CN106622141B - A kind of load has hydridization organic framework material of rare earth and the preparation method and application thereof - Google Patents
A kind of load has hydridization organic framework material of rare earth and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods for loading and having the hybridized metal organic framework material of rare earth, include the following steps: (1) by 1,4,5,8- naphthalenetetracarbacidic acidics and copper source are added in solvent, are uniformly mixed, then the first ultrasonic treatment is carried out, when there is sediment, soluble starch aqueous solution is added, continues the second ultrasonic treatment；(2) mixture after second ultrasonic treatment is filtered, then the solid being obtained by filtration is put into the aqueous acetone solution containing ammonium salt and is stirred, then refiltered, be washed with water and dry, obtain hybridized metal organic framework material；(3) rare earth metal inorganic salts are loaded into metal-organic framework materials, to obtain the hybridized metal organic framework material that load has rare earth.The hydridization organic framework material of this method preparation not only very heat-flash stability and suitable pore structure, and there is more active sites and good spatial symmetry, it is applicable to the fuel oil adsorption-desulfurizations process such as gasoline, diesel oil.
Description
Technical field
The present invention relates to a kind of load to have the hybridized metal organic framework material and preparation method thereof of rare earth to apply, especially
It is a kind of can be used for fuel oil absorption load have organic framework material of rare earth and the preparation method and application thereof.
Background technique
As countries in the world are to the increasingly strict of the pay attention to day by day of environmental protection and environmental regulation, low-sulfur and super is produced
Low sulphur fuel oil is just gradually concerned.Sulfide existence form in fuel is with mercaptan, thioether, disulphide and thiophene
Based on class organic sulfur compound, especially wherein thiophene-based content is big, is difficult to remove.Though conventional hydrodesulfurization can effectively remove thiophene
Pheno class sulfides, but there is loss octane number, the deficiencies of equipment investment and operating cost are big, thus there is an urgent need to it is other it is low at
This fuel oil deep desulfuration technology.Absorption desulfurization is mitigated with small investment, condition, the device space is small and it is beneficial not lose oil product
The advantages such as component have a good application prospect in terms of solving desulphurization problem.Present problems are the adsorption capacity of adsorbent
Universal relatively low, adsorption function existing defects, and adsorptive selectivity is poor, i.e., it may be by other materials one while desulfurization
And remove (such as alkene, nitrogenous compound).
Metal-organic framework materials (Metal-Organic Frameworks, MOFs) are by metal ion and organic to match
The hybrid inorganic-organic materials that body is formed by connecting by coordinate bond.Due to its changeable structure, higher specific surface area and orderly
Pore structure feature be concerned nearly ten years in porous adsorbing material field.Metal-organic framework materials are led in Gas Phase Adsorption
Domain has been provided with practical application value, after introducing other metal ions especially by doping vario-property, deposits in multiple metal ions
It is significantly improved in lower adsorption effect.Research of the metal-organic framework materials in fuel oil deep desulfuration field is at the early-stage, for
The material doped modified progress for improving adsorption effect is rarely reported.
CN102886244A discloses a kind of desulfurization metal organic framework hybridized film and its manufacturing method.The hybridized film with
High molecular polymer is host material, using metal-organic framework materials as functive, controls phase inversion membrane preparation process, prepares
Hybridized film with tridimensional network.Hybridized film shows certain effect during fuel oil adsorption-desulfurization.But this is miscellaneous
Changing film selects common metal organic framework material as load object, such as Cu3(BTC)2, such space structure is the gold of web colyliform
Belonging to organic framework material has stronger adsorption capacity for alkene containing double bonds in gasoline, i.e., keeps gasoline pungent in sweetening process
Alkane value is greatly lowered.Furthermore during simulating distillate, select one-component organic sulfur compound to remove object, not sufficiently
Consider the competitive Adsorption effect between thiophene, benzothiophene, dimethyl Dibenzothiophene.In addition, casting solution uses in the stage of preparation
The toxic reagents such as polyimides, dimethylformamide, tetrahydrofuran, therefore there are significant environment hidden danger.
CN102895954A discloses a kind of preparation method of new type gasoline removal of mercaptans adsorbent.Synthesis step includes will be molten
Agent, metal ion presoma, mesoporous material are uniformly mixed, ageing, and organic ligand, hydrothermal crystallizing processing is added.Then to crystallization
Product is filtered, is washed, is dry, obtains zeolite imidazole class framework material/mesoporous material compound.To compound compression molding, break
Broken screening finally obtains demercaptaning for gasoline adsorbent.This method, which alleviates caused by stone imidazoles framework material is reunited, spreads limit
System, Mercaptan removal rate can reach 90wt% or more.But imidazoles metal-organic framework materials development cost is very high, ligand first
Base imidazoles has corrosivity and expensive, therefore is unfavorable for product promotion application.In addition, the zeolite imidazole class in regenerative process
Framework material falls off, and leads to materials'use multi-cycle finite；And the adsorbent is fitted for sulfur in gasoline alkoxide component development
With being limited in scope, it is helpless to the petrol and diesel oil desulfurization application technology of increasingly in poor quality.
