CN110252384A - A kind of sub-nanometer cluster transition metal oxide/MCM-41 composite material, preparation method and applications - Google Patents
A kind of sub-nanometer cluster transition metal oxide/MCM-41 composite material, preparation method and applications Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/041—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41
- B01J29/045—Mesoporous materials having base exchange properties, e.g. Si/Al-MCM-41 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- 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
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
A kind of sub-nanometer cluster transition metal oxide/MCM-41 composite material, preparation method and applications, belongs to nano-catalytic and environmental protection technology crossing domain.Transition metal oxide precursor body is added in this method during the preparation process, and calcining obtains sub-nanometer cluster transition metal oxide/MCM-41.MCM-41 carrier is spheroid shape in the composite material being prepared into；Partial size is 50~500nm, and aperture is 2~3nm；Sub-nanometer cluster transition metal oxide high degree of dispersion, partial size is in 0.1~2.0nm.As heterogeneous catalysis, the oxidation sweetening process being applied in the simulation oil systems that dibenzothiophenes is desulfurization object may be implemented under room temperature using tert-butyl hydroperoxide as the catalytic oxidation desulfurization of oxide the composite material being prepared into.The present invention prepares sub-nanometer cluster transition metal oxide/MCM-41 simple process, safety；It can be improved transition metal oxide catalytic oxidation desulfurization activity, Oxidation at room temperature desulfurization may be implemented as oxidation-desulfurizing catalyst, there is good reusability.
Description
Technical field
The invention belongs to nano-catalytic and environmental protection technology crossing domain, be related to a kind of sub-nanometer cluster transition metal oxide/
MCM-41 composite material, preparation method and applications provide a kind of based on the room sub-nanometer cluster transition metal oxide/MCM-41
Warm oxidation desulfurizing method.
Background technique
The burning of Sulfur content in Fuel Oil brings numerous harm to human society, and the formation of acid rain can corrode communal facility, cause
Property loss.The presence of sulphur can make the catalyst inactivations such as fuel-cell catalyst, Three-component Catalytic Converters for Automobiles catalyst, influence
Industrial production.Human health also suffers from sulfur-containing compound and burns the seriously threatening of the particulate matter to be formed.As people's environmental protection is anticipated
The raising of knowledge, various countries are increasingly stringenter the regulation of Sulfur content in Fuel Oil content.If China provides, from 2018, derv fuel,
The sulfur content upper limit of gasoline is 10ppm.
Since steric hindrance is larger, dibenzothiophenes and its alkyl derivative become conventional hydrodesulfurization technology and are difficult to remove
The fragrant sulphur component of the stubbornness gone, generally requires and removes under conditions of 300 DEG C, 5MPa or more.High temperature, high pressure operating condition make
At hydrodesulfurization higher cost, the demand of economic development is not met.Sulphur atom electricity on dibenzothiophenes and its alkyl derivative
Sub- density is high, is easily oxidized to correspond to highly polar sulfone class, to be removed by processing such as absorption, extractions.Therefore oxygen
Change desulfurization to be widely studied as a kind of economic desulfurization method.
Transition metal oxide catalytic oxidation activity with higher is widely used as with tert-butyl hydroperoxide as oxidation
The active component of the catalytic oxidation desulfurization catalyst of agent.2003, Wang et al. was with Al2O3For carrier (Appl.Catal.A:
Gen., it is living that the catalyst that 2003,253,91), Mo load capacity is 16wt% presents excellent catalytic oxidation desulfurization at 110 DEG C
Property.2017, Wang etc. was with unordered mesoporous SiO2As carrier (RSC.ADV., 2017,7,44827), Mo load capacity is
Catalyst of the 0.2wt% material as catalytic oxidation desulfurization, sub-nanometer cluster MoO3It is de- that superior catalysis oxidation is presented at 60 DEG C
Sulphur activity.Although opposite hydrodesulfurization, has been realized in the oxidation sweetening under temperate condition, the Oxidation at room temperature without heating device
Desulfurization is still relatively difficult to achieve.
Based on the above content, this patent is intended to using the bigger ordered mesoporous silica dioxide MCM-41 of specific surface area as Asia
The carrier of nano-cluster transition metal oxide.Wish while increasing load capacity, keeps its size in sub-nanometer cluster rank, with
This improves the catalytic oxidation desulfurization ability of catalyst, realizes oxidation sweetening under room temperature.
