CN102744105A - Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst - Google Patents
Method for functionalizing porous metal-organic framework materials, solid acid catalyst using same, and method for evaporating alcohol using the solid acid catalyst Download PDFInfo
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
Abstract
The present invention relates to a method for functionalizing porous metal-organic framework materials which have a large surface area and molecular- or nano-scale pores, and which can thus be used for an absorbent, gas storage, a sensor, a membrane, a functional thin film, a catalyst, a catalyst carrier, and the like, to a method for preparing a solid acid catalyst using same, and to a method for evaporating alcohol using the catalyst.
Description
Technical field
The present invention relates to the functional method of porous metal-organic backbone material; In more detail, relate to porous metal-organic backbone material is carried out activation, thereby make it that unsaturated coordination site take place; With contain simultaneously can coordination bonding element and sulfydryl (compound SH) carries out coordination bonding; Thereby preparation is by the porous metal of functionalization-organic backbone material, and the oxidation sulfydryl is converted into sulfonic group (SO then
3H), thus obtain the technology of solid acid catalyst.
In addition, the invention still further relates to the solid acid catalyst and the multiple catalyst that utilize above-mentioned acquisition alcohol is carried out dehydration method.
Background technology
Porous metal-organic backbone material can be defined as central metallic ions combines formation with organic ligand porous organic-inorganic macromolecular compound; Expression organic matter and inorganic matter all are included in the skeleton structure, and have the crystallinity compound of the microcellular structure of molecular size or nanometer size.
Because porous metal-organic backbone material also contains organic components except inorganic matter,, has multiple application possibility though therefore compare poor heat stability with inorganic matter.
Have acid or multiple uses such as base catalyst and removal nuisance although have the porous metal-organic backbone material of acidity or alkalescence, the metal-organic framework material with acid and alkalescence is rare, in order to make these materials also in the middle of continuation research.Metal-organic framework structure with alkalescence can be synthesized and directly acquisition through containing amino organic matter as organic connector.The amino terephthalic acid (TPA) of use is for example arranged as connector, preparation has IRMOF-3, the MIL-47-NH of alkalescence
2And MIL-53-NH
2(Chemical Society's summary, 2011,40,498-519; The catalyst periodical, 261,75,2009; Inorganic chemistry 48,3057,2009Chem.Soc.Rev. (Chemical Society's summary), 2011,40,498-519; J.Catal. (catalyst periodical), 261,75,2009; Inorg.Chem. (inorganic chemistry) 48,3057,2009)).
But it is very expensive to contain amino connector, and amino alkalescence impacts synthetic, can produce the problem of the synthetic difficulty that becomes.
And, for the functionalization of metal-organic framework material, disclose the method for utilizing covalent bonding, but have expensive raw material price; Shortcoming (Chemical Society's summary, 2011,40,498-519 (Chem.Soc.Rev. that particularly preparation technology is very complicated; 2011,40,498-519)).
Chromium-benzene tricarbonic acid's the ester (applied chemistry periodical, 43,6296, the 2004 (Angew.Chem.Int.Ed. that are called as MIL-100 (Cr) and MIL-100 (Fe) in the metal-organic framework material; 43,6296,2004)) and iron-benzene tricarbonic acid's ester (chemical communication, 2820; 2007 (Chem.Commun., 2820,2007)) with the chromium-terephthalate (science, 309 that are called as MIL-101 (Cr); 2040,2005 (Science, 309; 2040,2005)) after dehydration, has the unsaturated position of coordination (coordinatiely unsaturated site; CUS) or empty metal position (open metal site), can utilize these to carry out functionalization.
Cu-BTC (science, 283,1148,1999 (Science, 283,1148,1999)) also can induce CUS through dehydration, can utilize it to carry out functionalization.Promptly, utilize material to carry out coordination bonding with element that can coordination, utilize the material of this bonding to make the metal-organic framework material functionization.As the material of functionalization, can use compound with coordination bonding position, especially can use to have amino compound etc.; Have and report that the ethylenediamine that amido functional group is present in two ends can use (applied chemistry periodical, 47,4144 as base catalyst; 2008 (Angew.Chem.Int.Ed.; 47,4144,2008)).
On the other hand; In alcohol; Polyalcohol can be defined as sorbierite (sorbitol), sweet mellow wine (mannitol), xylitol (xylitol), arabite (arabinitol) and their mixture; Mainly can be defined as the polyalcohol of hexose and pentose, also can be their mixture.
Polyalcohol can obtain useful chemical intermediates such as isobide available from the living beings that can regenerate through dehydration.These dehydrations can be carried out under the condition that multiple catalyst exists, commercial also be very important reaction.Catalyst can be liquid acid such as sulfuric acid, but also can use heteropoly acid, cationic ion-exchange resin, zeolite, metal-organic framework material (metal-organic frameworks), acid clay, sulfonic acid zirconia (sulfonate zirconia), aluminum phosphate and as the molecular sieve of mesoporous (mesoporous) material.
In dehydration, obtain water,, can make the conversion ratio that on characteristic, is difficult to improve reaction as the dehydration of balanced reaction if it is not removed as accessory substance.
Therefore, under multiple situation, adopt the pressure that reduces reactor to remove the water (US granted patent 7728156,7649099,7615652) of formation, improve the conversion ratio of balanced reaction through such mode.
