CN115029156A - Method for preparing carbon material by refining inferior heavy oil - Google Patents
Method for preparing carbon material by refining inferior heavy oil Download PDFInfo
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- CN115029156A CN115029156A CN202210670374.9A CN202210670374A CN115029156A CN 115029156 A CN115029156 A CN 115029156A CN 202210670374 A CN202210670374 A CN 202210670374A CN 115029156 A CN115029156 A CN 115029156A
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- heavy oil
- hydrogen bond
- inferior heavy
- carbon material
- refining
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- 239000000295 fuel oil Substances 0.000 title claims abstract description 89
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 29
- 238000007670 refining Methods 0.000 title claims abstract description 15
- 239000001257 hydrogen Substances 0.000 claims abstract description 51
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 51
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000002994 raw material Substances 0.000 claims abstract description 30
- 239000000203 mixture Substances 0.000 claims abstract description 27
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- 230000005496 eutectics Effects 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 19
- 239000002904 solvent Substances 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 17
- 238000004821 distillation Methods 0.000 claims abstract description 15
- 238000003756 stirring Methods 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 10
- 238000005520 cutting process Methods 0.000 claims abstract description 9
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000006068 polycondensation reaction Methods 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 238000004523 catalytic cracking Methods 0.000 claims description 15
- 239000002002 slurry Substances 0.000 claims description 15
- 239000003921 oil Substances 0.000 claims description 13
- 239000011302 mesophase pitch Substances 0.000 claims description 12
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 10
- 125000004434 sulfur atom Chemical group 0.000 claims description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- 238000005984 hydrogenation reaction Methods 0.000 claims description 6
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 claims description 5
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical group COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 5
- 235000019743 Choline chloride Nutrition 0.000 claims description 5
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 claims description 5
- 229960003178 choline chloride Drugs 0.000 claims description 5
- 235000019253 formic acid Nutrition 0.000 claims description 5
- 239000011295 pitch Substances 0.000 claims description 5
- RKHXQBLJXBGEKF-UHFFFAOYSA-M tetrabutylphosphanium;bromide Chemical compound [Br-].CCCC[P+](CCCC)(CCCC)CCCC RKHXQBLJXBGEKF-UHFFFAOYSA-M 0.000 claims description 5
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 4
- 239000004917 carbon fiber Substances 0.000 claims description 4
- 239000011280 coal tar Substances 0.000 claims description 4
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 239000011331 needle coke Substances 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 3
- 239000005977 Ethylene Substances 0.000 claims description 3
- 238000005087 graphitization Methods 0.000 claims description 3
- 238000002844 melting Methods 0.000 claims description 3
- 230000008018 melting Effects 0.000 claims description 3
- 239000011269 tar Substances 0.000 claims description 3
- 235000011054 acetic acid Nutrition 0.000 claims description 2
- 150000001735 carboxylic acids Chemical group 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 claims description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 claims description 2
- 235000019260 propionic acid Nutrition 0.000 claims description 2
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 2
- 238000009987 spinning Methods 0.000 claims description 2
- JRMUNVKIHCOMHV-UHFFFAOYSA-M tetrabutylammonium bromide Chemical compound [Br-].CCCC[N+](CCCC)(CCCC)CCCC JRMUNVKIHCOMHV-UHFFFAOYSA-M 0.000 claims description 2
- BGQMOFGZRJUORO-UHFFFAOYSA-M tetrapropylammonium bromide Chemical compound [Br-].CCC[N+](CCC)(CCC)CCC BGQMOFGZRJUORO-UHFFFAOYSA-M 0.000 claims description 2
- FBEVECUEMUUFKM-UHFFFAOYSA-M tetrapropylazanium;chloride Chemical compound [Cl-].CCC[N+](CCC)(CCC)CCC FBEVECUEMUUFKM-UHFFFAOYSA-M 0.000 claims description 2
- DASNDJBQHOUCAV-UHFFFAOYSA-N CCCCP(CCCC)(CCCC)CCCC.Br Chemical compound CCCCP(CCCC)(CCCC)CCCC.Br DASNDJBQHOUCAV-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000007513 acids Chemical class 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 37
- 230000023556 desulfurization Effects 0.000 abstract description 37
- 230000001590 oxidative effect Effects 0.000 abstract description 14
- 150000004945 aromatic hydrocarbons Chemical class 0.000 abstract description 6
