CN116747847A - Method for preparing titanium dioxide composite intermediate phase carbon microsphere applied to high-performance liquid chromatographic column filler - Google Patents
Method for preparing titanium dioxide composite intermediate phase carbon microsphere applied to high-performance liquid chromatographic column filler Download PDFInfo
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- CN116747847A CN116747847A CN202211657490.3A CN202211657490A CN116747847A CN 116747847 A CN116747847 A CN 116747847A CN 202211657490 A CN202211657490 A CN 202211657490A CN 116747847 A CN116747847 A CN 116747847A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 63
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 62
- 239000004005 microsphere Substances 0.000 title claims abstract description 57
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 33
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 20
- 239000007788 liquid Substances 0.000 title claims abstract description 19
- 239000002131 composite material Substances 0.000 title claims abstract description 15
- 239000000945 filler Substances 0.000 title claims abstract description 6
- 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 31
- 239000002931 mesocarbon microbead Substances 0.000 claims abstract description 29
- 238000012856 packing Methods 0.000 claims abstract description 21
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000002612 dispersion medium Substances 0.000 claims abstract description 13
- 238000004945 emulsification Methods 0.000 claims abstract description 13
- 238000009835 boiling Methods 0.000 claims abstract description 9
- 238000001035 drying Methods 0.000 claims abstract description 9
- 229910010413 TiO 2 Inorganic materials 0.000 claims abstract description 7
- 239000000126 substance Substances 0.000 claims abstract description 7
- 238000010000 carbonizing Methods 0.000 claims abstract description 6
- 238000005406 washing Methods 0.000 claims abstract description 6
- 238000003980 solgel method Methods 0.000 claims abstract description 5
- 239000002245 particle Substances 0.000 claims description 28
- 239000011302 mesophase pitch Substances 0.000 claims description 26
- 238000006243 chemical reaction Methods 0.000 claims description 13
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006068 polycondensation reaction Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000011280 coal tar Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 claims description 4
- 239000005977 Ethylene Substances 0.000 claims description 4
- 239000012300 argon atmosphere Substances 0.000 claims description 4
- CCDWGDHTPAJHOA-UHFFFAOYSA-N benzylsilicon Chemical compound [Si]CC1=CC=CC=C1 CCDWGDHTPAJHOA-UHFFFAOYSA-N 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 229920001921 poly-methyl-phenyl-siloxane Polymers 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 239000011269 tar Substances 0.000 claims description 4
- 239000011800 void material Substances 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 230000004913 activation Effects 0.000 claims description 3
- 238000004128 high performance liquid chromatography Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 239000000047 product Substances 0.000 claims description 3
- AGPLQTQFIZBOLI-UHFFFAOYSA-N 1-benzyl-4-phenylbenzene Chemical group C=1C=C(C=2C=CC=CC=2)C=CC=1CC1=CC=CC=C1 AGPLQTQFIZBOLI-UHFFFAOYSA-N 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- -1 alkyl naphthalene Chemical compound 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 230000001804 emulsifying effect Effects 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- 238000010907 mechanical stirring Methods 0.000 claims description 2
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 claims description 2
- 239000012066 reaction slurry Substances 0.000 claims description 2
- 229920002545 silicone oil Polymers 0.000 claims description 2
- 239000006228 supernatant Substances 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 230000004580 weight loss Effects 0.000 claims description 2
- 239000011325 microbead Substances 0.000 claims 2
- 239000003921 oil Substances 0.000 abstract description 12
- 239000002994 raw material Substances 0.000 abstract description 9
- 239000000295 fuel oil Substances 0.000 abstract description 7
- 230000003213 activating effect Effects 0.000 abstract description 4
- 238000004458 analytical method Methods 0.000 abstract description 3
- 238000013375 chromatographic separation Methods 0.000 abstract description 3
- 239000010426 asphalt Substances 0.000 abstract 2
- 238000000605 extraction Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 239000003575 carbonaceous material Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 2
- 239000010779 crude oil Substances 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 238000004321 preservation Methods 0.000 description 2
