CN110624548B - Preparation method of multistage iron oxide catalyst for removing heteroatoms in coal liquefied oil - Google Patents
Preparation method of multistage iron oxide catalyst for removing heteroatoms in coal liquefied oil Download PDFInfo
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 title claims abstract description 83
- 239000003054 catalyst Substances 0.000 title claims abstract description 69
- 125000005842 heteroatom Chemical group 0.000 title claims abstract description 56
- 239000003245 coal Substances 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 239000004005 microsphere Substances 0.000 claims abstract description 79
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 70
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 69
- 238000000034 method Methods 0.000 claims abstract description 45
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000012265 solid product Substances 0.000 claims abstract description 26
- 239000011148 porous material Substances 0.000 claims abstract description 22
- 239000002270 dispersing agent Substances 0.000 claims abstract description 21
- 238000001035 drying Methods 0.000 claims abstract description 21
- 238000005406 washing Methods 0.000 claims abstract description 21
- 238000002156 mixing Methods 0.000 claims abstract description 15
- 239000007788 liquid Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 238000000926 separation method Methods 0.000 claims abstract description 12
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000002149 hierarchical pore Substances 0.000 claims abstract description 5
- 239000000047 product Substances 0.000 claims description 42
- 238000006243 chemical reaction Methods 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 27
- 239000008103 glucose Substances 0.000 claims description 27
- 239000002244 precipitate Substances 0.000 claims description 20
- 239000007789 gas Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 239000008367 deionised water Substances 0.000 claims description 18
- 229910021641 deionized water Inorganic materials 0.000 claims description 18
- 238000001914 filtration Methods 0.000 claims description 16
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 16
- 239000002245 particle Substances 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 13
- 239000006185 dispersion Substances 0.000 claims description 12
- 239000006228 supernatant Substances 0.000 claims description 11
- 230000035484 reaction time Effects 0.000 claims description 10
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 239000000919 ceramic Substances 0.000 claims description 8
- 238000010907 mechanical stirring Methods 0.000 claims description 8
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 8
- 229920002401 polyacrylamide Polymers 0.000 claims description 8
- 229940006186 sodium polystyrene sulfonate Drugs 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 229930091371 Fructose Natural products 0.000 claims description 5
- 239000005715 Fructose Substances 0.000 claims description 5
- RFSUNEUAIZKAJO-ARQDHWQXSA-N Fructose Chemical compound OC[C@H]1O[C@](O)(CO)[C@@H](O)[C@@H]1O RFSUNEUAIZKAJO-ARQDHWQXSA-N 0.000 claims description 5
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 claims description 5
- 229930006000 Sucrose Natural products 0.000 claims description 5
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 5
- 239000012716 precipitator Substances 0.000 claims description 5
- 239000005720 sucrose Substances 0.000 claims description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- MVFCKEFYUDZOCX-UHFFFAOYSA-N iron(2+);dinitrate Chemical compound [Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MVFCKEFYUDZOCX-UHFFFAOYSA-N 0.000 claims description 4
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 22
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 abstract description 16
- 239000002028 Biomass Substances 0.000 abstract description 14
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 14
- 239000011593 sulfur Substances 0.000 abstract description 13
- 229910052717 sulfur Inorganic materials 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 11
- 229910052742 iron Inorganic materials 0.000 abstract description 8
- 239000012298 atmosphere Substances 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 239000000376 reactant Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 30
- 230000000694 effects Effects 0.000 description 17
- 239000002994 raw material Substances 0.000 description 15
- 229910021385 hard carbon Inorganic materials 0.000 description 14
- 239000000852 hydrogen donor Substances 0.000 description 14
- 239000002904 solvent Substances 0.000 description 14
- 239000003570 air Substances 0.000 description 9
- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000007787 solid Substances 0.000 description 8
- 239000000203 mixture Substances 0.000 description 7
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 6
- FCEHBMOGCRZNNI-UHFFFAOYSA-N 1-benzothiophene Chemical class C1=CC=C2SC=CC2=C1 FCEHBMOGCRZNNI-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 231100000053 low toxicity Toxicity 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229910000480 nickel oxide Inorganic materials 0.000 description 2
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 2
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- -1 azaanthracene Chemical compound 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- HCAUQPZEWLULFJ-UHFFFAOYSA-N benzo[f]quinoline Chemical compound C1=CC=C2C3=CC=CC=C3C=CC2=N1 HCAUQPZEWLULFJ-UHFFFAOYSA-N 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- QXLPXWSKPNOQLE-UHFFFAOYSA-N methylpentynol Chemical compound CCC(C)(O)C#C QXLPXWSKPNOQLE-UHFFFAOYSA-N 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009967 tasteless effect Effects 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
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-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
-
- 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
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the field of coal hydrogenation liquefaction, and particularly relates to a preparation method of a multi-level pore spherical iron oxide catalyst for removing heteroatoms in coal liquefaction oil. The method of the invention comprises the following steps: (1) preparing carbon microspheres: synthesizing biomass and a dispersing agent in a hydrothermal kettle to obtain carbon microspheres, and roasting under the air atmosphere condition to obtain hard hierarchical porous carbon microspheres; (2) mixing the hard hierarchical porous carbon microspheres roasted in the step (1) with ferric nitrate solution, and stirring; (3) carrying out solid-liquid separation on the solution in the step (2), washing a solid product, and drying; (4) and (4) roasting the solid product obtained in the step (3) to obtain the multi-stage pore spherical iron oxide catalyst. By adopting the process, the reactant obtained in the intermediate step is environment-friendly and pollution-free, the cost is low, the finally prepared hierarchical pore spherical iron oxide catalyst maintains a unique spherical structure while realizing simple operation, and the removal efficiency of the iron-based catalyst for removing sulfur, nitrogen and oxygen heteroatoms in coal liquefied oil is improved.
