CN104492383B - A kind of metal organic frame adsorbent and its preparation method and application - Google Patents
A kind of metal organic frame adsorbent and its preparation method and application Download PDFInfo
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
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- 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
- C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
- C10G25/06—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents with moving sorbents or sorbents dispersed in the oil
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- B01J2220/4812—Sorbents characterised by the starting material used for their preparation the starting material being of organic character
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- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
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- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
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Abstract
The invention discloses a kind of metal organic frame adsorbent, with metal-organic framework materials MIL-101 (the Cr)-SO of sulfonic acid funtionalized3H is carrier, and with Ag (I) for active component, described active component loads on carrier through ion-exchange reactions, and with the total amount of adsorbent for benchmark, load capacity is 10～40wt%.The preparation method that the invention also discloses described metal organic frame adsorbent, first prepares MIL-101 (Cr)-SO3H, then by MIL-101 (Cr)-SO3The solution mixing of H and Ag (I), through ion-exchange reactions, obtains described adsorbent MIL-101 (Cr)-SO3Ag.Preparation process is simple, mild condition, and the adsorbent prepared can realize the high Selective Separation to olefins/paraffins mixed gas, has good prospects for commercial application in deep desulfurization of fuel oil simultaneously.
Description
Technical field
The present invention relates to the technical field of adsorbing material, particularly relate to a kind of metal organic frame adsorbent and its preparation method and application.
Background technology
Alkene, alkane separation be separation process important in petroleum chemical industry, wherein with Ethylene-Ethane, the separation of propylene-propane is most representative.In olefin plant, use cryogenic rectification method separation alkene-alkane all the time.Although rectification is a kind of highly developed technique, but energy consumption is huge, research worker is devoted to seek a kind of method of efficient, energy-conservation, low cost to replace cryogenic rectification always, wherein absorption method is because it is efficient, energy-conservation and the advantage such as low cost, is acknowledged as one of most possible method replacing cryogenic separation at present.
Alkene, alkane the adsorbent selecting exactly there is relatively high-adsorption-capacity and large selectivity towards of adsorbing separation most critical.Document (Chem.Eng.Sci., 2008,63:4171) reports a series of adsorbents that molecular sieve EST and Na, K, Li etc. adopt ion exchange to prepare, and applies to the adsorbing separation of alkene alkane.What other application were more also has the adsorbents such as activated carbon, aluminium oxide, zeolite, but owing to their specific surface area, pore volume are generally relatively low, the adsorption capacity for alkene alkane is not high.
π solvay-type adsorbent, due to can optionally and the double bond of olefin hydrocarbon molecules produce stronger π complexing, after absorption, desorption is also relatively easy simultaneously, and is widely applied among the separation of alkene, alkane.π Separation by Complexation alkene is proposed in nineteen forty-one by (GillilandER, BlissHL, KipCE.Reactionofolefinswithsolidcuproushalides [J] .JACS, 1941,63:2088-2090) such as Gilliland the earliest, Cu+、Ag+Deng formation organotransition metal complex between transition metal and alkene, it is possible to olefine selective is separated.Transition metal is loaded to various carrier by scholars, such as activated carbon, molecular sieve, aluminium oxide, silicon dioxide, clay, resin etc., is prepared for number of types of π solvay-type adsorbent.
In recent years, metal-organic framework materials (reaches as high as 7000m owing to it has bigger specific surface area2/ g) and pore volume, and aperture is adjustable, the modifiable feature of hole inner structure, applies to gradually in the separation of alkene alkane.
At present, common such as Mg-MOF-74 (Langmuir, 2011,27:6368), Cu-BTC (Sep.Purif.Technol., 2008,60:30), ZIF series (J.Am.Chem.Soc., 2010,132:17704).These novel MOF materials, although the adsorbance of alkene alkane is higher, but there is also the problem that selectivity is not high equally.
In addition, metal-organic framework materials research in fuel oil deep removal sulfur-containing compound also gets more and more, compared to traditional hydrodesulfurization technology, metal-organic framework materials, for sterically hindered bigger dibenzothiophenes or 4,6-dimethyl Dibenzothiophene, it is also possible to show good adsorption effect, just can show bigger adsorbance to sulfur-containing compound at low concentrations especially for the adsorbing material (the unsaturated room of metal) containing special role site.