Summary of the invention
In view of the deficiencies in the prior art, the present invention provides a kind of hydridization organic framework materials and its system for loading and having rare earth
The application of Preparation Method and the hybridized metal organic framework material in gas absorption, gas absorption storage, gas absorption separation.
The load of method preparation of the invention has the hydridization organic framework material of rare earth not only very heat-flash stability and the pore structure for being suitable for,
And there is more active sites and good spatial symmetry, it is applicable to the fuel oil adsorption-desulfurizations process such as gasoline, diesel oil,
There is preferable removal effect particularly with dimethyl Dibenzothiophene class sulfide, while also can avoid under octane number
Drop.
A kind of load provided by the invention has the preparation method of the hybridized metal organic framework material of rare earth, including walks as follows
It is rapid:
(1) by Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics and copper source are added in solvent, are uniformly mixed, and are then carried out at the first ultrasound
Reason, when there is sediment, adds soluble starch aqueous solution, continues the second ultrasonic treatment；
(2) mixture after the second ultrasonic treatment is filtered, then the solid being obtained by filtration is put into containing ammonium salt
It stirs in aqueous acetone solution, then refilters, be washed with water and dried with first, obtain hybridized metal organic framework material；
(3) rare earth metal is loaded on hybridized metal organic framework material, so that obtaining load has rare earth oxide
Hybridized metal organic framework material.
Copper source and Isosorbide-5-Nitrae, the molar ratio of 5,8- naphthalenetetracarbacidic acidics are 1:(0.1~1.0), preferably 1:(0.35~
0.70), Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics, soluble starch aqueous solution and solvent quality ratio are 1:(0.01~0.2): (100~
1000), preferably 1:(0.02~0.15): (150~700).The present invention can select routine using copper source, and the copper source can
Selected from one or more of copper nitrate, copper sulphate and copper chloride, preferably copper nitrate.
The mass concentration of the soluble starch aqueous solution is 8wt%~65wt%, preferably 10wt%~35wt%.
In step (1), the solvent is aqueous acetone solution, and acetone and water volume ratio are 1:(0.1~15), preferably 1:(1~
10).
In step (1), in Isosorbide-5-Nitrae, after mixing, the pH of mixture is less than for 5,8- naphthalenetetracarbacidic acidics, copper source and solvent
2.0, preferably 0.3~0.9.
In step (1), the condition of first ultrasonic treatment and the second ultrasonic treatment may be the same or different.
The operating condition of first ultrasonic treatment are as follows: the frequency of ultrasonic wave is 10KHz~200KHz；The power of ultrasonic wave be 100W~
700W。
In step (1), the operating condition of second ultrasonic treatment are as follows: ultrasonic time is 5min~150min；Ultrasound
The frequency of wave is 10KHz~200KHz；The power of ultrasonic wave is 100W~700W.
In step (2), in the aqueous acetone solution containing ammonium salt, the ratio of the ammonium salt and aqueous acetone solution is 1g:
The volume ratio of (80mL~150mL), acetone and water is 1:(0.1~15), preferably 1:(1~10), the ammonium salt is selected from chlorine
Change one or more of ammonium, ammonium sulfate, ammonium nitrate.
In step (2), the mixing time be 10min~260min, preferably 100min~200min, it is described
Drying temperature is 75 DEG C~245 DEG C, preferably 100 DEG C~230 DEG C；Time is 60min~360min.
Hybridized metal organic framework material described in step (3) and rare earth metal inorganic salts are in terms of rare-earth oxide
Mass ratio is 1:(0.001~0.01), preferred 1:(0.001~0.045).In loading process, if using water, water can be with
It is 1:(0.001~10 according to the ratio of rare earth metal inorganic salts and water): (100~10000), preferably 1:(0.008~
0.045): (350~1200).
Rare earth metal inorganic salts are selected from one or more of the nitrate of lanthanum and cerium, chlorate, preferably Ce (NO3)3·
6H2O or La (NO3)3·6H2O。
In step (3), rare earth metal is loaded to hybridized metal organic framework material method can be using conventional load
Method, such as infusion process, mixing method and Monolayer Dispersion method etc., the preferably following method of the present invention: by hybridized metal organic backbone material
Material is mixed with water and rare earth metal inorganic salts, dry and roasting.
In step (3), the drying temperature is 70 DEG C~150 DEG C, and the time is 60min~360min.
In step (3), the temperature of the roasting is 200 DEG C~400 DEG C, preferably 250 DEG C~350 DEG C；Time is 600min
~1200min.The roasting preferably carries out in vacuum environment or inert atmosphere.
The resulting hybridized metal organic framework material of step (2) of the present invention has micropore and mesoporous pore structure.Present invention step
Suddenly (2) resulting hybridized metal organic framework material accounts for the 50%~75% of total pore volume in the Micropore volume of 0.7nm~1.0nm, excellent
It is selected as the mesoporous Kong Rong of 50%~65%, 2.0nm~3.5nm and accounts for the 4%~13% of total pore volume, preferably 4%~10%.
