CN109603911A - A kind of functionalized ion liquid/zeolite imidazole ester skeletal composite and its preparation method and application - Google Patents
A kind of functionalized ion liquid/zeolite imidazole ester skeletal composite and its preparation method and application Download PDFInfo
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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
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- 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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- 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
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- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
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- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
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- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
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Abstract
The invention discloses a kind of functionalized ion liquid/zeolite imidazole ester skeletal composites and its preparation method and application.The different ZIFs material of structure is prepared with glyoxaline ligand and inorganic salts, according to the molecular dimension size of acidic ion liquid, filter out the suitable ZIFs material of structure, pass through infusion process, realize anchoring of the functionalized ion liquid in ZIFs, the contact area that functionalized ion liquid can be increased effectively improves the catalysis oxidation efficiency, while functionalized ion liquid can be prevented to be lost in subsequent desulfurization application.The application reaction condition is mild, easy to operate, desulfurization effect is good, it is possible to prevente effectively from the problems such as oil product loss and oil quality caused by sweetening process decline.
Description
Technical field
The invention belongs to light industrys, chemical material field, and in particular to a kind of functionalized ion liquid/zeolite imidazole ester skeleton
Composite material and preparation method and application.
Background technique
The presence of sulfur-containing compound in gasoline causes it to generate SOx in combustion process and is discharged into atmosphere formation in turn
Acid rain or fumes of sulphuric acid etc. not only can bring irreversible pollution to ecological environment and cultural relics and historic sites etc., but also will cause
Serious human respiratory system's disease etc..Increasingly strict specification gasoline requires for the sulfur content of gasoline to be reduced in world wide
Extremely low level (can quote the standard of state VI) here.Under normal conditions, it is removed in oil plant by hydrodesulfurization (HDS)
Sulfur-containing compound in gasoline, but deep desulfuration of its gasoline difficult to realize, and that there are costs is big for this method, need to consume a large amount of
The problems such as hydrogen, short catalyst life.And the adsorbent of reported absorption desulfurization (ADS) process few can accomplish selectivity
The adsorption capacity for adsorbing sulfur-containing compound difficult to degrade and adsorbent is not high.The desulfurization of biological desulphurization (BDS) and abstraction desulfurization (EDS)
It is ineffective, the effect of deep desulfuration is not achieved.Comparatively, oxidation sweetening (ODS) reaction condition is mild, do not need using hydrogen
Gas, and be easier to remove the sulphur in the lower gasoline of sulfur content.Many oxidants can thiophene in catalytic oxidative desulfurization gasoline
Class compound, wherein H2O2Because its oxidisability is strong, the advantages that intermediate product no pollution to the environment, and it is widely used in catalysis oxidation
In sulfur removal technology.
Ionic liquid is a kind of novel green solvent, with its liquid journey is wide, steam forces down, designability is strong, physicochemical property
The unique property such as stable causes extensive concern in fuel oil catalytic oxidation desulfurization field.But ionic liquid viscosity
Circulation and stress after and reaction higher than other Conventional solvents is difficult.Supported ionic liquids are that ion is immobilized on porous material
On, it can not only overcome the problems, such as that viscosity of il is high, and can be easier to realize recycling and operating continuously for material, this
Kind composite material has both the excellent performance of carrier and ionic liquid.Wherein immobilized required carrier will have porous mostly
Structure and active surface nature, such as metal oxide, active carbon, molecular sieve and metal-organic framework materials (Metal
Organic Frameworks, abbreviation MOFs) etc..But currently used for the MOFs material thermal stability for preparing gasoline desulphurization catalyst
It is poor with chemical stability, the shortcomings that being collapsed there are long period of soaking structure.Therefore, how to prepare a kind of thermal stability and
Chemical stability is good, can be current problem to be solved without the catalyst for damaging its structure with long period of soaking.
Summary of the invention
To solve the shortcomings and deficiencies of the prior art, the primary purpose of the present invention is that providing a kind of functionalization ion
Liquid/zeolite imidazole ester skeletal composite.The functionalized ion liquid/zeolite imidazole ester skeletal composite is to pass through dipping
Functionalized ion liquid is anchored or is limited in ZIFs by method, to prevent it from sending out in subsequent desulfurization application and regenerative process
It is raw to be lost.
