CN116689014A - Multistage Kong Peng carbon-nitrogen material and preparation method and application thereof - Google Patents
Multistage Kong Peng carbon-nitrogen material and preparation method and application thereof Download PDFInfo
- Publication number
- CN116689014A CN116689014A CN202310881359.3A CN202310881359A CN116689014A CN 116689014 A CN116689014 A CN 116689014A CN 202310881359 A CN202310881359 A CN 202310881359A CN 116689014 A CN116689014 A CN 116689014A
- Authority
- CN
- China
- Prior art keywords
- carbon
- peng
- kong
- nitrogen
- nitrogen material
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000000463 material Substances 0.000 title claims abstract description 81
- CKUAXEQHGKSLHN-UHFFFAOYSA-N [C].[N] Chemical compound [C].[N] CKUAXEQHGKSLHN-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 58
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 58
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 52
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 26
- 239000007789 gas Substances 0.000 claims abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 24
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000004327 boric acid Substances 0.000 claims abstract description 18
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 13
- 229910052796 boron Inorganic materials 0.000 claims abstract description 13
- 239000004202 carbamide Substances 0.000 claims abstract description 11
- 239000002283 diesel fuel Substances 0.000 claims abstract description 11
- -1 dibenzothiophene aromatic sulfides Chemical class 0.000 claims abstract description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 3
- JKWMSGQKBLHBQQ-UHFFFAOYSA-N diboron trioxide Chemical compound O=BOB=O JKWMSGQKBLHBQQ-UHFFFAOYSA-N 0.000 claims abstract description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910052810 boron oxide Inorganic materials 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 239000010453 quartz Substances 0.000 claims description 27
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 27
- 239000007787 solid Substances 0.000 claims description 27
- 238000010438 heat treatment Methods 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 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 11
- 238000001816 cooling Methods 0.000 claims description 11
- 239000008103 glucose Substances 0.000 claims description 11
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 11
- 238000001354 calcination Methods 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000007254 oxidation reaction Methods 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 6
- 238000003837 high-temperature calcination Methods 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000010431 corundum Substances 0.000 claims description 4
- 229910052593 corundum Inorganic materials 0.000 claims description 4
- 229910001873 dinitrogen Inorganic materials 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- 239000001913 cellulose Substances 0.000 claims description 3
- 229920002678 cellulose Polymers 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 239000012298 atmosphere Substances 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000004328 sodium tetraborate Substances 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 238000006477 desulfuration reaction Methods 0.000 abstract description 33
- 230000023556 desulfurization Effects 0.000 abstract description 33
- DZVPMKQTULWACF-UHFFFAOYSA-N [B].[C].[N] Chemical compound [B].[C].[N] DZVPMKQTULWACF-UHFFFAOYSA-N 0.000 abstract description 22
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene sulfoxide Natural products C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 abstract description 17
- 230000003197 catalytic effect Effects 0.000 abstract description 16
- 239000003054 catalyst Substances 0.000 abstract description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 8
- 239000002243 precursor Substances 0.000 abstract description 6
- 150000003457 sulfones Chemical class 0.000 abstract description 5
- 230000003213 activating effect Effects 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 230000007547 defect Effects 0.000 abstract description 2
- 238000000197 pyrolysis Methods 0.000 abstract description 2
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000004090 dissolution Methods 0.000 abstract 1
- 238000001953 recrystallisation Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 24
- 230000001590 oxidative effect Effects 0.000 description 16
- 239000011148 porous material Substances 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 238000003917 TEM image Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 229910021529 ammonia Inorganic materials 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- MYAQZIAVOLKEGW-UHFFFAOYSA-N 4,6-dimethyldibenzothiophene Chemical compound S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 5
- 238000005119 centrifugation Methods 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- NICUQYHIOMMFGV-UHFFFAOYSA-N 4-Methyldibenzothiophene Chemical compound S1C2=CC=CC=C2C2=C1C(C)=CC=C2 NICUQYHIOMMFGV-UHFFFAOYSA-N 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- 238000000354 decomposition reaction Methods 0.000 description 4
- 239000007800 oxidant agent Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 150000004763 sulfides Chemical class 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- DGUACJDPTAAFMP-UHFFFAOYSA-N 1,9-dimethyldibenzo[2,1-b:1',2'-d]thiophene Natural products S1C2=CC=CC(C)=C2C2=C1C=CC=C2C DGUACJDPTAAFMP-UHFFFAOYSA-N 0.000 description 2
- 229910052582 BN Inorganic materials 0.000 description 2
- PZNSFCLAULLKQX-UHFFFAOYSA-N Boron nitride Chemical compound N#B PZNSFCLAULLKQX-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000003118 aryl group Chemical group 0.000 description 2
- 125000004432 carbon atom Chemical group C* 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000000295 fuel oil Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 230000002209 hydrophobic effect Effects 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 229910052815 sulfur oxide Inorganic materials 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- BGHCVCJVXZWKCC-UHFFFAOYSA-N tetradecane Chemical compound CCCCCCCCCCCCCC BGHCVCJVXZWKCC-UHFFFAOYSA-N 0.000 description 2
- 229910011255 B2O3 Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- IYYZUPMFVPLQIF-ALWQSETLSA-N dibenzothiophene Chemical group C1=CC=CC=2[34S]C3=C(C=21)C=CC=C3 IYYZUPMFVPLQIF-ALWQSETLSA-N 0.000 description 1
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001493 electron microscopy Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 1
- YCOZIPAWZNQLMR-UHFFFAOYSA-N heptane - octane Natural products CCCCCCCCCCCCCCC YCOZIPAWZNQLMR-UHFFFAOYSA-N 0.000 description 1
- 239000002638 heterogeneous catalyst Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000012229 microporous material Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 239000001294 propane Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- XTQHKBHJIVJGKJ-UHFFFAOYSA-N sulfur monoxide Chemical class S=O XTQHKBHJIVJGKJ-UHFFFAOYSA-N 0.000 description 1
- 230000002194 synthesizing effect 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- 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
-
- 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
- C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
- C10G2400/04—Diesel oil
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Materials Engineering (AREA)
- General Chemical & Material Sciences (AREA)
- Catalysts (AREA)
Abstract
The application discloses a multistage Kong Peng carbon-nitrogen material, a preparation method and application thereof, wherein hydrophilic carbon spheres with different sizes are used as hard templates and carbon sources, boric acid, boron oxide and the like are used as boron sources, urea, thiourea, melamine and the like are used as nitrogen sources, and a precursor is synthesized by a dispersion, dissolution and recrystallization method. And (3) forming micropores by utilizing a large amount of gas micromolecules generated by pyrolysis of the precursor through a method of pyrolyzing the precursor, constructing mesopores or macropores by utilizing a carbon sphere hard template, and finally forming multistage Kong Peng carbon nitrogen. The microporous structure of the multistage Kong Peng carbon-nitrogen catalyst prepared by the application can have a large number of defect sites, and can improve the concentration of the catalytic active sites of the boron carbon-nitrogen material; the macroporous and mesoporous structures can strengthen the mass transfer efficiency in the catalytic reaction process. The prepared multistage Kong Peng carbon-nitrogen material is used for activating oxygen diesel oil to oxidize and desulfurize, can realize ultra-deep desulfurization of diesel oil, and can directionally convert dibenzothiophene aromatic sulfides into sulfones with high added value.
