CN116355645A - Method for removing sulfur-containing organic compounds in oil products by using molybdenum phosphide composite catalyst - Google Patents
Method for removing sulfur-containing organic compounds in oil products by using molybdenum phosphide composite catalyst Download PDFInfo
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- molybdenum
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- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 title claims abstract description 111
- 239000003054 catalyst Substances 0.000 title claims abstract description 98
- 239000002131 composite material Substances 0.000 title claims abstract description 93
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 86
- 239000011593 sulfur Substances 0.000 title claims abstract description 86
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 69
- 238000000034 method Methods 0.000 title claims abstract description 52
- 150000002894 organic compounds Chemical class 0.000 title claims abstract description 49
- 238000006477 desulfuration reaction Methods 0.000 claims abstract description 33
- 230000023556 desulfurization Effects 0.000 claims abstract description 33
- 230000003197 catalytic effect Effects 0.000 claims abstract description 22
- 230000001590 oxidative effect Effects 0.000 claims abstract description 20
- IYYZUPMFVPLQIF-UHFFFAOYSA-N dibenzothiophene Chemical compound C1=CC=C2C3=CC=CC=C3SC2=C1 IYYZUPMFVPLQIF-UHFFFAOYSA-N 0.000 claims description 78
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 24
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- 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 claims description 10
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
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- IMQLKJBTEOYOSI-GPIVLXJGSA-N Inositol-hexakisphosphate Chemical compound OP(O)(=O)O[C@H]1[C@H](OP(O)(O)=O)[C@@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@H](OP(O)(O)=O)[C@@H]1OP(O)(O)=O IMQLKJBTEOYOSI-GPIVLXJGSA-N 0.000 claims description 8
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 8
- 229910052698 phosphorus Inorganic materials 0.000 claims description 8
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- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
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- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 4
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 4
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- YDULQTLSFNLWCO-UHFFFAOYSA-N 4,6-dimethyl-1-benzothiophene Chemical compound CC1=CC(C)=C2C=CSC2=C1 YDULQTLSFNLWCO-UHFFFAOYSA-N 0.000 description 1
- NBHONCYELIPHFE-UHFFFAOYSA-N CCCCCCCC.C1=CC=CC=2SC3=C(C21)C=CC=C3 Chemical compound CCCCCCCC.C1=CC=CC=2SC3=C(C21)C=CC=C3 NBHONCYELIPHFE-UHFFFAOYSA-N 0.000 description 1
- IMQLKJBTEOYOSI-UHFFFAOYSA-N Phytic acid Natural products OP(O)(=O)OC1C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C(OP(O)(O)=O)C1OP(O)(O)=O IMQLKJBTEOYOSI-UHFFFAOYSA-N 0.000 description 1
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- 230000007547 defect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- IKJFYINYNJYDTA-UHFFFAOYSA-N dibenzothiophene sulfone Chemical compound C1=CC=C2S(=O)(=O)C3=CC=CC=C3C2=C1 IKJFYINYNJYDTA-UHFFFAOYSA-N 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
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- 229940068041 phytic acid Drugs 0.000 description 1
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Classifications
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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
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a method for removing sulfur-containing organic compounds in oil products by using a molybdenum phosphide composite catalyst. The molybdenum phosphide composite catalyst prepared by the method has the advantages of strong catalytic activity, high selectivity, good stability and the like, can be widely used for removing sulfur-containing organic compounds in petroleum products, shows excellent oxidative desulfurization activity, can realize rapid and effective removal of the sulfur-containing organic compounds in the petroleum products, can achieve high-selectivity ultra-deep oxidative desulfurization, has the advantages of simple process, convenient operation, low cost, high removal efficiency, good removal effect and the like, and has good economic benefit and application prospect.
Description
Technical Field
The invention belongs to the technical field of heterogeneous catalysis and petrochemical industry thereof, relates to a method for removing sulfur-containing organic compounds in oil products, and in particular relates to a method for removing sulfur-containing organic compounds in oil products by using a molybdenum phosphide composite catalyst.
Background
In the last few decades, the combustion of large quantities of sulfur-containing fossil fuels has caused a dramatic increase in sulfur dioxide emissions, which inevitably presents a series of environmental problems that seriously affect the physical health of people. In 10 months 2017, the world health organization international cancer research institute classified sulfur dioxide as a class 3 carcinogen. Under the constant regulation of fuel laws, the sulfur content in fuels used in transportation vehicles has dropped drastically from 2000ppm to 10ppm over the last 20 years. This has made mass production of sulfur-free fuels more urgent. Therefore, there is an urgent need to develop a desulfurization technology with simple process, high efficiency and low cost.