Description
Technical Field
The invention belongs to the field of coal hydrogenation liquefaction, and particularly relates to a preparation method for preparing a multi-stage pore spherical iron oxide catalyst which is efficiently used for removing heteroatoms in coal liquefaction oil and takes hard carbon microspheres as a template.
Background
The composition of the coal-made liquid fuel product is complex, and the composition is closely related to the coal type, the production area and the preparation process condition. In addition to containing a large amount of polycyclic aromatic hydrocarbons, coal liquefaction oil also contains heteroatom compounds such as sulfur, nitrogen and oxygen. Wherein, the typical nitrogen content is generally 0.9-1.1% (wt%), which is much higher than the nitrogen content in petroleum, and mainly exists in the forms of quinoline, azaanthracene, azaphenanthrene and the like; the sulphur content generally ranges from 0.3% to 0.7% (wt%), being lower in comparison with petroleum, and being mainly present in the form of benzothiophene derivatives; the oxygen content is greatly influenced by the coal type and liquefaction process, and is usually 4% to 5% (wt%), mainly in the form of phenol and its derivatives. The existence of heteroatoms in the coal liquefaction oil can cause the poisoning of a hydrogenation catalyst, block and corrode reaction equipment, is not beneficial to further quality improvement of oil products, and can generate a large amount of gases containing SOx, NOx and other polycyclic aromatic hydrocarbons with carcinogenicity in the combustion process of the coal liquefaction oil, thereby damaging the ecological environment.
Therefore, the exploration and preparation of the catalyst with low toxicity, high activity and low price have important significance for improving the quality-improving processing technology of coal-to-oil products, cleaning and utilizing coal and protecting the environment. A method for preparing a hierarchical porous spherical iron oxide catalyst by taking carbon microspheres as a template belongs to one of methods for preparing functional catalysts by a hard template method. Due to the unique structural characteristics, the cage-shaped spherical functional material has unique physical, chemical and electrical properties and is widely applied to the fields of photoelectric materials, catalytic materials and the like.
For example, CN 108529692 a discloses a method for preparing hollow nickel oxide using carbon microspheres as templates, which comprises controlling the thickness of the adsorption layer of nickel ions on the surfaces of the carbon microspheres by changing the amount of ammonia water added, and removing the carbon microsphere templates by baking, thereby preparing hollow spherical nickel oxide. CN 107999081A provides a preparation method of a carbon-coated structure nano iron-based Fischer-Tropsch synthesis catalyst, which is characterized in that a carbon source, raw materials and a carbon microsphere carrier are added according to a certain mass percentage, and a co-impregnation-in-situ carbonization method is adopted to prepare the carbon-coated structure nano iron-based catalyst, so that the use of water is greatly reduced in the process, and the cost of wastewater treatment is saved.
CN 106972162 a discloses a method for preparing a battery cathode material applied in the field of sodium ion batteries, which mainly dopes phosphorus and sulfur in hard carbon microspheres, thereby improving the specific capacity and rate capability thereof. CN 108273536A discloses a preparation method of an iron-based catalyst for preparing low-carbon olefin by high-temperature Fischer-Tropsch synthesis, which is mainly used for doping nitrogen into a three-dimensional porous nano iron catalyst.
In the existing research literature, the catalyst prepared by the hard carbon spheres is mostly applied to the field of Fischer-Tropsch synthesis process or batteries, and the research applied to the field of coal liquefaction oil is less. The coal-to-liquid fuel route can effectively improve the utilization rate of coal, increase the economic added value of the coal and reduce the problem of environmental pollution caused by direct combustion of the coal.
Disclosure of Invention
Therefore, the invention aims to provide a preparation method of a multi-stage pore spherical iron oxide catalyst for efficiently removing sulfur, nitrogen and oxygen heteroatoms in coal liquefied oil. The method is a cage-shaped spherical catalyst prepared by taking hard carbon microspheres treated by relatively closed air as a template and ferric nitrate as a precursor. The method is simple to operate, environment-friendly and efficient; the catalyst has low toxicity, high activity and low cost.