Description
Technical Field
The application belongs to the field of functional catalytic material preparation and catalysis, and particularly relates to a multistage Kong Peng carbon-nitrogen material, a preparation method thereof and application thereof in fuel catalytic oxidation desulfurization.
Background
In recent years, the consumption of fossil fuels such as diesel oil has increased, and the pollution problem caused by combustion of sulfides therein has also been increasing. The emission of sulfur oxides (SOx) can lead to pollution problems such as acid rain, haze, etc. As a result, increasingly stringent regulations are being enacted in many countries and regions to limit the sulfur content of fuel to 10ppm or less. Hydrodesulfurization (HDS) is generally the most commonly used desulfurization technique in industry. It was found that HDS has a high removal capacity for aliphatic sulfides. However, HDS has low activity on aromatic sulfides such as dibenzothiophenes and derivatives thereof due to the aromaticity and steric hindrance of the aromatic sulfides. Researchers find that oxidative desulfurization is receiving a great deal of attention due to the advantages of high activity on aromatic sulfides, low cost, mild reaction conditions, etc. In particular, due to O 2 Green, low cost, wide source, etc. with oxygen (O) 2 ) Is a great concern for the oxidative desulfurization process of oxidizing agents. A high activity catalyst is designed to be realized by O 2 Is the key of the oxidative desulfurization of the oxidant.
Boron nitride materials are widely used in catalytic fields such as catalytic propane dehydrogenation (Science, 2016,354,1570-1573), oxidative desulfurization (Small, 2017,13,1701857) and the like due to their advantages of high specific surface area, good thermal stability, chemical stability, structural designability and the like. However, the applicant found in the previous research work that in the oxidative desulfurization system, commercial grade BN has limited oxidative activity on sulfides, and the aim of ultra-deep desulfurization (Green Energy & Environment,2020,5,166-172) cannot be achieved far enough, so that modification of boron nitride material is required to improve catalytic oxidative desulfurization performance.
The research shows that the construction of boron carbon nitrogen material by doping carbon atoms is a strategy capable of remarkably improving the catalytic activity of the boron carbon nitrogen material. The charge structure of the catalytic active site can be regulated and controlled by doping carbon atoms, so that the charge structure of the catalyst for O is obviously improved 2 Is improved in activation ability of O 2 Catalytic oxidative desulfurization activity (Microporous and Mesoporous Materials,2020,293,109788). However, the boron carbon nitrogen material is synthesized by introducing a carbon-containing organic precursor for pyrolysis, and has poor controllability and difficult pore structure modulation, so that the boron carbon nitrogen material has low content of catalytic active sites and is used for activating O 2 Mass transfer of oxidative desulfurization is blocked, and the like.
Disclosure of Invention
The application aims to: aiming at the defects of the prior art, the application provides a method for realizing the controllable preparation of the multistage Kong Peng carbon-nitrogen material by taking carbon spheres as a hard template and a carbon source.
In order to achieve the above purpose, the technical scheme adopted by the application is as follows:
a method for preparing a multistage Kong Peng carbon-nitrogen material, comprising the following steps:
(1) Preparing hydrophilic carbon spheres;
(2) Mixing hydrophilic carbon spheres, a boron source and a nitrogen source, uniformly dispersing in water, and stirring under an oil bath until the water is completely evaporated to dryness to obtain gray black solid;
(3) Calcining the gray black solid obtained in the step (2) at high temperature in the presence of ammonia gas, and naturally cooling to room temperature after the calcining is finished, thus obtaining the gray black solid.
Specifically, in the step (1), the hydrophilic carbon spheres are prepared from glucose or water-soluble cellulose serving as a raw material through a hydrothermal reaction, and specifically comprise the following steps: dissolving the raw materials in water, transferring to a reaction kettle, performing hydrothermal reaction for 6-18h (preferably 12-16 h) at 160-200 ℃ (preferably 160-180 ℃), naturally cooling to room temperature after the reaction is finished, centrifugally separating carbon spheres, washing with water and ethanol alternately, and drying to obtain hydrophilic carbon spheres with different sizes.
Specifically, the dosage ratio of the raw materials to water is (0.5-5.0 g): (50-80 mL), preferably (1.0-3.0 g): (50-60 mL); the hydrothermal reaction temperature is 160-180 ℃ and the hydrothermal time is 12-16h; centrifugal separation rotational speed is 6000-10000rpm, preferably 8000-10000rpm; centrifuging for 3-10min, preferably 5-8min; the volume of water during washing is 10-50mL, preferably 20-40mL; the volume of the ethanol is 10-50mL, preferably 20-40mL; the drying temperature is 80-160 ℃, preferably 100-120 ℃.
Specifically, in the step (2), the boron source adopts any one or more than two of boric acid, boric oxide and borax, and boric acid is preferred; the nitrogen source adopts any one or more than two of urea, melamine, dicyandiamide and thiourea, and urea and thiourea are preferred.
Specifically, in the step (2), the mass ratio of the boron source to the nitrogen source is 1:10-1:50, preferably 1:20-1:40; the mass ratio of the hydrophilic carbon spheres to the boron source is 1:10-1:50, preferably 1:20-1:40.
Specifically, in the step (2), the temperature of the oil bath is controlled to be 60-110 ℃, preferably 80-100 ℃; the stirring is carried out by magnetic stirring at a rotational speed of 100-1200rpm, preferably 600-800rpm.
Specifically, in the step (3), the gray-black solid is transferred into a square boat, and then is placed in a tube furnace for high-temperature calcination; the square boat is made of ceramics, quartz or corundum, and quartz is preferred; the furnace tube in the tube furnace is made of ceramics, quartz or corundum, preferably quartz; the high-temperature calcination temperature is 800-1200 ℃, preferably 800-1000 ℃; the holding time is 2-8 hours, preferably 4-6 hours; the heating rate of the tube furnace is 1-10 ℃/min, preferably 5-8 ℃/min; the calcination atmosphere is ammonia gas or a mixed gas of ammonia gas and nitrogen gas, preferably a mixed gas of ammonia gas and nitrogen gas, and the mixing ratio of ammonia gas and nitrogen gas is 20:80-80:20, preferably 50:50; the gas flow rate is 50-200mL/min, preferably 100mL/min.
Further, the multistage Kong Peng carbon-nitrogen material prepared by the preparation method is also in the protection scope of the application.
Further, the multistage Kong Peng carbon-nitrogen material prepared by the method is composed of three elements of boron, carbon and nitrogen, and has at least two structures of micropores, mesopores and macropores; wherein the size of the micropores is 0.1-1.8nm, preferably 0.2-1nm; the mesoporous size is 10-50nm, preferably 20-40nm; the macropores have a size of 60 to 200nm, preferably 80 to 120nm.
The preparation principle of the application is as follows:
the carbon spheres can be decomposed by high-temperature calcination in the presence of ammonia gas, and can be used as a hard template agent to synthesize a macroporous or mesoporous hard template. Meanwhile, the carbon sphere can also be used as a carbon source for synthesizing boron carbon nitrogen materials. In addition, a large amount of gas can be generated in the reaction process of the boron source and the nitrogen source, a large amount of gas small molecules can be generated in the decomposition process of the carbon spheres, a large number of micropores can be constructed, and the concentration of the catalytic active sites is improved. The application takes hydrophilic carbon spheres as a hard template agent and a carbon source, and utilizes the characteristic of high-temperature decomposition of the carbon spheres in the presence of ammonia gas as the hard template agent to construct a macroporous or mesoporous structure; and a microporous structure is constructed by utilizing gas micromolecules generated by decomposition of carbon spheres, a boron source and a nitrogen source. The prepared multistage Kong Peng carbon-nitrogen material has a micropore and mesopore structure at the same time, or has a micropore and macropore structure at the same time, or has a micropore, mesopore and macropore structure at the same time. Therefore, the multistage Kong Peng carbon-nitrogen material not only has abundant micropore structures to promote the catalytic activity, but also has ordered mesoporous or macroporous structures to strengthen and activate O 2 Mass transfer efficiency in oxidative desulfurization processes.
Furthermore, the application also claims the activation of the multistage Kong Peng carbon-nitrogen material in O 2 The application of catalyzing the oxidation of fuel oil to remove aromatic sulfides. Realize ultra-deep desulfurization of fuel oil such as diesel oil and realize directional conversion of sulfide into sulfone.
Preferably, the aromatic sulfide is dibenzothiophene aromatic sulfide.
Preferably, the multistage Kong Peng carbon nitrogen catalyst is added in an amount of 0.5 to 1.0g per 100mL of diesel.
Premixing a multistage Kong Peng carbon-nitrogen catalyst with diesel oil, then introducing oxygen as an oxidant, heating in a constant-temperature oil bath, magnetically stirring, taking out a small amount of supernatant at regular time, analyzing by using gas chromatography, and measuring the residual sulfur content in the oil product. Wherein, the adding amount of the multistage Kong Peng carbon-nitrogen catalyst is 0.5-1.0g per 100mL of model oil, the initial sulfide concentration in the model oil is 10-500ppmw, the pressure of the introduced oxygen is 0.1MPa, the flow rate of the oxygen is 20-200mL/min, the reaction temperature is 100-150 ℃, the reaction time is 2-8h, the magnetic stirring speed is 600-1200rpm, and the obtained desulfurization product is the corresponding sulfone.
The model oil comprises Dibenzothiophene (DBT) model oil, 4, 6-dimethyl dibenzothiophene (4, 6-DMDBT) model oil and 4-methyl dibenzothiophene (4-MDBT), wherein the effect of oxidizing and removing the 4,6-DMDBT is the best.
The desulfurization temperature is 120 ℃, and the oxidation desulfurization performance is best.
The magnetic stirring speed is 1000rpm, the oxidation desulfurization performance is best, and the deep desulfurization can be realized.
When the flow rate of oxygen is 100mL/min, the catalyst can have oil yield and desulfurization rate.
The desulfurization product sulfone refers to dibenzothiophene sulfone, 4, 6-dimethyl dibenzothiophene sulfone and 4-methyl dibenzothiophene sulfone, has high economic added value, and can improve the economy of the desulfurization process.
The beneficial effects are that:
(1) According to the application, hydrophilic carbon spheres are used as a hard template and a carbon source, a multistage Kong Peng carbon-nitrogen material is constructed, the charge regulation and control of catalytic active sites are realized, meanwhile, micropores of multistage holes can be used for constructing richer active site concentration, and a mesoporous or macroporous structure can be used for strengthening the transfer and diffusion of substrate molecules in the desulfurization process, so that the desulfurization efficiency is improved.
(2) Compared with the boron carbon nitrogen material synthesized by the traditional soft template, the multistage Kong Peng carbon nitrogen material prepared by the process route provided by the application has better controllability of the pore structure, can improve the catalytic performance and concentration of the catalytic active site, and promotes the activation of O 2 Catalytic diesel oxidation desulfurization to realize ultra-deep desulfurization of diesel oil<10ppm)。
(3) The multistage Kong Peng carbon-nitrogen material constructed by the application is a heterogeneous catalyst, can be efficiently separated from diesel oil, realizes recovery and regeneration of the catalyst after desulfurization reaction, and improves the recycling convenience of the catalyst.
(4) Oxygen used in the present applicationThe chemical agent is O 2 The source is wide and the price is low; meanwhile, other solvents are not needed to be added in the reaction process, and the method is environment-friendly and pollution-free.
Drawings
The foregoing and/or other advantages of the application will become more apparent from the following detailed description of the application when taken in conjunction with the accompanying drawings and detailed description.
FIG. 1 is a graph of electron microscopy and pore size distribution of a multistage Kong Peng carbon-nitrogen material prepared in example 1. Wherein a is an SEM image of a multistage Kong Peng carbon nitrogen material, b is a TEM image of a multistage Kong Peng carbon nitrogen material, c is a nitrogen adsorption desorption isotherm plot of a multistage Kong Peng carbon nitrogen material; d is the pore size distribution plot of the multistage Kong Peng carbon nitrogen material response.
FIG. 2 is an electron microscope and pore size distribution plot of a multi-stage Kong Peng carbon-nitrogen material prepared in example 2. Wherein a is an SEM image of a multistage Kong Peng carbon nitrogen material, b is a TEM image of a multistage Kong Peng carbon nitrogen material, c is a nitrogen adsorption desorption isotherm plot of a multistage Kong Peng carbon nitrogen material; d is the pore size distribution plot of the multistage Kong Peng carbon nitrogen material response.
FIG. 3 is a transmission electron microscopy image of a multi-stage Kong Peng carbon-nitrogen material prepared in example 3.
FIG. 4 is a transmission electron microscopy image of a multi-stage Kong Peng carbon-nitrogen material prepared in example 4.
FIG. 5 is a transmission electron microscopy image of a multi-stage Kong Peng carbon-nitrogen material prepared in example 5.
FIG. 6 is a multistage Kong Peng carbon nitrogen material catalyst for O activation 2 Effect data for oxidative removal of aromatic sulfides in diesel.
Fig. 7 is a transmission electron microscope image of the boron carbon nitrogen material prepared in comparative example 1.
FIG. 8 is a transmission electron micrograph of the boron carbon nitrogen material prepared in comparative example 2.
Detailed Description
The application will be better understood from the following examples.
Example 1:
(1) 2.0g of glucose was dissolved in 50mL of deionized water and then transferred to a 100mL hydrothermal reaction vessel where it was hydrothermally heated at 180℃for 12h and naturally cooled to room temperature. Followed by centrifugation in a high-speed centrifuge at 8000rpm for 5min. The white solid obtained was washed 3 times with 20mL of water, 3 times with 20mL of ethanol and dried at 100 ℃.
(2) Boric acid and urea (mass ratio 1:20) were dissolved in deionized water, followed by addition of the above carbon spheres (mass ratio of carbon spheres to boric acid 1:20), followed by transfer to a constant temperature oil bath, heating and stirring at 80 ℃ at 800rpm until the solvent was completely evaporated to dryness, giving an off-white solid.
(3) Transferring the off-white solid obtained in the step (2) into a quartz ark, placing the quartz ark into a tubular furnace made of a quartz tube material, introducing a mixed gas of ammonia and nitrogen at a gas flow rate of 100mL/min, heating to 900 ℃ at a heating rate of 5 ℃/min, keeping for 4 hours, and naturally cooling to room temperature to obtain the multistage Kong Peng carbon-nitrogen material. The Scanning Electron Microscope (SEM) and the Transmission Electron Microscope (TEM) are shown in fig. 1. As can be seen from the SEM image of fig. 1a, the synthesized boron carbon nitrogen material is assembled from two-dimensional thin-layer nanoplatelets, and the presence of holes can be observed; further, as can be seen from the TEM image in fig. 1b, the ordered mesoporous structure can be seen with hydrophilic carbon spheres as a hard template, and the size of the mesoporous is 25-35nm. Since the pore size was not observed in the TEM image, the obtained sample was further subjected to nitrogen adsorption-desorption isothermal analysis. From the nitrogen adsorption and desorption curve of fig. 1c, it can be seen that there is a significant rise in the low partial pressure zone, indicating the presence of a large number of microporous structures, while the presence of an H3-type hysteresis in the range of 0.4-1.0 indicates the presence of mesopores. It can further be seen from the pore size distribution of FIG. 1d that the resulting sample is present in a size of aboutMicropore and->Is a mesoporous structure.
Example 2:
(1) 1.0g of glucose was dissolved in 60mL of deionized water and then transferred to a 100mL hydrothermal reaction vessel where it was hydrothermal at 160℃for 18h and naturally cooled to room temperature. Followed by centrifugation in a high-speed centrifuge at 10000rpm for 7min. The white solid obtained was washed 3 times with 30mL of water, 3 times with 30mL of ethanol and dried at 100 ℃.
(2) Boric acid and urea (mass ratio 1:30) were dissolved in deionized water, followed by addition of the above carbon spheres (mass ratio of carbon spheres to boric acid 1:30), followed by transfer to a constant temperature oil bath, heating and stirring at 90 ℃ at 900rpm until the solvent was completely evaporated to dryness, giving an off-white solid.
(3) Transferring the off-white solid obtained in the step (2) into a quartz ark, placing the quartz ark into a tubular furnace made of a quartz tube material, introducing mixed gas of ammonia and nitrogen at a gas flow rate of 120mL/min, heating to 1000 ℃ at a heating rate of 4 ℃/min, keeping for 3 hours, and then naturally cooling to room temperature to obtain the multistage Kong Peng carbon-nitrogen material. The nitrogen adsorption and desorption isotherms and pore size distribution are shown in fig. 2. As can be seen from the SEM image of fig. 2a, the synthesized boron carbon nitrogen material is assembled from two-dimensional thin-layer nano-sheets, and exhibits a fluffy structure due to the existence of micropores and mesopores; further, as can be seen from the TEM image of FIG. 2b, the ordered mesoporous structure can be seen by taking the hydrophilic carbon spheres as a hard template, and the size of the mesoporous is as followsLeft and right. Since the pore size was not observed in the TEM image, the obtained sample was further subjected to nitrogen adsorption-desorption isothermal analysis. From fig. 2c, it can be seen that the adsorption and desorption curve of the nitrogen of the sample is suddenly increased in adsorption capacity in a low relative pressure region, which indicates that a large number of microporous structures exist, and that an H3-type hysteresis curve exists in a range of 0.4-1.0, which indicates that a mesoporous structure exists in the sample. As can also be seen from the pore size distribution curve calculated using adsorption count data, as shown in FIG. 2d, there are a large number of microporous mesoporous structures with pore sizes of about 4 and +.>
Example 3:
(1) 2.0g of glucose was dissolved in 50mL of deionized water and then transferred to a 100mL hydrothermal reaction vessel where it was hydrothermally heated at 180℃for 12h and naturally cooled to room temperature. Followed by centrifugation in a high-speed centrifuge at 8000rpm for 5min. The white solid obtained was washed 3 times with 20mL of water, 3 times with 20mL of ethanol and dried at 100 ℃.
(2) Boric acid and urea (mass ratio 1:20) were dissolved in deionized water, followed by addition of the above carbon spheres (mass ratio of carbon spheres to boric acid 1:20), followed by transfer to a constant temperature oil bath, heating and stirring at 80 ℃ at 800rpm until the solvent was completely evaporated to dryness, giving an off-white solid.
(3) Transferring the off-white solid obtained in the step (2) into a quartz ark, placing the quartz ark into a tubular furnace made of a quartz tube material, introducing a mixed gas of ammonia and nitrogen in a ratio of 50:50, heating to 1100 ℃ at a heating rate of 2 ℃/min at a gas flow rate of 100mL/min, keeping for 4 hours, and naturally cooling to room temperature to obtain the multistage Kong Peng carbon-nitrogen material. As can be seen from fig. 3, since the same carbon spheres as in example 1 are used as templates, the morphology of the obtained porous boron carbon nitrogen material is similar to that of example 1, which shows that the porous boron carbon nitrogen material can be synthesized at 1100 ℃ and the porous structure is mainly a hydrophilic carbon sphere template rather than the calcination temperature.
Example 4:
(1) 1.0g of glucose was dissolved in 60mL of deionized water and then transferred to a 100mL hydrothermal reaction vessel where it was hydrothermal at 160℃for 18h and naturally cooled to room temperature. Followed by centrifugation in a high-speed centrifuge at 10000rpm for 7min. The white solid obtained was washed 3 times with 30mL of water, 3 times with 30mL of ethanol and dried at 100 ℃.
(2) Boric acid and urea (mass ratio 1:30) were dissolved in deionized water, followed by addition of the above carbon spheres (mass ratio of carbon spheres to boric acid 1:30), followed by transfer to a constant temperature oil bath, heating and stirring at 90 ℃ at 900rpm until the solvent was completely evaporated to dryness, giving an off-white solid.
(3) Transferring the off-white solid obtained in the step (2) into a quartz ark, placing the quartz ark into a tubular furnace made of a quartz tube material, introducing mixed gas of ammonia and nitrogen at a gas flow rate of 120mL/min, heating to 800 ℃ at a heating rate of 5 ℃/min, keeping for 3 hours, and then naturally cooling to room temperature to obtain the multistage Kong Peng carbon-nitrogen material. As can be seen from fig. 4, since the same carbon spheres as in example 2 are used as templates, the morphology of the obtained porous boron carbon nitrogen material is similar to that of example 2, which shows that the porous boron carbon nitrogen material can be synthesized at 800 ℃ and the porous structure is mainly a hydrophilic carbon sphere template rather than the calcination temperature.
Example 5
(1) 0.5g of water-soluble cellulose was dissolved in 50mL of deionized water, followed by transfer to a 100mL hydrothermal reaction vessel where it was hydrothermally heated at 180℃for 12h and naturally cooled to room temperature. Followed by centrifugation in a high-speed centrifuge at 8000rpm for 5min. The white solid obtained was washed 3 times with 20mL of water, 3 times with 20mL of ethanol and dried at 100 ℃.
(2) Boric acid and urea (mass ratio 1:20) were dissolved in deionized water, followed by addition of the above carbon spheres (mass ratio of carbon spheres to boric acid 1:20), followed by transfer to a constant temperature oil bath, heating and stirring at 80 ℃ at 800rpm until the solvent was completely evaporated to dryness, giving an off-white solid.
(3) Transferring the off-white solid obtained in the step (2) into a quartz ark, placing the quartz ark into a tubular furnace made of a quartz tube material, introducing a mixed gas of ammonia and nitrogen at a gas flow rate of 100mL/min, heating to 900 ℃ at a heating rate of 5 ℃/min, keeping for 4 hours, and naturally cooling to room temperature to obtain the multistage Kong Peng carbon-nitrogen material. The Transmission Electron Microscope (TEM) is shown in fig. 5. As can be seen from the TEM image, the hydrophilic carbon spheres are taken as a hard template, a large number of micropores exist, the pore diameter of the micropores is about 1.5nm, a large number of ordered mesopores can be observed, and the mesopore size is about 50nm.
Examples 6 to 13
Multistage Kong Peng carbon Nitrogen Material catalyst obtained in examples 1-2 for O activation 2 And (3) oxidizing to remove aromatic sulfides in the diesel oil. The following is the oil type of the simulated diesel oil and the constitution of the oxidation desulfurization experimental device:
the configuration process of the model oil is as follows: DBT,4,6-DMDBT,4-MDBT were each dissolved in dodecane to prepare model oils with sulfide concentrations of 10-500ppmw, and n-tetradecane was added as an internal standard.
Adding model oil into a round bottom flask, adding a certain amount of multistage Kong Peng carbon-nitrogen catalyst obtained in example 1 or example 2, premixing with the model oil, introducing oxygen as an oxidant, heating in a constant-temperature oil bath, magnetically stirring, taking out a small amount of supernatant at regular time, analyzing by gas chromatography, measuring the residual sulfur content in the oil, and analyzing the obtained desulfurization product by GC-MS. The desulfurization rate calculation formula is as follows:
the experimental results of the embodiment are shown in fig. 6, and it can be seen that the multistage Kong Peng carbon-nitrogen material synthesized by the application can effectively remove aromatic sulfides, has good removal effect, can realize the desulfurization rate of more than 98% for different sulfides under the optimized reaction condition of the application, and can be directionally converted into sulfone.
Comparative example 1
(1) The literature reports that most oxygen-containing groups on the surface of carbon materials are eliminated after the carbon materials are subjected to high temperatures, and hydrophobicity is shown (inorganic chemistry report, 2022, 38,1-13). Thus, the carbon spheres obtained in example 1 were treated at high temperature under nitrogen protection at 900℃to obtain hydrophobic carbon spheres.
(2) Boric acid and urea (mass ratio 1:20) were dissolved in deionized water, followed by addition of the above carbon spheres (mass ratio of carbon spheres to boric acid 1:20), followed by transfer to a constant temperature oil bath, heating and stirring at 80 ℃ at 800rpm until the solvent was completely evaporated to dryness, giving an off-white solid.
(3) Transferring the off-white solid obtained in the step (2) into a quartz ark, placing the quartz ark into a tubular furnace made of a quartz tube material, introducing a mixed gas of ammonia and nitrogen in a ratio of 50:50, heating to 900 ℃ at a heating rate of 5 ℃/min at a gas flow rate of 100mL/min, keeping for 4 hours, and naturally cooling to room temperature to obtain the boron carbon nitrogen material. As the morphology results are shown in fig. 7, the carbon spheres cannot be highly dispersed in the precursor due to the hydrophobic nature of the carbon spheres, so that the obtained boron carbon nitrogen material has no obvious pore structure or obvious ordered structure.
(4) The DBT in the model diesel is removed from the boron carbon nitrogen material obtained by the method according to the condition of the example 6, and the DBT does not contain a porous structure, so that the exposure degree of an active site is low, the mass transfer efficiency in the reaction process is low, and the desulfurization rate is only 70%.
Comparative example 2
(1) The literature reports that boron carbon nitrogen materials can also be synthesized using organic matter as a carbon source (angel. Chem. Int. Ed.2018,57,5487.). Thus, as a control, the applicant selected glucose as a carbon source to synthesize a boron carbon nitrogen material.
(2) Boric acid and urea (mass ratio 1:20) were dissolved in deionized water, followed by addition of the above carbon spheres (mass ratio of carbon to boric acid in glucose was controlled at 1:20), followed by transfer to a constant temperature oil bath, heating and stirring at 80 ℃ at 800rpm until the solvent was completely evaporated to dryness, giving an off-white solid.
(3) Transferring the off-white solid obtained in the step (2) into a quartz ark, placing the quartz ark into a tubular furnace made of a quartz tube material, introducing a mixed gas of ammonia and nitrogen in a ratio of 50:50, heating to 900 ℃ at a heating rate of 5 ℃/min at a gas flow rate of 100mL/min, keeping for 4 hours, and naturally cooling to room temperature to obtain the boron carbon nitrogen material. The morphology results are shown in FIG. 8. Glucose is used as a carbon source and cannot be used as a hard template agent, so that an ordered pore structure cannot be formed, and only micropores created by a precursor and gas generated by glucose decomposition exist, so that the glucose is only represented as a layered structure of a two-dimensional material.