- 238000002360 preparation method Methods 0.000 abstract description 5
- 150000001732 carboxylic acid derivatives Chemical group 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 19
- 229910052717 sulfur Inorganic materials 0.000 description 19
- 239000011593 sulfur Substances 0.000 description 19
- -1 molybdenum ions Chemical class 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 7
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 6
- 239000010426 asphalt Substances 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- 150000003568 thioethers Chemical class 0.000 description 5
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical compound C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 238000010926 purge Methods 0.000 description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910018072 Al 2 O 3 Inorganic materials 0.000 description 1
- ZQRGREQWCRSUCI-UHFFFAOYSA-N [S].C=1C=CSC=1 Chemical compound [S].C=1C=CSC=1 ZQRGREQWCRSUCI-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
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000010000 carbonizing Methods 0.000 description 1
- 238000004517 catalytic hydrocracking Methods 0.000 description 1
- 238000003889 chemical engineering Methods 0.000 description 1
- 239000003245 coal Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000003502 gasoline Substances 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002074 melt spinning Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 235000006408 oxalic acid Nutrition 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003457 sulfones Chemical class 0.000 description 1
- 150000003462 sulfoxides Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
Classifications
-
- 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
- C10G57/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process
- C10G57/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by at least one cracking process or refining process and at least one other conversion process with polymerisation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
-
- 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
- C10C3/002—Working-up pitch, asphalt, bitumen by thermal means
-
- 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
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Civil Engineering (AREA)
- Structural Engineering (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
Abstract
The invention discloses a method for preparing a carbon material by refining inferior heavy oil, which comprises the following steps: 1) adding inferior heavy oil, a catalyst and hydrogen peroxide into a reactor in sequence, mixing, and reacting for 0.5-12 h under the condition of stirring at the reaction temperature of 30-150 ℃ to obtain an oxidized mixture; 2) cooling the oxidized mixture to room temperature, heating to 40-80 ℃, and standing for separation; 3) carrying out reduced pressure distillation on the separated heavy oil, and cutting to obtain a refined raw material at 350-520 ℃; 4) and carrying out heat treatment on the refined raw material to obtain the carbon material. The oxidative desulfurization catalyst is a carboxylic acid eutectic solvent and consists of a hydrogen bond donor and a hydrogen bond acceptor. Compared with the prior art, the desulfurization method in the method has the advantages of mild conditions, low aromatic hydrocarbon loss, high oxidative desulfurization efficiency and low cost, and is suitable for the preparation process of the carbon material.
Description
Technical Field
The invention relates to the technical field of petroleum processing, in particular to a method for preparing a carbon material by refining inferior heavy oil.
Background
The carbon material has the performances of corrosion resistance, high temperature resistance, good electric conduction, heat conduction and the like, and is widely applied to the fields of electronics, chemical engineering, aerospace, environmental protection and the like. With the aggravation of energy consumption and the enhancement of environmental awareness, the preparation of carbon materials by using cheap carbon-containing wastes becomes a research hotspot. Inferior heavy oil such as catalytic cracking slurry oil, coal tar, ethylene tar, atmospheric and vacuum residue oil and the like is a byproduct with low added value generated in the production process of coal chemical industry and petrochemical industry, the heavy oil has high density, high carbon-hydrogen atomic ratio and high aromatic hydrocarbon content, and can be used for preparing novel carbon material products with different purposes. However, the sulfur content of these inferior heavy oils is very high, and during the liquid phase carbonization process, the presence of S atoms can affect the parallel arrangement of aromatic molecules, which in turn affects the formation and quality of carbon materials. Therefore, before the carbon material is prepared by heat treatment, the inferior heavy oil needs to be subjected to desulfurization treatment.
