CN106622143B - A kind of hydridization organic framework material and the preparation method and application thereof - Google Patents
A kind of hydridization organic framework material and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of hybridized metal organic framework material, 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.Additionally provide hybridized metal organic framework material and the application of this method preparation.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 hybridized metal organic framework material and preparation method thereof applications, and especially one kind can be used for firing
The organic framework material and the preparation method and application thereof of material oil absorption.
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 material and preparation method thereof and it is somebody's turn to do
Application of the metal-organic framework materials in gas absorption, gas absorption storage, gas absorption separation.Method preparation of the invention
Hydridization organic framework material not only very heat-flash stability and suitable pore structure, and there are more active sites and well
Spatial symmetry is applicable to the fuel oil adsorption-desulfurizations process such as gasoline, diesel oil, particularly with dimethyl Dibenzothiophene class sulphur
Compound has preferable removal effect, while also can avoid octane number decline.
A kind of preparation method of hybridized metal organic framework material provided by the invention, includes the following steps:
(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 dry, obtain 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 (0.12~1.26): (0.01~
0.14): (100~600), preferably (0.50~0.85): (0.02~0.08): (150~500).The present invention can select often
Rule use copper source, and the copper source can be selected from one or more of copper nitrate, copper sulphate and copper chloride, preferably nitric acid
Copper.
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.
The present invention also provides a kind of hybridized metal organic framework materials of above method preparation.
Hybridized metal organic framework material of the present invention has micropore and mesoporous pore structure.Hybridized metal organic framework material exists
The Micropore volume of 0.7nm~1.0nm accounts for the 50%~75% of total pore volume, the mesoporous hole preferably 55%~65%, 2.0nm~3.5nm
Appearance accounts for the 4%~13% of total pore volume, preferably 4%~10%.
The specific surface area of hybridized metal organic framework material 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 0.60cm3·g-1~
0.85cm3·g-1。
Hybridized metal organic framework material 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 a kind of application of above-mentioned hybridized metal organic framework material in the desulfurization of fuel oil, preferably
Ground, application of the hybridized metal organic framework material in the organic sulfur compound that removing high steric hindrance influences.
Hydridization organic framework material of the invention, has the advantages that
(1) present invention adds water soluble starch in the synthesis process, and water soluble starch is in Isosorbide-5-Nitrae, the acid of 5,8- naphthalenetetracarbacidic acidics
Property effect under, it may occur that hydrolysis, oxygen bridge is broken when reaction, while hydrone is added, and water soluble starch is become by long-chain molecule
At short chain molecule, until oxygen bridge complete rupture, becomes glucose, wherein short chain molecule is polynary sugar, and these hydrolysates
In containing a certain number of hydroxyls and carboxymethyl and aldehyde radical, these hydroxyls and aldehyde radical can be with metal-organic framework materials central metals
Complexation reaction occurs for ion, 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) present invention uses aqueous acetone solution as solvent, avoids tradition during synthesizing metal-organic framework materials
Organic solvent bring environment hidden danger, and do not select toxic, harmful drug as reagent.In addition, selection ultrasound treatment patterns
Synthesis can shorten generated time, reduce energy consumption.
(4) 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 the thermogravimetric curve (TG) of the hybridized metal organic framework material A of embodiment 1；
Fig. 4 is the suction of the dimethyl Dibenzothiophene of the hybridized metal organic framework material A of embodiment 1 at normal temperatures and pressures
Attached thermoisopleth.
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
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
The soluble starch aqueous solution 0.27g of 25wt% maintains ultrasound condition constant, continues ultrasound 35min.To obtained mixed solution
Suction filtration processing, filter cake is put into the aqueous acetone solution containing ammonium chloride, and the mass ratio of filter cake and ammonium chloride is 1:1, ammonium chloride
It is 1g:120mL with the ratio of acetone, the volume ratio of acetone and water is 1:2, and revolving speed is mechanical stirring 60min under 70rpm.It is above-mentioned
The processing of solution suction filtration, it is multiple with water washing, much filtrate is dried, dry 180min, it is organic to obtain hybridized metal at 215 DEG C
Framework material A.
Embodiment 2
Essentially identical with the method and raw material of embodiment 1, difference is: copper source is changed to etc. to the CuSO of quality4·
5H2O, other reaction conditions and material composition are constant, obtain hybridized metal organic framework material B.
Embodiment 3
Essentially identical with the method and raw material of embodiment 1, difference is: by the acetone and water volume ratio in aqueous acetone solution
It is adjusted to 1:10, the acetone and water volume ratio in the aqueous acetone solution containing ammonium chloride are adjusted to 1:10, other reaction conditions and material
It forms constant, obtains hybridized 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 hybridized 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 hybridized 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 hybridized 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 hybridized 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 hybridized 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 hybridized metal organic framework material I.
Embodiment 10
Essentially identical with the method and raw material of embodiment 1, difference is: drying temperature being reduced to 100 DEG C, other reactions
Condition and material composition are constant, obtain hybridized metal organic framework material J.
Comparative example 1
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 metal-organic framework materials K.
Comparative example 2
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 metal-organic framework materials L.
Comparative example 3
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 M.
Comparative example 4
According to the method that CN102895954A is described, 50mL n,N-Dimethylformamide is mixed with 0.7g zinc nitrate, is added
Enter 0.5COOH-SBA-15, ultrasonic disperse 0.5h, 0.5g imidazoles is then added and 0.2g 2- nitroimidazole is uniformly mixed, stirring,
Ageing, 100 DEG C of crystallization 72h, the ZIF-68/SBA-15 adsorbent N for filtering, washing, being obtained after vacuum drying, wherein adsorbent S
In metallic framework material ZIF-68 and molecular sieve it is mutually compound.
Test case 1
The difference of the hybridized metal organic framework material and existing same type of material that prepare in order to further illustrate the present invention, will
The physicochemical property of above-mentioned material is listed in table 1.Wherein, specific surface area, Kong Rong are measured by low temperature liquid nitrogen absorption method.
The physicochemical property and test result of the hybridized metal organic framework material of 1 embodiment and comparative example of table
| Sample | BET specific surface Product/m2·g-1 | Total pore volume/ cm3·g-1 | 0.7nm~1.0nm's is micro- Pore structure accounts for total pore volume/% | 2.0nm~3.5nm Meso-hole structure account for Total pore volume/% | Skeleton is broken Damage temperature/ ℃ | Dimethyl dibenzo The conversion ratio of thiophene/ wt% | The absorption of sulphur is held Amount/mgSg-1 |
| A | 1350 | 0.85 | 65 | 10 | 425 | 76 | 107 |
| B | 1033 | 0.73 | 51 | 6 | 407 | 61 | 100 |
| C | 1172 | 0.75 | 59 | 7 | 409 | 65 | 102 |
| D | 1079 | 0.74 | 55 | 6 | 401 | 63 | 101 |
| E | 995 | 0.69 | 47 | 4 | 395 | 55 | 91 |
| F | 983 | 0.65 | 45 | 4 | 390 | 54 | 90 |
| G | 980 | 0.61 | 42 | 4 | 391 | 51 | 87 |
| H | 1117 | 0.75 | 58 | 7 | 402 | 65 | 100 |
| I | 1075 | 0.74 | 59 | 6 | 400 | 63 | 101 |
| J | 990 | 0.68 | 45 | 4 | 393 | 55 | 90 |
| K | 930 | 0.62 | 35 | 0.5 | 356 | 17 | 25 |
| L | 870 | 0.45 | 30 | 0.1 | 360 | 10 | 9 |
| M | 810 | 0.51 | 37 | 0.2 | 321 | 7 | 25 |
| N | 730 | 0.49 | 31 | 0.7 | 309 | 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 conversion of the material of testing example 1-10 and comparative example 1-4 dimethyl Dibenzothiophene in catalytic cracking diesel oil
The adsorption capacity of rate and sulphur, the results are shown in Table 1.The conversion ratio of dimethyl Dibenzothiophene completes (model by gas chromatographic analysis
Agilent 6890A).
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 732 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
76wt%, the sulphur adsorption capacity of adsorbent are more than 107mg S/g.
As shown in Figure 4, the hybridized metal skeleton organic material of embodiment 1 has dimethyl Dibenzothiophene preferably de-
Except effect.With the increase of dimethyl Dibenzothiophene content in oil product, the adsorption capacity of sulphur is also in increase trend；When in oil product
When dimethyl Dibenzothiophene content reaches 2000 μ g/g S, the adsorption capacity of sulphur is more than 50mg S/g.
Test case 3
The material of testing example 1,3 and comparative example 1-4 are in the removal efficiency for desulfurization degree and alkene in direct steaming gasoline
It is listed in table 2.Wherein, 370 μ g/g of sulfur content, olefin(e) centent 37wt% in direct steaming gasoline.
Test method is static adsorptive method: weighing the sample of certain mass, is put into vacuum oven, takes out at 150 DEG C true
Impurity molecule in empty 12h removal duct, then mixes adsorbent with gasoline, magnetic force in closed container according to a certain percentage
3h, sulfur content and olefin(e) centent in the oil product of measurement absorption front and back are stirred, and calculates adsorbent to sulfide and olefin removal rate.