The specific surface area of the resulting hybridized metal organic framework material of step (2) of the present invention is 900m2·g-1~
1500m2·g-1, preferably 950m2·g-1~1350m2·g-1, total pore volume 0.50cm3·g-1~0.90cm3·g-1, preferably
For 0.60cm3·g-1~0.85cm3·g-1。
The resulting hybridized metal organic framework material of step (2) of the present invention is anorthic system, and cell parameter is a=7.270
(2), b=8.531 (2), c=9.637 (3), α=82 °, β=75 °, γ=78 °, unit cell volume V=587.4 (3)3, Z=
1, Dc=1.815mg/cm3。
The present invention also provides the hybridized metal organic framework materials that a kind of load of above method preparation has rare earth.
The present invention also provides a kind of above-mentioned loads to have the hybridized metal organic framework material of rare earth in the desulfurization of fuel oil
In application, it is preferable that the hybridized metal organic framework material removing high steric hindrance influence organic sulfur compound in
Application.
Hydridization organic framework material of the invention, has the advantages that
(1) present invention adds water soluble starch during synthesizing hybridized metal organic backbone, water soluble starch in Isosorbide-5-Nitrae,
Under the acid effect of 5,8- naphthalenetetracarbacidic acidics, it may occur that hydrolysis, oxygen bridge is broken when reaction, while hydrone is added, water-soluble
Starch becomes short chain molecule by long-chain molecule, until oxygen bridge complete rupture, becomes glucose, wherein short chain molecule is polynary
Sugar, and containing a certain number of hydroxyls and carboxymethyl and aldehyde radical in these hydrolysates, these hydroxyls and aldehyde radical can with metal from
Sub- Cu2+Complexation reaction occurs, i.e. water soluble starch hydrolysate and organic ligand competitive coordination is in central metal copper ion.
In this way, the present invention, successfully by Isosorbide-5-Nitrae, the hydrolysate of 5,8- naphthalenetetracarbacidic acidics and water soluble starch is matched as organic
Body, and make it with after copper source complexation reaction, to generate the space symmetr structure of cubic lattice, avoid the occurrence of similar Cu3(BTC)2
Web wheel-like structure.Furthermore water soluble starch can modify metal-organic framework materials network, and carry out to duct thin
Change and intertextureizations, can promote material generation multi-stage artery structure, such as generate more micropores and mesoporous.And it starch or is hydrolyzed into
More carbon glucose units have the network of branch, can further modify metal-organic framework materials network, generate
More complicatedization, the cellular structure more to narrow.
(2), hybridized metal organic framework material prepared by the present invention and existing metal-organic framework materials (such as Cu3
(BTC)2) compare, with very strong thermal stability and suitable pore structure, especially there is multi-stage artery structure (such as 0.7nm
The meso-hole structure between microcellular structure and 2.0nm~3.5nm between~1.0nm), in this way in material inner surface absorption size
Biggish dimethyl Dibenzothiophene (> 1.5nm) provides possibility.
Hybridized metal organic framework material prepared by the present invention not only has more active with sulphur atom Absorptive complex wave
Position is conducive to improve de- efficiency, and there is space to unfold structure, can further counteract methyl in dimethyl Dibenzothiophene
The steric interference of functional group makes it can smoothly enter into material inner surface, enhances desulfurization effect.
Hybridized metal organic framework material prepared by the present invention has extraordinary spatial symmetry, double with containing in gasoline
Key olefin component suction-operated is very weak, can effectively reduce and contain double bond alkene in hybridized metal organic framework material and gasoline
Reaction between component reduces loss of octane number.And bad (such as Cu of spatial symmetry of existing metal-organic framework materials3
(BTC)2With web wheel-like structure), and it is very strong with the suction-operated of double bond olefin component is contained in gasoline, in easy and gasoline
It is reacted containing double bond olefin component, so that octane number declines.
Therefore, hybridized metal organic framework material of the invention is applicable to the fuel oil adsorption-desulfurizations mistake such as gasoline, diesel oil
Journey has preferable removal effect particularly with dimethyl Dibenzothiophene class sulfide, while also can avoid octane number
Decline.
(3) hybridized metal organic framework material of the invention is dilute by dry and calcination process after impregnating rare earth metal
Native oxide (such as CeO2) new alkali center is formed inside hybridized metal organic framework material, can preferably with organic sulfide
Adsorption reaction, the i.e. adsorption efficiency of reinforcing material occur for object, therefore it adsorbs significant desulfurization effect and improves.Simultaneously as part
The presence at alkali center can be greatly lowered nitrogenous compound and the competition containing double bond alkene and sulfide in fuel oil and inhale
It is attached, that is, improve the desulfuration selectivity of hybridized metal organic framework material.The scope of application is more extensive, also can be used for fine chemicals
Desulfuration field.
(4) present invention uses aqueous acetone solution as solvent, avoids during synthesizing hybridized metal organic framework material
Conventional organic solvents bring environment hidden danger, and do not select toxic, harmful drug as reagent.In addition, selection ultrasonic treatment
Mode synthesizes, and can shorten generated time, reduces energy consumption.
(5) present invention uses the aqueous acetone solution for containing ammonium salt as post-processing solvent, can make ammonium salt and remain in crystalline substance
Isosorbide-5-Nitrae in body, 5,8- naphthalenetetracarbacidic acidic molecules chemically react, and thoroughly remove Residual reactants, dredge duct.Due to impurity and
Residual reactants completely remove, more unsaturation Cu2+Active sites are exposed, and the absorption desulfurization energy of material is significantly improved
Power.
Detailed description of the invention
Fig. 1 is X-ray diffraction (XRD) figure of the hybridized metal organic framework material a of embodiment 1；
Fig. 2 is scanning electron microscope (SEM) photo of the hybridized metal organic framework material a of embodiment 1；
Fig. 3 is loaded with CeO for embodiment 12Hybridized metal organic framework material A scanning electron microscope (SEM) photo；
Fig. 4 is that embodiment 1 is loaded with CeO2The dimethyl dibenzo of hybridized metal organic framework material A at normal temperatures and pressures
The adsorption isotherm of thiophene.
Specific embodiment
The preparation process of hybridized metal organic framework material of the present invention is further illustrated below by embodiment, but is not answered
Think that wt% is mass fraction present invention is limited only by embodiment below.
Embodiment 1
(1) hybridized metal organic framework material a is prepared
Weigh 5gCu (NO3)2·3H2O, 3g1,4,5,8- naphthalenetetracarbacidic acidics are added in 2000g aqueous acetone solution, acetone and
The volume ratio of water is 1:2, and pH after mixing is 0.73, closed to be placed in ultrasonic oscillator, adjusts ultrasonic frequency
For 100KHz, ultrasonic power 450W, ultrasonic vibration is to there is sky blue sediment at room temperature.Mass concentration, which is added dropwise, is
Aqueous solution containing 0.27g soluble starch, wherein the concentration of soluble starch is 25wt%, maintains ultrasound condition constant, after
Continuous ultrasound 35min.Mixed solution suction filtration processing to obtaining, filter cake is put into the aqueous acetone solution containing ammonium chloride, filter cake
It is 1:1 with the mass ratio of ammonium chloride, the ratio of ammonium chloride and acetone is 1g:120mL, and the volume ratio of acetone and water is 1:2, is turned
Speed is mechanical stirring 60min under 70rpm.Above-mentioned solution suction filtration processing, it is multiple with water washing, much filtrate is dried, 215 DEG C
Lower dry 180min obtains hybridized metal organic framework material a.
(2) supported rare earth
100mg hybridized metal organic framework material is added in 30mL water again, then adds the Ce (NO of 1mg3)3·6H2O,
300rpm stirs 180min, and products therefrom is first dry at 100 DEG C, then roasts 720min at 300 DEG C, obtains being loaded with CeO2
Hybridized metal organic framework material A.
Embodiment 2
Essentially identical with the method and raw material of embodiment 1, difference is: copper source is changed to CuSO4·5H2O is other anti-
It answers condition and material to form constant, obtains being loaded with CeO2Hybridized metal organic framework material B.
Embodiment 3
Essentially identical with the method and raw material of embodiment 1, difference is: acetone and water volume ratio are improved in solvent to 1:
10, other reaction conditions and material composition are constant, obtain being loaded with CeO2Hybridized metal organic framework material C.
Embodiment 4
Essentially identical with the method and raw material of embodiment 1, difference is: by the Quality advance of aqueous acetone solution to 3000g,
Other reaction conditions and material composition are constant, obtain being loaded with CeO2Hybridized metal organic framework material D.
Embodiment 5
Essentially identical with the method and raw material of embodiment 1, difference is: the mass concentration of soluble starch aqueous solution is subtracted
It is as little as 10wt%, other reaction conditions and material composition are constant, obtain being loaded with CeO2Hybridized metal organic framework material E.
Embodiment 6
Essentially identical with the method and raw material of embodiment 1, difference is: ultrasonic frequency and power are respectively increased
200KHz and 700W, other reaction conditions and material composition are constant, obtain being loaded with CeO2Hybridized metal organic framework material F.
Embodiment 7
Essentially identical with the method and raw material of embodiment 1, difference is: the ultrasonic reaction time is reduced to 5min, other anti-
It answers condition and material to form constant, obtains being loaded with CeO2Hybridized metal organic framework material G.
Embodiment 8
Essentially identical with the method and raw material of embodiment 1, difference is: reducing in the aqueous acetone solution containing ammonium salt, chlorine
Change the ratio of ammonium and acetone as 1g:80mL, the volume ratio of acetone and water is 0.1:1, and other reaction conditions and material composition are not
Become, obtains being loaded with CeO2Hybridized metal organic framework material H.
Embodiment 9
Essentially identical with the method and raw material of embodiment 1, difference is: the mechanical stirring time is reduced to 20min, it is other
Reaction condition and material composition are constant, obtain being loaded with CeO2Hybridized metal organic framework material I.
Embodiment 10
Essentially identical with the method and raw material of embodiment 1, difference is: the drying temperature in step (1) is adjusted to 100
DEG C, other reaction conditions and material composition are constant, obtain being loaded with CeO2Hybridized metal organic framework material J.
Embodiment 11
Essentially identical with the method and raw material of embodiment 1, difference is: by Ce (NO3)3·6H2O such as is substituted at the quality
La(NO3)3·6H2O, other reaction conditions and material composition are constant, obtain being loaded with La2O3Hybridized metal organic framework material K.
Embodiment 12
Essentially identical with the method and raw material of embodiment 1, difference is: by Ce (NO3)3·6H2The quality of O is reduced to
0.5mg, other reaction conditions and material composition are constant, obtain being loaded with CeO2Hybridized metal organic framework material L.
Embodiment 13
Essentially identical with the method and raw material of embodiment 1, difference is: load C e (NO3)3·6H2During O, it will stir
Mixing the time shorten to 30min, and other reaction conditions and material composition are constant, obtain being loaded with CeO2Hybridized metal organic backbone material
Expect M.
Embodiment 14
Essentially identical with the method and raw material of embodiment 1, difference is: load C e (NO3)3·6H2During O, it will walk
Suddenly the maturing temperature in (2) is reduced to 250 DEG C, and other reaction conditions and material composition are constant, obtains being loaded with CeO2Hydridization gold
Belong to organic framework material N.
Comparative example 1
Essentially identical with the method and raw material of embodiment 1, difference is: rare earth ion is not impregnated, only with synthesis
Hybridized metal organic framework material O is as absorption sulfur removal material.
Comparative example 2
Essentially identical with the method and raw material of embodiment 1, difference is: soluble starch aqueous solution is not added, it is other anti-
It answers condition and material to form constant, obtains being loaded with CeO2Metal-organic framework materials P.
Comparative example 3
Essentially identical with the method and raw material of embodiment 1, difference is: the aqueous acetone solution of ammonium chloride is replaced equivalent second
Alcohol solution, other reaction conditions and material composition are constant, obtain being loaded with CeO2Metal-organic framework materials Q.
Comparative example 4
According to the method that CN102886244A is described, Cu is prepared first3(BTC)2Metal-organic framework materials, then by metal
Organic framework material is added in N-Methyl pyrrolidone solvent and stirs, preparative separation film.After preparing casting solution, by casting solution in glass
After striking is at plate membrane in glass plate, it is organic to obtain metal in 250 DEG C of baking 3h after draining for solidified forming in alcohol solidification bath
Skeleton hybridized film R.
Comparative example 5
According to the method that CN102895954A is described, 50mL n,N-Dimethylformamide is mixed with 0.7g zinc nitrate, is added
Enter 0.5gCOOH-SBA-15, ultrasonic disperse 0.5h, 0.5g imidazoles is then added and 0.2g 2- nitroimidazole is uniformly mixed, stirs
It mixes, be aged, 100 DEG C of crystallization 72h, the ZIF-68/SBA-15 adsorbent S for filtering, washing, being obtained after vacuum drying, wherein absorption
Metallic framework material ZIF-68 and molecular sieve in agent S is mutually compound.
Test case 1
What is prepared in order to further illustrate the present invention is loaded with CeO2Hybridized metal organic framework material and existing similar material
The load of embodiment 1-14 and comparative example 2-3 is had the metal-organic framework materials of rare earth and comparative example 1, right by the difference of material
The physicochemical property of the metal-organic framework materials of ratio 4 and 5 is listed in table 1.Wherein, specific surface area, Kong Rong are adsorbed by low temperature liquid nitrogen
Method measures.
The physicochemical property and test result of each material of table 1
| Sample | BET specific surface area/ m2·g-1 | Total pore volume/cm3·g-1 | The micropore knot of 0.7nm~1nm Structure accounts for total pore volume/% | The mesoporous knot of 2nm~3.5nm Structure accounts for total pore volume/% | Skeleton breakage temperature/DEG C | Dimethyl Dibenzothiophene Conversion ratio/wt% | Adsorption capacity/mgS of sulphur g-1 |
| A | 1189 | 0.79 | 63 | 9 | 425 | 85 | 159 |
| B | 1001 | 0.68 | 49 | 6 | 407 | 72 | 126 |
| C | 1052 | 0.70 | 55 | 7 | 409 | 77 | 132 |
| D | 1007 | 0.71 | 52 | 5 | 401 | 73 | 128 |
| E | 973 | 0.69 | 51 | 5 | 395 | 70 | 122 |
| F | 963 | 0.67 | 50 | 5 | 390 | 68 | 119 |
| G | 950 | 0.65 | 50 | 5 | 391 | 67 | 112 |
| H | 1017 | 0.71 | 54 | 6 | 402 | 76 | 131 |
| I | 1005 | 0.70 | 54 | 6 | 400 | 73 | 121 |
| J | 967 | 0.65 | 51 | 5 | 393 | 67 | 110 |
| K | 1105 | 0.74 | 61 | 9 | 417 | 79 | 142 |
| L | 1078 | 0.71 | 59 | 6 | 419 | 70 | 121 |
| M | 1092 | 0.73 | 62 | 7 | 409 | 62 | 116 |
| N | 998 | 0.69 | 63 | 6 | 398 | 60 | 110 |
| O | 1350 | 0.85 | 65 | 10 | 395 | 76 | 107 |
| P | 827 | 0.51 | 31 | 0.2 | 253 | 15 | 23 |
| Q | 753 | 0.41 | 26 | 0.1 | 297 | 7 | 5 |
| R | 810 | 0.51 | 37 | 0.2 | 265 | 7 | 25 |
| S | 730 | 0.49 | 31 | 0.7 | 271 | 3 | 8 |
As can be seen from the data in table 1, hybridized metal organic framework material obtained of the invention, BET specific surface area reach
1350m2·g-1, total pore volume reaches 0.85cm3·g-1, the microcellular structure of 0.7nm~1.0nm accounts for total pore volume and reaches 65%, 2.0nm
The meso-hole structure of~3.5nm accounts for total pore volume and reaches 10%；Specific surface area also reaches 1189 m after supported rare earth2·g-1, total pore volume reaches
To 0.79cm3·g-1, the microcellular structure of 0.7nm~1.0nm, which accounts for total pore volume and reaches 63%, 2.0nm~3.5nm meso-hole structure, to be accounted for
Total pore volume reaches 9%.Such pore structure is to adsorb larger-size dimethyl Dibenzothiophene (> 1.5nm) in material inner surface
Provide chance.