Currently, the most common desulfurization method used in industry is hydrodesulfurization. The hydrodesulfurization is to utilize hydrogen to reduce and crack sulfides in the heavy oil and convert the sulfides into H 2 And S, thereby achieving the aim of desulfurization. Patent CN107858173A discloses a hydrocracking desulfurization method for an inferior heavy oil suspension bed, which comprises the steps of mixing inferior heavy oil with a hydrogenation catalyst, and then carrying out hydrogenation reaction in a suspension bed reactor, wherein the reaction temperature is 340-450 ℃, and the reaction pressure is 5-20 MPa. In the method, the hydrogenation catalyst is solid powder and is dispersed in the heavy oil, and the catalyst powder is difficult to remove after hydrogenation. Patent CN112745931A discloses a process for hydrodesulfurization of heavy oils which uses a liquid desulfurization catalyst containing molybdenum ions and cobalt ions to avoid the introduction of solid impurities into the heavy oil. The hydrodesulfurization method has high desulfurization rate when treating heavy oil, but the hydrodesulfurization is a high-temperature and high-pressure reaction, the conditions are very harsh, and the requirement on reaction equipment is high. In addition, aromatic ring saturation can occur during hydrodesulfurization, which results in loss of aromatic hydrocarbon components and is not beneficial to the preparation of carbon materials.
Oxidative desulfurization is a novel desulfurization technique. Oxidative desulfurization refers to oxidizing sulfides in oil products into sulfones or sulfoxides with stronger polarity and higher boiling point by using oxidants such as oxygen, hydrogen peroxide and the like, so that the sulfides can be separated from the oil products more easily in a subsequent extraction or distillation mode. Compared with hydrodesulfurization, the oxidative desulfurization has mild reaction conditions, higher reaction selectivity on thiophene sulfur-containing compounds and low loss of aromatic hydrocarbon components after desulfurization, and is suitable for preparation of carbon materials. Patent CN108753344A discloses a method for oxidative desulfurization of heavy oil, which comprises introducing oxygen or ozone into sulfur-containing heavy oil, and performing oxidative desulfurization reaction at 135-150 ℃. The method has poor oxidative desulfurization effect because oxygen or ozone is difficult to uniformly disperse in heavy oil. Patents such as CN105754635A, CN108179021A and CN110194965A take ionic liquid, heteropoly acid salt or boric acid eutectic solvent as a catalyst and hydrogen peroxide as an oxidant to oxidize and remove sulfides in fuel oil, and the desulfurization rate can reach 60-99.5%. However, the above patent only has a good desulfurization effect on light oil such as gasoline and diesel oil, and is not good for heavy oil.
Disclosure of Invention
The invention provides a method for preparing carbon materials by refining inferior heavy oil, aiming at the problems of harsh hydrodesulfurization conditions, large aromatic hydrocarbon loss, poor desulfurization effect of the existing oxidative desulfurization method on the heavy oil and the like.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing a carbon material by refining inferior heavy oil specifically comprises the following steps:
1) adding inferior heavy oil, a catalyst and hydrogen peroxide into a reactor in sequence, mixing, reacting for 0.5-12 h under the condition of stirring, wherein the reaction temperature is 30-150 ℃, and obtaining an oxidized mixture;
the catalyst is a carboxylic acid eutectic solvent and consists of a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is at least one of formic acid, acetic acid, propionic acid and oxalic acid, the hydrogen bond acceptor is any one of tetrapropylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium bromide, tetrabutylphosphonium bromide and choline chloride, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1-30: 1; hydrogen in hydrogen peroxide 2 O 2 The molar ratio of the hydrogen bond donor to sulfur atoms in the inferior heavy oil is 1-10: 1, and the molar ratio of the hydrogen bond donor in the catalyst to sulfur atoms in the inferior heavy oil is 1-12: 1;
2) cooling the oxidized mixture to room temperature, heating to 40-80 ℃, standing for 0.5-3 h, and separating;
3) carrying out reduced pressure distillation on the separated heavy oil, and cutting to obtain a refined raw material at 350-520 ℃;
4) and carrying out heat treatment on the refined raw material to obtain the carbon material.
In the technical scheme, the inferior heavy oil in the step 1) is preferably one or more of catalytic cracking slurry oil, coal tar, ethylene tar, atmospheric residue oil and vacuum residue oil, and the content of polycyclic aromatic hydrocarbon in the inferior heavy oil is not less than 50 wt%.
Further, the reaction temperature in the step 1) is preferably 60-100 ℃.