But, reactor is maintained the method for vacuum or high pressure, not only see not have economy from reactor formation face; And operation costs are also very expensive; Therefore a kind of dehydration technology of more easy alcohol need be provided, and this technology is without high pressure or decompression, and need not to remove water byproduct.
Promptly, available from reproducible living beings; And the products such as isobide that generated by the dehydration of polyalcohol are very useful compounds; Can be as macromolecule with copolymer (copolymer); For example when high molecular polymers such as preparation polyethyleneterephthalate, can be used as additive use etc.; And be used for medicine (encephaledema, promote to urinate and to treat glaucoma etc.).
Therefore; Actual conditions do, not only need study the solid acid catalyst that has used porous metal more effective and stable in dehydration of alcohols-organic backbone material, also need utilize multiple catalyst; Easy to more, and the dehydration of improved alcohol is studied.
Summary of the invention
(1) the present invention's technical problem that will solve
The present invention provides the new function method of the porous metal-organic backbone material that can be used as the multiple use use, and the acid solid acid catalyst that has that utilizes this method preparation also is provided.
In addition, the present invention also provides and uses solid acid catalyst of the present invention or multiple catalyst to come alcohol is carried out dehydration method.
In addition, the present invention does not also provide and need pressurize or reduce pressure, and with microwave as thermal source, under condition of no solvent, use multiple acid catalyst, can be optionally, and effectively various alcohol are implemented the methods of dehydrations.
(2) technical scheme
The present invention relates to following technical scheme.
The functional method of porous metal-organic backbone material, this method comprises: a) will have the porous metal-organic backbone material of unsaturated coordination site and have simultaneously can coordination point and the compound of sulfydryl mix the step of supending; And b) step of the above-mentioned suspension of heating.
The functional method of described porous metal-organic backbone material, it also comprises: c) use oxidant oxidation b) suspension of step heating or to b) suspension of step heating carries out solid that Separation of Solid and Liquid the obtains step with the oxidant oxidation; D) from c) step of separating solids the reactant of step; And e) solid separated is carried out dry step.
The metal ingredient of said metal-organic framework material is more than one metal or its metallic compound that is selected among Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb or the Bi, and organic matter is for having the carbonyldioxy of being selected from, carbonate anion base, amino (NH
2), imino group (
), amide groups (CONH
2), sulfonic group (SO
3H), sulfonic acid anion base (SO
3-), methane two thio group (CS
2H), methane two sulfo-anion base (CS
2-), more than one compound or its mixture of functional group in pyridine radicals or the pyrazinyl.
The said compound that has point and sulfydryl that can coordination simultaneously is to be selected from cysteamine, 3-amino-1-propane diols, 2-amino-1-propane diols, 1-amino-propane diols, 4-amino-butanediol, 3-amino-1-butanediol, 2-amino-1-butanediol, 1-amino-1-butanediol, 5-amino-1-pentanediol, 4-amino-1-pentanediol, 3-amino-1-pentanediol, 2-amino-1-pentanediol and the 1-amino-1-pentanediol any one.
Said unsaturated coordination site is handled under 25～500 ℃ or is handled and generate with vacuum for porous metal-organic backbone material is placed under the vacuum.
Said porous metal-organic backbone the material that possibly have unsaturated coordination site is selected from a kind of among MIL-100 (Cr), MIL-100 (Fe), MIL-101 (Cr), Cu-BTC, MOF-505, MOF-4, Mn-BTT, SLUG-22, SLUG-21, MOF-74 and the UMCM-150.
The heating of said step b) is under 35～200 ℃ temperature, to implement.
Said oxidant is hydrogen peroxide, oxygen, air and TBHP.
The invention still further relates to prepare by the porous metal of functionalization-organic backbone material.
The invention still further relates to said by the method for the porous metal of functionalization-organic backbone material absorption removal heavy metal.
The invention still further relates to the dewatering of alcohol; This method comprises: 1) under condition of no solvent, and the step that the pure and mild a kind of catalyst by in the porous metal of functionalization-organic backbone material, liquid acid, heteropoly acid, cationic ion-exchange resin, zeolite, acid clay, sulfonic acid zirconia (sulfonate zirconia) and the aluminum phosphate that is selected from the claim 9 is mixed; 2) heat as the mixture of thermal source with microwave, make the step of its reaction above-mentioned steps; 3) step of the reactant of above-mentioned steps being cooled off; 4) reactant of the above-mentioned cooling of separation, the step of acquisition product; And 5) product to above-mentioned steps carries out dry step.
Said alcohol is selected from a kind of in sorbierite, sweet mellow wine, xylitol, arabite, propyl alcohol and the butanols.
Said cationic ion-exchange resin is Amberlyst-15 or Amberlyst-35; Said metal-organic framework material is to be selected from a kind of among MIL-101, MIL-53 and the MIL-100; Said zeolite is selected from a kind of among H-ZSM-5, H-FAU, H-mordenite, H-MCM-22 and the H-BEA.
Said heating is under 120～220 ℃ temperature, to implement.
Furtherly; The present invention relates to the effective functional method of porous metal-organic backbone material; The functional method of porous metal-organic backbone material is provided; This method comprises: a) will have the porous metal-organic backbone material of unsaturated coordination site and have simultaneously can coordination point and the compound of sulfydryl mix the step of supending; And b) heats the step of the suspension in the above-mentioned a) step.
