stationary phase in the column is gamma neutral alumina, the gamma neutral alumina is activated for 4 hours at 490 ℃, is cooled to 20 ℃, is added with 3.5 wt.% deionized water and is mixed evenly, and then is added into the chromatographic column. The clarified oil was diluted with a small amount of benzene and loaded onto a chromatographic column. The volume ratio of 6: 4, using the benzene-ethanol as a mobile phase to wash the stationary phase; continuously using the mixture with the volume ratio of 5: 5, using benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. Taking the elution phase to evaporate the solvent to obtain the aromatic-rich component,the yield of the aromatic-rich component was 48 wt.%.
The basic properties of the aromatic-rich component were 0.39% nitrogen, 0.40% sulfur, 1.10 atomic ratio of C/H, 4.9% saturates, 86.2% aromatics, 8.2% gums, and 0.7% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 420 ℃, the reaction pressure is 3MPa, the stirring speed is 400r/min, and the constant-temperature reaction is carried out for 7 hours, so that the anisotropic content of the mesophase pitch is 97%, and the softening point is 268 ℃.
Example 8:
hydrocracking tail oil is used as a raw material, a commercial filter (the material of a filter element is usually stainless steel powder or porous metal sintered by a wire mesh, the filtering pore diameter is 0.2-20 mu m) is used, and high-temperature filtering, removing and deashing operation is carried out at 100 ℃. The yield of clarified oil was 92 wt.%, the ash removal was 89%, and the ash was 79 ppm.
The stationary phase in the column is gamma neutral alumina, the gamma neutral alumina is activated for 3.5 hours at 500 ℃, cooled to 20 ℃, added with 4 wt.% deionized water and mixed evenly, and then added into the chromatographic column. The clarified oil was diluted with a small amount of benzene and loaded onto a chromatographic column. The volume ratio of 5: 5, using the benzene-ethanol as a mobile phase to wash the stationary phase; the volume ratio of the mixture is continuously used as 6: 4, using benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 48 wt.%.
The basic properties of the aromatic-rich component were 0.37% nitrogen, 0.40% sulfur, 1.15 atomic ratio of C/H, 4.2% saturates, 84.6% aromatics, 10.4% gums, and 0.8% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 430 ℃, the reaction pressure is 2.5MPa, the stirring speed is 400r/min, and the constant temperature reaction is carried out for 8 hours, so that the mesophase pitch with the anisotropic content of 97 percent and the softening point of 278 ℃ is obtained.
Example 9:
ethylene tar was used as the raw material, and electrostatic deliming was used, wherein the yield of clarified oil was 80 wt.%, the ash removal rate was 90%, and the ash content was 91 ppm.
The stationary phase in the column is gamma neutral alumina, the gamma neutral alumina is activated for 3 hours at the temperature of 450 ℃, 4.5 wt.% of deionized water is added after the gamma neutral alumina is cooled to 20 ℃, and the mixture is uniformly mixed and then added into a chromatographic column. The clarified oil was diluted with a small amount of benzene and loaded onto a chromatographic column. The volume ratio of 4: 6, taking the benzene-ethanol as a mobile phase to wash the stationary phase; the volume ratio of 3: 7, using benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 49 wt.%.
The basic properties of the aromatic-rich component were 0.30% nitrogen, 0.42% sulfur, 1.11 atomic C/H ratio, 4.4% saturates, 86.7% aromatics, 8.2% gums, and 0.7% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 440 ℃, the reaction pressure is 2MPa, the stirring speed is 400r/min, and the constant-temperature reaction is carried out for 9 hours to obtain the mesophase pitch with the anisotropic content of 98 percent and the softening point of 270 ℃.
Example 10:
the distillate of medium-low temperature coal tar below 460 ℃ is used as a raw material, and is filtered by an inorganic membrane, so that the yield of clarified oil is 95 wt.%, the ash removal rate is 97%, and the ash content is 70 ppm.
The stationary phase in the column is gamma neutral alumina, the gamma neutral alumina is activated for 2.5 hours at the temperature of 4600 ℃, 5 wt.% of deionized water is added after the gamma neutral alumina is cooled to 20 ℃, and the mixture is uniformly mixed and then added into the chromatographic column. The clarified oil was diluted with a small amount of benzene and loaded onto a chromatographic column. The volume ratio of 3: 7, taking the benzene-ethanol as a mobile phase to wash the stationary phase; the volume ratio of 2: 8, using benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3Obtaining an elution phase, the whole process is carried out at a constant temperature of 50 DEG CThe process is carried out. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 48 wt.%.