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000004523 catalytic cracking Methods 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 239000007770 graphite material Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 230000008595 infiltration Effects 0.000 description 1
- 238000001764 infiltration Methods 0.000 description 1
- 238000000462 isostatic pressing Methods 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000013049 sediment Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/281—Sorbents specially adapted for preparative, analytical or investigative chromatography
- B01J20/282—Porous sorbents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D15/00—Separating processes involving the treatment of liquids with solid sorbents; Apparatus therefor
- B01D15/08—Selective adsorption, e.g. chromatography
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- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing a titanium dioxide composite intermediate phase carbon microsphere applied to a high-performance liquid chromatographic column filler, which takes heavy oil as a raw material, insoluble substances are separated by n-heptane extraction, intermediate phase asphalt is prepared by using deasphalted oil, the intermediate phase asphalt and nano-scale alumina are added into a high-boiling point dispersion medium to be emulsified into balls, and the intermediate phase carbon microsphere containing a large number of holes is obtained after washing, activating, drying and carbonizing, and titanium dioxide grows in the carbonized holes by a sol-gel method. The invention has the advantages that the invention takes cheap and easily obtained heavy oil as raw material, adopts the emulsification process to prepare the intermediate phase carbon microsphere, has the advantages of high yield, uniform grain diameter and adjustable and controllable grain diameter, and in addition, realizes the modification of the intermediate phase carbon microsphere to form MCMB/TiO 2 The method is applied to the high-performance liquid chromatographic column packing, so that the method has important significance in chromatographic separation analysis.
Description
Technical Field
The invention relates to a method for preparing titanium dioxide composite intermediate phase carbon microsphere applied to high performance liquid chromatographic column filler, which specifically uses heavy oil as raw material, adds alumina, prepares alumina doped intermediate phase carbon microsphere through emulsification process, obtains intermediate phase carbon microsphere containing a large number of holes after washing, activating, drying and carbonizing, and grows titanium dioxide in the holes to prepare MCMB/TiO 2 The mesocarbon microbeads with the structure are applied to high-performance liquid chromatographic column packing, so that the mesocarbon microbeads have important significance in chromatographic separation analysis.
Background
World crude oil has a tendency to be heavy, and thick oil production is increasing. The yields of the crude oil processed including vacuum residuum, atmospheric residuum, catalytic cracking slurry oil, coal tar, ethylene tar and the like are increased year by year, and the production of the high-added-value carbon material provides an effective utilization mode for heavy oil.
Mesophase pitch is a liquid crystal phase compound containing a considerable amount of mesophase, which is formed by a series of reactions such as bond breaking, deoxidization, polycondensation, stacking and the like of organic compounds such as petroleum heavy oil, coal tar, pure aromatic compounds and the like at high temperature. The mesophase pitch generally has higher purity and aromaticity, the unique orientation arrangement of aromatic macromolecules ensures that the mesophase pitch has optical anisotropy, and the mesophase pitch has low preparation cost, high oxidation activity and higher carbon purity, and is a high-quality matrix for preparing high-performance carbon materials.
The carbon microsphere is a novel carbon material, has the characteristics of good chemical stability, thermal stability, excellent electric conduction, heat conduction and the like, and has wide application prospect. Because the mesophase carbon microsphere has a structure of parallel stacking of lamellar molecules and also has the characteristic of sphere, the sphere diameter is small and the distribution is uniform, and the mesophase carbon microsphere becomes a base material of a plurality of novel carbon materials, such as: the isostatic pressing graphite material, the ultrahigh power electrode, the lithium ion battery cathode material, the high-density isotropic carbon, the high specific surface active carbon, the filling material of the high-performance liquid chromatographic column, the catalyst carrier and the like can be widely applied to the fields of mechanical industry, nuclear energy industry, chemical industry, semiconductor industry, new energy, environmental protection and the like.