The most common method for removing sulfur-containing organic compounds from fuel is hydrodesulfurization, but this method is not ideal for removal of difficult benzothiophenes such as benzothiophene, dibenzothiophene, and 4, 6-dimethyldibenzothiophene, and the reaction needs to be carried out at high temperature and pressure (300 to 400 ℃ and 30 to 130 atm), which results in high desulfurization costs. Oxidative desulfurization as an alternative or complementary technology to hydrodesulfurization has received extensive attention due to its mild reaction conditions (60-100 ℃) and high removal rate of refractory benzothiophene. In oxidative desulfurization, sulfur-containing organic compounds are oxidized by an oxidant and catalyst to the corresponding sulfoxides and sulfones, which have a higher polarity than other hydrocarbons and their parent sulfur compounds, which can be removed from the fuel by various separation methods. However, the efficiency of oxidative desulfurization is always dependent on the activity of the catalyst. Therefore, the development of high performance catalysts is a key scientific issue for achieving this technology.
Among the numerous catalysts, molybdenum phosphide is expected to exert a great catalytic effect in oxidative desulfurization due to its unique electronic characteristics, multiparty composition and structure. First, molybdenum phosphide readily reacts with oxidants to form electrophilically reactive intermediates, which is considered to be the driving force for efficient ODS. In addition, molybdenum phosphide has a rich free electron, which means that it is more prone to generate a large number of unsaturated metal sites, which is essential for promoting efficient oxidation of aromatic organosulfur compounds. Nevertheless, the preparation of molybdenum phosphide requires severe conditions, using flammable phosphorus and highly toxic phosphine as phosphating agents, which undoubtedly hampers scale-up and application. Therefore, the molybdenum phosphide composite catalyst with strong catalytic activity, high selectivity and good stability and the preparation method matched with the molybdenum phosphide composite catalyst with simple process, convenient operation and low cost are obtained, and have great significance for realizing the effective conversion of sulfur-containing organic pollutants in petroleum products and improving the availability of the petroleum products.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide the method for removing the sulfur-containing organic compounds in the oil product by using the molybdenum phosphide composite catalyst, which has the advantages of low cost, high removal efficiency and good removal effect.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for removing sulfur-containing organic compounds in oil products by using molybdenum phosphide composite catalyst comprises the steps of carrying out catalytic oxidation treatment on sulfur-containing organic compounds in oil products by using molybdenum phosphide composite catalyst; the molybdenum phosphide composite catalyst comprises a nitrogen-phosphorus co-doped carbon nano-sheet, and molybdenum phosphide nano-particles are loaded on the nitrogen-phosphorus co-doped carbon nano-sheet.
According to the method, the mass ratio of the molybdenum phosphide particles to the nitrogen-phosphorus co-doped carbon nano-sheets in the molybdenum phosphide composite catalyst is 2-40; the mass fraction of nitrogen element in the nitrogen-phosphorus co-doped carbon nano-sheet is 2% -8% of that of the nitrogen-phosphorus co-doped carbon nano-sheet; the mass fraction of the phosphorus element is 4% -15% of the nitrogen-phosphorus co-doped carbon nano-sheet.
The method is further improved, and the preparation method of the molybdenum phosphide composite catalyst comprises the following steps:
s1, preparing molybdenum-based metal organic frameworks into molybdenum-based metal organic framework dispersion liquid, adding melamine dispersion liquid, and stirring to prepare molybdenum-based metal organic frameworks/melamine dispersion liquid;
s2, mixing the molybdenum-based metal organic framework/melamine dispersion liquid obtained in the step S1 with a phytic acid solution to perform solvothermal reaction, centrifuging, and freeze-drying to obtain molybdenum phosphide composite catalyst precursor powder;
and S3, calcining the molybdenum phosphide composite catalyst precursor powder obtained in the step S2 in an argon atmosphere to obtain the molybdenum phosphide composite catalyst.
In the above method, further improved, in step S1, the preparation method of the molybdenum-based metal organic framework includes the following steps:
(1) Adding molybdenum trioxide into ultrapure water, and stirring to obtain molybdenum trioxide dispersion; the mass ratio of the molybdenum trioxide to the ultrapure water is 1: 70-100 parts; the stirring time is 0.5-2 h;
(2) Adding imidazole into the molybdenum trioxide dispersion liquid obtained in the step (1) for hydrothermal reaction, washing and drying to obtain the molybdenum-based metal organic framework. The mass ratio of the imidazole to the molybdenum trioxide is 0.48-0.50: 1, a step of; the temperature of the hydrothermal reaction is 100-140 ℃; the hydrothermal reaction time is 12-24 hours; the washing is to wash the filtered product 3-6 times by ultrapure water; the drying process is carried out under vacuum conditions; the drying temperature is 40-80 ℃.