Further, the hydrogen bond donor in the step 1) is preferably at least one of formic acid and acetic acid, the hydrogen bond acceptor is preferably one of tetrabutyl phosphonium bromide and choline chloride, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is preferably 10-20: 1, and H in hydrogen peroxide 2 O 2 The mol ratio of the sulfur atoms in the inferior heavy oil to the hydrogen-bond donors in the catalyst is preferably 2-6: 1, and the mol ratio of the hydrogen-bond donors in the catalyst to the sulfur atoms in the inferior heavy oilThe preferred molar ratio is 2-8: 1.
In the technical scheme, the standing temperature in the step 2) is preferably 40-60 ℃.
In the technical scheme, in the step 3), after the heavy oil is separated out, 1-5 times of water in volume is added into the residual liquid containing the eutectic solvent and then the mixture is fully mixed, the water phase is removed through reduced pressure distillation to obtain the eutectic solvent, and the recovered eutectic solvent can be reused.
In the above technical solution, the heat treatment in step 4) to obtain the carbon material comprises heat treatment to obtain isotropic pitch; the method comprises the following steps of carrying out thermal polycondensation to obtain mesophase pitch, wherein the thermal polycondensation method is preferably one or a combination of more of direct thermal polycondensation, pressurized thermal polycondensation, vacuum thermal polycondensation, hydrogenation thermal polycondensation, catalytic thermal polycondensation and co-carbonization; comprises heat treatment to obtain carbon microspheres; comprises the steps of heat treatment to obtain needle coke; comprises the steps of thermal polycondensation, spinning, non-melting, carbonization and graphitization to obtain the carbon fiber.
The method for refining and preparing the carbon material by using the inferior heavy oil has the beneficial effects that:
1) compared with hydrodesulfurization, the heavy oil desulfurization method has mild conditions, small loss of aromatic hydrocarbon components, no introduction of impurities into heavy oil, and suitability for the preparation process of carbon materials;
2) compared with the existing oxidative desulfurization method, the oxidative desulfurization method has higher efficiency of oxidative desulfurization of the heavy oil.
Detailed Description
The technical solution and the advantages of the present invention will be further described with reference to the following specific examples.
Example 1:
in the embodiment, catalytic cracking slurry A is used as a raw material, wherein the content of 2-5 cyclic aromatic hydrocarbons in the raw material is 53 wt%, and the content of sulfur in the raw material is 2.01 wt%.
Mixing the catalytic cracking slurry A with 30 wt% of hydrogen peroxide and a fresh eutectic solvent, and reacting for 2 hours at the temperature of 65 ℃ under the condition of stirring. Wherein the fresh eutectic solvent takes acetic acid as a hydrogen bond donor, tetrabutyl phosphonium bromide as a hydrogen bond acceptor, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptorIs 10:1, H in hydrogen peroxide 2 O 2 The molar ratio of the hydrogen bond donor to the sulfur in the raw material is 2:1, and the molar ratio of the hydrogen bond donor to the sulfur in the raw material is 2: 1. After the oxidation desulfurization reaction, cooling the oxidized mixture to room temperature, then heating to 40 ℃, standing for 1h at constant temperature, and separating out heavy oil, wherein the content of 2-5 cyclic aromatic hydrocarbon in the oxidized heavy oil is 49 wt%, the content of sulfur is 0.46 wt%, and the desulfurization rate is 77.1%. And carrying out reduced pressure distillation on the separated heavy oil, and cutting to obtain refined heavy oil at 350-520 ℃.
And (3) putting the refined heavy oil into a reaction kettle, and reacting for 5 hours at the temperature of 380 ℃ under the blowing of nitrogen gas of 0.1L/min to obtain isotropic asphalt, wherein the softening point of the isotropic asphalt is 224 ℃.
Example 2:
in the embodiment, the catalytic cracking slurry B is used as a raw material, wherein the content of 2-5 cyclic aromatic hydrocarbons in the raw material is 76 wt%, and the content of sulfur in the raw material is 2.38 wt%.
