GB2600900A - Monolithic catalyst preparation method employing 3D printing, and application of monolithic catalyst - Google Patents
Monolithic catalyst preparation method employing 3D printing, and application of monolithic catalyst Download PDFInfo
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- GB2600900A GB2600900A GB2202504.3A GB202202504A GB2600900A GB 2600900 A GB2600900 A GB 2600900A GB 202202504 A GB202202504 A GB 202202504A GB 2600900 A GB2600900 A GB 2600900A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- 238000010146 3D printing Methods 0.000 title claims abstract description 12
- 239000000295 fuel oil Substances 0.000 claims abstract description 19
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- IYDGMDWEHDFVQI-UHFFFAOYSA-N phosphoric acid;trioxotungsten Chemical compound O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.O=[W](=O)=O.OP(O)(O)=O IYDGMDWEHDFVQI-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007639 printing Methods 0.000 claims abstract description 3
- 150000003568 thioethers Chemical class 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 238000000016 photochemical curing Methods 0.000 claims description 6
- 238000002791 soaking Methods 0.000 claims description 6
- 238000002207 thermal evaporation Methods 0.000 claims description 6
- 238000001354 calcination Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000011347 resin Substances 0.000 claims description 4
- 229920005989 resin Polymers 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 239000002994 raw material Substances 0.000 claims description 3
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229920000058 polyacrylate Polymers 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 239000003921 oil Substances 0.000 abstract description 32
- 238000006477 desulfuration reaction Methods 0.000 abstract description 30
- 230000023556 desulfurization Effects 0.000 abstract description 30
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 abstract description 7
- 238000000034 method Methods 0.000 abstract description 7
- 230000001590 oxidative effect Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- -1 DBT Chemical class 0.000 abstract description 3
- 238000011068 loading method Methods 0.000 abstract description 2
- 238000003763 carbonization Methods 0.000 abstract 1
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 description 18
- 230000000694 effects Effects 0.000 description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 10
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 9
- 150000004763 sulfides Chemical class 0.000 description 9
- 229910052717 sulfur Inorganic materials 0.000 description 9
- 239000011593 sulfur Substances 0.000 description 9
- 238000005516 engineering process Methods 0.000 description 7
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 6
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229960000583 acetic acid Drugs 0.000 description 5
- 239000012362 glacial acetic acid Substances 0.000 description 5
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- XOCUXOWLYLLJLV-UHFFFAOYSA-N [O].[S] Chemical compound [O].[S] XOCUXOWLYLLJLV-UHFFFAOYSA-N 0.000 description 3
- 238000004817 gas chromatography Methods 0.000 description 3
- 150000003464 sulfur compounds Chemical class 0.000 description 3
- 239000008399 tap water Substances 0.000 description 3
- 235000020679 tap water Nutrition 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 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 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000000769 gas chromatography-flame ionisation detection Methods 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y80/00—Products made by additive manufacturing
-
- 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
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
-
- B01J35/56—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
- B01J37/0203—Impregnation the impregnation liquid containing organic compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0215—Coating
- B01J37/0219—Coating the coating containing organic compounds
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/28—Phosphorising
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B33—ADDITIVE MANUFACTURING TECHNOLOGY
- B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
- B33Y10/00—Processes of additive manufacturing
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G27/00—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation
- C10G27/04—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen
- C10G27/12—Refining of hydrocarbon oils in the absence of hydrogen, by oxidation with oxygen or compounds generating oxygen with oxygen-generating compounds, e.g. per-compounds, chromic acid, chromates
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Abstract
A monolithic catalyst preparation method employing 3D printing, and an application of a monolithic catalyst in oxidative desulfurization of fuel oil. The method comprises: printing a three-dimensional model using a light-curing printer, and then performing carbonization at a high temperature; and loading a formed three-dimensional carbide with phosphotungstic acid so as to prepare and obtain a monolithic catalyst for deep oxidative desulfurization by means of 3D printing. The prepared catalyst can be easily separated from oil after the reaction has ended, and the operation is simple. Moreover, the catalyst facilitates the removal of sulfides such as DBT, 4-MDBT, and 4,6-DMDBT from model oil, and provides good catalytic performance and cycle performance.