In the method, in a further improved step S1, the concentration of the molybdenum-based metal organic frame dispersion liquid is 25-200 g/L; the concentration of the melamine dispersion liquid is 30-50 g/L; the stirring time is 0.5-2 h;
in the method, in the step S2, the mass fraction of the phytic acid solution is 16% -20%; the volume ratio of the phytic acid solution to the molybdenum-based metal organic framework/melamine dispersion is 0.5-0.8: 1, a step of; the solvothermal reaction temperature is 60-80 ℃; the solvothermal reaction time is 12-24 hours; the freeze drying time is 12-24 hours;
in the method, further improved, in the step S3, the calcining temperature is 800-900 ℃; the temperature rising rate of the calcination is 2-10 ℃/min.
The method is further improved, and the molybdenum phosphide composite catalyst is adopted to carry out catalytic oxidation treatment on sulfur organic compounds in oil products, and comprises the following steps: mixing molybdenum phosphide composite catalyst, acetonitrile and hydrogen peroxide with sulfur-containing organic compound oil, performing physical mixing and heating to start catalytic oxidation reaction, and removing sulfur organic compound in the oil by extraction separation.
According to the method, the dosage of the molybdenum phosphide composite catalyst is 1-3 g of the molybdenum phosphide composite catalyst added into each liter of sulfur-containing organic compound oil; the molar ratio of the hydrogen peroxide to the sulfur in the sulfur-containing organic compound oil product is 6:1; the sulfur-containing organic compound in the sulfur-containing organic compound oil product is at least one of dibenzothiophene and 4, 6-dimethyl dibenzothiophene; the concentration of the sulfur-containing organic compound in the sulfur-containing organic compound oil product is 1000-2000 ppm; the catalytic oxidation reaction is carried out at the temperature of 50-70 ℃; the time of the catalytic oxidation reaction is 30-60 min.
The method is further improved, and the high-sulfur fuel oil is subjected to desulfurization treatment by adopting an oxidation desulfurization reaction device; the oxidation desulfurization reaction device comprises a mixing tank, a reactor, an extractor, a separator, a buffer tank and a finished product tank, and the desulfurization treatment of the high-sulfur fuel oil comprises the following steps:
1) Adding the molybdenum phosphide composite catalyst, the high-sulfur fuel oil, the extractant and the oxidant into a mixing tank, and uniformly mixing;
2) Pumping the solution uniformly mixed in the step 1) into a reactor for oxidation desulfurization reaction;
3) Conveying the reaction product solution obtained by the oxidation desulfurization reaction in the step 2) to an extractor for extraction treatment;
4) Conveying the mixed solution obtained after the extraction treatment in the step 3) to a separator, and naturally settling for 10-30 min to obtain an upper oil phase, a lower extractant, an unconsumed oxidant and a catalyst mixed phase;
5) Sequentially conveying the upper oil phase separated in the step 4) to a buffer tank and a finished product tank to obtain clean fuel oil, returning the lower mixed phase to a mixing tank to mix with the high-sulfur fuel oil again, and completing continuous desulfurization treatment of the high-sulfur fuel oil;
according to the method, the bottom of the mixing tank is provided with the three-blade stirrer, and the reactor is internally provided with the heat exchange device and a plurality of three-blade stirrers; a three-blade stirrer is arranged in the extractor; the separator is in an inverted cone shape, and the upper part and the lower part of the separator are both provided with discharge pipes.
Compared with the prior art, the invention has the advantages that:
(1) The invention provides a method for removing sulfur-containing organic compounds in oil products by using a molybdenum phosphide composite catalyst, which has the advantages of strong catalytic activity, high selectivity, good stability and the like, can be widely used for removing sulfur-containing organic compounds (such as dibenzothiophene and 4, 6-dimethylbenzothiophene) in petroleum products, and can realize the rapid and effective removal of the sulfur-containing organic compounds in the petroleum products, so that when the molybdenum phosphide composite catalyst is used for carrying out catalytic oxidation treatment on the sulfur-containing organic compounds in the oil products, the effective conversion of the sulfur-containing organic compounds in the fuel products can be rapidly and efficiently realized, the ultrahigh-efficiency and ultra-deep oxidative desulfurization can be achieved, and the method has the advantages of simple process, convenient operation, low cost, high removal efficiency, good removal effect and the like, and has excellent economic benefit and application prospect. More importantly, the molybdenum phosphide composite catalyst adopted by the invention can be used for selectively removing the organic sulfur compounds in the oil product, can be used for rapidly and completely removing the organic sulfur compounds in the oil product on the premise of ensuring the quality of the oil product, has very good adaptability, and has very high use value and very good application prospect.
