Oxidation process in fluidised bed reactor

Abstract

A process for reacting in a fluid bed reactor at least one oxidisable reactant with molecular oxygen in the presence of a catalytically active fluidised bed of solid particles. In the process a molecular oxygen-containing gas having an oxygen concentration greater than that of air is introduced into the fluidised bed whilst the fluidised bed is maintained in a turbulent regime. The process is suitable for oxidation, ammoxidation and carboxylation processes, including the production of maleic anhydride, acrylonitrile, ethylene, acetic acid and vinyl acetate.

1 . A process for reacting in a fluid bed reactor, at least one oxidisable reactant with molecular oxygen in the presence of a catalytically active fluidised bed of solid particles in which process a molecular oxygen-containing gas having an oxygen concentration greater than that of air is introduced into said fluidised bed whilst said fluidised bed is maintained in a turbulent regime.  
   
   
       2 . A process according to  claim 1  wherein the turbulent regime has the ratio of transition velocity (U k ) : terminal velocity (U t ) in the range 0.1:1 to 25:1.  
   
   
       3 . A process according to  claim 1  or  claim 2  wherein the solid particles have a particle diameter in the range 20 to 300 microns.  
   
   
       4 . A process according to  claim 3  wherein the particle diameter size distribution is at least 20 microns.  
   
   
       5 . A process according to  claim 1  or  claim 2  wherein the fluidised bed comprises solid particles having sizes according to one or more of the following independent criteria: (i) at least 65% of the particles have particle diameters in the range 20-120 microns; (ii) less than 15% of the particles have a particle diameter less than 45 microns; and (iii) less than 5% of the particles have a particle diameter greater than 105 microns.  
   
   
       6 . A process according to  claim 1  or  claim 2  wherein the concentration of oxygen in the molecular oxygen-containing gas is in the range 50 to 100% by volume.  
   
   
       7 . A process according to  claim 1  or  claim 2  wherein the at least one oxidisable reactant is introduced into the fluidised bed as a gas and/or liquid through one or more inlets.  
   
   
       8 . A process according to  claim 7  wherein the at least one oxidisable reactant is introduced into the fluidised bed as a gas and is a component of the fluidising gas.  
   
   
       9 . A process according to  claim 7  wherein the oxidisable reactant is ethylene.  
   
   
       10 . A process according to  claim 8  wherein the oxidisable reactant is ethylene.  
   
   
       11 . A process according to  claim 1  or  claim 2  wherein the fluidised bed has a particle density of at least 0.6 g/cm 3 .  
   
   
       12 . A process according to  claim 1  or  claim 2  wherein the fluidised bed has a settled bed density of at least 0.4 g/cm 3 .  
   
   
       13 . A process according to  claim 1  or  claim 2  wherein the fluidised bed is catalytically active for any one of oxidation, ammoxidation and carboxylation processes.  
   
   
       14 . A process according to  claim 13  wherein the fluidised bed is catalytically active for the ammoxidation of hydrocarbons by reaction with molecular oxygen and ammonia.  
   
   
       15 . A process according to  claim 13  wherein the fluidised bed is catalytically active for the oxidation of hydrocarbons by reaction with molecular oxygen.  
   
   
       16 . A process according to  claim 15  wherein the hydrocarbon is ethane and the ethane is reacted with molecular oxygen to produce ethylene and/or acetic acid.  
   
   
       17 . A process according to  claim 15  wherein the hydrocarbon is ethylene and the ethylene is reacted with molecular oxygen to produce acetic acid.  
   
   
       18 . A process according to  claim 15  wherein the hydrocarbon is a mixture of ethane and ethylene and the mixture is reacted with molecular oxygen to produce acetic acid and optionally ethylene.  
   
   
       19 . A process according to  claim 13  wherein the fluidised bed is catalytically active for the carboxylation of alkenes to produce unsaturated esters by reaction of a carboxylic acid, an olefin and molecular oxygen.  
   
   
       20 . A process according to  claim 19  wherein the alkene is ethylene, the carboxylic acid is acetic acid and the unsaturated ester is vinyl acetate.  
   
   
       21 . A process according to any one of  claims 1  to  12  and  claims 14  to  17  wherein the at least one oxidisable reactant is selected from at least one of ethane and ethylene, the molecular-oxygen containing gas is oxygen and the at least one of ethane and ethylene are reacted with the oxygen to produce acetic acid and the total linear gas flow through the fluidised bed is up to 50 cm/s.  
   
   
       22 . A process according to  claim 1  or  claim 2  wherein the oxidisable reactants are ethylene and acetic acid, the molecular-oxygen containing gas is oxygen and the ethylene and acetic acid are reacted with the oxygen to produce vinyl acetate and the total linear gas flow through the fluidised bed is up to 30 cm/s.  
   
   
       23 . A process for the production of vinyl acetate by the reaction of ethylene and acetic acid with molecular oxygen in a fluid bed reactor in the presence of a catalytically active fluidised bed of solid particles having a particle diameter in the range 20 to 300 microns and having a particle diameter size distribution of at least 20 microns, and in which process a molecular oxygen-containing gas having an oxygen concentration greater than that of air is introduced into the fluidised bed, and the fluidised bed is maintained in a turbulent regime by using solid particles having a particle density of at least 0.6 g/cm 3  and a settled bed density of at least 0.4 g/cm 3  and by operating at a pressure in the fluid bed reactor of at least 4 bara with a total linear gas flow through the fluidised bed of from 2 to 30 cm/s inclusive.  
   
   
       24 . A process according to  claim 23  wherein the total linear gas flow through the fluidised bed is from 2 to 25 cm/s inclusive.  
   
   
       25 . A process according to  claim 23  or  claim 24  wherein the solid particles have a particle density in the range 1.1 to 1.5 g/cm 3 .  
   
   
       26 . A process according to  claim 23  or  claim 24  wherein the solid particles comprise a Group VIII metal, a catalyst promoter and an optional co-promoter.  
   
   
       27 . A process according to  claim 26  wherein the Group VIII metal is palladium and the catalyst promoter is selected from gold, copper, cerium and mixtures thereof.  
   
   
       28 . A process for the reaction of molecular oxygen with (a) ethane to produce ethylene and/or acetic acid, (b) ethylene to produce acetic acid or (c) mixtures of ethane and ethylene to produce acetic acid, optionally with ethylene, in a fluid bed reactor in the presence of a catalytically active fluidised bed of solid particles having a particle diameter in the range 20 to 300 microns and having a particle diameter size distribution of at least 20 microns, and in which process a molecular oxygen-containing gas having an oxygen concentration greater than that of air is introduced into the fluidised bed, and the fluidised bed is maintained in a turbulent regime by using solid particles having a particle density of at least 0.6 g/cm 3  and a settled bed density of at least 0.4 g/cm 3  and by operating at a pressure in the fluid bed reactor of at least 4 bara with a total linear gas flow through the fluidised bed of from 2 to 35 cm/s, inclusive.  
   
   
       29 . A process according to  claim 28  wherein the solid particles have a particle density of 1.25 to 3.5 g/cm 3 .  
   
   
       30 . A process according to  claim 28  or  claim 29  wherein the solid particles are of a composition comprising in combination with oxygen the elements: 
       Mo a .W b .Ag c .Ir d .X e .Y f   
     wherein X is the elements Nb and V; 
 Y is one or more elements selected from the group consisting of:  
 Cr, Mn, Ta, Ti, B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Rh, Cu, Au, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Ti, U, Re and Pd;  
 a, b, c, d, e and f represent the gram atom ratios of the elements such that 
 0<a≦1, 0≦b<1 and a+b=1;  
 0<(c+d)≦0.1;  
 0<e≦2; and  
 0<f≦2.  
 
 
   
   
       31 . A process according to  claim 28  or  claim 29  wherein the solid particles are of a composition comprising in combination with oxygen the elements: 
 molybdenum, vanadium, niobium and gold in the absence of palladium according to the empirical formula:     Mo a W b Au c V d Nb e Y f     wherein Y is one or more elements selected from the group consisting of: Cr, Mn, Ta, Ti, B, Al, Ga, In, Pt, Zn, Cd, Bi, Ce, Co, Rh, Ir, Cu, Ag, Fe, Ru, Os, K, Rb, Cs, Mg, Ca, Sr, Ba, Zr, Hf, Ni, P, Pb, Sb, Si, Sn, Ti, U, Re, Te, and La;    a, b, c, d, e and f represent the gram atom ratios of the elements such that: 
 0<a≦1; 0≦b≦1 and a+b=1;  
 10 −5 <c≦0.02;  
 0<d≦21  
 0<e≦1; and  
 0<f≦2.  
   
   
   
       32 . A process according to  claim 23  or  claim 24  or  claim 28  or  claim 29  wherein the fluidised bed of solid particles has a particle diameter size distribution of at least 50 microns.  
   
   
       33 . A process according to  claim 23  or  claim 24  or  claim 28  or  claim 29  wherein the fluidised bed comprises catalyst particles which have a particle size distribution in which (i) at least 65% of the particles have particle diameters in the range 20-120 microns, (ii) less than 15% of the particles have a particle diameter of less than 45 microns and (iii) less than 5% of the particles have a particle diameter of greater than 105 microns.  
   
   
       34 . A process according to  claim 1  or  claim 2  or  claim 23  or  claim 24  or  claim 28  or  claim 29  wherein the solid particles comprise a support.  
   
   
       35 . A process according to  claim 34  wherein the support is selected from silica, alumina, silica/alumina, titania, silica/titania, zirconia and mixtures thereof.  
   
   
       36 . A process according to  claim 1  or  claim 2  or  claim 23  or  claim 24  or  claim 28  or  claim 29  wherein the particle density of the solid particles is modified by the use of a densifier during the preparation of the particles.  
   
   
       37 . A process according to  claim 36  wherein the densifier is used during preparation of the support.  
   
   
       38 . A process according to  claim 37  wherein the densifier is an inert oxide.  
   
   
       39 . A process according to  claim 38  wherein the inert oxide is tin oxide.  
   
   
       40 . A process according to  claim 36  wherein the particle density is modified by substitution of at least one metal of the solid particles by at least one metal having a higher atomic weight.  
   
   
       41 . A process according to  claim 40  wherein the at least one substituting metal is chemically equivalent to the at least one substituted metal.  
   
   
       42 . A process according to  claim 40  wherein the solid particles comprise at least one of Mo, V and Nb, and the particle density of the particles is modified by substituting at least one of Mo, V, Nb by at least one of Sn, Te, La, Ta, W, Re, Pb, Bi, Ce, Pr, Gd and Yb.  
   
   
       43 . A process according to  claim 1  or  claim 2  or  claim 23  or  claim 24  or  claim 28  or  claim 29  wherein the particle density of the solid particles is modified by the use of a fluidising gas.  
   
   
       44 . A process according to  claim 43  wherein the fluidising gas comprises ethylene.  
   
   
       45 . A process according to  claim 44  wherein the concentration of ethylene in the fluidising gas is at least 30 mol % by volume.  
   
   
       46 . A process according to  claim 45  wherein the concentration of ethylene is at least 30 mol % to 85 mol %.