Description
PREPARATION METHOD OF 3D-PRINTED MONOLITHIC CATALYST AND
APPLICATION THEREOF
TECHNICAL FIELD
The present invention belongs to the field of catalytic material preparation, and particularly relates to a preparation method of a 3D-printed monolithic catalyst, and an application thereof in oxidative desulfurization of fuel oil.
BAC KGROUND
The SOx emissions from the combustion of sulfur compounds in fuel oil have become one of the main sources of environmental pollution. With the increasingly prominent environmental problems, the requirements for sulfur compounds in the fuel oil become more and more strict In industry, the sulfur compounds in the fuel oil are usually removed by hydrodesulfurization (HDS), but hydrodesulfurization needs to be realized at high reaction temperature and operating pressure.
However, hydrodesulfurization has a poor activity on aromatic sulfur compounds, and more stringent reaction conditions are needed to realize deep desulfurization by the HDS process. Therefore, many new desulfurization technologies, such as extraction desulfurization (EDS), adsorption desulfurization (ADS) and oxidative desulfurization (ODS), have been widely studied. Among these methods, ODS has a high activity on the aromatic sulfur compounds under mild conditions, and is considered as a promising desulfurization method.
As a new manufacturing strategy, 3D printing technology has attracted more and more attention around the world. With the 3D printing technology, the molding of catalysts with different structures, especially those with complex structures, can be easily realized through fewer steps. In addition, the 3D printing technology can significantly improve the utilization rate of raw materials.
At present, a technology of preparing catalysts by combining 3D printing with oxidative desulfurization has not been reported yet.
SUMMARY
According to the present invention, a monolithic catalyst is directly generated by 3D printing, so that the catalyst is easily separated from the reaction system. The monolithic catalyst built by the 3D printing technology can overcome the shortcomings of traditional powder catalysts, thus making the 3D printing technology more promising in oxidative desulfurization of fuel oil.
The present invention provides a 3D-printed monolithic catalyst and a preparation method and application thereof.
In order to achieve the above-mentioned objects, the present invention provides a preparation method of a 3D-printed monolithic catalyst, comprising the following steps of: (1) designing a three-dimensional model with a macroporous structure by 3Ds Max software, and printing the designed three-dimensional model by a photocuring 3D printer; (2) placing the printed three-dimensional model in a temperature programmed tube furnace, heating to a certain temperature for calcination under the protection of inert gas, and naturally cooling to room temperature to obtain a carbonized three-dimensional carbide; and (3) dissolving a certain amount of phosphotungstic acid in ethanol, adding the three-dimensional carbide prepared in step (2) into a reaction flask, magnetically stirring, soaking, removing the ethanol solution by thermal evaporation, and drying in an oven to obtain the catalyst.
In step (1), a 3D printing raw material is photocurable resin, and a main component of the photocurable resin is an acrylate polymer.
In step (1), the three-dimensional model by the 3D printer is a porous and hollow white transparent three-dimensional model.
In step (2), the inert gas is nitrogen.
In step (2), the calcination is performed at 800°C to 900°C for 2 hours; and the temperature programmed rate is 0.5°C/min.
In step (3), a capacity of the phosphotungstic acid in the catalyst is 1% to 10%, and the magnetic stirring lasts for 24 hours.
The 3D-printed monolithic catalyst obtained by the method above is a porous three-dimensional structure.
The foregoing 3D-printed monolithic catalyst may be used for removing sulphides in fuel oil.
An application method of the 3D-printed monolithic catalyst above in oxidative desulfurization of fuel oil, wherein a specific application method comprises: under the condition of magnetic stirring, adding the 3D-printed monolithic catalyst, an H202 aqueous solution and a glacial acetic acid into fuel oil for reaction, and simply filtering the catalyst after the reaction to realize the separation of the catalyst from the fuel oil.
The fuel oil comprises DBT model oil, 4-MDBT model oil and 4,6-DMDBT model oil, wherein the desulfurization effect to the DBT model oil is the best.
The desulfurization effect is the best when the desulfurization reaction temperature is 70°C.
The desulfurization effect is the best when the capacity of the phosphotungstic acid in the catalyst is 7%.