The preparation method of the multistage ferric oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) preparing carbon microspheres: synthesizing a biomass solution and a dispersing agent in a hydrothermal kettle to obtain carbon microspheres;
the biomass solution is obtained by dispersing biomass into water to obtain a biomass solution; the biomass is at least one of glucose, sucrose and fructose;
the dispersing agent is at least one of sodium dodecyl sulfate, methyl amyl alcohol, sodium polystyrene sulfonate and polyacrylamide;
(2) roasting the carbon microspheres obtained in the step (1) in a gas environment at the temperature of 600-1000 ℃ to obtain hard hierarchical porous carbon microspheres; the gas environment is at least one of nitrogen, argon and air;
(3) mixing the hard hierarchical porous carbon microspheres obtained by roasting in the step (2) with ferric nitrate solution, and stirring;
(4) carrying out solid-liquid separation on the solution obtained in the step (3), washing a solid product and drying; or centrifuging the solution obtained in the step (3), removing supernatant, washing precipitate, and drying;
(5) and (4) roasting the solid product obtained by drying in the step (4) to obtain the multi-stage pore spherical iron oxide catalyst.
Preferably, in (1), the biomass solution is obtained by dispersing the biomass in water by a mechanical stirring, ultrasonic or microwave method to obtain the biomass solution.
The preparation method of the multistage ferric oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) preparing carbon microspheres: dispersing at least one of glucose, sucrose and fructose into water by using a mechanical stirring, ultrasonic or microwave method to obtain a dispersion solution as biomass;
then synthesizing the biomass and a dispersing agent in a hydrothermal kettle to obtain carbon microspheres, wherein the reaction temperature is 150-210 ℃, and the reaction time is 1-48 hours to obtain the carbon microspheres;
the dispersing agent is at least one of sodium dodecyl sulfate, methyl amyl alcohol, sodium polystyrene sulfonate and polyacrylamide, and the mass ratio of the using amount of the dispersing agent to the biomass solution is as follows: 1: 1000-1: 100;
(2) roasting the carbon microspheres obtained in the step (1) in a gas environment at the temperature of 600-1000 ℃ to obtain hard hierarchical porous carbon microspheres; the gas environment is at least one of nitrogen, argon and air;
(3) mixing the carbon microspheres roasted in the step (2) with an iron nitrate solution, stirring, and reacting for 0.1-48 hours at a constant temperature of 20-100 ℃;
the concentration of the ferric nitrate solution is more than 0.1mol/L, and at least one of ammonia water, ammonium nitrate and ammonium carbonate is added as a nitrogen-containing precipitator during mixing;
(4) filtering the solution in the step (3) by using a porous ceramic filter with the pore diameter of 50 nm-5 mu m, washing for 3-4 times by using deionized water and absolute ethyl alcohol in sequence in the filtering process, and drying the obtained solid product in an oven at 70-90 ℃;
(5) and (4) roasting the solid product obtained in the step (4) at 500-800 ℃ to obtain the hierarchical porous spherical iron oxide catalyst.
Controlling the pH value of the biomass solution in the step (1) to be 6.8-7.2, the reaction temperature to be 160 ℃, the reaction time to be 3.5-4.5 hours, and selecting carbon microspheres with the particle size of 80-120 nm.
Preferably, the preparation method of the multistage iron oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) preparing carbon microspheres: dispersing at least one of glucose, sucrose and fructose into water by using mechanical stirring, ultrasound and microwave methods to obtain a dispersion solution;
then, synthesizing the dispersion solution and a dispersing agent in a hydrothermal synthesis kettle, wherein the reaction temperature is 150-210 ℃, the reaction time is 1-48 hours, and the pH value of the reaction solution is 6.8-7.2 to obtain carbon microspheres;
the dispersing agent is at least one of sodium dodecyl sulfate, methyl amyl alcohol, sodium polystyrene sulfonate and polyacrylamide, and the mass ratio of the using amount of the dispersing agent to the glucose is as follows: 1: 1000-1: 100;
the pH value of the reaction solution is 6.8-7.2, the reaction temperature is 150-170 ℃, the reaction time is 3-5 hours, and carbon microspheres with the particle size of 80-120 nm are selected;
(2) roasting the carbon microspheres obtained in the step (1) in a gas environment at the temperature of 600-1000 ℃ to obtain hard hierarchical porous carbon microspheres; the gas environment is a mixed gas of at least two of nitrogen, argon and air;
(3) mixing the carbon microspheres roasted in the step (2) with an iron nitrate solution, stirring, keeping the constant temperature at 20-100 ℃, and reacting for 0.1-48 hours; stirring for 10-14 hours at the temperature of 60-80 ℃;
the concentration of the ferric nitrate solution is more than 0.1mol/L, and at least one of ammonia water, ammonium nitrate and ammonium carbonate is added as a nitrogen-containing precipitator during mixing;
(4) filtering the solution in the step (3) by using a porous ceramic filter with the pore diameter of 50 nm-5 mu m, washing for 3-4 times by using deionized water and absolute ethyl alcohol in sequence in the filtering process, and drying the obtained solid product in an oven at 70-90 ℃;
or putting the solution in the step (3) into a centrifuge tube, performing solid-liquid separation by using a centrifuge with the rotation speed of 3500-4500 r/min, removing supernatant, washing the obtained precipitate for 3-4 times by using deionized water and absolute ethyl alcohol in sequence, and drying the obtained solid product in an oven at 70-90 ℃;
(4) and (3) placing the washed precipitate in a muffle furnace, and roasting at the temperature of 500-600 ℃, wherein the roasted product is the hierarchical porous spherical iron oxide catalyst.