Summary of the invention
In order to realize catalytic oxidation desulfurization under room temperature, the present invention provide a kind of sub-nanometer cluster transition metal oxide/
The preparation method of MCM-41 is prepared composite material as heterogeneous catalysis, may be implemented under room temperature with tert-butyl
Catalytic oxidation desulfurization of the hydrogen peroxide as oxide has superior reusability.
In order to achieve the above object, the technical solution adopted by the present invention are as follows:
A kind of preparation method of sub-nanometer cluster transition metal oxide/MCM-41 composite material, comprising the following steps:
(1) cationic surfactant cetyl trimethylammonium bromide is added to the water, wherein cation surface activating
Agent concentration is 4.0~8.0 × 10-6mol/L；60 DEG C~80 DEG C are warming up to, is stirred to clarify under 700~900rpm revolving speed；To
After reaction system is cooled to room temperature (20~30 DEG C), the 25wt% ammonium hydroxide of 0.007~0.167mL, stirring are added in every milliliter of water
After 5~30min, continue the precursor solution that instillation 0.02~0.1mL concentration is 0.05~0.1mol/L in every milliliter of water, after
It is continuous to stir 10~60min, 0.017~0.033mL tetraethyl orthosilicate is added dropwise in every milliliter of water.After continuing 1~4h of stirring,
Obtain reaction solution.
The presoma includes ammonium heptamolybdate, single ammonium molybdate, ammonium metatungstate, ammonium metavanadate.
(2) 10~12min is centrifuged under 8000~10000rpm revolving speed in the reaction solution that step (1) obtains,
Liquid phase is removed, obtained solid phase uses ethanol washing, dry 10~12 h at 100 DEG C~120 DEG C.
(3) it after the sample after being dried step (2) is cooled to room temperature, is ground into powdered.In air atmosphere,
4~6h of calcination processing is carried out after being warming up to 550 DEG C in Muffle furnace, obtains transition metal oxide/MCM-41 composite material.Institute
The heating rate stated is 2~5 DEG C/min.
The sub-nanometer cluster transition metal oxide/MCM-41 composite material obtained using above-mentioned preparation method, the composite wood
MCM-41 carrier is spheroid shape in material；Composite material partial size is 50~500nm, and aperture is 2~3 nm；Sub-nanometer cluster transition metal
Oxide high degree of dispersion, partial size is in 0.1~2.0nm.
The sub-nanometer cluster transition metal oxide/MCM-41 composite material obtained using above-mentioned preparation method is applied to hexichol
Bithiophene is the oxidation sweetening process in the simulation oil systems of desulfurization object, as oxidation-desulfurizing catalyst.The simulation oil
In system, using decahydronaphthalene as solvent, dibenzothiophenes is sulfur containing species, and tert-butyl hydroperoxide is desulfurization oxidant.Described
Under room temperature progress of the oxidation sweetening process at 20 DEG C~30 DEG C, reaction time are 10~15min.
The sub-nanometer cluster transition metal oxide/MCM-41 composite material obtained using above-mentioned preparation method is as catalyst
Regeneration treatment, use methanol or acetone as detergent, dry 1 h obtains regenerated catalysis under the conditions of 100 DEG C after washing
Agent.
Beneficial effects of the present invention:
(1) sub-nanometer cluster transition metal oxide/catalyst of the MCM-41 as oxidation sweetening of the invention, preparation process
Simply, mild condition is conducive to large-scale industrial production.
(2) sub-nanometer cluster transition metal oxide/catalyst of the MCM-41 as oxidation sweetening of the invention, may be implemented
Using tert-butyl hydroperoxide as the Oxidation at room temperature desulfurization of oxidant, while there is excellent reusability.
Detailed description of the invention
Fig. 1 (a) is the sub-nanometer cluster MoO that case study on implementation 1 is prepared3The nitrogen adsorption desorption curve graph of/MCM-41 material；
Box indicates adsorption curve figure in figure, and circle zero indicates desorption curve figure.