In addition, the functional method of porous metal of the present invention-organic backbone material also provides and comprises: c) use oxidant oxidation b) suspension of step heating or to b) suspension of step heating carries out the step that solid that Separation of Solid and Liquid obtains uses the oxidant oxidation; D) from c) step of separating solids the reactant of step; And e) solid separated is carried out the functional method of the porous metal-organic backbone material of dry step.
The invention is characterized in; The effective functional method that relates to porous metal-organic backbone material; Utilize have simultaneously can coordination point and the compound of sulfydryl import sulfydryl, after the importing, with sulfhydryl oxidase; Make porous-metal-organic framework material have sulfonic group, thereby make its functionalization.
Functional method according to the present invention can be Powdered by the porous metal of functionalization-organic backbone material, or film or film (membrane) form.
The porous metal of one embodiment of the present of invention-which kind of structure of organic backbone material or composition in addition, the present invention relates to the functional method of porous metal-organic backbone material, no matter can both be suitable for.Promptly, porous metal-organic backbone material comprises metallics and organic substance, as the representational example of metal-organic framework material can give an example chromium terephthalate, aluminium terephthalate, vanadium terephthalate etc.
The metallics of one of formation element of metal-organic framework material is restriction not; But the transition metal that preferably can prepare complex well; Best, for example can be more than one metal or the compound of this metal that is selected among Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb or the Bi.
The metal-organic framework material that be fit to use has with little compound such as water and carries out coordination, adopts methods such as heating or application of vacuum, makes the structure that the compounds such as water of coordination can desorption.
In addition; Functional method according to the present invention is also referred to as connector by the organic substance of the porous metal of functionalization-organic backbone material; So long as have functional group that can coordination any organic matter can, functional group that can coordination has the carbonyldioxy of being selected from, carbonate anion base, amino (NH
2), imino group (
), amide groups (CONH
2), sulfonic group (SO
3H), sulfonic acid anion base (SO
3-), methane two thio group (CS
2H), methane two sulfo-anion base (CS
2-), more than one compound or its mixture of functional group in pyridine radicals or the pyrazinyl.
Promptly, can be organic matter with point that can coordination, also can be under reaction condition, to change into compound with point that can coordination.As a concrete example, can use organic acids such as terephthalic acid (TPA), after reaction, can be with terephthalate and metal ingredient bonding, have potentially can coordination point.
In porous metal-organic backbone material,, has no restriction so long as can have the structure of the unsaturated position of coordination.Structure example representative in such porous metal-organic backbone material is if any MIL-101 (Cr), MIL-100 (Cr), MIL-100 (Fe), Cu-BTC, MOF-505 (applied chemistry periodical, 2005,44,4745 (Angew.Chem.Int.Ed., 2005,44,4745)), MOF-4 (JACS; 2000,122,1391 (J.Am.Chem.Soc, 2000,122,1391)), Mn-BTT (JACS; 2008,130,5854 (J.Am.Chem.Soc., 2008,130,5854)), SLUG-22 (JACS 2010; 132,7202 (J.Am.Chem.Soc., 2010,132,7202)), SLUG-21 (Chem.Mater., 2010; 22,2027 (materials chemistry, 2010,22,2027)), MOF-74 (J.Am.Chem.Soc., 2006; 128,3494 (JACS, 2006,128,3494)), UMCM-150 (American Chemical Society, 2009; But be not limited to these 131,18198 (J.Am.Chem.Soc., 2009,131,18198)) etc..Representative porous metal-organic backbone material is metal-carboxylate, metal-terephthalate and metal-benzene tricarbonic acid's esters such as MIL-101 (Cr), MIL-100 (Cr), MIL-100 (Fe) and Cu-BTC, more preferably has the iron that is called MIL-100 (Fe, Cr), MIL-101 (Cr) and Cu-BTC (or being called HKUST-1) or chromium-benzene tricarbonic acid's ester, chromium-terephthalate, the copper-benzene tricarbonic acid's ester of highly porous and chemical stability.
Among the present invention, the method for in porous metal-organic backbone material, giving unsaturated coordination site is under 25～500 ℃, handles with vacuum, breaks away from coordination material such as water and makes.
Below, to of the present invention have simultaneously can coordination point and the compound of sulfydryl describe.
Above-mentioned have simultaneously can coordination point and the compound of sulfydryl have no particular limits.Not only obtaining easily; And it is cheap; And molecular structure is simple; Thereby, be preferably and be selected from cysteamine, 3-amino-1-propane diols, 2-amino-1-propane diols, 1-amino-propane diols, 4-amino-butanediol, 3-amino-1-butanediol, 2-amino-1-butanediol, 1-amino-1-butanediol, 5-amino-1-pentanediol, 4-amino-1-pentanediol, 3-amino-1-pentanediol, 2-amino-1-pentanediol and the 1-amino-1-pentanediol any one easily to the aspect of porous metal-organic backbone material diffusion.
Below, the functional method concrete to the present invention describes.
Function among the present invention turns to and comprises and carry out oxidation after above-mentioned suspension heated or heat, thereby gives functional.