Another object of the present invention is to provide above-mentioned functionalized ion liquid/zeolite imidazole ester skeletal composite systems
Preparation Method.Functionalized ion liquid is carried on zeolitic imidazolate framework material (Zeolitic by infusion process
Imidazolate Framework, abbreviation ZIFs), synthesize a kind of functionalized ion liquid/zeolite imidazole ester skeleton composite wood
Material.
A further object of the present invention is to provide above-mentioned functionalized ion liquid/zeolite imidazole ester skeletal composites in vapour
Application in oily desulfurization.
The object of the invention is achieved through the following technical solutions:
A kind of preparation method of functionalized ion liquid/zeolite imidazole ester skeletal composite, comprising the following steps:
(1) glyoxaline ligand and inorganic salts are dissolved in organic solvent, 48~72h is reacted at 85~140 DEG C, terminated anti-
It answers, product mixtures is filtered, washing, drying, obtain zeolite imidazole ester skeleton (ZIFs) material；
(2) the ZIFs material of step (1) is added in functionalized ion liquid solution, stirs for 24 hours, filters at room temperature,
Vacuum drying, obtains functionalized ion liquid/zeolite imidazole ester skeletal composite；
Glyoxaline ligand described in step (1) is the imidazoles with formula (i) structure, the 2- methyl miaow with formula (ii) structure
At least one of azoles, the 2- ethyl imidazol(e) with formula (iii) structure and benzimidazole with formula (iv) structure,
The molar ratio of inorganic salts, glyoxaline ligand and organic solvent described in step (1) is 1:2.67:260 or 1:4:
432；
The ratio of functionalized ion liquid and ZIFs material is 0.1 in functionalized ion liquid solution described in step (2)
~0.5mmol/g.
Preferably, glyoxaline ligand described in step (1) is mixture, benzimidazole and the miaow of 2-methylimidazole and imidazoles
Mixture, 2- ethyl imidazol(e) or the benzimidazole of azoles.
Preferably, the cation of step (1) described inorganic salts is Zn2+And Co2+One of, anion NO3-。
It is furthermore preferred that the molar ratio of the inorganic salts, 2- ethyl imidazol(e) or benzimidazole and organic solvent is 1:2.67:
260；The inorganic salts, 2-methylimidazole, imidazoles and organic solvent molar ratio be 1:1:3:432；The inorganic salts, benzene
And the molar ratio of imidazoles, imidazoles and organic solvent is 1:1:3:432.
Preferably, organic solvent described in step (1) is n,N-Dimethylformamide (DMF) and/or N, N- dimethyl second
Amide (DEF).
Preferably, the method for suction filtration, washing, drying described in step (1) are as follows: product mixtures are cooled to room temperature, are taken out
Filter, the solid crude product being collected into n,N-Dimethylformamide (DMF) or n,N-dimethylacetamide (DEF) are washed 3 times, 80 DEG C
Lower vacuum drying 12h obtains required ZIFs material.
Preferably, the concentration of functionalized ion liquid solution described in step (2) is 9~21mmol/L.
Preferably, the cation of functionalized ion liquid is imidazoles in functionalized ion liquid solution described in step (2)
Class, the carboxylic acid group of sulfonic acid group or (vi) structural formula in side chain with (v) structural formula, wherein the carbon chain lengths of R are C2
~C4,
Preferably, functionalized ion liquid is acidic ion liquid in functionalized ion liquid solution described in step (2),
Its anion is [HSO4]-And/or Cl-。
Preferably, functionalized ion liquid is 1- butyl sulfonic acid -3- in functionalized ion liquid solution described in step (2)
Methylimidazolium hydrogen sulphate salt, 1- carboxymethyl -3- methylimidazole villaumite, 1- carboxymethyl -3- methylimidazolium hydrogen sulphate salt, 1- carboxylic second
Base -3- methylimidazolium hydrogen sulphate salt, 1- propyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt and 1- propyl sulfonic acid -3- methylimidazole chlorine
At least one of salt.