(2) In the invention, the mass ratio of the nitrogen-phosphorus co-doped carbon nano-sheet to the molybdenum phosphide particles in the molybdenum phosphide composite catalyst is 2-40. The catalytic activity of the catalyst can be more effectively improved by optimizing the mass ratio of the nitrogen-phosphorus co-doped carbon nano-plate to the molybdenum phosphide particles, so that the organic sulfur compounds in the oil product can be more efficiently removed; meanwhile, the mass fraction of nitrogen element in the nitrogen-phosphorus co-doped carbon nano sheet is 2% -8%, and the mass fraction of phosphorus element is 4% -15%. The abundant nitrogen and phosphorus doping can effectively regulate the electronic structure of the carbon substrate, and improve the interaction between the carbon substrate and molybdenum phosphide so as to improve the stability of the activity of the catalyst, thus being capable of removing organic sulfur compounds in oil products deeply and in a long-term way.
(3) According to the invention, the molybdenum-based metal organic framework is used as a molybdenum precursor, phytic acid is used as a phosphorus source, melamine is used as a carbon source, strong coordination is easy to occur between the precursors to form a cross-linking structure, and the nano-structure molybdenum phosphide anchored on the nitrogen-phosphorus co-doped carbon nano-sheet can be obtained through simple one-step pyrolysis. Therefore, the method for preparing the molybdenum phosphide composite catalyst has the advantages of simple process, low cost, environment friendliness, no pollution and the like, does not use inflammable phosphorus and highly toxic phosphine as a phosphating agent, has low equipment requirement and strong repeatability, can realize large-scale production, and is beneficial to industrial application.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more clear, the technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
FIG. 1 is a graph showing the effect of the molybdenum phosphide composite catalyst (MoP@NPC-0.10, moP@NPC-0.15, moP@NPC-0.20, moP@NPC-0.25, moP@NPC-0.30) in the example 1 of the invention on removal of dibenzothiophene sulfur in fuel oil.
FIG. 2 is a graph showing the effect of sulfur conversion when the molybdenum phosphide composite catalyst (MoP@NPC-0.25) in example 2 of the present invention was used for removing dibenzothiophene and 4, 6-dimethyldibenzothiophene from fuel oil.
FIG. 3 is a graph showing the effect of sulfur conversion corresponding to the molybdenum phosphide composite catalyst (MoP@NPC-0.25) of example 3 of the present invention when dibenzothiophene in fuel oil is removed under the condition of different oxidant usage amounts.
FIG. 4 is a graph showing the effect of sulfur conversion corresponding to the molybdenum phosphide composite catalyst (MoP@NPC-0.25) of example 4 of the present invention when dibenzothiophene in fuel oil was removed under different extractant dosage conditions.
FIG. 5 is a graph showing the selective removal efficiency of dibenzothiophene in fuel in the presence of various representative interferents for a molybdenum phosphide composite catalyst (MoP@NPC-0.25) according to example 5 of the present invention.
FIG. 6 is a flow chart of the process for removing sulfur-containing organic compounds from oil by using molybdenum phosphide composite catalyst in example 6 of the present invention.
Detailed Description
The invention is further described below in connection with the drawings and the specific preferred embodiments, but the scope of protection of the invention is not limited thereby.
In the embodiment of the invention, the adopted raw materials and instruments are all commercially available. Unless otherwise specified, the process employed was conventional, the equipment employed was conventional, and the data obtained were averages of three or more replicates.
Example 1
A method for removing sulfur-containing organic compounds in oil products by using a molybdenum phosphide composite catalyst, in particular to a method for removing dibenzothiophene in oil products by using a molybdenum phosphide composite catalyst, comprising the following steps:
the catalytic oxidation desulfurization activity of the molybdenum phosphide composite catalyst of the invention is examined, and specifically, the molybdenum phosphide composite catalyst prepared in examples 1-5 is adopted to remove dibenzothiophene in oil products, and the method comprises the following steps:
10mg of molybdenum phosphide composite catalyst (MoP@NPC-0.10, moP@NPC-0.15, moP@NPC-0.20, moP@NPC-0.25 and MoP@NPC-0.30) are respectively and accurately weighed and respectively added into 10mL of Dibenzothiophene (DBT) -n-octane solution with the concentration of 1000ppm (namely simulated petroleum containing the dibenzothiophene), 2mL of acetonitrile solution with the mass fraction of 99% is added, and the mixture is stirred for 10min to achieve extraction balance. Then, 36. Mu.L of a 30% by mass hydrogen peroxide (oxidant, molar ratio of O/S: 6) solution was added, and the catalytic oxidation reaction was carried out at 60℃under magnetic stirring (rotation speed: 600 r/min) for 60 minutes. The catalytic oxidation reaction is carried out in acetonitrile, dibenzothiophene is converted into dibenzothiophene sulfone and is reserved in acetonitrile, and the removal of the dibenzothiophene in the oil product is completed. After the reaction was completed, the acetonitrile phase (lower layer) was separated from the oil phase (upper layer) to obtain clean fuel oil.
