Integrated process for the preparation of compounds useful as fuel components

Patent metadata

Field	Value
Publication number	US-10590356-B2
Application number	US-201414767400-A
Country	US
Kind code	B2
Filing date	Feb 11, 2014
Priority date	Feb 14, 2013
Publication date	Mar 17, 2020
Grant date	Mar 17, 2020

Abstract

The invention relates to an integrated process for the production of fuel components starting from materials of a biological origin which comprises: (A) transformation of glycerine into an alkoxy-propanediol having formula RO—CH2—CHOH—CH2OH, wherein R is a linear or branched C1-C8 alkyl, (B) transformation of glycerine into 1,2-propanediol CH3—CHOH—CH2OH, (C) dehydration of the 1,2-propanediol obtained in (B) to propionic aldehyde, (D) reaction of part of the propionic aldehyde obtained in (C) with the alkoxy-propanediol having formula RO—CH2—CHOH—CH2OH obtained in (A) to give an acetal having formula (a) wherein R is a linear or branched C1-C8 alkyl, (E) transformation of part of the propionic aldehyde obtained in (C) to a propionate having formula CH3—CH2—COOR′, wherein R′ is a linear or branched C1-C8 alkyl. Particular components for gasolines and/or diesel are also described.

First claim

The invention claimed is:

1. An integrated process for producing fuel components from glycerine, the process comprising purifying glycerine obtained from materials of biological origin to obtain a purified glycerine having a purity of at least 98%, and:
(A) transforming a stream of the purified glycerine into an alkoxy-propanediol having formula: RO—CH 2 —CHOH—CH 2 OH, by etherification of the purified glycerine with an alcohol having formula ROH, wherein R is a C 1 -C 8 alkyl, in the presence of an acid catalyst;
(B) transforming another stream of the purified glycerine into 1,2-propanediol by reducing the purified glycerine with hydrogen in the presence of a reduction catalyst selected from the group consisting of copper chromite, a mixed chrome-zinc-copper oxide, a noble metal on coal, and a noble metal on iron oxide;
(C) dehydrating the 1,2-propanediol obtained in the transforming (B), in the presence of a solid acid catalyst at a temperature ranging from 200 to 350° C. and a pressure ranging from 0.1 to 10 atmospheres, to obtain propionic aldehyde;
(D) reacting part of the propionic aldehyde obtained in the dehydrating (C) with the alkoxy-propanediol obtained in the transforming (A), in the presence of an acid catalyst at a temperature ranging from −10 to 120° C. and a pressure ranging from 0.1 to 20 atmospheres, to obtain an acetal having formula (a):

 and
(E) transforming a remaining part of the propionic aldehyde obtained in the dehydrating (C) to obtain a propyl propionate, by performing a Tishchenko reaction in the presence of a solid base catalyst.

2. The process according to claim 1 , wherein:
R is selected from the group consisting of CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , and C 5 H 11 ; and
R′ is selected from the group consisting of CH 3 , C 2 H 5 , C 3 H 7 , C 4 H 9 , and C 5 H 11 .

3. The process according to claim 2 , wherein R and R′ are each independently selected from the group consisting of ethyl, n-propyl, iso-propyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 3-methyl-1-butyl and 2-methyl-1-butyl.

4. The process according to claim 1 , wherein the acid catalyst is selected from the group consisting of an acid exchange resin, an acid zeolite, a silico alumina and a supported phosphoric acid.

5. The process according to claim 1 , wherein the transforming (A) is carried out at a temperature ranging from 50 to 200° C. and a pressure ranging from 1 to 20 atmospheres.

6. The process according to claim 1 , wherein the transforming (B) is carried out at a temperature ranging from 100 to 300° C. under a hydrogen pressure ranging from 1 to 100 atmospheres.

7. The process according to claim 1 , wherein the solid acid catalyst is selected from the group consisting of an alumina, a silico-alumina, a zeolite, cerium oxide (IV), thorium oxide and zirconia.

8. The process according to claim 1 , wherein the acid catalyst in the reacting (D) is selected from the group consisting of an acid exchange resin, a zeolite and a silico alumina.

9. The process according to claim 1 , wherein the solid base catalyst is selected from the group consisting of an aluminum alcoholate having formula: Al(OR) 3 , wherein R is a linear or branched alkyl group ranging from C 2 to C 6 , magnesium oxide, calcium oxide, strontium oxide, barium oxide, zinc oxide, a zeolite partially or fully exchanged with at least one alkaline metal, and a hydrotalcite having formula: M 2+ a M 3+ 2 (OH) 16 X.nH 2 O, wherein M 2+ is a bivalent metal cation selected from the group consisting of Mg 2+ , Fe 2+ , Ni 2+ , Zn 2+ , Cd 2+ and Co 2+ , M 3+ is a trivalent metal cation selected from the group consisting of Al 3+ , Fe 3+ , Ga 3+ , Cr 3+ , Mn 3+ and Co 3+ , X is an anion selected from the group consisting of CO 3 2− , OH 3− and NO 3− , and a is an integer ranging from 10 to 4.

10. The process according to claim 1 , wherein the transforming (E) is carried out at a temperature ranging from −20 to 150° C. and a pressure ranging from 0.1 to 50 bar.

11. The process according to claim 1 , wherein:
the glycerine obtained from materials of biological origin is glycerine comprising impurities of salts, water and optionally methanol; and
the purifying comprises:
removing the salts by treating the glycerine on at least one acid exchange resin; and
removing the water and optionally the methanol by fractionated distillation.

Assignees

• Eni Spa

Inventors

• Bellussi Giuseppe
• De Angelis Alberto Renato
• Assanelli Giulio
• Pollesel Paolo

Classifications

• C07C41/09

  by dehydration of compounds containing hydroxy groups · CPC title

• C10L10/10

  for improving the octane number · CPC title

• C07C29/60

  by elimination of -OH groups, e.g. by dehydration (C07C29/34 takes precedence) · CPC title

• C07C45/52

  by dehydration and rearrangement involving two hydroxy groups in the same molecule · CPC title

• C07C67/44

  by oxidation-reduction of aldehydes, e.g. Tishchenko reaction · CPC title