Preferably, the solvent in functionalized ion liquid solution described in step (2) is n,N-Dimethylformamide
(DMF), at least one of water, methanol and ethyl alcohol.
Preferably, the vacuum drying time described in step (2) is 12h, and temperature is 80 DEG C.
The present invention further provides a kind of functionalized ion liquid/zeolite imidazole ester skeletal composite, the composite woods
Material is prepared by the above method, and wherein load capacity of the functionalized ion liquid on ZIFs is 0.1~0.5mmol ionic liquid
Body/g carrier.
Above-mentioned functionalized ion liquid/application of the zeolite imidazole ester skeletal composite in gasoline desulfurization.
The application is using functionalized ion liquid/zeolite imidazole ester skeletal composite as catalyst, with H2O2For oxidation
Agent, using acetonitrile as extractant, by aoxidizing and extracting the sulfur-containing compound in removing gasoline.
In the application, functionalized ion liquid/zeolite imidazole ester skeletal composite is 70.65 to the desulfurization degree of gasoline
~83.22%.
Compared with prior art, the present invention has the following advantages and beneficial effects:
(1) functionalized ion liquid is supported on zeolitic imidazolate framework material by the present invention using infusion process, Ke Yizeng
Add contact area, effectively improves the catalysis oxidation efficiency, while the loss of ionic liquid can be prevented.
(2) application conditions of the present invention are mild, easy to operate, removal effect is good, it is possible to prevente effectively from oily in sweetening process
The problems such as product loss and oil quality decline.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail, and embodiments of the present invention are not limited thereto.
Embodiment 1
A kind of preparation method of functionalized ion liquid/zeolite imidazole ester skeletal composite, comprising the following steps:
(1) stirring and dissolving in 60mL DMF is added in 8mmol benzimidazole, then by 3mmol Co (NO3)2·6H2O is added
It is stirred evenly in the above solution, 48h is reacted at 140 DEG C, filtered, washed three times with DMF (50mL × 3), by responseless benzene
And imidazoles and Co (NO3)2·6H2O sufficiently washs removing, and 12h is dried in vacuo at 80 DEG C, removes in material surface and duct
Extra solvent, to obtain ZIF-12；
(2) by 0.045mmol 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphate ionic liquid ([BSO3HMIm]HSO4]),
It is dispersed with stirring in 5mL dehydrated alcohol, then ZIF-12 crude product 150mg made from step (1) is taken to be added thereto uniformly mixed, room temperature
Lower stirring is for 24 hours.It filters, is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1-
The ZIF-12 of butyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt, resulting composite material are denoted as 0.3 [BSO3HMIm][HSO4]/ZIF-
12, by determination of elemental analysis, the load capacity of ionic liquid is 0.3mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
72.38%.
Embodiment 2
A kind of preparation method of functionalized ion liquid/zeolite imidazole ester skeletal composite, comprising the following steps:
(1) stirring and dissolving in 60mL DMF is added in 8mmol 2- ethyl imidazol(e), then by 3mmol Zn (NO3)2·6H2O
(purchase is in Guangzhou Qian Huihua glass Instrument Ltd.), which is added in the above solution, to stir evenly, and 48h is reacted at 140 DEG C, is filtered, is used
DMF (50mL × 3) is washed three times, by responseless 2- ethyl imidazol(e) and Zn (NO3)2·6H2O sufficiently washs removing, 80
It is dried in vacuo 12h at DEG C, solvent extra in material surface and duct is removed, to obtain ZIF-14；
(2) by 0.045mmol 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphate ionic liquid ([BSO3HMIm]HSO4]),
It is dispersed with stirring in 5mL dehydrated alcohol, then ZIF-14 crude product 150mg made from step (1) is taken to be added thereto uniformly mixed, room temperature
Lower stirring is for 24 hours.It filters, is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1-
The ZIF-14 of butyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt, resulting composite material are denoted as 0.3 [BSO3HMIm][HSO4]/ZIF-
14, by determination of elemental analysis, the load capacity of ionic liquid is 0.3mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
70.86%.
Embodiment 3
A kind of preparation method of functionalized ion liquid/zeolite imidazole ester skeletal composite, comprising the following steps:
(1) stirring and dissolving in 60mL DMF is added in the 2-methylimidazole of 5.4mmol imidazoles and 1.8mmol, then will
1.8mmol Zn(NO3)2·6H2O is added in above solution and stirs evenly, and 48h is reacted at 140 DEG C, filters, with DMF (50mL ×
3) it washs three times, by responseless imidazoles, 2-methylimidazole and Zn (NO3)2·6H2O sufficiently washs removing, at 80 DEG C
It is dried in vacuo 12h, solvent extra in material surface and duct is removed, to obtain ZIF-60；
(2) by 0.045mmol 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphate ionic liquid ([BSO3HMIm]HSO4]),
It is dispersed with stirring in 5mL dehydrated alcohol, then ZIF-60 crude product 150mg made from step (1) is taken to be added thereto uniformly mixed, room temperature
Lower stirring is for 24 hours.It filters, is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1-
The ZIF-60 of butyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt, resulting composite material are denoted as 0.3 [BSO3HMIm][HSO4]/ZIF-
60, by determination of elemental analysis, the load capacity of ionic liquid is 0.3mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
74.02%.
Embodiment 4
A kind of preparation method and applications of functionalized ion liquid/zeolite imidazole ester skeletal composite, including it is following
Step:
(1) stirring and dissolving in 60mL DMF is added in the benzimidazole of 5.4mmol imidazoles and 1.8mmol, then will
1.8mmol Zn(NO3)2·6H2O is added in above solution and stirs evenly, and 48h is reacted at 140 DEG C, filters, with DMF (50mL ×
3) it washs three times, by responseless imidazoles, benzimidazole and Zn (NO3)2·6H2O sufficiently washs removing, true at 80 DEG C
The dry 12h of sky, removes solvent extra in material surface and duct, to obtain ZIF-62；
(2) by 0.045mmol 1- butyl sulfonic acid -3- methylimidazolium hydrogen sulphate ionic liquid ([BSO3HMIm]HSO4]),
It is dispersed with stirring in 5mL dehydrated alcohol, then ZIF-62 crude product 150mg made from step (1) is taken to be added thereto uniformly mixed, room temperature
Lower stirring is for 24 hours.It filters, is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1-
The ZIF-62 of butyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt, resulting composite material are denoted as 0.3 [BSO3HMIm][HSO4]/ZIF-
62, by determination of elemental analysis, the load capacity of ionic liquid is 0.3mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
73.89%.
Embodiment 5
A kind of preparation method and applications of functionalized ion liquid/zeolite imidazole ester skeletal composite, including it is following
Step:
(1) stirring and dissolving in 60mL DMF is added in the benzimidazole of 5.4mmol imidazoles and 1.8mmol, then will
1.8mmol Zn(NO3)2·6H2O is added in above solution and stirs evenly, and 48h is reacted at 140 DEG C, filters, with DMF (50mL ×
3) it washs three times, by responseless imidazoles, benzimidazole and Zn (NO3)2·6H2O sufficiently washs removing, true at 80 DEG C
The dry 12h of sky, removes solvent extra in material surface and duct, to obtain ZIF-62；
(2) by 0.045mmol 1- carboxymethyl -3- methylimidazole villaumite ionic liquid ([HOOCMMIm] Cl]), stirring point
It is dispersed in 5mL dehydrated alcohol, then to take ZIF-62 crude product 150mg made from step (1) to be added thereto uniformly mixed, stirs at room temperature
24h.It filters, is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1- carboxymethyl-
The ZIF-62 of 3- methylimidazole villaumite, resulting composite material are denoted as 0.3 [HOOCMMIm] Cl/ZIF-62, pass through elemental analysis
Measurement, the load capacity of ionic liquid are 0.3mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
73.89%.
