US4266981A
Expired / Lapsed
US
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Process for recovering and utilizing cellulose using sulfuric acid
Assignee: Purdue Research Foundation
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Filing: 1979-10-03
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Granted: 1981-05-12
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Expires: 1999-10-03
Abstract
Abstract A process for recovering cellulose using sulfuric acid and utilizing the recovered cellulose by hydrolysis to yield glucose. Cellulosic raw materials are hydrolyzed by dilute sulfuric acid to remove hemicellulose, after which the solid residue is separated and is treated with concentrated sulfuric acid to dissolve cellulose contained therein. After blending and mixing of the residue in the concentrated sulfuric acid under mild reaction conditions, cellulose is reprecipitated by addition of water or an organic solvent such as methanol. The recovered cellulose can then be hydrolyzed by cellulose enzymes and/or dilute acids to provide a high yield of glucose. High level recovery and reconcentration of the sulfuric acid is also disclosed.
Inventors
- 👤 George T. Tsao
- 👤 Terry Y. Chou
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 18:27
CPC Classifications
C; C13; C13K; C13K1/00; C13K1/02; D; D21; D21C; D21C3/00; D21C3/04
Claims Analysis
Total Claims: 23
Claim 1
Independent Claim
139 words
A process for recovering cellulose from a cellulosic material which contains hemicellulose, cellulose and lignin, which comprises the steps of: contacting the cellulosic material with dilute acid under mild conditions to hydrolyze only the hemicellulose portion thereof; removing the hydrolyzed hemicellulose portion from the remainder of the cellulosic material residue, said residue being in solid form; blending and mixing said residue with concentrated sulfuric acid under mild conditions to dissolve and partially hydrolyze the cellulose portion of said residue, the lignin portion being substantially unaffected by the mild reaction conditions and remaining as a solid; and reprecipitating the dissolved and partially hydrolyzed cellulose by adding a reprecipitating agent to the reaction mass resulting from said blending and mixing step, said reprecipitating agent being a member selected from the group consisting of water, water soluble organic solvents and mixtures thereof.
Claim 2
Dependent Claim
139 words
A process for recovering cellulose from a cellulosic material which contains hemicellulose, cellulose and lignin, which comprises the steps of: contacting the cellulosic material with dilute acid under mild conditions to hydrolyze only the hemicellulose portion thereof; removing the hydrolyzed hemicellulose portion from the remainder of the cellulosic material residue, said residue being in solid form; blending and mixing said residue with concentrated sulfuric acid under mild conditions to dissolve and partially hydrolyze the cellulose portion of said residue, the lignin portion being substantially unaffected by the mild reaction conditions and remaining as a solid; and reprecipitating the dissolved and partially hydrolyzed cellulose by adding a reprecipitating agent to the reaction mass resulting from said blending and mixing step, said reprecipitating agent being a member selected from the group consisting of water, water soluble organic solvents and mixtures thereof.
Claim 3
Dependent Claim
12 words
The process of claim 1 wherein said dilute acid is sulfuric acid.
Claim 4
Dependent Claim
20 words
The process of claim 2 wherein said concentrated sulfuric acid has the strength of about 60 to 90% by weight.
Claim 5
Dependent Claim
24 words
The process of claim 2 wherein said blending and mixing of said residue in said concentrated sulfuric acid is performed at about room temperature.
Claim 6
Dependent Claim
30 words
The process of claim 1 wherein said reprecipitating agent is water and about 2 to 5 volumes of water are added to the blended reaction mass to reprecipitate said cellulose.
Claim 7
Dependent Claim
11 words
The process of claim 1 wherein said reprecipitating agent is methanol.
Claim 8
Dependent Claim
22 words
The process of claim 5 wherein about 97% by weight of the cellulose in the cellulosic material is reprecipitated in solid form.
Claim 9
Dependent Claim
18 words
The process of claim 1 wherein said concentrated acid is recovered after addition of said reprecipitating agent thereto.
Claim 10
Dependent Claim
16 words
The process of claim 8 wherein at least a portion of the recovered acid is recycled.
Claim 11
Dependent Claim
16 words
The process of claim 9 wherein about 90% or more of said recovered acid is recycled.
Claim 12
Dependent Claim
34 words
The process of claim 1 wherein said reprecipitated cellulose has a lowered DP and has its internal structure and lignin seal disrupted whereby said cellulose may be readily substantially completely hydrolyzed to yield glucose.
Claim 13
Dependent Claim
34 words
The process of claim 11 further comprising the step of hydrolyzing said reprecipitated cellulose to glucose by means of cellulase enzymes or a dilute acid or a mixture of a dilute acid and enzymes.
Claim 14
Dependent Claim
156 words
A process for recovering cellulose from a cellulosic material which includes hemicellulose, cellulose and lignin, said process comprising: hydrolyzing the cellulosic material with dilute sulfuric acid to remove the hemicellulose portion of the cellulosic material in the form of a liquid hydrolysate; separating solid residue including the cellulose and lignin portions of the cellulosic material from said liquid hydrolysate; adding from about 0.2 to about 5 ml/gm of concentrated sulfuric acid having a strength of between about 60% to 90% by weight to said solid residue to dissolve and partially hydrolyze the cellulose therein; blending and mixing said solid residue and said concentrated sulfuric acid at about room temperature; and reprecipitating the cellulose from said concentrated sulfuric acid by addition of from about 0.5 to about 5 ml of a reprecipitating agent per ml of said concentrated sulfuric acid, said reprecipitating agent being selected from the group consisting of water or a water soluble organic solvent.
Claim 15
Dependent Claim
156 words
A process for recovering cellulose from a cellulosic material which includes hemicellulose, cellulose and lignin, said process comprising: hydrolyzing the cellulosic material with dilute sulfuric acid to remove the hemicellulose portion of the cellulosic material in the form of a liquid hydrolysate; separating solid residue including the cellulose and lignin portions of the cellulosic material from said liquid hydrolysate; adding from about 0.2 to about 5 ml/gm of concentrated sulfuric acid having a strength of between about 60% to 90% by weight to said solid residue to dissolve and partially hydrolyze the cellulose therein; blending and mixing said solid residue and said concentrated sulfuric acid at about room temperature; and reprecipitating the cellulose from said concentrated sulfuric acid by addition of from about 0.5 to about 5 ml of a reprecipitating agent per ml of said concentrated sulfuric acid, said reprecipitating agent being selected from the group consisting of water or a water soluble organic solvent.
Claim 16
Dependent Claim
115 words
A process for providing a high yield of glucose from cellulose recovered from a cellulosic material, said process comprising: hydrolyzing a cellulosic material with dilute sulfuric acid to remove hemicellulose therefrom as a liquid hydrolysate; separating a solid residue from said liquid hydrolysate; adding concentrated sulfuric acid to said residue under mild conditions to dissolve and partially hydrolyze the cellulose therein without degrading the lignin therein; blending and mixing said residue in said concentrated sulfuric acid under mild reaction conditions; reprecipitating said dissolved cellulose by diluting said sulfuric acid with water or a water soluble organic solvent; and hydrolyzing said reprecipitated cellulose by exposure to cellulase enzymes and/or a dilute acid to yield glucose therefrom.
Claim 17
Dependent Claim
115 words
A process for providing a high yield of glucose from cellulose recovered from a cellulosic material, said process comprising: hydrolyzing a cellulosic material with dilute sulfuric acid to remove hemicellulose therefrom as a liquid hydrolysate; separating a solid residue from said liquid hydrolysate; adding concentrated sulfuric acid to said residue under mild conditions to dissolve and partially hydrolyze the cellulose therein without degrading the lignin therein; blending and mixing said residue in said concentrated sulfuric acid under mild reaction conditions; reprecipitating said dissolved cellulose by diluting said sulfuric acid with water or a water soluble organic solvent; and hydrolyzing said reprecipitated cellulose by exposure to cellulase enzymes and/or a dilute acid to yield glucose therefrom.
Claim 18
Dependent Claim
25 words
A process according to claim 14 in which said hydrolysis is achieved by exposing said cellulose to a combination of dilute acid and cellulase enzymes.
Claim 19
Dependent Claim
153 words
A process for recovering cellulose from cellulosic materials, said process comprising: hydrolyzing cellulosic materials with dilute sulfuric acid to remove hemicellulose therefrom in the form of a liquid hydrolysate; separating a solid residue including cellulose and lignin from said liquid hemicellulose hydrolysate; washing said solid residue and removing the washing liquid therefrom; adding concentrated sulfuric acid having a strength of between about 60% to 90% to said solid residue to dissolve and partially hydrolyze the cellulose therein; said concentrated sulfuric acid being added in an amount of from about 0.2 to about 5 ml per gm of said solid residue; blending and mixing said solid residue in said concentrated sulfuric acid under mild reaction conditions to substantially avoid the formation of any undesirable degradation products; and reprecipitating the dissolved and partially hydrolyzed cellulose by addition of from about 0.5 to 5 volumes of a reprecipitating agent per volume of said concentrated sulfuric acid.
Claim 20
Dependent Claim
153 words
A process for recovering cellulose from cellulosic materials, said process comprising: hydrolyzing cellulosic materials with dilute sulfuric acid to remove hemicellulose therefrom in the form of a liquid hydrolysate; separating a solid residue including cellulose and lignin from said liquid hemicellulose hydrolysate; washing said solid residue and removing the washing liquid therefrom; adding concentrated sulfuric acid having a strength of between about 60% to 90% to said solid residue to dissolve and partially hydrolyze the cellulose therein; said concentrated sulfuric acid being added in an amount of from about 0.2 to about 5 ml per gm of said solid residue; blending and mixing said solid residue in said concentrated sulfuric acid under mild reaction conditions to substantially avoid the formation of any undesirable degradation products; and reprecipitating the dissolved and partially hydrolyzed cellulose by addition of from about 0.5 to 5 volumes of a reprecipitating agent per volume of said concentrated sulfuric acid.
Claim 21
Dependent Claim
28 words
The process of claim 1 wherein the dissolved and partially hydrolyzed cellulose is separated from the solid lignin portion of the cellulosic material before the cellulose is reprecipitated.
Claim 22
Dependent Claim
11 words
The process of claim 1 wherein said reprecipitating agent is water.
Claim 23
Dependent Claim
11 words
The process of claim 13 wherein said reprecipitating agent is water.
References Cited (Backward Citations)
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1984-05-11 | 1984-11-10 | 1985-05-12 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1988-05-11 | 1988-11-10 | 1989-05-12 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1992-05-11 | 1992-11-10 | 1993-05-12 | $7700.00 | Window Closed / Lapsed |