Microporous Amorphous Material, Preparation Method Thereof and Use of Same in the Catalytic Conversion of Organic Compounds

Abstract

The invention relates to a microporous amorphous material which is characterised in that it has a chemical composition in the calcined and anhydrous state which can be represented by the empirical formula x (M 1/n XO 2 ):y YO 2 :SiO 2 , wherein: x has a value of less than 0.2 and can be equal to zero; y has a value of less than 0.2 and can be equal to zero; M is selected from among H + , one or more inorganic cations having a +n charge and a mixture of same; X is one or more chemical elements in oxidation state +3; and Y is one or more elements in oxidation state +4. The inventive material is also characterised in that it has a uniform pore distribution, a micropore volume of greater than or equal to 0.05 cm 3 .g −1 and a specific surface area of greater than 100 m 2 .g −1 . The invention also relates to the preparation method thereof and use of same.

1 . A microporous amorphous material wherein it has a chemical composition in the calcined and anhydrous state which can be represented by the following empirical formula:  
       x(M 1/n XO 2 ):y YO 2 :SiO 2    wherein:    x has a value of less than 0.2, and can be equal to zero,    y has a value of less than 0.2, and can be equal to zero,    M is selected from among H + , one or more inorganic cations having a charge +n and a mixture of same;    X is one or more chemical elements in oxidation state +3; and    Y is one or more elements in oxidation state +4,    which has a uniform pore distribution and a micropore volume of greater than or equal to 0.05 cm 3 .g −1  and    which has a specific surface area of greater than 100 m 2 .g −1      
   
   
       2 . A microporous amorphous material according to  claim 1 , wherein it has a chemical composition in the calcined and anhydrous state which can be represented by the following empirical formula:  
       x(M 1/n XO 2 ):y YO 2 :SiO 2    wherein:    x has a value of less than 0.1, and can be equal to zero,    y has a value of less than 0.1, and can be equal to zero,    M is selected from among H + , one or more inorganic cations having a charge +n and a mixture of same;    X is one or more chemical elements in oxidation state +3; and    Y is one or more chemical elements with oxidation state +4.    
   
   
       3 . A microporous amorphous material according to  claim 1 , wherein X is selected from among Al, Ga, B, Fe, Cr and a mixture of same.  
   
   
       4 . A microporous amorphous material according to  claim 1 , wherein Y is selected from among Ti, Ge, Sn, V and a mixture of same.  
   
   
       5 . A microporous amorphous material according to  claim 1 , wherein its composition corresponds to the formula:  
       x(M 1/n XO 2 ):SiO 2    where:    x has a value of less than 0.2, and can be equal to zero,    M is selected from among H + , one or more inorganic cations having a charge +n and a mixture of same, and    X is one or more chemical elements in oxidation state +3.    
   
   
       6 . A microporous amorphous material according to  claim 1 , wherein its composition in the calcined and anhydrous state can be represented by the formula:  
       y YO 2 :SiO 2    where:    y has a value of less than 0.2, and can be equal to zero; and    Y is one or more chemical elements with oxidation state +4.    
   
   
       7 . A microporous amorphous material according to  claim 1 , wherein its chemical composition in the calcined and anhydrous state can be represented by the empirical formula:  
       x(HXO 2 ):SiO 2    where:    x has a value of less than 0.2, and can be equal to zero; and    X is one or more chemical elements in oxidation state +3.    
   
   
       8 . A microporous amorphous material according to  claim 1 , wherein its chemical composition in the calcined and anhydrous state is represented by the formula SiO 2 .  
   
   
       9 . A method for synthesising a microporous amorphous material defined in  claim 1 , comprising: 
 preparing a reaction mixture comprising at least: 
 a source of SiO 2,    
 one or more organic compounds, and  
 water,  
   subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:    ROH/SiO 2 =0.01-3.0,    H 2 O/SiO 2 =1-100,    where R is one or more organic compounds.    
   
   
       10 . A method for synthesising an amorphous material according to  claim 9 , wherein the reaction mixture furthermore comprises a source of fluoride ions.  
   
   
       11 . A method for synthesising an amorphous material according to  claim 9 , comprising: 
 preparing a reaction mixture comprising at least:    a source of SiO 2,  
 a source of one or more tetravalent elements Y,  
 one or more organic compounds,  
 water,  
   subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:    ROH/SiO 2 =0.01-3.0,    H 2 O/SiO 2 =1-100, and    YO 2 /SiO 2 =0.001-0.2    where Y is one or more elements in an oxidation state +4, and R is one or more organic compounds.    
   
   
       12 . A method for synthesising an amorphous material according to  claim 9 , comprising: 
 preparing a reaction mixture comprising at least: 
 a source of SiO 2,    
 a source of one or more trivalent elements X,  
 one or more organic compounds, and  
 water,  
   subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:    ROH/SiO 2 =0.01-3.0,    H 2 O/SiO 2 =1-100, and    X 2 O 3 /SiO 2 =0.001-0.1,    where X is one or more elements in an oxidation state +3 and R is one or more organic compounds.    
   
   
       13 . A method for synthesising an amorphous material according to  claim 9 , comprising: 
 preparing a reaction mixture comprising at least: 
 a source of SiO 2,    
 a source of one or more trivalent elements X,  
 one or more elements M of charge +n,  
 one or more organic compounds, and  
 water,  
   subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:    ROH/SiO 2 =0.01-3.0,    H 2 O/SiO 2 =1-100, and    X 2 O 3 /SiO 2 =0.001-0.1,    where X is one or more elements in an oxidation state +3, M is selected from among H + , one or more inorganic cations of charge +n and mixtures of same; and R is one or more organic compounds.    
   
   
       14 . A method for synthesising an amorphous material according to  claim 9 , comprising: 
 preparing a reaction mixture comprising at least: 
 a source of SiO 2 ,  
 a source of one or more trivalent elements X,  
 a source of one or more tetravalent elements Y,  
 one or more elements M of charge +n,  
 one or more organic compounds, and  
 water,  
   subjecting said mixture to heating with or without stirring at a temperature between 80 and 200° C., until achieving the formation of the amorphous material, and in which the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals:    ROH/SiO 2 =0.01-3.0,    H 2 O/SiO 2 =1-100,    X 2 O 3 /SiO 2 =0.001-0.1,    YO 2 /SiO 2 =0.001-0.2    where X is one or more elements in an oxidation state +3, Y is one or more elements in an oxidation state +4, M is selected from among H + , one or more inorganic cations of charge +n and mixtures of same; and R is one or more organic compounds.    
   
   
       15 . A method for synthesising an amorphous material according to  claim 14 , wherein the reaction mixture has a composition, in terms of molar ratios of oxides, lying between the intervals 
 ROH/SiO 2 =0.1-1.0,    X 2 O 3 /SiO 2 =0.001-0.05    YO 2 /SiO 2 =0.001-0.1    H 2 O/SiO 2 =1-50    where X is one or more trivalent elements selected from among Al, B, Ga, Fe and Cr and Y is one or more tetravalent elements selected from among Ti, Ge, Sn and V.    
   
   
       16 . A method for synthesising an amorphous material according to  claim 14 , wherein the reaction mixture has a composition which accords with the empirical formula:  
       a ROH:b M 1/n F:x X 2 O 3 :y YO 2 :SiO 2 :w H 2 O  
     where X is one or more elements in an oxidation state +3, Y is one or more elements in an oxidation state +4, M is selected from among H + , one or more inorganic cations of charge +n and mixtures of same; and R is one or more organic compounds,  
     and the values a, b, x, y and w are in the ranges: 
 a=ROH/SiO 2 =0.1-3.0,  
 b=M 1/n F/SiO 2 =0.1-3.0,  
 x=X 2 O 3 /SiO 2 =0-0.05,  
 y=YO 2 /SiO 2 =0-0.1, and  
 w=H 2 O/SiO 2 =1-50,  
 
   
   
       17 . A method for synthesising an amorphous material according to  claim 9 , wherein the mixture is subjected to heating with or without stirring at a temperature between 100 and 200° C.  
   
   
       18 . A method for synthesising an amorphous material according to  claim 9 , wherein the organic compound R is in hydroxide form.  
   
   
       19 . A method for synthesising an amorphous material according to  claim 9 , wherein the organic compound comprises one or more amine groups.  
   
   
       20 . A method for synthesising an amorphous material according to  claim 9 , wherein the organic compound comprises one or more ammonium groups.  
   
   
       21 . A method for synthesising an amorphous material according to  claim 9 , wherein the organic compound is selected from among N(16)-methylsparteinium, 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, 1,8-bisquinuclidiniumoctane hydroxide, 1,4-biscyclohexylpyrrolidiniumbutane hydroxide, hexamethonium hydroxide and tetraethylammonium hydroxide.  
   
   
       22 . Method of use of an amorphous material of  claim 1 , as catalyst in a conversion process for organic compounds consisting of placing a feed in contact with a quantity of that catalyst.  
   
   
       23 . Method of use according to  claim 22 , wherein the process can be a process of catalytic cracking of organic compounds.  
   
   
       24 . Method of use of an amorphous material according to  claim 23 , wherein said organic compounds are hydrocarbons.  
   
   
       25 . Method of use of an amorphous material according to  claim 22 , wherein the process is selected from among a hydrocracking process, gentle hydrocracking of hydrocarbons, gentle hydrocracking of functionalised hydrocarbons, gentle hydrocracking of hydrocarbons and functionalised hydrocarbons, hydroisomerisation of olefins, an isomerisation process of light paraffins, deparaffining, isodeparaffining and an alkylation process.  
   
   
       26 . Method of use of an amorphous material according to  claim 25 , wherein the alkylation process is selected from among alkylation of isoparaffins with olefins, alkylation of olefins with isoparaffins, alkylation of aromatics with olefins or alcohols, alkylation of substituted aromatics with olefins or alcohols, alkylation of thiophenic compounds with olefins or alcohols, alkylation of alkylthiophenic compounds with olefins or alcohols, alkylation of alkylbenzothiophenic compounds with olefins or alcohols.  
   
   
       27 . Method of use of an amorphous material according to  claim 25 , wherein the alkylation process is the alkylation of benzene with propylene.  
   
   
       28 . Method of use of an amorphous material according to  claim 22 , wherein the process is an acylation reaction of substituted aromatic compounds using acids, acid chlorides or organic acid anhydrides as acylating agents.  
   
   
       29 . Method of use of an amorphous material according to  claim 22 , wherein the process is a selective oxidation of organic compounds using an oxidising agent selected from among H 2 O 2 , organic peroxides and organic hydroperoxides.  
   
   
       30 . Method of use of an amorphous material according to  claim 22 , wherein the process is selected from among a Meerwein-Pondorf-Verley type oxidation reaction and a Baeyer-Villiger type oxidation reaction.  
   
   
       31 . Method of use of an amorphous material according to  claim 22 , wherein said amorphous material contains Ti and the process is selected from among: 
 a process of epoxidation of olefins,    oxidation of alkanes, oxidation of alcohols,    oxidation of organic compounds containing sulphur and which can produce sulphoxides and sulphones, using organic or inorganic hydroperoxides or molecular oxygen as oxidising agents and    ammoximation of ketones.    
   
   
       32 . Method of use of an amorphous material according to  claim 22 , wherein said amorphous material contains Sn and the process is an oxidation in Baeyer-Villiger reactions using H 2 O 2  as oxidising agent.