Calcium hydroxide pretreatment of biomass

• US 5,693,296 A
• Filed: 09/06/1994
• Issued: 12/02/1997
• Est. Priority Date: 08/06/1992
• Status: Expired due to Term

• Current Assignee: Texas A&M University System
• Original Assignee: Texas A&M University System
• Inventors: Holtzapple, Mark T., Nagwani, Murlidhar, Davison, Richard R.
• Primary Examiner(s): Mullis, Jeffrey C.
• Application Number:
  US08/300,543
• Time in Patent Office: 1,183 Days
• Field of Search: 536/56, 536/124, 162/29, 162/90, 162/190, 530/500, 426/312, 426/635, 426/636, 127/37, 423/165
• US Class Current: 423/165
• CPC Class Codes: A23K 10/32 from hydrolysates of wood or straw
• CPC Class Codes: C01F 11/18 Carbonates
• 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

Lignocellulose-containing materials are treated with lime (calcium hydroxide) and water at a relatively high temperature and for a certain period of time under certain conditions. The process variables were: lime loading which ranged from about 2 to about g Ca(OH)₂ /100 g dry material; water loading which ranged from about 6 to about 19 g water/g dry material; treatment temperature which varied from about 50° C. to about 150° C.; and treatment time which varied from about 1 to about 36 hours. The effects of treatment time and temperature were interdependent.

A process for lime recovery is developed. The soluble Ca(OH)₂ was washed out of the pretreated material with water and converted to insoluble CaCO₃, by reacting with CO₂, and was thus separated. The CaCO₃ can be heated to produce CaO and CO₂. The CaO is hydrated to Ca(OH)₂ which can be reused as the lignocellulose treatment agent. Carbon dioxide is reused for lime recovery.

Claims

1. A method for recovering calcium from a biomass pretreatment process comprising:

a) pretreating the biomass by adding calcium oxide or hydroxide and water to the biomass to form a mixture and maintaining the mixture at ambient pressure and at greater than ambient temperature for a period of time sufficient to enhance susceptibility of the biomass to hydrolysis;

b) carbonating the pretreated biomass;

c) precipitating calcium carbonate or bicarbonate from the carbonated biomass; and

d) recovering precipitated calcium carbonate or bicarbonate.

2. The method of claim 1 wherein the mixture contains between about 6 to about 19 grams of water per gram of dry biomass.

3. The method of claim 1 wherein the mixture contains between about 9 to about 11 grams of water per gram of dry biomass.

4. The method of claim 1 wherein the mixture contains between about 2 to about 30 grams of calcium oxide or hydroxide per 100 grams of dry biomass.

5. The method of claim 1 wherein the mixture contains between about 10 to about 15 grams of calcium oxide or hydroxide per 100 grams of dry biomass.

6. The method of claim 1 wherein the lignocellulose-containing biomass is selected from the group consisting of grass, wood, bagasse, straw, paper, plant material, and combinations thereof.

7. The method of claim 1 wherein the mixture is maintained at the temperature of between about 40°

C. to about 100°

C.

8. The method of claim 1 wherein the mixture is maintained at the temperature of between about 40°

C. and about 70°

C.

9. The method of claim 1 wherein the mixture is maintained at the temperature of between about 50°

C. and about 65°

C.

10. The method of claim 1 wherein the mixture is maintained at the temperature of between about 70°

C. and about 100°

C.

11. The method of claim 1 wherein the period of time is between about 1 and about 36 hours.

12. The method of claim 1 wherein the period of time is between about 1 and about 20 hours.

13. The method of claim 1 wherein the period of time is between about 15 and about 25 hours.

14. The method of claim 1 wherein the period of time is about 24 hours.

15. The method of claim 1 wherein the period of time is between about 1 and about 2 hours.

16. The method of claim 1 wherein the mixture is maintained at a temperature of between about 40°

C. and about 100°

C., and the period of time is between about 1 and about 36 hours.

17. The method of claim 1 wherein lignin content of the biomass is reduced between about 10% to about 20% by pretreatment.

18. The method of claim 1 wherein the pH of the carbonated biomass is between about 8.5 and about 10.5.

19. The method of claim 1 wherein the pH of the carbonated biomass is between about 9.0 and about 10.

20. The method of claim 1 wherein the recovered calcium oxide is hydrated to form calcium hydroxide.

21. The method of claim 1 further comprising heating the carbonated biomass to form carbon dioxide and calcium oxide.

22. The method of claim 21 wherein the precipitated calcium oxide is recovered by filtration, hydroclone separation, sedimentation, centrifugation, or a combination thereof.

23. A method for recovering calcium from a biomass pretreatment process comprising:

a) pretreating the biomass by adding calcium oxide or hydroxide and water to the biomass to form a mixture and maintaining the mixture at ambient pressure and at greater than ambient temperature for a period of time sufficient to enhance susceptibility of the biomass to hydrolysis;

b) adding a carbonating agent to the pretreated mixture to form calcium carbonate or bicarbonate;

c) heating the calcium carbonate or bicarbonate to form calcium oxide; and

recovering the calcium oxide.

24. The method of claim 23 wherein lignin content of the biomass is reduced between about 10% to about 20% by pretreatment.

25. The method of claim 23 wherein the carbonating agent is carbon dioxide gas.

26. The method of claim 23 wherein said pretreated mixture contains lignin and wherein the lignin is burned to heat the calcium carbonate or bicarbonate of step b.

27. The method of claim 23 further comprising the step of digesting the carbonated mixture.

28. The method of claim 27 wherein digestion is performed by acid hydrolysis, enzymatic action, fermentation or a combination thereof.

29. The method of claim 23 wherein the mixture is dry mixed before pretreatment.

30. The method of claim 23 wherein the mixture is continuously mixed during pretreatment.