PROCESS OF PRODUCING LIQUID FUEL FROM CELLULOSIC BIOMASS

• US 20090326286A1
• Filed: 08/03/2009
• Published: 12/31/2009
• Est. Priority Date: 02/01/2007
• Status: Active Grant

• Current Assignee: China Fuel (Huaibei) Bioenergy Technology Development Co., Ltd.
• Original Assignee: China Fuel Bioenergy Technology Developme Company Limited
• Inventors: Zhu, Zuolin, Yie, Hongping, Sun, Meg M.
• Granted Patent: US 8,618,341 B2
• Time in Patent Office: Days
• US Class Current: 585/240
• CPC Class Codes: B01J 21/04 Alumina
• CPC Class Codes: B01J 21/18 Carbon
• CPC Class Codes: B01J 23/42 Platinum
• CPC Class Codes: B01J 23/462 Ruthenium
• CPC Class Codes: C01B 32/342 characterised by non-gaseous activating agents
• CPC Class Codes: C07C 29/00 Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
• CPC Class Codes: C07C 31/18 Polyhydroxylic acyclic alcohols
• CPC Class Codes: C07C 31/26 Hexahydroxylic alcohols
• CPC Class Codes: C07C 67/08 by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
• CPC Class Codes: C07C 69/21 of hydroxy compounds with more than three hydroxy groups esters of sugars C07H
• CPC Class Codes: C10G 1/065 in the presence of a solvent
• CPC Class Codes: C10G 1/08 with moving catalysts
• CPC Class Codes: C10G 1/083 in the presence of a solvent
• CPC Class Codes: C10G 1/086 Characterised by the catalyst used
• CPC Class Codes: C10L 1/06 for spark ignition
• CPC Class Codes: C10L 1/08 for compression ignition
• CPC Class Codes: Y02P 30/20 using bio-feedstock

Abstract

A liquid fuel production process from cellulosic biomass comprises the following steps: (1) providing a mixture of cellulose and water; (2) subjecting the obtained mixture to hydrolysis and catalytic hydrogenation under the presence of acid to obtain mono-sugar alcohol and optional solid material lignin, or subjecting the obtained mixture to hydrolysis to obtain monosaccharide; (3) esterifying the obtained mono-sugar with C₂-C₅ organic acid to obtain a liquid fuel II, or subjecting the obtained mono-sugar alcohol or monosaccharide to dehydration/hydrogenation to obtain an organic liquid fuel I consisting of alkanes. This process avoids the loss of organic carbon atoms during fermentation, and the sugar derived from cellulosic biomass can be converted to organic carbon in the liquid fuel. The lignin produced by the process can be used for preparing aromatics.

Claims

1. A highly effective process of producing liquid fuel from cellulosic biomass, comprising:

the first step;

providing a mixture of cellulosic biomass and water, wherein the amount of the cellulosic biomass in water is 1-60 w.t. %;

the second step;

carrying out step (a) or (b) as follows;

(a) the mixture obtained in the first step is catalytically hydrogenated and hydrolyzed under acidic conditions to produce a liquid product, namely a monosaccharide alcohol solution, and an optional solid product, namely lignin;

or

(b) the mixture obtained in the first step is hydrolyzed to produce monosaccharides;

the third step;

The monosaccharide alcohols or monosaccharides obtained in the second step are subjected to the following reactions;

(i) the monosaccharide alcohols obtained in (a) of the second step are esterified with a C2-C5 organic acid to produce liquid fuel II which is the esterification product of monosaccharide alcohols;

or

(ii) the monosaccharide alcohols obtained in (a) or the monosaccharides obtained in (b) of the second step are subjected to the dehydroxylation-polymerization-hydrogenation to produce liquid fuel I which is an organic product of alkanes.

2. A process of claim 1, further comprising:

pretreating the cellulosic biomass starting material to give the mixture of cellulosic biomass and water as described in the first step.

3. A process of claim 1, wherein:

the catalytic hydrogenation in (a) of the second step is carried out in the presence of an acid amounting to 0.1 w.t. %-2.0 w.t. % of the cellulosic biomass; and

/or

the hydrogenation catalyst of the catalytic hydrogenation in (a) of the second step amounts to 0.1 w.t. %-20 w.t. % of the cellulosic biomass; and

/or

the hydrogen pressure in (a) of the second step ranges from 1 to 200 atm.; and

/or

the reaction temperature in (a) of the second step ranges from 0 to 200°

C.; and

/or

the reaction time in (a) of the second step ranges from 1 to 100 hours; and

/or

the hydrolyzation in (b) of the second step is catalyzed by an acid or an enzyme.

4. A process of claim 3, wherein:

the hydrogenation catalyst in (a) of the second step includes;

a heterogeneous catalyst comprising a transition metal dispersed on a support, wherein the transition metal is selected from ruthenium, nickel, platinum, palladium and combinations thereof;

or

a homogeneous catalyst which includes a complex of ruthenium with triphenyl phosphine, a complex of ruthenium with sulfonated phenyl phosphine and combinations thereof.

5. A process of claim 4, wherein:

the support of the heterogeneous catalyst is an actived carbon prepared using saccharide as starting material; and

/or

the amount of the transition metal in the heterogeneous catalyst is 0.1-5.5 w.t. % of the support.

6. A process of claim 5, wherein the actived carbon is prepared by a method comprising the steps as follows:

(A) the saccharide is dehydrated for 16-20 hours at 350-500°

C. under an inert atmosphere to give crude actived carbon;

(B) the crude actived carbon from step (A) is crushed and put into concentrated sulfuric acid at a concentration of >

96% up to that of oleum in inert atmosphere to remove acid soluble species, giving acid treated actived carbon;

(C) the acid treated actived carbon from step (B) is washed until no sulfate ion is detected, and then dried to give actived carbon.

7. A process of claim 1, wherein:

the molar ratio between the monosaccharide alcohols and the C2-C5 organic acid ranges from 1;

1 to 1;

10 in (i) of the third step; and

/or

the reaction in (i) of the third step is carried out in the presence of a non-nucleophilic inorganic strong acid catalyst or an acidic ion exchange resin catalyst; and

/or

the reaction in (i) of the third step is carried out at 15°

C. to 200°

C.; and

/or

the dehydroxylation-polymerization-hydrogenation in (ii) of the third step is carried out in the presence of an acid, wherein the molar ratio between the acid and the monosaccharide alcohols or monosaccharides is 1;

1-1;

20; and

/or

the dehydroxylation-polymerization-hydrogenation in (ii) of the third step is carried out at 100°

C.-300°

C.; and

/or

the dehydroxylation-polymerization-hydrogenation in (ii) of the third step is carried out in the presence of a catalyst amounting to 0.1-20 w.t. % of the monosaccharide alcohols or monosaccharides; and

/or

the dehydroxylation-polymerization-hydrogenation in (ii) of the third step is carried out for 10-100 hours; and

/or

in (ii) of the third step, the organic products of alkanes are further separated from water phase to give separated liquid fuel I.

8. A process of producing lignin, comprising the steps as follows:

(1) providing a mixture of cellulosic biomass and water, wherein the amount of cellulosic biomass in water is 1-60 w.t. %;

(2) the mixture obtained in step (1) is catalytically hydrogenated and hydrolyzed under acidic conditions to produce a solid product, namely lignin, and liquid product, namely monosaccharide alcohols.

9. A process of claim 8, wherein:

the mixture in step (1) is obtained by a method comprising the steps as follows;

the cellulosic biomass starting material is pretreated to give the mixture of cellulosic biomass and water as described in step (1), wherein the pretreatment is done by a physical process; and

/or

the catalytic hydrogenation in step (2) is carried out in the presence of an acid amounting to 0.1 w.t. %-2.0 w.t. % of the cellulosic biomass; and

/or

the hydrogenation catalyst of the catalytic hydrogenation in step (2) amounts to 0.1 w.t. %-20 w.t. % of the cellulosic biomass; and

/or

the hydrogen pressure in step (2) ranges from 1 to 200 atm.; and

/or

the reaction temperature in step (2) ranges from 0 to 200°

C.; and

/or

the reaction time in step (2) ranges from 1 to 100 hours.

10. A process of claim 9, wherein:

the hydrogenation catalyst in step (2) includes;

a heterogeneous catalyst comprising a transition metal dispersed on a support, wherein the transition metal is selected from ruthenium, nickel, platinum, palladium and combinations thereof;

or

a homogeneous catalyst which includes a complex of ruthenium with triphenyl phosphine, a complex of ruthenium with sulfonated phenyl phosphine and combinations thereof.