TW200302219A - Process for preparing lactam - Google Patents

Abstract

The present invention relates to the preparation of lactam by cyclizing esters and amides of 6- aminocaproic acid. This reaction is carried out in the vapour state and in the presence of a solid catalyst such as alumina.

Description

200302219 ⑴ 发明, description of the invention (the description of the invention should state: the technical field to which the invention belongs, the prior art, the content, the embodiment and the schematic description) The present invention relates to esters and 醯 of cyclized 6-aminohexanoic acid Method for preparing lactams from amines. S1 amines in the family, such as ε-caprolactam, are the basic compounds for preparing polyamines (polyamines 6 of caprolactam). One of the known ways to prepare these lactams is to carry out the cyclization hydrolysis of the corresponding aminonitrile, especially the unbranched aliphatic aminonitrile, through water in the vapor phase over the solid catalyst. Accordingly, U.S. Patent No. 2 357 484 describes a method for preparing lactam in the vapor phase ' comprising passing a mixture of water and aminonitrile through a catalyst, such as activated alumina, silicone, or backfill acid. U.S. Patent No. 4,628,085 describes a method for preparing lactam in the vapor phase, which includes contacting an aliphatic or aromatic amino nitrile with water, typically in the presence of argon and ammonia, to have a BET surface area greater than 250 square meters per gram. And the Shi Xi substrate catalyst in the form of spherical particles with an average pore diameter of less than 20 microns. Another possible route to obtain caprolactam is the cyclization of compounds such as 6-aminocaproic acid, 6-aminocaproic acid, 6-aminocaprolactam, or mixtures thereof. Thus, patents 98/370 63 and 1028 1 0 9 describe a method for cyclizing these compounds in the presence of superheated steam. U.S. Patent No. 5 9 7 3 1 4 3 also shows that these compounds use a ring of an alcohol such as a solvent in a liquid vehicle ^ ------- These methods are also performed in the absence of a cyclization catalyst. One of the objects of the present invention is to propose the implementation of these compounds in the presence of a catalyst (2) (2) 200302219

Cyclization. Specifically, the present invention relates to a method for preparing lactam by cyclizing a compound selected from the group consisting of paper or amidine or a mixture thereof including 6-aminohexanoic acid in the vapor phase, and is characterized by a reaction system Implemented in the presence of a solid catalyst. In a preferred embodiment of this month, the reaction is carried out in the presence of water in the form of steam. This water can limit the production of by-products and promote the recovery of caprolactam. According to the characteristics of the present invention, the catalyst of the present invention is selected from the group consisting of metal oxides such as oxide oxides, such as buddha, clay, and metal phosphonates. Therefore, the clay suitable for the present invention is especially phyllosilicate, which is classified into groups according to its properties and physicochemical properties. The territory, serpentine, montmorillonite or montmorillonite, illite or Mica-type 'sea green cormorant' gaseous or warp stones, stone evening magnesite or sepiolite, clay with mixed layer, spodumene or gibbsite and clay with high content of alumina. Some clays have a layered structure that can expand the network. The characteristic shown is that it absorbs various solvents, such as β, and then water. Between the sheets made, the bean causes the solid to swell with the weakening of the # ^ / ^ e ^ key between the sheets. These clays basically belong to the montmorillonite group (or montmorillonite, Gonggan & + gangue group) and some of them belong to the buried stone group. Its structure is composed of a paleo-, two-layered "basic" sheet. Simple two-layered tetrahedron Si04, whose φ · β, and silicon portion can be other cations such as Al3 at the tetrahedral position. + Or maybe Fe3 + is changed again, and between this two-layered tetrahedron, there is an octant gas, in ... the body layer is composed of the tightly packed oxygen derived from the peak of the previous tetra & These oxygen-tight hexahedral networks contain six octahedral cavities. 200302219 (3) Fai said that when the metal cations occupy 4 of these cavities (for example, 2 of 3 cavities in the case of aluminum), this layer is called an octahedron; when it occupies With all cavities (for example 3 out of 3 in the case of magnesium), this layer is called a trioctahedron.