The functional method of porous metal of the present invention-organic backbone material; Its functionalization temperature; Be the in fact not restriction of heating-up temperature of step b), but preferably high than room temperature, and than the low-boiling temperature of the compound that has point and sulfydryl that can coordination simultaneously.More preferably 35～200 ℃, more preferably 50～120 ℃ again.If temperature is low excessively, functionalization speed is slow, and can reduce functionalization efficient, if the functionalization temperature is too high side reaction can take place, the shortcoming that exists device to become complicated, and the structure of reaction kinetic device is uneconomical.
Reaction kinetic also can be implemented under the condition of solvent not having, but under the condition that solvent exists, implements more easily.If there is solvent to exist, can make the control of mixing and temperature become easy.Solvent can be any solvent, so long as can dissolve the solvent that a part time has the compound of point and sulfydryl that can coordination, particularly obtains easily and cheap any solvent can.
Reaction kinetic can be implemented by batch (-type), also can continous way implement.Hourly the yielding poorly of batch (-type) reaction kinetic device, the functionalization of therefore suitable a spot of metal-organic framework material is though the expensive investment cost of flow reactor is fit to a large amount of functionalization.The reaction kinetic time is adapted at about 1 minute to 100 hours under step situation, if the reaction kinetic overlong time is sneaked into foreign body easily, energy efficiency is low.If the reaction kinetic time is short, then functionalization efficient is low.The reaction kinetic time that is fit to more is 1 minute to 24 hours, further implements ultrasonic wave or microwave irradiation, can realize shortening the purpose of functionalization time.The retention time of continous way reaction kinetic device is suitably for about 1 minute to 1 hour.If retention time is long, then productivity ratio is low, and causes side reaction easily, if retention time is too short, then the reaction kinetic conversion ratio is low.It is 1 minute to 20 minutes that retention time is more suitable for.In intermittent reaction, also can reaction stirred, mixing speed is suitably for 100～1000rpm, but does not have also can implement under the condition of whipping process.Utilize hyperacoustic reaction kinetic,,, also can cause functionalization effectively therefore even without whipping process owing to make suspension to mix well according to ultrasonic wave.
Of the present invention by the functional method of the porous metal of functionalization-organic backbone material; Have no particular limits for oxidant, but preferred cheap and have peroxide such as hydrogen peroxide, oxygen, air and TBHP of simple molecular structure.
In addition, it is prepared in accordance with the present invention by the porous metal of functionalization-organic backbone material that the present invention also provides, and provide use to be adsorbed the method for removing heavy metal with this by the porous metal of functionalization-organic backbone material.
In addition, the present invention also provides to use and is selected from liquid acid, is above-mentionedly come alcohol is carried out dehydration method by a kind of catalyst in the porous metal of functionalization-organic backbone material, heteropoly acid, cationic ion-exchange resin, zeolite, acid clay, sulfonic acid zirconia and the aluminum phosphate.
More specifically, the dewatering of alcohol of the present invention comprises:
1) under condition of no solvent, is selected from above-mentioned step of being mixed by a kind of catalyst in the porous metal of functionalization-organic backbone material, liquid acid, heteropoly acid, cationic ion-exchange resin, zeolite, acid clay, sulfonic acid zirconia and the aluminum phosphate with pure and mild;
2) heat as the mixture of thermal source with microwave, make the step of its reaction above-mentioned steps;
3) step of the reactant of above-mentioned steps being cooled off;
4) reactant of the above-mentioned cooling of separation, the step of acquisition product; And
5) product to above-mentioned steps carries out dry step.
The dewatering of alcohol of the present invention in the middle of alcohol, relates in particular to the dewatering of capable of regeneration polyalcohol; In dehydration,, therefore it is characterized in that owing to adopted microwave; Go down to dewater at low-pressure, or, also can carry out dehydration effectively even without HIGH PRESSURE TREATMENT such as hydrogen, nitrogen.
In addition, the present invention uses microwave as thermal source in the dehydration of alcohol, thereby also will provide a kind of dehydration conversion ratio of alcohol that makes shockingly to be improved, and the method for the material of the dehydration that can obtain with higher yield acquisition hope.
Alcohol for embodiments of the invention has no particular limits; But polyalcohol is more favourable; Polyalcohol for the embodiment of the invention can be the polyalcohol of pentose or hexose, can be to be selected from a kind of in sorbierite, sweet mellow wine, xylitol, arabite, propyl alcohol and the butanols for the alcohol in the embodiment of the invention.
In addition, target product of the present invention can be any one dehydration product, but each polyalcohol molecule to slough the material of a hydrone or two hydrones be main object product.Dehydration with sorbierite is an example, and in the dehydration of sorbierite, sorbitan (sorbitan) and the isobide (isosorbide) of sloughing 1 or 2 hydrone respectively are the representative product.
Below, the catalyst of dehydration is described.
Dehydration is carried out under the condition that acid catalyst exists easily, especially compares with liquid acid, and solid acid is favourable aspect separation and environment.Promptly, can use liquid acid such as sulfuric acid among the present invention, can also use heteropoly acid, cationic ion-exchange resin, zeolite, porous metal-organic backbone material (metal-organic frameworks), acid clay, sulfonic acid zirconia (sulfonate zirconia), aluminum phosphate and mesoporous material equimolecular sieve.