Embodiment 6
A kind of preparation method and applications of functionalized ion liquid/zeolite imidazole ester skeletal composite, including it is following
Step:
(1) stirring and dissolving in 60mL DMF is added in 8mmol benzimidazole, then by 3mmol Co (NO3)2·6H2O is added
It is stirred evenly in the above solution, 48h is reacted at 140 DEG C, filtered, washed three times with DMF (50mL × 3), by responseless benzene
And imidazoles and Co (NO3)2·6H2O sufficiently washs removing, and 12h is dried in vacuo at 80 DEG C, removes in material surface and duct
Extra solvent, to obtain ZIF-12；
(2) by 0.045mmol 1- carboxymethyl -3- methylimidazolium hydrogen sulphate salt ([HOOCMMIm] HSO4), it is dispersed with stirring
In 5mL dehydrated alcohol, then to take ZIF-12 crude product 150mg made from step (1) to be added thereto uniformly mixed, stirs at room temperature for 24 hours.
It filters, is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1- carboxymethyl -3- first
The ZIF-12 of base imidazole bisulfate, resulting composite material are denoted as 0.3 [HOOCMMIm] HSO4/ ZIF-12 passes through element point
Analysis measurement, the load capacity of ionic liquid are 0.3mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
81.48%.
Embodiment 7
A kind of preparation method and applications of functionalized ion liquid/zeolite imidazole ester skeletal composite, including it is following
Step:
(1) stirring and dissolving in 60mL DMF is added in 8mmol benzimidazole, then by 3mmol Co (NO3)2·6H2O is added
It is stirred evenly in the above solution, 48h is reacted at 140 DEG C, filtered, washed three times with DMF (50mL × 3), by responseless benzene
And imidazoles and Co (NO3)2·6H2O sufficiently washs removing, and 12h is dried in vacuo at 80 DEG C, removes in material surface and duct
Extra solvent, to obtain ZIF-12；
(2) by 0.060mmol 1- carboxymethyl -3- methylimidazolium hydrogen sulphate salt ([HOOCMMIm] HSO4), it is dispersed with stirring
In 5mL dehydrated alcohol, then to take ZIF-12 crude product 150mg made from step (1) to be added thereto uniformly mixed, stirs at room temperature for 24 hours.
It filters, is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1- carboxymethyl -3- first
The ZIF-12 of base imidazole bisulfate, resulting composite material are denoted as 0.4 [HOOCMMIm] HSO4/ ZIF-12 passes through element point
Analysis measurement, the load capacity of ionic liquid are 0.4mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
83.22%.
Comparative example 1
A kind of preparation method and applications of functionalized ion liquid/zeolite imidazole ester skeletal composite, including it is following
Step:
(1) stirring and dissolving in 60mL DMF is added in 8mmol benzimidazole, then by 3mmol Co (NO3)2·6H2O is added
It is stirred evenly in the above solution, 48h is reacted at 140 DEG C, filtered, washed three times with DMF (50mL × 3), by responseless benzene
And imidazoles and Co (NO3)2·6H2O sufficiently washs removing, and 12h is dried in vacuo at 80 DEG C, removes in material surface and duct
Extra solvent, to obtain ZIF-12；
(2) by 0.105mmol 1- carboxymethyl -3- methylimidazolium hydrogen sulphate salt ([HOOCMMIm] HSO4), it is dispersed with stirring
In 5mL dehydrated alcohol, then to take ZIF-12 crude product 150mg made from step (1) to be added thereto uniformly mixed, stirs at room temperature for 24 hours.
It filters, is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1- propyl sulfonic acid -3-
The ZIF-12 of methylimidazole villaumite, resulting composite material are denoted as 0.7 [HOOCMMIm] HSO4/ ZIF-12, passes through elemental analysis
Measurement, the load capacity of ionic liquid are 0.7mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
67.56%.