The mesocarbon microbeads have good chemical stability, meet the requirements of liquid chromatographic column packing in the aspects of acid resistance, chemical corrosion resistance and high temperature resistance, and the lamellar material after graphitization has improved stability, can resist solvent infiltration without swelling, and is very suitable for being used as the high-performance liquid chromatographic column packing.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, improve the preparation process of the mesocarbon microbeads and realize the co-doping of alumina of the mesocarbon microbeads in the process of preparing the mesocarbon microbeads. The high-quality wide-area mesophase pitch is prepared by taking heavy oil as a raw material through an emulsification process, and a large amount of alumina-doped mesophase carbon microspheres are prepared by taking the heavy oil as the raw material, so that the production process is optimized, titanium dioxide grows in holes after the activation and carbonization of the microspheres, and MCMB/TiO is prepared 2 The mesocarbon microbeads with the structure are applied to high-performance liquid chromatographic column packing, so that the mesocarbon microbeads have important significance in chromatographic separation analysis.
The invention aims at realizing the following technical scheme:
the method for preparing the titanium dioxide composite intermediate phase carbon microsphere applied to the high-performance liquid chromatographic column filler takes one or more of medium-low temperature coal tar, high temperature coal tar and fractions thereof, vacuum residuum, ethylene tar and FCC slurry oil as raw oil, and is characterized by comprising the following steps:
(1) Extracting and separating insoluble substances from raw oil by n-heptane, and performing polycondensation on the raw oil for 6-9 hours at the reaction temperature of 400-430 ℃ and the reaction pressure of 0.5-1.5 MPa by using deasphalted oil under the protection of inert gas to obtain wide-area mesophase pitch;
(2) After cooling to 270-300 ℃, adding two kinds of alumina particles with different particle diameters into wide area mesophase pitch, preserving heat for 2 hours at 270-300 ℃, wherein the stirring speed is 500-600 r/min, the alumina particles are respectively 50-100 nm and 300-500 nm, and the proportion of the mesophase pitch to the alumina particles with 50-100 nm and 300-500 nm is 180-200 g: 6-10 g: 3-4 g, adding the mesophase pitch mixed with the two alumina particles with different particle diameters into a high-boiling-point dispersion medium, mixing the mesophase pitch and the high-boiling-point dispersion medium according to the proportion of 1:50-1:80 g/ml, pouring the mixture into a high-pressure reaction kettle equipped with mechanical stirring, heating the mixture to an emulsification temperature, and keeping the temperature for a period of time. A certain stirring rate is maintained in the whole emulsification process. After the emulsification was completed, the reaction slurry was rapidly cooled to room temperature. Washing and drying to obtain alumina doped mesophase carbon microspheres;
the mesophase content of the wide-area mesophase pitch prepared in the step (1) is 90-100%, and the softening point is 200-250 ℃; cooling wide-area mesophase pitch to 270-300 ℃ in a high-temperature reaction kettle, adding 50-100 nm and 300-500 nm alumina particles, fully mixing, proportioning mesophase pitch and a high-boiling point dispersion medium according to a ratio of 1:50-1:80 g/ml, emulsifying the mesophase pitch particles into balls under the conditions of a reaction temperature of 350-380 ℃ and a stirring speed of 500-600 r/min, centrifuging the suspension of the silicone oil and the balls formed after emulsification by using a high-speed centrifuge of 5000r/min, wherein supernatant of the mixture obtained by centrifugation is a high-boiling point dispersion medium, and lower-layer sediment is alumina-doped mesophase carbon microspheres.
The boiling point of the high-boiling point dispersion medium in the step (2) is more than 350 ℃, and the dispersion medium comprises one or more of alkyl naphthalene heat conduction oil, benzyl biphenyl heat conduction oil and phenyl methyl silicone oil; the yield of the obtained alumina doped mesophase carbon microsphere is about 90 percent, and the median diameter is 5-20 mu m; the structure of the alumina doped mesophase carbon microsphere is that a large amount of 300-500 nm alumina particles are filled in the mesophase carbon microsphere, a small amount of 50-100 nm alumina particles are filled among 300-500 nm alumina particles, and the surface of the mesophase carbon microsphere is mainly covered with 50-100 nm alumina particles.