Cationic ion-exchange resin is preferred cheap and have porous materials such as high catalyst concentration, metal-organic framework material and zeolite, because they have little pore, so after dehydration, can prevent the side reaction of secondary and favourable.In order to make zeolite, molecular sieve, ion exchange resin, metal-organic framework material and mesoporous material have acidity, needing to transform or importing is proton (H
+) type.
The dehydration of alcohol is solid acid more preferably; According to the present invention, adopt the solid acid preparation by the porous metal of functionalization-organic backbone material and zeolite facies ratio, have high conversion ratio and selectivity; And compare with resin catalyst; Have high heat endurance, from these aspects, more favourable.
In addition, the ion exchange resin among the present invention is meant by containing sulfonic organic polymer and forms, and has the material of ion-exchange capacity, mainly is meant Amberlyst-15, Amberlyst-35 and Nafion resin, but is not limited to these.
In addition, the zeolite among the present invention is meant by Si, Al, O and constitutes skeleton structure, is neutral in order to make electric charge, further has Na
+, H
+Etc. cationic material.May be used to the present invention so long as have any one acid zeolite, can use H-ZSM-5 (MH-MFI), H-Y (H-FAU), H-mordenite (H-MOR), H-beta (H-BEA), H-MCM-22 (H-MWW) etc. effectively, but be not limited to these.
Catalyst among the present invention can be liquid acid recited above, heteropoly acid, cationic ion-exchange resin, zeolite, metal-organic framework material, acid clay, sulfonic acid zirconia and aluminum phosphate.
In the above-mentioned operable various catalyst; Catalyst is under the situation of cationic ion-exchange resin; Preferably have macropore
and strong Amberlyst-15 or the Amberlyst-35 of ion-exchange capacity; Catalyst is under the situation of metal-organic framework material, preferred excellent in stability and have porous MIL-101 (chromium terephthalate), MIL-53 (the chromium terephthalate of aluminium terephthalate and rhombic form is included in wherein) and MIL-100 (iron or chromium benzene tricarbonic acid ester).In addition, in zeolite catalyst, useful especially is H-ZSM-5 (MH-MFI), H-Y (H-FAU), H-mordenite (H-MOR), H-beta (H-BEA), H-MCM-22 (H-MWW), and its reason has high acid strength and excellent stability for these zeolites.
The present invention at high temperature carries out, and uses the thermal source of heating using microwave as reaction, and the frequency of microwave is the arbitrarily electromagnetic wave of scope in the electromagnetic wave of 1～30GHz, and simple and effective is in industry, and more what use is the microwave of frequency as 2.45GHz.Can be continuously or irradiating microwaves off and on, advantageously set time and intensity that the reaction temperature of hoping is regulated irradiation.
The dehydration temperature is restriction practically, be preferably higher and than room temperature than alcohol, especially than the low-boiling temperature of polyalcohol.Reaction temperature can be the above any temperature of room temperature, and suitable temperature is the temperature more than 100 ℃ that reaction is carried out fast, is preferably 120～220 ℃, more preferably 150～200 ℃.If reaction temperature is spent low, then reaction speed is too slow, and is unactual, if too high, side reaction takes place then, thus the reaction efficiency step-down.
Dehydration can be carried out under any pressure, and optimal pressure is normal pressure or self-generated pressure (autogeneous pressure).When maintaining low pressure,, reaction speed and efficient are improved, but expense is high, when maintaining high pressure, also needs other gas, the shortcoming that still exists operation costs to increase owing to remove water byproduct.In addition,, can increase reaction speed through the removal of water, and help to suppress color is played the generation of the impurity of inducing, help to improve more efficient of the present invention in addition because hydrogen is flowed into.
Dehydration can be implemented by batch (-type), also can continous way implement.The batch (-type) dehydration reactor is hourly to yield poorly, and therefore is fit to the dehydration of a spot of polyalcohol, though the expensive investment cost of flow reactor is fit to a large amount of dehydrations.The dehydration time is adapted at about 1 minute to 100 hours under step situation, if the dehydration overlong time is sneaked into foreign body easily, energy efficiency is low.If the dehydration time is too short, then dewatering efficiency is low.The dehydration time that is fit to more is 1 minute to 24 hours.The retention time of continous way dehydration reactor is suitably for about 1 minute to 1 hour.If retention time is long, then productivity ratio is low, and causes side reaction easily, if retention time is too short, then the dehydration conversion ratio is low.It is 1 minute to 20 minutes that retention time is more suitable for.In intermittent reaction, also can reaction stirred, mixing speed is suitably for 100～1000rpm, but does not have also can implement under the condition of whipping process.
(3) beneficial effect
The functional method of porous metal of the present invention-organic backbone material was both simple, and effective again.
In addition, of the present inventionly used solid acid as catalyst, can alcohol dewatered, can be applied to catalyst, catalyst carrier and adsorbent etc. owing to have acidity by the porous metal of functionalization-organic backbone material.
In addition, the of the present invention use by the dehydration of the alcohol of the porous metal of functionalization-organic backbone material, its dehydration conversion ratio is high, and its product selectivity is also high.
The dewatering of alcohol of the present invention uses microwave as thermal source, is not needing vacuum or HIGH PRESSURE TREATMENT also can carry out dehydration effectively, and this dewatering is not only simple but also economic dewatering.
