CN106693899A - Metal organic framework material/functional ionic liquid composite material as well as preparation and application thereof - Google Patents
Metal organic framework material/functional ionic liquid composite material as well as preparation and application thereof Download PDFInfo
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- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
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- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0285—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre also containing elements or functional groups covered by B01J31/0201 - B01J31/0274
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
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Abstract
The invention discloses a metal organic framework material/functional ionic liquid composite material as well as preparation and application thereof, and belongs to the technical field of light industry and chemical engineering materials. As a functional ionic liquid is synthesized and loaded on a meal organic framework material by using a 'ship-in-a-bottle synthesis' method, the circulation use efficiency of the ionic liquid can be effectively improved, and the use amount of the ionic liquid can be reduced; and due to the diversity of the metal organic framework material, a series of different metal organic framework materials/functional ionic liquid composite materials can be synthesized. The metal organic framework material/functional ionic liquid composite material disclosed by the invention can be applied to gasoline catalytic oxidation desulfurization, and the purposes of improving the catalytic property of a system, reducing the amount of the ionic liquid and facilitating product separation and catalyst recycling can be achieved. The composite material disclosed by the invention can be used as a catalyst for adsorbing, oxidizing, extracting and removing sulfur-containing substances in gasoline, and is gentle in reaction condition, good in desulfurization effect and easy in catalyst recycling.
Description
Technical field
The invention belongs to light industry, the technical field of chemical materials, more particularly to a kind of metal-organic framework materials/function
Change ionic liquid composite material and preparation method and application.
Background technology
With the fast development of global economy, the recoverable amount of Global Auto increases year by year, it is contemplated that various to the year two thousand fifty whole world
The total recoverable amount of automobile will rise to 2,500,000,000 amounts.Automobile quantity is continuously increased, and to result in gasoline demand amount increase year by year.In gasoline
The burning of sulfur-containing compound can produce oxysulfide (SOx), wherein SO2It is the main cause for causing acid rain.SO2Because it is soluble in
Water, after respiratory tract is entered, major part is arrested in the upper respiratory tract, and generation has corrosive sulfurous on the mucous membrane of moistening
Acid, sulfuric acid and sulfate, make stimulation stronger.And sulfur dioxide can also be rapidly absorbed into blood, produce poison secondary whole body
Effect, the vigor of its energy destructive enzyme, there is certain infringement to liver.
Existence and life in order to avoid SOx on the mankind cause further influence, and countries in the world have been formulated one and have been in succession
Strict standard is arranged to limit the content of sulfide in petrol.2008, the sulfur content of Japanese gasoline have decreased to 10mg/kg；
European Union also came into effect Euro V emissions from 2009, it is desirable to which sulfur content is less than 10mg/kg in automobile-used petrol and diesel oil；In March, 2014
3, Environmental Protection Agency promulgated automobile emission and fuel oil quality new standard, new legislation specify sulfur content in gasoline from
30mg/kg is down to 10mg/kg.As can be seen here, the production low-sulfur even fuel oil without sulphur is the main trend of future world fuel oil development.
In order to be integrated with the world, China has also made a series of strict sulfur-bearing standards in succession.On May 12nd, 2011, China's issue
Motor petrol state IV standards, it is stipulated that vehicle gasoline and sulfur content in vehicle gasoline is less than 50mg/kg.Opened from 31 days zero May in 2012 Beijing
Begin to carry out capital V motor petrol standards, normal benzine sulfur content is less than 10mg/kg.Due to China's oil Refining Technologies and developed country's phase
Than also there is certain gap, therefore, comprehensive this target in line with international standards of sulfur content standard in gasoline is realized, task will more
It is arduousness, therefore there is the deep desulfurization of gasoline technology of research and development economical and efficient highly important economic implications and society to anticipate
Justice.Traditional hydrodesulfurization technology is to aromatics sulfide, and the removal effect of such as dibenzothiophenes and its derivative is bad.Be up to
To the purpose of deep desulfuration, it is necessary to improve pressure and use noble metal catalyst, this necessarily increases operating cost and equipment investment.
At present, because its reaction condition is gentle, the equipment investment amount of money is few, desulfurized effect is good, especially for catalytic oxidation desulfurization
There is selectivity well for the thiophene that is difficult to remove in hydrodesulfurization, dibenzothiophenes class organic sulfur, and be increasingly becoming
Study hotspot.
