CN114029066A - Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst and preparation method thereof - Google Patents
Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst and preparation method thereof Download PDFInfo
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- 238000006477 desulfuration reaction Methods 0.000 title claims abstract description 39
- 230000023556 desulfurization Effects 0.000 title claims abstract description 39
- 239000003054 catalyst Substances 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 93
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000007864 aqueous solution Substances 0.000 claims abstract description 16
- 229910052742 iron Inorganic materials 0.000 claims abstract description 14
- 229910052748 manganese Inorganic materials 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 14
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 9
- 150000002500 ions Chemical class 0.000 claims abstract description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- 238000001035 drying Methods 0.000 claims description 35
- 238000003756 stirring Methods 0.000 claims description 31
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 24
- 238000010992 reflux Methods 0.000 claims description 22
- 229910002651 NO3 Inorganic materials 0.000 claims description 14
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 14
- 238000005342 ion exchange Methods 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 7
- 239000000295 fuel oil Substances 0.000 claims description 4
- 235000015393 sodium molybdate Nutrition 0.000 claims description 4
- 239000011684 sodium molybdate Substances 0.000 claims description 4
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 4
- 230000007547 defect Effects 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims description 3
- 239000002135 nanosheet Substances 0.000 claims description 2
- 239000011148 porous material Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 150000003464 sulfur compounds Chemical class 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims 1
- 238000006243 chemical reaction Methods 0.000 abstract description 31
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 18
- 229910052717 sulfur Inorganic materials 0.000 abstract description 18
- 239000011593 sulfur Substances 0.000 abstract description 18
- 230000003647 oxidation Effects 0.000 abstract description 15
- 238000007254 oxidation reaction Methods 0.000 abstract description 15
- 230000001590 oxidative effect Effects 0.000 abstract description 10
- 150000001875 compounds Chemical class 0.000 abstract description 5
- 239000007800 oxidant agent Substances 0.000 abstract description 5
- 150000003457 sulfones Chemical class 0.000 abstract description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 abstract description 3
- 239000003795 chemical substances by application Substances 0.000 abstract description 2
- 150000002823 nitrates Chemical class 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract description 2
- 239000002699 waste material Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
- 239000003921 oil Substances 0.000 description 30
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 18
- 238000004064 recycling Methods 0.000 description 11
- 238000005119 centrifugation Methods 0.000 description 10
- 238000004817 gas chromatography Methods 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 9
- 235000018660 ammonium molybdate Nutrition 0.000 description 9
- 239000011609 ammonium molybdate Substances 0.000 description 9
- 229940010552 ammonium molybdate Drugs 0.000 description 9
- 238000005273 aeration Methods 0.000 description 5
- 230000000694 effects Effects 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000004134 energy conservation Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 2
- MYAQZIAVOLKEGW-UHFFFAOYSA-N DMDBT Natural products S1C2=C(C)C=CC=C2C2=C1C(C)=CC=C2 MYAQZIAVOLKEGW-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8898—Manganese, technetium or rhenium containing also molybdenum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- 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
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- 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
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/30—Physical properties of feedstocks or products
- C10G2300/305—Octane number, e.g. motor octane number [MON], research octane number [RON]
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Abstract
The invention belongs to the field of petrochemical industry, and discloses a Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst and a preparation method thereof. Firstly, preparing HEPO by utilizing graphene and La, Cu, Co, Fe, Mn and Ni nitrates; and then introducing HEPO into an aqueous solution containing Mo ions, and treating to obtain the Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst Mo/HEPO. Mo/HEPO is used as a catalyst, air is used as an oxidant, and a DBT cyclohexane solution is used as model oil to perform oxidation desulfurization reaction, so that the sulfur content is reduced from 200ppm to 0, and the efficient oxidation desulfurization is realized. And the sulfone sulfur-containing compound with higher added value can be obtained by simple separation. The method has simple operation process and mild reaction condition, uses GO as a template agent to prepare the Mo-based high-entropy perovskite oxide monatomic catalyst with rich mesoporous structure, uses air as an oxidant, realizes the ultra-deep oxidation desulfurization of oil products under the condition of low energy consumption, and realizes the 'changing waste into valuable' of DBT.