The desulfurization effect is the best when a molar ratio of the sulfides in the fuel oil to the H202 is 1:8.
The oxidation reaction conditions of the present invention are mild, and the reaction is performed at normal temperature and pressure.
The present invention provides a preparation method of a novel 3D-printed monolithic catalyst. The catalyst can efficiently remove sulfides from fuel oil, is easy to operate and separate, and can be recycled. The preparation method is simple with low cost.
The present invention has the following advantages.
1. By loading the phosphotungstic acid with high activity, the 3D-printed monolithic catalyst has a good desulfurization effect, and the purpose of reducing the amount of the catalyst is achieved.
2. The obtained 3D-printed monolithic catalyst can achieve the effects of simple operation, 15 easy separation and recovery.
BRIEF DESCRIPTION OF DRAWINGS
In FIG. 1, (a) is a 3Ds Max design drawing of Embodiment 1, (b) is an optical photograph of a 3D-printed three-dimensional model, (c) is an optical photograph of a three-dimensional carbide, and (d) is an optical photograph of a 3D-printed monolithic catalyst.
FIG. 2 is a FT-IR graph of the prepared 3D-printed monolithic catalyst. FIG. 3 is an XRD graph of the prepared 3D-printed monolithic catalyst.
FIG. 4 is a catalytic activity curve of the 3D-printed monolithic catalyst prepared in Embodiment 1 on different sulfides in model oil.
FIG. 5 is an activity graph of the 3D-printed monolithic catalyst prepared in Embodiment 1 on a DBT sulfide in the model oil after five cycles.
DETAILED DESCRIPTION
The preparation of the 3D-printed monolithic catalyst and the effects for desulfurization of 30 fuel oil thereof will be described in detail with reference to the embodiments below. The technical solutions of the present invention are not limited to the specific embodiments listed below, but also include any combination of the various specific embodiments.
A preparation method of a 3D-printed monolithic catalyst according to the embodiments specifically comprises the following steps.
(1) A three-dimensional model is designed by 3Ds Max software, and the designed three-dimensional model is printed by a photocuring 3D printer.
(2) The 3D-printed three-dimensional model is placed in a temperature programmed tube furnace, heated to 800°C to 900°C at a rate of 0.5°C/min in a nitrogen atmosphere and kept for 2 5 hours, and naturally cooled to room temperature to obtain a carbonized three-dimensional carbide.
(3) A certain amount of phosphotungstic acid is dissolved in ethanol, and then, the three-dimensional carbide prepared is added into a reaction flask, and magnetically stirred for 24 hours. After soaking, the ethanol solution is removed by thermal evaporation, and the obtained catalyst is dried in an oven.
The following are the fuel oil types used in the embodiments: (1) DBT model oil is model oil with a sulfur content of 200 ppm prepared by dissolving dibenzothiophene (DBT) in dodecane.
(2) 4-MDBT model oil is model oil with a sulfur content of 200 ppm prepared by dissolving 4-rnethyldibenzotthopfiene (4-MDBT) in dodecane.
(3) 4,6-DMDBT model oil is model oil with a sulfur content of 200 ppm by dissolving 4,6-dimethyldibenzothiophene (4,6-DMDBT) in dodecane.
An oil product is added into a double-necked flask, and then a catalyst, a glacial acetic acid and H201 are added into the oil product, magnetically stirred at a set temperature, and then the catalyst is separated from the oil product by simple filtration. A sulfide content in the oil product is 20 detected by gaschromatograph (GC-FID) during the reaction to calculate a desulfurization rate: Total sulfur content E oil product -Residual sulfur content E oil product Desulfurization rate i,% I=x 100% Total sulfur content E oil product In the following embodiments, the preparation method of the 3D-printed monolithic catalyst was as follows.
Embodiment 1: (1) A three-dimensional sphere model with a diameter of 1 cm was designed by 3Ds Max soft ware, and the designed three-dimensional model was printed by a photocuring 3D printer.
(2) The 3D-printed three-dimensional model was placed in a temperature programmed tube fur nace, heated to 900°C at a rate of 0.5°C/min in a nitrogen atmosphere and kept for 2 hours, and nat urally cooled to room temperature to obtain a carbonized three-dimensional carbide.
