JPH03505443A - A method of removing organic hydrolysis by-products by treatment with an organic hydrolyzable polymeric chalcogenide precursor and sandwiching the polymeric chalcogenide between metal chalcogenides in an organic swelling layer. - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed description of the invention] Organic hydrolysis is achieved by treatment with an organic hydrolyzable polymeric chalcogenide precursor. Water decomposition by-products are removed and the polymeric chalcogenide is converted into an organic swollen layer of metal chalcogenide. The present invention is a method of sandwiching a layered metal containing a leaf-shaped polymeric chalcogenide between the layers. The present invention relates to a method for producing chalcogenide. In one embodiment, the present invention provides for glabellar lobe Multilayer metal oxide containing flaky metal oxide For example, multilayer containing flaky silica between the layers Regarding titanium oxide. For the purposes of this invention, the term "metal" refers to the elemental working element, silicon. It can be considered to include elements such as phosphorus, phosphorus, and arsenic.

Many layered materials with three-dimensional structures exhibiting their strongest chemical bonds in only two dimensions It has been known. In such materials, stronger chemical bonds are formed in a two-dimensional plane. A three-dimensional solid is formed by laying such planes on top of each other. formed by However, the interaction between the planes is due to the chemistry that holds the individual planes together. weaker than a bond. Weak bonds are generally caused by attractive forces between layers, e.g. van der Waals forces, electrostatic arises from physical interactions and hydrogen bonds. The multilayer structure allows only van der Waals forces to pass through. In such cases, with electrically neutral sheets interacting with each other, the plane becomes When the layers slide over each other without encountering the energy barrier created by the bond between the layers, The smoothness of the image becomes clear. Graphite is an example of such a material. many clay objects The layers of high-quality silicates interact with each other due to electrostatic attraction mediated by ions located between the layers. Retained. In addition, hydrogen bond interactions are directly induced between adjacent complementary sites on top of each other. It can be mediated by epithelial or interlamellar binding molecules.

Layered materials such as clays can be modified to increase their surface area. On the bone, la The distance between layers can be adjusted using various swelling agents such as water, ethylene glycol, and amines. , is substantially increased by the absorption of ketones etc., which enters the interlamellar space and Press the layers apart. However, the space between the lamellae of such a multilayer material is Such molecules are removed by exposing the clay to high temperatures, for example. Layered materials are suitable for use in chemical processes involving even moderately harsh conditions. do not have.

The degree of separation between layers is a basis also known as "repeat distance" or "d-spacing". To determine the interplanar spacing of can.

These values are, for example, the distance between the largest edge of one layer and the largest edge of its adjacent layer. Show distance. If the layer thickness is known, the interlayer spacing is It is found by subtracting the layer thickness from the distance.

Ab-ade stocks provide a layered material with increased interlayer distance that has thermal stability is employed to do so. Multilayer technology uses inorganic "pillars" to support layers of multilayer materials. It relies on the introduction of ``agents''.

A layered metal chalcogenide material with good thermal stability is disclosed in European Patent Publication No. 0205 It can be produced by the method described in No. 711. Method of swollen layered material It is a cation that exchanges with the leaflet-like cation between the layers in order to Organic compounds such as ammonium in n-alkaline or organic compounds capable of forming cations For example, a loalkylamine can remove leaf-like cations between the layers associated with it. 4 = 5-12 to 15.20 to 33.38 to 5 1. Single-layer chalco of at least one element having the number of atoms of 56 to 83 and 90 or more It consists of treating a genide such as oxide. Interlaminar lobed polymeric calco -conversion to tetraethylorthosilicate, for example, by electricity. A neutral compound is then applied to the layer of swollen layered chalcogenide. transformation The compound then forms interlaminar lamellar polymeric chalcogenides, e.g. by hydrolysis. to form a layered material.

In the past, such layered materials formed columns under ambient temperature and pressure conditions. Conversion to polymeric chalcogenide by hydrolysis to form the product 5. A method of bringing an electrically neutral organic compound into contact with an organic swollen multilayer material. Manufactured by. There are also organic swollen compounds such as belobsite-related layered metal oxides. It has been found that the layered material is demagnetized or impossible to sandwich in this manner.

These materials also often require long periods of time to convert to polymeric chalcogenides. However, the columnar products formed only indicate the adsorption capacity and surface area after calcination. stomach. A multilayered material comprising interlaminar lamellar or interlaminated polymeric chalcogenides comprises: We now know that it can be manufactured from layered materials that are difficult to process using conventional techniques. I was taken out. This method is (-A layer of organic multi-layered metal chalcogenide is formed by hydrolysis into a polymeric form. Organic hydrolyzable polymeric chalcogenide precursors that can be converted to chalcogenides and 伽）　Organic hydrolysis from the reaction system than occurs under external conditions, i.e. room temperature and atmospheric pressure. The compound is added to the polymeric cartilage in the form of leaflets under conditions that promote faster removal of by-products. Polymeric chalcogenides are converted into organic compounds by a method characterized by conversion to cogenides. It consists of a swollen layered metal chalcogenide.

In one embodiment of the invention, the rearrangement is carried out in the presence of water. Preferably the water is It is added to the reaction system after step (a) is completed.

After conversion to polymeric chalcogenide, the product has increased surface area and water and carbonization. Showing increased adsorption capacity for hydrogen. I don't want to be limited by theory, but , hydrolyzing the precursor under conditions that promote removal of organic hydrolysis by-products. This is thought to be a major driving force for hydrolysis. Also, these conditions If includes temperature, the rate of hydrolysis is further accelerated due to the increased kinetic energy. It seems that it will.

For this purpose, the polymeric chalcogenide has two or more repeating units, preferably three Chalcogenide of more than 4 repeating units, such as 4 or more repeating units or exactly 5 or more repeating units It is thought to contain Nido. Degree of monopoly of lamellar polymeric chalcogenide between layers is considered to perform the final glabellar separation of the one-layer metal plate product that forms the pillar. .

An organic #moistened multilayer solution to form the organic swollen feedstock used in the present invention. The lucogenide material is preferably a layered oxide, sulfide, selenide or telluride. It is a multilayer oxide material such as an element other than the elements of group MB of the periodic table, ie, OlS.

Suitable interlayer oxide materials include Group IA metals such as titanium, zirconium, and hafnia. Multilayered oxides such as multilayered trititanates such as U.S. Pat. No. 4,600,503 and and Ti1 containing alkali metals as disclosed in No. 2496993. Contains Na1Tis07 consisting of a "Oy-" layer.If the polymeric silica is Such trititanates are known as silicotitanates. The present invention Other multilayered chalcogenide materials used to perform this treatment include KTiTaOs as well as alkaline Interlayer oxides of mina and silicon, such as clays such as bentonite. In particular, the present invention is known as a high-silica alkaline siliphyte whose layers lack octahedral sheets. It makes it easier for people who are in the first layer of Silicut. These 7 grades are relatively moderate. It can be prepared hydrothermally from a water-containing reaction mixture containing 7 Lika and an alkali at a temperature and pressure of and contains a four-coordinate skeleton other than 8i. Among these materials are magaziite, na trosilite, kunyite, makatite, nekoite, kanemite, okenite, Dehalite, McDonaldite and Ropesite are preferably acid exchangers. Including shapes.

In other multilayered chalcogenides that serve as pillars according to the present invention, each layer of metal thickening has the general formula %formula% [In the formula, M is a small number of atomic valences n (however, n is an integer of 0 to 7, preferably 2 or 3) (Both are one type of metal, [ ] indicates a vacant position, 2 is a tetravalent metal, preferably titanium) and q=47-x(n-4), preferably α6 to 0.9, and 0<x+y< 2] 1 layer gold JliII! Titanometalate-type multi-layered metal oxide product consisting of compounds It is a product.

Sandwiched between the oxide layers is a charge tn (where m is an order of 1 to 3, preferably 1). There is a charge balance cation A with a number of Preferably, A is Cg, IJ) and A large alkali metal cation selected from the group consisting of Kumo 1191 Mgp SCm Mn, Fee CryNl+ Cus Zne　Imp　Divalent or trivalent metal cation selected from Ga and At. Ru. For example, both M are In and Ga. Structurally, these metal oxides Sharing a trance edge in one dimension, a cis edge in a second dimension, and a cis edge in a third dimension. forming double octahedral layers separated by cations at the base (M, (), or Z ) It is thought to consist of a 1-Os octahedron. These materials are (1) gold (2) carbonates or nitrates of alkali metals, and (3) duplication of tetravalent metals. by high temperature fusion of mixtures of materials such as titanium dioxide, or alkali metalates and It can be produced by fusing a mixture of valent metal dioxides. Such fusion is a reagent is ground into a homogeneous mixture and then ceramicized at temperatures ranging from 600-1100℃. It can be done in air in a vase. The resulting product is an organic engraving and polymer 0.853~α066 謔(20~250 METSUKUYU) before the oxidation process of crushed into

Detailed explanations of multilayer titanometalate raw materials and their manufacturing methods can be found in the following literature: I can take it out.

Re1d, A, F, : Mumme, W-G, ;Wad sley, A-D.

Mercy, c, ; Raveau, B-J, 5olid 5tate Chem.

; Goodenough, J, B: Wiseman, P, J, J-5 solid State Chem, 1983.49 300° 1 layer raw material The use of these layered metal oxides as a metal oxide allows the introduction of different metal atoms into the electrolyte material being processed. The stable layer itself contains potential catalytically active sites. So Above, varying amounts of metal atoms are added to the catalyst to achieve optimal activity for a particular method. bring about. Furthermore, for example, instead of the three-block structure shared by Na1Tis07, The layer structure of the titanometalate-type multilayer metal oxide that shares the edges of an infinite transformer is , as a possible mechanism for thermal or hydrothermal decomposition of calcined human materials. sharing can be reduced or eliminated. These titanometalate type materials are silicone It has greater thermal stability than tannate molecular sieves. In addition, the number of metal oxides Variable charge density on the oxide layer, possible in these layered metal oxides due to the plating state The variable stoichiometry of the metal atoms and materials so that the organic cations exchanged into the material change the amount of water. This then creates a final oxide column between the layers of the final product. Vary the concentration.

The metal oxide product contains α5 to 20, preferably 1 to 10, by weight of the element M. include. Materials containing vacancies (where y is greater than zero) are particularly amenable to treatment by the method of the invention. suitable for reason.

Polymeric chalcogenide processed titanometalate type metal plate according to the present invention The product consists of at least 111 glabellar leaves of the element separating the metal oxide layers. From flaky polymeric chalcogenides and multilayer titanometalate type multilayer metal oxides Become. Preferably, such material after support on the posts is thermally stable and readily available. that is, at least as little as possible without significant reduction in interlayer spacing (e.g. less than 10 or 20%). It can also resist fiK at a temperature of 450°C for 2 hours.

The method of the invention also applies to leaf-like polymers in which the interlayer material is a perovskite-related interlayer oxide. It can also be used to produce thermally stable electrical layer materials containing chalcogenides. Perop Skite-related interlayer oxides are known for their decomposition, and analogous materials and their Organic swollen analogues, such as those swollen with octylamine, are described in U.S. Pat. No. 459 No. 3013. These materials are treated with the method of the present invention to contain A chalcogenide in the form of a leaf-like polymer can be introduced. Here are these documents as reference examples. Add to. F again.

Written by Ga1asso, Pergamon Press, 1969 8truc tureProperties and Preparation of Pe rovskite Compound, and Inorg-C of Jacobson et al. hem, 1985°24.3727 as a reference example.

The perovskite-related multilayer oxide used in the present invention has the general formula Mm (An-IBn Osn 10s) [where M is a charge balance lobed cation] and 56° [ mu n-IBHOsn+t) is a perovskite-like layer [formula in which human is a 12-coordination site (sa B is one or more metal atoms that can occupy a 6-coordination site m is thicker than 0 (preferably 1 or less, and n is 2 or more , preferably 3 or more and 7 or less.

Each layer shares a corner with A occupying the central 12-coordination site of each cube BO@ It has a cubic arrangement of octahedra. For the purposes of this invention, the term "cubic" "Arrangement" may include a normal cubic arrangement or a pseudocubic arrangement.

The thickness of each layer, viewed as a BO-octahedron, is denoted by n. In other words, these layers are Based on perovskite-like layered materials, e.g. with thickness between 3 and 780-octahedral It can change. The perovskite-like multi-layered material treated by the method of the present invention has a multi-basin shape. A more common propping agent is used before inserting the lucogenide precursor. It is preferable to have a layer with a low charge density to exhibit the ion exchange properties necessary for insertion. stomach. Some peropskite-like layered materials have charge densities per formula unit of 2 or more; The perovskite-like layered material treated according to the invention preferably has a charge density of less than 1. Motsu. However, struts of desired shape and charge are found in leaflet-like structures in materials where m is greater than 1. Exchange it with thione.

During the production of perovskite-related multilayer oxides according to the method of the present invention, temperatures above ambient temperature, That is, for example, cationic housing or cationic housing at 70-110°C, % to 100°C. It has been found desirable to carry out the swelling step using a recursor. Similarly, leaf pieces Form 1 combined chalcogenide precursor is heated at a temperature above the ambient temperature, e.g. 70-100°C. It is preferable to introduce it into the multilayer oxide at a temperature of 80 to 90°C.

The products thus obtained are listed in the periodic table IB, JIB, mA.

Elements JIB, WA, IVB, VA, VB, MA, WA and mAM, preferably is a leafy polymeric oxide of an element of group IVB of the periodic table, such as a leafy polymeric oxide. Thermostable compositions and tables of perovskite-related layered oxides containing silica It can be manifested. One such l1g product is a flaky polymeric acid such as a flaky polymeric silica. It consists of a perovskite-like layer of the formula Ca1NblO1. containing oxides.

M is a monovalent, divalent or trivalent cation, preferably Li.

A monovalent cation selected from Na, K, Rh, Cs* Nus and H , A is one or more selected from the group consisting of IA, MA, B and lanthanide. B can be a valent, divalent or trivalent cation, and B can be Re, IVB, VB and It can be one or more transition metals selected from the Mm group. In one preferred embodiment, AH-t can be Ca@Na n-73 and B is Nb. In other words , this perovskite layer is represented by the formula Ca2Nan-3NbnOsH+t @In these cases, preferably V is K and n is 3, for example in KCa snow Nb5Ots be.

The organic swelling agent used to swell the layered starting materials used in the present invention is a separately supported raw material. In order to carry out the exchange of leaflet-shaped cations between the layers giving rise to It consists of a source of organic cations such as organic ammonium containing itself. q#, Rotonated alkylamines are preferred.

Frequently, the alkylammonium cation is n-dodecylammonium, n- Octylammonium, n-heptylammonium, n-hexylammonium Contains n-propylammonium. The leaflet-like cations between the layers are hydrogen or hydrogen. The source of organic cations in these cases, including ronium ions, is swollen or Neutral compounds that are converted to cationic analogues during processing, including organic amines. . Among these materials, C1-C1, preferably C6-C-alkyl amines are preferred. or n-alkylamine or C5-cm. Preferably C6-C-alkanol Preferred are n-alkanols. This method would otherwise be difficult to support with pillars. Interlayer lobes with ammonium (1%”) ions located between difficult layers. Found to be particularly useful for strut materials that do not contain alkali metals e.g. .

The interlaminar lamellar polymeric chalcogenide pillars are then interlayered with organic swollen interlayered metal carbons. formed between the layers of the lucogenide raw material and zirconium or titanium or more preferably Or periodic table of substances other than carbon (Fischer ScientificCompa) ny Cat, Na3-702-10. Selected from Group Ⅰ of 1978) chalcogenides of the elements silicon, germanium, tin and lead, preferably polymeric chalcogenides; Contains cogenides.

Other suitable chalcogenides are those of group V, such as V.

Contains Nb and Ta, those of group 11A such as Kg or those of group B such as B . Most preferably, the pillars include monolithic silica. Furthermore, one chalcogenide pillar is It contains an element, preferably aluminum, which provides catalytically active acid sites on the pillars.

The chalcogenide pillars are formed from a precursor material, which is preferably cationic. introduced between the layers of organic "supporting" compounds as a component, or more preferably in place. a layer of an electrically neutralized hydrolyzable compound of the desired element, e.g. of Group JVB. introduced in between. The precursor material is preferably an organic gold that is liquid under ambient conditions. It is a genus compound.

% of the desired element of the column as a precursor of a hydrolyzable compound e.g. alkoxide - Used as a. Suitable polymeric silica precursor materials include tetraalkyl lucilifut e.g. tetrapyl orthocuricute, tetramethyl orthosilicate cate and most preferably tetranibal orthosilifute. Pillars are stationery When required to contain polymeric metal oxides such as alumina or titania , the hydrolyzable compound of the metal is a silicon compound and a titanometalate as a pillar. The organic "support" can be contacted before, after, or simultaneously with the contact with the organic "support". preferably The hydrolyzable aluminum compound used is aluminum alkoxide. For example, aluminum isopropoxide. If the pillar contains titania , hydrolyzable titanium compounds such as titanium alkoxides such as titanium isopropyl Poxides can be used.

Furthermore, chalcogenide precursors include zeolite precursors and conversion conditions. A crossroads into the matter is the interlayered lobed zeolae as at least some chalcogenide pillars. This results in the formation of light material. Polymeric silica and polymeric alumina or polymers Columns of titanium and polymeric titania are particularly preferred.

After the final hydrolysis and calcination to remove the organic support agent to produce chalcogenide pillars, the final The final product contains the remaining exchangeable cations. This in layered material Residual cations such as is ion-exchanged with other cations by well-known methods. Appropriate 1il! ! positive is cesium.

Cerium, cobalt, nickel iX, zinc, manganese.

Platinum, tan/tan, aluminum, ammonium, hydronium and mixtures thereof Including things.

The resulting pillar product has a substantial sorption capacity t (for H x 0 and C hydrocarbons). Thermal stability at temperatures of 500°C or higher with about lθ~25% S) shows.

The pillar products of silica are atoms of divalent metals such as Mg.

When Ni, Cu and Zn are present as metals M in the product, layers larger than 12A trivalent metal atoms e.g. Sc, Mn.

The silica pillar product containing Fe, Cr, In, Ga and At is , with an interlayer separation of 6-15A.

Layered materials containing interlaminar lamellar polymeric chalcogenides are This treatment aids in the removal of organic hydrolysis by-products that are harvested during the conversion to chalcogenides. It is improved when it includes the following items. For example, tetraalkylorthosilyphytes are The alkanol used as a recursor is produced during hydrolysis. this The rate and extent of hydrolysis can be increased by maintaining the temperature to increase the removal of by-products such as increases. When tetraethylorthosilic-) (TE01) is used , ethanol is a byproduct of hydrolysis. Polymeric chalcogenide precursor Hydrolysis at 50-170°C, preferably 75-85°C, e.g. about 80°C The implementation of this method produces a pillar product with increased crystallinity and interlayer spacing I will be built. Moreover, the removal of organic hydrolysis byproducts from the system This is facilitated by carrying out hydrolysis 5 in a system that releases the product. Preferably, this A better system may include means to prevent the introduction of water from outside the system, such as a silicone fluid bubbler. including the outlet pipe connected to the

The invention is further illustrated by the following examples. In these examples, X Linear diffraction data were obtained by standard techniques using one alpha doublet of the copper radiation. Obtained.

Nitrogen surface area is reported as rn''/f.

Example KsCOs 200 ts CaCO56cLQ 4 F and Nb, 0°39 &36F, a well-ground mixture with a molar ratio of 1:4:3 was heated to 75% in air. KCazNb30 was reacted at 0°C for 6 hours and then heated to 1149°C for 24 hours. The material was cooled, reground and reheated at 1149° C. for 24 hours.

Then, 100 t of KCalNbsOn was added at 60℃ for 2 hours in 6MHC4300m. The mixture was stirred for 4 hours. The resulting solid is cooled, filtered, washed with water and hydrated by drying overnight. HCalNlgOl· was obtained. Stir this material 309 in 200 d of water for 1 hour. Then, 37.25 f of n-octylamine was added from the Ryokawa funnel.

The resulting mixture was heated to reflux and stirred for 24 hours. The reaction mixture was then filtered and poured with warm water 1 Washed at 500 m and dried in air overnight. X-Iwao diffraction pattern of powder obtained from this reaction exhibited a layer (d) spacing of 315 angstroms. This solid tetraether The mixture was stirred at 80° C. in the dark at 72 hours in Tgos 7 Likut (Tgos sr/solid). child The material was filtered, air dried, and calcined at 500° C. for 4 hours. X-Iwao diffraction of this powder The pattern exhibited a low angle d-spacing of 2'16 angstroms. CagNb The thickness of the sθ1+1 layer is approximately 120 angstroms, with 1 & 6 angstroms thick. The distance between the layers was left as follows.

This experiment was repeated under the same conditions except that TE01 was added at room temperature. Low angle for product No degree d-spacing was observed, indicating that strut formation did not occur.

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Claims (10)

[Claims] 1. a) A polymeric chalcogen is formed between the layers of an organic swollen multilayered metal chalcogenide by hydrolysis. Contains a hydrolyzable polymeric chalcogenide precursor compound that can be converted to a genide. and b) increase of organic hydrolysis by-products from the reaction system than would occur under ambient conditions. converting the compound into leafy polymeric chalcogenides under conditions that promote faster removal. A polymeric chalcogenide characterized by the conversion of an organic swollen multilayered metal chalcogenide into How to enter cogenide so. 2. A method according to claim 1, wherein said conversion is carried out in the presence of ice. 3. 2. The method of claim 1, wherein said conditions comprise warming to promote removal of said organic by-products. 4. 5. The method of claim 4, wherein said temperature is about 50-170<0>C. 5. the leaflet-like polymeric chalcogenide is a leaflet-like polymeric oxide; 2. The method of claim 1, wherein the multilayer metal chalcogenide is a multilayer oxide. 6. 2. The method of claim 1, wherein said leaflet-like polymeric oxide comprises polymeric silica. 7. The layered metal chalcogenide has the formula Mm[An-1BnO3n+1] Here, M is a charge balance leaflet cation, and [An-1BnO3n+1] is indicates a perovskite-like layer, where A is one or more molecules that can occupy 12-coordination sites. is a metal atom, B is a metal atom that can occupy a 6-coordination site, and m is is a perovskite-related oxide, which is greater than zero, and n is 2 or more. and each layer has a cubic configuration or co-arrangement with A occupying a 12-coordination site at the center of each cube. 2. The method of claim 1, wherein the method comprises BO6 octahedrons with shared inner edges. 8. Each layer of the multilayer metal chalcogenide has the general formula [Mx[]yZ2-(x+y)O 4] q - where M is at least a valence n (where n is an integer between 0 and 7) 1 type of metal, [ ] represents a vacancy, and Z is a tetravalent metal, preferably titanium. , and q=4y-x(n-4), and 0<x+y<2. The product according to claim 1, which is a titanometalate type multilayer metal oxide product consisting of an oxide. Method. 9. The layered metal chalcogenide is magaziite, natrosilite, kenyaite, maca Taite, Nekoito, Kanemito, Okenito, DeHaerito, McDonaldjito and Rode 2. The high silica alkali silicate selected from the group consisting of Method. 10. The following claim, wherein the electrically neutral compound is a tetraalkyl orthosilicate. The method described in 1.