(3) Filtering the solution in the step (2) by using a porous ceramic filter with the aperture of 500nm, washing for 3-4 times by using deionized water and absolute ethyl alcohol in sequence in the filtering process, and drying the obtained solid product in an oven at 80 ℃;
or putting the solution in the step (2) into a centrifuge tube, performing solid-liquid separation by using a centrifuge with the rotation speed of 4000r/min, removing supernatant, washing the obtained precipitate for 3-4 times by using deionized water and absolute ethyl alcohol in sequence, and drying the obtained solid product in an oven at 80 ℃.
(4) The roasting temperature of the medium solid product is controlled at 550 ℃, and the multi-level pore spherical ferric oxide catalyst maintaining the spherical structure is obtained after roasting.
The diameter of the iron-based catalyst is distributed in the size range of 100-300 nm, and the shape of the iron-based catalyst is spherical.
The preparation method of the multistage ferric oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) preparing carbon microspheres: dispersing 1.5mol/L glucose into water by using a mechanical stirring, ultrasonic and microwave method to obtain a dispersion solution;
then, the dispersion solution and a dispersant are synthesized in a hydrothermal kettle, the reaction temperature is 160 ℃, and the reaction time is 4 hours; obtaining hard hierarchical porous carbon microspheres;
the dispersing agent is at least one of sodium dodecyl sulfate, methyl amyl alcohol, sodium polystyrene sulfonate and polyacrylamide, and the mass ratio of the using amount of the dispersing agent to the glucose is as follows: 1: 500, a step of;
(2) roasting the carbon microspheres obtained in the step (1) in a gas environment at 800 ℃ to obtain hard hierarchical porous carbon microspheres; the gas environment is at least two of nitrogen, argon and air;
(3) mixing the carbon microspheres roasted in the step (2) with ferric nitrate solution, stirring, keeping the constant temperature at 60 ℃, and reacting for 24 hours;
the concentration of the ferric nitrate solution is more than 0.1mol/L, and ammonia water, ammonium nitrate and ammonium carbonate are added as nitrogen-containing precipitating agents during mixing;
(4) filtering the solution in the step (3) by using a porous ceramic filter with the pore diameter of 500nm, washing for 3-4 times by using deionized water and absolute ethyl alcohol in sequence in the filtering process, and drying the obtained solid product in an oven at 80 ℃;
or putting the solution in the step (3) into a centrifuge tube, performing solid-liquid separation by using a centrifuge with the rotation speed of 4000r/min, removing supernatant, washing the obtained precipitate for 3-4 times by using deionized water and absolute ethyl alcohol in sequence, and drying the obtained solid product in an oven at 80 ℃;
(5) and (4) roasting the solid product obtained in the step (4) at 550 ℃ to obtain the multi-level pore spherical iron oxide catalyst.
The application of the catalyst obtained by the preparation method of the multistage iron oxide catalyst in removing the heteroatoms in the coal liquefied oil is also within the protection scope of the invention.
According to the preparation method of the high-dispersion spherical hierarchical pore spherical iron oxide catalyst, the appearance of the obtained product is brownish red or red powdery solid and is tasteless. Through microscopic detection, the catalyst maintains the spherical structure of the template, and has uniform particle size distribution, about 100nm size, stable yield and good repeating effect.
The process method provided by the invention is reasonable, fully utilizes environment-friendly, low-cost, environment-friendly and pollution-free reactants, and effectively controls the particle size of the carbon microsphere to be about 100nm by adding a certain amount of additives under the appropriate hydrothermal reaction condition; the carbon microspheres are roasted at high temperature under relatively closed conditions, so that the specific surface area of the carbon microspheres is effectively increased; the hierarchical pore spherical iron oxide catalyst is prepared by adopting a template method, so that the unique spherical structure is maintained while the simple operation is realized, and the removal efficiency of the iron-based catalyst for removing sulfur, nitrogen and oxygen heteroatoms in coal liquefied oil is improved.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) photograph of a carbon microsphere prepared according to the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of a multi-stage pore spherical iron oxide catalyst prepared according to the present invention;
FIG. 3 is a GC-MS plot of starting materials, blanks, and example 5 for sulfur-containing model compounds (thiophene, benzothiophene, and thiophenol);
FIG. 4 is a process flow diagram of example 1 of the present invention.