Summary of the invention
The preparation method that the invention provides a kind of metal organic frame adsorbent, with the metal-organic framework materials of sulfonic acid funtionalized for carrier, with Ag (I) for active component, Ag (I) is replaced to the sulfonic acid functional group of metal-organic framework materials by the method exchanged by ion, preparation process is simple, mild condition, the adsorbent prepared can realize the high Selective Separation to olefins/paraffins mixed gas, and shows extremely strong desulfurized effect compared to the sulfonic acid adsorbent before exchange.
A kind of metal organic frame adsorbent, described metal organic frame adsorbent is with metal-organic framework materials MIL-101 (the Cr)-SO of sulfonic acid funtionalized3H is carrier, and with Ag (I) for active component, described active component loads on carrier through ion-exchange reactions, and with the total amount of adsorbent for benchmark, load capacity is 10～40wt%.
The preparation method that the invention also discloses described metal organic frame adsorbent, comprises the steps:
(1)MIL-101(Cr)-SO3The preparation of H；
(2) by MIL-101 (Cr)-SO3The solution mixing of H and Ag (I), through ion-exchange reactions, obtains described adsorbent MIL-101 (Cr)-SO3Ag。
Particularly as follows:
(1)MIL-101(Cr)-SO3The preparation of H: metal chromic salts, sodium monosulfate p-phthalic acid, water and Fluohydric acid. are mixed, after stirring, carries out hydro-thermal reaction, obtain MIL-101 (Cr)-SO then through purification3H；
(2) preparation of adsorbent: MIL-101 (the Cr)-SO that step (1) is obtained3The acetonitrile/water solution of H and the Ag (I) that concentration is 20～40mg/ml mixes, and obtains described adsorbent through lucifuge stirring, filtration, dried；
Described MIL-101 (Cr)-SO3The mass ratio of H and Ag (I) is 1:1～5.
As preferably, in step (1), the mass ratio of described metal chromic salts, sodium monosulfate p-phthalic acid, water and Fluohydric acid. is 1:0.67～1.34:15:0.15.Described hydrothermal reaction condition is: hydro-thermal reaction 20～24h at 180～200 DEG C.The yield that hydrothermal temperature is too low or the time is so short that very much is all very low, it is preferred that can reach higher productivity under hydrothermal condition.
Described metal chromic salts can be nine water chromic nitrates, the one in chromic acid.
It is preferred that, the concentration of the acetonitrile/water solution of described Ag (I) is 40mg/ml, described MIL-101 (Cr)-SO3The mass ratio of H and Ag (I) is 1:3.2.
As preferably, in step (1), after hydro-thermal reaction, being slowly cooled to room temperature by reactant liquor, cooldown rate is 2 DEG C/min.Adopt this cooldown rate, it is possible to make unreacted part crystallize out with bigger needle form, it is simple to the purification that product is follow-up.
In step (1), described purge process particularly as follows:
The product of hydro-thermal reaction is successively after water, washing with alcohol several times, and centrifugal filtration, then through dried, described baking temperature is 120～150 DEG C, and drying time is 8～12h.To guarantee MIL-101 (Cr)-SO3Moisture and lower boiling solvent in H duct are fully removed.
In step (2), the compound of described Ag (I) is AgBF4Or AgNO3, it is preferred to AgBF4, the adsorbent that obtains after ion exchange, for olefins/paraffins mixed gas separating property more preferably.
The exchange capacity of silver ion can be impacted by the polarity of solvent, adopts the mixed solvent of acetonitrile/water in the present invention, is more beneficial for the exchange of Ag (I).As preferably, in step (2), in described acetonitrile/water mixed solvent, the volume ratio of acetonitrile and water is 0.5～1:1.
Mixing time should not be too short and to ensure lucifuge, and silver ion diffuses in duct the problem that there is diffusional resistance from solution, and mixing time is too short, and not, reaction is thorough not in contact, and as preferably, the time of lucifuge stirring is 24～48h.After exchange reaction completes, then through centrifugal, vacuum drying treatment, baking temperature is 120～150 DEG C, and drying time is 8～12 hours.
In the adsorbent preferably prepared, the load capacity of Ag (I) is 18～38wt%, more preferably 38wt%, the preferably adsorbent under this load capacity, the equilibrium separation selectivity of olefins/paraffins mixed gas is best, the adsorbance of alkene, alkane still can be met the requirement in practical application simultaneously.