Mixing the catalytic cracking slurry B with 30 wt% of hydrogen peroxide and a fresh eutectic solvent, and reacting for 4 hours at the temperature of 75 ℃ under the stirring condition. Wherein the fresh eutectic solvent takes acetic acid as a hydrogen bond donor, choline chloride as a hydrogen bond acceptor, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 20:1, and H in hydrogen peroxide 2 O 2 The molar ratio of the hydrogen bond donor to the sulfur in the raw material is 6:1, and the molar ratio of the hydrogen bond donor to the sulfur in the raw material is 6: 1. After the oxidation desulfurization reaction, cooling the oxidized mixture to room temperature, then heating to 60 ℃, standing at a constant temperature for 2.5 hours, and separating out heavy oil, wherein the content of 2-5 cyclic aromatic hydrocarbons in the oxidized heavy oil is 72 wt%, the content of sulfur is 0.41 wt%, and the desulfurization rate is 82.8%. And carrying out reduced pressure distillation on the separated heavy oil, and cutting to obtain refined heavy oil at the temperature of 350-520 ℃. And mixing the liquid mixture obtained after the heavy oil is separated with water with the volume 4 times that of the liquid mixture, fully stirring to uniformly mix the liquid mixture, then carrying out reduced pressure distillation to remove water, and recycling to obtain the eutectic solvent.
Putting refined heavy oil into a reaction kettle, and reacting for 6 hours at the temperature of 430 ℃ and the pressure of 3MPa to obtain pre-condensed asphalt; and then reacting for 3 hours under the nitrogen purging of 0.3L/min at the temperature of 420 ℃ to obtain the mesophase pitch, wherein the softening point of the mesophase pitch is 301 ℃, the mesophase content is 98.4 percent, and the optical configuration of the mesophase pitch is a wide-area streamline.
Example 3:
in the embodiment, a mixture of catalytic cracking slurry B and coal tar is used as a raw material, wherein the content of 2-5 cyclic aromatic hydrocarbons in the mixed raw material is 88 wt%, and the content of sulfur in the mixed raw material is 1.87 wt%.
The raw materials are taken to be mixed with 30 wt% of hydrogen peroxide and the eutectic solvent recovered in the embodiment 2, and the mixture is reacted for 3 hours under the conditions of temperature of 80 ℃ and stirring. After the oxidation desulfurization reaction, the oxidized mixture is cooled to room temperature, then the temperature is raised to 50 ℃, the mixture is kept stand at the constant temperature for 2.5 hours, heavy oil is separated, the content of 2-5 cyclic aromatic hydrocarbons in the oxidized heavy oil is 83 wt%, the content of sulfur is 0.35 wt%, and the desulfurization rate is 81.3%. And carrying out reduced pressure distillation on the separated heavy oil, and cutting to obtain refined heavy oil at 350-520 ℃. And mixing the liquid mixture remaining after the heavy oil is separated with water with the volume 4 times that of the heavy oil, fully stirring the mixture to uniformly mix the mixture, then carrying out reduced pressure distillation to remove water, and recycling the obtained eutectic solvent.
Putting refined heavy oil and tetrahydroquinoline in a reaction kettle, wherein the mass ratio of the refined heavy oil to the tetrahydroquinoline is 2:1, and reacting for 10 hours at the temperature of 420 ℃ and the pressure of 1MPa to obtain pre-condensed asphalt; then, the reaction is carried out for 2 hours at the temperature of 380 ℃ and the pressure of 5kPa, and the mesophase pitch is obtained, wherein the softening point of the mesophase pitch is 289 ℃, and the content of the mesophase is 100%. And carrying out melt spinning on the mesophase pitch at 330 ℃ to obtain pitch fiber, carrying out non-melting treatment on the pitch fiber at 260 ℃ in the air atmosphere for 3h, and then carrying out carbonization at 1200 ℃ and graphitization treatment at 2800 ℃ to obtain the carbon fiber. The average diameter of the prepared carbon fiber is 12.3 mu m, the tensile strength is 1425MPa, the tensile modulus is 140GPa, and the elongation at break is 1.3%.
Example 4:
in the embodiment, a mixture of catalytic cracking slurry B and vacuum residue is used as a raw material, and the content of 2-5 cyclic aromatic hydrocarbons in the mixed raw material is 79 wt%, and the content of sulfur in the mixed raw material is 2.52 wt%.
The raw materials are taken to be mixed with 30 wt% of hydrogen peroxide and the eutectic solvent recovered in the embodiment 3, and the mixture is reacted for 4 hours under the condition of stirring at the temperature of 70 ℃. After the oxidation desulfurization reaction, cooling the oxidized mixture to room temperature, then heating to 50 ℃, standing at a constant temperature for 3 hours, and separating out heavy oil, wherein the oxidized heavy oil contains 75 wt% of 2-5 cyclic aromatic hydrocarbons, 0.45 wt% of sulfur and 82.1% of desulfurization rate. And carrying out reduced pressure distillation on the separated heavy oil, and cutting to obtain refined heavy oil at 350-520 ℃.
Putting refined heavy oil into a reaction kettle, and reacting for 8 hours at the temperature of 410 ℃ under nitrogen purging at 0.3L/min to obtain a polycondensation product; mixing the polycondensation product and quinoline according to the mass ratio of 1:3, fully stirring, centrifuging at 180 ℃ and 3000r/min for 2min, removing supernatant, washing the lower-layer precipitate with quinoline for three times, finally washing with ethanol, and drying to obtain the carbon microspheres. The obtained carbon microspheres have the average particle diameter of 15.6 mu m and the specific surface area of 1.54m 2 The fixed carbon content is higher than 99.95 percent.
Example 5:
in the embodiment, catalytic cracking slurry C is used as a raw material, wherein the content of 2-5 cyclic aromatic hydrocarbons in the raw material is 64 wt%, and the content of sulfur in the raw material is 2.23 wt%.
Mixing the catalytic cracking slurry C with 30 wt% of hydrogen peroxide and a fresh eutectic solvent, and reacting for 6 hours at the temperature of 65 ℃ under the condition of stirring. Wherein the fresh eutectic solvent takes formic acid as a hydrogen bond donor, tetrabutyl phosphonium bromide as a hydrogen bond acceptor, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 15:1, and H in hydrogen peroxide 2 O 2 The molar ratio of the hydrogen bond donor to the sulfur in the raw material is 6:1, and the molar ratio of the hydrogen bond donor to the sulfur in the raw material is 4: 1. After the oxidation desulfurization reaction, cooling the oxidized mixture to room temperature, then heating to 55 ℃, standing at a constant temperature for 2 hours, and separating out heavy oil, wherein the oxidized heavy oil contains 58 wt% of 2-5 cyclic aromatic hydrocarbons, 0.38 wt% of sulfur and 83.0% of desulfurization rate. And carrying out reduced pressure distillation on the separated heavy oil, and cutting to obtain refined heavy oil at 350-520 ℃.
And (3): putting refined heavy oil into a reaction kettle, and reacting for 4 hours at the temperature of 460 ℃ under the nitrogen purging of 0.3L/min to obtain a polycondensation product; and (3) putting the polycondensation product into a tube furnace, and carbonizing for 7 hours at 500 ℃ under the nitrogen purging of 0.02L/min to obtain needle coke. The needle coke has a coefficient of thermal expansion of 0.717X 10 -6 /℃。
Comparative example 1:
the comparative example uses catalytic cracking slurry B as the feedstock. And (3) directly carrying out reduced pressure distillation on the catalytic cracking slurry oil B without any desulfurization treatment to obtain heavy oil at 350-520 ℃, and carrying out polycondensation by using the heavy oil as a raw material, wherein the polycondensation step and conditions are the same as those in the example 2, so as to finally obtain the mesophase pitch. The softening point of the mesophase pitch is 323 ℃, the content of quinoline insoluble substances is 69%, the content of the mesophase pitch is 91.2%, and the optical configuration of the mesophase pitch is mosaic type.
Comparative example 2:
the comparative example uses catalytic cracking slurry B as the feedstock. The catalytic cracking slurry B is subjected to hydrotreating in a fixed bed reactor to obtain CoMo/Al 2 O 3 Is used as a catalyst, the reaction temperature is 370 ℃, the reaction pressure is 8MPa, the hydrogen-oil ratio is 500:1, and the space velocity is 1h -1 . The content of 2-5 cyclic aromatic hydrocarbon in the hydrogenated heavy oil is 35 wt%, the content of sulfur is 0.24 wt%, and the desulfurization rate is 89.9%. And carrying out reduced pressure distillation on the hydrogenated heavy oil, and cutting to obtain the hydrofined heavy oil at the temperature of 350-520 ℃. The hydrorefined heavy oil was subjected to polycondensation in the same manner as in example 2, and the polycondensation pitch was finally obtained. The polycondensation asphalt has a softening point of 178 ℃, a mesophase content of 16.6%, and is a mixture of isotropic asphalt and mesophase globules.
The above-mentioned embodiments are merely illustrative of specific embodiments of the present patent, and the description thereof is in detail, but not construed as limiting the scope of the present patent application. Without departing from the concept of the present patent, several changes and modifications may be made within the scope of the present application.
Claims (8)
1. A method for preparing a carbon material by refining inferior heavy oil is characterized by comprising the following steps:
1) adding inferior heavy oil, a catalyst and hydrogen peroxide into a reactor in sequence, mixing, and reacting for 0.5-12 h under the condition of stirring at the reaction temperature of 30-150 ℃ to obtain an oxidized mixture;
wherein the catalyst is a carboxylic acid eutectic solvent, and consists of a hydrogen bond donor and a hydrogen bond acceptor, wherein the hydrogen bond donor is formic acid, acetic acid, propionic acid and grassAt least one of acids, wherein the hydrogen bond acceptor is any one of tetrapropylammonium bromide, tetrapropylammonium chloride, tetrabutylammonium bromide, tetrabutylphosphonium bromide and choline chloride, and the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 1-30: 1; hydrogen in hydrogen peroxide 2 O 2 The molar ratio of the hydrogen bond donor to sulfur atoms in the inferior heavy oil is 1-10: 1, and the molar ratio of the hydrogen bond donor in the catalyst to sulfur atoms in the inferior heavy oil is 1-12: 1;
2) cooling the oxidized mixture to room temperature, heating to 40-80 ℃, standing for 0.5-3 h, and separating;
3) carrying out reduced pressure distillation on the separated heavy oil, and cutting to obtain a refined raw material at 350-520 ℃;
4) and carrying out heat treatment on the refined raw material to obtain the carbon material.
2. The method for refining inferior heavy oil to prepare carbon material according to claim 1, wherein the inferior heavy oil in step 1) is one or more of catalytic cracking slurry oil, coal tar, ethylene tar, atmospheric residue oil, and vacuum residue oil, and the content of polycyclic aromatic hydrocarbons in the inferior heavy oil is not less than 50 wt%.
3. The method for refining and preparing the carbon material from the inferior heavy oil according to claim 1, wherein the reaction temperature in the step 1) is 60-100 ℃.
4. The method for preparing the carbon material for refining the inferior heavy oil according to claim 1, wherein the hydrogen bond donor is at least one of formic acid and acetic acid, the hydrogen bond acceptor is one of tetrabutyl phosphine bromide and choline chloride, the molar ratio of the hydrogen bond donor to the hydrogen bond acceptor is 10-20: 1, and H is hydrogen in hydrogen peroxide 2 O 2 The molar ratio of the hydrogen bond donor to sulfur atoms in the inferior heavy oil is 2-6: 1, and the molar ratio of the hydrogen bond donor in the catalyst to sulfur atoms in the inferior heavy oil is 2-8: 1.
5. The method for refining and preparing the carbon material from the inferior heavy oil according to claim 1, wherein the standing temperature in the step 2) is 40-60 ℃.
6. The method for refining and preparing the carbon material from the inferior heavy oil according to claim 1, wherein in the step 3), after the heavy oil is separated, 1-5 times of water is added into the residual liquid containing the eutectic solvent, the mixture is fully mixed, the water phase is removed through reduced pressure distillation, and the eutectic solvent is recovered.
7. The method for preparing carbon material for refining inferior heavy oil according to claim 1, wherein the heat treatment in the step 4) is to obtain carbon material, and comprises heat treatment to obtain isotropic pitch, heat polycondensation to obtain mesophase pitch, heat treatment to obtain carbon microsphere, heat treatment to obtain needle coke, and heat polycondensation, spinning, non-melting, carbonization, and graphitization to obtain carbon fiber.
8. The method for preparing carbon material by refining inferior heavy oil according to claim 7, wherein the thermal polycondensation method is one or more of direct thermal polycondensation, pressurized thermal polycondensation, vacuum thermal polycondensation, hydrogenation thermal polycondensation, catalytic thermal polycondensation and co-carbonization.
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