Fig. 1 (b) is the sub-nanometer cluster MoO that case study on implementation 1 is prepared3The graph of pore diameter distribution of/MCM-41 material；
Fig. 2 is the sub-nanometer cluster MoO that case study on implementation 1 is prepared3The TEM that/MCM-41 material scale is 200nm schemes；
Fig. 3 is the sub-nanometer cluster MoO that case study on implementation 1 is prepared3The TEM that/MCM-41 material scale is 50nm schemes；
Fig. 4 is the sub-nanometer cluster MoO that case study on implementation 1 is prepared3The HADDF-STEM of/MCM-41 material schemes；
Fig. 5 (a) is 4 sub-nanometer cluster MoO of case study on implementation3The reuse result figure of/MCM-41 catalyst；
Fig. 5 (b) is 5 sub-nanometer cluster MoO of case study on implementation3The reuse result figure of/MCM-41 catalyst；
Specific embodiment
Below with reference to case is given alms, the present invention is described in further detail, and the present invention is not limited to following specific certainly
Case study on implementation.
Case study on implementation 1
0.135g cationic surfactant cetyl trimethylammonium bromide is taken to be added in flask as template, with
60mL deionized water is added afterwards, is stirred to clarify at 60 DEG C with 900rpm revolving speed.30 DEG C are cooled to reaction system, is added
10mL 25wt% ammonium hydroxide continues after stirring 10min, and the Ammoniun Heptamolybdate Solution that 2.4mL concentration is 0.05mol/L is added.Sufficiently
After stirring 20min, 2mL tetraethyl orthosilicate is added dropwise, after reacting 2h, reaction solution is shifted in 10mL centrifuge tube,
10min is centrifugated under 10000rpm revolving speed.Second is added to remaining solid in the liquid phase that centrifuge separation is then removed by toppling over
Alcohol washing.Solidliquid mixture after washing is further centrifugated, 10 min are equally centrifugated under 10000rpm revolving speed.
Topple over after removing ethanol washes, remaining solid is placed in 100 DEG C of baking ovens dry 12h.Sample after to be dried is cooled to
Room temperature, be ground to it is powdered, by it as in Muffle furnace.Muffle furnace heating rate is 2 DEG C/min, is kept after being warming up to 550 DEG C
6h, is passed through air in the process, and holding air speed is 40mL/min.Composite material obtained measures Mo via ICP-MS
Load capacity is 2.0wt%.Fig. 1 (a) is the sub-nanometer cluster MoO that case study on implementation 1 is prepared3The nitrogen of/MCM-41 material is inhaled de-
Attached curve graph；Fig. 1 (b) is the sub-nanometer cluster MoO that case study on implementation 1 is prepared3The graph of pore diameter distribution of/MCM-41 material；Fig. 2 is
The sub-nanometer cluster MoO that case study on implementation 1 is prepared3The TEM that/MCM-41 material scale is 200nm schemes；Fig. 3 is case study on implementation 1
The sub-nanometer cluster MoO being prepared3The TEM that/MCM-41 material scale is 50 nm schemes；Fig. 4 is what case study on implementation 1 was prepared
Sub-nanometer cluster MoO3The HADDF-STEM of/MCM-41 material schemes.
Case study on implementation 2
Remaining implementation process and case study on implementation 1 are consistent, and using the material prepared in case 1 as the catalysis of oxidation sweetening
Agent.
It is to represent object with the lower dibenzothiophenes of activity in oxidation sweetening, the dibenzothiophenes of 100mg is dissolved in 100mL
In decahydronaphthalene, preparation obtains the simulation oil of the dibenzothiophenes containing 1000ppm.A certain amount of tert-butyl hydroperoxide is separately taken to be dissolved in
Uses in decahydronaphthalene as oxidizing agent solution, so that tert-butyl hydroperoxide and above-mentioned simulation oil in oxidizing agent solution under same volume
Molar ratio (O/S) value of middle sulphur is 2.It takes 1mL simulation oil in reaction tube, the above-mentioned catalyst of 1.9mg is added.1mL is then added
Oxidizing agent solution, so that DBT content is 500ppm in reaction system.15min is reacted at 30 DEG C, is turned by GC-FID detection DBT
Rate reaches 89.6%.20min is reacted at 30 DEG C, conversion ratio reaches 100%.
Case study on implementation 3
Remaining implementation process and case study on implementation 2 are consistent, the difference is that catalyst amount is 19mg.