In this example, after the completion of the reaction, the sulfur content in the dibenzothiophene in the resultant solution was measured by a gas chromatograph, and the conversion of sulfur in the dibenzothiophene was obtained by calculation, and the result is shown in fig. 1. FIG. 1 is a graph showing the effect of the molybdenum phosphide composite catalyst (MoP@NPC-0.10, moP@NPC-0.15, moP@NPC-0.20, moP@NPC-0.25, moP@NPC-0.30) in the example 1 of the invention on removal of dibenzothiophene sulfur in fuel oil. As can be seen from FIG. 1, all molybdenum phosphide composite catalysts can effectively catalyze and oxidize to remove dibenzothiophene in fuel oil, wherein the removal rate of MoP@NPC-0.25 and MoP@NPC-0.30 to sulfur in dibenzothiophene in oil products can reach 100% within 60min. The results show that the molybdenum phosphide composite catalyst prepared by the invention has better catalytic oxidation performance. The total sulfur content in the oil product treated by the molybdenum phosphide composite catalyst prepared by the invention is less than 10ppm, meets the Euro V fuel standard, and the total desulfurization rate is up to 100%. Particularly, the molybdenum phosphide composite catalyst (MoP@NPC-0.25) shows excellent dibenzothiophene catalytic oxidation effect under the condition of low metal loading, and has good economic benefit and industrial application prospect.
In the embodiment, the molybdenum phosphide composite catalyst (MoP@NPC-0.25) comprises a nitrogen-phosphorus co-doped carbon nano sheet, wherein nano-scale molybdenum phosphide particles are loaded on the nitrogen-phosphorus co-doped carbon nano sheet, and the mass ratio of the nano-scale molybdenum phosphide particles to the nitrogen-phosphorus co-doped carbon nano sheet is 26.62%; the nitrogen content in the nitrogen-phosphorus co-doped carbon nano sheet is 6.3 percent, and the phosphorus content is 12.9 percent.
In the embodiment, the preparation method of the molybdenum phosphide composite catalyst (MoP@NPC-0.25) comprises the following steps:
(1) Adding 1.05g of molybdenum trioxide into 80mL of ultrapure water, and stirring for 20min to obtain molybdenum trioxide dispersion;
(2) Adding 0.50g of imidazole into the dispersion liquid obtained in the step (1), performing hydrothermal reaction at 120 ℃ for 12 hours, centrifuging to separate a solid product, and performing vacuum drying at 50 ℃ for 12 hours to obtain a molybdenum-based metal organic frame;
(3) Weighing 0.25g of the molybdenum-based metal organic frame obtained in the step (2) and 1.00g of melamine, adding into 40mL of ultrapure water, and carrying out ultrasonic treatment for 30min to obtain molybdenum-based metal organic frame/melamine dispersion;
(4) Adding 20mL of phytic acid solution with mass fraction of 15.3% into the molybdenum-based metal organic frame/melamine dispersion liquid obtained in the step (3), and stirring for 20h at 60 ℃ to obtain a precursor solution;
(5) And (3) cooling the precursor solution obtained in the step (4) to room temperature, centrifugally separating to obtain a solid product, freeze-drying for 12h, and calcining for 3h at a temperature rising rate of 5 ℃/min at 800 ℃ in an argon atmosphere to obtain the molybdenum phosphide composite catalyst, namely MoP@NPC-0.25.
In this example, the molybdenum phosphide composite catalyst (MoP@NPC-0.10) used was substantially the same as MoP@NPC-0.25, except that: in MoP@NPC-0.10, the mass ratio of the nanoscale molybdenum phosphide particles to the nitrogen-phosphorus co-doped carbon nano sheet is 4.21%.
In this example, the molybdenum phosphide composite catalyst (MoP@NPC-0.15) used was substantially the same as MoP@NPC-0.25, except that: in MoP@NPC-0.15, the mass ratio of the nanoscale molybdenum phosphide particles to the nitrogen-phosphorus co-doped carbon nano sheet is 8.84%.
In this example, the molybdenum phosphide composite catalyst (MoP@NPC-0.20) used was substantially the same as MoP@NPC-0.25, except that: in MoP@NPC-0.20, the mass ratio of the nanoscale molybdenum phosphide particles to the nitrogen-phosphorus co-doped carbon nano sheet is 18.93%.
In this example, the molybdenum phosphide composite catalyst (MoP@NPC-0.30) used was substantially the same as MoP@NPC-0.25, except that: in MoP@NPC-0.30, the mass ratio of the nanoscale molybdenum phosphide particles to the nitrogen-phosphorus co-doped carbon nano sheet is 36.64%.