In more detail; The present invention uses microwave as thermal source particularly in the dehydration of polyalcohols such as sorbierite, sweet mellow wine, xylitol and arabite, and is not only easy but also carry out dehydration effectively; It is high to have the dehydration conversion ratio, also can improve optionally advantage of its product.
In addition, the polyalcohol that dewaters according to the dewatering of alcohol of the present invention can be as the additive and the medical compound of Polymer Synthesizing.
Description of drawings
Fig. 1 be functional method according to the present invention by X-line diffraction (XRD) collection of illustrative plates of the MIL-101 of functionalization (Cr), a, b and c correspond respectively to refining MIL-101 (Cr), MIL-101 (Cr)-SH and MIL-101 (Cr)-SO among Fig. 1
3H.
Fig. 2 be functional method according to the present invention by the FTIR collection of illustrative plates of the MIL-101 of functionalization (Cr), a, b and c correspond respectively to refining MIL-101 (Cr), MIL-101 (Cr)-SH and MIL-101 (Cr)-SO among Fig. 2
3H.
Fig. 3 shows use MIL-101 (the Cr)-SO that obtains according to functional method of the present invention
3The dehydration result of the propyl alcohol of H, 2-butanols and 1-butanols.
The specific embodiment
Below, specify the present invention through specific embodiment, but these specific embodiments can not limit scope of the present invention.
Embodiment 1 (functionalization of MIL-101 (Cr))
Synthetic MIL-101 (Cr)-AS (crystal growth design, 10,1860,2010 (Crystal Growth Design; 10,1860,2010)); Utilize this material in teat glass, to add MIL-101 (Cr)-AS of 0.3g then, add the DMF of 20ml then, process suspension.After being heated to 70 ℃, utilize supersonic generator (VC * 750, sound & material (Sonic&materials)) that the suspension in the test tube is carried out 60 minutes ultrasonic irradiations.After the cooling, filter out solid and recovery, drying is 5 hours under 100 ℃, obtains the refining MIL-101 (Cr) of 0.25g.To through the MIL-101 (Cr) of 2 refining 0.3g that collect under the vacuum condition of 0.8 air pressure, under 150 ℃, carry out drying back and cool off, the cysteamine with 0.096g (1.25mmol) joined in the ethanol of 30ml then, 80 ℃ of following reflux 8 hours.Filter then, the MIL-101 (Cr) that dry back obtains 0.3g (is called MIL-101 (Cr)-SH).With the H of MIL-101 (the Cr)-SH that adopts the synthetic 0.4g of this method with 20ml (15%)
2O
245 ℃ of following oxidations 2 hours.Close on oxidation and finish to reserve 15 minutes, finally add the 0.2M sulfuric acid of 10ml, thereby accomplish acidifying, behind the filtration drying final obtain about 0.4g by the material of functionalization (called after MIL-101 (Cr)-SO
3H).
Fig. 1 and Fig. 2 show according to the X-ray diffraction of functionalization step and FTIR spectrum, do not have disintegration to be kept according to functionalization step crystal structure, demonstrate through functionalization to have the C-N key.MIL-101 (Cr), MIL-101 (Cr)-SH and MIL-101 (Cr)-SO
3H has shown 3084,1908 respectively, 1592m
2The BET surface area of/g can be known and keep excellent porous.
Embodiment 2 (uses MIL-101 (Cr)-SO
3The dehydration of the sorbierite of H)
Use MIL-101 (the Cr)-SO that obtains among the embodiment 1
3The H catalyst has carried out the dehydration of sorbierite.With the sorbierite of 10g and the MIL-101 of 0.2g (Cr)-SO
3The H catalyst joins in the microwave reactor, in micro-wave oven (MARS-5, CEM company), reacts 3 hours down in 180 ℃ then.Cool off after the reaction, open reactor, at high temperature filter, thereby solid catalyst is dry under 110 ℃ with the product that obtains then, removes water.The Acme 9000HPLC that the younglin company of RI detector and Asahipak NH2P-504E (N712004 number) post is equipped with in use analyzes the composition of product.Reaction condition and result simply are recorded in the table 1.
The dehydration conversion ratio is 100%, and the yield of the isobide of acquisition is 49.6%.
Embodiment 3 (uses MIL-101 (Cr)-SO
3The dehydration of the 2-butanols of H)
Use MIL-101 (Cr)-SO of the 0.1g that obtains among the embodiment 1
3The H catalyst has carried out dehydration with gas phase to the 2-butanols.The space velocity of reactant is 1h
-1, catalyst dewaters under 300 ℃, and reaction temperature is 275 ℃.As shown in Figure 3, to have confirmed can be easy to obtain the butylene class with GC with dehydration, catalyst performance can be stablized maintenance more than 4 hours.
Embodiment 4
The sorbierite of 15.0g and the ion-exchange resin catalyst of 0.3g (Amberlyst-15) are packed in the Teflon reactor, build the back with micro-wave oven (MARS-5, CEM company) 150 ℃ down heating carried out dehydration in 1 hour.Cool off after the reaction, open reactor, at high temperature filter and solid catalyst, the product that obtains is dry under 110 ℃, removed water.The Acme 9000HPLC that the younglin company of RI detector and Asahipak NH2P-504E (N712004 number) post is equipped with in use analyzes the composition of product.Reaction condition and result simply are recorded in the table 1.