Case study on implementation 4
Remaining implementation process and case study on implementation 3 are consistent, and the reaction solution after reaction is transferred in 10mL centrifuge tube,
10min is centrifuged under 10000rpm revolving speed.After being poured off liquid phase, solid phase is washed.Selection methanol is detergent, is remained to above-mentioned
8mL methanol is added in remaining solid phase, it is centrifuged after ultrasonic 5min.It is centrifuged 10min under 10000rpm revolving speed, is taken
The residue for being poured off methanol cleaning solution is solid in baking oven.At 100 DEG C after dry 1h, regenerated catalysis is obtained to its cooling
Agent.The catalyst lived again is applied in Oxidation at room temperature desulfurization according to case 5, obtains the DBT conversion ratio of second of reuse
It is still 100%.It repeats the above process to obtain the DBT conversion ratio that third time is reused and drops to 81.0%.Third time is repeated
After the catalyst recycling used, except washing, drying steps, this process of 3h of calcining is added at 550 DEG C.Regenerated catalyst
The 4th reuse is carried out, DBT conversion ratio restores 100%.It can be seen that calcination process, which can remove, is adsorbed in catalyst surface not
Clean dibenzothiophene sulphone.Catalyst is down to 80.8% without calcining, DBT conversion ratio during 5th reuse.Fig. 5
It (a) is 4 sub-nanometer cluster MoO of case study on implementation3The reuse result figure of/MCM-41 catalyst.
Case study on implementation 5
Remaining implementation process and case study on implementation 3 are consistent, and the reaction solution after reaction is transferred in 10mL centrifuge tube,
10min is centrifuged under 10000rpm revolving speed.After being poured off liquid phase, solid phase is washed.Selection methanol is detergent, is remained to above-mentioned
8mL acetone is added in remaining solid phase, it is centrifuged after ultrasonic 5min.It is centrifuged 10min under 10000rpm revolving speed, is taken
The residue for being poured off acetone washing liquid is solid in baking oven.At 100 DEG C after dry 1h, regenerated catalysis is obtained to its cooling
Agent.The catalyst lived again is applied in Oxidation at room temperature desulfurization according to case 5, obtains the DBT conversion ratio of second of reuse
It is still 100%.After reusing 5 times, DBT conversion ratio still may remain in 95.5%.It can be seen that acetone washing can keep being catalyzed
The excellent reusability of agent.Fig. 5 (b) is 5 sub-nanometer cluster MoO of case study on implementation3The reuse result of/MCM-41 catalyst
Figure.
Case study on implementation 6
0.095g cationic surfactant cetyl trimethylammonium bromide is taken to be added in flask as template, with
60mL deionized water is added afterwards, is stirred to clarify at 80 DEG C with 700rpm revolving speed.30 DEG C are cooled to reaction system, is added
0.4mL 25wt% ammonium hydroxide continues after stirring 5min, and the Ammoniun Heptamolybdate Solution that 1.2mL concentration is 0.05mol/L is added.Sufficiently
After stirring 10min, 1.0mL tetraethyl orthosilicate is added dropwise.After reacting 1h, reaction solution is shifted in 10mL centrifuge tube,
12min is centrifugated under 8000rpm revolving speed.Second is added to remaining solid in the liquid phase that centrifuge separation is then removed by toppling over
Alcohol washing.Solidliquid mixture after washing is further centrifugated, is equally centrifugated 12min under 8000rpm revolving speed.
Topple over after removing ethanol washes, remaining solid is placed in 120 DEG C of baking ovens dry 10h.Sample after to be dried is cooled to
Room temperature, be ground to it is powdered, by it as in Muffle furnace.Muffle furnace heating rate is 5 DEG C/min, is kept after being warming up to 550 DEG C
4h, is passed through air in the process, and holding air speed is 40mL/min.
Case study on implementation 7
0.190g cationic surfactant cetyl trimethylammonium bromide is taken to be added in flask as template, with
60mL deionized water is added afterwards, is stirred to clarify at 70 DEG C with 800rpm revolving speed.30 DEG C are cooled to reaction system, is added
5.0mL 25wt% ammonium hydroxide continues after stirring 30min, and single ammonium molybdate solution that 6mL concentration is 0.1mol/L is added.Sufficiently stir
After mixing 60min, 2.0mL tetraethyl orthosilicate is added dropwise.After reacting 4h, reaction solution is transferred in centrifuge tube,
10min is centrifugated under 10000rpm revolving speed.Second is added to remaining solid in the liquid phase that centrifuge separation is then removed by toppling over
Alcohol washing.Solidliquid mixture after washing is further centrifugated, is equally centrifugated 10min under 10000rpm revolving speed.