Description
Technical Field
The invention belongs to the field of petrochemical industry, and particularly relates to a Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst and a preparation method thereof.
Background
In recent years, with the recent development of the automobile industry, fuel consumption has been increasing year by year, and vulcanization in fuel has been carried outCombustion of the substances to produce SOxIncreasingly, the pollution to air quality and ecological environment of China is serious, and the realization of oil product desulfurization is imminent. Hydrodesulfurization (HDS) is the most widely used fuel oil desulfurization technology at present. However, as environmental regulations become more stringent, the upgrading and upgrading of oil products require more severe reaction conditions, such as high temperature (high pressure) and high temperature (high pressure) for realizing ultra-deep desulfurization to reduce the sulfur content in fuel oil to below 10ppm and maintain the octane number of the oil products>350 ℃), high pressure (6MPa), additional consumption of hydrogen) and more expensive catalysts, leading to a significant increase in enterprise production costs. Therefore, how to prepare the catalyst with ultra-deep desulfurization performance to remove or convert the sulfur-containing compounds in the oil products into sulfone sulfur-containing compounds with higher added values to ensure that the sulfur content in the diesel oil meets the national VI standard is one of the research hotspots in the field of petrochemical industry all the time.
Disclosure of Invention
Aiming at the problems of harsh reaction conditions, high treatment cost, great increase of enterprise production cost caused by environmental pollution and the like in the conventional fuel desulfurization technology, the invention aims to provide the oil product desulfurization method which has low treatment cost and mild conditions, maintains the octane number of an oil product and can achieve the purposes of energy conservation and emission reduction.
A preparation method of a Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst comprises the following steps:
(1) firstly, dispersing Graphene (GO) in ethylene glycol to prepare a solution A; dissolving a nitrate mixture of La, Cu, Co, Fe, Mn and Ni into an ethylene glycol solution to prepare a solution B; dropwise adding the solution A into the solution B, and stirring, refluxing, centrifuging, drying and roasting at high temperature to prepare a high-entropy perovskite oxide carrier HEPO;
(2) introducing HEPO prepared in the step (1) into an aqueous solution containing Mo ions, fully stirring, adsorbing under hydrothermal condition, centrifuging, drying, roasting, and reacting with NH4And exchanging and roasting the Cl solution to prepare the Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst (Mo/HEPO).
Further, in the step (1), the refluxing is performed for 4 hours at 70 ℃ and then for 4 hours at 170 ℃; the high-temperature roasting temperature is 850-1000 ℃, and the high-temperature roasting time is more than or equal to 2 hours.
Further, in the step (1), the mass ratio of the nitrate mixture to GO is 60-350: 1; wherein, in the nitrate mixture, the mass ratio of La, Cu, Co, Fe, Mn and Ni is 5:1:1:1: 1.
In the step (2), the dosage ratio of HEPO and the aqueous solution containing Mo ions is 1.0 g: 50mL, wherein the solute in the aqueous solution containing Mo ions is sodium molybdate, and the concentration of the sodium molybdate is 0.01 g/mL.
In the step (2), the adsorption temperature under the hydrothermal condition is 90 ℃ and the time is 2-4 days; the drying temperature was 110 ℃.
In the step (2), the temperature of the two times of roasting is 400-550 ℃, and the time is 4 hours.
In step (2), NH4The Cl solution exchange is to put Mo/HEPO into 0.20mol/L NH4And carrying out ion exchange on the Cl solution for 6-12 h.
The Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst prepared by the method is in a two-dimensional nanosheet shape with abundant pore structures and defect sites, wherein the Mo monatomic load is 0.30 wt.%.
