KR101569662B1 - Composite comprising crystalline hybrid nanoporous material powder and alumina and preparation thereof - Google Patents

Abstract

The present invention relates to a MOF-alumina molding composite and a method for manufacturing the same, wherein hybrid nano-porous body (MOF) powders and activated alumina particles are mixed and formed and aged and dried at a low temperature, And contact sites of the nanoporous material particles are chemically connected to form a three-dimensional structure.
The MOF-alumina formed body according to the present invention is hardly affected by physical properties and catalytic performance of the MOF itself in the molding step due to the mild condition of the MOF, and alumina derived from activated alumina acts as a binder to provide excellent mechanical strength It does not limit the physical properties and catalytic performance of the MOF incorporated into the shaped body. Further, since the mechanical strength can be controlled according to the content of alumina, a molded composite having suitable mechanical strength can be produced as required.

Description

Technical Field [0001] The present invention relates to hybrid nanoporous materials and composites comprising alumina and a method for producing the composite nanoporous material,

 The present invention relates to a MOF-alumina composite comprising a hybrid nano-porous body (MOF) powder and an alumina powder, wherein the particles of the alumina powder are chemically bonded to particles of other alumina particles and hybrid nanoporous body powders, and a hybrid nano- (MOF) powders, activated alumina powders and optional water are mixed, molded and dried.

The hybrid nanoporous material or the crystalline organic / inorganic hybrid nanoporous material may be defined as a porous organic polymer compound formed by bonding a central metal with an organic ligand. The hybrid nanoporous material may include both organic and inorganic materials in the skeleton structure, Means a crystalline compound having a pore structure.

These organic / inorganic hybrid nanoporous materials are used in a broad sense and are generally referred to as porous coordination polymers (Angew. Chem. Intl. Ed., 43, 2334, 2004], also referred to as a metal-organic framework (MOF) [Chem. Soc. Rev., 32, 276, 2003].

MOF as a novel material has the following advantages: (i) it can realize a larger pore size than currently used zeolite; (ii) has a larger internal surface area than currently used porous material; (iii) (Iv) not only can easily functionalize the outer surface of the MOF, but also make it possible to easily functionalize the organic framework components forming the inner surface (e.g., Curr Solid State Mater. Sci., 3, 71, 1998, Chem. Lett., 6, 624, 2000; J. Mater.

As such, due to the flexibility of pores and deformation of high surface area, molecular size or nano size, MOF has been widely studied as a novel material having applications such as adsorbents, gas separation, gas storage, sensors, membranes, functional thin films, catalysts and catalyst carriers . In addition, application of guest molecules smaller than pore size to enclose guest molecules or separation of molecules larger than pore size has been actively studied (Chem. Rev. 97, 2373, 1997; J. Mater. Chem. 16, 626, 2006 ).

Since MOF contains a polar metal ion and an anionic ligand in a crystalline skeleton and a non-polar aromatic compound group coexists, it can have both hydrophilicity and hydrophobicity. Since MOF has a permanent porosity, it has potential applications in a variety of fields and is therefore of primary interest in the field of catalysis, absorption and / or adsorption, ion exchange materials, chromatography materials, storage of materials and freshwater production to be.

Such a MOF can be produced by a hydrothermal reaction using a metal or a metal precursor and an organic ligand, or a thermal reaction of a solvent. By adopting a microwave heating source instead of an electric heating source, it is possible to produce a finer, (See also PCT / KR2007 / 000648).

However, MOF based on the metal-organic compound framework is generally obtained as a brittle, powder or paste, which is low in density and small in particle size, making it inconvenient for practical applications. Moreover, these powders are difficult to recover, easily deactivated, and are also agglomerated. Therefore, the permeability of the gas and the liquid is poor, so that it can not be easily used in most fields. Therefore, MOF is trying to find various forms such as composites so that it can be widely used in these fields.

Korean Patent Application No. 10-2004-7019328 (or PCT / EP2003 / 005546) and Korean Patent Application No. 10-2007-7012702 (or USP No. 7,524,444) (applicant REAGENT OF CALIFONIA UNIVERSITY) disclose that MOF is converted into a complex such as pellets A method of manufacturing an MOF compact having a compressive strength of 5 to 200 N, preferably 16 to 51 N, is disclosed. It is noted in this document that the ratio of the surface area per volume of the resulting compact and the surface area per volume of MOF feedstock powder is at least 1.6: 1, but rather from these figures it can be seen that the surface area can be significantly impaired compared to the MOF feedstock powder, In addition, although titanium dioxide, hydrated titanium dioxide, hydrated alumina or other aluminum-containing binder, a mixture of silicon and aluminum compounds, a silicon compound, a clay mineral, an alkoxysilane and an amphipathic substance are mentioned as inorganic binders, examples thereof using a small amount of graphite But no examples of using other binders in an effective amount are given.

Although Korean Patent Application No. 10-2011-7018964 and Korean Patent Application No. 10-2011-7018531 (Applicant BASF) also describe the molding of MOF using an inorganic binder, only a molded article containing a trace amount of graphite (0.4 wt% or less) And there is no description about the physical properties of the molded articles and / or the physical properties of the molded articles themselves compared with the MOF.