Detailed Description
For the purpose of facilitating an understanding of the present invention, the present invention will now be described by way of examples. It should be understood by those skilled in the art that the examples are only for the purpose of facilitating understanding of the present invention and should not be construed as specifically limiting the present invention.
The following examples are given to illustrate the present invention, but the scope of the present invention is not limited to the following examples.
Example 1
The preparation method of the multi-level pore spherical iron oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) adding 50mL of 0.7mol/L glucose solution (biomass solution) and 5mg of sodium dodecyl sulfate into a 100mL hydrothermal kettle, reacting for 12 hours at 180 ℃ to obtain carbon microspheres, and then roasting the carbon microspheres in a relatively closed air atmosphere at 800 ℃ for 2 hours to obtain the hard hierarchical porous carbon microspheres;
the glucose solution was obtained as follows: dispersing glucose into water by adopting a mechanical stirring method to obtain a glucose solution;
(2) mixing 10g of hard carbon microspheres with the particle size of 100nm with 200mL of 0.5mol/L ferric nitrate solution, and stirring for 12 hours at the temperature of 70 ℃;
(3) filtering the obtained mixture with a porous ceramic filter with the pore diameter of 500nm, sequentially washing with deionized water and absolute ethyl alcohol for 3 times in the filtering process, and drying the obtained solid product in an oven at 80 ℃;
(4) and (3) placing the dried solid product in a muffle furnace, and roasting at 550 ℃, wherein the roasted product is the hierarchical porous spherical iron oxide catalyst.
The obtained product is red powdery solid, and is observed to be spheres with similar size and 100nm particle size under a scanning electron microscope. The product is used as a catalyst, a sulfur-containing model compound, a nitrogen-containing model compound, an oxygen-containing model compound and a liquefied oil product are respectively used as reaction raw materials, tetrahydronaphthalene is used as a hydrogen donor solvent (the mass ratio of the reaction raw materials to the hydrogen donor solvent is 1:1), and the determination for the effect of removing the heteroatom is carried out in a high-pressure reaction kettle. The sample shows good effect of removing the heteroatom, the removal rate of the heteroatom in the model compound is more than 94.2 percent, and the removal rate of the heteroatom in the liquefied oil product is 90.3 percent.
Example 2
The preparation method of the multi-level pore spherical iron oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) adding 50mL of 0.9mol/L glucose solution and 5mg of methyl amyl alcohol into a 100mL hydrothermal kettle, reacting for 6 hours at 190 ℃ to obtain carbon microspheres, and then roasting the carbon microspheres for 2 hours at 700 ℃ in an argon atmosphere to obtain the hard hierarchical porous carbon microspheres;
the glucose solution was obtained as follows: dispersing glucose into water by adopting an ultrasonic method to obtain a glucose solution;
(2) dispersing 10g of hard carbon microspheres in 200mL of 0.7mol/L ferric nitrate solution, and stirring at 90 ℃ for 12 hours;
(3) performing solid-liquid separation on the mixture at a centrifugal rate of 3500r/min, removing supernatant, washing the precipitate for 3 times by using deionized water and absolute ethyl alcohol in sequence, and drying the precipitate in an oven;
(4) and placing the dried precipitate in a muffle furnace, and roasting at 650 ℃, wherein the roasted product is the hierarchical porous spherical iron oxide catalyst.
The obtained product is red powdery solid, and is observed to be spheres with similar size and the particle size of 100nm-150nm under a scanning electron microscope. The product is used as a catalyst, a sulfur-containing model compound, a nitrogen-containing model compound, an oxygen-containing model compound and a liquefied oil product are respectively used as reaction raw materials, tetrahydronaphthalene is used as a hydrogen donor solvent (the mass ratio of the reaction raw materials to the hydrogen donor solvent is 1:1), and the determination for the effect of removing the heteroatom is carried out in a high-pressure reaction kettle. The sample shows good effect of removing the heteroatom, the removal rate of the heteroatom in the model compound is more than 97.5 percent, and the removal rate of the heteroatom in the liquefied oil product is 92.3 percent.
Example 3
The preparation method of the multi-level pore spherical iron oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) adding 40mL of 1.2mol/L glucose solution and 10mg of sodium polystyrene sulfonate into a 100mL hydrothermal kettle, reacting for 8 hours at 180 ℃ to obtain carbon microspheres, and then roasting the carbon microspheres for 2 hours at 900 ℃ in a relatively closed air atmosphere to obtain hard carbon microspheres;
the glucose solution was obtained as follows: dispersing glucose into water by adopting a microwave method to obtain a glucose solution;
(2) dispersing 10g of hard carbon microspheres in 200mL of 0.9mol/L ferric nitrate solution, stirring for 24 hours at the temperature of 60 ℃, and adding 10mL of ammonia water with the mass concentration of 50% as a precipitator;
(3) performing solid-liquid separation on the mixture at a centrifugal rate of 4000r/min, removing supernatant, washing the precipitate for 4 times by using deionized water and absolute ethyl alcohol in sequence, and drying the precipitate in an oven;
(4) and (3) placing the dried precipitate in a muffle furnace, and roasting at 550 ℃, wherein the roasted product is the hierarchical porous spherical iron oxide catalyst.