Topple over after removing ethanol washes, remaining solid is placed in 120 DEG C of baking ovens dry 10h.Sample after to be dried is cooled to
Room temperature, be ground to it is powdered, by it as in Muffle furnace.Muffle furnace heating rate is 3 DEG C/min, is kept after being warming up to 550 DEG C
5h, is passed through air in the process, and holding air speed is 40mL/min.
Case study on implementation 8
Remaining implementation process and case study on implementation 1 are consistent, and the ammonium metavanadate solution that 6mL concentration is 0.1mol/L is substituted
2.4mL concentration is the Ammoniun Heptamolybdate Solution of 0.05mol/L.
Case study on implementation 9
Remaining implementation process and case study on implementation 1 are consistent, and the ammonium metatungstate solution that 1.2mL concentration is 0.05mol/L is substituted
2.4mL concentration is the Ammoniun Heptamolybdate Solution of 0.05mol/L.
Embodiment described above only expresses embodiments of the present invention, and but it cannot be understood as to the invention patent
Range limitation, it is noted that for those skilled in the art, without departing from the inventive concept of the premise, also
Several modifications and improvements can be made, these are all belonged to the scope of protection of the present invention.
Claims (6)
1. a kind of preparation method of sub-nanometer cluster transition metal oxide/MCM-41 composite material, which is characterized in that including following
Step:
(1) cationic surfactant cetyl trimethylammonium bromide is added to the water, wherein cationic surfactant is dense
Degree is 4.0~8.0 × 10-6mol/L；60 DEG C~80 DEG C are warming up to stir to clarify；After reaction system is cooled to room temperature, every milli
Rise water in be added 0.007~0.167mL 25wt% ammonium hydroxide, stir 5~30min after, continue in every milliliter of water instillation 0.02~
0.1mL concentration is the precursor solution of 0.05~0.1mol/L, continues 10~60min of stirring, is added dropwise in every milliliter of water
0.017~0.033mL tetraethyl orthosilicate；Continue after being stirred to react 1~4h, obtains reaction solution；
The presoma includes ammonium heptamolybdate, single ammonium molybdate, ammonium metatungstate, ammonium metavanadate；
(2) liquid phase will be removed after the centrifuge separation of reaction solution that step (1) obtains, obtained solid phase uses ethanol washing, it is dry at
Reason；
(3) it after the sample after being dried step (2) is cooled to room temperature, is ground into powdered；In air atmosphere, in horse
4~6h of calcination processing is carried out after being not warming up to 550 DEG C in furnace, obtains transition metal oxide/MCM-41 composite material.
2. a kind of preparation method of sub-nanometer cluster transition metal oxide/MCM-41 composite material according to claim 1,
It is characterized in that, drying temperature is 100 DEG C~120 DEG C in the step (2), drying time is 10~12h.
3. a kind of preparation side of sub-nanometer cluster transition metal oxide/MCM-41 composite material according to claim 1 or 2
Method, which is characterized in that heating rate is 2~5 DEG C/min in the step (3).
4. multiple using sub-nanometer cluster transition metal oxide/MCM-41 that any preparation method of claim 1-3 obtains
Condensation material, which is characterized in that MCM-41 carrier is spheroid shape in the composite material；Composite material partial size is 50~500nm,
Aperture is 2~3nm；Sub-nanometer cluster transition metal oxide high degree of dispersion, partial size is in 0.1~2.0nm.
5. multiple using sub-nanometer cluster transition metal oxide/MCM-41 that any preparation method of claim 1-3 obtains
The application of condensation material, which is characterized in that urged using sub-nanometer cluster transition metal oxide/MCM-41 composite material as oxidation sweetening
Agent, the oxidation sweetening process being applied in the simulation oil systems that dibenzothiophenes is desulfurization object；The oxidation sweetening mistake
Under room temperature progress of the journey at 20 DEG C~30 DEG C, reaction time are 10~15min.
6. the application of sub-nanometer cluster transition metal oxide/MCM-41 composite material according to claim 5, feature exist
In the sub-nanometer cluster transition metal oxide/regeneration treatment of the MCM-41 composite material as oxidation-desulfurizing catalyst: making
Use methanol or acetone as detergent, dry 1h obtains regenerated catalyst under the conditions of 100 DEG C after washing.
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