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).
Adsorption effect of each hybridized metal organic framework material of table 2 for alkene in gasoline
| Sample | Desulfurization degree/% | Olefin removal rate/% |
| A | 99 | 1.0 |
| C | 97 | 1.3 |
| K | 80 | 32 |
| L | 85 | 27 |
| M | 92 | 50 |
| N | 91 | 53 |
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, it can keeps octane level constant while desulfurization.Such as the hybridized metal bone of embodiment 1
Frame organic material is 99.5% to the desulfurization degree of gasoline, and olefin removal rate is only 0.6% in gasoline, and comparative example 3 and the metal with 4
Although organic framework material reaches 50% or more to gasoline also desulfurization degree with higher, to the removal efficiency of alkene, due to alkene
Hydrocarbon is the important component of high-knock rating gasoline, after excessive adsorbing and removing olefin component, octane number is be easy to cause to decline, unfavorable
In production high-knock rating gasoline.
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.
The thermogravimetric curve of Fig. 3 can be seen that due to selecting the higher Isosorbide-5-Nitrae of rigid structure, 5,8- naphthalenetetracarbacidic acidics as ligand,
The thermal stability of metal-organic framework materials is significantly better than existing similar product (universal < 400 DEG C).
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 (25)
1. a kind of preparation method of hybridized metal organic framework material, 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.
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. method according to claim 1 or 2, it is characterised in that: in step (2), the drying temperature is 100
DEG C~230 DEG C.
18. a kind of hybridized metal organic framework material of the method preparation as described in any in claim 1-17.
19. hybridized metal organic framework material according to claim 18, it is characterised in that: hybridized metal organic backbone material
Material contains micropore canals structure and mesopore orbit structure.
20. hybridized metal organic framework material described in 8 or 19 according to claim 1, it is characterised in that: the organic bone of hybridized metal
Frame material is total in the mesoporous Kong Rong Zhan of 50%~75%, 2.0nm~3.5nm that the Micropore volume of the 0nm of 0.7nm~1. accounts for total pore volume
The 4%~13% of Kong Rong.
21. hybridized metal organic framework material described in 8 or 19 according to claim 1, it is characterised in that: the organic bone of hybridized metal
Frame material is total in the mesoporous Kong Rong Zhan of 55%~65%, 2.0nm~3.5nm that the Micropore volume of the 0nm of 0.7nm~1. accounts for total pore volume
The 4%~10% of Kong Rong.
22. hybridized metal organic framework material described in 8 or 19 according to claim 1, it is characterised in that: the organic bone of hybridized metal
The specific surface area of frame material is 900m2·g-1~1500m2·g-1, total pore volume 0.50cm3·g-1~0.90cm3·g-1。
23. hybridized metal organic framework material described in 8 or 19 according to claim 1, it is characterised in that: the organic bone of hybridized metal
The specific surface area of frame material is 950m2·g-1~1350m2·g-1, total pore volume 0.60cm3·g-1~0.85cm3·g-1。
24. hybridized metal organic framework material described in 8 or 19 according to claim 1, it is characterised in that: the organic bone of hybridized metal
Frame material 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。
25. application of any hybridized metal organic framework material of claim 18-24 in the desulfurization of fuel oil.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
| 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 |
| CN104096542A (en) * | 2014-06-23 | 2014-10-15 | 广西师范大学 | Novel magnetic Fe / C@ MOF composite absorbent and preparation method thereof |
| US20150034500A1 (en) * | 2013-08-05 | 2015-02-05 | Numat Technologies, Inc. | Metal organic frameworks for electronic gas storage |
-
2015
- 2015-11-03 CN CN201510734035.2A patent/CN106622143B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101585856A (en) * | 2008-05-23 | 2009-11-25 | 安徽大学 | With single-stage or the nano aperture metal-organic framework materials of multi-stage artery structure and its preparation |
| 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 |
| US20150034500A1 (en) * | 2013-08-05 | 2015-02-05 | Numat Technologies, Inc. | Metal organic frameworks for electronic gas storage |
| CN104096542A (en) * | 2014-06-23 | 2014-10-15 | 广西师范大学 | Novel magnetic Fe / C@ MOF composite absorbent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| A Review on Breathing Behaviors of Metal-Organic-Frameworks (MOFs) for Gas Adsorption;Mays Alhamami,ET.AL.;《Materials》;20140421;第7卷;第3198-3250页 |
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