The obtained product is red powdery solid, and is observed to be spheres with similar size and 120nm particle size under a scanning electron microscope. The product is used as a catalyst, a sulfur-containing model compound, a nitrogen-containing model compound, an oxygen-containing model compound and a liquefied oil product are respectively used as reaction raw materials, tetrahydronaphthalene is used as a hydrogen donor solvent (the mass ratio of the reaction raw materials to the hydrogen donor solvent is 1:1), and the determination for the effect of removing the heteroatom is carried out in a high-pressure reaction kettle. The sample shows good effect of removing the heteroatom, the removal rate of the heteroatom in the model compound is over 95.7 percent, and the removal rate of the heteroatom in the liquefied oil product is 92.6 percent.
Example 4
The preparation method of the multi-level pore spherical iron oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) adding 35mL of 1.5mol/L glucose solution and 20mg of polyacrylamide into a 100mL hydrothermal kettle, reacting for 12 hours at 200 ℃ to obtain carbon microspheres, and then roasting the carbon microspheres for 2 hours at 700 ℃ in a relatively closed nitrogen atmosphere to obtain hard carbon microspheres;
(2) dispersing 10g of hard carbon microspheres in 200mL of 0.8mol/L ferric nitrate solution, and stirring at 90 ℃ for 18 hours;
(3) performing solid-liquid separation on the mixture at the centrifugal rate of 4500r/min, removing supernatant, washing the precipitate for 4 times by using deionized water and absolute ethyl alcohol in sequence, and drying the precipitate in an oven;
(4) and (3) placing the dried precipitate in a muffle furnace, and roasting at the temperature of 600 ℃, wherein the roasted product is the hierarchical porous spherical iron oxide catalyst.
The obtained product is red powdery solid, and is observed to be spheres with similar size and the particle size of 150nm-200nm under a scanning electron microscope. The product is used as a catalyst, a sulfur-containing model compound, a nitrogen-containing model compound, an oxygen-containing model compound and a liquefied oil product are respectively used as reaction raw materials, tetrahydronaphthalene is used as a hydrogen donor solvent (the mass ratio of the reaction raw materials to the hydrogen donor solvent is 1:1), and the determination for the effect of removing the heteroatom is carried out in a high-pressure reaction kettle. The sample shows good effect of removing the heteroatom, the removal rate of the heteroatom in the model compound is more than 93.5 percent, and the removal rate of the heteroatom in the liquefied oil product is 90.1 percent.
Example 5
The preparation method of the multi-level pore spherical iron oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) adding 50mL of 1.3mol/L glucose solution and 15mg of methylpentanol into a 100mL hydrothermal kettle, reacting for 6 hours at 180 ℃ to obtain carbon microspheres, and then roasting the carbon microspheres for 2 hours at 1000 ℃ in a relatively closed air atmosphere to obtain hard carbon microspheres;
(2) dispersing 10g of hard carbon microspheres in 200mL of 1.5mol/L ferric nitrate solution, and stirring for 30 hours at the temperature of 60 ℃;
(3) performing solid-liquid separation on the mixture at a centrifugal rate of 4500r/min, removing supernatant, washing the precipitate for 3-4 times by using deionized water and absolute ethyl alcohol in sequence, and drying the precipitate in an oven;
(4) and (3) placing the dried precipitate in a muffle furnace, and roasting at 550 ℃, wherein the roasted product is the hierarchical porous spherical iron oxide catalyst.
The obtained product is red powdery solid, and is observed to be spheres with similar size and 100nm particle size under a scanning electron microscope. The product is used as a catalyst, a sulfur-containing model compound, a nitrogen-containing model compound, an oxygen-containing model compound and a liquefied oil product are respectively used as reaction raw materials, tetrahydronaphthalene is used as a hydrogen donor solvent (the mass ratio of the reaction raw materials to the hydrogen donor solvent is 1:1), and the determination for the effect of removing the heteroatom is carried out in a high-pressure reaction kettle. The sample shows good effect of removing the heteroatom, the removal rate of the heteroatom in the model compound is more than 98.0 percent, and the removal rate of the heteroatom in the liquefied oil product is 96.4 percent.
Comparative example 1
Same as example 1 except that in step a) no sodium lauryl sulfate was added.
The obtained product is red powdery solid, and is observed to be spheres with similar size and 300nm particle size under a scanning electron microscope. The product is used as a catalyst, a sulfur-containing model compound, a nitrogen-containing model compound, an oxygen-containing model compound and a liquefied oil product are respectively used as reaction raw materials, tetrahydronaphthalene is used as a hydrogen donor solvent (the mass ratio of the reaction raw materials to the hydrogen donor solvent is 1:1), and the determination for the effect of removing the heteroatom is carried out in a high-pressure reaction kettle. The sample shows good effect of removing the heteroatom, the removal rate of the heteroatom in the model compound is more than 68%, and the removal rate of the heteroatom in the liquefied oil is 70.4%.