(3) A certain amount of phosphotungstic acid was dissolved in ethanol, and then, the three-dim ensional carbide prepared was added into a reaction flask, and magnetically stirred for 24 hours. Aft er soaking, the ethanol solution was removed by thermal evaporation, and the obtained catalyst was dried in an oven to obtain the catalyst with a diameter of 0.5 cm.
Embodiment 2: (1) A three-dimensional sphere model was designed by 3Ds Max software, and the designed th ree-dimensional model was printed by a photocuring 3D printer.
(2) The 3D-printed three-dimensional model was placed in a temperature programmed tube fur nace, heated to 850°C at a rate of 0.5°C/min in a nitrogen atmosphere and kept for 2 hours, and nat 5 urally cooled to room temperature to obtain a carbonized three-dimensional carbide.
(3) A certain amount of phosphotungstic acid was dissolved in ethanol, and then, the three-dim ensional carbide prepared was added into a reaction flask, and magnetically stirred for 24 hours. Aft er soaking, the ethanol solution was removed by thermal evaporation, and the obtained catalyst was dried in an oven.
Embodiment 3: (1) A three-dimensional sphere model was designed by 3Ds Max software, and the designed th ree-dimensional model was printed by a photocuring 3D printer.
(2) The 3D-printed three-dimensional model was placed in a temperature programmed tube fur nace, heated to 800°C at a rate of 0.5°C/min in a nitrogen atmosphere and kept for 2 hours, and nat 15 urally cooled to room temperature to obtain a carbonized three-dimensional carbide.
(3) A certain amount of phosphotungstic acid was dissolved in ethanol, and then, the three-dim ensional carbide prepared was added into a reaction flask, and magnetically stirred for 24 hours. Aft er soaking, the ethanol solution was removed by thermal evaporation, and the obtained catalyst was dried in an oven.
Desulfurization test 1: mL of DBT model oil were added into a double-necked flask, five 3D-printed monolithic catalysts (about 0.020 g) obtained in Embodiment 1, 1 mL of glacial acetic acid and 30wt%11202 were added into the model oil, a molar ratio of sulfides in the fuel oil to the 11202 being 1: 8 (oxygen-sulfur ratio was 8), and magnetically stirred and reacted in a constant temperature water bath environment of 70°C, and then, simultaneously condensed and refluxed with tap water. During the reaction, samples were taken at regular intervals, and the sulfur contents of the samples were detected by gas chromatography to calculate the desulfurization rates. The 3D-printed monolithic catalyst prepared by Embodiment 1 had a desulfurization rate of 100% on the sulphide DBT in the model oil within 150 minutes.
Desulfurization test 2: mL of 4-MDBT model oil were added into a double-necked flask, five 3D-printed monolithi c catalysts (about 0.020 g) obtained in Embodiment 1, 1 mL of glacial acetic acid and 30 wt% H202 were added into the model oil, a molar ratio of sulfides in the fuel oil to the 11202 being 1: 8 (oxyge n-sulfur ratio was 8), magnetically stirred and reacted in a constant temperature water bath environ ment of 70°C, and then, simultaneously condensed and refltixed with tap water. During the reaction, samples were taken at regular intervals, and the sulfur contents of the samples were detected by gas chromatography to calculate the desulfurization rates. The 3D-printed monolithic catalyst prepared by Embodiment 1 had a desulfurization rate of 100% on the sulphide 4-MDBT in the model oil within 150 minutes.
Desulfurization test 3: mL of 4,6-DMDBT model oil were added into a double-necked flask, five 3D-printed monolithic catalysts (about 0.020 g) obtained in Embodiment 1, 1 mL of glacial acetic acid and 30 wt% H202 were added into the model oil, a molar ratio of sulfides in the fuel oil to the H202 being 1: 8 (oxygen-sulfur ratio was 8), magnetically stirred and reacted in a constant temperature water bath environment of 70°C, and then, simultaneously condensed and refluxed with tap water. During the reaction, samples were taken at regular intervals, and the sulfur contents of the samples were detected by gas chromatography to calculate the desulfurization rates. The 3D-printed monolithic catalyst prepared by Embodiment 1 had a desulfurization rate of 100% on the sulphide 4,6-DMDBT in the model oil within 150 minutes.