Taking 20-30 g of alumina doped mesophase carbon microspheres obtained in the step (2), adding enough potassium hydroxide into the beaker, performing ultrasonic activation for 0.5-1 h, then cleaning and separating with deionized water, putting the mixture into an oven for drying at 50-60 ℃ for 2-2.5 h, and carbonizing the dried mesophase carbon microspheres in a tubular furnace under argon atmosphere at 700-850 ℃ for 2h. The carbonized intermediate phase carbon microsphere is structurally characterized in that aluminum oxide originally existing on the surface and the inside of the intermediate phase carbon microsphere is activated by potassium hydroxide and disappears, a large number of holes are formed on the surface and the inside of the intermediate phase carbon microsphere after carbonization, the intermediate phase carbon microsphere becomes a spherical carbon skeleton, the weight loss of the intermediate phase carbon microsphere is 40% -60%, and the volume void ratio is 50% -60%.
Titanium dioxide prepared by sol-gel method grows in the cavities of the mesocarbon microbeads to form MCMB/TiO 2 "Structure". TiO prepared by sol-gel method using butyl titanate as titanium source 2 . Uniformly mixing 6-7 g of carbonized intermediate phase carbon microsphere with 50-60% of volume void ratio, naOH and 100-150 mL of deionized water, uniformly mixing 30-50 mL of absolute ethyl alcohol and 10-20 mL of butyl titanate, ultrasonically dispersing 6-7 g of carbonized intermediate phase carbon microsphere and a NaOH solution at 60 ℃ for 10-15 min, slowly dropwise adding the absolute ethyl alcohol and the butyl titanate solution under ultrasonic, placing into a baking oven for drying at 50-70 ℃ for 3-4 h, placing the dried intermediate phase carbon microsphere into a tubular furnace for heating under argon atmosphere, and heating at 100-150 ℃ for 2-3 h to obtain MCMB/TiO 2 "mesocarbon microbeads of structure".
Under the same test conditions, the column pressure of the intrinsic chromatographic column is 307-385 bar, and the column pressure of the commercial column is 353-502 bar.
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention has the advantages of rich sources of raw materials, low cost of additives and high degree of freedom; reasonable design, precise production process, high raw material treatment depth, low equipment requirement and easy realization of industrialization.
(2) The process organically combines a direct thermal condensation method with an emulsification method, is favorable for realizing continuous operation in industrial application, and can be used as a high-quality raw material for preparing the mesophase carbon microsphere by the emulsification method, wherein the high-quality raw material with uniform molecular weight is prepared into mesophase pitch with excellent properties through polycondensation reaction.
(3) According to the invention, alumina is added, and the prepared pellets are activated, so that the stable spherical carbon skeleton is formed after the subsequent high-temperature carbonization of the mesocarbon microbeads, and titanium dioxide can be grown in the holes.
(4)“MCMB/TiO 2 The process design of the structural mesocarbon microbeads is reasonable, the production process is precise, and the requirements of high-performance liquid chromatographic column packing can be met.
Drawings
FIG. 1 shows the structure of a large number of holes formed in the surface and the inside of a mesocarbon microbead after carbonization.
FIG. 2 shows TiO growth in mesophase carbon microsphere pores 2 Is a structure of (a).
Detailed Description
The following examples are further illustrative of a method for preparing a titania composite mesocarbon microbead for use in high performance liquid chromatography column packing.
Example 1
Extracting ethylene tar fraction with N-heptane solvent to obtain N-heptane insoluble matter, evaporating solvent to dry, collecting 190g, adding into high pressure reactor at 420 deg.C, and N 2 Reacting for 7h under the protection of atmosphere to perform thermal polycondensation reaction; the mass of the alumina particles added to the polycondensation heavy product at 50 to 100nm and 300 to 500nm when the temperature is lowered to 300 ℃ is 7g:3g, mixing with phenyl methyl silicone oilThe ratio of the mixture is 1:60 (g/ml), the mesophase pitch is granulated into balls under the conditions of the reaction temperature of 360 ℃, the heat preservation of 2h and the stirring speed of 550r/min, and the mesophase carbon microsphere is obtained after washing, activating, drying and carbonizing, wherein the porosity of the obtained mesophase carbon microsphere is 54%, and the particle size is 15 mu m. The column packing pressure of the column packing is 307bar to 385bar, and the column packing pressure of the commodity column is 353bar to 502bar.