In Korean Patent Application No. 10-2009-0111937 (Applicant KRICT), MOF powder in slurry state obtained in the synthesis process is wet-coated or vacuum-extruded to prepare a shaped body and dried and heat-treated at a temperature of about 80 to 120 ° C. The coating or formed body thus produced has been described for the specific surface area, but does not mention the compressive strength.

As described above, when the MOF is formed by a conventional catalyst or ceramic molding method, the molding environment such as high temperature and / or high pressure may cause deterioration of the physical properties and / or external shape of the MOF itself, As well as the performance of the MOF may be hampered or limited due to the carrier and / or binder.

On the other hand, conventional inorganic nanoporous materials have been used to remove pores by using an organic binder or additives and to remove them by sintering at a high temperature in order to provide interstitial porosity in the production of molded articles. However, since MOF has low thermal stability and can not be calcined, It is not easy to provide voids using additives.

In other words, MOF is likely to be deformed when it is baked at a high temperature. Therefore, there is a problem that the MOF should not be sintered at a high temperature when the MOF is formed, and an organic binder is often used rather than an inorganic binder. However, since the organic binder is not easy to secure the porosity unlike the inorganic binder having porosity, the organic binder may interfere with or restrict the contact between the MOF as the catalytic material and the object, .

In addition, since MOF is a material having high crystallinity and porosity characteristics based on a skeleton formed of a metal and an organic material, the mechanical stability is generally low, so that the skeleton structure is easily collapsed even at a relatively low pressure and the characteristics of the porous material There is a tendency to decrease. In the case of MOF with the property of forming unsaturated metal sites in the structure during dehydration or desolvation, the production of the composite by powder compression causes the reduction of the active surface due to the loss of the unsaturated metal sites.

Accordingly, the most important point when converting the MOF powder into a composite or molded body having a certain shape is to minimize the surface area, porosity and reduction of the active surface, which are characteristics of the MOF. Another important thing to note in the production of molded articles or composites of MOF is the stability or hardness of the composite. Usually stability is dependent on the pressure used to form the composite or shaped body. The hardness of the shaped body is closely related to its stability. Stable composites are preferred on the one hand, but on the other hand care should be taken as the pressure applied to obtain the shaped body will reduce the surface area and the active surface.

On the other hand, inorganic nanoporous materials containing zeolite are based on a crystalline or amorphous skeleton composed of a metal and / or an inorganic material, and have high stability, but have low mutual aggregability and are mixed with a binder or an additive Mechanical pressing is a necessary process, and molding by compression of zeolite and the like is described in U.S. Publication No. 2009-0048092 and U.S. Publication No. 2011-0105301.

As a result, the surface area during the production of the composite by the compression method is greatly reduced as compared with the surface area of the powder due to the decrease due to the decrease in the crystallinity and the decrease due to the pore entrance blocking as well as the decrease in the amount of the binder or additive added. Because the aforementioned beneficial effect of the material comprising the nanoporous material is closely related to the surface area of the material, the reduction of the surface area of the material comprising the nanoporous material is related to the efficiency of their absorption, storage, catalysis and other properties It is not preferable.

It is important to note when molding nanoporous material such as zeolite or MOF that the active surface of the nanoporous material is almost always present inside the nanoporous material, so that it can be quickly and smoothly accessed inside the nanoporous material during adsorption or absorption of guest molecules. It is important to secure the connection channel and the channel, that is, the void volume, with the nano-pores of the nanoporous body powder present inside the molded article from the outer surface. Conventionally, in inorganic nanoporous materials such as zeolite, an organic compound binder is added and molded, followed by calcination at a high temperature in the air to oxidize the organic binder existing between the nanoporous material powders, thereby generating voids. However, since the crystalline hybrid nano-porous material such as MOF is bound to an organic ligand in the skeleton, it is generally weak to heat. In particular, when the material is fired in air containing oxygen, there is a problem that the material itself disappears or the structure collapses. Can not be used as it is. To solve this problem, new voids or new void retaining or forming methods are needed.

Accordingly, there remains a need for a molded body or composite having sufficient stability while maintaining the physical properties and performance of the nanoporous body powder when converting the nanoporous body powder into a molded body or composite, have. To this end, efforts are also being made to develop suitable binders and / or new molding processes that can impart good mechanical properties to the carrier without high temperature firing.

On the other hand, a method of molding activated alumina without high-temperature firing is known. For example, in Korean Patent Application No. 10-1998-0054925, a spherical granular assembly is prepared by using amorphous alumina powder obtained by rapid thermal decomposition of aluminum hydroxide as a binder in water, hydrated, dried and calcined, A method of manufacturing an activated alumina compact having a surface area and a large pore volume, comprising the steps of: 1) preparing a spherical compact by adding water as a binder to the amorphous alumina powder obtained by rapid thermal decomposition and pulverization of aluminum hydroxide, 2) a pretreatment step of forming hydrated gel and pseudoboehmite crystal nuclei in a water chamber at a temperature of 5 to 60 ° C and a relative humidity of 50 to 100%, and 3) a hydration reaction at 70 to 100 ° C for 1 to 5 hours Hydration step, 4) drying and optional calcination step.

Korean Patent Application 10-1998-0054925 Korean Patent Application 10-2009-0111937

A method of forming a hybrid nanoporous material or a powder of a crystalline organic / inorganic hybrid nanocomposite material (MOF) using a porous inorganic binder, the method comprising the steps of: subjecting the MOF material to high temperature firing or a separate heat treatment process And to develop a new molding method capable of imparting excellent mechanical properties to a carrier.