Example 2
A method for removing sulfur-containing organic compounds in oil products by using a molybdenum phosphide composite catalyst, specifically, removing dibenzothiophene and 4, 6-dimethyl dibenzothiophene in the oil products by using a molybdenum phosphide composite catalyst (MoP@NPC-0.25), and basically the same as in example 1, wherein the difference is that: the simulated petroleum of example 2 was either a dibenzothiophene-n-octane solution or a 4, 6-dimethyldibenzothiophene-n-octane solution with a sulfur concentration of 1000 ppm.
In this example, the reaction system was sampled at the time of the reaction for 5min, 10min, 20min, 30min, 45min and 60min, the sulfur content in dibenzothiophene and 4, 6-dimethyldibenzothiophene in the obtained product solution was measured at the reaction time, and the conversion of sulfur in dibenzothiophene and 4, 6-dimethyldibenzothiophene was obtained by calculation, and the results are shown in fig. 2. FIG. 2 is a graph showing the effect of sulfur conversion when the molybdenum phosphide composite catalyst (MoP@NPC-0.25) in example 2 of the present invention was used for removing dibenzothiophene and 4, 6-dimethyldibenzothiophene from fuel oil. As can be seen from FIG. 2, the molybdenum phosphide composite catalyst (MoP@NPC-0.25) can be used for rapidly and efficiently removing sulfur-containing organic compounds in fuel oil, the removal rates of dibenzothiophene and 4, 6-dimethyldibenzothiophene respectively reach 100% and 87.45% after 60min of reaction, and the apparent reaction rate constants of oxidation desulfurization of the molybdenum phosphide composite catalyst (MoP@NPC-0.25) on the dibenzothiophene and the 4, 6-dimethyldibenzothiophene respectively reach 0.0698min -1 And 0.0303min -1 。
Example 3
A method for removing sulfur-containing organic compounds in oil products by using a molybdenum phosphide composite catalyst, specifically removing dibenzothiophene in the oil products by using a molybdenum phosphide composite catalyst (MoP@NPC-0.25), is basically the same as in example 1, and differs only in that: the oxidative desulfurization reaction of example 3 used hydrogen peroxide in various amounts of 12. Mu.L, 24. Mu.L, 36. Mu.L, 48. Mu.L, 60. Mu.L, respectively.
FIG. 3 is a graph showing the effect of sulfur conversion corresponding to the molybdenum phosphide composite catalyst (MoP@NPC-0.25) of example 3 of the present invention when dibenzothiophene in fuel oil is removed under the condition of different oxidant usage amounts. As can be seen from FIG. 3, the efficiency of the molybdenum phosphide composite catalyst (MoP@NPC-0.25) for removing dibenzothiophene in oil products by catalytic oxidation is continuously improved with the increase of the hydrogen peroxide. When the amount of hydrogen peroxide reached 36 μl (O: s=6), the molybdenum phosphide composite catalyst (mop@npc-0.25) was able to completely remove dibenzothiophene at a concentration of 1000ppm in the simulated fuel oil within 60min. The result shows that the molybdenum phosphide composite catalyst (MoP@NPC-0.25) can achieve good desulfurization efficiency under the condition of the existence of a small amount of oxidant, and has very high economical practicability.
Example 4
A method for removing sulfur-containing organic compounds in oil products by using a molybdenum phosphide composite catalyst, specifically removing dibenzothiophene in the oil products by using a molybdenum phosphide composite catalyst (MoP@NPC-0.25), is basically the same as in example 1, and differs only in that: the oxidative desulfurization reaction of example 4 used different amounts of acetonitrile, 1mL, 2mL, 5mL, and 10mL, respectively.
FIG. 4 is a graph showing the effect of sulfur conversion corresponding to the molybdenum phosphide composite catalyst (MoP@NPC-0.25) of example 4 of the present invention when dibenzothiophene in fuel oil was removed under different extractant dosage conditions. As can be seen from FIG. 4, the molybdenum phosphide composite catalyst (MoP@NPC-0.25) was able to completely remove dibenzothiophene at a concentration of 1000ppm in the simulated fuel oil within 60 minutes even at a dosage of 1mL of acetonitrile. The result shows that the molybdenum phosphide composite catalyst (MoP@NPC-0.25) can achieve good desulfurization efficiency under the condition of the existence of a very small amount of acetonitrile, and has very high economical practicability.
Example 5
A method for removing sulfur-containing organic compounds in oil products by using a molybdenum phosphide composite catalyst, specifically removing dibenzothiophene in the oil products by using a molybdenum phosphide composite catalyst (MoP@NPC-0.25), is basically the same as in example 1, and differs only in that: the simulated petroleum of dibenzothiophene of example 5 was added with 10% by mass of cyclohexane, 1-butene, toluene, and naphthalene, respectively.
