WO2016028087A1 - Microporous sp-copper silicate having plane quadrilateral cu(o)4 structure in which cu(o)4 unit is not linked by bridging oxygen, sp-copper silicate in which part of cu is substituted with one or more other metal atoms, and use thereof - Google Patents

Abstract

The present invention relates to: a copper silicate in which some or all of a first unit selected from the group consisting of Cu(O)₄, Cu(O)₅, and Cu(O)₆ and a second unit selected from the group consisting of Cu(O)₄, Cu(O)₅, and Cu(O)₆ are not linked by bridging oxygen; a copper silicate containing, among a group of units M_an consisting of M_an(O)₄, M_an(O)₅ and M_an(O)₆ (where n is an integer of 1 to 20, and M_a1, M_a2 . . . and M_an are different transition metals or main group metals), a first unit selected from a group of units where n is 1, a second unit selected from a group of units where n is 2 . . . and an n ^th unit selected from a group of units where n is n , wherein some or all of the units adjacent to each other are not linked by bridging oxygen; and a use thereof.

Description

Microporous SP-copper silicate having a planar quadrangle CU (O) 4 structure in which CU (O) 4 units are not linked by crosslinked oxygen, and SP-copperilicate in which a portion of the CU is substituted with at least one other metal atom, and Its use

The present invention relates to novel microporous copper silicates, novel microporous copper silicates in which a portion of the framework Cu is substituted with one or more other metals and their use.

The novel microporous copper silicate according to one embodiment of the invention was named SGU-29.

Typically, microporous metal silicate is a compound in which at least one metal and silicon form a microporous oxide. Microporous titanosilicates in which the metal is titanium (Ti) are used as various ion exchangers, photocatalysts, thermal catalysts, and adsorbents. Among them, microporous titanosilicate, called ETS-10, is widely used as a photocatalyst, a thermal catalyst, and an ion exchanger, and has excellent adsorption ability to lead (Pb), mercury (Hg), and cadmium (Cd) ions. Figure 1 shows a schematic diagram of titanosilicates of the ETS-10 structure. As shown in FIG. 1, ETS-10 has a quantum line in which Ti atoms (blue balls) are connected by an oxygen atom (red balls) to a unique silica skeleton (yellow bars: silicon atoms, red bars: oxygen atoms). wire, -O-Ti (O) ₄ -O-Ti (O) ₄ -O-), and these quantum wires are orthogonal to each other and arranged regularly. In titanosilicates of the ETS-10 structure, Ti atoms are surrounded by two oxygen atoms (red balls) on the quantum line and four oxygen atoms (red bars) on the silica skeleton to form an octahedral structure.

Instead of Ti of ETS-10, materials in which other metals have been partially or fully substituted have been known. For example, instead of Ti of ETS-10, there are modified ETS-10-based materials in which various kinds of metals such as Co, Ni, and Mn are substituted by about 10%. These modified ETS-10 materials differ from ETS-10 due to the substitution of some of the other metals, resulting in gas adsorption, ion exchange and catalytic properties. There is also a vanadate silicate called AM-6 in which all Ti atoms of ETS-10 are substituted with V atoms.

On the other hand, the inventors of the present invention is an octahedral microporous copper silicate (Tihedral type) in which all of the Ti of the ETS-10 is substituted with Cu, so that -O-Cu (O) ₄ -O-Cu (O) ₄ -O- quantum wires exist. OH-gurisilicate, named SCuS-10, has been patented for the material (FIG. 2) and its preparation (registered patent KR10-1243274). Here, Cu atoms are surrounded by two oxygen atoms (red balls) placed on a quantum line and four oxygen atoms (red bars) on a silica skeleton to form an octahedral structure.

It is an object of the present invention to provide a variety of microporous metal silicates, such as microporous copper silicates, of novel structures and novel components that can be used as adsorbents, ion exchangers, catalysts.

A first aspect of the invention provides a first unit selected from the group consisting of Cu (O) ₄ , Cu (O) ₅ , and Cu (O) ₆ and Cu (O) ₄ , Cu (O) ₅ , and Cu (O). It provides a microporous copper silicate characterized in that some or all of the second unit selected from the group consisting of ₆ ) is not connected by crosslinked oxygen.

A second aspect of the present invention provides a group of units consisting of M _an (O) ₄ , M _an (O) ₅ and M _an (O) ₆ , in which _an integer of n = 1 to 20, M _a1 , M _a2,. .., And M _an are different transition metals or main group metals), a first unit selected from the group of units having n = 1, a second unit selected from the group of units having n = 2,. And in the copper silicate containing the n-th unit selected from the group of units n = n, it provides a copper silicate characterized in that some or all of the adjacent units are not connected by cross-linked oxygen.

According to a third aspect of the present invention, there is provided a method for producing a microporous copper silicate in which some or all of the first unit, the second unit, and the nth unit are not connected with crosslinked oxygen according to the first or second aspect. Source; Transition or primary group metal source of the first unit; Transition or main group metal source of the second unit; … ; Transition or main group metal source of the nth unit; Alkali metal sources; Optionally a structurant; salt; And a first step of preparing water by mixing water; A second step of aging the mixture for 0 to 300 hours; And it provides a method for producing microporous copper silicate comprising a third step of heating for 1 to 300 hours at 50 ℃ to 300 ℃ in a pressure reactor.

