Steamcracking bio-naphtha produced from complex mixtures of natural occurring fats and oils

Abstract

A process for making a bio-naphtha and optionally bio-propane from a complex mixture of natural occurring fats & oils, wherein said complex mixture is subjected to a refining treatment for removing the major part of non-triglyceride and non-fatty acid components, thereby obtaining refined fats & oils; said refined fats & oils are transformed into linear or substantially linear paraffin's as the bio-naphtha by an hydrodeoxygenation or from said refined fats & oils are obtained fatty acids that are transformed into linear or substantially linear paraffin's as the bio-naphtha by hydrodeoxygenation or decarboxylation of the free fatty acids or from said refined fats & oils are obtained fatty acids soaps that are transformed into linear or substantially linear paraffin's as the bio-naphtha by decarboxylation of the soaps.

What is claimed: 
     
         1 - 16 . (canceled) 
     
     
         17 . A process comprising:
 (a) making a bio-naphtha and optionally bio-propane from a complex mixture of natural occurring raw fats and oils, wherein the raw fats and oils are subjected to a refining pretreatment including a degumming and a bleaching for removing non-triglyceride and non-fatty acid components, thereby obtaining refined fats and oils;   (b1) wherein the refined fats and oils are physically refined by vacuum distillation or steam distillation to recover mixed fatty acids as overhead product and triglycerides as bottom product; and wherein either:
 (c1) the refined fats and oils still containing free fatty acids or the physically refined triglycerides are sent to a hydrodeoxygenation section and converted into bio-naphtha and bio-propane; or 
 (c2) the mixed fatty acids are sent to a hydrodeoxygenation section and converted into bio-naphtha or are sent to a decarboxylation section and converted into bio-naphtha; or 
 (b2) the refined fats and oils are saponificated to recover soaps and glycerol or soaps are obtained during a chemical refining step of the raw fats and oils by a neutralisation step; or soaps are obtained via neutralisation of fatty acids obtained by steam splitting/hydrolysis of the refined fats and oils producing fatty acids and glycerol and the soaps are sent to a decarboxylation section and converted into bio-naphtha; and 
   wherein the complex mixture of natural occurring raw fats and oils comprises vegetable oils, animal fats, or mixtures thereof.   
     
     
         18 . The process of  claim 17 , wherein the complex mixture of natural occurring raw fats and oils comprises inedible oils. 
     
     
         19 . The process of  claim 17 , wherein the complex mixture of natural occurring raw fats and oils comprises highly saturated oils. 
     
     
         20 . The process of  claim 17 , wherein the complex mixture of natural occurring raw fats and oils comprises waste food oils. 
     
     
         21 . The process of  claim 17 , wherein the complex mixture of natural occurring raw fats and oils comprises by-products of a refining of vegetable oils. 
     
     
         22 . The process of  claim 17 , wherein the refining pretreatment comprises:
 a physical refining comprising degumming, bleaching, and steam refining-deodorisation producing free fatty acids; or   a chemical refining comprising degumming, neutralisation producing soaps that are split into free fatty acids, bleaching, and deodorisation.   
     
     
         23 . The process of  claim 17 , wherein the fatty acids are obtained by acidulation of soaps. 
     
     
         24 . The process of  claim 17 , wherein the refined fats and oils are hydrolysed to produce mixed fatty acids and glycerol. 
     
     
         25 . The process of  claim 17 , wherein a quality of the mixed fatty acids is improved by hydrogenation of double bonds in the acyl-moiety or before hydrolysis the fats and oils are hydrogenated to remove remaining double bonds and subsequently sent to a hydrolysis step. 
     
     
         26 . The process of  claim 17 , wherein a quality of the soaps is improved by hydrogenation of double bonds in the acyl-moiety or before saponification or hydrolysis, the fats and oils are hydrogenated to remove remaining double bonds and subsequently sent to a saponification or hydrolysis step. 
     
     
         27 . The process of  claim 17 , wherein in step (c1) the hydrodeoxygenation is conducted in the presence of hydrogen and at least one catalyst selected among Ni, Mo, Co, NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW, CoMoW oxides or sulphides, optionally supported on high surface area carbon, alumina, silica, titania or zirconia. 
     
     
         28 . The process of  claim 27 , wherein the hydrodeoxygenation is carried out at a temperature from 200 to 500° C., under a pressure from 1 MPa to 10 MPa and with a hydrogen to feed ratio from 100 to 2000 Nl/l. 
     
     
         29 . The process of  claim 17 , wherein in step (c2) the hydrodeoxygenation or decarboxylation is conducted in the presence of hydrogen and of at least one catalyst selected from:
 Ni, Mo, Co, NiW, NiMo, CoMo, NiCoW, NiCoMo, NiMoW, and CoMoW oxides or sulphides, optionally supported on high surface area carbon, alumina, silica, titania, or zirconia; or   group 10 metals, group 11 metals, or alloy mixtures thereof optionally supported on high surface area carbon, magnesia, zinc-oxide, spinels, perovskites, calciumsilicates, alumina, silica, silica-alumina, or mixtures thereof   
     
     
         30 . The process of  claim 29 , wherein in step (c2) the hydrodeoxygenation is carried out at a temperature from 200 to 500° C., under a pressure from 1 MPa 15 to 10 MPa and with a hydrogen to feedstock ratio from 100 to 2000 Nl/l. 
     
     
         31 . The process of  claim 17 , wherein the decarboxylation of the fatty acids is carried out on basic oxides either as bulk material or dispersed on basic or neutral carriers, dispersed on basic zeolites. 
     
     
         32 . The process of  claim 31 , wherein the decarboxylation is carried out at a temperature from 100 to 550° C., under a pressure from 0.1 MPa to 10 MPa and with a hydrogen to feedstock ratio from 0 to 2000 Nl/l. 
     
     
         33 . The process of  claim 17 , wherein the decarboxylation of the soaps is carried out at from 100 to 550° C. under pressure from 0.1 MPa to 10 MPa and in presence of water. 
     
     
         34 . The process of  claim 17 , wherein the decarboxylation of the soaps is carried out with a water to feedstock ratio of at least 1 mole water per mole of soap. 
     
     
         35 . The process of  claim 17 , further comprising using the bio-naphtha as a direct feedstock of a steamcracker, optionally combined with the bio-propane or blended with LPG, naphtha, or gasoil, in order to obtain cracked products including bio-ethylene, bio-propylene, bio-butadiene, bio-isoprene, bio-cyclopentadiene and bio-piperylenes, bio-benzene, bio-toluene, bio-xylene, or bio-gasoline, wherein in the steamcracking process the hydrocarbon feedstock is mixed with steam in a ratio of 0.3 to 0.45 kg steam per kg hydrocarbon feedstock. 
     
     
         36 . The process of  claim 35 , wherein the hydrocarbon feedstock is mixed with steam in a ratio of 0.3 to 0.4 kg steam per kg hydrocarbon feedstock. 
     
     
         37 . The process of  claim 35 , wherein the hydrocarbon feedstock is heated up to a temperature of 750-950° C. and is steamed cracked for a residence time of 0.05 to 0.5 seconds. 
     
     
         38 . The process of  claim 35 , wherein the hydrocarbon feedstock is heated up to a temperature of 750-950° C. is steamed cracked for a residence time of 0.05 to 0.15 seconds. 
     
     
         39 . The process of  claim 35 , wherein the obtained cracked products exhibit an ethylene to methane weight ratio of at least 3.