Comparative example 2
Same as example 2, except that the carbon microspheres in step a) were not subjected to a high temperature calcination treatment.
The obtained product is red powdery solid, and is observed to be spheres with similar size and 200nm particle size under a scanning electron microscope. The product is used as a catalyst, a sulfur-containing model compound, a nitrogen-containing model compound, an oxygen-containing model compound and a liquefied oil product are respectively used as reaction raw materials, tetrahydronaphthalene is used as a hydrogen donor solvent (the mass ratio of the reaction raw materials to the hydrogen donor solvent is 1:1), and the determination for the effect of removing the heteroatom is carried out in a high-pressure reaction kettle. The sample shows good effect of removing the heteroatom, the removal rate of the heteroatom in the model compound is over 60.5 percent, and the removal rate of the heteroatom in the liquefied oil is 64.6 percent.
Comparative example 3
The difference from the example 1 is that, in the step (1), 50mL of 0.7mol/L glucose solution and 5mg of additive are added into a 100mL hydrothermal kettle, the reaction is carried out for 12 hours at 120 ℃, the product after the reaction is washed and dried, and the hard carbon microspheres are obtained after the product is roasted for 2 hours at 800 ℃ in a relatively closed air atmosphere; the rest is the same as in example 1.
Comparative example 4
The difference from example 1 is that, in (2), 2g of hard carbon microspheres with the particle size of 100nm are dispersed in 200mL of 0.5mol/L ferric nitrate solution and stirred for 12 hours at the temperature of 70 ℃; the rest is the same as in example 1.
TABLE 1 removal of heteroatom by product of examples and comparative examples (%)
As can be seen from the data in the above tables, in the present invention, in examples 1 to 5, the removal rate of the heteroatoms in the model compound or the removal rate of the heteroatoms in the liquefied oil product both reached more than 90%; while the removal rates of both of comparative examples 1 to 4 were significantly reduced. This indicates that, by changing the conditions of the present invention, the product used for the removal of the heteroatoms will also vary.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (8)
1. The preparation method of the multistage ferric oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) preparing carbon microspheres: dispersing at least one of glucose, sucrose and fructose into water by using mechanical stirring, ultrasound and microwave methods to obtain a dispersion solution;
then, synthesizing the dispersion solution and a dispersing agent in a hydrothermal synthesis kettle, wherein the reaction temperature is 150-210 ℃, the reaction time is 1-48 hours, and the pH value of the reaction solution is 6.8-7.2 to obtain carbon microspheres;
the dispersing agent is at least one of sodium dodecyl sulfate, methyl amyl alcohol, sodium polystyrene sulfonate and polyacrylamide, and the mass ratio of the using amount of the dispersing agent to the glucose is as follows: 1: 1000-1: 100;
the pH value of the reaction solution is 6.8-7.2, the reaction temperature is 150-170 ℃, the reaction time is 3-5 hours, and carbon microspheres with the particle size of 80-120 nm are selected;
(2) roasting the carbon microspheres obtained in the step (1) in a gas environment at the temperature of 600-1000 ℃ to obtain hard hierarchical porous carbon microspheres; the gas environment is a mixed gas of argon and air;
(3) mixing the carbon microspheres roasted in the step (2) with an iron nitrate solution, stirring, keeping the constant temperature at 20-100 ℃, and reacting for 0.1-48 hours;
the concentration of the ferric nitrate solution is more than 0.1mol/L, and at least one of ammonia water, ammonium nitrate and ammonium carbonate is added as a nitrogen-containing precipitator during mixing;
(4) filtering the solution in the step (3) by using a porous ceramic filter with the pore diameter of 50 nm-5 mu m, washing for 3-4 times by using deionized water and absolute ethyl alcohol in sequence in the filtering process, and drying the obtained solid product in an oven at 70-90 ℃;
(5) and (3) placing the washed and dried solid product in a muffle furnace, and roasting at the temperature of 500-600 ℃, wherein the roasted product is a hierarchical porous spherical iron oxide catalyst.
2. The method for preparing the multistage iron oxide catalyst for removing the heteroatoms in the coal liquefied oil according to claim 1, wherein the method comprises the following steps:
(4) and (3) filtering the solution in the step (3) by using a porous ceramic filter with the pore diameter of 500nm, washing for 3-4 times by using deionized water and absolute ethyl alcohol in sequence in the filtering process, and drying the obtained solid product in an oven at 80 ℃.
3. The preparation method of the multistage ferric oxide catalyst for removing the heteroatoms in the coal liquefied oil comprises the following steps:
(1) preparing carbon microspheres: dispersing at least one of glucose, sucrose and fructose into water by using mechanical stirring, ultrasound and microwave methods to obtain a dispersion solution;
then, synthesizing the dispersion solution and a dispersing agent in a hydrothermal synthesis kettle, wherein the reaction temperature is 150-210 ℃, the reaction time is 1-48 hours, and the pH value of the reaction solution is 6.8-7.2 to obtain carbon microspheres;
the dispersing agent is at least one of sodium dodecyl sulfate, methyl amyl alcohol, sodium polystyrene sulfonate and polyacrylamide, and the mass ratio of the using amount of the dispersing agent to the glucose is as follows: 1: 1000-1: 100;
the pH value of the reaction solution is 6.8-7.2, the reaction temperature is 150-170 ℃, the reaction time is 3-5 hours, and carbon microspheres with the particle size of 80-120 nm are selected;
(2) roasting the carbon microspheres obtained in the step (1) in a gas environment at the temperature of 600-1000 ℃ to obtain hard hierarchical porous carbon microspheres; the gas environment is a mixed gas of argon and air;
(3) mixing the carbon microspheres roasted in the step (2) with an iron nitrate solution, stirring, keeping the constant temperature at 20-100 ℃, and reacting for 0.1-48 hours;
the concentration of the ferric nitrate solution is more than 0.1mol/L, and at least one of ammonia water, ammonium nitrate and ammonium carbonate is added as a nitrogen-containing precipitator during mixing;
(4) putting the solution in the step (3) into a centrifugal tube, performing solid-liquid separation by using a centrifugal machine with the rotating speed of 3500-4500 r/min, removing supernatant, washing the obtained precipitate for 3-4 times by using deionized water and absolute ethyl alcohol in sequence, and drying the obtained solid product in an oven at 70-90 ℃;
(5) and (3) placing the washed and dried solid product in a muffle furnace, and roasting at the temperature of 500-600 ℃, wherein the roasted product is the hierarchical porous spherical iron oxide catalyst.
4. The method for preparing the multistage iron oxide catalyst for removing the heteroatoms in the coal liquefied oil according to claim 3, wherein the method comprises the following steps:
(4) and (3) placing the solution in the step (3) in a centrifuge tube, performing solid-liquid separation by using a centrifuge with the rotation speed of 4000r/min, removing supernatant, washing the obtained precipitate for 3-4 times by using deionized water and absolute ethyl alcohol in sequence, and placing the obtained solid product in an oven to be dried at 80 ℃.
5. The method for preparing the multistage iron oxide catalyst for removing the heteroatoms in the coal liquefied oil according to claim 4, wherein the method comprises the following steps:
(5) the roasting temperature of the medium solid product is controlled at 550 ℃, and the multi-level pore spherical ferric oxide catalyst maintaining the spherical structure is obtained after roasting.
6. The method for preparing the multistage iron oxide catalyst for removing the heteroatoms in the coal liquefied oil according to claim 5, wherein the method comprises the following steps:
the diameter of the hierarchical pore spherical iron oxide catalyst is distributed in the size range of 100-300 nm, and the shape of the hierarchical pore spherical iron oxide catalyst is spherical.
7. The method for preparing the multistage iron oxide catalyst for removing the heteroatoms in the coal liquefied oil according to claim 1, comprising the following steps:
(1) preparing carbon microspheres: dispersing 1.5mol/L glucose into water by using a mechanical stirring, ultrasonic and microwave method to obtain a dispersion solution;
then, the dispersion solution and a dispersant are synthesized in a hydrothermal kettle, the reaction temperature is 160 ℃, and the reaction time is 4 hours; obtaining hard hierarchical porous carbon microspheres;
the dispersing agent is at least one of sodium dodecyl sulfate, methyl amyl alcohol, sodium polystyrene sulfonate and polyacrylamide, and the mass ratio of the using amount of the dispersing agent to the glucose is as follows: 1: 500, a step of;
(2) roasting the carbon microspheres obtained in the step (1) in a gas environment at 800 ℃ to obtain hard hierarchical porous carbon microspheres; the gas environment is a mixed gas of argon and air;
(3) mixing the carbon microspheres roasted in the step (2) with ferric nitrate solution, stirring, keeping the constant temperature at 60 ℃, and reacting for 24 hours;
the concentration of the ferric nitrate solution is more than 0.1mol/L, and ammonia water, ammonium nitrate and ammonium carbonate are added as nitrogen-containing precipitating agents during mixing;
(4) filtering the solution in the step (3) by using a porous ceramic filter with the pore diameter of 500nm, washing for 3-4 times by using deionized water and absolute ethyl alcohol in sequence in the filtering process, and drying the obtained solid product in an oven at 80 ℃;
or putting the solution in the step (3) into a centrifuge tube, performing solid-liquid separation by using a centrifuge with the rotation speed of 4000r/min, removing supernatant, washing the obtained precipitate for 3-4 times by using deionized water and absolute ethyl alcohol in sequence, and drying the obtained solid product in an oven at 80 ℃;
(5) and (4) roasting the solid product obtained in the step (4) at 550 ℃ to obtain the multi-level pore spherical iron oxide catalyst.
8. Use of the catalyst obtained by the method of preparing a multi-stage iron oxide catalyst according to claim 1 for removing heteroatoms in coal liquefaction oil.
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