The content of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the invention is to provide a kind of metal organic framework
The preparation method of material/functionalized ion liquid composite.Ionic liquid is existed by " ship construction method in bottle " specifically
Synthesize and be limited in metal-organic framework materials in empty cage.
It is another object of the present invention to provide the metal-organic framework materials/function of being prepared by above-mentioned preparation method
Change ionic liquid composite material.
It is yet a further object of the present invention to provide above-mentioned metal-organic framework materials/functionalized ion liquid composite
Application.
The purpose of the present invention is achieved through the following technical solutions：
A kind of preparation method of metal-organic framework materials/functionalized ion liquid composite, comprises the following steps：
(1) inorganic salts and organic ligand are mixed, being subsequently adding stirring solvent dissolves it, insulation；Make after the completion of reaction
It is cooled to room temperature, and washing precipitation is multiple, then filters, and is dried to obtain metal-organic framework materials；
(2) in the metal-organic framework materials input precursor A for obtaining step (1), stirring；Precursor B is subsequently adding,
Continue to stir, then the ionic liquid H to being obtained2SO4Carry out ion exchange and obtain acidic ion liquid；Suction filtration, it is then right
It is vacuum dried, so as to obtain metal-organic framework materials/functionalized ion liquid composite.
The cation of the inorganic salts described in step (1) is Cu2+、Zn2+、Zr4+、Cr3+、Fe3+And Al3+In at least one
Kind；
The anion of the inorganic salts described in step (1) is NO3 -、Cl-And COO-In at least one.
Organic ligand described in step (1) is terephthalic acid (TPA) (a), trimesic acid (b), 2,6- naphthalenedicarboxylic acids (c),
At least one in 2,4,6- tri- (4- carboxyl phenyls) -1,3,5-triazines (d), its structural formula is
Solvent described in step (1) is N,N-dimethylformamide (DMF), N, N- DEFs (DEF), second
At least one in alcohol, hydrofluoric acid (HF) and water.
The cation of the inorganic salts described in step (1) is 8 with the mol ratio of organic ligand：25~15:1, solvent
Consumption is 40~60mL；
The condition of the insulation described in step (1) is 85~220 DEG C of 8~48h of insulation；
Dry condition described in step (1) is 80~200 DEG C of 12~15h of drying；
Precursor A described in step (2) is N- methylimidazoles.
Precursor B described in step (2) is n-Propyl Bromide or 1,3- propane sultones.
The condition of the stirring described in step (2) is to stir 15h at room temperature；
The condition that continuation described in step (2) is stirred is 60 DEG C of stirring 24h；
Precursor A and the mol ratio of precursor B described in step (2) are 1:1~1：2；Preferably 1:1.2.
Vacuum drying condition described in step (2) is 80 DEG C of vacuum drying 24h；
A kind of metal-organic framework materials/functionalized ion liquid composite, are prepared by above-mentioned preparation method.
Described metal-organic framework materials/application of the functionalized ion liquid composite in gasoline desulfurization.
The application is with metal-organic framework materials/functionalized ion liquid composite as catalyst and adsorbent,
With H2O2It is oxidant, with acetonitrile as extractant, the sulfide in gasoline is removed by the coupled modes of adsorbing-oxidising-extraction.
The present invention has the following advantages and effect relative to prior art：
(1) functionalized ion liquid is synthesized and is supported on metal-organic framework materials by the present invention using " ship construction method in bottle "
On, the recycling efficiency of ionic liquid and the consumption of reduction ionic liquid can be effectively improved；
(2) present invention can synthesize a series of organic bones of different metals due to the diversity of metal-organic framework materials
Frame material/functionalized ion liquid composite.
(3) metal-organic framework materials/functionalized ion liquid composite that the present invention is obtained is used for gasoline catalyzing oxygen
Change desulfurization, reach raising system catalytic performance, the mesh for reducing ionic liquid consumption, being easy to product separation and catalyst recycle
's.
(4) composite that the present invention is obtained is used for sulfur-bearing thing in adsorbing-oxidising-extraction removing gasoline as catalyst
Matter, its reaction condition is gentle, desulfurized effect is good, catalyst is easily reclaimed.
Specific embodiment
With reference to embodiment, the present invention is described in further detail, but embodiments of the present invention not limited to this.