The basic properties of the aromatic-rich component were 0.32% nitrogen, 0.40% sulfur, 1.08 atomic ratio of C/H, 3.2% saturates, 83.7% aromatics, 12.7% gums, and 0.4% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 450 ℃, the reaction pressure is 1.5MPa, the stirring speed is 400r/min, and the constant-temperature reaction is carried out for 10 hours, so that the intermediate phase asphalt with the anisotropy content of 96 percent and the softening point of 289 ℃ is obtained.
Example 11:
the method comprises the following steps of taking a fraction of vacuum residue at a temperature of less than 540 ℃ as a raw material, adding 1 wt% of a commercial settling auxiliary agent, uniformly mixing, standing and settling for 24 hours at a temperature of 90 ℃, and taking supernatant oil, wherein the yield of the supernatant oil is 87 wt%, the ash removal rate is 92%, and the ash content is 95 ppm.
The stationary phase in the column is gamma neutral alumina, activated for 2 hours at 470 ℃, cooled to 20 ℃, added with 5.5 wt.% deionized water, mixed evenly, and then added into the chromatographic column. The clarified oil was diluted with a small amount of benzene and loaded onto a chromatographic column. The volume ratio of 2: 8, taking the benzene-ethanol as a mobile phase to wash the stationary phase; continuing to use the mixture with the volume ratio of 1: 9, using benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 52 wt.%.
The basic properties of the aromatic-rich component were 0.37% nitrogen, 0.29% sulfur, 1.15 atomic ratio of C/H, 4.1% saturates, 87% aromatics, 8.2% gums, and 0.7% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 380 ℃, the reaction pressure is 1MPa, the stirring speed is 400r/min, and the constant-temperature reaction is carried out for 11 hours, so that the anisotropic content of the mesophase pitch is 96%, and the softening point is 279 ℃.
Example 12:
the fraction of ethylene tar at a temperature of less than 480 ℃ is used as a raw material, electrostatic deashing is used, and the yield of clarified oil is 92%, the ash removal rate is 90 wt.%, and the ash content is 92 ppm.
The stationary phase in the column is gamma neutral alumina, the gamma neutral alumina is activated for 2.8 hours at 480 ℃, cooled to 20 ℃, added with 6 wt.% deionized water and mixed evenly, and then added into the chromatographic column. The clarified oil was diluted with a small amount of benzene and loaded onto a chromatographic column. The volume ratio of 1: 9, taking the benzene-ethanol as a mobile phase to wash the stationary phase; continuing to use the mixture with the volume ratio of 0: 10 benzene-ethanol is used as a mobile phase to wash the stationary phase, and the dosage of the washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 40 wt.%.
The basic properties of the aromatic-rich component were 0.39% nitrogen, 0.42% sulfur, 1.01 atomic ratio of C/H, 3.7% saturates, 86.7% aromatics, 9.2% gums, and 0.4% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 410 ℃, the reaction pressure is 5.2MPa, the stirring speed is 400r/min, and the constant-temperature reaction is carried out for 12 hours, so that the intermediate phase asphalt with the anisotropic content of 96 percent and the softening point of 281 ℃ is obtained.
Example 13:
the fraction of FCC slurry oil at the temperature of less than 520 ℃ is used as raw material, inorganic membrane filtration is used for deashing, wherein the yield of clarified oil is 88 wt.%, the removal rate of ash is 94 percent, and the ash content is 20 ppm.
The stationary phase in the column is gamma neutral alumina, the gamma neutral alumina is activated for 4.5 hours at 490 ℃, is cooled to 20 ℃, is added with 3.3 wt.% deionized water and is mixed evenly, and then is added into the chromatographic column. The clarified oil was diluted with a small amount of benzene and loaded onto a chromatographic column. The volume ratio used was 8: 2, taking toluene-methanol as a mobile phase to wash a stationary phase; the volume ratio of 4: 6 toluene-methanol is used as a mobile phase to wash the stationary phase, and the dosage of the washing agent is 1mL/g Al2O3Obtaining an elution phase, passing the wholeThe process is carried out at a constant temperature of 50 ℃. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 40 wt.%.
The basic properties of the aromatic-rich component were 0.41% nitrogen, 0.32% sulfur, 1.15 atomic ratio of C/H, 4.8% saturates, 87.8% aromatics, 6.5% gums, and 0.9% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 420 ℃, the reaction pressure is 0.9MPa, the stirring speed is 400r/min, and the constant temperature reaction is carried out for 12 hours, so that the intermediate phase asphalt with the anisotropic content of 96 percent and the softening point of 269 ℃ is obtained.