A fourth aspect of the present invention provides a CO ₂ adsorbent comprising the microporous copper silicate according to the first or second aspect.

A fifth aspect of the present invention provides a NO adsorbent comprising the microporous copper silicate according to the first or second aspect.

A sixth aspect of the invention provides a heavy metal adsorbent comprising the microporous copper silicate according to the first or second aspect.

A seventh aspect of the present invention provides an inert gas adsorbent comprising the microporous copper silicate according to the first or second aspect.

An eighth aspect of the invention provides a catalyst comprising a microporous copper silicate according to the first or second aspect.

Hereinafter, the present invention will be described in detail.

The inventors have microporous OH- copper silicate (SCuS-10) in which some or all between the Cu (O) ₄ units and Cu (O) ₄ units if not put an organic or inorganic reducing agent required for the production because not lead to cross-linking oxygen It has been found that SP-copper silicates (eg, SGU-29) with planar or strained planar cubic Cu (O) ₄ structures can be produced reproducibly. In addition, even if an organic or inorganic reducing agent is used, when it is properly controlled, some or all of the Cu (O) ₄ unit and the Cu (O) ₄ unit are not connected to the crosslinked oxygen, so that the planar quadrilateral or distorted planar quadrilateral Cu ( It was found that a copper silicate having an O) ₄ structure can be prepared.

In general, microporous materials with nanopores are used as adsorbents for various gas molecules, ion exchangers for various metal ions, and catalysts for various chemical reactions. Ion exchange characteristics, catalyst characteristics for various catalytic reactions, and the like are different. In particular, if the transition state or the coordination state of the main group metal forming the skeleton of the microporous material is changed, the adsorption characteristics, ion exchange characteristics, and catalyst characteristics are greatly changed. In particular, when the coordination number of the transition metal constituting the skeleton of the microporous material is less than 6, the binding force with the adsorbed gas molecules is increased to compensate for the insufficient coordination water, thereby improving the adsorptive properties, and in particular, the preference for specific gas molecules. In addition, the catalytic efficiency and catalytic reaction selectivity for specific chemical reactions are increased.

Based on this reason, the inventors have _{- O -Cu (O) 4 -} O -Cu (O) 4 - O - , which exists proton microporous OH- copper silicate in Cu (SCuS-10) (O) 4 A microporous SP-copper silicate material was prepared for the first time in which some or all of the oxygen atoms linking the units were removed.

The structure of the microporous planar quadrilateral copper silicate (SGU-29) is shown in FIG. 3, and since there is no oxygen atom directly connecting Cu and Cu atoms in the SCuS-10 structure, -O-Cu (O) ₄ -O-Cu (O) ₄ -O- mothayeo fulfill the proton Cu atoms silica backbone and only the four oxygen atoms bonded to the plane quadrangle exists in the (square planar) structure that _{is, Cu (O) 4 Cu (} O) 4 Cu (O) _Will be ₄

In addition, the present inventors also prepared for the first time a microporous SP-copper silicate in which a part of copper atoms in the microporous SP-copper silicate (SGU-29) is substituted with one or more metals (FIG. 4) or two or more metals (FIG. 5). It was.

Furthermore, the present inventors have found that heavy metals such as carbon dioxide (CO ₂ ), nitrogen monoxide (NO), inert gas, cadmium (Cd), lead (Pb), etc., because the microporous SP-copper silicate (SGU-29) has a four-coordinate copper atom. It was found to be excellent in performance as an adsorbent of ions. In particular, even if there is moisture, carbon dioxide adsorption is possible, and the structure is not destroyed by moisture, so it can be reused, and desorption is possible through high temperature or vacuum, and CO ₂ , CO, CH ₄ , N ₂ , O ₂ , H _2, etc. It was found that the adsorption selectivity for CO ₂ was excellent even in a mixed gas having various molecules together.

On the other hand, microporous SP-copper silicate (SGU-29) also substitutes some copper atoms with one or more other metals M (M = Ti, Cr, Mn, Fe, Co, Ni, Zn, Nb, Mo, W, etc.). In this case, M (O) _4, M (O) ₅ , M (O) _6, etc. may be substituted according to the coordination number of the substituted M oxygen, and the other metal M (O) ) ₄ , M (O) ₅ , M (O) _6, etc., and the Cu (O) ₄ unit is Cu (O) ₅ form with some square pyramidal structure and Cu (octahedral) structure with Cu ( O) It may have a structure containing ₆ structures.

Microporous SP-copper silicate substituted with dissimilar metal M (SGU-29) is expected to have significantly different gas adsorption, ion exchange, and catalytic properties compared to the parent microporous SP-copper silicate. do.

The present invention is based on this finding.

The microporous copper silicate according to the present invention comprises a first unit selected from the group consisting of Cu (O) ₄ , Cu (O) ₅ , and Cu (O) ₆ and Cu (O) ₄ , Cu (O) 5, and Cu. Some or all of the second units selected from the group consisting of (O) ₆ are not linked with crosslinked oxygen.