Do not need vacuum and HIGH PRESSURE TREATMENT, use microwave as thermal source, carried out dehydration in the 1 hour very short time, the dehydration conversion ratio is 100%, and isobide has also obtained 40% generation yield.
Embodiment 5
Except changing 2 hours heat time heating time into, all the other employings have been carried out dehydration with embodiment 4 identical methods.Its result is organized in the table 1.
Even without vacuum and HIGH PRESSURE TREATMENT, dehydration has also obtained 100% conversion ratio, and isobide still can obtain 60% high yield.
Embodiment 6
Except changing 4 hours heat time heating time into, all the other employings have been carried out dehydration with embodiment 4 identical methods.Its result is organized in the table 1.
Even without the HIGH PRESSURE TREATMENT of vacuum and hydrogen or nitrogen, utilize microwave as thermal source, also easily carried out dehydration, the dehydration conversion ratio has reached 100%, and the yield of isobide has reached 70%.
Embodiment 7
Except heating 4 hours down at 130 ℃, all the other employings have been carried out dehydration with embodiment 4 identical methods.Its result is organized in the table 1.
The conversion ratio of dehydration is 100%, and the yield of isobide is 35%.
Comparative example 1 (using the dehydration of the sorbierite of MIL-101 (Cr))
Except the MIL-101 (Cr) that has only carried out making with extra care that will not carry out functionalization used as catalyst, all the other employings had been implemented dehydration with embodiment 2 identical methods.
The conversion ratio of sorbierite is in 10%, can know that the yield of isobide is very low.Comparative example 2 (using the dehydration of the 2-butanols of MIL-101 (Cr))
Except the MIL-101 (Cr) that has only carried out making with extra care that will not carry out functionalization used as catalyst, all the other employings had been implemented dehydration with embodiment 3 identical methods.
The conversion ratio that can know the 2-butanols is in 10%, and is very low.
Comparative example 3
Except thermal source is changed into the Electric heating, all the other employings have been implemented dehydration with embodiment 1 identical method, and its result is organized in the table 1.
The dehydration conversion ratio is 80%, and the yield of isobide is merely 10%.
Do not carry out microwave irradiation, carry out dehydration with electrical heating, dehydration not only can not reach satisfied level, and the yield of isobide is also very low.
Comparative example 4
Except using Electric heating as the thermal source heating 5 hours, all the other employings have been implemented dehydration with embodiment 1 identical method, and its result is organized in the table 1.
Though the dehydration conversion ratio is along with the increase of time has 100% height, the yield of the compound isobide of dehydration is 30%, and is very low.Do not carry out microwave irradiation like this, carry out dehydration with electrical heating, even heat 5 hours so long time, dehydration can not reach satisfied level.
Comparative example 5
Except using Electric heating to heat 6 hours down at 130 ℃ as thermal source, all the other employings have been implemented dehydration with embodiment 1 identical method, and its result is organized in the table 1.
Even heat time heating time is very long, the dehydration conversion ratio also has only 60%, and very low, the yield of isobide has only 10% only, and is very low.
Promptly, can know and carry out dehydration with electrical heating that even heat 6 hours so long time down at 130 ℃, dehydration can not reach satisfied level without microwave irradiation.
The dehydration condition and the result of table 1 polyalcohol
Can know from the result of embodiment 1 to 3 and comparative example 1 to 2; The present invention utilizes the amineothiot class to import coordinate bond; Carry out oxidation then, the functional method that makes porous metal-organic backbone material have acid porous metal-organic backbone material is a kind ofly can easily give functional cost-effective functional method to porous metal-organic backbone material.
In addition, can know that the porous metal-organic backbone material as the such acidity of having of catalyst can successfully be applied in the dehydration of alcohol such as sorbierite or 2-butanols.
Can know with the result of comparative example 3 to 5 from embodiment 2 and 4 to 7; The dewatering that utilizes microwave as the polyalcohol of thermal source of the present invention; Also can also easily make the polyalcohol dehydration very soon even without the water of removing byproduct of reaction or HIGH PRESSURE TREATMENT operation; Its dehydration conversion ratio is high, and from the product of dehydration, can optionally obtain the isobide of high yield.In contrast, from the result of comparative example, do not carry out the dehydration of microwave irradiation, even heating for a long time, the dehydration conversion ratio is also very low, and the yield of isobide is also very low, but the principal reaction activity is very low.
Polyalcohols such as sorbierite, sweet mellow wine, xylitol and arabite are induced by living beings, the product of dehydration comonomer (comonomer) and medical aspect very important, so these are simply easy, and successful dehydration is extremely important.
Claims (14)
1. the functional method of porous metal-organic backbone material is characterized in that, this method comprises:
A) will have the porous metal-organic backbone material of unsaturated coordination site and have simultaneously can coordination point and the compound of sulfydryl mix the step of supending; And
B) step of the above-mentioned suspension of heating.
2. the functional method of porous metal according to claim 1-organic backbone material is characterized in that it also comprises:
C) use oxidant oxidation b) suspension of step heating or to b) suspension of step heating carries out solid that Separation of Solid and Liquid the obtains step with the oxidant oxidation;
D) from c) step of separating solids the reactant of step; And
E) solid separated is carried out dry step.