The catalyst prepared by the invention is used for removing sulfur compounds of dibenzothiophene and derivatives thereof in fuel oil.
Mo/HEPO is used as a catalyst, air is used as an oxidant, and a DBT cyclohexane solution is used as model oil; the method specifically comprises the following steps: the Mo/HEPO prepared by the invention is put into a DBT cyclohexane solution, air is introduced, and the mixture is stirred in a constant-temperature oil bath for oxidation desulfurization reaction. After the reaction is finished, the catalyst after the reaction is subjected to centrifugation, washing and drying for recycling. And (3) taking the centrifuged solution, measuring the concentration of DBT in the model oil by using gas chromatography, and finally reducing the sulfur content from 200ppm to 0 to realize high-efficiency oxidative desulfurization. And the sulfone sulfur-containing compound with higher added value can be obtained by simple separation.
The amount of catalyst used in the reaction was 20mg and the model oil was 20mL containing 500ppm DBT.
The oxidant was synthetic air (21 vol.% O)2，79vol.％N2) The air flow rate is 50-300 mL/min.
And the stirring speed in the oxidation desulfurization reaction process is 200-800 rpm.
In the oxidation desulfurization process, the temperature of the constant-temperature oil bath is 120-140 ℃ and the time is 90 min.
The invention has the following advantages and remarkable effects:
(1) the graphene is used as a hard template agent for the first time to prepare the two-dimensional Mo/HEPO monatomic high-entropy perovskite oxide catalyst with a rich mesoporous structure. The mesoporous structure is beneficial to the exposure of active sites and the mass transfer of reactant molecules, and can promote the oxidative desulfurization reaction efficiency; secondly, the load amount of Mo in the monatomic catalyst is only 0.30 wt.%, so that the preparation cost is greatly saved, and no relevant report of the method exists in the previous research on oxidative desulfurization;
(2) the oxidant used in the oxidation desulfurization reaction is air, rather than the traditional hydrogen peroxide with higher cost. Also, the reaction can have very high activity at 120 ℃. The catalytic activity (TOF value) of the catalyst is far higher than that of the oxidative desulfurization catalyst reported at present, and the result is not seen in the previous oxidative desulfurization research;
(3) the high-entropy perovskite has excellent hydrothermal stability and rich defect sites, can realize the recycling of the catalyst, achieves the purposes of energy conservation and emission reduction, realizes the ultra-deep desulfurization of oil products, can recover sulfone sulfur-containing compounds with higher added values after reaction, and realizes the purpose of changing waste into valuable.
Detailed Description
The present invention will be further described with reference to the following examples to assist in further understanding of the invention.
Example 1:
0.30g of Graphene (GO) is dispersed in 150mL of glycol solution, and the solution A is prepared by fully stirring. And dissolving 0.05mol of La, Cu, Co, Fe, Mn and Ni nitrate into 50mL of glycol solution to prepare a solution B. Then dropwise adding the solution A into the solution B, stirring at room temperature, refluxing at 70 deg.C for 4h, refluxing at 170 deg.C for 4h, centrifuging at 10000rpm, drying at 110 deg.C, and drying at 90 deg.CRoasting at 0 ℃ for 2h to prepare the high-entropy perovskite oxide carrier HEPO. 1.0g of HEPO prepared as described above was introduced into 50mL of an aqueous solution containing 0.50g of ammonium molybdate, sufficiently stirred, hydrothermally treated at 90 ℃ for 4 days, and then mixed with 0.20mol/L NH4And carrying out ion exchange on the Cl solution, drying at 110 ℃, and roasting at 550 ℃ for 4 hours to prepare the Mo-based monatomic high-entropy perovskite oxide (Mo/HEPO).