FIG. 5 is a graph showing the selective removal efficiency of dibenzothiophene in fuel in the presence of various representative interferents for a molybdenum phosphide composite catalyst (MoP@NPC-0.25) according to example 5 of the present invention. As can be seen from FIG. 5, when 10% cyclohexane, 1-butene, toluene and naphthalene are respectively present in the oil, the removal rate of the molybdenum phosphide composite catalyst (MoP@NPC-0.25) to dibenzothiophene with a concentration of 1000ppm in the oil can reach 98.34%, 100%, 94.88% and 100%, respectively. The result shows that the molybdenum phosphide composite catalyst (MoP@NPC-0.25) can selectively remove sulfur-containing organic matters in oil products.
Example 6
A method for removing sulfur-containing organic compounds in oil products by using a molybdenum phosphide composite catalyst, in particular to a method for continuously desulfurizing high-sulfur fuel oil by using the molybdenum phosphide composite catalyst, wherein the treatment process flow chart is shown in figure 6, and the method comprises the following steps:
1) 2g of molybdenum phosphide composite catalyst (MoP@NPC-0.25), 2L of high-sulfur fuel oil, 200mL of acetonitrile and 7.2mL of 30% hydrogen peroxide are added into a mixing tank (filled with 2L of dibenzothiophene simulated fuel oil with the concentration of 1000 ppm), and a stirrer is started to be uniformly mixed;
2) Pumping the solution uniformly mixed in the step 1) into a reactor, and starting a stirrer and a heat exchanger to perform oxidative desulfurization reaction for 60min;
3) Conveying the reaction product solution obtained by the oxidation desulfurization reaction in the step 2) into an extractor, and starting the mixer to perform extraction treatment;
4) Conveying the mixed solution obtained after the extraction treatment in the step 3) to a separator, and naturally settling for 10-30 min to obtain an upper oil phase, a lower extractant, an unconsumed oxidant and a catalyst mixed phase;
5) Sequentially conveying the upper oil phase separated in the step 4) to a buffer tank and a finished product tank from an upper discharge pipe to obtain clean fuel oil, and returning the lower mixed phase to a mixing tank from a lower discharge pipe to be mixed with the high-sulfur fuel oil again to complete continuous desulfurization treatment of the high-sulfur fuel oil;
6) And (5) continuously desulfurizing the sulfur-containing fuel oil according to the method of repeating the steps (1) to (5).
In the embodiment, the bottom of the mixing tank is provided with a three-blade stirrer, and a heat exchange device and a plurality of three-blade stirrers are arranged in the reactor; the three-blade stirrer is arranged in the extractor; the separator is in the shape of an inverted cone, and the upper part and the lower part of the separator are both provided with a discharge pipe.
The above examples are only preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the concept of the invention belong to the protection scope of the invention. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be within the scope of the present invention.
Claims (9)
1. A method for removing sulfur-containing organic compounds in oil products by using a molybdenum phosphide composite catalyst is characterized in that the method adopts the molybdenum phosphide composite catalyst to carry out catalytic oxidation treatment on the sulfur-containing organic compounds in the oil products; the molybdenum phosphide composite catalyst comprises a nitrogen-phosphorus co-doped carbon nano-sheet, and molybdenum phosphide nano-particles are loaded on the nitrogen-phosphorus co-doped carbon nano-sheet.
2. The method for removing sulfur-containing organic compounds from oil products by using the molybdenum phosphide composite catalyst according to claim 1, wherein the mass ratio of molybdenum phosphide particles to nitrogen-phosphorus co-doped carbon nano-sheets in the molybdenum phosphide composite catalyst is 2-40; the mass fraction of nitrogen element in the nitrogen-phosphorus co-doped carbon nano-sheet is 2% -8% of that of the nitrogen-phosphorus co-doped carbon nano-sheet; the mass fraction of the phosphorus element is 4% -15% of the nitrogen-phosphorus co-doped carbon nano-sheet.
3. The method for removing sulfur-containing organic compounds from oil products by using the molybdenum phosphide composite catalyst according to claim 1 or 2, wherein the preparation method of the molybdenum phosphide composite catalyst comprises the following steps:
s1, preparing molybdenum-based metal organic frameworks into molybdenum-based metal organic framework dispersion liquid, adding melamine dispersion liquid, and stirring to prepare molybdenum-based metal organic frameworks/melamine dispersion liquid;
s2, mixing the molybdenum-based metal organic framework/melamine dispersion liquid obtained in the step S1 with a phytic acid solution to perform solvothermal reaction, centrifuging, and freeze-drying to obtain molybdenum phosphide composite catalyst precursor powder;
and S3, calcining the molybdenum phosphide composite catalyst precursor powder obtained in the step S2 in an argon atmosphere to obtain the molybdenum phosphide composite catalyst.
