Imprinted biomimetic catalysts for cellulose hydrolysis

• US 9,637,599 B2
• Filed: 03/02/2010
• Issued: 05/02/2017
• Est. Priority Date: 03/25/2009
• Status: Active Grant

• Current Assignee: Trustees Of The University Of Pennsylvania (University of Pennsylvania)
• Original Assignee: Stephen Roth, Trustees Of The University Of Pennsylvania (University of Pennsylvania)
• Inventors: Roth, Stephen, Lee, Daeyeon
• Primary Examiner(s): Chu, Yong
• Assistant Examiner(s): WRIGHT, SONYA N
• Application Number:
  US13/259,912
• Publication Number:
  US 20120136180A1
• Time in Patent Office: 2,618 Days
• Field of Search: 568902
• CPC Class Codes: B01J 21/08 Silica
• CPC Class Codes: B01J 2231/40 Substitution reactions at carbon centres, e.g. C-C or C-X, i.e. carbon-hetero atom, cross-coupling, C-H activation or ring-opening reactions
• CPC Class Codes: B01J 2531/96 Water
• CPC Class Codes: B01J 31/0225 comprising sulfonic acid groups or the corresponding salts
• CPC Class Codes: B01J 31/0277 comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
• CPC Class Codes: B01J 31/0284 of an aromatic ring, e.g. pyridinium
• CPC Class Codes: B01J 31/067 Molecularly imprinted polymers catalytic antibodies C12N9/0002
• CPC Class Codes: B01J 31/069 Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups nitrogen containing groups on mineral substrates B01J31/0254; organometallic polymers B01J31/123; coordination complexes immobilised on an inorganic support B01J31/1616; coordination polymers, e.g. metal-organic frameworks B01J31/1691
• CPC Class Codes: B01J 31/10 sulfonated
• CPC Class Codes: B01J 37/0018 Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
• CPC Class Codes: C08G 77/02 Polysilicates
• CPC Class Codes: C12P 2203/00 Fermentation products obtained from optionally pretreated or hydrolyzed cellulosic or lignocellulosic material as the carbon source
• CPC Class Codes: C12P 7/10 substrate containing cellulosic material
• CPC Class Codes: C13K 1/02 obtained by saccharification of cellulosic materials manufacture of fodder A23K10/32
• CPC Class Codes: Y02E 50/10 Biofuels, e.g. bio-diesel

Abstract

The present disclosure describes methods and biomimetic catalysts useful for hydrolyzing glucose polymers, such as cellulose, and oligomers, such as cellobiose, to glucose for the subsequent production of ethanol.

Claims

1. A biomimetic catalyst, said catalyst comprising:

a polymeric silica matrix, wherein preparation of the matrix comprises reacting at least one tetraorthosilicate with at least one silane in the presence of an imprinting molecule to form said polymeric silica matrix impregnated with said imprinting molecule, and removing said imprinting molecule from said impregnated polymeric silica matrix via washing or burning;

wherein at least 1 mol percent of said at least one silane is an acid functionalized silane;

wherein said imprinting molecule is at least one selected from the group consisting of cellulose, cellobiose, linear oligomeric β

(1-4) linked glucose chains longer than cellobiose but shorter than cellulose, carboxymethylcellulose, methylcellulose, hydropropylcellulose, linear and branched α

-linked glucose oligomer and polymers, sucrose, lactose, trehalose, fructans, pectins, glycosaminoglycans, agar, gum Arabic, karageenan, glucose, and D-glucose 6-phosphate;

at least one active site imprinted into said matrix, wherein said active site binds and hydrolyzes at least one glucose substrate to glucose,

wherein said glucose substrate is at least one selected from the group consisting of cellulose, cellobiose, linear oligomeric β

(1-4) linked glucose chains longer than cellobiose but shorter than cellulose, and linear and branched α

-linked glucose oligomers and polymers, and

wherein at least one said acid functionalized silane is incorporated in said polymeric silica matrix and is present in said active site.

2. The biomimetic catalyst of claim 1, wherein said at least one acidic functionality is selected from the group consisting of a phenol, a carboxylic acid, and a sulfonic acid.

