Process for producing oxygenated products

Abstract

A process for producing oxygenated products from an olefin-rich feedstock comprise reacting, in a hydroformylation stage, a Fischer-Tropsch derived olefinic product comprising linear and methyl branched olefins, with carbon monoxide and hydrogen in the presence of a catalytically effective quantity of a hydroformylation catalyst and under hydroformylation reaction conditions, to produce oxygenated products comprising linear and methyl branched aldehydes and/or alcohols. The Fischer-Tropsch derived olefinic product is that obtained by subjecting a synthesis gas comprising carbon monoxide (CO) and hydrogen (H 2 ) to Fischer-Tropsch reaction conditions in the presence of a Fischer-Tropsch catalyst.

1 . A process for producing oxygenated products from an olefin-rich feedstock, which process comprises reacting, in a hydroformylation stage, a Fischer-Tropsch derived olefinic product comprising linear and methyl branched α-olefins obtained by subjecting a synthesis gas comprising carbon monoxide (CO) and hydrogen (H 2 ) to such Fischer-Tropsch reaction conditions in the presence of a suitable Fischer-Tropsch catalyst to obtain said Fischer-Tropsch derived olefinic product, with carbon monoxide and hydrogen in the presence of a catalytically effective quantity of a hydroformylation catalyst and under hydroformylation reaction conditions, to produce oxygenated products comprising linear and methyl branched aldehydes and/or linear and methyl branched alcohols.  
     
     
         2 . A process for producing oxygenated products, which process comprises 
 subjecting, in a Fischer-Tropsch reaction stage, a synthesis gas comprising carbon monoxide (CO) and hydrogen (H 2 ) to such Fischer-Tropsch reaction conditions in the presence of a suitable Fischer-Tropsch catalyst, to obtain linear and methyl branched olefinic products;    optionally, working up the linear and methyl branched olefinic products to remove unwanted components therefrom and/or to separate a particular olefinic component comprising linear and methyl branched α-olefins therefrom; and    feeding the linear and methyl branched α-olefinic products or the olefinic component comprising linear and methyl branched α-olefins as a feedstock to a hydroformylation stage in which the feedstock is reacted with carbon monoxide and hydrogen in the presence of a catalytically effective quantity of a hydroformylation catalyst and under hydroformylation reaction conditions, to produce oxygenated products comprising linear and methyl branched aldehydes and/or linear and methyl branched alcohols.    
     
     
         3 . A process according to  claim 2 , wherein the Fischer-Tropsch catalyst is iron-based, and comprises iron and/or iron oxides which have been precipitated, fused, or impregnated on a carrier/support.  
     
     
         4 . A process according to  claim 3 , wherein the Fischer-Tropsch reaction stage comprises a fluidized bed reactor, and wherein the Fischer-Tropsch reaction conditions include a reaction temperature of between 300° C. and 340° C.  
     
     
         5 . A process according to  claim 4 , wherein the Fischer-Tropsch catalyst is that derived from the fusion of magnetite with an oxide or a metal of Mn, Ti, Mg, Cr, Ca, Si, Al or Cu or combinations thereof, as structural promoter, and an alkali oxide as a promoter for influencing product selectivities.  
     
     
         6 . A process according to  claim 5  wherein, in the Fischer-Tropsch catalyst, the alkali oxide to structural promoter mass ratio is between 0:1 and 20:1, and wherein the structural promoter content thereof expressed as grams of structural promoter per 100 grams Fe, is between 0,1 and 2.  
     
     
         7 . A process according to any one of  claims 2  to  6  inclusive, wherein the branched olefins comprise mono-methyl and/or dimethyl α-olefins so that the linear and methyl branched aldehydes, when present, comprise mono-methyl and/or dimethyl aldehydes, and the alcohols, when present, comprise mono-methyl and/or dimethyl alcohols, with the hydroformylation stage feedstock optionally including non-olefinic components with different functional groups.  
     
     
         8 . A process according to any one of  claims 2  to  7  inclusive, wherein the Fischer-Tropsch reaction stage and the hydroformylation stage are integrated so that the olefinic products from the Fischer-Tropsch stage pass directly to the hydroformylation stage with at most said working up of the olefin products and intermediate storage thereof between the stages taking place.  
     
     
         9 . A process according to  claim 8 , wherein the carbon monoxide and hydrogen required for the hydroformylation are in the form of sulphur-free synthesis gas, which is the same as that used in the Fischer-Tropsch reaction stage.  
     
     
         10 . A process for producing oxygenated products, which process comprises 
 subjecting, in a Fischer-Tropsch reaction stage, a synthesis gas comprising carbon monoxide (CO) and hydrogen (H 2 ) to such Fischer-Tropsch reaction conditions in the presence of a suitable Fischer-Tropsch catalyst, to obtain an olefinic product;    without working up the olefinic product to remove unwanted components therefrom and/or to separate a particular olefinic component therefrom, feeding the olefinic product as a feedstock to a hydroformylation stage in which the feedstock is reacted winch carbon monoxide and hydrogen in the presence of a catalytically effective quantity of a hydroformylation catalyst and under reaction conditions, to produce oxygenated products comprising aldehydes and/or alcohols, with any non-olefinic components present in single or multiple carbon number fractions in the Fischer-Tropsch reaction stage product, then acting as a reaction medium and/or a solvent medium in the hydroformylation stage.    
     
     
         11 . A process according to  claim 10 , wherein the Fischer-Tropsch reaction stage comprises a slurry bed reactor, and wherein the Fischer-Tropsch reaction conditions include a reaction temperature of between 190° C. and 270° C.  
     
     
         12 . A process according to  claim 10 , wherein the Fischer-Tropsch reaction stage comprises a fixed bed reactor, and wherein the Fischer-Tropsch reaction conditions include a reaction temperature of between 200° C. and 250° C.  
     
     
         13 . A process according to  claim 11  or  claim 12 , wherein the Fischer-Tropsch catalyst includes an oxide or a metal of Mn, Ti, Mg, Cr, Ca, Si, Al or Cu or combinations thereof, as a structural promoter, and an alkali oxide as a promoter for influencing product selectivities.  
     
     
         14 . A process according to  claim 13  wherein, in the Fischer-Tropsch catalyst, the alkali oxide to structural promoter mass ratio is between 0:1 and 20:1 and wherein the structural promoter content thereof, expressed as grams of structural promoter per 100 grams active element of the Fischer-Tropsch catalyst, is between 10 and 40.  
     
     
         15 . A process according to any one of  claims 10  to  14  inclusive, wherein the Fischer-Tropsch catalyst is cobalt-based, and comprises cobalt and/or a cobalt oxide which has been precipitated, sintered or impregnated onto a support.  
     
     
         16 . A process according to  claim 15 , wherein the cobalt-based catalyst comprises an oxide of Ti, Mn, Si, Al or combinations thereof as the support, and a metal and/or an oxide of Pt, Ru, Zr, Re or combinations thereof, as a promoter.  
     
     
         17 . A process according to  claim 15  or  claim 16 , wherein the cobalt catalyst has the following composition: 
 5-30 g cobalt per 100 g of support; and  
 0-10 g promoter per 100 g of support.  
 
     
     
         18 . A process according to any one of  claims 10  to  17  inclusive, wherein the Fischer-Tropsch reaction stage and the hydroformylation stage are integrated so that the olefinic product from the Fischer-Tropsch stage passes directly to the hydroformylation stage with at most said intermediate storage thereof between the stages taking place.  
     
     
         19 . A process according to  claim 18 , wherein the carbon monoxide and hydrogen required for the hydroformylation are in the form of sulphur-free synthesis gas, which is the same as that used in the Fischer-Tropsch stage.  
     
     
         20 . A process according to any one of  claims 2  to  19  inclusive, wherein the Fischer-Tropsch reaction conditions include an inlet synthesis gas pressure to the reaction stage of between 1 and 50 bar, and a H 2 :CO molar ratio of 1,5:1 to 2,5:1 in respect of the synthesis gas.  
     
     
         21 . A process according to  claim 20 , wherein a gas recycle to the reaction stage is optionally employed with the ratio of the gas recycle rate to the fresh synthesis gas feed rate, on a molar basis, being between 1:1 and 3:1, and wherein a space velocity, in m 3  (kg catalyst)− 1  hour− 1 , of from 1 to 20 is used in the reaction stage.  
     
     
         22 . A process according to any one of  claims 1  to  21  inclusive, wherein the hydroformylation catalyst is a phosphine and/or phosphite ligand modified rhodium (Rh), cobalt (Co) or ruthenium (Ru) homogeneous catalyst.  
     
     
         23 . A process according to  claim 22 , wherein the hydroformylation catalyst is a tri-aryl phosphorous derivative used as a ligand with rhodium, or an alkyl phosphorous derivative used as a ligand with cobalt.  
     
     
         24 . A process according to  claim 23 , which includes introducing a rhodium, cobalt or ruthenium metal precursor and the phosphorous derivative separately into the hydroformylation process stage, with the catalyst then forming in situ.  
     
     
         25 . A novel process for producing oxygenated products, substantially as described and illustrated herein.  
     
     
         26 . Oxygenated products when produced by the process of any one of  claims 1  to  25  inclusive, and/or derivatives thereof.  
     
     
         27 . Mono-methyl and/or dimethyl branched alcohols and/or aldehydes, when produced by the process of any one of  claims 1  to  25  inclusive, and/or derivatives thereof.