Example 2
Extracting FCC slurry fraction with N-heptane solvent to obtain N-heptane insoluble matter, evaporating solvent to dryness, collecting 190g, adding into high pressure reactor at 430 deg.C, N 2 Carrying out thermal polycondensation reaction for 8 hours under the protection of atmosphere; the mass of the alumina particles added to the polycondensation heavy product at 50 to 100nm and 300 to 500nm when the temperature is lowered to 300 ℃ is 7g:4g, fully mixing and proportioning with phenyl methyl silicone oil at 1:60 (g/ml), granulating mesophase pitch into balls under the conditions of a reaction temperature of 360 ℃, heat preservation of 2h and a stirring speed of 600r/min, washing, activating, drying and carbonizing to obtain mesophase carbon microspheres, wherein the porosity of the obtained mesophase carbon microspheres is 58%, and the particle size of the obtained mesophase carbon microspheres is 12 mu m. The column packing pressure of the column packing is 307bar to 385bar, and the column packing pressure of the commodity column is 353bar to 502bar.
Claims (9)
1. The method for preparing the titanium dioxide composite intermediate phase carbon microsphere applied to the high-performance liquid chromatographic column filler takes one or more of medium-low temperature coal tar, high temperature coal tar and fractions thereof, vacuum residuum, ethylene tar and FCC slurry oil as raw oil, and is characterized by comprising the following steps:
(1) Extracting and separating insoluble substances from raw oil by n-heptane, and performing polycondensation on the raw oil for 6-9 hours at the reaction temperature of 400-430 ℃ and the reaction pressure of 0.5-1.5 MPa by using deasphalted oil under the protection of inert gas to obtain wide-area mesophase pitch;
(2) After cooling to 270-300 ℃, adding two kinds of alumina particles with different particle diameters into wide area mesophase pitch, preserving heat for 2 hours at 270-300 ℃, wherein the stirring speed is 500-600 r/min, the alumina particles are respectively 50-100 nm and 300-500 nm, and the proportion of the mesophase pitch to the alumina particles with 50-100 nm and 300-500 nm is 180-200 g: 6-10 g: 3-4 g, adding the mesophase pitch mixed with two alumina particles with different particle diameters into a high-boiling-point dispersion medium, mixing the mesophase pitch and the high-boiling-point dispersion medium according to the proportion of 1:50-1:80 g/ml, pouring the mixture into a high-pressure reaction kettle equipped with mechanical stirring, heating the mixture to an emulsification temperature and keeping the temperature for a period of time; maintaining a certain stirring rate in the whole emulsification process; after the emulsification is completed, the reaction slurry is rapidly cooled to room temperature; washing and drying to obtain alumina doped mesophase carbon microspheres;
the mesophase content of the wide-area mesophase pitch prepared in the step (1) is 90-100%, and the softening point is 200-250 ℃; the boiling point of the high-boiling point dispersion medium in the step (2) is more than 350 ℃, and the dispersion medium comprises one or more of alkyl naphthalene heat conduction oil, benzyl biphenyl heat conduction oil and phenyl methyl silicone oil.
2. The method for preparing the titanium dioxide composite mesocarbon microbeads applied to the high-performance liquid chromatographic column packing according to claim 1, wherein the method comprises the following steps of: the yield of the alumina doped mesophase carbon microsphere obtained in the step (2) is about 90 percent, and the median diameter is 5-20 mu m.