3. the functional method of porous metal according to claim 1-organic backbone material; It is characterized in that; The metal ingredient of said metal-organic framework material is more than one metal or its metallic compound that is selected among Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W, Mn, Re, Fe, Ru, Os, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Hg, Mg, Ca, Sr, Ba, Sc, Y, Al, Ga, In, Tl, Si, Ge, Sn, Pb, As, Sb or the Bi, and organic matter is for having the carbonyldioxy of being selected from, carbonate anion base, amino (NH
2), imino group (
), amide groups (CONH
2), sulfonic group (SO
3H), sulfonic acid anion base (SO
3-), methane two thio group (CS
2H), methane two sulfo-anion base (CS
2-), more than one compound or its mixture of functional group in pyridine radicals or the pyrazinyl.
4. the functional method of porous metal according to claim 1-organic backbone material; It is characterized in that the said compound that has point and sulfydryl that can coordination simultaneously is to be selected from cysteamine, 3-amino-1-propane diols, 2-amino-1-propane diols, 1-amino-propane diols, 4-amino-butanediol, 3-amino-1-butanediol, 2-amino-1-butanediol, 1-amino-1-butanediol, 5-amino-1-pentanediol, 4-amino-1-pentanediol, 3-amino-1-pentanediol, 2-amino-1-pentanediol and the 1-amino-1-pentanediol any one.
5. the functional method of porous metal according to claim 1-organic backbone material; It is characterized in that; Said unsaturated coordination site is handled under 25～500 ℃ or is handled and generate with vacuum for porous metal-organic backbone material is placed under the vacuum.
6. the functional method of porous metal according to claim 1-organic backbone material; It is characterized in that the said porous metal-organic backbone material that possibly have unsaturated coordination site is selected from a kind of among MIL-100 (Cr), MIL-100 (Fe), MIL-101 (Cr), Cu-BTC, MOF-505, MOF-4, Mn-BTT, SLUG-22, SLUG-21, MOF-74 and the UMCM-150.
7. the functional method of porous metal according to claim 1-organic backbone material is characterized in that, the heating of said step b) is under 35～200 ℃ temperature, to implement.
8. the functional method of porous metal according to claim 2-organic backbone material is characterized in that, said oxidant is hydrogen peroxide, oxygen, air and TBHP.
According to claim 1 to 8 prepare by the porous metal of functionalization-organic backbone material.
10. use the method for being adsorbed the removal heavy metal in the claim 9 by the porous metal of functionalization-organic backbone material.
11. the dewatering of alcohol is characterized in that this method comprises:
1) under condition of no solvent, the step that the pure and mild a kind of catalyst by in the porous metal of functionalization-organic backbone material, liquid acid, heteropoly acid, cationic ion-exchange resin, zeolite, acid clay, sulfonic acid zirconia (sulfonate zirconia) and the aluminum phosphate that is selected from the claim 9 is mixed;
2) heat as the mixture of thermal source with microwave, make the step of its reaction above-mentioned steps;
3) step of the reactant of above-mentioned steps being cooled off;
4) reactant of the above-mentioned cooling of separation, the step of acquisition product; And
5) product to above-mentioned steps carries out dry step.
12. the dewatering of alcohol according to claim 11 is characterized in that, said alcohol is selected from a kind of in sorbierite, sweet mellow wine, xylitol, arabite, propyl alcohol and the butanols.
13. the dewatering of alcohol according to claim 11 is characterized in that, said cationic ion-exchange resin is Amberlyst-15 or Amberlyst-35;
Said metal-organic framework material is to be selected from a kind of among MIL-101, MIL-53 and the MIL-100;
Said zeolite is selected from a kind of among H-ZSM-5, H-FAU, H-mordenite, H-MCM-22 and the H-BEA.
14. the dewatering of alcohol according to claim 11 is characterized in that, said heating is under 120～220 ℃ temperature, to implement.
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| KR10-2011-0035698 | 2011-04-18 | ||
| KR1020110035698A KR20120118240A (en) | 2011-04-18 | 2011-04-18 | A functionalization method of porous metal-organic framework materials, solid acid catalysts using the same materials and methods to dehydrate alcohols with the same catalysts |
| KR10-2011-0036302 | 2011-04-19 | ||
| KR1020110036302A KR101323631B1 (en) | 2011-04-19 | 2011-04-19 | A method to dehydrate polyols |
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| CN115090289B (en) * | 2022-07-20 | 2024-02-02 | 上海理工大学 | Novel perovskite in-situ growth FeCo-MOFs derived nanocarbon microwave catalyst and preparation method and application thereof |
Citations (1)
| 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 |
-
2012
- 2012-04-06 WO PCT/KR2012/002618 patent/WO2012144758A2/en active Application Filing
- 2012-04-18 CN CN201210114890XA patent/CN102744105A/en active Pending
Patent Citations (1)
| 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 |
Non-Patent Citations (2)
| Title |
|---|
| DO-YOUNG HONG ET AL: "Porous Chromium Terephthalate MIL-101 with Coordinatively Unsaturated Sites: Surface Functionalization, Encapsulation, Sorption and Catalysis", 《ADV. FUNCT. MATER.》 * |
| 袁先友等: "微波辐射活性炭负载磷钨酸催化环己醇脱水制环己烯", 《化学试剂》 * |
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| WO2012144758A3 (en) | 2013-01-10 |
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