20mg of Mo/HEPO was mixed with 20mL of DBT containing 500ppm, and air (200mL/min) was blown in to react for 90min at 120 ℃ with stirring in an oil bath at 800 rpm. After the reaction is finished, the catalyst after the reaction is subjected to centrifugation, washing and drying for recycling. And (3) taking the centrifuged solution, measuring the concentration of DBT in the model oil by using gas chromatography, and finally reducing the sulfur content from 200ppm to 0ppm to realize efficient deep oxidation desulfurization.
Example 2:
0.30g of Graphene (GO) is dispersed in 150mL of glycol solution, and the solution A is prepared by fully stirring. And dissolving 0.05mol of La, Cu, Co, Fe, Mn and Ni nitrate into 50mL of glycol solution to prepare a solution B. And then dropwise adding the solution A into the solution B, stirring at room temperature, refluxing at 70 ℃ for 4h, refluxing at 170 ℃ for 4h, centrifuging at 10000rpm, drying at 110 ℃, and roasting at high temperature of 900 ℃ for 2h to prepare the high-entropy perovskite oxide carrier HEPO. 1.0g of HEPO prepared as described above was introduced into 50mL of an aqueous solution containing 0.50g of ammonium molybdate, sufficiently stirred, hydrothermally treated at 90 ℃ for 4 days, and then mixed with 0.20mol/L NH4And carrying out ion exchange on the Cl solution, drying at 110 ℃, and roasting at 550 ℃ for 4 hours to prepare the Mo-based monatomic high-entropy perovskite oxide (Mo/HEPO).
20mg of Mo/HEPO was mixed with 20mL of DBT containing 500ppm, and reacted for 90min at 120 ℃ with stirring in an oil bath at 400rpm with aeration of air (200 mL/min). After the reaction is finished, the catalyst after the reaction is subjected to centrifugation, washing and drying for recycling. And (3) taking the centrifuged solution, measuring the concentration of DBT in the model oil by using gas chromatography, and finally reducing the sulfur content from 200ppm to 6ppm to realize efficient deep oxidation desulfurization.
Example 3:
0.30g of Graphene (GO) is dispersed in 150mL of glycol solution, and the solution A is prepared by fully stirring. 0.05mol of La and CAnd dissolving the nitrates of u, Co, Fe, Mn and Ni into 50mL of glycol solution to prepare a solution B. And then dropwise adding the solution A into the solution B, stirring at room temperature, refluxing at 70 ℃ for 4h, refluxing at 170 ℃ for 4h, centrifuging at 10000rpm, drying at 110 ℃, and roasting at high temperature of 900 ℃ for 2h to prepare the high-entropy perovskite oxide carrier HEPO. 1.0g of HEPO prepared as described above was introduced into 50mL of an aqueous solution containing 0.50g of ammonium molybdate, sufficiently stirred, hydrothermally treated at 90 ℃ for 4 days, and then mixed with 0.20mol/L NH4And carrying out ion exchange on the Cl solution, drying at 110 ℃, and roasting at 550 ℃ for 4 hours to prepare the Mo-based monatomic high-entropy perovskite oxide (Mo/HEPO).
20mg of Mo/HEPO was mixed with 20mL of DBT containing 500ppm, and reacted for 90min at 120 ℃ with stirring in an oil bath at 200rpm with aeration of air (200 mL/min). After the reaction is finished, the catalyst after the reaction is subjected to centrifugation, washing and drying for recycling. The centrifuged solution was taken and the DBT concentration in the model oil was measured by gas chromatography, finally reducing the sulfur content from 200ppm to 20 ppm.
Example 4:
0.30g of Graphene (GO) is dispersed in 150mL of glycol solution, and the solution A is prepared by fully stirring. And dissolving 0.05mol of La, Cu, Co, Fe, Mn and Ni nitrate into 50mL of glycol solution to prepare a solution B. And then dropwise adding the solution A into the solution B, stirring at room temperature, refluxing at 70 ℃ for 4h, refluxing at 170 ℃ for 4h, centrifuging at 10000rpm, drying at 110 ℃, and roasting at high temperature of 900 ℃ for 2h to prepare the high-entropy perovskite oxide carrier HEPO. 1.0g of HEPO prepared as described above was introduced into 50mL of an aqueous solution containing 0.50g of ammonium molybdate, sufficiently stirred, hydrothermally treated at 90 ℃ for 4 days, and then mixed with 0.20mol/L NH4And carrying out ion exchange on the Cl solution, drying at 110 ℃, and roasting at 550 ℃ for 4 hours to prepare the Mo-based monatomic high-entropy perovskite oxide (Mo/HEPO).
20mg of Mo/HEPO was mixed with 20mL of DBT containing 500ppm, and reacted at 130 ℃ for 90min with aeration of air (200mL/min) under oil bath stirring at 800 rpm. After the reaction is finished, the catalyst after the reaction is subjected to centrifugation, washing and drying for recycling. And (3) taking the centrifuged solution, measuring the concentration of DBT in the model oil by using gas chromatography, and finally reducing the sulfur content from 200ppm to 0ppm to realize efficient deep oxidation desulfurization.
Example 5:
0.30g of Graphene (GO) is dispersed in 150mL of glycol solution, and the solution A is prepared by fully stirring. And dissolving 0.05mol of La, Cu, Co, Fe, Mn and Ni nitrate into 50mL of glycol solution to prepare a solution B. And then dropwise adding the solution A into the solution B, stirring at room temperature, refluxing at 70 ℃ for 4h, refluxing at 170 ℃ for 4h, centrifuging at 10000rpm, drying at 110 ℃, and roasting at high temperature of 900 ℃ for 2h to prepare the high-entropy perovskite oxide carrier HEPO. 1.0g of HEPO prepared as described above was introduced into 50mL of an aqueous solution containing 0.50g of ammonium molybdate, sufficiently stirred, hydrothermally treated at 90 ℃ for 4 days, and then mixed with 0.20mol/L NH4And carrying out ion exchange on the Cl solution, drying at 110 ℃, and roasting at 550 ℃ for 4 hours to prepare the Mo-based monatomic high-entropy perovskite oxide (Mo/HEPO).
20mg of Mo/HEPO was mixed with 20mL of DBT containing 500ppm, and reacted with aeration (200mL/min) at 140 ℃ for 60min with stirring in an oil bath at 800 rpm. After the reaction is finished, the catalyst after the reaction is subjected to centrifugation, washing and drying for recycling. And (3) taking the centrifuged solution, measuring the concentration of DBT in the model oil by using gas chromatography, and finally reducing the sulfur content from 200ppm to 0ppm to realize efficient deep oxidation desulfurization.
Example 6:
0.30g of Graphene (GO) is dispersed in 150mL of glycol solution, and the solution A is prepared by fully stirring. And dissolving 0.05mol of La, Cu, Co, Fe, Mn and Ni nitrate into 50mL of glycol solution to prepare a solution B. And then dropwise adding the solution A into the solution B, stirring at room temperature, refluxing at 70 ℃ for 4h, refluxing at 170 ℃ for 4h, centrifuging at 10000rpm, drying at 110 ℃, and roasting at high temperature of 900 ℃ for 2h to prepare the high-entropy perovskite oxide carrier HEPO. 1.0g of HEPO prepared as described above was introduced into 50mL of an aqueous solution containing 0.50g of ammonium molybdate, sufficiently stirred, hydrothermally treated at 90 ℃ for 4 days, and then mixed with 0.20mol/L NH4And carrying out ion exchange on the Cl solution, drying at 110 ℃, and roasting at 550 ℃ for 4 hours to prepare the Mo-based monatomic high-entropy perovskite oxide (Mo/HEPO).
20mg of Mo/HEPO was mixed with 20mL of DBT containing 500ppm, and reacted for 180min at 120 ℃ with aeration (200mL/min) in an oil bath at 800 rpm. After the reaction is finished, the catalyst after the reaction is subjected to centrifugation, washing and drying for recycling. And (3) taking the centrifuged solution, measuring the concentration of DBT in the model oil by using gas chromatography, and finally reducing the sulfur content from 300ppm to 10ppm to realize efficient deep oxidation desulfurization.
Example 7:
0.30g of Graphene (GO) is dispersed in 150mL of glycol solution, and the solution A is prepared by fully stirring. And dissolving 0.05mol of La, Cu, Co, Fe, Mn and Ni nitrate into 50mL of glycol solution to prepare a solution B. And then dropwise adding the solution A into the solution B, stirring at room temperature, refluxing at 70 ℃ for 4h, refluxing at 170 ℃ for 4h, centrifuging at 10000rpm, drying at 110 ℃, and roasting at high temperature of 900 ℃ for 2h to prepare the high-entropy perovskite oxide carrier HEPO. 1.0g of HEPO prepared as described above was introduced into 50mL of an aqueous solution containing 0.50g of ammonium molybdate, sufficiently stirred, hydrothermally treated at 90 ℃ for 4 days, and then mixed with 0.20mol/L NH4And carrying out ion exchange on the Cl solution, drying at 110 ℃, and roasting at 550 ℃ for 4 hours to prepare the Mo-based monatomic high-entropy perovskite oxide (Mo/HEPO).
20mg of Mo/HEPO was mixed with 20mL of DBT containing 500ppm, and air (200mL/min) was blown in to react for 150min at 120 ℃ with stirring in an oil bath at 800 rpm. After the reaction is finished, the catalyst after the reaction is subjected to centrifugation, washing and drying for recycling. And (3) taking the centrifuged solution, measuring the concentration of 4,6-DMDBT in the model oil by using gas chromatography, and finally reducing the sulfur content from 200ppm to 0ppm to realize efficient deep oxidation desulfurization.
Example 8:
0.30g of Graphene (GO) is dispersed in 150mL of glycol solution, and the solution A is prepared by fully stirring. And dissolving 0.05mol of La, Cu, Co, Fe, Mn and Ni nitrate into 50mL of glycol solution to prepare a solution B. And then dropwise adding the solution A into the solution B, stirring at room temperature, refluxing at 70 ℃ for 4h, refluxing at 170 ℃ for 4h, centrifuging at 10000rpm, drying at 110 ℃, and roasting at high temperature of 900 ℃ for 2h to prepare the high-entropy perovskite oxide carrier HEPO. 1.0g of HEPO prepared as described above was introduced into 50mL of an aqueous solution containing 0.50g of ammonium molybdate, sufficiently stirred, hydrothermally treated at 90 ℃ for 4 days, and then mixed with 0.20mol/L NH4Ion exchange of Cl solution, drying at 110 ℃ and high-temperature roasting at 550 ℃ for 4h to prepare Mo-based monatomic high-entropy perovskite oxygenCompound (Mo/HEPO).
20mg of Mo/HEPO was mixed with 20mL of DBT containing 500ppm, and air (200mL/min) was blown in to react for 150min at 120 ℃ with stirring in an oil bath at 800 rpm. After the reaction is finished, the catalyst after the reaction is subjected to centrifugation, washing and drying for recycling. And taking the centrifuged solution, measuring the concentration of the 4-MDBT in the model oil by using gas chromatography, and finally reducing the sulfur content from 200ppm to 0ppm to realize efficient deep oxidation desulfurization.
Example 9:
0.30g of Graphene (GO) is dispersed in 150mL of glycol solution, and the solution A is prepared by fully stirring. And dissolving 0.05mol of La, Cu, Co, Fe, Mn and Ni nitrate into 50mL of glycol solution to prepare a solution B. And then dropwise adding the solution A into the solution B, stirring at room temperature, refluxing at 70 ℃ for 4h, refluxing at 170 ℃ for 4h, centrifuging at 10000rpm, drying at 110 ℃, and roasting at high temperature of 900 ℃ for 2h to prepare the high-entropy perovskite oxide carrier HEPO. 1.0g of HEPO prepared as described above was introduced into 50mL of an aqueous solution containing 0.50g of ammonium molybdate, sufficiently stirred, hydrothermally treated at 90 ℃ for 4 days, and then mixed with 0.20mol/L NH4And carrying out ion exchange on the Cl solution, drying at 110 ℃, and roasting at 550 ℃ for 4 hours to prepare the Mo-based monatomic high-entropy perovskite oxide (Mo/HEPO).
20mg of Mo/HEPO was mixed with 20mL of DBT containing 500ppm, and air (200mL/min) was blown in to react for 90min at 120 ℃ with stirring in an oil bath at 800 rpm. After the reaction is finished, the catalyst after the reaction is subjected to centrifugation, washing and drying for recycling. And (3) taking the centrifuged solution, measuring the concentration of DBT in the model oil by using gas chromatography, and finally reducing the sulfur content from 200ppm to 0ppm to realize efficient deep oxidation desulfurization. And after 8 times of cyclic use, the activity is still almost unchanged.
Description of the drawings: the above embodiments are only used to illustrate the present invention and do not limit the technical solutions described in the present invention; thus, while the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted; all such modifications and variations are intended to be included herein within the scope of this disclosure and the present invention and protected by the following claims.
Claims (9)
1. A preparation method of a Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst is characterized by comprising the following steps:
(1) firstly, dispersing graphene GO in ethylene glycol to prepare a solution A; dissolving a nitrate mixture of La, Cu, Co, Fe, Mn and Ni into an ethylene glycol solution to prepare a solution B; dropwise adding the solution A into the solution B, and stirring, refluxing, centrifuging, drying and roasting at high temperature to prepare a high-entropy perovskite oxide carrier HEPO;
(2) introducing HEPO prepared in the step (1) into an aqueous solution containing Mo ions, fully stirring, adsorbing under hydrothermal condition, centrifuging, drying, roasting, and reacting with NH4And exchanging and roasting the Cl solution to prepare the Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst Mo/HEPO.
2. The preparation method of claim 1, wherein in the step (1), the mass ratio of the nitrate mixture to GO is 60-350: 1; wherein, in the nitrate mixture, the mass ratio of La, Cu, Co, Fe, Mn and Ni is 5:1:1:1: 1.
3. The method according to claim 1, wherein in the step (1), the refluxing is carried out at 70 ℃ for 4 hours and at 170 ℃ for 4 hours; the high-temperature roasting temperature is 850-1000 ℃, and the high-temperature roasting time is more than or equal to 2 hours.
4. The production method according to claim 1, wherein in the step (2), the amount ratio of HEPO to the aqueous solution containing Mo ions is 1.0 g: 50mL, wherein the solute in the aqueous solution containing Mo ions is sodium molybdate, and the concentration of the sodium molybdate is 0.01 g/mL.
5. The preparation method according to claim 1, wherein in the step (2), the temperature of adsorption under hydrothermal conditions is 90 ℃ and the time is 2 to 4 days; the drying temperature was 110 ℃.
6. The preparation method of claim 1, wherein in the step (2), the temperature of the two times of roasting is 400-550 ℃ and the time is 4 hours.
7. The method according to claim 1, wherein in the step (2), NH is added4The Cl solution exchange is to put Mo/HEPO into 0.20mol/L NH4And carrying out ion exchange on the Cl solution for 6-12 h.
8. A Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst, which is prepared by the preparation method of any one of claims 1 to 7, and is in a two-dimensional nanosheet shape with abundant pore structures and defect sites, wherein the Mo monatomic loading is 0.30 wt.%.
9. Use of the Mo-based monatomic high-entropy perovskite oxide desulfurization catalyst of claim 8 for removing sulfur compounds of dibenzothiophene and derivatives thereof in fuel oil.
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