In FIG. 1, (a) is a 3Ds Max design drawing of the obtained 3D-printed monolithic catalyst, (b) is an optical photograph of the 3D-printed three-dimensional model, (c) is an optical photograph of the three-dimensional carbide, and (d) is an optical photograph of the 3D-printed monolithic catalyst. It can be seen from the figures that the 3D-printed model is a transparent porous three-dimensional model, the three-dimensional carbide is a silver-gray porous three-dimensional model with metallic luster, and the 3D-printed monolithic catalyst is a black porous three-dimensional model.
FIG. 2 is a Fourier transformed infrared graph (FT-IR) of the prepared 3D-printed monolithic catalyst. Typical characteristic peaks of Keggin structure of phosphotungstic acid appear in FT-IR g 25 raph at 1,076 cm-I, 978 cm', 890 cm' and 800 cm-I.
FIG. 3 is an X-ray diffraction graph (XRD) of the prepared 3D-printed monolithic catalyst. In the XRD graph, the characteristic diffraction peaks of phosphotungstic acid are clearly shown at 20 = 10.3°, 20.7°, 23.1°, 25.4° and 29.5°.
FIG. 4 is a catalytic activity curve of the 3D-printed monolithic catalyst prepared in 30 Embodiment 1 on different sulfides in model oil. It can be seen from the figure that the catalyst has good removal effects on all the three sulfides.
FIG. 5 is an activity graph of the 3D-printed monolithic catalyst prepared in Embodiment 1 on a DBT sulfide in the model oil after five cycles. It can be seen from the figure that the 3D-printed monolithic catalyst has higher stability, and can still maintain a higher activity after five cycles.
Claims (8)
- CLAIMS1. A preparation method, comprising the following steps of: (1) designing a three-dimensional model with a macroporous structure by 3Ds Max software, and printing the designed three-dimensional model by a photocuring 3D printer; (2) placing the printed three-dimensional model in a temperature programmed tube furnace, heating to a certain temperature for calcination under the protection of inert gas, and naturally cooling to room temperature to obtain a carbonized three-dimensional carbide; and (3) dissolving a certain amount of phosphotungstic acid in ethanol, adding the three-dimensional carbide prepared in step (2) into a reaction flask, magnetically stirring, soaking, to removing the ethanol solution by thermal evaporation, and drying in an oven to obtain the catalyst.
- 2. The preparation method according to claim 1, wherein in step (1), a 3D printing raw material is photocurable resin, and a main component of the photocurable resin is an acrylate polymer.
- 3. The preparation method according to claim 1, wherein in step (1), the three-dimensional 15 model by the 3D printer is a porous and hollow white transparent three-dimensional model.
- 4. The preparation method according to claim 1, wherein in step (2), the inert gas in the temperature programmed tube furnace is nitrogen.
- 5. The preparation method according to claim 1, wherein in step (2), the temperature programmed rate is 0.5°C/min, and the calcination is performed at 800°C to 900°C for 2 hours.
- 6. The preparation method according to claim 1, wherein in step (3), a capacity of the phosphotungstic acid in the catalyst is 1% to 10%, and the magnetic stirring lasts for 24 hours.
- 7. A 3D-printed monolithic catalyst, wherein the 3D-printed monolithic catalyst is prepared by the preparation method according to any one of claims 1 to 6, and the catalyst has a porous three-dimensional structure.
- 8. An application of the 3D-printed monolithic catalyst according to claim 7 to removal of sulfides in fuel oil.
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| PCT/CN2020/087576 WO2021022848A1 (en) | 2019-08-05 | 2020-04-28 | Monolithic catalyst preparation method employing 3d printing, and application of monolithic catalyst |
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| CN112023909A (en) * | 2020-09-10 | 2020-12-04 | 华东理工大学 | Preparation method of structured electric heating porous carbon-based catalyst with quick response and high thermal efficiency |
| CN113289626B (en) * | 2021-04-25 | 2023-04-21 | 南京师范大学 | Preparation method and application of 3D printing monolithic catalyst applied to Fenton/persulfate-like system |
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| GB202202504D0 (en) | 2022-04-06 |
| CN110479331A (en) | 2019-11-22 |
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