The basic sheets of these clays are negatively charged and are composed of exchangeable basic metal cations such as LiT, Nat, Kτ, exchangeable soil metal cations such as Mg2f, Ca2 +, and optionally hydrogen ions Ι 2 (T exists Montmorillonite has a lower charge density on the sheet than vermiculite-type clay: about 0.6 per charge per basic sieve. 1 to 1.4 charges per vertex of vermiculite. Compensating cations in Mongolia Quartzite is basically sodium and calcium, and vermiculite is magnesium and calcium. From the viewpoint of charge density, montmorillonite and vermiculite are intermediates between talc and pyrophyllite. On the other hand, its sheet It is neutral and mica; on the other hand, it is characterized by a high charge density on the sheet (about 2 per basic sieve), usually compensated by Γ ions. Cross ions in montmorillonite and vermiculite can borrow ions Exchange with other ions such as ammonium ions or alkaline earth metal or rare earth metal ions. The swelling characteristics of clay depends on various factors, including the charge density and the properties of compensating cations. Therefore, montmorillonite with a lower charge density than vermiculite has Expansiveness is obviously greater than the latter, Therefore, it constitutes a very favorable type of solid. The repeating distance or basic space represents the shortest distance of the same unit of crystallography located in the two adjacent sheets. The basic space of montmorillonite can thus be expanded to reach a range of about 1 micrometer to 2 micrometers. The above detection._ In the "expansive" phyllite silicate of montmorillonite, the main solid of the following formula can be mentioned: 200302219

(4) (Min +) x / n (M2) 2VI (M3) 4lV 〇10 (〇H) 2 where Ml is a cross cation, M2 is a metal at the octahedral position, M3 is a metal at the tetrahedral position, and the reason is The number of charges provided by the cation Mi—octahedral montmorillonite (HJa'Cai / zKMgxAh-xHI Si4IV 010 (〇H) 2 Bedek (H, Na, Cai / 2) xAl2VI (AlxSi4 — x) IV 〇i〇 (〇H) 2 cystite (H, Na, Cai / 2…) x (Fe, Al) 2VI (AlxSi4 —x) IV 〇1〇 (〇h) 2 Hectorite Nax (LixMg3-x) VI Si4lV 0! 〇 (〇H) 2 Polystone NaxMg3VI (AlxSi4-xIV 01〇 (〇H) 2 Mg-rich montmorillonite Na2xMg3-xVI Si4IV O1〇 (〇h) 2 in adsorption After the saturation of water or organic polar solvents in montmorillonite, the cross space (between the two sheets) becomes the largest. It can reach a value close to 丨 microns. Therefore, these solids are quite advantageous in terms of catalysis, because The latent specific surface area and acidity are high. According to the preferred mode of the present invention, the catalyst that cyclizes the esters or amidoamines of 6-aminohexanoic acid to form yttrium is montmorillonite. Specifically, f, clay is Mongolia Stone removal. Some clays have disadvantages. When heated to

plus. This situation is particularly relevant for montmorillonite. The prior art has explained various methods for introducing pillars or bridges between the slabs of montmorillonite so that they will lose their expansion ratio when exposed to heat ^ 8-200302219 _ Guang 5) The bridge montmorillonite still maintains a high cross space after reading the page.

The method consisting of the introduction of oligomers of metal hydroxides, especially bridges of aluminum hydroxide, has been described in Clay and Clay Materials by LAHAV, SHA Μ I and SHABT AI, vol. 26 (No · 2), P 1 0 7- 1 1 5 (1 978) and French Patent No. 2, 3 9 4, 3 2 4. The formation of bridges composed of oligomers of mixed hydroxides of silicon and hafnium is described in U.S. Patent No. 4,248,739. The technique of bridging montmorillonite by dialysis and aluminum hydroxide, chromium, zirconium and titanium is described in European Patent 0, 0 73, 71 8. The principles of these methods include contacting the clay with a solution containing ionic species that are low-polymerized to a greater or lesser extent, in the case of aluminum. This operation is usually carried out in a solution at a temperature below 80 ° C and, if possible, in a solution that will not be highly concentrated in the absence of turbidity formed when metal hydroxide precipitation begins. The concentration of metal ions and clay should be optimized to form sufficiently solid pillars and the porosity of the clay will not be greatly reduced by the insertion of excess metal oxides Λ / 〇

Bridged montmorillonite can be used when the alkaline or alkaline earth metal ions are directly exchanged for protons assisted by extremely dilute solutions, or preferably exchanged with ammonium salts, and then calcined and replaced between 300 ° C and 0 ° C. It has a strong acidity, although substantially lower than conventional zeolites of the gamma or mordenite type, for example. According to a preferred embodiment of the present invention, the clay used as a catalyst for the 6-aminohexanoic acid esters or amidines to cyclize to lactam is bridged. According to the special example of the present invention, in addition to the point of soil, the contact may also cause one or more other metal compounds, often called dopants, such as chromium, titanium, molybdenum, tungsten, iron, and zinc compounds. Of these dopants, chromium and / or iron and / -9-200302219 issuance key said that 续 or titanium compounds are considered the most advantageous. These dopants are usually expressed as 0% to 10%, preferably 0% to 5%, based on the weight of the clay. The term metal compound means a metal element or a metal ion or any combination containing a metal element. Another preferred catalyst of the present invention consists of at least one element that forms at least one element selected from the group consisting of Shi Xi, Ming, Titanium, Titanium, Titanium, Thallium, Sharp, Tantalum, Tungsten, I, Iron, and Rare Earth. Fine particles obtained by mixing inorganic oxides

Catalyst. According to the invention, the particulate catalyst contains at least one large pore, characterized in that the pore volume corresponding to a pore having a diameter greater than 500 angstroms is greater than or equal to 5 ml / 100 g. This macropore can be advantageously formed during the process of forming particles by techniques such as pyrogen addition. The catalyst can be used in various forms such as beads, abrasives, extrudates in the form of hollow or solid cylindrical particles, honeycombs or pellets, which can be formed using adhesives as needed.

This may first include beads of inorganic oxides derived from oil droplet formation (or droplet solidification). Such beads can be prepared, for example, by a method similar to that described in European Patent A-0 015 801 or European Patent A-0 0 97 53 9 to form aluminum oxide beads. The control of porosity can be achieved in particular by the method of European Patent A-0 0 9 7 5 3 9 through the dripping of suspensions or dispersions of inorganic oxides. _ Beads can also be obtained by coagulation using a rotating drum or granulator. This may also include extrudates of inorganic oxides. It can be obtained by blending, followed by the extrusion of organic oxide-based materials. Control of the porosity of these extrudates can be achieved by selecting the oxide used and by preparing the oxide or by blending the oxide before extrusion. Therefore, the inorganic oxidation residue can be mixed with the pyrogen during blending. For example, the extrudate can be prepared by the method described in U.S. Patent No. 3,856,708. Similarly, beads of controlled porosity can be obtained by coagulation by adding pyrogens and rotating bowls or granulators, or by the "oil drop" method.

According to another characteristic of the present invention, the catalyst particles have a specific surface area greater than 10 m2 / g and a pore volume equal to or greater than 10 ml / 100 g, corresponding to a pore volume greater than or equal to a pore having a diameter greater than 500 angstroms. 10 ml / 100 g. According to another characteristic of the present invention, the catalyst particles have a specific surface area greater than 50 square meters per gram.

Preferably, it has a total pore volume greater than or equal to 15 ml / 100 g, corresponding to a pore volume greater than or equal to 15 ml / 100 g, and more preferably 20 ml / 100 g. These particulate catalysts may also contain at least one element selected from the group consisting of silicon, titanium, zirconium, vanadium, niobium, hafnium, tungsten, molybdenum, iron, rare earth metals or by depositing and / or adsorbing at least one oxide compound, It has at least one element selected from elements belonging to groups 1 to 16 belonging to the general element classification (new classification). This group also includes rare earth metals. These elements or compounds are deposited or adsorbed on the particulate catalyst. In the process of supporting the oxidizing compound by the porous particulate catalyst containing the elements, these elements preferably come from including Shi Xi, Qin, Lu, Xi, Rui, Group, Crane, Molybdenum, Scale, Mi, Iron, Metal, Examine soil metal, rare earth metal group. -11-200302219 (8) Issuing key said continuation page The oxidizing compound is preferably a simple or mixed oxide of one or more of the above elements. In this specific example, the porous catalyst is preferably alumina. This alumina preferably has the pore distribution and specific surface area characteristics defined above. The weight concentration of the oxidizing compound on the porous support is preferably between 1000 ppm and 30% is expressed as the mass of the oxidizing compound element relative to the total mass of the catalyst. This concentration is more preferably between 0.5 and 15% by weight. When the porous support corresponds to the alumina according to the present invention, the latter is usually obtained by dehydration of gibbsite, bayerite, alumina trihydrate, or various mixtures thereof. Various methods for preparing alumina are described in the KIRK-OTHMER encyclopedia, voi. 2, p. 29, p. 297. The subdivided form of hydrated alumina can be brought into contact with the hot air flow between 400 ° C and 100 ° C, and then the contact between the hydrate and the gas is maintained for 1 to 10 seconds, and finally the partial dehydration is separated Alumina and hot gas to prepare the alumina used in the method of the present invention. In particular, reference may be made to the method described in U.S. Patent No. 2,915,365. It can also be used in an aqueous medium, if necessary, in the presence of an acid, at a temperature greater than 100 ° C, preferably between 150 ° C and 25 (TC). It is preferably between 1 and 20 hours, and then dried and then calcined. The calcination temperature is set so that the pore volume and specific surface area are within the range shown above.-The catalyst of the present invention preferably has a ratio of more than 50 square grams per gram. Specific surface area.- In addition, it preferably has pores with a diameter greater than 0.1 micron, and the pore surface area provided by such pores is greater than or equal to 5 ml / 100 g, preferably greater than or equal to 10 (9) 200302219

Ml / 100 g. In a preferred embodiment of the present invention, the pores are equal to or larger than 0.5 micrometers. These catalysts also include pores with a diameter of 100 g, preferably larger than or equal to, and the surface area of the pores should be equal to or larger than 5 millimeters. Gugu- 丄; 10 亳 L / 100g 0 This is 〇 畑 L produced by pores with straight 偟 greater than 500 angstroms, Λ-/ jb, ^ ^ is preferably greater than 0.1 micrometer, and most preferably greater than 0.5 micrometer A catalyst with a high cycle life can be obtained by volume as a catalyst for the reaction that deteriorates 6-amine organic caproic acid or ammonium to lactam. Therefore, the catalyst can

Release T is an industrial method for making linacamide. According to the present invention, a catalyst-containing oxidizing compound supported by a porous catalyst is usually impregnated with a salt of the above-mentioned element or a solution of a compound, especially an oxide, and then dried and calcined at a temperature equal to or greater than 400 ° C so This compound or salt is preferably converted into an oxidizing compound, preferably an oxide, if necessary. The oxide is deposited on the pore surface of the porous catalyst. In another specific example, the compound of the element may be added to the material constituting the porous catalyst before or during the formation. The calcination of the impregnated catalyst is preferably carried out under an oxidizing gas pressure such as air. According to another specific example of the present invention, the catalyst may be a metal salt of the general formula. (P〇4) n Hh M, (Imp) p where: -M represents divalent, trivalent, tetravalent, or pentavalent Valence element, selected from a mixture of elements such as the periodicity of the elements or M = 0, -Imp represents an immersion immersion compound, which is determined by chemistries or soil metals or some of this-13-200302219

(ίο) is composed of a mixture of other metals and combined with a balanced anion to ensure electrical neutrality, -η represents 1, 2 or 3, -h represents 〇, 1 or 2, and -P represents a number between 0 and 1/3, and Corresponds to the molar ratio between the impregnated material and the impregnated material (P04) nHhM. In the classification of elements of the periodic table, 2a, 3b, 4b, 5b, 6b, 7b, 8, 2b, 3a, 4a and 5a metals, in particular, beryllium, magnesium, calcium, strontium, barium, aluminum, boron , Gallium, indium, yttrium, lanthanide rare earth elements such as lanthanum, osmium, osmium, 钐, osmium, osmium, osmium, osmium, erbium, osmium, osmium, osmium, and osmium, titanium, vanadium, niobium, iron, tungsten , Tin, Syria. Among the lanthanide rare earth phosphates, the first family can be distinguished, and its family together with orthophosphates of light rare earth metals, also known as high rhenium rare earth metals, includes steel, trim, rhenium, ', rhenium, and thorium. These orthophosphates are distorted. It has a mountain structure and when heated to 600 to 800 ° C, it changes to a monoclinic frontal structure. The second family of phosphates of the lanthanide rare earth element and the orthophosphoric acid salts of plutonium, europium, and pin. These orthophosphates have the same structure as the orthophosphates of high rhenium rare earth metals, but also have a second crystalline phase with a secondary structure at high temperatures (about 170 (TC)). The third branch together with the heavy rare earth metals' also known as the positive filling salts of rare earth metals, including the compounds, series, chains, rhenium and osmium. These compounds slowly crystallize in the secondary form. In the various salts of acid salts, it is preferred to use high rare earth rare earths. ___ Metal phosphates of the above formula can be used, which is a mixture of several metal canister salts or a mixture of several metals mentioned above, or contains one of the above. 200302219

(11) Mixed phosphates of one or more metals with one or more other metals, such as test or soil test metals. Equilibrium anions entering the impregnation compound Imp formula are empirical. In particular, hydroxide, phosphate, hydrogen phosphate, dihydrogen phosphate, gaseous, fluoride, nitrate, benzoate or oxalate ions can be used without being limited by these examples. The Mohr ratio p is preferably between 0.02 and 0.2. If reference is made to the general technique for the preparation of phosphates (especially "PASCAL P. Nouveau traite de chimie minera1e ^ vo1ume X (1956), P.821-823 and" GMELINS Handbuch der anorganischen Chmie ,, (8thedition) volume 16 (C), p. 202-206 (1965)), distinguishing between two ways to obtain phosphonates. In one aspect, soluble metal salts (gases, nitrates) are precipitated with ammonium hydrogen phosphate or phosphoric acid. On the other hand, phosphoric acid for metal oxides or carbonates (insoluble) is usually dissolved in a hot state 'and then precipitated.

The precipitated phosphate obtained according to one of the routes can be dried, treated with organic rhenium (such as ammonia) or inorganic base (such as alkali metal hydroxide), and calcined. These three operations can be performed sequentially or out of sequence. . The metal phosphate of the above formula, where the symbol P is greater than 0, can be obtained by impregnating the compound (P04) nHhM prepared according to one of the above techniques with Imp in a volatile solvent such as a solution or suspension in water, preferably preparation. The more soluble, the better the combined old fruit of the new I. Therefore, the preferred methods for preparing these phosphates include: -15- 200302219

(12) a) carrying out the synthesis of compound (P04) nHhM; preferably without separating (P04) nHhM from the reaction medium; b) introducing the impregnating agent I nip into the reaction medium; c) separating from the reaction solid Any residual liquid; d) Dry and calcined if necessary. The performance of these catalysts, especially their resistance to deactivation, can be further enhanced by calcination. The calcination temperature is usually between 300 ° C and 1000 ° C, preferably between 400 ° C and 900 ° C. The calcination period can be varied within a wide range. Usually, it is between 1 hour and 24 hours. In the preferred formula (II) catalyst of the method of the present invention, lanthanum discoate, calcined lanthanum phosphate, scaly acid steel combined with rhenium, rhenium, or potassium derivatives, calcined rhenium phosphate, and rhenium, Osmium phosphate in combination with organic or potassium compounds, acid filling in combination with brocade, osmium or bell compounds #, reading end inscriptions, wall acid inscriptions in combination with 铷 '锻 or potassium compounds, calcination filling acid range, and Potassium compound combined with niobium phosphate, calcined zirconium hydrogen phosphate, hydrogen phosphate combined with hafnium, rhenium or potassium compounds. The cyclization reaction preferably requires the presence of water to limit the formation of Sl ## ^^^^^ by-products. The Mo ^, s ^ ^ Λ ratio between the water used and the compound to be cyclized is usually between 0.5 and 50, preferably between 1 and 20. The compound to be cyclized can be mixed with water in its vapor phase # Pre-vaporization, but for example, nitrogen, helium or separably introduced into the reactor. The reagent-combinable chamber can use an inert gas, gas or argon, which does not have the disadvantages of a carrier. -16- 200302219 (13) Fa Li said: Key continued 的 The temperature at which the method of the present invention is carried out should be sufficient for the reagent to indeed show a vapor state. It is usually between 200 ° C and 4 50 ° C, preferably between 250 ° C and 400 ° C. The contact time between the compound to be cyclized and the catalyst is not important. The end depends on the device used. This contact time is preferably between 0.5 and 200 seconds, and still more preferably between 1 and 100 seconds. Pressure is not an important processing parameter. Therefore, the procedure can be carried out at a pressure of 10 "bar to 200 bar. The procedure is preferably carried out at a pressure of 0.1 · 2 bar to 20 bar. It is not excluded to use inert solvents such as paraffin, cyclic chain under reaction conditions Alkanes, aromatic hydrocarbons, or one of these hydrocarbons in the halogenated form, thereby having a liquid phase in the reaction stream. The test is performed according to the following procedure: A medium containing ethyl hexanoate in water or methanol solution With the help of a push-type syringe, it was introduced into a hot glass tube vertically placed in a furnace at a temperature of 300 ° C at a flow rate of 4.3 liters / hour and flushed with a nitrogen flow of 5.3 liters / hour. 2 grams of catalyst Aluminum, sold by the company PROCATALYSE under the name SCM 139 XL) is placed between two layers of glass powder with a volume of 5¾ liters. Injection is performed just above the top layer of the glass, and a stream of nitrogen passes through the catalyst bed to load the product. At the exit of the furnace, The gas is condensed in a tube placed in an ice bath and analyzed by gas chromatography. Example 1: The medium contains 60% by weight of methyl aminohexanoate.纨 Selection rate · 26% Example 2: 17- 20030 2219 (14) Sprouting said sprouting Continued The medium contains 40% by weight of aminoethylhexanoate. The conversion of ethylaminohexanoate is complete, and the selectivity related to caprolactam is 68%.

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Claims (1)

200302219 Patent application scope 1. A method for preparing lactam by using a compound selected from the group consisting of esters of hexanohexanoic acid or amidines or mixtures thereof, characterized in that the reaction is in a vapor state And solid catalyst. 2. The method according to item 1 of the patent application, characterized in that the solid catalyst is selected from the group consisting of metal oxides, zeolites, clays, and metal phosphates. 3. The method according to item 2 of the patent application, characterized in that the clay system is selected from the group consisting of kaolin, serpentine, montmorillonite or montmorillonite, illite or mica, chlorite, chloride or warp stone , Crushed magnesite or sepiolite, clay with mixed layers, hydralite or chrysotile and clay with high content of oxidized IS. 4. The method of claim 3 in the scope of patent application, characterized in that the clay is montmorillonite. 5. The method according to any one of claims 3 and 4, wherein the clay is bridged. 6. The method according to item 1 or 2 of the scope of patent application, characterized in that the catalyst is formed by at least one element selected from the group consisting of crushed, shao, titanium, copper, hafnium, sharp, tantalum, town, platinum, iron, and rare earth metals. A particulate catalyst composed of at least one simple or mixed inorganic oxide formed by the group and characterized in that it contains at least one large pore, which is characterized by a pore volume corresponding to a pore having a diameter greater than 50 angstroms Greater than or equal to 5 ml / 100 g. 7. The method of claim 6 in the scope of patent application, characterized in that the particulate catalyst has a specific surface area greater than 10 square meters per gram and a total pore volume greater than or equal to 10 ml per 100 grams, corresponding to having 200302219 for holes with a diameter greater than 50 Angstroms The pore volume is greater than or equal to 10 liters / 100 grams. 8. The method of claim 6 or 7, characterized in that the catalyst has a specific surface area greater than 50 m2 / g. 9. The method according to any one of claims 6 to § of the patent application, characterized in that the catalyst has a total pore volume greater than or equal to 20 ml / 100 g. The pore volume is greater than or equal to 20 ml / 100 g. 10. The method according to any one of claims 6 to 9 in the scope of patent application, characterized in that the particulate catalyst is a gasification inscription. 11. The method according to any one of claims 6 to 10 in the scope of patent application, characterized in that it contains at least one element selected from the group consisting of silicon, titanium, vanadium, niobium, buttons, tungsten, molybdenum, iron, and rare earth metals. Group consisting of at least one oxidizing compound consisting of elements from the group of 16 to 16 in the general element classification (new classification). This group also includes rare earth metals, which are deposited or adsorbed on particulate catalysts. As simple or mixed inorganic oxide. 12. The method according to any one of claims 1 and 2, wherein the catalyst is a metal phosphate of the following formula: (P04, n is called M, (Im) p where: -M Represents bivalent, trivalent, tetravalent, or pentavalent elements, and is selected from the Periodic Table Classification of the Elements 2 &, 31), 41), 513,613,713,8,21), Groups 33,43, and 58 or some of these elements Mixture or M = 0, basic I decontaminates my composition, composed of earth metal or a mixture of several of these metals, combined with a balanced anion to ensure electrical neutrality, -2- 200302219 -η represents 1, 2 or 3, -h represents 0, 1, or 2,-p represents the number between 0 and 1/3 and corresponds to the mole between the impregnated material Imp and the impregnated material (P04) nHhM ratio. 13. The method according to any one of the previous patent applications, characterized in that the temperature is between 200 ° C and 450 ° C, preferably between 250 ° C and 400 ° C. 14. The method according to any one of the previous patent applications, characterized in that it is carried out in the presence of water. Call on 200302219 Lu, (1), the designated design of the case is as follows: Figure _ (b), the representative symbols of the representative diagram are briefly explained: 柒, if there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention :