CN114797826A - Preparation method of carbon nanotube-containing dual-activity desulfurizer - Google Patents
Preparation method of carbon nanotube-containing dual-activity desulfurizer Download PDFInfo
- Publication number
- CN114797826A CN114797826A CN202210467086.3A CN202210467086A CN114797826A CN 114797826 A CN114797826 A CN 114797826A CN 202210467086 A CN202210467086 A CN 202210467086A CN 114797826 A CN114797826 A CN 114797826A
- Authority
- CN
- China
- Prior art keywords
- carbon nanotube
- dichloromethane
- preparation
- carboxylated
- carbon nano
- 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
Images
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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
- B01J21/185—Carbon nanotubes
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0234—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds
- B01J31/0271—Nitrogen-, phosphorus-, arsenic- or antimony-containing compounds also containing elements or functional groups covered by B01J31/0201 - B01J31/0231
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/158—Carbon nanotubes
- C01B32/168—After-treatment
- C01B32/174—Derivatisation; Solubilisation; Dispersion in solvents
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
Abstract
The invention belongs to the technical field of environmental protection, and particularly relates to a preparation method of a carbon nanotube-containing dual-activity desulfurizer. The preparation method of the invention is to carry out surface modification on carboxyl bonds and nitroxide radicals to improve the dispersion performance of the carbon nano-tubes in the solution, and the carboxylated carbon nano-tubes are carboxylated multi-wall carbon nano-tubes or carboxylated single-wall carbon nano-tubes. The prepared desulfurizer can be recycled, so that the catalytic oxidation process is simplified, and the production cost is reduced; has obvious degradation effect on thiophene, low toxicity, high product purity and desulfurization efficiency of over 90 percent, can achieve deep desulfurization, and can be widely used in the heavy crude oil and heavy oil deep processing process.
Description
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to a preparation method of a carbon nanotube-containing dual-activity desulfurizer.
Background
In the heavy oil and heavy oil deep processing process, chemical raw material gases produced by using natural gas, petroleum, coal and the like as raw materials contain some sulfides, wherein inorganic sulfur mainly exists in the form of hydrogen sulfide, and organic sulfur mainly comprises carbonyl sulfide, carbon disulfide, thiophene, mercaptan and dibenzothiophene. The existence of sulfide can corrode equipment, pollute the environment and influence the quality of products; secondly, the sulfide easily poisons the catalyst in the chemical raw material gas processing and treating process; the sulfide can generate sulfur oxide after being oxidized, and the sulfur oxide is combined with water molecules in the atmosphere to form acid rain and cause environmental pollution. The importance of fuel oil in daily life is self-evident, and the limit of sulfur content of vehicle fuel oil is more severe along with the environmental protection laws and regulations in China, so that the raw material gas must be desulfurized, and sulfides in the raw material gas are removed to meet different requirements. The ultralow sulfuration of the crude oil is a necessary choice for national civilian life, environmental protection and ecology at present.
The oxidative desulfurization technology is one of the key technologies which are researched more at present and can carry out deep desulfurization on fuel oil, and the nitroxide radical is an organic compound containing C, N, O and spin one electron. Because single electrons exist in the molecules of the nitroxide radicals, the single electrons have the distribution characteristics on nitrogen atoms and oxygen atoms, the single electrons can be used in the field of oxidative desulfurization by obtaining electrons, and secondly, the nitroxide radicals are simple to prepare, safe, nontoxic and low in price, but are difficult to recycle due to the water solubility of small molecules.
The carbon nano tube has a porous graphite structure, is a potential high-performance adsorbent, is combined with a large number of surface groups, and has huge surface area and surface hydrophobicity; however, the carbon nanotubes are very easily aggregated in an aqueous solution, and the available sites for binding with a target adsorption object are greatly reduced, thereby limiting the application in practical production.
Disclosure of Invention
The invention provides a preparation method of a carbon nanotube-containing dual-active desulfurizer, which aims to reduce the problem of free radical agglomeration and simultaneously connect more active free radical groups on a carbon nanotube to prepare a desulfurizer with higher activity.
In order to achieve the aim, the preparation method of the carbon nanotube-containing bifunctional fuel oil desulfurizer provided by the invention comprises the following steps:
weighing 0.200-0.800g of carboxylated carbon nanotube and 15-50ml of thionyl chloride, placing the materials in a three-necked flask, heating and refluxing for 4-8h, evaporating the redundant thionyl chloride, and placing the reaction flask in an ice water bath for cooling; then adding 50-200ml of dichloromethane and 2-6ml of triethylamine, slowly dripping 30-100ml of dichloromethane solution dissolved with 1.0-6.0g of L-prolinol into a three-necked bottle, removing an ice water bath after dripping, stirring for 5-15h at room temperature, and removing the solvent to obtain a light yellow intermediate L-1;
weighing 0.2-1.5g of the light yellow intermediate L-1, 0.19-1.4g of TCCA (trichloroisocyanuric acid) and 10-45mL of dichloromethane, placing the mixture into a 50-250mL single-neck flask, placing the flask into an ice bath, and adding a trace amount of TEMPO (2,2,6, 6-tetramethylpiperidine oxide) to initiate reaction; stirring for 5-10 min, removing the ice water bath, stirring at room temperature for 15-30min, suction filtering, washing the filter cake with a small amount of dichloromethane, collecting orange filtrate, washing, and drying to obtain a white oily intermediate L-2;
weighing the above 0.2-1.2g white oily intermediate L-2, 0.12-0.72g 2-3-dihydroxylamine-2-3-dimethylbutane and 20-50ml chromatographic methanol, placing into a single-neck flask, heating and refluxing for 10-18 hours; removing the solvent by rotary evaporation, dissolving the residual substance in 20-80ml dichloromethane, and placing in ice water bath; adding 30-200mg of sodium nitrite, refluxing and stirring for 1-5 h. Removing dichloromethane under reduced pressure to obtain dark red viscous liquid, centrifuging, washing, and vacuum pumping to obtain yellowish viscous product free radical.
The washing and drying process of the orange-yellow viscous liquid comprises the following steps: the orange-yellow viscous liquid was washed with 10 to 30ml of a saturated sodium carbonate solution, a 0.1mol/L hydrochloric acid solution and a saturated saline solution in this order, and the resulting organic layer was diluted in color, dried over anhydrous sodium sulfate, and the solvent was removed to obtain a white oily intermediate L-2.
The deep red solution is centrifugally washed by distilled water and absolute ethyl alcohol respectively.
The carboxylated carbon nanotube is a carboxylated multi-wall carbon nanotube or a carboxylated single-wall carbon nanotube.
Compared with the prior art for preparing the desulfurization catalyst, the invention has the beneficial effects that:
1) according to the invention, the carboxyl bond and the nitroxide radical are subjected to surface modification to improve the dispersion performance of the carbon nanotube in the solution, so that the mutual aggregation of the carbon nanotube in the aqueous solution can be reduced, and the interaction between the carbon nanotube and an adsorption object is greatly increased, thereby improving the removal capacity of the carbon nanotube in the pre-enrichment of pollutants, and experiments show that the carbon nanotube functionalized by combining the nitroxide radical is easier to disperse in water; meanwhile, the carbon nano tube enables the nitroxide free radicals to be easily recycled, and the defect that the nitroxide free gene micromolecules are good in water solubility and difficult to recycle is overcome;
2) the carbon nanotube-containing bifunctional fuel oil desulfurizer prepared by the invention can achieve good desulfurization effect by introducing air to oxidize fuel oil at room temperature, and does not need an auxiliary catalyst;
3) the invention uses oxygen in the air as the circulating oxidant, realizes the recycling of the desulfurizer, simplifies the catalytic oxidation process and reduces the production cost;
4) the desulfurization test proves that: the desulfurizer has obvious degradation effect on thiophene, can rapidly degrade sulfide-thiophene in fuel, has low toxicity and high product purity, achieves the desulfurization efficiency of more than 90 percent, and can achieve deep desulfurization;
5) the application range is wide: the method can be used for deep desulfurization of chemical raw material gas produced by taking natural gas, petroleum, coal and the like as raw materials in the processes of crude oil heaving and heavy oil deep processing.
Drawings
FIG. 1 is a process for preparing a dual active desulfurization agent containing carbon nanotubes according to the present invention;
FIG. 2 is a result of an experiment of simulating desulfurization activity of fuel oil by oxidizing a multi-walled carbon nanotube-containing dual-activity desulfurizer;
FIG. 3 is a graph showing the results of a cycle stability test of a double-active desulfurizing agent containing multi-walled carbon nanotubes.
Detailed Description
The present invention will be described in further detail with reference to specific examples, but the embodiments of the present invention include, but are not limited to, the scope shown in the following examples.
The invention provides a preparation method of a carbon nanotube-containing dual-activity desulfurizer.
Embodiment 1 a method for preparing a double-activity desulfurizer containing multi-walled carbon nanotubes, comprising the following steps:
weighing 0.500g of carboxylated multi-walled carbon nanotube MWCTs-COOH and 20ml of thionyl chloride, placing the mixture in a 250ml three-necked flask, heating and refluxing for 5 hours, evaporating excessive thionyl chloride, and placing the reaction flask in an ice-water bath for cooling. Then 100ml of dichloromethane and 5ml of triethylamine were added, 60ml of dichloromethane solution containing 3.0g of L-prolinol (30mmol) was slowly added dropwise to a three-necked flask, after the dropwise addition, the ice-water bath was removed, and the mixture was stirred at room temperature for 10 hours to remove the solvent, thereby obtaining a pale yellow intermediate L-1(2.4 g). IR (KBr)3436,2929,1752,1636,1379,1197,756cm -1 .
1.0g of the intermediate L-1(4.0mmol), 0.93g of TCCA (trichloroisocyanuric acid) and 30ml of dichloromethane are weighed and placed in a 100ml single-neck flask, ice bath is placed, and 0.006g of TEMPO (2,2,6, 6-tetramethylpiperidine oxide) is added for initiating the reaction. After stirring for 8 minutes, the ice-water bath was removed, the mixture was stirred at room temperature for 20 minutes, filtered and the filter cake was washed with 20mL of dichloromethane, the filtrate was collected and orange-yellow in color, and 20mL of saturated carbonic acid was addedThe organic layer was washed with sodium solution, hydrochloric acid solution (0.1mol/L) and saturated brine in this order to obtain a pale organic layer, which was then dried over anhydrous sodium sulfate, and the solvent was removed to obtain intermediate L-2(0.72g) as a white oily substance. IR (KBr)3426,2365,1711,1551,1388,1185,734cm -1 .
0.62g (2.5mmol) of intermediate L-2, 0.37g of 2-3-dihydroxylamine-2-3-dimethylbutane (2.5mmol) and 30ml of chromatographic methanol were weighed into a 100ml single-neck flask and heated under reflux for 16 hours. The solvent was removed by rotary evaporation and the remaining material was dissolved in 40ml dichloromethane and placed in an ice water bath with stirring switched on. Sodium nitrite (103mg, 1.5mmol) was added and stirred under reflux for 2 h. Removing dichloromethane under reduced pressure to obtain dark red viscous liquid, centrifuging with distilled water and anhydrous ethanol respectively, washing under reduced pressure, and draining to obtain yellowish viscous product free radical L-3(0.23g) IR (KBr)3422,2840,1716,1558,1430,1106,768cm -1 .
Embodiment 2 a method for preparing a double-activity desulfurizer containing single-walled carbon nanotubes, comprising the following steps:
0.300g of carboxylated single-walled carbon nanotube SWNT-COOH and 15ml of thionyl chloride are weighed and placed in a 250ml three-necked flask, heated and refluxed for 5 hours, excessive thionyl chloride is evaporated, and the reaction flask is placed in an ice-water bath for cooling. Then 60ml of dichloromethane and 3ml of triethylamine are added, 30ml of dichloromethane solution dissolved with 1.5g of L-prolinol (15mmol) is slowly dripped into a three-necked flask, after the dripping is finished, an ice water bath is removed, the mixture is stirred for 8 hours at room temperature, and the solvent is removed to obtain a light yellow intermediate L-1(0.7 g). IR (KBr)3390,2899,1716,1598,1333,1098,743cm -1 .