(4) The DBT in the model diesel oil is removed from the boron carbon nitrogen material according to the conditions of the example 6, and the DBT only contains micropores and no ordered mesoporous or macroporous structure, so that the mass transfer efficiency in the reaction process is lower, and the desulfurization rate is only 80%.
The application provides a multistage Kong Peng carbon-nitrogen material, a preparation method and an application thought and a method thereof, and particularly the method and the method for realizing the technical scheme are numerous, the above is only a preferred embodiment of the application, and it should be pointed out that a plurality of improvements and modifications can be made to those skilled in the art without departing from the principle of the application, and the improvements and modifications are also considered as the protection scope of the application. The components not explicitly described in this embodiment can be implemented by using the prior art.
Claims (10)
1. A method for preparing a multistage Kong Peng carbon-nitrogen material, which is characterized by comprising the following steps:
(1) Preparing hydrophilic carbon spheres;
(2) Mixing hydrophilic carbon spheres, a boron source and a nitrogen source, uniformly dispersing in water, and stirring under an oil bath until the water is completely evaporated to dryness to obtain gray black solid;
(3) Calcining the gray black solid obtained in the step (2) at high temperature in the presence of ammonia gas, and naturally cooling to room temperature after the calcining is finished, thus obtaining the gray black solid.
2. The method for preparing the multistage Kong Peng carbon-nitrogen material according to claim 1, wherein in the step (1), the hydrophilic carbon spheres are prepared from glucose or water-soluble cellulose by a hydrothermal reaction, and specifically comprise: dissolving the raw materials in water, transferring to a reaction kettle, performing hydrothermal reaction at 160-200 ℃ for 6-18h, naturally cooling to room temperature after the reaction is finished, centrifugally separating carbon spheres, alternately washing with water and ethanol, and drying to obtain hydrophilic carbon spheres with different sizes.
3. The method of preparing a multi-stage Kong Peng carbon-nitrogen material of claim 2, wherein the raw material to water ratio is (0.5-5.0 g): (50-80 mL); the hydrothermal reaction temperature is 160-180 ℃ and the hydrothermal time is 12-16h; centrifuging at 6000-10000rpm for 3-10min; the drying temperature is 80-160 ℃.
4. The method for preparing a multi-stage Kong Peng carbon-nitrogen material according to claim 1, wherein in the step (2), the boron source is any one or a mixture of two or more of boric acid, boron oxide and borax; the nitrogen source adopts any one or more than two of urea, melamine, dicyandiamide and thiourea.
5. The method for producing a multi-stage Kong Peng carbon-nitrogen material according to claim 1, wherein in the step (2), the mass ratio of the boron source to the nitrogen source is 1:10-1:50, and the mass ratio of the hydrophilic carbon sphere to the boron source is 1:10-1:50.
6. The method for preparing a multi-stage Kong Peng carbon-nitrogen material as claimed in claim 1, wherein in the step (2), the temperature of the oil bath is controlled to be 60-110 ℃, and the stirring is performed by magnetic stirring at a speed of 100-1200rpm.
7. The method of producing a multi-stage Kong Peng carbon-nitrogen material according to claim 1, wherein in step (3), the gray-black solid is transferred to a ark, and then placed in a tube furnace for high-temperature calcination; the square boat is made of ceramics, quartz or corundum; the furnace tube in the tube furnace is made of ceramics, quartz or corundum; the high-temperature calcination temperature is 800-1200 ℃, and the retention time is 2-8h; the heating rate of the tube furnace is 1-10 ℃/min; the calcination atmosphere is ammonia gas or the mixed gas of ammonia gas and nitrogen gas, and the gas flow rate is 50-200mL/min.
8. A multistage Kong Peng carbon-nitrogen material prepared by the method of any one of claims 1 to 7.
9. The multi-stage Kong Peng carbon-nitrogen material of claim 8, wherein said multi-stage Kong Peng carbon-nitrogen material is comprised of three elements, boron, carbon and nitrogen, and has at least two of microporous, mesoporous and macroporous structures; wherein, the size of the micropores is 0.1-1.8nm; the mesoporous size is 10-50nm; the size of the macropores is 60-200nm.