3. The method for preparing the titanium dioxide composite mesocarbon microbeads applied to the high-performance liquid chromatographic column packing according to claim 1, wherein the method comprises the following steps of: and (2) obtaining wide-area mesophase pitch in the step (1), cooling to 270-300 ℃ in a high-temperature reaction kettle, adding aluminum oxide particles of 50-100 nm and 300-500 nm, fully mixing, proportioning the mesophase pitch and a high-boiling point dispersion medium according to the ratio of 1:50-1:80 g/ml, emulsifying the mesophase pitch particles into balls under the conditions of the reaction temperature of 350-380 ℃ and the stirring speed of 500-600 r/min, centrifuging the suspension of the silicone oil and the microspheres formed after emulsification by using a high-speed centrifuge of 5000r/min, wherein the supernatant of the mixture obtained by centrifugation is the high-boiling point dispersion medium, and the lower layer of the mixture is precipitated into the alumina-doped mesophase carbon microspheres.
4. The method for preparing the titanium dioxide composite mesocarbon microbeads applied to the high-performance liquid chromatographic column packing according to claim 1, wherein the method comprises the following steps of: the structure of the alumina-doped mesophase carbon microsphere obtained in the step (2) is that a large amount of 300-500 nm alumina particles are filled in the mesophase carbon microsphere, a small amount of 50-100 nm alumina particles are filled among 300-500 nm alumina particles, and the surface of the mesophase carbon microsphere is mainly covered with 50-100 nm alumina particles.
5. The method for preparing the titanium dioxide composite mesocarbon microbeads applied to the high-performance liquid chromatographic column packing according to claim 1, wherein the method comprises the following steps of: taking 20-30 g of alumina doped mesophase carbon microspheres obtained in the step (2), adding enough potassium hydroxide into the beaker, performing ultrasonic activation for 0.5-1 h, then cleaning and separating with deionized water, putting the mixture into an oven for drying at 50-60 ℃ for 2-2.5 h, and carbonizing the dried mesophase carbon microspheres in a tubular furnace under argon atmosphere at 700-850 ℃ for 2h; the carbonized intermediate phase carbon microsphere is structurally characterized in that aluminum oxide originally existing on the surface and the inside of the intermediate phase carbon microsphere is activated by potassium hydroxide and disappears, a large number of holes are formed on the surface and the inside of the intermediate phase carbon microsphere after carbonization, the intermediate phase carbon microsphere becomes a spherical carbon skeleton, the weight loss of the intermediate phase carbon microsphere is 40% -60%, and the volume void ratio is 50% -60%.
6. A method for preparing titanium dioxide composite mesophase carbon microspheres applied to high-performance liquid chromatographic column packing is characterized by comprising the following steps: titanium dioxide prepared by sol-gel method grows in the cavities of the mesocarbon microbeads to form MCMB/TiO 2 "Structure".
7. A method of preparing titanium dioxide composite mesophase carbon microbeads for use in high performance liquid chromatography column packing as in claim 6, wherein: tiO prepared by sol-gel method using butyl titanate as titanium source 2 The method comprises the steps of carrying out a first treatment on the surface of the Taking claim 1Uniformly mixing 6-7 g of carbonized intermediate-phase carbon microspheres with the volume void ratio of 50-60% with NaOH and 100-150 mL of deionized water, uniformly mixing 30-50 mL of absolute ethyl alcohol and 10-20 mL of butyl titanate, ultrasonically dispersing 6-7 g of carbonized intermediate-phase carbon microspheres with a NaOH solution at 60 ℃ for 10-15 min, slowly dropwise adding the absolute ethyl alcohol and the butyl titanate solution under ultrasonic conditions, placing the solution into a baking oven for baking at 50-70 ℃ for 3-4 h, placing the baked intermediate-phase carbon microspheres into a tubular furnace for heating under argon atmosphere, and heating at 100-150 ℃ for 2-3 h to obtain MCMB/TiO 2 "mesocarbon microbeads of structure".
8. A method of preparing titanium dioxide composite mesophase carbon microbeads for use in high performance liquid chromatography column packing as in claim 6, wherein: under the same test conditions, the column pressure of the intrinsic chromatographic column is 307-385 bar, and the column pressure of the commercial column is 353-502 bar.
9. The titanium dioxide composite mesocarbon microbead product applied to the high-performance liquid chromatographic column packing prepared by the method of any one of claims 1-8.
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