The microporous copper silicate according to the present invention has a planar quadrilateral or distorted planar quadrilateral Cu (O) ₄ structure because some or all of the Cu (O) ₄ units and Cu (O) ₄ units are not connected by crosslinked oxygen. It can have

The microporous copper silicate according to the present invention may have a planar quadrilateral or a distorted planar quadrilateral Cu (O) ₄ structure instead of the octahedral TiO ₆ of the ETS-10 structure.

In addition, the copper silicate according to the present invention does not form a quantum wire because some or all of the first unit and the second unit is not connected by crosslinked oxygen, or quantum wires present in the same plane are discontinuously present. For example, it may have a very short quantum wire structure.

Newly prepared SP-copper silicate (SGU-29) according to one embodiment of the present invention 1) has the same silica skeleton as the ETS-10 structure, but instead of the tetrahedral type TiO ₆ of the ETS-10 structure, planar quadrilateral Cu (O) As a material having _four structures,

2) Cu (O) ₄ plane quadrilateral unit instead of -O-Ti (O) ₄ -O-Ti (O) ₄ -O-Ti (O) ₄ -O- quantum wire of ETS-10 structure Is a structure in which Cu (O) ₄ tetragonal monomers, which are not directly cross-linked with oxygen, are repeatedly present between and Cu (O) ₄ tetragonal monomers.

3) The X-ray powder diffraction pattern is similar to ETS-10, but may have a structure in which diffraction peaks (FIG. 6) are moved at slightly higher angles (FIG. 7). However, the copper silicate of the present invention is not limited thereto.

In the microporous copper silicate according to the present invention, a part or the whole of the second unit is M _a1 (O) ₄ , M _a1 (O) ₅ , M _a1 (O) ₆ , M _a2 (O) ₄ , M _a2 (O) ₅ , M _a2 (O) ₆ . M _an (O) ₄ , M _an (O) ₅ , M _an (O) _6, or a combination thereof ( _an integer from n = 1 to 20, M _a1 , M _a2 , ..., and M _an is Cu Other transition metals or main group metals).

At this time, M _a1 , M _a2 ,..., And M _an may each independently be Ti, Cr, Mn, Fe, Co, Ni, Zn, Nb, Mo, and W.

In one embodiment, the microporous copper silicate according to the present invention further comprises some or all of the copper atoms as a kind of other metal atoms such as Ti, Cr, Mn, Fe, Co, Ni, Zn, Nb, etc. It may be substituted with a dissimilar metal atom.

In another embodiment, the microporous copper silicate according to the present invention is a part or all of the copper atoms of two or more different metal atoms, such as two or more kinds (Ni, Co), (Ni, Cr), (Ni Or two or more heterometal atoms such as (Ti), (Co, Cr), (Co, Ti), (Ti, Nb) may be substituted at the same time.

Further, according to the present invention, a group of monomers consisting of M _an (O) ₄ , M _an (O) ₅ and M _an (O) ₆ (M _an integer of n = 1 to 20, M _a1 , M _a2 , .. And M _an is a transition metal or main group metal different from each other, a first unit selected from the group of units having n = 1, a second unit selected from the group of units having n = 2,. Copper silicate containing the n-th unit selected from the group of units of n = n is characterized in that some or all of the adjoining units are not connected by cross-linked oxygen.

At this time, M _a1 , M _a2 ,..., And M _an may be each independently Cu, Ti, Cr, Mn, Fe, Co, Ni, Zn, Nb, Mo, and W.

For example, some or all of the M _a1 (O) ₄ units and the M _a1 (O) ₄ units or the M _a2 (O) ₄ units are not linked by cross-linked oxygen, so that they are either planar or deformed planar quadrilaterals M _a1 ( O) ₄ or M _a2 (O) _{4 It} may have a structure.

In the first and second unit-containing microporous silicates according to the present invention, some or all of the M _a1 (O) ₄ units and the M _a1 (O) ₄ units or the M _a2 (O) ₄ units are not linked by crosslinked oxygen. So that it may have a planar quadrilateral or a deformed planar quadrilateral M _a1 (O) ₄ or M _a2 (O) ₄ structure.

Further, the first unit and the second unit-containing microporous copper silicate according to the present invention have a planar quadrilateral or a distorted planar quadrilateral M _a1 (O) ₄ structure instead of the tetrahedral TiO ₆ having an ETS-10 structure. Can be.

The microporous copper silicate according to the present invention does not form a quantum wire because some or all of the adjacent units are not connected by bridging oxygen, or have a structure in which quantum wires present on the same plane are discontinuously present. Can be.

According to the present invention, a method of preparing a microporous copper silicate in which some or all of the first unit, the second unit, and the n-th unit is not connected with crosslinked oxygen,

Si source; Transition or primary group metal source of the first unit; Transition or main group metal source of the second unit; … ; Transition or main group metal source of the nth unit; Alkali metal sources; Optionally a structurant; salt; And a first step of preparing water by mixing water;

A second step of aging the mixture for 0 to 300 hours; And

And a third step of heating at 50 ° C. to 300 ° C. for 1 to 300 hours in a pressure reactor.

According to the present invention, the method for producing microporous copper silicate, in which part or all of the units are not connected by crosslinked oxygen, does not use an organic or inorganic reducing agent. However, it is also within the scope of the present invention when a small amount of reducing agent is used, unless some or all of the units are linked by crosslinked oxygen.

In the first step, each of the components may be mixed simultaneously or sequentially, and may be performed under heating, cooling, reflux, and / or vacuum if necessary, but is not limited thereto.

The pH of the mixture of the first step is preferably 8 to 12. Sulfuric acid can also be used for pH adjustment.

The mixture may be aged before hydrothermal reaction. The aging process can be carried out, for example, by stirring the reaction mixture at room temperature or above or below, and by this aging process the reaction mixture can be transformed into a gel state. The second step may be performed by leaving it at room temperature, and may be omitted.

The hydrothermal reaction of the third step may be performed by introducing the reaction mixture into a high pressure reactor such as an autoclave and heating to a constant temperature in a closed state.

The molar ratio of the Si source: the metal source: the base: the alkali metal source: sulfuric acid: water (H ₂ O) is from 1 to 10: 1 to 10: 1 to 20: 1 to 20: 0 to 0.5: 30 To 700.

The Si source is selected from the group consisting of silicate salts of alkali or alkaline earth metals, colloidal silica, silica hydrogels, silicic acid, fumed silica, tetraalkylorthosilicates, silicon hydroxides, and combinations thereof. Can be. The Si source may preferably be an aqueous solution in which silica particles of size 100 microns are dispersed at 1 nanometer in ludox or colloidal state, and may be Na ₂ SiO ₃ or the like.

The metal source may be a salt such as a halogen salt, oxide, sulfide, phosphide, perchlorate, chloride, acetate or mixtures thereof.

When the transition metal is copper, the source of copper may be copper salt, copper oxide, copper sulfide, copper phosphide, copper perchlorate, copper acetate, and non-limiting examples include CuSO ₄ , Cu (OAc) ₂ , CuX ₂ ( X = F, Cl, Br, I), CuO, Cu ₂ O, Cu (NO ₃ ) ₂ , Cu (ClO ₄ ) _2, and the like.

When manufacturing the copper silicate substituted by one kind of dissimilar metal atom, a copper supply source and one kind of dissimilar metal source can be used as a metal supply source.

When producing copper silicates substituted with two or more dissimilar metal atoms, a copper source and two dissimilar metal sources such as dissimilar metal-A sources, dissimilar metals A -B source or a dissimilar metal-C source can be used.

Salt is M'X (M '= Li, Na, K, Rb, Cs; X = F, Cl, Br, I) or M'X ₂ (M' = Mg, Ca, Sr, Ba; X = F, Cl, Br, I) or mixtures thereof.

In the present invention, the alkali metal includes an alkaline earth metal, and non-limiting examples of alkali metals include Li, Na, K, Rb, Cs, and the like. Non-limiting examples of alkaline earth metals include Be, Mg, Ca, Sr, Ba and the like.

The alkali metal source may be M “OH (M“ = Li, Na, K, Rb, Cs) or M “(OH) ₂ (M“ = Be, Mg, Ca, Sr, Ba) or mixtures thereof.

Structure-forming agent is also put should be put, non-limiting examples of _{(C n H 2n + 1)} 4 N + OH -, ( wherein, n = 1 to _{30), Ar 4-n R} n N + OH - (Ar = aryl, R = hydrogen or _{C 1 ~ 4 alkyl), R} 1 R 2 R 3 R 4 N + OH - and the like ^{_{-, Ar 1 Ar 2 Ar 3}} Ar 4 N + OH. Preference is given to tetra alkyl ammonium hydroxides such as Tetramethylammonium hydroxide (TMAOH).

It is preferable to further include a seed crystal before the third step. In this case, the seed may be OH- copper silicate, SP- copper silicate (SG-29), AM-6, or ETS-10 according to the present invention.

Since the copper silicate according to the present invention is a microporous material, not only can be used as various thermal catalysts and photocatalysts, but also has a good preference for a specific molecule or ion, so that only a specific molecule from a mixture containing a specific molecule or a mixture containing a specific ion can be used. Alternatively, it may be used as an adsorbent and an ion exchanger capable of selectively adsorbing only specific ions.

Specifically, the silicate according to the present invention or the silicate in which some or all of the first unit, the second unit, and the n-th unit are not connected by crosslinked oxygen is oxygen dioxide, heavy metal, nitrogen monoxide, inert gas. Strongly adsorbs. In particular, even when the water absorption of carbon dioxide is excellent in the high selectivity of CO _2, CO, CH ₄ of CO _2. In addition, the adsorption amount per unit volume is large, the desorption is possible at a high temperature of 150 ~ 300 ℃, and even desorption is possible by flowing nitrogen gas in the vacuum can be reused.

Furthermore, mercury and lead are not released when adsorbed.

Thus, the copper silicate according to the present invention can be used as a selective gas adsorbent, selective ion exchanger, molecular separation membrane, for example, carbon dioxide adsorbent, carbon dioxide adsorbed selectively in the mixed gas or air containing carbon dioxide, is released after burning fossil fuel fuel It can be used as carbon dioxide adsorption, nitrous acid adsorption, carbon dioxide separation membrane, nitrous acid separation membrane, gas separation membrane, inert gas adsorbent, heavy metal adsorbent or ion exchanger in the exhaust gas.

Non-limiting examples of the inert gas in the inert gas adsorbent include He, Ar, Kr, Xe and the like.

In addition, the silicates according to the present invention or silicates in which some or all of the first unit, the second unit, and the n-th unit are not linked by crosslinked oxygen can be used as a selective adsorbent for benzene.

Industrially, cyclohexane is produced by hydrogenation of benzene using a hydrogenation catalyst such as nickel or palladium. The cyclohexane thus prepared is converted to cyclohexanone and eventually used as a raw material of ε-caprolactam, adipic acid, hexamethylenediamine, nylon such as 6-nylon, 6,6-nylon. Cyclohexane's own use is mainly a cleaning liquid or an adhesive in an organic solvent state. It is also used as a test gas for gas masks.

Copper silicates according to the present invention or silicates according to the present invention in which some or all of the first unit, the second unit, and the nth unit are not linked by crosslinked oxygen, have a selective adsorption capacity for benzene to form cyclohexane from benzene. Only benzene can be selectively removed from the mixture of benzene and cyclohexane obtained in the manufacturing process.

In particular, in the process of hydrogenating benzene to obtain cyclohexane and then converting it to nylon, when benzene is present together with the cyclohexane as a raw material, the conversion efficiency of nylon may be reduced. Therefore, the copper silicate according to the present invention or a silicate in which part or all of the first unit, the second unit, and the n-th unit according to the present invention are not linked by crosslinked oxygen is adsorbed and removed only benzene, and then cyclohexane is nylon. Conversion may lead to increased nylon productivity.

Accordingly, the present invention relates to a mixture comprising benzene with a silicate according to the present invention or a silicate in which some or all of the first, second, and n-th monomers according to the present invention are not linked by crosslinked oxygen. It is possible to provide a method for removing adsorption of benzene comprising the step of contacting.

In addition, the present invention is a step a to obtain cyclohexane by reacting benzene under a hydrogenation catalyst; The product of step a is contacted with a copper silicate according to the present invention or a silicate in which part or all of the first unit, the second unit, and the nth unit according to the present invention are not linked with crosslinked oxygen to adsorb and remove benzene. Step b; And it can provide a method for producing nylon comprising a step c to convert the cyclohexane obtained in step b to nylon.

The adsorbent according to the present invention may be in the form of a powder, pellet, foam, film or a fixed bed column filled with the adsorbent, and may be in the form of a molded article to which the adsorbent is attached. The molding may be made of fiber, including clothing.

Furthermore, the copper silicate according to the present invention or the microporous copper silicate in which part or all of the first unit, the second unit, and the n-th unit according to the present invention are not linked with crosslinked oxygen may reduce carbon dioxide contained in the pores. It can also be used as a thermal catalyst and a photocatalyst of various chemical reactions.

Further, the copper silicate according to the present invention or the microporous copper silicate in which part or all of the first unit, the second unit, and the n-th unit according to the present invention are not linked with crosslinked oxygen may be used as a catalyst for the dehydrogenation reaction of alcohol. Can be.

As used herein, the term "dehydrogenation of alcohol" refers to a reaction in which hydrogen is released from an alcohol molecule, and is also referred to as a hydrogen dehydration reaction of an alcohol. This is a kind of oxidation reaction, and can be called a reverse reaction of hydrogenation.

In one aspect, the copper silicate according to the present invention or the microporous copper silicate in which some or all of the first unit, the second unit, and the n-th unit according to the present invention are not connected with crosslinked oxygen is represented by the following Scheme 1 It can be used as a catalyst for the dehydrogenation reaction of the secondary alcohol, in which a common cocatalyst or additive can be used. In addition, the microsilicate copper silicate according to the present invention or the microporous copper silicate in which some or all of the first unit, the second unit, and the nth unit is not connected with crosslinked oxygen is used as a catalyst for the dehydrogenation reaction of the secondary alcohol. May also be used. The dehydrogenation of the alcohol may be a vapor phase reaction in which a gaseous reactant reacts under a catalyst in solid form, or a liquid phase reaction in which a reactant dissolved or dispersed in a solvent reacts under a catalyst in solid form. It may be.

Scheme 1

Copper silicates according to the present invention or microporous copper silicates in which part or all of the first, second and nth units are not linked by crosslinked oxygen according to the present invention can be used as catalysts for dehydrogenation of alcohols. Specific examples of the alcohol include, but are not limited to, ethanol, propanol, cyclohexanol, and the like. For example, it can be converted to acetaldehyde and hydrogen when using ethanol, to acetone and hydrogen when using isopropyl alcohol, and to cyclohexanone and hydrogen when using cyclohexanol. .

The present invention has found copper silicates and substituents thereof in which some or all of the Cu (O) ₄ units and Cu (O) ₄ units are not linked by crosslinked oxygen, and the copper silicates of the present invention are oxygen dioxide, heavy metals, monoxide nitrogen, as well as excellent as an adsorbent of an inert gas, is high, even if a water excellent in carbon dioxide adsorption, and the choice of CO _2, CO, CH ₄ of CO ₂ also, a large amount per unit volume of the adsorption, desorption is to be under a high-temperature or vacuum It is reusable and furthermore it does not release when it adsorbs mercury and lead.

1 is a schematic diagram of a microporous titanium silicate having an ETS-10 structure.

Ti atoms (blue balls) form a quantum wire connected to a microporous silica skeleton (yellow bars: silicon atoms, red bars: oxygen atoms) by oxygen atoms (red balls). It is surrounded by two oxygen atoms (red balls) placed on a line and four oxygen atoms (red bars) on a silica skeleton to form an octahedral structure.

2 is a schematic diagram of a microporous OH-copper silicate having an ETS-10 structure.

Cu atoms (green balls) form a quantum wire connected to the microporous silica backbone (yellow bars: silicon atoms, red bars: oxygen atoms) by oxygen atoms (red balls). It is surrounded by two oxygen atoms (red balls) placed on a line and four oxygen atoms (red bars) on a silica skeleton to form an octahedral structure.

3 is a schematic diagram of microporous SP-copper silicate (SGU-29).

It is a structure in which Cu atoms (green balls) are arranged in a microporous silica skeleton (yellow bar: silicon atom, red bar: oxygen atom), but there is no oxygen atom between Cu atoms, thereby forming a quantum wire. Cu atoms are surrounded by only four oxygen atoms (red bars) on the silica backbone to form a square planar or distorted planar quadrilateral structure.

4 is a schematic diagram of a microporous SP-copper silicate (SGU-29) containing a dissimilar metal element.

Cu atoms (green balls) and other metal atoms A are aligned in the microporous silica backbone (yellow bars: silicon atoms, red bars: oxygen atoms), but there are no oxygen atoms between the Cu and other metal atoms, so the quantum wire As a non-structured structure, Cu atoms and other metal atoms A are surrounded by only four oxygen atoms (red bars) on the silica skeleton to form a square planar or distorted planar quadrilateral structure. Depending on the type, other metal atoms may have an octahedral structure.

5 is a schematic diagram of SP-copper silicate including two or more kinds of dissimilar metal elements.

Cu atoms (green balls) and other metal atoms A and B are aligned in the silica backbone (yellow bar: silicon atom, red bar: oxygen atom), but there is no oxygen atom between Cu and other metal atoms A and B As a structure that does not form a quantum wire, Cu atoms and other metal atoms A and B are surrounded by only four oxygen atoms (red bars) on a silica skeleton, so that they are square planar or distorted. Planar quadrilateral structure. Depending on the type of other metal atoms, the other metal atoms may have an octahedral structure, so that adjacent copper atoms may also have a Cu (O) ₅ form and an octahedral structure, depending on the type of other metal atoms. It may have a structure containing a Cu (O) ₆ structure that is a type structure.

FIG. 6 shows the XRD patterns of microporous SP-copper silicate (SGU-29) and ETS-10 molecular sieve.

Figure 7 shows the XRD angle and d-spacing value of the microporous SP-copper silicate and ETS-10 molecular sieve.

8 compares the Raman spectrum of the microporous SP-copper silicate prepared in Example 1 with the ETS-10 molecular sieve.

9 is a SEM photograph of the microporous SP-copper silicate prepared in Example 1. FIG.

10 is a SEM photograph of the microporous Ti-containing SP-copper silicate (Ti; 47%) prepared in Example 2. FIG.

11 is an EDS spectrum of Ti (47%)-SP-copper silicate prepared in Example 2. FIG.

12 is an SEM photograph of Ni (26%)-SP-copper silicate prepared in Example 3. FIG.

FIG. 13 is an EDS spectrum of Ni (26%)-SP-coppersilicate prepared in Example 3.

FIG. 14 shows breakthrough results of a CO ₂ -N ₂ mixture, a CO ₂ -CH ₄ mixture, and a CO ₂ -H ₂ mixture using SP-copper silicate prepared in Example 1. FIG.

15 is a result of comparing the selectivity of Pb ²⁺ , Cd ²⁺ , Cu ²⁺ ions using SP-copper silicate prepared in Example 1 with other materials.

16 shows the results of benzene adsorptive separation experiments using SP-copper silicate prepared in Example 1. FIG.

17 is a result of investigating the dehydrogenation conversion rate of alcohol using various copper silicates according to the present invention.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are intended to illustrate the present invention more specifically, but the scope of the present invention is not limited by these examples.

Example 1 Synthesis of Copper Silicate

Ludox brand of water soluble colloidal silica (10 nm) was used.

40 wt.% Water soluble colloidal silica (12.7 g), 25% TMAOH (10 g), NaOH (1.82 g), NaCl (8 g), KCl (3 g), CuSO ₄ (3.58 g), water (20-70 g) was added and mixed with stirring to prepare a synthetic gel. Aged at room temperature for 14 hours, and heated at 210 ℃ for 24 hours using a pressure reactor. The synthesized copper silicate was washed with a sufficient amount of deionized distilled water and dried at 100 ° C. for 1 hour.

The SEM photograph of the obtained copper silicate is shown in FIG. 9. In addition, the obtained copper silicate sample can be represented by the general formula (Na _x K _y ) TM ACuSi ₅ O ₁₂ nH ₂ O (x + y = 1).

The Raman spectrum of the obtained copper silicate is shown in FIG. 8, from which it can be seen that the copper silicate is partially or completely disconnected from copper and oxygen.

Example 2: Synthesis of Ti (47%)-SP-Curisilicate

Na ₂ SiO ₃ (9.4 g), 25% TMAOH (3 g), NaOH (0.5 g), NaCl (4.6 g), KCl (1.5 g), CuSO ₄ (1.25 g), Ti (iPrO) ₄ (0.5 g ), And copper silicate was synthesized in the same manner as in Example 1, except that water (10-40 g) was added thereto and mixed with stirring.

SEM images of the obtained Ti (47%)-copper silicates are shown in FIG. 10. In addition, the obtained copper silicate sample may be represented by the general formula (Na _x K _y ) TMA (Ti _0.47 Cu _0.53 ) Si ₅ O _12.47 nH ₂ O (x + y = 1). And the EDS spectrum of the prepared Ti (47%)-copper silicate is shown in FIG.

Example 3: Synthesis of Ni (26%)-SP-Curisilicate

40 wt.% Water soluble colloidal silica (12.7 g), 25% TMAOH (10 g), NaOH (2.6 g), NaCl (8 g), KCl (3 g), NiCl (1.0 g), CuSO ₄ (4.5 g) , Water (40-70 g) was added and mixed with stirring to prepare a synthetic gel. Aged at room temperature for 22 hours, and heated at 210 ℃ for 24 hours using a pressure reactor. The subsequent procedure is the same as in Example 1.

SEM pictures of the obtained Ni (26%)-SP-coppersilicate are shown in FIG. 12. In addition, the obtained copper silicate sample can be represented by the general formula (Na _x K _y ) TM ACuSi ₅ O ₁₂ nH ₂ O (x + y = 1). And the EDS spectrum of the prepared Ni (26%)-SP- copper silicate is shown in FIG.

Example 4: Breakthrough Test

In a glove-filled glove box filled with 1 g of SP-copper silicate in a stainless steel tube with an inner diameter of 4 mm and an outer diameter of 6.4 mm, it was brought out of the glove box and connected to a breakthrough device. After evacuating the inside, a 1: 9 mixture of CO ₂ and nitrogen, CO ₂ and oxygen, CO ₂ and methane is passed at a rate of 3 mL per minute. Plot over time. 14 shows breakthrough results of different materials under the same conditions.

Example 5: Heavy Metal Ion Exchange Experiment

Prepare 50 mL of solutions with concentrations of 1, 5, 10, 20, 40, 60, 80, and 100 ppm of each heavy metal ion, add 50 mg of SP-copper silicate to each solution, and mix with a magnetic stirrer for the required period. gave. After a certain period of time, the supernatant obtained through centrifugation was examined for the concentration change of the corresponding heavy metal ion using ICP-MS. The result is shown in FIG.

Example 6 Benzene Adsorption Separation Experiment

In a glove-filled glove box filled with 1 g of SP-copper silicate in a stainless steel tube with an inner diameter of 4 mm and an outer diameter of 6.4 mm, it was brought out of the glove box and connected to a breakthrough device. After allowing the interior to become a vacuum, a mixture of 5% benzene and 95% cyclohexane on a molar basis was passed through the SP-gurisilicate-filled tube at a rate of 3 mL per minute as shown in FIG. Was quantified by gas chromatography and plotted over time. The results are shown in FIG.

16, it was confirmed that the copper silicate according to the present invention can obtain cyclohexane having a purity of 100% as a material passing through the copper silicate by adsorbing only benzene for a predetermined time.

Example 7 Experiment of Dehydrogenation of Alcohol

Cu-SiO ₂ , Cu / Cu-silicate Ce / Cu-silicate and Au / Cu / Cu-silicate, respectively, as catalysts were used to convert ethanol to acetaldehyde and hydrogen by dehydrogenation at 300 ° C. The conversion of acetaldehyde of ethanol for each catalyst was investigated. The results are shown in FIG.

17, it can be seen that the copper silicate according to the present invention exhibits a conversion rate equivalent to or better than that of the existing Cu-SiO ₂ catalyst.

Claims (27)

1. _{Cu (O) 4, Cu (} O) 5, and a Cu (O) from the group consisting of: ₆ and the selected first monomer _{Cu (O) 4, Cu (} O) 5, and a Cu (O) _6, selected from the group consisting of Microporous copper silicate, characterized in that some or all of the second unit is not connected by cross-linked oxygen.
2. 2. The copper of claim 1, wherein some or all of the Cu (O) ₄ units and the Cu (O) ₄ units are not connected with crosslinked oxygen and thus have a planar quadrilateral or distorted planar cubic Cu (O) ₄ structure. Silicate.
3. The structure of claim 1, wherein some or all of the first unit and the second unit are not connected to each other by crosslinked oxygen, thereby forming a structure in which a quantum wire does not form or discontinuously exists in the same plane. Microporous copper silicate characterized by having.
4. The method of claim 1, wherein a portion of the second unit is M _a1 (O) ₄ , M _a1 (O) ₅ , M _a1 (O) ₆ , M _a2 (O) ₄ , M _a2 (O) ₅ , M _a2 (O ) ₆ . M _an (O) ₄ , M _an (O) ₅ , M _an (O) _6, or a combination thereof ( _an integer from n = 1 to 20, M _a1 , M _a2 , ..., and M _an is Cu Copper silicate, characterized in that substituted by a different transition metal or main group metal).
5. The copper silicate according to claim 4, wherein M _a1 , M _a2 , ..., and M _an are each independently Ti, Cr, Mn, Fe, Co, Ni, Zn, Nb, Mo, W. 6.
6. The copper silicate according to claim 1, wherein the copper silicate has a planar quadrilateral or a distorted planar quadrilateral Cu (O) ₄ structure instead of the tetrahedral TiO _{6 having an} ETS-10 structure.
7. A group of monomers consisting of M _an (O) ₄ , M _an (O) ₅ and M _an (O) _6, where M _an integer from n = 1 to 20, M _a1 , M _a2 , ..., and M _an are Transition metals or main group metals different from each other), a first unit selected from a group of units having n = 1, a second unit selected from a group of units having n = 2,. And a copper silicate containing an n-th unit selected from the group of units where n = n,

   Copper silicate, characterized in that some or all of the units adjacent to each other are not connected by cross-linked oxygen.
8. 8. The copper of claim 7, wherein some or all of the adjacent units are not connected to each other by cross-linked oxygen, thereby forming a structure in which quantum wires do not form or discontinuously present quantum wires present on the same plane. Silicate.
9. 8. The method of claim 7, wherein M _a1 , M _a2 , ..., and M _an are each independently selected from the group consisting of Cu, Ti, Cr, Mn, Fe, Co, Ni, Zn, Nb, Mo, and W Copper silicate characterized by.
10. The plane of claim 7, wherein some or all of the M _a1 (O) ₄ units and the M _a1 (O) ₄ units or the M _a2 (O) ₄ units are not linked with crosslinked oxygen, thereby making a plane quadrilateral or distorted plane. A copper silicate characterized by having a quadrilateral M _a1 (O) ₄ or M _a2 (O) ₄ structure.
11. 8. The copper silicate according to claim 7, wherein the copper silicate has a planar quadrilateral or a distorted planar quadrilateral M _a1 (O) ₄ structure instead of the tetrahedral TiO _{6 having an} ETS-10 structure.
12. A method for producing a microporous copper silicate according to any one of claims 1 to 11, wherein some or all of the first unit, the second unit, and the nth unit are not linked by crosslinked oxygen.

    Si source; Transition or primary group metal source of the first unit; Transition or main group metal source of the second unit; … ; Transition or main group metal source of the nth unit; Alkali metal sources; Optionally a structurant; salt; And a first step of preparing water by mixing water;

    A second step of aging the mixture for 0 to 300 hours; And

    Method for producing a microporous copper silicate, characterized in that it comprises a third step of heating for 1 to 300 hours at 50 ℃ to 300 ℃ in a pressure reactor.
13. 13. The method of claim 12, wherein the pH of the mixture of the first step is 8-12.
14. 13. The method of claim 12, further comprising seed crystals prior to the third step.
15. 15. The method of claim 14, wherein the seed is copper silicate, SP-copper silicate, AM-6 or ETS-10 prepared by the process of claim 12.
16. The molar ratio of the Si source: the metal source: the base: the alkali metal source: water (H ₂ O) is from 1 to 10: 1 to 10: 1 to 20: 1 to 20: 30. Microporous copper silicate production method characterized in that from to 700.
17. The method of claim 12 wherein the Si source is a silicate salt of an alkali metal or alkaline earth metal, colloidal silica, silica hydrogel, silicic acid, fumed silica, tetraalkylorthosilicate, silicon hydroxide and their Microporous copper silicate manufacturing method characterized in that selected from the group consisting of a combination.
18. 13. The method of claim 12, wherein the metal source comprises salts, oxides, sulfides, phosphides, perchlorates, chlorides, acetates or mixtures thereof.
19. The method of claim 12, wherein the salt is M'X (M '= Li, Na, K, Rb, Cs, X = F, Cl, Br, I) or M'X ₂ (M' = Mg, Ca, Sr , Ba, X = F, Cl, Br, I) or a mixture thereof, characterized in that it comprises a microporous copper silicate.
20. The method of claim 12, wherein the alkali metal source is M “OH (M“ = Li, Na, K, Rb, Cs) or M “(OH) ₂ (M“ = Be, Mg, Ca, Sr. Ba) or Method for producing a microporous copper silicate, characterized in that a mixture thereof.
21. CO ₂ adsorbent comprising the microporous copper silicate according to any one of claims 1 to 11.
22. The NO adsorbent containing the microporous copper silicate as described in any one of Claims 1-11.
23. A heavy metal adsorbent comprising the microporous copper silicate according to any one of claims 1 to 11.
24. An inert gas adsorbent comprising the microporous copper silicate according to any one of claims 1 to 11.
25. A benzene adsorbent comprising the microporous copper silicate according to any one of claims 1 to 11.
26. A catalyst comprising the microporous copper silicate according to any one of claims 1 to 11.
27. 27. The catalyst of claim 26 which is a catalyst for dehydrogenation of alcohols.

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