Embodiment 8
A kind of preparation method and applications of functionalized ion liquid/zeolite imidazole ester skeletal composite, including it is following
Step:
(1) stirring and dissolving in 60mL DMF is added in 8mmol benzimidazole, then by 3mmol Co (NO3)2·6H2O is added
It is stirred evenly in the above solution, 48h is reacted at 140 DEG C, filtered, washed three times with DMF (50mL × 3), by responseless benzene
And imidazoles and Co (NO3)2·6H2O sufficiently washs removing, and 12h is dried in vacuo at 80 DEG C, removes in material surface and duct
Extra solvent, to obtain ZIF-12；
(2) by 0.045mmol 1- carboxymethyl -3- methylimidazole villaumite ([HOOCMMIm] Cl), be dispersed with stirring 5mL without
In water-ethanol, then to take ZIF-12 crude product 150mg made from step (1) to be added thereto uniformly mixed, stirs at room temperature for 24 hours.It filters,
Dry 12h is placed in a vacuum drying oven at 80 DEG C to get to target product desulphurization catalyst, loads 1- propyl sulfonic acid -3- methyl
The ZIF-12 of imidazoles villaumite, resulting composite material are denoted as 0.3 [HOOCMMIm] Cl/ZIF-12, by determination of elemental analysis, from
The load capacity of sub- liquid is 0.3mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
70.65%.
Embodiment 9
A kind of preparation method and applications of functionalized ion liquid/zeolite imidazole ester skeletal composite, including it is following
Step:
(1) stirring and dissolving in 60mL DMF is added in 8mmol benzimidazole, then by 3mmol Co (NO3)2·6H2O is added
It is stirred evenly in the above solution, 48h is reacted at 140 DEG C, filtered, washed three times with DMF (50mL × 3), by responseless benzene
And imidazoles and Co (NO3)2·6H2O sufficiently washs removing, and 12h is dried in vacuo at 80 DEG C, removes in material surface and duct
Extra solvent, to obtain ZIF-12；
(2) by 0.045mmol 1- carboxyethyl -3- methylimidazolium hydrogen sulphate salt ([HOOCEMIm] HSO4), it is dispersed with stirring
In 5mL dehydrated alcohol, then to take ZIF-12 crude product 150mg made from step (1) to be added thereto uniformly mixed, stirs at room temperature for 24 hours.
It filters, is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1- propyl sulfonic acid -3-
The ZIF-12 of methylimidazole villaumite, resulting composite material are denoted as 0.3 [HOOCEMIm] HSO4/ ZIF-12, passes through elemental analysis
Measurement, the load capacity of ionic liquid are 0.3mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
71.38%.
Embodiment 10
A kind of preparation method and applications of functionalized ion liquid/zeolite imidazole ester skeletal composite, including it is following
Step:
(1) stirring and dissolving in 60mL DMF is added in 8mmol benzimidazole, then by 3mmol Co (NO3)2·6H2O is added
It is stirred evenly in the above solution, 48h is reacted at 140 DEG C, filtered, washed three times with DMF (50mL × 3), by responseless benzene
And imidazoles and Co (NO3)2·6H2O sufficiently washs removing, and 12h is dried in vacuo at 80 DEG C, removes in material surface and duct
Extra solvent, to obtain ZIF-12；
(2) by 0.045mmol 1- propyl sulfonic acid -3- methylimidazolium hydrogen sulphate salt ([PrSO3HMIm]HSO4), it is dispersed with stirring
In 5mL dehydrated alcohol, then to take ZIF-12 crude product 150mg made from step (1) to be added thereto uniformly mixed, stirs at room temperature
24h.It filters, is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1- propyl sulphur
The ZIF-12 of acid -3- methylimidazolium hydrogen sulphate salt, resulting composite material are denoted as 0.3 [PrSO3HMIm]HSO4/ ZIF-12, passes through
Determination of elemental analysis, the load capacity of ionic liquid are 0.3mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
71.25%.
Embodiment 11
A kind of preparation method and applications of functionalized ion liquid/zeolite imidazole ester skeletal composite, including it is following
Step:
(1) stirring and dissolving in 60mL DMF is added in 8mmol benzimidazole, then by 3mmol Co (NO3)2·6H2O is added
It is stirred evenly in the above solution, 48h is reacted at 140 DEG C, filtered, washed three times with DMF (50mL × 3), by responseless benzene
And imidazoles and Co (NO3)2·6H2O sufficiently washs removing, and 12h is dried in vacuo at 80 DEG C, removes in material surface and duct
Extra solvent, to obtain ZIF-12；
(2) by 0.045mmol 1- propyl sulfonic acid -3- methylimidazole villaumite ([PrSO3HMIm] Cl), it is dispersed with stirring in 5mL
In dehydrated alcohol, then to take ZIF-12 crude product 150mg made from step (1) to be added thereto uniformly mixed, stirs at room temperature for 24 hours.It takes out
Filter is placed in a vacuum drying oven at 80 DEG C dry 12h to get to target product desulphurization catalyst, loads 1- propyl sulfonic acid -3- first
The ZIF-12 of base imidazoles villaumite, resulting composite material are denoted as 0.3 [PrSO3HMIm] Cl/ZIF-12, is surveyed by elemental analysis
Fixed, the load capacity of ionic liquid is 0.3mmol/g.
It is dissolved in normal octane using dibenzothiophenes as analog gasoline, wherein sulfur content is formulated as 50ppm.Take above-mentioned mould
Quasi- gasoline 10mL, sequentially adds catalyst 50mg later, extractant acetonitrile 10mL, 30% 29 μ L of hydrogen peroxide solution, 60 DEG C of perseverances
3h is stirred at reflux under warm oil bath, stratification takes upper layer analog gasoline Microcoulomb instrument to measure sulfur content, and desulfurization degree reaches
74.70%.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (10)
1. a kind of functionalized ion liquid/zeolite imidazole ester skeletal composite preparation method, which is characterized in that including following
Step:
(1) glyoxaline ligand and inorganic salts are dissolved in organic solvent, 48~72h is reacted at 85~140 DEG C, reaction was completed, will
Product mixtures are filtered, are washed, is dry, obtain ZIFs material；
(2) the ZIFs material of step (1) is added in functionalized ion liquid solution, stirs for 24 hours, filters, vacuum at room temperature
It is dry, obtain functionalized ion liquid/zeolite imidazole ester skeletal composite；
Glyoxaline ligand described in step (1) be imidazoles with formula (i) structure, the 2-methylimidazole with formula (ii) structure,
2- ethyl imidazol(e) with formula (iii) structure and at least one of the benzimidazole with formula (iv) structure,
The molar ratio of inorganic salts, glyoxaline ligand and organic solvent described in step (1) is 1:2.67:260 or 1:4:432；
In functionalized ion liquid solution described in step (2) ratio of functionalized ion liquid and ZIFs material be 0.1~
0.5mmol/g。
2. a kind of functionalized ion liquid according to claim 1/zeolite imidazole ester skeletal composite preparation method,
It is characterized in that, glyoxaline ligand described in step (1) is the mixture, benzimidazole and imidazoles of 2-methylimidazole and imidazoles
Mixture, 2- ethyl imidazol(e) or benzimidazole；
The cation of step (1) described inorganic salts is Zn2+And Co2+One of, anion NO3-。
3. a kind of functionalized ion liquid according to claim 1 or 2/zeolite imidazole ester skeletal composite preparation side
Method, which is characterized in that the molar ratio of inorganic salts described in step (1), 2- ethyl imidazol(e) or benzimidazole and organic solvent is 1:
2.67:260；The inorganic salts, 2-methylimidazole, imidazoles and organic solvent molar ratio be 1:1:3:432；Described is inorganic
Salt, benzimidazole, imidazoles and organic solvent molar ratio be 1:1:3:432.
4. a kind of functionalized ion liquid according to claim 1 or 2/zeolite imidazole ester skeletal composite preparation side
Method, which is characterized in that the concentration of functionalized ion liquid solution described in step (2) is 9~21mmol/L.
5. a kind of functionalized ion liquid according to claim 1 or 2/zeolite imidazole ester skeletal composite preparation side
Method, which is characterized in that functionalized ion liquid is acidic ion liquid in functionalized ion liquid solution described in step (2),
Its anion is [HSO4]-And/or Cl-。
6. a kind of functionalized ion liquid according to claim 1 or 2/zeolite imidazole ester skeletal composite preparation side
Method, which is characterized in that the cation of functionalized ion liquid is imidazoles in functionalized ion liquid solution described in step (2)
Class, the carboxylic acid group of sulfonic acid group or (vi) structural formula in side chain with (v) structural formula, wherein the carbon chain lengths of R are C2
~C4,
7. a kind of functionalized ion liquid according to claim 1 or 2/zeolite imidazole ester skeletal composite preparation side
Method, which is characterized in that organic solvent described in step (1) is n,N-Dimethylformamide and/or n,N-dimethylacetamide；
The method of the suction filtration, washing, drying are as follows: product mixtures are cooled to room temperature, are filtered, the solid crude product being collected into
Vacuum drying 12h at 3 times, 80 DEG C, which is washed, with n,N-Dimethylformamide or n,N-dimethylacetamide obtains required ZIFs material
Material.
8. a kind of functionalized ion liquid according to claim 1 or 2/zeolite imidazole ester skeletal composite preparation side
Method, which is characterized in that the solvent in functionalized ion liquid solution described in step (2) is n,N-Dimethylformamide, water, first
At least one of pure and mild ethyl alcohol；The vacuum drying time is 12h, and temperature is 80 DEG C.
9. a kind of functionalized ion liquid according to any one of claims 1 to 8/zeolite imidazole ester skeletal composite.
10. a kind of functionalized ion liquid/zeolite imidazole ester skeletal composite as claimed in claim 9 is in gasoline desulfurization
Using.
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| Publication number | Priority date | Publication date | Assignee | Title |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896001A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Preparation method for cascade porous ZIFs and hydrogen desulfurization catalyst |
| CN102921469A (en) * | 2012-10-16 | 2013-02-13 | 中国石油大学(北京) | Preparation method for novel gasoline hydrodesulfurization catalyst |
| CN106693899A (en) * | 2016-12-07 | 2017-05-24 | 华南理工大学 | Metal organic framework material/functional ionic liquid composite material as well as preparation and application thereof |
| CN108097015A (en) * | 2016-11-25 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of amine liquid desulfurization absorbent and its preparation method and application |
| CN108435254A (en) * | 2018-03-20 | 2018-08-24 | 华南理工大学 | A kind of acidic ion liquid gasoline desulphurization catalyst and the preparation method and application thereof |
-
2018
- 2018-12-29 CN CN201811633202.4A patent/CN109603911A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896001A (en) * | 2012-10-16 | 2013-01-30 | 中国石油大学(北京) | Preparation method for cascade porous ZIFs and hydrogen desulfurization catalyst |
| CN102921469A (en) * | 2012-10-16 | 2013-02-13 | 中国石油大学(北京) | Preparation method for novel gasoline hydrodesulfurization catalyst |
| CN108097015A (en) * | 2016-11-25 | 2018-06-01 | 中国石油化工股份有限公司 | A kind of amine liquid desulfurization absorbent and its preparation method and application |
| CN106693899A (en) * | 2016-12-07 | 2017-05-24 | 华南理工大学 | Metal organic framework material/functional ionic liquid composite material as well as preparation and application thereof |
| CN108435254A (en) * | 2018-03-20 | 2018-08-24 | 华南理工大学 | A kind of acidic ion liquid gasoline desulphurization catalyst and the preparation method and application thereof |
Cited By (13)
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|---|---|---|---|---|
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| CN110041533A (en) * | 2019-05-29 | 2019-07-23 | 福州大学 | A kind of method that ionic liquid ligand displacement method prepares functional metal organic framework material |
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| CN112430429A (en) * | 2020-11-23 | 2021-03-02 | 广东电网有限责任公司电力科学研究院 | Metal organic framework material, preparation method thereof and coating |
| CN112430429B (en) * | 2020-11-23 | 2022-03-22 | 广东电网有限责任公司电力科学研究院 | Metal organic framework material, preparation method thereof and coating |
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| CN114682224A (en) * | 2020-12-31 | 2022-07-01 | 中国石油化工股份有限公司 | Chlorobenzene-containing organic waste gas adsorbent and preparation method and application thereof |
| CN112851476A (en) * | 2021-01-12 | 2021-05-28 | 山东科技大学 | Method for extracting and separating trifluoroethanol and water azeotrope by using porous ionic liquid |
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