0.5g of the intermediate L-1(2.0mmol), 0.46g of TCCA (trichloroisocyanuric acid) and 20ml of dichloromethane are weighed and placed in a 100ml single-neck flask, ice bath is carried out, and 0.003g of TEMPO (2,2,6, 6-tetramethylpiperidine oxide) is added to initiate the reaction. After stirring for 8 minutes, the ice-water bath was removed, the mixture was stirred at room temperature for 16 minutes, the filter cake was filtered and washed with 10mL of dichloromethane, the filtrate was collected and orange-yellow in color, the filtrate was washed with 10mL of a saturated sodium carbonate solution, a hydrochloric acid solution (0.1mol/L) and a saturated saline solution, respectively, and the resulting organic layer was diluted in color, dried over anhydrous sodium sulfate, and the solvent was removed to give intermediate L-2(0.4g) as a white oily substance. IR (KBr))3396,2289,1726,1566,1379,1158,756cm -1 .
0.3g (1.2mmol) of intermediate L-2, 0.2g of 2-3-dihydroxylamine-2-3-dimethylbutane (1.3mmol) and 25ml of chromatographic methanol were weighed into a 100ml single-neck flask and heated under reflux for 12 hours. The solvent was removed by rotary evaporation and the remaining material was dissolved in 30ml dichloromethane and placed in an ice water bath with stirring switched on. Sodium nitrite (56mg, 0.7mmol) was added and stirred under reflux for 1.5 h. Removing dichloromethane under reduced pressure to obtain dark red viscous liquid, centrifuging with distilled water and anhydrous ethanol respectively, washing under reduced pressure, and draining to obtain yellowish viscous product free radical L-3(0.15g) IR (KBr)3395,2813,1743,1569,1396,1099,725cm -1 .
The desulfurization experiment of the double-activity desulfurizer containing the multi-wall carbon nano-tubes in the example 1 on thiophene model fuel oil is as follows: 15mL of FCC gasoline is put into a reactor with a condensation reflux and magnetic stirring device, and a proper amount of air is introduced. The double-activity desulfurizer containing the multi-wall carbon nano-tube prepared in the example 1 is added at room temperature, and the mixture is magnetically stirred to react for 1 hour. The mixture was filtered, the filtrate was diluted with dichloromethane, and the supernatant was taken and the product sulfur concentration was measured with an ultraviolet fluorescence analyzer, and the desulfurization rate was calculated. The catalyst after reaction is washed by ethanol and distilled water and dried at (105 +/-5) DEG C for further use.
In the formula, C. The sulfur mass concentration before reaction (mg/L), C the sulfur mass concentration after reaction (mg few), and eta the desulfurization rate (%).
The experimental results are as follows:
the desulfurization data obtained by the desulfurization rate of the thiophene model fuel oil by the double-activity desulfurizer containing the multi-wall carbon nano tubes is plotted, and as can be seen from the graph 2, compared with a single multi-wall carbon nano tube, the content of thiophene is gradually reduced along with the extension of the stirring time, and the degradation effect is obvious. The above description is only a preferred embodiment of the present invention, and is not intended to limit the scope of the present invention. Fig. 3 shows that after the double-activity desulfurizer containing the multiwalled carbon nanotubes is recycled for 5 times, the catalytic activity of desulfurization is weakened, but the weakening is not obvious and still reaches over 90 percent, which indicates that the double-activity desulfurizer containing the multiwalled carbon nanotubes prepared by the invention has stable performance and can still keep good desulfurization effect after being recycled for many times.
Claims (4)
1. A preparation method of a carbon nanotube-containing bifunctional fuel oil desulfurizer comprises the following steps:
weighing 0.200-0.800g of carboxylated carbon nanotube and 15-50ml of thionyl chloride, placing the materials in a three-necked flask, heating and refluxing for 4-8h, evaporating the redundant thionyl chloride, and placing the reaction flask in an ice water bath for cooling; then adding 50-200ml of dichloromethane and 2-6ml of triethylamine, slowly dripping 30-100ml of dichloromethane solution dissolved with 1.0-6.0g of L-prolinol into a three-necked bottle, removing an ice water bath after dripping, stirring for 5-15h at room temperature, and removing the solvent to obtain a light yellow intermediate L-1;
weighing light yellow intermediate L-10.2-1.5 g, 0.19-1.4g TCCA (trichloroisocyanuric acid) and 10-45mL dichloromethane, placing in a 50-250mL single-neck flask, putting in an ice bath, and adding a trace amount of TEMPO (2,2,6, 6-tetramethylpiperidine oxide) to initiate reaction; stirring for 5-10 min, removing the ice water bath, stirring at room temperature for 15-30min, suction filtering, washing the filter cake with a small amount of dichloromethane, collecting orange filtrate, washing, and drying to obtain a white oily intermediate L-2;
weighing 0.2-1.2g of white oily intermediate L-2, 0.12-0.72g of 2-3-dihydroxylamine-2-3-dimethylbutane and 20-50ml of chromatographic methanol, putting into a single-neck flask, and heating and refluxing for 10-18 hours; removing the solvent by rotary evaporation, dissolving the residual substance in 20-80ml dichloromethane, and placing in ice water bath; adding 30-200mg of sodium nitrite, refluxing and stirring for 1-5 h;
removing dichloromethane under reduced pressure to obtain dark red viscous liquid, centrifuging, washing, and vacuum pumping to obtain yellowish viscous product free radical.
2. The preparation method of the carbon nanotube-containing bifunctional fuel oil desulfurizing agent according to claim 1, which is characterized by comprising the following steps:
the washing and drying process of the orange viscous liquid is as follows: the orange-yellow viscous liquid was washed with 10 to 30ml of a saturated sodium carbonate solution, a 0.1mol/L hydrochloric acid solution and a saturated saline solution in this order, and the resulting organic layer was diluted in color, dried over anhydrous sodium sulfate, and the solvent was removed to obtain a white oily intermediate L-2.
3. The preparation method of the carbon nanotube-containing bifunctional fuel oil desulfurizing agent according to claim 1 or 2, which is characterized by comprising the following steps: and centrifugally washing the dark red solution by using distilled water and absolute ethyl alcohol respectively.
4. The preparation method of the carbon nanotube-containing bifunctional fuel oil desulfurizing agent according to claim 3, which is characterized by comprising the following steps: the carboxylated carbon nano tube is a carboxylated multi-wall carbon nano tube or a carboxylated single-wall carbon nano tube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210467086.3A CN114797826A (en) | 2022-04-29 | 2022-04-29 | Preparation method of carbon nanotube-containing dual-activity desulfurizer |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210467086.3A CN114797826A (en) | 2022-04-29 | 2022-04-29 | Preparation method of carbon nanotube-containing dual-activity desulfurizer |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114797826A true CN114797826A (en) | 2022-07-29 |
Family
ID=82508868
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210467086.3A Pending CN114797826A (en) | 2022-04-29 | 2022-04-29 | Preparation method of carbon nanotube-containing dual-activity desulfurizer |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114797826A (en) |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2588109A1 (en) * | 2004-11-16 | 2006-05-26 | Hyperion Catalysis International, Inc. | Methods for preparing catalysts supported on carbon nanotube networks |
| CN105536708A (en) * | 2015-12-28 | 2016-05-04 | 北京林业大学 | Novel composite material based on metal-organic framework material and carbon nanotube and preparation method of novel composite material |
| US20170121611A1 (en) * | 2015-10-29 | 2017-05-04 | King Fahd University Of Petroleum And Minerals | Method for removing sulfur compounds from a hydrocarbon fluid using an adsorbent |
| CN111943935A (en) * | 2020-08-21 | 2020-11-17 | 西安工业大学 | Prolinol rapid desulfurizing agent and preparation method thereof |
| CN112430237A (en) * | 2020-12-11 | 2021-03-02 | 西安工业大学 | Desulfurizing agent containing phthalocyanine double activity, preparation method and application thereof |
-
2022
- 2022-04-29 CN CN202210467086.3A patent/CN114797826A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2588109A1 (en) * | 2004-11-16 | 2006-05-26 | Hyperion Catalysis International, Inc. | Methods for preparing catalysts supported on carbon nanotube networks |
| US20170121611A1 (en) * | 2015-10-29 | 2017-05-04 | King Fahd University Of Petroleum And Minerals | Method for removing sulfur compounds from a hydrocarbon fluid using an adsorbent |
| CN105536708A (en) * | 2015-12-28 | 2016-05-04 | 北京林业大学 | Novel composite material based on metal-organic framework material and carbon nanotube and preparation method of novel composite material |
| CN111943935A (en) * | 2020-08-21 | 2020-11-17 | 西安工业大学 | Prolinol rapid desulfurizing agent and preparation method thereof |
| CN112430237A (en) * | 2020-12-11 | 2021-03-02 | 西安工业大学 | Desulfurizing agent containing phthalocyanine double activity, preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 焦庆玲等: "多壁碳纳米管吸附噻吩的研究", 纳米科技, no. 05, pages 11 - 14 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Li et al. | A lignin-biochar with high oxygen-containing groups for adsorbing lead ion prepared by simultaneous oxidization and carbonization | |
| Tahir et al. | Deep eutectic solvents as alternative green solvents for the efficient desulfurization of liquid fuel: A comprehensive review | |
| Wang et al. | Performance evaluation of the carbon nanotubes supported Cs2. 5H0. 5PW12O40 as efficient and recoverable catalyst for the oxidative removal of dibenzothiophene | |
| Xu et al. | Review on the ionic liquids affecting the desulfurization of coal by chemical agents | |
| Ma et al. | Mass production of highly fluorescent full color carbon dots from the petroleum coke | |
| Zhou et al. | Constructing efficient ɑ-Fe2O3/g-C3N4/HNTs-loaded heterojunction photocatalysts for photocatalytic oxidative desulfurization: Influencing factors, kinetics, and mechanism | |
| CN112430237B (en) | Desulfurizing agent containing phthalocyanine double activity, preparation method and application thereof | |
| CN112979985A (en) | Composite metal organic framework material and preparation method thereof | |
| Wang et al. | Ultra‐Deep Oxidative Desulfurization of Model Oil Catalyzed by In Situ Carbon‐Supported Vanadium Oxides Using Cumene Hydroperoxide as Oxidant | |
| Ren et al. | Fe–N complex biochar as a superior partner of sodium sulfide for methyl orange decolorization by combination of adsorption and reduction | |
| He et al. | Preparation and adsorption studies of β‐cyclodextrin grafted onto multi‐walled carbon nanotube | |
| Dou et al. | Removal of gaseous H2S using microalgae porous carbons synthesized by thermal/microwave KOH activation | |
| Gao et al. | Desulfurization of liquid hydrocarbon fuels via Cu2O catalyzed photo-oxidation coupled with liquid–liquid extraction | |
| CN114797826A (en) | Preparation method of carbon nanotube-containing dual-activity desulfurizer | |
| CN112645426B (en) | Modified nano ferrous sulfide composite material and preparation method and application thereof | |
| US20200216762A1 (en) | Process for oxidation of organosulfur compounds | |
| CN116444531A (en) | Method for catalyzing and desulfurizing amphiphilic cobalt phthalocyanine and application | |
| Ren et al. | Nontoxic fluorescent wood with reconstructed porous structure and increased sorption sites towards selective detection and efficient removal of Hg (II) | |
| Li et al. | Synthesis of carboxyl-rich biosorbent by UV-induced graft polymerization method for high efficiency adsorption of Ce 3+ from aqueous solution: activation and adsorption mechanism | |
| Bai et al. | V2CTx MXene: A Promising Catalyst for Low-Temperature Aerobic Oxidative Desulfurization | |
| CN110560177B (en) | Preparation method and application of carbonized silkworm mercerization catalyst | |
| Gao et al. | Encapsulated peroxophosphotungstates catalyst into magnetic MOF: Magnetically recoverable heterogeneous high efficiency desulfurization catalyst | |
| CN107892940A (en) | A kind of method that persulfate of fluid coupling containing cobalt ions carries out desulfurizing oil | |
| CN111961001B (en) | Desulfurizing agent for removing dibenzothiophene and 4, 6-dimethyldibenzothiophene in oil product and preparation method and application thereof | |
| 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 |