The invention discloses the application in olefins/paraffins mixed gas separates of the described adsorbent, described alkene is at least one in ethylene, propylene, butylene, and alkane is carbon number is at least one in ethane, propane, butane；The use condition of adsorbent: temperature is 20～40 DEG C, pressure is 0～100kPa.As preferably, the adsorbent that the present invention prepares is more suitable for the separation of ethylene/ethane, propylene/propane mixing gas.Especially under lower pressure, as, under 1kPa, adsorbent prepared by the present invention separation selectivity to ethylene/ethane, up to 238.
Described adsorbent after a procedure or adsorb saturated after, only need to heat under vacuum conditions to 50～150 DEG C, keep within 1～9 hour, can realizing regenerating.
Also disclosing the application at fuel oil deep removal sulfur-containing compound of the described adsorbent, described sulfur-containing compound is thiophene, benzothiophene, dibenzothiophenes or 4,6-dimethyl Dibenzothiophene.The use condition of adsorbent: temperature 20～50 DEG C, simulation fuel oil preparation solvent is normal octane.
Compared with prior art, present invention have the advantage that
The present invention is with the metal-organic framework materials of sulfonic acid funtionalized for adsorbing agent carrier, Ag (I) is active component, Ag (I) is replaced to the sulfonic acid functional group of metal-organic framework materials by the method exchanged by ion, active component in the present invention with chemical bonding on carrier, compared in traditional solution dipping method by the mode load of physical absorption on carrier, the adsorbent that this method prepares has water stability more preferably, still original framing structure is remained after having exchanged, still can keep after repeatedly regenerating and regenerating being efficiently separating selectivity；And after exposing the long period in humid air, absorption property does not decline.Compared to existing Cu-lyt. supported sorbents, there is the component selections of ethylene-ethane of good superelevation higher than most of zeolitic materials and nearly all MOF material reported at present.
Adsorbent MIL-101 (Cr)-SO after the immobilized Ag (I) that the present invention prepares3Sulfur-containing compound is shown extremely strong adsorption by Ag, can show bigger adsorbance under low concentration.Compared to MIL-101 (Cr)-SO3H, the adsorbance of sulfur-containing compound can be improved 10～30 times by it.
Accompanying drawing illustrates:
Fig. 1 is MIL-101 (the Cr)-SO of preparation in embodiment 43H and MIL-101 (Cr)-SO3The XRD phenogram of Ag；
Fig. 2 is adsorbent MIL-101 (the Cr)-SO of preparation in embodiment 43The SEM figure of Ag, and distribution diagram of element main in adsorbent: (a) SEM image, (b) Ag, (c) S, (d) (Cr)；
Fig. 3 is adsorbent MIL-101 (the Cr)-SO of preparation in embodiment 43Ag separating ethene/ethane, the adsorption isotherm of propylene/propane, temperature: 30 DEG C, pressure 0～100kPa；
Fig. 4 is adsorbent MIL-101 (the Cr)-SO of preparation in embodiment 43The Ag repeatability investigation to ethylene absorption performance, temperature: 30 DEG C, pressure 0～100kPa；
Fig. 5 is adsorbent MIL-101 (the Cr)-SO of preparation in embodiment 43Ag and MIL-101 (Cr)-SO3The H adsorbance curve to dibenzothiophenes, adsorption temp: 30 DEG C；
Fig. 6 is adsorbent MIL-101 (the Cr)-SO of preparation in embodiment 43The Ag reperformance test to dibenzothiophenes absorption property, eluant is acetone, temperature: 30 DEG C.
Detailed description of the invention
The present invention will be further described by the following examples, but present disclosure is not limited to this completely.