4. The method for removing sulfur-containing organic compounds from oil products by using molybdenum phosphide composite catalyst according to claim 3, wherein in step S1, the preparation method of the molybdenum-based metal organic framework comprises the following steps:
(1) Adding molybdenum trioxide into water, and stirring to obtain molybdenum trioxide dispersion; the mass ratio of the molybdenum trioxide to the water is 1:70-100; the stirring time is 0.5-2 h;
(2) Adding imidazole into the molybdenum trioxide dispersion liquid obtained in the step (1) for hydrothermal reaction, washing and drying to obtain the molybdenum-based metal organic framework. The mass ratio of the imidazole to the molybdenum trioxide is 0.48-0.50:1; the temperature of the hydrothermal reaction is 100-140 ℃; the hydrothermal reaction time is 12-24 hours; the washing is to wash the filtered product 3-6 times by ultrapure water; the drying process is carried out under vacuum conditions; the drying temperature is 40-80 ℃.
5. The method for removing sulfur-containing organic compounds from oil products by using a molybdenum phosphide composite catalyst according to claim 4, wherein in step S1, the concentration of the molybdenum-based metal organic framework dispersion liquid is 25-200 g/L; the concentration of the melamine dispersion liquid is 30-50 g/L; the stirring time is 0.5-2 h;
in the step S2, the mass fraction of the phytic acid solution is 16% -20%; the volume ratio of the phytic acid solution to the molybdenum-based metal organic framework/melamine dispersion is 0.5-0.8:1; the solvothermal reaction temperature is 60-80 ℃; the solvothermal reaction time is 12-24 hours; the freeze drying time is 12-24 hours;
in the step S3, the calcining temperature is 800-900 ℃; the temperature rising rate of the calcination is 2-10 ℃/min.
6. The method for removing sulfur-containing organic compounds from oil products by using molybdenum phosphide composite catalyst according to any one of claims 1-5, characterized in that the molybdenum phosphide composite catalyst is used for catalytic oxidation treatment of sulfur-containing organic compounds in oil products, comprising the following steps: mixing molybdenum phosphide composite catalyst, acetonitrile and hydrogen peroxide with sulfur-containing organic compound oil, performing physical mixing and heating to start catalytic oxidation reaction, and removing sulfur organic compound in the oil by extraction separation.
7. The method for removing sulfur-containing organic compounds from oil products by using the molybdenum phosphide composite catalyst according to claim 6, wherein the dosage of the molybdenum phosphide composite catalyst is 1-3 g of the molybdenum phosphide composite catalyst added into each liter of sulfur-containing organic compound oil products; the molar ratio of the hydrogen peroxide to the sulfur in the sulfur-containing organic compound oil product is 6:1; the sulfur-containing organic compound in the sulfur-containing organic compound oil product is at least one of dibenzothiophene and 4, 6-dimethyl dibenzothiophene; the concentration of the sulfur-containing organic compound in the sulfur-containing organic compound oil product is 1000-2000 ppm; the catalytic oxidation reaction is carried out at the temperature of 50-70 ℃; the time of the catalytic oxidation reaction is 30-60 min.
8. The method for removing sulfur-containing organic compounds from oil products by using a molybdenum phosphide composite catalyst according to claim 7, wherein the high-sulfur fuel oil is subjected to desulfurization treatment by using an oxidation desulfurization reaction device; the oxidation desulfurization reaction device comprises a mixing tank, a reactor, an extractor, a separator, a buffer tank and a finished product tank, and the desulfurization treatment of the high-sulfur fuel oil comprises the following steps:
1) Adding the molybdenum phosphide composite catalyst, the high-sulfur fuel oil, the extractant and the oxidant into a mixing tank, and uniformly mixing;
2) Pumping the solution uniformly mixed in the step 1) into a reactor for oxidation desulfurization reaction;
3) Conveying the reaction product solution obtained by the oxidation desulfurization reaction in the step 2) to an extractor for extraction treatment;
4) Conveying the mixed solution obtained after the extraction treatment in the step 3) to a separator, and naturally settling for 10-30 min to obtain an upper oil phase, a lower extractant, an unconsumed oxidant and a catalyst mixed phase;
5) And (3) sequentially conveying the upper oil phase separated in the step (4) to a buffer tank and a finished product tank to obtain clean fuel oil, and returning the lower mixed phase to a mixing tank to mix with the high-sulfur fuel oil again, thereby completing the continuous desulfurization treatment of the high-sulfur fuel oil.
9. The method according to claim 8, wherein the bottom of the mixing tank is provided with a three-blade stirrer, and the reactor is provided with a heat exchange device and a plurality of three-blade stirrers; a three-blade stirrer is arranged in the extractor; the separator is in an inverted cone shape, and the upper part and the lower part of the separator are both provided with discharge pipes.
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