Integrated process for the production of ethylene-butylene copolymer, an ethylene-butylene copolymer and the use of ethylene and 1-butylene, as comonomer, sourced from renewable natural raw materials

Abstract

An ethylene-butylene copolymer prepared from integrated processes for the production of ethylene-butylene copolymers produced from at least one renewable natural raw material, wherein, in the ethylene monomer used in the polymerization of the ethylene copolymer with 1-butylene, as the comonomer, ethylene is obtained by the ethanol dehydration reaction, in which ethanol is produced by the fermentation of sugars, and the 1-butylene comonomer is obtained according to at least one of dehydration reactions involving 1-butanol and the dimerization reaction of ethylene produced by the dehydration of ethanol obtained from the fermentation of sugars, followed by the isomerization of the 2-butylene isomers then formed. The ethylene-butylene copolymer thus produced is completely based on carbon atoms originated from renewable natural raw materials which, upon incineration, produce CO 2 from a non-fossil origin.

1 . An ethylene-butylene copolymer, 1-butylene being a comonomer, ethanol and the butanol being raw materials, which are obtained from vegetable sourced materials, via the fermentation of sugars extracted therefrom prepared from an integrated process, comprising the steps of:
 a) producing sugars through extraction and processing of the vegetable sourced raw materials;   b) feeding the sugar streams to a vat under ethanol producing must fermentation conditions;   c) distilling the ethanol containing leavened must stream in a distiller for the separation of ethanol;   d) dehydrating ethanol in the ethanol stream in a dehydration reactor, for obtaining an ethylene stream, to be purified in a distiller, producing ethylene to be fed to a reactor;   e) dehydrating a portion of the ethanol stream, in a dehydrogenation reactor, for obtaining an acetaldehyde stream, and/or optionally feeding a portion of the ethanol stream to a direct synthesis reactor, for directly obtaining a 1-butanol stream;   f) aldolic condensation of the acetaldehyde stream from the dehydrogenation reactor, in a condensation reactor for obtaining a 3 hydroxy-butanol exit stream;   g) dehydrating 3 hydroxy-butanol from the condensation reactor, in a dehydration reactor to obtain a crotonaldehyde exit stream;   h) hydrogenating crotonaldehyde from the dehydrating reaction, in a hydrogenating reactor to obtain 1-butanol;   i) optionally, feeding sugar streams to vats, under 1-butanol producing must fermentation conditions;   j) distilling 1-butanol containing leavened must stream, in a distiller, for separating 1-butanol;   k) dehydrating 1-butanol from the 1-butanol stream, from step e), and/or from the 1-butanol stream, from step h), and/or from the mixtures thereof, and/or from the fermentation of sugars in steps i) and j), in the presence of alumina, silica, silico-alumina, zeolites and other metallic oxide catalysts, with a residence time varying from 0.1 to 60 seconds, and at temperatures ranging from 150° C. to 380° C., in an adiabatic or isothermic, fluidized or fixed bed dehydration reactor, for obtaining butylene isomers mixture;   l) distilling the butylene isomers mixture stream, from the dehydration reactor, in a distiller, which outputs the 1-butylene stream, and 2-butylene isomer streams;   m) isomerizing the 2-butylene isomers stream in the isomerization reactor, for obtaining the 1-butylene and 2-butylene isomer mixture stream which returns to the distiller; and   n) polymerizing ethylene from the ethylene streams and 1-butylene from the 1-butylene stream, in the polymerization reactor, for obtaining the ethylene-butylene copolymer which has 100% carbon content from renewable natural raw materials, as determined by the essay method according to technical ASTM D 6866-06 Norm and, when burned, does not generate fossil carbon into the atmosphere.   
     
     
         2 . The copolymer according to  claim 1 , wherein the mass percent content of the 1-butylene comonomer is in the range of from 0.5% to 30%. 
     
     
         3 . The copolymer according to  claim 2 , wherein the mass percent content of the 1-butylene comonomer is in the range of from 2% to 20%. 
     
     
         4 . The copolymer according to  claim 1 , with a density ranging from 0.900 to 0.960 g/cm 3 . 
     
     
         5 . Packaging film, industrial bags, sanitary napkins, frigorific packaging, the linings of carton packaging and adherent lining layers produced from the ethylene-1 butylene copolymer of  claim 1 . 
     
     
         6 . An ethylene-butylene copolymer obtained by the following process steps of:
 a) producing sugars through extraction and processing of the vegetable sourced raw materials;   b) feeding the sugar streams to a vat under ethanol producing must fermentation conditions;   c) distilling the ethanol containing leavened must stream in a distiller for the separation of ethanol;   d) optionally, feeding sugar streams to vats, under 1-butanol producing must fermentation conditions;   e) distilling 1-butanol containing leavened must stream, in a distiller, for separating 1-butanol;   f) simultaneous dehydrating ethanol and 1-butanol from the alcohols mixture, from ethanol and 1-butanol streams, in the presence of catalysts, such as alumina, silica, silico-alumina, zeolites, and metallic oxides, at temperatures ranging from 150° C. to 380° C., preferably from 250° C. to 370° C., and residence times of from 0.1 to 60 seconds, preferably from 1 to 30 seconds, in an adiabatic or isothermic, fluidized or fixed bed dehydration reactor, for obtaining the ethylene and butylenes mixture;   g) distilling the ethylene, 1-butylene and 2-butylene isomers mixture, from step k), in a distiller, that supplies a first ethylene and 1-butylene mixture stream and a second 2-butylene isomers stream;   h) isomerizing 2-butylene isomers stream, in an isomerization reactor, for obtaining 1-butylene and 2-butylene isomer streams; which returns to the distiller; and   i) polymerizing the ethylene and 1-butylene from the first ethylene and 1-butylene mixture stream; in a polymerization reactor, to obtain the ethylene-butylene copolymer, which has 100% renewable natural origin carbon,   wherein the copolymer, when burned, does not generate fossil carbon into the atmosphere.   
     
     
         7 . Packaging film, industrial bags, sanitary napkins, frigorific packaging, the linings of carton packaging and adherent lining layers produced from the ethylene-1 butylene copolymer of  claim 6 . 
     
     
         8 . An ethylene-butylene copolymer obtained by the following process steps of:
 a) producing sugars through extraction and processing of vegetable sourced raw materials;   b) feeding sugar streams to a vat under ethanol producing must fermentation conditions;   c) distilling the ethanol containing leavened must stream, in a distiller, for separating the ethanol;   d) dehydrating ethanol from the ethanol stream, in a dehydration reactor, for obtaining an ethylene stream, to be purified in a distiller for obtaining ethylene to be fed to a reactor;   e) dimerizing a portion of the ethylene stream, from step d), in a dimerization reactor for obtaining a 1-butylene and 2-butylene isomers mixture;   f) distilling the 1-butylene and 2-butylene isomer mixture, in a distiller for obtaining the 1-butylene stream and the 2-butylene isomer stream;   g) isomerizing the 2-butylene isomers stream, in an isomerization reactor, for obtaining a 1-butylene and 2-butylene isomer stream, which returns to the distiller; and   h) polymerizing ethylene from the other portion of the ethylene from step d), and 1-butylene from the 1-butylene stream, from step f), in a polymerization reactor, for obtaining the ethylene-butylene copolymer which has 100% renewable natural origin carbon,   wherein the copolymer, when burned, does not generate fossil carbon into the atmosphere.   
     
     
         9 . Packaging film, industrial bags, sanitary napkins, frigorific packaging, the linings of carton packaging and adherent lining layers produced from the ethylene-1 butylene copolymer of  claim 8 .