10. The multi-stage Kong Peng carbon-nitrogen material of claim 8 in the activation of O 2 The application of catalyzing diesel oil oxidation to remove aromatic sulfides.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310881359.3A CN116689014A (en) | 2023-07-18 | 2023-07-18 | Multistage Kong Peng carbon-nitrogen material and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202310881359.3A CN116689014A (en) | 2023-07-18 | 2023-07-18 | Multistage Kong Peng carbon-nitrogen material and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN116689014A true CN116689014A (en) | 2023-09-05 |
Family
ID=87845256
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202310881359.3A Pending CN116689014A (en) | 2023-07-18 | 2023-07-18 | Multistage Kong Peng carbon-nitrogen material and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN116689014A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922296A (en) * | 2014-04-30 | 2014-07-16 | 辽宁大学 | Spherical boron nitride and application thereof |
| CN107265417A (en) * | 2017-07-24 | 2017-10-20 | 江苏大学 | A kind of boron defect boron nitride nanosheet and its production and use |
| WO2017190677A1 (en) * | 2016-05-06 | 2017-11-09 | 苏州汉瀚储能科技有限公司 | Method for preparing boron-doped porous carbon sphere |
| CN110498400A (en) * | 2019-09-27 | 2019-11-26 | 福州大学 | A kind of preparation method and its H of the porous BCN of two-dimensional layer2S selective oxidation application |
| CN112371149A (en) * | 2020-10-23 | 2021-02-19 | 江苏大学 | Preparation method and application of tungsten oxide confinement-supported boron carbon nitrogen nanotube catalyst material |
| CN115036152A (en) * | 2022-07-09 | 2022-09-09 | 电子科技大学 | Hollow spherical boron-carbon-nitrogen material and preparation method thereof |
| CN115072698A (en) * | 2022-05-09 | 2022-09-20 | 中国空间技术研究院 | Heteroatom-doped aperture-controllable two-dimensional carbon material and preparation method thereof |
| CN115448263A (en) * | 2022-08-05 | 2022-12-09 | 深圳市宝硼新材料科技有限公司 | Nano spherical boron nitride and preparation method thereof |
-
2023
- 2023-07-18 CN CN202310881359.3A patent/CN116689014A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103922296A (en) * | 2014-04-30 | 2014-07-16 | 辽宁大学 | Spherical boron nitride and application thereof |
| WO2017190677A1 (en) * | 2016-05-06 | 2017-11-09 | 苏州汉瀚储能科技有限公司 | Method for preparing boron-doped porous carbon sphere |
| CN107265417A (en) * | 2017-07-24 | 2017-10-20 | 江苏大学 | A kind of boron defect boron nitride nanosheet and its production and use |
| CN110498400A (en) * | 2019-09-27 | 2019-11-26 | 福州大学 | A kind of preparation method and its H of the porous BCN of two-dimensional layer2S selective oxidation application |
| CN112371149A (en) * | 2020-10-23 | 2021-02-19 | 江苏大学 | Preparation method and application of tungsten oxide confinement-supported boron carbon nitrogen nanotube catalyst material |
| CN115072698A (en) * | 2022-05-09 | 2022-09-20 | 中国空间技术研究院 | Heteroatom-doped aperture-controllable two-dimensional carbon material and preparation method thereof |
| CN115036152A (en) * | 2022-07-09 | 2022-09-09 | 电子科技大学 | Hollow spherical boron-carbon-nitrogen material and preparation method thereof |
| CN115448263A (en) * | 2022-08-05 | 2022-12-09 | 深圳市宝硼新材料科技有限公司 | Nano spherical boron nitride and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIE ZHU等: "3D-printing of integrated spheres as a superior support of phosphotungstic acid for deep oxidative desulfurization of fuel", 《JOURNAL OF ENERGY CHEMISTRY》, vol. 45, 14 October 2019 (2019-10-14), pages 91 - 97, XP086098804, DOI: 10.1016/j.jechem.2019.10.001 * |
| YANCHEN WEI等: "Synthesis of hierarchical porous BCN using ternary deep eutectic solvent as precursor and template for aerobic oxidative desulfurization", 《MICROPOROUS AND MESOPOROUS MATERIALS》, vol. 293, 2 October 2019 (2019-10-02), pages 109788, XP085945770, DOI: 10.1016/j.micromeso.2019.109788 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109110742B (en) | Mesoporous carbon prepared by manganese compound and preparation method thereof | |
| CN103007944A (en) | Preparation method of graphene-based magnetic composite visible light catalysis material Fe3O4-G-TiO2 | |
| CN110732308B (en) | Preparation method of MOFs-based solid acid ammonia gas adsorbent | |
| CN112844444A (en) | Method for preparing cerium dioxide catalytic material by utilizing carrier pore channel self-adsorption principle | |
| CN113877558A (en) | Ni-Fe hydrotalcite biochar composite catalyst and preparation method and application thereof | |
| CN112938971A (en) | Coconut shell based mesoporous activated carbon and preparation method and application thereof | |
| CN112934217B (en) | Hierarchical porous composite metal oxide and preparation method and application thereof | |
| CN111762770A (en) | Preparation method of oxygen-containing functional group functionalized porous carbon spheres | |
| Tian et al. | Sulfonic acid-functionalized mesoporous carbon/silica as efficient catalyst for dehydration of fructose into 5-hydroxymethylfurfural | |
| CN109967111A (en) | Activate the preparation method and applications of the nitrogen sulphur codope graphene of persulfate | |
| CN113943030A (en) | Biomass carbon-coated nano zero-valent iron composite material for treating chlorobenzene-polluted water body by activating peroxymonosulfate and preparation and application thereof | |
| CN112371149A (en) | Preparation method and application of tungsten oxide confinement-supported boron carbon nitrogen nanotube catalyst material | |
| CN109529903B (en) | Method for preparing nickel-nitrogen co-doped carbon material by using hydrotalcite as template | |
| CN116689014A (en) | Multistage Kong Peng carbon-nitrogen material and preparation method and application thereof | |
| CN113213478A (en) | Porous carbon-based nano material and preparation method and application thereof | |
| CN114433073B (en) | Manganese-based catalyst and preparation method and application thereof | |
| CN114950524B (en) | Porous carbon nitride-tungsten trioxide composite material and preparation method and application thereof | |
| CN114367271B (en) | Load type MnO X Preparation method of @ NiCo-MOF composite material | |
| CN110590175A (en) | Cerium oxide with inverse opal structure and preparation method and application thereof | |
| KR101713658B1 (en) | Process of preparing mesoporous and macroporous carbon | |
| KR101157861B1 (en) | Ordered Mesoporous Carbon Catalyst Loaded with Metal, Method for Preparing the Same and Method for Manufacturing Propanediol from Glycerol Using the Same | |
| CN115212884A (en) | Preparation method and application of catalyst based on metal ion reinforced free radical leading | |
| CN113171785A (en) | Nitrogen-sulfur co-doped ordered mesoporous carbon material and preparation method and application thereof | |
| KR101549058B1 (en) | The method for preparation of meso-porous particles coated with metal oxide and photocatalyst with it | |
| CN113842948A (en) | Nano phenolic resin-based desulfurization catalyst and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |