Fractionation process for the unsaponifiable material derived from black-liquor soaps

Abstract

The present invention relates to a fractionation process of the unsaponifiable material derived from black-liquor soaps of the cellulose industry. Through this procedure fractions that essentially contain free sterols, fatty alcohols, sterol esters and fatty alcohol esters respectively are separated. Fractions containing sterols or fatty alcohols can be used as such in the alimentary, cosmetic and pharmaceutical industries or they can be used as raw materials for transforming into other useful products.

What is claimed is:  
     
         1 . A method to separate components from a raw material containing neutral compounds of black liquor soaps CHARACTERIZED because it includes: 
 a) To feed the raw material to a short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 100 and 200° C. and the column condenser is at a temperature between 60 and 100° C. to form a distillate whose weight is between 35 and 55% in weight of the fed raw material weight.    b) To collect the distillate as essentially sterol and pitch free wax.    c) A short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm.    d) A residence time in the feeding material column shorter than 15 minutes.    
     
     
         2 . A method to separate components from a raw material containing neutral compounds of black liquor soaps CHARACTERIZED because it includes: 
 a) To feed the raw material to a first short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 200 and 300° C. and the column condenser is at a temperature between 100 and 180° C. to form a first distillate whose weight is between 70 and 90% in weight of the fed raw material weight.    b) To collect the first distillate.    c) To feed the first distillate collected in b) or a portion of this distillate to a second short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 100 and 200° C. and the column condenser is at a temperature between 50 and 120° C. to form a second distillate whose weight is between 45 and 60% in weight of the feeding weight of the second column.    d) To collect the second distillate as essentially sterol and pitch free wax.    e) A short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm and a second short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm.    f) A residence time shorter than 15 minutes in the first column of the feeding material and a residence time shorter than 15 minutes in the second column of the feeding material.    
     
     
         3 . A method according to claims  1  or  2  to produce a fatty alcohol concentrate of approximately between 20 and 26 carbons CHARACTERIZED because it involves: 
 a) To mix the distillate collected in b) or a fraction of this distillate with an organic solvent or mix the second distillate collected in d) or a fraction of this distillate with an organic solvent.  
 b) To heat or reflux the a) mixture.  
 c) To cool down the b) mixture up to a temperature between −20 and 20° C. or less.  
 d) To collect the solids produced in c).  
 e) To dessolvent the d) solids.  
 f) To collect the e) solids.  
 
     
     
         4 . A method according to  claim 3  CHARACTERIZED because the a) solvent is hexane, heptane or any aliphatic hydrocarbon containing 6 or 10 atoms of carbon, benzene, xylene or toluene or a mixture of two or more of any of these solvents.  
     
     
         5 . A method according to claims  2  or  3  CHARACTERIZED because the c) solids contain not less than 70% in weight of docosanol and tetracosanol.  
     
     
         6 . A method to separate components from a raw material containing neutral compounds of black liquor soaps CHARACTERIZED because it includes: 
 a) To feed the raw material to a first short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 200 and 300° C. and the column condenser is at a temperature between 100 and 180° C. to form a first distillate whose weight is between 70 and 90% in weight of the fed raw material weight.    b) To collect the first distillate.    c) To feed the first distillate collected in b) or a portion of this first distillate to a second short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 100 and 200° C. and the column condenser is at a temperature between 60 and 100° C. to form a second residue whose weight is between 35 and 55% in weight of the feeding weight of the second column.    d) To collect the second residue as essentially wax and pitch free sterols.    e) A first short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm and a second short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm.    f) A residence time shorter than 15 minutes in the first column of the feeding material and a residence time shorter than 15 minutes in the second column of the feeding material.    
     
     
         7 . A method to separate components from a raw material containing neutral compounds of black liquor soaps CHARACTERIZED because it includes: 
 a) To feed the raw material to a first short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 100 and 200° C. and the column condenser is at a temperature between 60 and 100° C. to form a first distillate whose weight is between 40 and 55% in weight of the fed raw material weight.    b) To collect the first residue.    c) To feed the first residue collected in b) or a portion of this first residue to a second short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 200 and 300° C. and the column condenser is at a temperature between 100 and 150° C. to form a second distillate whose weight is between 45 and 65% in weight of the feeding weight of the second column.    d) To collect the second distillate as essentially wax and pitch free sterols.    e) A first short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm and a second short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm.    f) A residence time shorter than  15  minutes in the first column of the feeding material and a residence time shorter than 15 minutes in the second column of the feeding material.    
     
     
         8 . A method according to claims  6  o  7  to produce a fatty alcohol concentrate of approximately between 20 and 26 carbons CHARACTERIZED because it involves: 
 a) To mix the second residue collected in d) or a fraction of this second residue with an organic solvent or mix the second distillate collected in d) or a fraction of this second distillate with an organic solvent.  
 b) To heat or reflux the a) mixture.  
 c) To cool down the b) mixture up to a temperature between −20 and 20° C.  
 d) To separate the solids produced in c).  
 e) To dessolventize the d) solids.  
 f) To collect the e) solids.  
 
     
     
         9 . A method according to  claim 8  CHARACTERIZED because the a) solvent is acetone, methyl ethyl ketone or any dialkylketone containing 3 or 10 atoms of carbon, methanol, ethanol or any aliphatic alcohol of 1 or 6 carbon atoms or a mixture of two or more of any of these solvents.  
     
     
         10 . A method according to claims  8  or  9  CHARACTERIZED because the solids dessolvent in f) contain not less than 90% in weight of free sterols and stanols.  
     
     
         11 . A method according to  6  or  7  to produce a sterol composition CHARACTERIZED because it involves: 
 a) To mix the second residue collected in d) or a fraction of this second residue with an organic solvent or mix the second distillate collected in d) or a fraction of this second distillate with an organic solvent.  
 b) To agitate the a) mixture at room temperature or at temperature lower than room temperature.  
 c) To separate the solid and liquid phases of b) mixture.  
 d) To dessolventize the c) solid phase.  
 e) To collect the d) solids.  
 
     
     
         12 . A method according to  claim 11  CHARACTERIZED because the a) solvent is acetone, methyl ethyl ketone or any dialkylketone containing 3 or 10 atoms of carbon, methanol, ethanol or any aliphatic alcohol of 1 or 6 carbon atoms or a mixture of two or more of any of these solvents.  
     
     
         13 . A method according to claims  11  or  12  CHARACTERIZED because the dessolvented crystals of stage a) contain at least 90% in weight of free sterols or stanols.  
     
     
         14 . A method to separate components from a raw material containing neutral compounds of black liquor soaps CHARACTERIZED because it includes: 
 a) To feed the raw material to a short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 200 and 300° C. and the column condenser is at a temperature between 100 and 180° C. to form a residue whose weight is between 10 and 30% in weight of the fed raw material weight.    b) To collect the residue as essentially sterol and wax free pitch.    c) A short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm.    d) A residence time shorter than 15 minutes in the column of the feeding material.    
     
     
         15 . A method to separate components from a raw material containing neutral compounds of black liquor soaps CHARACTERIZED because it includes: 
 a) To feed the raw material to a first short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 100 and 200° C. and the column condenser is at a temperature between 60 and 100° C. to form a first residue whose weight is between 40 and 55% in weight of the fed raw material weight.    b) To collect the first residue.    c) To feed the first residue collected in b) or a portion of this first residue to a second short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 200 and 300° C. and the column condenser is at a temperature between 100 and 200° C. to form a second residue whose weight is between 25 and 35% in weight of the feeding weight of the second column.    d) To collect the second residue as essentially wax and sterol free pitch.    e) A first short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm and a second short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm.    f) A residence time shorter than 15 minutes in the first column of the feeding material and a residence time shorter than 15 minutes in the second column of the feeding material.    
     
     
         16 . A method according to claims  14  or  15  to produce a composition of sterol or stanol esters or fatty alcohols CHARACTERIZED because it includes: 
 a) To feed the residue collected in b) or a fraction of this residue or to feed the second residue of stage d) or a fraction of this residue to a short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at 300° C. and the column condenser is at a temperature between 120 and 200° C. to form a distillate whose weight is higher than 90% in weight of the fed raw material weight.  
 b) To collect the distillate as a composition of sterol or stanol esters.  
 c) A short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm.  
 d) A residence time shorter than 15 minutes in the column of the feeding material.  
 
     
     
         17 . A method according to claims  14 ,  15 ,  16  or  38  to produce a composition of sterol or stanol esters or fatty alcohols CHARACTERIZED because it involves: 
 a) To dissolve the residue collected in b) or a fraction of this residue in an organic solvent or dissolve the second residue of d) or a fraction of this residue in an organic solvent or dissolve the solids of f) or a fraction of these solids in an organic solvent.  
 b) To contact the solution of a) to an adsorbent.  
 c) To separate the solution and the adsorbent of b).  
 d) To dessolventize the solution of c).  
 e) To collect the dessolventized solids of d).  
 
     
     
         18 . A method according to  claim 17  CHARACTERIZED because the organic solvent of a) is an aromatic hydrocarbon or a chloro-hydrocarbon.  
     
     
         19 . A method according to  claim 18  CHARACTERIZED because the organic solvent of a) is chloroform or carbon tetrachloride.  
     
     
         20 . A method according to claims  17 ,  18  or  19  CHARACTERIZED because the adsorbent of b) is active carbon or alumina or silicates or diatomaceous soils.  
     
     
         21 . A method according to claims  16 ,  17 ,  18 ,  19  or  20  CHARACTERIZED because the composition of sterol or stanol or fatty alcohol esters contains not lower than 90% in weight of these esters.  
     
     
         22 . A method according to claims  14 ,  15 ,  16 ,  17 ,  18 ,  19 ,  20 ,  21  or  38  to produce a composition of free sterols, stanols or fatty alcohols CHARACTERIZED because it involves: 
 a) To mix the residue collected in b) or a fraction of this residue or to mix the second residue of d) or a fraction of this second residue or to mix the solids of e) dr a fraction of these solids or to mix the composition of sterol or stanol or fatty alcohol esters or to mix the solids of f) or a fraction of these solids with an aqueous or alcoholic solution of sodium or potassium or ammonium hydroxide or pure ammoniac and an organic solvent.  
 b) To heat the mixture of a) at a temperature between 100 and 300° C. for a suitable period of time.  
 c) To cool down the mixture of b).  
 d) To separate the organic phase of the c) mixture.  
 e) To mix the organic phase of d) with water.  
 f) To separate the organic phase and the water of e).  
 g) To dessolventize the separated organic phase of f).  
 h) To collect the solids produced in g).  
 
     
     
         23 . A method according to  claim 22  CHARACTERIZED because the solvent of a) is an aromatic or aliphatic hydrocarbon.  
     
     
         24 . A method according to  claim 23  CHARACTERIZED because the solvent is toluene or xylene or hexane.  
     
     
         25 . A method according to claims  22 ,  23  or  24  CHARACTERIZED because the composition of solids of h) contains at least 50% in weight of free sterols, stanols or fatty alcohols.  
     
     
         26 . A method to separate components of a raw material containing neutral compounds of black liquor soaps CHARACTERIZED because it involves: 
 a) To feed the raw material to a short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 200 and 300° C. and the column condenser is at a temperature between 80 and 120° C. to form a distillate whose weight is between 70 and 90% in weight of the fed raw material weight.    b) To collect the distillate as essentially pitch free wax and sterols.    c) A short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm.    d) A residence time shorter than 15 minutes in the column of the feeding material.    
     
     
         27 . A method according to  claim 26  to produce a composition of free sterols CHARACTERIZED because it involves: 
 a) To mix the distillate collected in b) or a fraction of this distillate with an organic solvent.  
 b) To heat or reflux the a) mixture.  
 c) To cool down the b) mixture up to a temperature between −20 and 20° C.  
 d) To separate the mother liquor solids of c).  
 e) To dessolventize the d) solids.  
 f) To collect the e) solids.  
 
     
     
         28 . A method according to  claim 27  CHARACTERIZED because the a) solvent is acetone, methyl ethyl ketone or any dialkylketone containing 3 or 10 atoms of carbon, methanol, ethanol or any aliphatic alcohol of 1 or 6 carbon atoms or a mixture of two or more of any of these solvents.  
     
     
         29 . A method according to claims  27  or  28  CHARACTERIZED because the composition of sterols contains at least 90% in weight of free sterols or stanols.  
     
     
         30 . A method to produce a concentrate of fatty alcohols according to  claim 26  CHARACTERIZED because it involves: 
 a) To mix the distillate collected in b) or a portion of this distillate with an organic solvent.  
 b) To heat or reflux the a) mixture.  
 c) To cool down the boiled mixture up to a temperature between −20 and 20° C. or less.  
 d) To separate the mother liquor from solids produced in c).  
 e) To dessolventize the mother liquor of d).  
 f) To mix the solids produced in e) with an organic solvent.  
 g) To heat or reflux the f) mixture.  
 h) To cool down the boiled mixture of g) up to a temperature between −20 and 20° C. or less.  
 i) To separate the h) solids.  
 j) To dessolventize the i) solids.  
 
     
     
         31 . A method according to  claim 30  CHARACTERIZED because the a) solvent is acetone, methyl ethyl ketone or any dialkylketone containing 3 or 10 atoms of carbon, methanol, ethanol or any aliphatic alcohol of 1 or 6 carbon atoms or a mixture of two or more of any of these solvents.  
     
     
         32 . A method according to  claim 31  CHARACTERIZED because the a) solvent is hexane, heptane, xylene or toluene or a mixture of two or more of any of these solvents.  
     
     
         33 . A method according to claims  29 ,  30  or  32  CHARACTERIZED because the concentrate of fatty alcohols contains at least 50% in weight of docosanol and tetracosanol.  
     
     
         34 . A method to separate components of a raw material containing neutral compounds of black liquor soaps CHARACTERIZED because it involves: 
 a) To feed the raw material to a short path distillation column at a pressure between 0.01 and 5 mbar, the column evaporator is at a temperature between 100 and 200° C. and the column condenser is at a temperature between 60 and 100° C. to form a residue whose weight is between 45 and 65% in weight of the fed raw material weight.    b) To collect the residue as essentially wax free pitch and sterols.    c) A short path distillation column that has an evaporation surface and a condensation surface separated by a distance not longer than 50 cm.    d) A residence time shorter than 15 minutes in the column of the feeding material.    
     
     
         35 . A method according to  claim 34  to produce a composition of sterols CHARACTERIZED because it involves: 
 a) To mix the residue collected in b) or a fraction of this residue with an organic solvent.  
 b) To heat or reflux the a) mixture.  
 c) To cool down the b) mixture up to a temperature between −20 and 20° C.  
 d) To separate the solids of c).  
 e) To dessolventize the d) solids.  
 f) To collect the e) solids.  
 
     
     
         36 . A method according to  claim 35  CHARACTERIZED because the a) solvent is acetone, methyl ethyl ketone or any dialkylketone containing 3 or 10 atoms of carbon, methanol, ethanol or any aliphatic alcohol of 1 or 6 carbon atoms or a mixture of two or more of any of these solvents.  
     
     
         37 . A method according to claims  35  or  36  CHARACTERIZED because the composition of sterols contains at least 90% in weight of free sterols and stanols.  
     
     
         38 . A method according to  claim 34  to produce a composition of free sterols, stanols or fatty alcohols CHARACTERIZED because it involves: 
 a) To mix the residue collected in b) or a fraction of this residue with an organic solvent.  
 b) To heat or reflux the a) mixture.  
 c) To cool down the boiled mixture up to a temperature between −20 and 20° C.  
 d) To separate the mother liquor solids of c).  
 e) To dessolventize the d) mother liquor.  
 f) To collect the e) solids.  
 g) To mix the solids of f) or a fraction of these solids with an aqueous or alcoholic solution of sodium or potassium or ammonium hydroxide or pure ammonia and an organic solvent.  
 h) To heat the mixture at a temperature between 100 and 300° C. for a suitable period of time  
 i) To separate the organic phase of the c) mixture.  
 j) To mix the organic phase of i) with water.  
 k) To separate the organic phase and the water of j).  
 l) To dessolventize the organic phase separated in k).  
 m) To collect the solids of l)  
 
     
     
         39 . A method according to  claim 38  CHARACTERIZED because the a) solvent is acetone, methyl ethyl ketone or any alkylketone containing 3 or 10 atoms of carbon, methanol, ethanol or any aliphatic alcohol of 1 or 6 carbon atoms or a mixture of two or more of any of these solvents.  
     
     
         40 . A method according to  claim 39  CHARACTERIZED because the a) solvent is hexane, heptane, xylene or toluene or a mixture of two or more of any of these solvents.  
     
     
         41 . A method according to claims  38 ,  39  or  40  CHARACTERIZED because the composition of free sterols, stanols or fatty alcohols contains not less than 50% in weight of free sterols, stanols or fatty alcohols.