Embodiment 1
(1)MIL-101(Cr)-SO3The preparation of H: by 4g nine water chromic nitrate, 5.4g sodium monosulfate p-phthalic acid, 60g deionized water and 0.6g Fluohydric acid. (～40wt%) (proportioning: 1mmol:2mmol:6g:0.06g) join in reactor, ultrasonic agitation is uniform, then 190 DEG C are reacted 24 hours, can obtain ((Cr))-MIL-101-SO containing impurity3H.The MOF initially synthesized is used deionized water successively, and ethanol washs 2～3 times respectively, centrifugal, filters, finally vacuum drying 12 hours at 120 DEG C, can be prepared by the MIL-101 after purification (Cr)-SO3H, specific surface area is 1856m2/ g, pore volume is 1.35cm3/ g.Unless stated otherwise, following instance is MIL-101 (the Cr)-SO adopting the method synthesis3H。
(2) adsorbent MIL-101 (Cr)-SO3The preparation of Ag: take MIL-101 (the Cr)-SO after purification in 250mg step (1)3H joins in container.Add 20ml and concentration is the AgBF of 40mg/ml4Acetonitrile/water (volume ratio 1:1) solution in, lucifuge stirs 6 hours, centrifugal, removes supernatant, vacuum drying 12 hours at 120 DEG C, can obtain MIL-101 (the Cr)-SO that Ag (I) load capacity is 18.5wt%3Ag。
After tested, at 30 DEG C, under 100kPa, the adsorbance of ethylene is 2.21mmol/g by adsorbent prepared by the present embodiment, and the adsorbance to ethane is that 1.45mmol/g, IAST calculate C2H4/C2H6(1:1) separation selectivity is 8.
Embodiment 2
Adsorbent MIL-101 (Cr)-SO3The preparation of Ag: take MIL-101 (the Cr)-SO after purification in 250mg embodiment 1 step (1)3H joins in container, adds the AgNO of 20ml, 40mg/ml3Acetonitrile/water (volume ratio 1:1) solution in.Lucifuge stirs 6 hours, centrifugal, removes supernatant, vacuum drying 12 hours at 120 DEG C, can obtain MIL-101 (the Cr)-SO that Ag (I) load capacity is 17.6wt%3Ag。
30 DEG C, under 100kPa, the adsorbance of ethylene is 2.15mmol/g by adsorbent, and the adsorbance to ethane is 1.48mmol/g.It appeared that AgNO3AgBF is not had as active component4Effective, therefore ensuing experiment all adopts AgBF4As active component.
Embodiment 3
Adsorbent MIL-101 (Cr)-SO3The preparation of Ag: take MIL-101 (the Cr)-SO after purification in 250mg example 1 step (1)3H joins in container, adds the AgBF of 20ml, 40mg/ml4Acetonitrile/water (volume ratio 1:1) solution in.Lucifuge stirs 12 hours, centrifugal, removes supernatant, vacuum drying 12 hours at 120 DEG C, can obtain MIL-101 (the Cr)-SO that Ag (I) load capacity is 24.8wt%3Ag。
30 DEG C, under 100kPa, the adsorbance of ethylene is 2.43mmol/g by adsorbent, and the adsorbance to ethane is that 1.37mmol/g, IAST calculate C2H4/C2H6(1:1) separation selectivity is 12.
Embodiment 4
Adsorbent MIL-101 (Cr)-SO3The preparation of Ag: take MIL-101 (the Cr)-SO after purification in 250mg example 1 step (1)3H joins in container, adds the AgBF of 20ml, 40mg/ml4Acetonitrile/water (volume ratio 1:1) solution in.Lucifuge stirs 24 hours, centrifugal, removes supernatant, and repeated exchanged process 2 times, is finally centrifuged, vacuum drying 12 hours at 120 DEG C, can obtain MIL-101 (the Cr)-SO that Ag (I) load capacity is 37.8wt%3Ag.Finding through repeatedly repeating experiment, 37.8wt% is maximum Ag (I) load capacity.
30 DEG C, under 100kPa, the adsorbance of ethylene is 2.61mmol/g by adsorbent, and the adsorbance to ethane is that 1.22mmol/g, IAST calculate C2H4/C2H6(1:1) separation selectivity is 16；30 DEG C, separation selectivity is 238 under 1kPa.
30 DEG C, under 100kPa, the adsorbance to propylene is 4.32mmol/g, and the adsorbance to propane is that 3.00mmol/g, IAST calculate C3H6/C3H8(1:1) separation selectivity is that under 8,1kPa, separation selectivity is 32.
Application examples 1 olefins/paraffins mixed gas separates
In order to investigate MIL-101 (the Cr)-SO of synthesis3Ag reuses effect, takes the adsorbent that 100mg embodiment 4 prepares, and ethylene carries out adsorption/desorption 8 circulation repeatedly, and desorption temperature is 90 DEG C.30 DEG C, under 1bar, 8 loop tests, the equilibrium adsorption capacity of ethylene is shown in Fig. 4.