The present inventors have found that a shaped composite obtained by molding or coating a mixture obtained by adding active alumina powder and optional water as a binder to a MOF powder and hydrating and drying the resulting molded body or coating at room temperature can be obtained by using MOF ), Which has high porosity as a characteristic of an inorganic binder and has excellent mechanical strength. In addition, even when a small amount of activated alumina is used in a small amount of 10% by weight or less, the mechanical properties The strength is expected to be excellent, and the present invention has been completed.

Alumina derived from activated alumina in the catalyst preform according to the present invention acts as a carrier and binder to provide porous and excellent mechanical strength to the shaped composite as well as to hardly limit the physical properties and catalytic performance of the MOF incorporated into the shaped body .

In the MOF-alumina compact according to the present invention, the physical properties and the catalytic performance of the MOF itself (raw MOF) are hardly impaired in the molding step due to the mild forming condition, and alumina derived from activated alumina acts as a carrier and binder To provide porosity and excellent mechanical strength, as well as hardly to limit the physical properties and catalytic performance of the MOF incorporated into the shaped body. Further, since the mechanical strength can be controlled according to the content of alumina, a molded composite having suitable mechanical strength can be produced as required.

1 is a graph showing the physical adsorption isotherms (N ₂ , -196 ° C) measured on a spherical composite pellet containing MIL-100 (Fe) powder and the powder.
Figure 2 is a graph showing the physical adsorption isotherms (N ₂ , -196 ° C) measured for UiO-66 (Zr) _NH ₂ powder and spherical composite pellets containing the powder.
Figure 3 is a graph showing the physical adsorption isotherms (N ₂ , -196 ° C) measured for UiO-66 (Zr) _2CO ₂ H powder and spherical composite pellets containing the powder.
Figure 4 is a graph showing the physical adsorption isotherms (N ₂ , -196 ° C) measured for a UiO-66 (Zr) _CO ₂ H powder and spherical composite pellets containing the powder.
Fig. 5A ~ F is MIL-53 (Al), MIL -53 (Al) _NH 2, MIL-100 (Fe) _NF, UiO-66 (Zr) _2CO 2 H, UiO-66 (Zr) _CO 2 H and UiO -66 (Zr) _NH ₂ , and X-ray diffraction (XRD) analysis results of spherical shaped bodies containing these powders, respectively.
6 is a scanning electron microscope (FE-SEM) photograph of a section of a MIL-100 (Fe) _NF spherical molded body.

A first object of the present invention is to provide a composite or molded article of MOF-alumina comprising hybrid nano-porous body (MOF) and alumina, wherein the particles of alumina described above are chemically bonded to other alumina particles and nano- To form a three-dimensional structure as a whole.

A second object of the present invention is to provide a method for producing a composite or a molded article comprising hybrid nanoporous material and alumina comprising mixing hybrid nano-porous material (MOF) powder and activated alumina powder, May include:

(1) The hybrid nanoporous material powder and activated alumina powder were mixed at a weight ratio of 2: 98 to 98: 2,

(2) In some cases, a solvent such as water and / or alcohol is further added to the resultant mixture,

(3) forming the resulting mixture into any shape, molding, coating on the support,

(4) The molded body or coating is dried at a temperature of 5 to 80 캜.

In the present invention, the term "chemical link" means not only a physical connection by means of mixing, kneading, compression or pressing, but also a chemical bonding of light. For example, a chemical bond such as a covalent bond, Chemical bonding by bonding or the like.

For example, the chemical bond between alumina particles is Al-O-Al or Al-OH ... Al bonding or the like, which bond can be formed by dehydration reaction of aluminum hydroxide Al (OH) ₃ or hydrated alumina contained in activated alumina. Al-O-Al bonds in alumina are covalently bonded, such as Si-O-Si bonds in silica, and are usually formed by polycondensation of Al-OH.

In the present invention, the composite refers to a material including MOF, alumina and any solvent, and may also be referred to as a composite or molded body that is shaped if shaped into any shape. The composite may further contain, if necessary, inorganic oxide particles derived from a void agent, a functional auxiliary coagent, and / or other active inorganic oxide.

&Quot; Powder "means a mixture of microparticles, which when used in a solvent is meant to encompass a dispersion or paste, and" particles " But are not strictly classified.

Hereinafter, the hybrid nanoporous material (MOF), activated alumina and shaped composite will be described in more detail.

One. hybrid Nanoporous material

In the present invention, the hybrid nanoporous material described above refers to a porous hybrid inorganic-organic material or MOF (Metal-Organic Framework) such as CuBTC, MIL-100 (Fe), MIL-101 (Cr), MIL- Al), MIL-53 (Al ) _NH 2 and MIL-125 (Ti), MIL -125 (Ti) _NH 2, UiO-66 (Zr), UiO-66 (Zr) _2COOH (UiO-66 (Zr) - BTEC), hybrid nanoporous materials named UiO-66 (Zr) _COOH (UiO-66 (Zr) -BTC), UiO-66 (Zr) _NH ₂ and the like.

In one embodiment, the porous organic-inorganic hybrid material or the hybrid nanoporous material (MOF) may be at least one compound selected from a compound represented by the following formula or a hydrate thereof:

_{M 3 X (H 2 O)} 2 O [C 6 Z 4 -y Z 'y (CO 2) 2] 3 (M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I, F, or OH; Z or _{Z '= H, NH 2,} Br, I, NO 2 or OH; 0 ≤ y ≤ 4) ;

M ₃ O (H ₂ O) ₂ X [C ₆ Z _{3 - y} Z ' _y - (CO ₂ ) ₃ ] ₂ (M = Cu, Fe, Mn, Cr, V, Al, Ti, Zr or Mg; X = Cl, Br, I, F, or OH; Z or _{Z '= H, NH 2,} Br, I, NO 2 or OH; 0 ≤ y ≤ 3) ;

M ₃ O (H ₂ O) ₂ X _{1 -y} (OH) _y [C ₆ H ₃ - (CO ₂ ) ₃ ] ₂ (0 ≤ y ≤ 1; M = Cu, Fe, Mn, Cr, , Ti, Zr or Mg, X = Cl, Br, I or F); or

_{M 3 X 1 -y (OH)} y (H 2 O) 2O [C 6 H 4 (CO 2) 2] 3 (0 ≤ y ≤ 1; M = Cu, Fe, Mn, Cr, V, Al, Ti , Zr or Mg, X = Cl, Br, I or F).

In one embodiment, the porous organic-inorganic hybrid material or the hybrid nanoporous material (MOF) may be at least one compound selected from a compound represented by the following formula or a hydrate thereof:

_{M 6 O 4 (OH) 4} [C 6 Z 4 -y Z 'y (CO 2) 2] 12 (M = Ti, Sn , or Zr; Z or _{Z' = H, NH 2,} Br, I, NO 2 Or OH; 0? Y? 4); or

M ₂ (dhtp) (H ₂ O) ₂ (M = Ni, Co, Mg, Mn and Fe; dhtp = 2,5-dihydroxyterephthalic acid).

Examples of the porous organic-inorganic hybrid materials or hybrid nanoporous materials include: copper terephthalate, iron terephthalate, manganese terephthalate, chrome terephthalate, vanadium terephthalate, aluminum terephthalate, titanium terephthalate, zirconium terephthalate , Magnesium terephthalate, copper benzenetricarboxylate, iron benzenetricarboxylate, manganese benzenetricarboxylate, chromium benzenetricarboxylate, vanadium benzenetricarboxylate, aluminum benzenetricarboxylate, titanium benzene tri Magnesium dihydroxy terephthalate, manganese dihydroxy terephthalate, iron dihydroxy terephthalate, zinc dihydroxy terephthalate, zinc dihydroxy terephthalate, zinc dihydroxy terephthalate, Hydroxybenzene tribenzoate, aluminum benzene tribenzoate, derivatives thereof, solvates thereof, hydrates thereof, or combinations thereof.

According to one embodiment of the present invention, the porous organic-inorganic hybrid material or the hybrid nanoporous material (MOF) is not limited to the above-mentioned materials, and the above-mentioned prior art documents (e.g. Korean Patent Application No. 10-2004-7019328 10-2007-7012702, 10-2011-7018964, 10-2011-7018531, 10-2009-0111937) can be used.

The porous organic-inorganic hybrid material or hybrid nanoporous material (MOF) used in the present invention may have an average particle size of 3 to 1000 nm, specifically 10 to 800 nm, particularly 20 to 500 nm, Although not limited, it is preferable to have a uniform size if possible.

Methods for producing porous organic-inorganic hybrid materials or hybrid nanoporous materials (MOF) used in the present invention are well known in many documents, and the present invention can be incorporated into these documents as needed.

2. Activated alumina and its preparation

In the present invention, the term "crystalline alumina" means aluminum oxide (Al ₂ O ₃ ) having a crystalline form, the term "amorphous alumina" means aluminum hydroxide or hydrated alumina and optionally amorphous aluminum oxide Al ₂ O ₃ ), and the term "activated alumina" includes alumina containing at least 1 atomic percent of amorphous alumina selected from amorphous alumina, specifically Al (OH) ₃ (aluminum hydroxide) it means.

Generally, activated alumina refers to alumina (hydrate) that is dehydrated or partially dehydrated to have a large surface area including both crystalline and amorphous, and is produced by thermal dehydration or activation of aluminum hydroxide (Al (OH) ₃ ) . The aluminum hydroxide or hydrated alumina contained in the activated alumina is converted into Al ₂ O ₃ through aging including dehydration and is chemically connected with the surrounding Al ₂ O ₃ , for example, the Al-O-Al bond and the Al- / Or Al-OH ... Al bond to form a dense structure. Molded bodies made of activated alumina are porous and are often used for drying adsorbents or chromatography.

"Activated alumina (size)" as used herein refers to an amorphous alumina (particle) is selected from the partial dehydration of aluminum hydroxide (particle) or parts hydrated alumina (particle), and, Al (OH) ₃ (Aluminum Hydroxide) Or at least 1 atomic% of hydrated alumina. As used herein, "activated alumina (particle)" may have a water content of at least 1 wt%, specifically at least 3 wt%, especially at least 5 wt%, preferably at least 7 wt% And may have an average particle diameter of 900 nm, specifically 10 to 700 nm, preferably 20 to 500 nm.

In the present invention, the content of amorphous alumina selected from aluminum hydroxide or hydrated alumina in activated alumina is not critical and is generally not less than 1 atomic%, specifically not less than 2 atomic%, preferably not less than 5% And more preferably 10 atomic% or more.

In the activated alumina, the form in which the amorphous alumina component is continuously or discontinuously present on the particle surface of the activated alumina is more advantageous than the form in which the amorphous alumina component is uniformly dispersed throughout the particles of the activated alumina. According to one preferred embodiment of the present invention, it may be desirable for the amorphous alumina component to be present at 5% or more, specifically 10% or more, preferably 20% or more, of the surface area of particles of activated alumina.

According to one embodiment of the present invention, the activated alumina powder can be prepared by known methods (e.g. Korean Patent Application No. 10-1998-0054925, the contents of which are incorporated herein by reference) Aluminum hydroxide (Al) (OH) ₃ powder is rapidly pyrolyzed at 375 to 830 ° C within 0.05 to 3 seconds to convert it to amorphous rho (ρ) -alumina and then pulverized to produce activated alumina containing amorphous alumina . The alumina compact formed from the activated alumina thus produced has a specific surface area of 270 to 400 m 2 / g (BET, nitrogen adsorption), a pore volume of 0.4 to 0.9 cc / g, an average compressive strength of 120 to 200 N, And 45% by weight of water adsorption property.

In the present invention, the term "activated alumina powder" is used not only in powder form, but also in the form of a paste mixed with a dispersion and a solvent dispersed in a solvent.

According to another embodiment of the present invention, as active alumina, aluminum hydroxide-alumina composite particles having an aluminum hydroxide layer formed by hydration reaction on the surface of alumina particles (e.g. Korean Patent Application No. 10-2005-0107984, , Incorporated herein by reference).

The composite particles composed of the aluminum hydroxide shell-alumina core described above have an average particle diameter of 5 to 300 nm, preferably 10 to 200 nm, and a specific surface area of 10 to 480 m 2 / g, preferably 10 to 400 m 2 / g (Alpha), gamma, delta, chi, eta, rho, kappa, theta and combinations thereof. , And aluminum hydroxide can be obtained by heat treatment at a temperature of 400 to 800 占 폚, preferably 400 to 700 占 폚.

In activated alumina, aluminum hydroxide or hydrated alumina can be used as a catalyst in gibbsite, boehmite, bayerite, diaspore, nordstrandite, pseudo boehmite or They may have the form of a composite phase thereof.

3. Composite manufacturing step

The MOF-alumina composite according to the present invention can be molded or shaped in any shape, for example in the form of spherical or pseudo spherical granules, granules, monoliths or honeycomb filters, injection-molded bodies, films or coatings.

According to the present invention, the amount of the hybrid nanoporous material and activated alumina to be used is not particularly limited, but may be, for example, 98: 2 to 2:98, specifically 95: 5 to 5:95, : 7 to 7: 93, preferably 90: 10 to 10: 90. If less than 2% by weight of active alumina is used in the above range, the mechanical strength of the shaped body may be insufficient. The use range of the hybrid nanoporous material is given by reference, and it is not deviated from the scope of the present invention even if it is used in an amount smaller than the above range depending on the application field or application environment.

As one of the excellent effects of the present invention, even when a small amount of activated alumina is used in a small amount, for example, 3 to 5% by weight relative to MOF, the resulting composite or shaped body can be used as a catalyst or an adsorbent in various fields It is possible to have a sufficiently high mechanical strength.

As another effect of the present invention, the mechanical strength of the composite can be adjusted according to the content of alumina, so that a molded composite having suitable mechanical strength can be produced as required.

According to one embodiment of the present invention, the above-mentioned mixture comprising the hybrid nanoporous material (MOF) and activated alumina may further contain water, alcohol or the like as a dispersion medium or a solvent. Solvents such as water and alcohols serve as binders when added in small amounts, but also act as solvents or dispersants when added in excess.

Therefore, the amount of the solvent or dispersion medium such as water or alcohol to be added is not particularly limited and may be varied depending on the molding method. For example, when a molded body is produced by a pressure molding method such as compression molding, a solvent or a dispersion medium may be added in a small amount of 0 to 20% by weight based on the activated alumina powder. However, In the case of producing a molded article, a solvent or a dispersion medium may be added in an amount of 10 to 100% by weight. On the other hand, when the film is prepared by a coating method in which a dispersion medium or a solvent is used in an excessive amount, a solvent or a dispersion medium may be used in an amount of about 50 to 300% by weight.

For example, when a molded body is produced by a non-pressure molding method such as simple molding using amorphous alumina as the activated alumina, water can be added as a dispersion medium in an amount of about 30 to 50% by weight based on the amorphous alumina powder , Thereby maintaining the shape of the feature through a liquid bridge. If the amount of water used is too small, it may be difficult to form the liquid crosslinking depending on the water content in the amorphous alumina. If the amount is excessively used in excess, the molding itself becomes impossible. Those skilled in the art will be able to properly adjust the amount of water added depending on the state of the amorphous alumina and the type of the desired shaped body.

Then, a molded body or a film is prepared from a mixture containing activated alumina, MOF, and optional dispersion medium, and this is molded at room temperature, specifically at 5 to 80 캜, particularly at 10 to 60 캜, preferably at 20 to 50 캜 For 10 minutes to 48 hours, specifically 30 minutes to 24 hours, particularly 1 to 12 hours, to obtain a MOF-alumina composite or a molded body having excellent mechanical strength. One of the preferable advantages of the present invention is that it is possible to obtain a MOF-alumina composite having excellent mechanical strength without performing a heat treatment at a temperature of 200 DEG C or more, preferably 100 DEG C or more.

The above-described aging and drying process can be carried out under atmospheric pressure, reduced pressure or pressure and / or relative humidity of 50 to 100%, if necessary, but the above-mentioned pressure and humidity conditions are not particularly limited. The activated alumina particles form chemical linkages at the contact sites with other activated alumina particles and / or nanoporous body powders through the above-described aging and drying processes, and due to such chemical linkage, alumina particle-alumina particles and alumina particles- The three-dimensional structure formed of the porous body particles is more firmly formed, and the formed body appears to have high mechanical strength.

According to one preferred embodiment of the present invention, the above-described aging and drying processes are performed by aging at a low temperature of 50 ° C or lower to form hydrated gel and pseudoboehmite crystal nuclei, followed by hydration and drying at a high temperature of 50 ° C or higher It can be divided into two stages.

The composite prepared according to the present invention has a density of 0.1 kgf or more, specifically 0.2 kgf or more, particularly 0.5 kgf or more, preferably 1 kgf or more, more preferably 2 kgf or more, and most preferably, (Average) compressive strength of 4 kgf or more, and has an average compressive strength of, for example, 0.1 to 20 kgf, specifically 0.2 to 15 kgf, particularly 0.5 to 10 kgf. When the alumina content was approximately 5% by weight, the composite according to the present invention could have an average compressive strength of 0.14 to 0.39 kgf, specifically 0.20 to 0.35 kgf. However, it may have further compressive strength depending on the type of activated alumina and / or drying and aging conditions, and this is also included in the scope of the present invention.

The composite formed according to the method of the present invention has a three-dimensional structure of chemically bonded alumina particle-alumina particles and / or alumina particle-nanoporous material particles, and the MOF particles And the molded body can have overall excellent mechanical strength. In the three-dimensional structure, the alumina particles and the nanoporous body powders are not always regularly arranged but can be arranged amorphous or disorderly depending on the size and amount of the particles.

The present invention can be further illustrated by the following examples.

[Example]

In the following Examples, the catalyst composite was prepared in a spherical or pseudo spherical shape, an injection molded article, a monomer shape, a honeycomb shape, or a support using a hybrid nanoporous material (MOF) powder obtained in the production example and an activated alumina binder obtained in the production example Coated film. ≪ / RTI >

Manufacturing example  One: hybrid Nanoporous material  Synthesis of powder

Using the known method, hybrid nano-pore powder named HKUST-1 (Cu-BTC), MIL-, UiO-, etc. were respectively synthesized. The surface area, solvent, preparation method and the like of the powder obtained in this Production Example are shown in Table 1 below.

matter The Surface area
( m ² / g ) menstruum Way MIL-100 (Fe)
(Using F) _{[{Fe 3 O (H 2} O) 2 OH x F y {C 6 H 3 (CO 2) 3} 2] (x + y = 1) 2000-2300 H ₂ O Heat MIL-100 (Fe)
(Using F) _{[{Fe 3 O (H 2} O) 2 OH x F y {C 6 H 3 (CO 2) 3} 2] (x + y = 1) 2000-2300 H ₂ O microwave MIL-100 (Fe)
(Do not use F) [{Fe ₃ O (H ₂ O) ₂ OH {C ₆ H ₃ (CO ₂ ) ₃ } ₂ ] 2000-2300 H ₂ O Heat MIL-101 (Cr) _{[{Cr 3 O (H 2} O) 2 OH x F y {C 6 H 3 (CO 2) 2} 3] (x + y = 1) 4000-4200 H ₂ O Heat HKUST-1
(Cu-BTC) Cu ₃ {(C ₆ H ₃ (CO ₂ ) ₃ } ₂ } 1600-1800 EG microwave MIL-127 (Fe) Fe ₃ O (OH) [C ₁₆ N ₂ O ₈ H ₆ ] _1.5 1200-1380 DMF reflux MIL-47 (V) V ₃ (OH) {O ₂ CC ₆ H ₄ -CO ₂ } x (HO ₂ CC ₆ H ₄ -CO ₂ H) (X = - 0.75) 800-950 H ₂ O Heat MIL-53 (Cr) Cr (OH) ₂ [O ₂ C (C ₆ H ₄ ) CO ₂ ] 850-1000 H ₂ O Heat MIL-53 (Al) _{Al (OH) [O 2 C} (C 6 H 4) CO 2] 940-1144 H ₂ O Heat MIL-96 (Al) Al ₁₂ O (OH) ₁₈ (H ₂ O) ₃ (Al ₂ (OH) ₄ ) [BTC] ₆ 441-532 H ₂ O Heat MIL-100 (Al) {Al ₃ (? ₃ -O) (OH) (H ₂ O) ₂ [C ₆ H ₃ (CO ₂ ) ₃ ] ₂ 1950-2175 H ₂ O Heat MIL-100 (V) V ₃ OH (H ₂ O) ₂ O [C ₆ H ₃ (CO ₂ ) ₃ ] ₂ 1584-2318 H ₂ O Heat MIL-110 (Al) _{Al 8 (OH) 16 (H} 2 O) 3 (BTC) 3 1300-1450 H ₂ O Heat MIL-125 (Ti) Ti ₈ O ₈ (OH) ₄ (O ₂ CC ₆ H ₄ -CO ₂ ) ₆ 1562-1870 DMF reflux MIL-125 (Ti) _NH ₂ Ti ₈ O ₈ (OH) ₄ (O ₂ CC ₆ H ₄ N-CO ₂ ) ₆ 1229-1623 DMF Heat UiO-66 (Zr) Zr ₆ O ₄ (OH) ₄ (CO ₂ C ₆ H ₄ CO ₂ ) ₆ 1000-1400 DMF reflux UiO-66 (Zr) _NH ₂ Zr ₆ O ₄ (OH) ₄ (CO ₂ C ₆ H ₃ NH ₂ CO ₂ ) ₆ 1000-1100 DMF reflux UiO-66 (Zr) _NH ₂ Zr ₆ O ₄ (OH) ₄ (CO ₂ C ₆ H ₃ NH ₂ CO ₂ ) ₆ 1000-1100 H ₂ O Heat UiO-66 (Zr) _NH ₂
(250 nm or less nanoparticles) Zr ₆ O ₄ (OH) ₄ (CO ₂ C ₆ H ₃ NH ₂ CO ₂ ) ₆ 1000-1100 H ₂ O Heat _{UiO-66 (Zr) _2CO 2} H Zr ₆ O ₄ (OH) ₄ [(O ₂ C) -C ₆ H ₂ - (CO ₂ H) ₂ -CO ₂ ]] ₆ 600-690 H ₂ O reflux _{UiO-66 (Zr) _CO 2} H Zr ₆ O ₄ (OH) ₄ [(O ₂ C) -C ₆ H ₃ - (CO ₂ H) -CO ₂ )] ₆ 580-690 H ₂ O reflux _{UiO-66 (Zr) _SO 3} H Zr ₆ O ₄ (OH) ₄ [(O ₂ C) -C ₆ H ₃ - (SO ₃ H) -CO ₂ )] ₆ 400-800 H ₂ O Heat

Manufacturing example  One: ( MIL -100 ( Fe ))

FeCl ₃ 16.5g of the Teflon reactor And 5.6 g of 1,3,5-benzenetricarboxylic acid (BTC) were added and distilled water was added. The final molar ratio of the reactants was FeCl ₃ : BTC: H ₂ O = 1: 0.66: 54. The reaction product was stirred at 500 rpm for 20 minutes at room temperature to obtain a homogeneous reaction product.

The Teflon reactor containing the pretreated reaction product was maintained at a reaction temperature of 160 ° C. for 8 hours to perform a crystallization reaction, followed by cooling to room temperature. The product which had been cooled to room temperature was purified at least once with distilled water at 80 DEG C and then further purified with ethanol at 60 DEG C and dried at 100 DEG C to obtain Fe-based hybrid nanoporous material. In order to obtain a high surface area, the reaction was further carried out at a temperature of 70 ° C. for 1 hour or more using a 0.1 M ammonium fluoride (NH ₄ F) aqueous solution. The form of the X-ray diffraction spectrum is described in Chem. Comm., 2007, 2820]. -The low-temperature nitrogen adsorption experiment at 196 ° C showed that the BET surface area of the material obtained in this Preparation Example was 1870 m ² / g And the adsorption amount was 550 mL / g at P / P0 = 0.5. The BET surface area of the powder obtained in this Production Example and the cut-off ratio are shown in Table 1 above.

Manufacturing example  2: ( UiO -66 ( Zr ))

ZrCl4, 1,4-benzene dicarboxylic acid (BDC) was added to the Teflon reactor and DMF was used as a solvent so that the final molar ratio of the reactants was Zr: BDC: DMF = 1: 1: 1423. The Teflon reactor containing the reactants is placed in an electric oven, reacted at 120 ° C for 48 hours, slowly cooled to room temperature, washed with DMF, and dried. The morphology of the X-ray diffraction spectrum is shown in J. Am. Chem. Soc, 2008, 130, 13850]. The BET surface area of the powder obtained in this Production Example and the cut-off ratio are shown in Table 1 above.

Manufacturing example  3: ( UiO -66 ( Zr ) _ NH ₂ Lt; / RTI &

The final molar ratio of Zr: NH2-BDC: DMF = 1: 1: 1423 was determined by adding ZrCl4,2-amino-1,4-benzene dicarboxylic acid (NH2-BDC) Respectively. The Teflon reactor containing the reactants is placed in an electric oven, reacted at 120 ° C for 48 hours, slowly cooled to room temperature, washed with DMF, and dried. The morphology of the X-ray diffraction spectrum is shown in J. Am. Chem. Soc, 2008, 130, 13850]. The BET surface area of the powder obtained in this Production Example and the cut-off ratio are shown in Table 1 above.

Manufacturing example  4: ( MIL -101 ( Cr ))

After adding 0.52 g of metal chromium powder (Cr Metal) and 1.41 g of 1,3,5-benzene tricarboxylic acid (BTC) to a Teflon reactor, 48 g of water and 4 mL of HF were added to give a final molar ratio of the reactants of Cr : BTC: H ₂ O: HF = 1: 0.67: 289: 2. The reaction product was placed in a Teflon reactor, stirred at room temperature for 30 minutes, mounted in a stainless steel reaction system, and crystallized at 220 ° C for 2 days in an electric oven capable of stirring. After the synthesis, the product was cooled to room temperature and purified with distilled water at 80 ° C for 1 hour, then purified with ethanol at 60 ° C for 2 hours and dried at 100 ° C to obtain a hybrid nanoporous material named MIL-100 (Cr). The form of the X-ray diffraction spectrum of the material obtained by the above procedure is described in Angew. Chem. Int. Ed., 2004, 43, 6296], which is the same as the MIL-100 (Cr) structure.

Manufacturing example  5: Preparation of activated alumina powder

(Al (OH) ₃ , gibbsite) powder having an average particle size of 50 mu m is rapidly pyrolyzed in a fluidized bed or a rotary kiln at a temperature of 375 to 830 DEG C within 0.05 to 3 seconds Activated alumina is prepared and finely pulverized in a range of 1 to 7 mu m by using a ball mill, a vibrating mill or a jet mill to produce activated alumina powder. The obtained activated alumina had a water content of about 5 to 10%.

Example  1 to 4: Preparation of spherical complex

The hybrid nanoporous material (MOF) powders obtained in Preparation Examples 1 to 4 were mixed with the activated alumina powders obtained in Preparation Example 5 at a weight ratio of 20: 1 and granulated into spherical or pseudolite spheres having a diameter of 0.5 to 5 mm, And dried at 25 DEG C for about 12 hours to prepare a molded article of a MOF-alumina composite. The resulting composite had an average compressive strength of 0.14 to 0.39 kgf (corresponding to about 1.4 to 3.9 N).

FIG. 1 shows that the specific surface area of spherical shaped body pellets prepared from MIL-100 (Fe) powder according to Example 1 does not greatly differ from the specific surface area of MIL-100 (Fe) powder itself, (Specific surface area) of the MOF in the process of producing the molded article according to the present invention.

2 to 4 are schematic cross-sectional views of spherical molded body pellets prepared from UiO-66 (Zr), UiO-66 (Zr) _NH ₂ and MIL-101 The specific surface area does not show a large difference from the specific surface area of each MOF powder itself. From this, it can be seen that no damage is caused to the physical properties (specific surface area) of the MOF during the production of the molded article according to the present invention.

Example  5 and 6: Molded  Preparation of Catalyst Composites

The hybrid nanoporous material powders obtained in Production Examples 1 to 4, the amorphous alumina powder obtained in Production Example 5 and water were kneaded at a predetermined weight ratio [(powder + binder): water (solvent) = 10: 2] The dough can be molded into a desired shape and size, such as a monolith filter and a honeycomb structure.

The resulting composite had an average compressive strength similar to that of the composite prepared without the addition of water.

Example  7: Coating film  ≪ / RTI >

The hybrid nanoporous material powders obtained in Production Examples 1 to 4, the amorphous alumina powders obtained in Production Example 5 and water were mixed at a predetermined weight ratio [(powder + binder): water (solvent) = 1: 10] And coated on a support to form a coated film.

The present invention can be applied to the molding field of MOF and can be used in industrial fields where MOF is used as an adsorbent or catalyst.

Claims (10)

Hybrid nanoporous material (MOF) and alumina, wherein the alumina particles described above are chemically connected at the contact sites with other alumina particles and particles of the nanoporous material to form a three-dimensional structure, and the alumina particles Chemical bonding between Al-O-Al or Al-OH ... Al bond. ≪ RTI ID = 0.0 > 11. < / RTI > 2. The MOF-alumina composite according to claim 1, wherein the chemical bond is at least one selected from the group consisting of covalent bond, ionic bond, hydrogen bond and coordination bond. 2. The MOF-alumina composite according to claim 1, wherein said particles of alumina have an average particle diameter of from 3 nm to 900 nm. 2. The MOF-alumina composite according to claim 1, wherein said composite has the form of spherical or similar spherical granules, granules, monoliths or honeycomb filters, injection-molded bodies, or coatings or films. A process for producing a MOF-alumina composite according to claim 1, comprising mixing, shaping and drying the hybrid nanoporous material (MOF) powder and the activated alumina powder. 6. The method of claim 5, wherein the MOF-alumina composite comprises:
(1) Hybrid nanoporous particles and activated alumina particles were mixed at a weight ratio of 2: 98 to 98: 2,
(2) molding or coating the resulting mixture on a support, and
(3) drying the resultant shaped body or coating at a temperature of from 5 to 80 DEG C, The activated alumina according to claim 5 or 6, wherein the activated alumina is alumina containing at least one element% of amorphous alumina selected from aluminum hydroxide or hydrated alumina, or is a composite particle composed of aluminum hydroxide-alumina , A method for producing a MOF-alumina composite. 6. The method according to claim 5 or 6, wherein the mixture of step (1) described above further comprises water, wherein the hybrid nanoporous material and alumina. A process for producing a MOF-alumina composite according to claim 5 or 6, wherein said complex is in the form of a spherical or pseudo spherical granule, a granule, a monolith or a honeycomb filter, an injection-molded article, . A method of using a MOF-alumina composite according to claim 1 or a MOF-alumina composite prepared according to the method of claim 5 as an adsorbent, a gas separation, a gas storage, a sensor, a membrane, a functional thin film, a catalyst or a catalyst carrier.

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