Example 14:
the method is characterized in that the distillate of the atmospheric residue at the temperature of less than 500 ℃ is used as a raw material, a commercial catalytic slurry oil filter (the filter core material is usually stainless steel powder or porous metal sintered by a wire mesh, and the filter pore diameter is 0.2-20 mu m) is used, and high-temperature filtration, separation and deashing operations are carried out at the temperature of 100 ℃. The yield of clarified oil was 92 wt.%, the ash removal rate was 90%, and the ash content of the clarified oil was 83 ppm.
The stationary phase in the column is gamma neutral alumina, activated for 2 hours at 470 ℃, cooled to 20 ℃, added with 5.5 wt.% deionized water, mixed evenly, and then added into the chromatographic column. The clarified oil was diluted with a small amount of benzene and loaded onto a chromatographic column. The volume ratio of 2: 8, taking the benzene-ethanol as a mobile phase to wash the stationary phase; continuing to use the mixture with the volume ratio of 1: 9, using benzene-ethanol as a mobile phase to wash the stationary phase, wherein the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 52 wt.%.
The basic properties of the aromatic-rich component were 0.4% nitrogen, 0.8% sulfur, 1.17 atomic ratio of C/H, 4.2% saturates, 90.1% aromatics, 5.3% gums, and 0.4% asphaltenes.
Adding 100g of the aromatic-rich component into a stainless steel high-pressure reaction kettle; introducing nitrogen to purge the air in the kettle, wherein the nitrogen flow is 3L/min, the temperature is raised to 100 ℃, stirring is started, the reaction temperature is 440 ℃, the reaction pressure is 3MPa, the stirring speed is 400r/min, and the constant-temperature reaction is carried out for 14 hours, so that the intermediate phase asphalt with the anisotropic content of 95 percent and the softening point of 268 ℃ is obtained.
In order to further illustrate that the technical scheme of the invention has substantial technical effects compared with the prior art, the invention lists the following comparative examples:
comparative example 1:
the deliming procedure was exactly the same as in example 1. Activating gamma neutral alumina at 490 ℃ for 6h in the aromatic hydrocarbon enrichment step, cooling to 20 ℃, directly adding the gamma neutral alumina into a chromatographic column without adding deionized water, and obtaining the yield of the aromatic hydrocarbon-rich component of 38 wt.% through the same other steps. The basic properties of the resulting rich aromatic fraction were 0.47% nitrogen, 0.61% sulfur, 1.05 atomic C/H ratio, 14.3% saturates, 70.2% aromatics, 13.1% gums, and 2.4% asphaltenes. The asphaltene and the saturation fraction are obviously increased.
The comparison shows that the total yield of the aromatic-rich components in the comparative example is 38 wt.% of the raw materials, and compared with the total yield of the aromatic-rich components in the example 1, the total yield of the aromatic-rich components is reduced by about 22 percent, so that a large amount of waste of the raw materials is caused in actual use, and the yield of the mesophase pitch is reduced. Therefore, the process for separating the aromatic hydrocarbon by the solid-liquid adsorption method has substantial technical effects.
Comparative example 2
The deliming procedure was exactly the same as in example 1. In the aromatic hydrocarbon enrichment step, gamma neutral alumina is activated for 6 hours at 490 ℃, and is directly added into a chromatographic column without adding deionized water after being cooled to 20 ℃. Diluting the clarified oil with a small amount of benzene, adding into a chromatographic column, and washing the stationary phase with n-heptane as a mobile phase; toluene is continuously used as a mobile phase to wash the stationary phase, and the dosage of a washing agent is 1mL/g Al2O3To obtain an elution phase, and the whole process is carried out at a constant temperature of 50 ℃. And (4) evaporating the solvent from the elution phase to obtain the aromatic-rich component, wherein the yield of the aromatic-rich component is 25 wt.%.
The basic properties of the resulting rich aromatic fraction were 0.48% nitrogen, 0.66% sulfur, 1.02 atomic C/H ratio, 14.9% saturates, 66.6% aromatics, 14.4% gums, and 4.1% asphaltenes. The asphaltene and the saturation fraction are obviously increased. The liquid phase carbonization steps are completely the same. The mesophase pitch obtained has an anisotropy content of 71% and a softening point of 171 ℃.
As can be seen by comparison, the total yield of the aromatic-rich components in the comparative example is 25 wt.% of the raw material, which is reduced by about 35% compared with the total yield of the aromatic-rich components in example 1, resulting in a great waste of raw material during actual use and a reduction in the yield of mesophase pitch. Therefore, the mixed flushing solvent prepared by adjusting the polarity of the alumina stationary phase through deionized water and using the benzene-ethanol ratio is obviously superior to the pure n-heptane and toluene flushing solvent. The method can effectively improve the yield of the aromatic-rich component, can also obviously reduce the content of saturated components and asphaltene, effectively reduce the reaction rate, improve the optical anisotropy content of the mesophase pitch and improve the softening point. Therefore, the process for separating the aromatic hydrocarbon by the solid-liquid adsorption method has substantial technical effects.
The present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof, and it is therefore intended that all such changes and modifications as fall within the true spirit and scope of the invention as defined by the appended claims be interpreted in accordance with the breadth to which they are fairly, if not explicitly recited herein.
Claims (14)
1. The method for preparing the mesophase pitch by using the heavy oil is characterized by comprising the following steps of:
step (1): deashing heavy oil to obtain clarified oil;
step (2): separating the clarified oil obtained in the step (1) by adopting a solid-liquid adsorption method, respectively adjusting the polarity of an alumina stationary phase and the washing strengths of a first mobile phase and a second mobile phase according to the difference of components in heavy oil, and performing step elution through the first mobile phase and the second mobile phase to obtain an aromatic-rich component;
and (3): and (3) carrying out liquid-phase carbonization reaction on the aromatic-rich component obtained in the step (2) in a high-pressure reaction kettle to obtain the mesophase pitch.
2. The method for preparing mesophase pitch from heavy oil according to claim 1, wherein the heavy oil is at least one of medium-low temperature coal tar, high temperature coal tar, atmospheric residue, vacuum residue, catalytic cracking slurry oil, hydrocracking tail oil, ethylene tar heavy oil and fractions thereof.
3. The method for preparing mesophase pitch from heavy oil according to claim 1, wherein in the step (1), the deashing treatment is at least one of aid settling deashing, filtration deashing, electrostatic deashing and inorganic membrane filtration deashing.
4. The process for producing mesophase pitch with heavy oil according to claim 3, characterized in that the deashing treatment is inorganic membrane filtration deashing.
5. The process for producing mesophase pitch with heavy oil according to claim 1, wherein ash content of decant oil in the step (1) is 100ppm or less.
6. The method for preparing the mesophase pitch by using the heavy oil as claimed in claim 1, wherein in the step (2), the polarity of the alumina stationary phase is adjusted by activating gamma neutral alumina at 450-500 ℃ for 2-6h, cooling to 20-30 ℃, and then adding 1.5-6.0 wt.% of deionized water to adjust the polarity of the alumina stationary phase.
7. The method for preparing mesophase pitch from heavy oil according to claim 6, wherein the deionized water is added in an amount of 2 to 4 wt.%.
8. The process for producing mesophase pitch with heavy oil according to claim 1, wherein in the step (2), the first mobile phase and the second mobile phase are mixed solvents or a single solvent.
9. The process for producing mesophase pitch with heavy oil according to claim 8, characterized in that the first mobile phase and the second mobile phase are mixed solvents comprising a low wash strength solvent and a high wash strength solvent; the flushing intensity of the first mobile phase and the second mobile phase is adjusted in a way that the volume content of the low-flushing-intensity solvent in the first mobile phase is 10-100%, the volume content of the low-flushing-intensity solvent in the second mobile phase is 0-90%, and the flushing intensity of the second mobile phase is greater than that of the first mobile phase.
10. The process for producing mesophase pitch with heavy oil according to claim 9, characterized in that the low wash strength solvent is benzene and/or toluene, preferably benzene; the high washing strength solvent is methanol and/or ethanol, preferably ethanol.
11. The process for producing mesophase pitch with heavy oil according to claim 9, wherein the volume content of low wash strength solvent in the first mobile phase is 20% to 80% and the volume content of low wash strength solvent in the second mobile phase is 10% to 70%.
12. The method for preparing mesophase pitch from heavy oil according to claim 1, wherein in the step (2), the nitrogen content of the aromatic-rich component is less than 0.5%, the sulfur content is less than 0.5%, the atomic ratio of C/H is more than 0.88, the saturation content is less than 5%, the aroma content is 80-90%, the colloid content is 5-15%, and the asphaltene content is less than 1%.
13. The method for preparing the mesophase pitch from the heavy oil according to claim 1, wherein in the step (3), the reaction temperature of the liquid-phase carbonization reaction is 380 to 450 ℃, the reaction pressure is 1 to 5MPa, and the reaction time is 3 to 14 hours.
14. The mesophase pitch obtained by the method for preparing the mesophase pitch from the heavy oil according to any one of claims 1 to 13, wherein the softening point of the mesophase pitch is 220 to 350 ℃, and the content of the mesophase pitch is more than 95%.
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Application publication date: 20220527 |