In order to investigate MIL-101 (the Cr)-SO of synthesis3Ag, the stability to air and light, the adsorbent that embodiment 4 is prepared, it is exposed in air (air humidity is 95%) after 2 days, studies its absorption property.After tested, 30 DEG C, it is 2.58mmol/g to the equilibrium adsorption capacity of ethylene under 1bar, illustrates that the adsorbent that the present invention prepares has splendid stability.
The elimination of sulfur-containing compound in application examples 2 fuel oil
In order to investigate MIL-101 (the Cr)-SO of synthesis3Ag, contrasts MIL-101 (Cr)-SO simultaneously3The desulfurized effect of H, takes MIL-101 (the Cr)-SO prepared in the adsorbent and example 1 step (1) that 200mg embodiment 4 prepares respectively3H, tests its adsorption effect to dibenzothiophenes.
After tested, at 30 DEG C, after absorption reaches balance, MIL-101 (Cr)-SO3Ag and MIL-101 (Cr)-SO3H, is followed successively by the adsorbance of dibenzothiophenes: 37.295mgS g-1With 1.628mgS g-1, concrete adsorption isotherm is shown in Fig. 5.
For investigating MIL-101 (the Cr)-SO of synthesis further3Ag repeats the effect of desulfurization, and we are with acetone for eluant, by MIL-101 (the Cr)-SO after absorption3Ag cyclic washing 2～3 times, dries, tests its adsorption effect to dibenzothiophenes, repeats experiment through 5 times, and the adsorbance of dibenzothiophenes is substantially free of and changes by it, remains able to maintain higher level.Concrete adsorbance is shown in Fig. 6.
Claims (7)
1. a metal organic frame adsorbent, it is characterised in that described metal organic frame adsorbent is with metal-organic framework materials MIL-101 (the Cr)-SO of sulfonic acid funtionalized3H is carrier, and with Ag (I) for active component, described active component loads on carrier through ion-exchange reactions, and with the total amount of adsorbent for benchmark, load capacity is 10～40wt%；
The preparation method of described metal organic frame adsorbent, particularly as follows:
(1)MIL-101(Cr)-SO3The preparation of H: metal chromic salts, sodium monosulfate p-phthalic acid, water and Fluohydric acid. are mixed, after stirring, carries out hydro-thermal reaction, obtain MIL-101 (Cr)-SO then through purification3H；
The mass ratio of described metal chromic salts, sodium monosulfate p-phthalic acid, water and Fluohydric acid. is 1:0.67～1.34:15:0.15, and described hydrothermal reaction condition is: hydro-thermal reaction 20～24h at 180～200 DEG C；
(2) preparation of adsorbent: MIL-101 (the Cr)-SO that step (1) is obtained3The acetonitrile/water solution of H and the Ag (I) that concentration is 20～40mg/ml mixes, and obtains described adsorbent through lucifuge stirring, filtration, dried；
Described MIL-101 (Cr)-SO3The mass ratio of H and Ag (I) is 1:1～5.
2. metal organic frame adsorbent according to claim 1, it is characterised in that in step (1), after hydro-thermal reaction, be slowly cooled to room temperature by reactant liquor, cooldown rate is 2 DEG C/min.
3. metal organic frame adsorbent according to claim 1, it is characterised in that in step (1), described purge process particularly as follows:
The product of hydro-thermal reaction is successively after water, washing with alcohol several times, and centrifugal filtration, then through dried, described baking temperature is 120～150 DEG C, and drying time is 8～12h.
4. metal organic frame adsorbent according to claim 1, it is characterised in that in step (2), the compound of described Ag (I) is AgBF4Or AgNO3；In acetonitrile/water mixed solvent, the volume ratio of acetonitrile and water is 0.5～1:1.
5. metal organic frame adsorbent according to claim 1, it is characterised in that in step (2), the time of lucifuge stirring is 24～48h.
6. an adsorbent according to claim 1 application in olefins/paraffins mixed gas separates, it is characterised in that described alkene is at least one in ethylene, propylene, butylene, and alkane is at least one in ethane, propane, butane.
7. an adsorbent according to claim 1 is in the application of fuel oil deep removal sulfur-containing compound, it is characterised in that described sulfur-containing compound is thiophene, benzothiophene, dibenzothiophenes or 4,6-dimethyl Dibenzothiophene.
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