Test case 2
The adsorption capacity and dimethyl of sulphur of the material of testing example 1-14 and comparative example 1-5 in catalytic cracking diesel oil
The conversion ratio of dibenzothiophenes and the adsorption capacity of sulphur, the results are shown in Table 1.The conversion ratio of dimethyl Dibenzothiophene is by gas-chromatography
(model Agilent 6890A) is completed in analysis.
Static adsorptive method: weighing the sample of certain mass, be put into vacuum oven, and 12h removal hole is vacuumized at 150 DEG C
Then impurity molecule in road mixes adsorbent with catalytic cracking diesel oil in closed container according to a certain percentage, magnetic force stirs
3h, the sulfur content in the oil product of measurement absorption front and back are mixed, and calculates adsorbent to the removal efficiency of sulfide.
The adsorption capacity calculation method of the conversion ratio of dimethyl Dibenzothiophene, sulphur are as follows:
The adsorption capacity of sulphur: q=V(c0-ce)/m
The adsorption capacity (mg S/g) of q expression sulphur；V indicates diesel fuel volume (mL)；c0Initial sulfur concentration (the ng/ μ of diesel oil
L)；ceThe remaining sulphur concentration (ng/ μ L) of diesel oil when Static Adsorption reaches balance；M is the quality (g) of adsorbent；
The conversion ratio of dimethyl Dibenzothiophene: M%=(d0-de)/d0×100%
M indicates the conversion ratio (%) of dimethyl Dibenzothiophene, d0The initial dimethyl Dibenzothiophene concentration (ng/ of diesel oil
μ L)；deThe remaining dimethyl Dibenzothiophene concentration (ng/ μ L) of diesel oil when Static Adsorption reaches balance.
When sulfur content is 1825 μ g/g in catalytic cracking diesel oil, wherein dimethyl Dibenzothiophene content is 875 μ g/g S
When, test result is shown in Table 1, and the conversion ratio of the dimethyl Dibenzothiophene of material of the invention in catalytic cracking diesel oil reaches
85wt%, the sulphur adsorption capacity of adsorbent are more than 159mg S/g.
Fig. 4 is it is found that the load of embodiment 1 has the hybridized metal skeleton organic material of rare earth to have dimethyl Dibenzothiophene
There is preferably removal effect.With the increase of dimethyl Dibenzothiophene content in oil product, the adsorption capacity of adsorbent is also in increase
Add trend；When dimethyl Dibenzothiophene content reaches 2000 μ g/g S in oil product, the adsorption capacity of adsorbent is more than 70mg
S/g。
Test case 3
The material of testing example 1,3 and comparative example 1-5 desulfurization degree, olefin removal rate, denitrogenation in for direct steaming gasoline
Rate is listed in table 2.Wherein, 370 μ g/g of sulfur content, nitrogen content 90 μ g/g, olefin(e) centent 37wt% in direct steaming gasoline.
Test method is static method: weighing the sample of certain mass, is put into vacuum oven, vacuumizes 12h at 150 DEG C
The impurity molecule in duct is removed, is then mixed adsorbent in closed container according to a certain percentage with gasoline, magnetic agitation
3h, sulfur content, nitrogen content and olefin(e) centent in the oil product of measurement absorption front and back, and calculate adsorbent to the removal efficiency of sulfide,
Alkene and denitrification percent.
The calculation method of desulfurization degree, olefin removal rate
Olefin removal rate: R%=(a0-ae)/a0
R indicates olefin removal rate (%)； a0The olefin streams concentration (wt%) of gasoline；aeGasoline when Static Adsorption reaches balance
Residual olefin concentration (wt%)；
Desulfurization degree: N%=(b0-be)/b0×100%
N indicates desulfurization degree (%)；b0The initial sulfur concentration (ng/ μ L) of gasoline；beGasoline is surplus when Static Adsorption reaches balance
Remaining sulphur concentration (ng/ μ L)；
Denitrification percent: T%=(c0-ce)/c0×100%
T indicates denitrification percent (%)；c0The initial nitrogen concentration (wt%) of gasoline；ceThe residue of gasoline when Static Adsorption reaches balance
Nitrogen concentration (wt%).
Adsorption effect of each material of table 2 for gasoline
| Sample | Desulfurization degree/% | Olefin removal rate/% | Denitrification percent % |
| A | 99.5 | 0.6 | 25 |
| C | 99.1 | 0.8 | 26 |
| O | 99 | 1.0 | 40 |
| P | 83.5 | 30 | 41 |
| Q | 87 | 23 | 35 |
| R | 92 | 50 | 55 |
| S | 91 | 53 | 57 |
As shown in Table 2, sample prepared by the present invention is except having higher organic sulfur compound absorption property, for the alkene of gasoline
The hydrocarbon component adsorbance is less, and reduces denitrification percent.As the load of embodiment 1 has the hybridized metal skeleton organic material pair of rare earth
The desulfurization degree of gasoline is 99.5%, and olefin removal rate is 0.6% in gasoline, denitrification percent 25%, and comparative example 4 and is had with 5 metal
Although machine framework material reaches 50% or more to gasoline also desulfurization degree with higher, to the desorption rate of alkene, due to alkene
It is the important component of high-knock rating gasoline, after excessive adsorbing and removing olefin component, be easy to cause octane number to decline, be unfavorable for
High-knock rating gasoline is produced, and denitrification percent reaches 57%.
Fig. 1 gives the XRD diffraction maximum spectrogram of hybridized metal organic framework material, it is seen that the not formed web wheel of its space structure
Shape symmetrical structure does not have higher Selective adsorption for alkene containing double bonds, and diffraction peak intensity is higher, that is, closes
It is less at the impurity of product, crystallinity is higher.SEM(Fig. 2) photo shows, crystal is in wheat head shape pattern, long and narrow duct knot
Structure is conducive to the organic sulfur compound absorption of the macromoleculars such as dibenzothiophenes, dimethyl Dibenzothiophene.
SEM(Fig. 2 and Fig. 3) photo shows before and after supported rare earth metal ion not to hybridized metal organic framework material
Pattern damage, load C eO2After, hybridized metal organic framework material has still kept wheat head shape pattern, long and narrow
Cellular structure is conducive to the organic sulfur compound absorption of the macromoleculars such as dibenzothiophenes, dimethyl Dibenzothiophene.
Metallic framework organic material of the invention has preferably removal effect to the sulphur of oil and gasoline.Present invention preparation
Hybridized metal organic framework material have higher desulfuration selectivity, i.e. the scope of application is more extensive, also can be used for fine chemistry
Product desulfuration field.
Claims (33)
1. a kind of load the preparation method for having the hybridized metal organic framework material of rare earth, which comprises the steps of:
(1) by Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics and copper source are added in solvent, are uniformly mixed, and the first ultrasonic treatment is then carried out,
When there is sediment, soluble starch aqueous solution is added, the second ultrasonic treatment is continued；
(2) mixture after second ultrasonic treatment is filtered, then the solid being obtained by filtration is put into containing ammonium salt
It stirs in aqueous acetone solution, then refilters, be washed with water and dry, obtain hybridized metal organic framework material；
(3) rare earth metal is loaded into hybridized metal organic framework material, has the hybridized metal of rare earth organic to obtain load
Framework material.
2. according to the method for claim 1, it is characterised in that: the molar ratio of copper source and Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics is
1:(0.1~1.0), Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics, soluble starch aqueous solution and solvent quality ratio are 1:(0.01~0.2):
(100~1000).
3. according to the method for claim 1, it is characterised in that: the molar ratio of copper source and Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics is
1:(0.35~0.70), Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics, soluble starch aqueous solution and solvent quality ratio are 1:(0.02~0.15):
(150~700).
4. method according to claim 1 or 2, it is characterised in that: copper source is selected from copper nitrate, copper sulphate and copper chloride
One or more of.
5. method according to claim 1 or 2, it is characterised in that: copper source is selected from copper nitrate.
6. method according to claim 1 or 2, it is characterised in that: the mass concentration of the soluble starch aqueous solution is
8wt%~65wt%.
7. method according to claim 1 or 2, it is characterised in that: the mass concentration of the soluble starch aqueous solution is
10wt%~35wt%.
8. method according to claim 1 or 2, it is characterised in that: the solvent is aqueous acetone solution, acetone and water volume
Than for 1:(0.1~15).
9. method according to claim 1 or 2, it is characterised in that: the solvent is aqueous acetone solution, acetone and water volume
Than for 1:(1~10).
10. method according to claim 1 or 2, it is characterised in that: in step (1), in Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics,
After mixing, the pH of mixture is less than 2.0 for copper source and solvent.
11. method according to claim 1 or 2, it is characterised in that: in step (1), in Isosorbide-5-Nitrae, 5,8- naphthalenetetracarbacidic acidics,
After mixing, the pH of mixture is 0.3~0.9 for copper source and solvent.
12. method according to claim 1 or 2, it is characterised in that: in step (1), the behaviour of first ultrasonic treatment
Make condition are as follows: the frequency of ultrasonic wave is 10KHz~200KHz；The power of ultrasonic wave is 100W~700W.
13. method according to claim 1 or 2, it is characterised in that: in step (1), the behaviour of second ultrasonic treatment
Make condition are as follows: ultrasonic time is 5min~150min, and the frequency of ultrasonic wave is 10KHz~200KHz, and the power of ultrasonic wave is
100W~700W.
14. method according to claim 1 or 2, it is characterised in that: in step (2), in the acetone containing ammonium salt
In aqueous solution, the ratio of the ammonium salt and aqueous acetone solution is 1g:(80mL~150mL), the volume ratio of acetone and water is 1:
(0.1~15.0), the ammonium salt are selected from one or more of ammonium chloride, ammonium sulfate, ammonium nitrate.
15. according to the method for claim 14, it is characterised in that: the volume ratio of acetone and water is 1:(1~10).
16. method according to claim 1 or 2, it is characterised in that: in step (2), the drying temperature is 75 DEG C
~245 DEG C；Time is 60min~360min.
17. according to method described in claim 16, it is characterised in that: in step (2), the drying temperature is 100 DEG C~
230℃。
18. according to the method for claim 1, it is characterised in that: in step (3), rare earth metal is loaded to hybridized metal
The specific steps of organic framework material: hybridized metal organic framework material is mixed with water and rare earth metal inorganic salts, it is dry and
Roasting.
19. according to the method for claim 18, it is characterised in that: hybridized metal organic framework material described in step (3)
It is 1:(0.001~0.01 with mass ratio of the rare earth metal inorganic salts in terms of rare-earth oxide).
20. according to the method for claim 18, it is characterised in that: hybridized metal organic framework material described in step (3)
It is 1:(0.001~0.045 with mass ratio of the rare earth metal inorganic salts in terms of rare-earth oxide).
21. according to the method for claim 18, it is characterised in that: rare earth metal inorganic salts be selected from lanthanum and cerium nitrate,
One or more of chlorate.
22. according to the method for claim 18, it is characterised in that: rare earth metal inorganic salts are selected from Ce (NO3)3·6H2O or
La(NO3)3·6H2O。
23. according to the method for claim 18, it is characterised in that: in step (3), the drying temperature be 70 DEG C~
150 DEG C, the time is 60min~360min.
24. according to the method for claim 18, it is characterised in that: in step (3), the temperature of roasting is 200 DEG C~400
℃；Time is 600min~1200min.
25. according to method described in claim 24, it is characterised in that: in step (3), the temperature of roasting is 250 DEG C~350 DEG C.
26. according to the method described in claim 1, it is characterized by: the resulting hybridized metal organic framework material of step (2) contains
There are micropore canals structure and mesopore orbit structure.
27. according to claim 1 or method described in 26, it is characterised in that: the resulting hybridized metal organic backbone material of step (2)
Expect that the mesoporous Kong Rong of 50%~75%, 2.0nm~3.5nm that total pore volume is accounted in the Micropore volume of the 0nm of 0.7nm~1. accounts for total pore volume
4%~13%.
28. method described in claims 1 or 26, it is characterised in that: the resulting hybridized metal organic framework material of step (2) exists
The mesoporous Kong Rong of 50%~65%, 2.0nm~3.5nm that the Micropore volume of the 0nm of 0.7nm~1. accounts for total pore volume accounts for the 4% of total pore volume
~10%.
29. according to claim 1 or method described in 26, it is characterised in that: the resulting hybridized metal organic backbone material of step (2)
The specific surface area of material is 900m2·g-1~1500m2·g-1, total pore volume 0.50cm3·g-1~0.90cm3·g-1。
30. according to claim 1 or method described in 26, it is characterised in that: the resulting hybridized metal organic backbone material of step (2)
The specific surface area of material is 950m2·g-1~1350m2·g-1, total pore volume 0.60cm3·g-1~0.85cm3·g-1。
31. according to claim 1 or method described in 26, it is characterised in that: the resulting hybridized metal organic backbone material of step (2)
Material be anorthic system, cell parameter be a=7.270 (2), b=8.531 (2), c=9.637 (3), α=82 °, β=75 °, γ=
78 °, unit cell volume V=587.4 (3)3, Z=1, Dc=1.815mg/cm3。
32. the hybridized metal organic backbone material that a kind of load of the method preparation as described in any in claim 1-31 has rare earth
Material.
33. load described in claim 32 has application of the hybridized metal organic framework material of rare earth in the desulfurization of fuel oil.
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| CN101429209A (en) * | 2008-12-11 | 2009-05-13 | 重庆大学 | Method for low-temperature atmosphere-pressure hydrothermal synthesis of stephanoporate metal-organic framework |
| CN101596465A (en) * | 2009-06-30 | 2009-12-09 | 北京大学 | Based on metallic catalyst of metal-organic framework and its production and application |
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| CN101429209A (en) * | 2008-12-11 | 2009-05-13 | 重庆大学 | Method for low-temperature atmosphere-pressure hydrothermal synthesis of stephanoporate metal-organic framework |
| CN101596465A (en) * | 2009-06-30 | 2009-12-09 | 北京大学 | Based on metallic catalyst of metal-organic framework and its production and application |
| CN104549161A (en) * | 2013-10-24 | 2015-04-29 | 中国石油化工股份有限公司 | Preparation method of ferrous metal organic framework material and application of ferrous metal organic framework material |
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