Embodiment 1
A kind of preparation method of metal-organic framework materials/functionalized ion liquid composite is present embodiments provided,
The preparation method specifically includes following steps：
(1) 60mL distilled water is added in the reactor of polytetrafluoroethyllining lining first, is subsequently adding 5.00g
(12.5mmol)Cr(NO3)3·9H2O and 2.08g (12.5mmol) terephthalic acid (TPA), stir 20min, are eventually adding 0.63g HF
(40%), 220 DEG C of heating 8h, are cooled to room temperature, are filtrated to get green solid.Solid is washed with DMF, ethanol, will finally be obtained
Solid dried one the whole night at 150 DEG C, obtain MIL-101 (Cr).
(2) toward addition 0.5g MIL-101 (Cr) in 50mL flasks, 4.106g (0.05mol) N- methylimidazoles, room are added
The lower stirring 15h of temperature.Add 7.3795g (0.06mol) n-Propyl Bromide, 60 DEG C of stirring 24h.Suction filtration, washes three times, every time with ethanol
Resulting solid is added 20mL ethanol by 10mL, adds excessive H2SO4, 24h is stirred at room temperature, filter, washing, 80 DEG C are true
Sky dries 24h, finally obtains metal-organic framework materials/functionalized ion liquid composite, as catalyst A：[PMIm]
HSO4@MIL-101(Cr)。
Dibenzothiophenes is dissolved in normal octane by the dibenzothiophenes of more difficult removing as target sulphide with hydrodesulfurization,
It is configured to the analog gasoline that sulfur content is 50ppm.Analog gasoline 10mL is taken, catalyst A0.06g mixes with analog gasoline.Add
Hydrogen peroxide and 10mL acetonitriles, with hydrogen peroxide as oxidant, acetonitrile is added to the mixed liquor of fuel gasoline and catalyst for extractant
In, at a temperature of 60 DEG C, 2h being stirred, the mol ratio of the S in O and analog gasoline in hydrogen peroxide is 50.Stratification after suction filtration,
It is 9ppm to take upper strata analog gasoline high performance liquid chromatography and determine sulfur content, and desulfurization degree reaches 82%.
Embodiment 2
A kind of preparation method of metal-organic framework materials/functionalized ion liquid composite is present embodiments provided,
The preparation method specifically includes following steps：
(1) 60mL DMF are added in the reactor of polytetrafluoroethyllining lining first, are subsequently adding 1.75g ZrCl4
(7.5mmol) and 1.25g (7.5mmol) terephthalic acid (TPA), stirs 20min, dissolves it, 120 DEG C of heating 24h, is cooled to room
Temperature, is filtrated to get solid.Solid is washed with DMF, methyl alcohol, the solid that will finally obtain dries one the whole night at 80 DEG C, obtains
UiO-66。
(2) toward addition 0.5g UiO-66 in 50mL flasks, 4.106g (0.05mol) N- methylimidazoles are added, is stirred at room temperature
Mix 15h.Add 7.3795g (0.06mol) n-Propyl Bromide, 60 DEG C of stirring 24h.Suction filtration, is washed three times, each 10mL with ethanol.
Resulting solid is added into 20mL ethanol, excessive H is added2SO4, 24h is stirred at room temperature, filter, washing, 80 DEG C of vacuum are done
Dry 24h, finally obtains metal-organic framework materials/functionalized ion liquid composite, as catalyst B：[PMIm]HSO4@
UiO-66。
Dibenzothiophenes is dissolved in normal octane by the dibenzothiophenes of more difficult removing as target sulphide with hydrodesulfurization,
It is configured to the analog gasoline that sulfur content is 50ppm.Analog gasoline 10mL is taken, catalyst B 0.06g mix with analog gasoline.Add
Hydrogen peroxide and 10mL acetonitriles, with hydrogen peroxide as oxidant, acetonitrile is added to the mixed liquor of fuel gasoline and catalyst for extractant
In, at a temperature of 60 DEG C, 2h being stirred, the mol ratio of the S in O and analog gasoline in hydrogen peroxide is 50.Stratification after suction filtration,
It is 7.5ppm to take upper strata analog gasoline high performance liquid chromatography and determine sulfur content, and desulfurization degree reaches 85%.
Embodiment 3
A kind of preparation method of metal-organic framework materials/functionalized ion liquid composite is present embodiments provided,
The preparation method specifically includes following steps：
(1) 50mL DEF are added in the reactor of polytetrafluoroethyllining lining first, are subsequently adding 0.6g Zn
(NO3)2(3.2mmol) and 2.20g (10mmol) NDA, stirs 20min, dissolves it, 95 DEG C of heating 12h, cooling
To room temperature, solid is filtrated to get.Solid is washed with DEF, the solid that will finally obtain dries one the whole night at 200 DEG C, obtains
IRMOF-8。
(2) toward addition 0.5g IRMOF-8 in 50mL flasks, 4.106g (0.05mol) N- methylimidazoles are added, at room temperature
Stirring 15h.Add 7.3795g (0.06mol) n-Propyl Bromide, 60 DEG C of stirring 24h.Suction filtration, washes three times, every time with ethanol
10mL.Resulting solid is added into 20mL ethanol, excessive H is added2SO4, 24h is stirred at room temperature, filter, washing, 80 DEG C are true
Sky dries 24h, finally obtains metal-organic framework materials/functionalized ion liquid composite, as catalyst C：[PMIm]
HSO4@IRMOF-8。
Dibenzothiophenes is dissolved in normal octane by the dibenzothiophenes of more difficult removing as target sulphide with hydrodesulfurization,
It is configured to the analog gasoline that sulfur content is 50ppm.Analog gasoline 10mL is taken, catalyst C 0.06g mix with analog gasoline.Add
Hydrogen peroxide and 10mL acetonitriles, with hydrogen peroxide as oxidant, acetonitrile is added to the mixed liquor of fuel gasoline and catalyst for extractant
In, at a temperature of 60 DEG C, 2h being stirred, the mol ratio of the S in O and analog gasoline in hydrogen peroxide is 50.Stratification after suction filtration,
It is 10ppm to take upper strata analog gasoline high performance liquid chromatography and determine sulfur content, and desulfurization degree reaches 80%.
Embodiment 4
A kind of preparation method of metal-organic framework materials/functionalized ion liquid composite is present embodiments provided,
The preparation method specifically includes following steps：
(1) 40mL DMF are added in the reactor of polytetrafluoroethyllining lining first, are subsequently adding 2.90g Cu
(NO3)2·3H2O (12mmol) and 0.35g (0.8mmol) 2,4,6- tri- (4- carboxyl phenyls) -1,3,5-triazines, stir 20min,
Dissolve it, 85 DEG C of heating 48h are cooled to room temperature, are filtrated to get solid.Solid is washed with DMF, the solid that will finally obtain exists
One is dried at 80 DEG C the whole night, PCN-6 is obtained.
(2) toward addition 0.5g PCN-6 in 50mL flasks, 4.106g (0.05mol) N- methylimidazoles are added, is stirred at room temperature
Mix 15h.Add 7.3795g (0.06mol) n-Propyl Bromide, 60 DEG C of stirring 24h.Suction filtration, is washed three times, each 10mL with ethanol.
Resulting solid is added into 20mL ethanol, a certain amount of H is added2SO4, 24h is stirred at room temperature, filter, washing, 80 DEG C of vacuum
24h is dried, metal-organic framework materials/functionalized ion liquid composite, as catalyst D is finally obtained：[PMIm]
HSO4@PCN-6。
Dibenzothiophenes is dissolved in normal octane by the dibenzothiophenes of more difficult removing as target sulphide with hydrodesulfurization,
It is configured to the analog gasoline that sulfur content is 50ppm.Analog gasoline 10mL is taken, catalyst D 0.06g mix with analog gasoline.Add
Hydrogen peroxide and 10mL acetonitriles, with hydrogen peroxide as oxidant, acetonitrile is added to the mixed liquor of fuel gasoline and catalyst for extractant
In, at a temperature of 60 DEG C, 2h being stirred, the mol ratio of the S in O and analog gasoline in hydrogen peroxide is 50.Stratification after suction filtration,
It is 8.5ppm to take upper strata analog gasoline high performance liquid chromatography and determine sulfur content, and desulfurization degree reaches 83%.
Embodiment 5
A kind of preparation method of metal-organic framework materials/functionalized ion liquid composite is present embodiments provided,
The preparation method specifically includes following steps：
(1) 60mL distilled water is added in the reactor of polytetrafluoroethyllining lining first, is subsequently adding 5.00g
(12.5mmol)Cr(NO3)3·9H2O and 2.08g (12.5mmol) terephthalic acid (TPA), stir 20min, are eventually adding 0.63g HF
(40%), 220 DEG C of heating 8h, are cooled to room temperature, are filtrated to get green solid.Solid is washed with DMF, ethanol, will finally be obtained
Solid dried one the whole night at 150 DEG C, obtain MIL-101 (Cr).
(2) toward addition 0.5g MIL-101 (Cr) in 50mL flasks, 4.106g (0.05mol) N- methylimidazoles, room are added
The lower stirring 15h of temperature.Add 7.3284g (0.06mol) PS, 60 DEG C of stirring 24h.Suction filtration, three are washed with ethanol
It is secondary, each 10mL.Resulting solid is added into 20mL ethanol, excessive H is added2SO4, 24h is stirred at room temperature, filter, wash
Wash, 80 DEG C of vacuum drying 24h finally obtain metal-organic framework materials/functionalized ion liquid composite, as catalyst
E：[BSO3PMIm]HSO4@MIL-101(Cr)。
Dibenzothiophenes is dissolved in normal octane by the dibenzothiophenes of more difficult removing as target sulphide with hydrodesulfurization,
It is configured to the analog gasoline that sulfur content is 50ppm.Analog gasoline 10mL is taken, catalyst E 0.06g mix with analog gasoline.Add
Hydrogen peroxide and 10mL acetonitriles, with hydrogen peroxide as oxidant, acetonitrile is added to the mixed liquor of fuel gasoline and catalyst for extractant
In, at a temperature of 60 DEG C, 2h being stirred, the mol ratio of the S in O and analog gasoline in hydrogen peroxide is 50.Stratification after suction filtration,
It is 4.5ppm to take upper strata analog gasoline high performance liquid chromatography and determine sulfur content, and desulfurization degree reaches 91%.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment
Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification,
Equivalent substitute mode is should be, is included within protection scope of the present invention.
Claims (10)
1. the preparation method of a kind of metal-organic framework materials/functionalized ion liquid composite, it is characterised in that including with
Lower step：
(1) inorganic salts and organic ligand are mixed, being subsequently adding stirring solvent dissolves it, insulation；Make its cold after the completion of reaction
But room temperature is arrived, washing precipitation is multiple, then filters, and is dried to obtain metal-organic framework materials；
(2) in the metal-organic framework materials input precursor A for obtaining step (1), stirring；Precursor B is subsequently adding, is continued
Stir, then the ionic liquid H to being obtained2SO4Carry out ion exchange and obtain acidic ion liquid；Suction filtration, then enters to it
Row vacuum drying, so as to obtain metal-organic framework materials/functionalized ion liquid composite.
2. the preparation method of metal-organic framework materials according to claim 1/functionalized ion liquid composite, its
It is characterised by：
The cation of the inorganic salts described in step (1) is Cu2+、Zn2+、Zr4+、Cr3+、Fe3+And Al3+In at least one；
The anion of the inorganic salts described in step (1) is NO3 -、Cl-And COO-In at least one.
3. the preparation method of metal-organic framework materials according to claim 1/functionalized ion liquid composite, its
It is characterised by：
Organic ligand described in step (1) is terephthalic acid (TPA), trimesic acid, 2,6- naphthalenedicarboxylic acids, (the 4- carboxylics of 2,4,6- tri-
Base phenyl) at least one in -1,3,5- triazines.
4. the preparation method of metal-organic framework materials according to claim 1/functionalized ion liquid composite, its
It is characterised by：
Solvent described in step (1) is N,N-dimethylformamide, N, in N- DEFs, ethanol, hydrofluoric acid and water
At least one.
5. the preparation method of metal-organic framework materials according to claim 1/functionalized ion liquid composite, its
It is characterised by：
The cation of the inorganic salts described in step (1) is 8 with the mol ratio of organic ligand：25~15:1, the consumption of solvent
It is 40~60mL.
6. the preparation method of metal-organic framework materials according to claim 1/functionalized ion liquid composite, its
It is characterised by：
The condition of the insulation described in step (1) is 85~220 DEG C of 8~48h of insulation；
Dry condition described in step (1) is 80~200 DEG C of 12~15h of drying.
7. the preparation method of metal-organic framework materials according to claim 1/functionalized ion liquid composite, its
It is characterised by：
Precursor A described in step (2) is N- methylimidazoles；
Precursor B described in step (2) is n-Propyl Bromide or 1,3- propane sultones.
8. the preparation method of metal-organic framework materials according to claim 1/functionalized ion liquid composite, its
It is characterised by：
Precursor A and the mol ratio of precursor B described in step (2) are 1:1~1：2.
9. a kind of metal-organic framework materials/functionalized ion liquid composite, it is characterised in that by claim 1~8
Preparation method described in any one is prepared.
10. the metal-organic framework materials described in claim 9/functionalized ion liquid composite in gasoline desulfurization should
With.
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