3. A method of preparing the biomimetic catalyst of claim 1, said method comprising:

reacting at least one tetraorthosilicate with at least one silane in the presence of an imprinting molecule to form a polymeric silica matrix impregnated with said imprinting molecule, wherein at least 1 mol percent of said at least one silane is an acid functionalized silane;

wherein said imprinting molecule is at least one selected from the group consisting of cellulose, cellobiose, linear oligomeric β

(1-4) linked glucose chains longer than cellobiose but shorter than cellulose, carboxymethylcellulose, methylcellulose, hydropropylcellulose, linear and branched α

-linked glucose oligomer and polymers, sucrose, lactose, trehalose, fructans, pectins, glycosaminoglycans, agar, gum Arabic, karageenan, glucose, and D-glucose 6-phosphate;

isolating said impregnated polymeric silica matrix; and

removing said imprinting molecule from said impregnated polymeric silica matrix via washing or burning to form a silica matrix imprinted with the structure of said imprinting molecule,

wherein said matrix comprises at least one active site,

wherein said active site comprises at least one said acid functionalized silane that is incorporated in said polymeric silica matrix and binds and hydrolyzes at least one glucose substrate to glucose,

wherein said glucose substrate is at least one selected from the group consisting of cellulose, cellobiose, linear oligomeric β

(1-4) linked glucose chains longer than cellobiose but shorter than cellulose, and linear and branched α

-linked glucose oligomers and polymers.

4. The method of claim 3, wherein said at least one tetraorthosilicate is selected from the group consisting of Formulas I, II, III and IV:

5. The method of claim 4, wherein R¹ is CH₂CH₃ at each occurrence.

6. The method of claim 3, wherein said at least one silane is a compound selected from the group consisting of Formulas V, VI, and VII:

7. A method of producing glucose, said method comprising:

dissolving a glucose substrate in a solvent;

contacting said glucose substrate in said solvent with at least one biomimetic catalyst of claim 1 to hydrolyze said glucose substrate to glucose, said biomimetic catalyst comprising;

a polymeric silica matrix, wherein preparation of said matrix comprises reacting at least one tetraorthosilicate with at least one silane in the presence of an imprinting molecule to form said polymeric silica matrix impregnated with said imprinting molecule, and removing said imprinting molecule from said impregnated polymeric silica matrix via washing or burning;

wherein at least 1 mol percent of said at least one silane is an acid functionalized silane;

wherein said imprinting molecule is at least one selected from the group consisting of cellulose, cellobiose, linear oligomeric β

(1-4) linked glucose chains longer than cellobiose but shorter than cellulose, carboxymethylcellulose, methylcellulose, hydropropylcellulose, linear and branched α

-linked glucose oligomer and polymers, sucrose, lactose, trehalose, fructans, pectins, glycosaminoglycans, agar, gum Arabic, karageenan, glucose, and D-glucose 6-phosphate;

at least one active site imprinted into said matrix, wherein said active site binds and hydrolyzes at least one glucose substrate to glucose,

wherein said glucose substrate is at least one selected from the group consisting of cellulose, cellobiose, linear oligomeric β

(1-4) linked glucose chains longer than cellobiose but shorter than cellulose, and linear and branched α

-linked glucose oligomers and polymers, and

wherein at least one said acid functionalized silane is incorporated in said polymeric silica matrix and is present in said active site.

8. The method of claim 7, wherein said solvent is an ionic liquid or molten salt.

9. A method of producing ethanol, said method comprising:

dissolving a glucose substrate in a solvent;

wherein the glucose substrate is at least one selected from the group consisting of cellulose, cellobiose, linear oligomeric β

(1-4) linked glucose chains longer than cellobiose but shorter than cellulose, and linear and branched α

-linked glucose oligomers and polymers;

contacting said glucose substrate in said solvent with at least one biomimetic catalyst of claim 1 to completely or partially hydrolyze said glucose substrate to glucose, said biomimetic catalyst comprising;

a polymeric silica matrix, wherein preparation of said matrix comprises reacting at least one tetraorthosilicate with at least one silane in the presence of an imprinting molecule to form said polymeric silica matrix impregnated with said imprinting molecule, and removing said imprinting molecule from said impregnated polymeric silica matrix via washing or burning;

wherein at least 1 mol percent of said at least one silane is an acid functionalized silane;

wherein said imprinting molecule is at least one selected from the group consisting of cellulose, cellobiose, linear oligomeric β

(1-4) linked glucose chains longer than cellobiose but shorter than cellulose, carboxymethylcellulose, methylcellulose, hydropropylcellulose, linear and branched α

-linked glucose oligomer and polymers, sucrose, lactose, trehalose, fructans, pectins, glycosaminoglycans, agar, gum Arabic, karageenan, glucose, and D-glucose 6-phosphate;

at least one active site imprinted into said matrix, wherein said active site binds and hydrolyzes said glucose substrate to glucose, and wherein at least one said acid functionalized silane is incorporated in said polymeric silica matrix and is present in said active site;

isolating said glucose; and

converting said glucose to ethanol.