Method for producing furfural, acetic acid and formic acid from spent pulp-cooking liquor

• US 6,955,743 B2
• Filed: 12/28/2001
• Issued: 10/18/2005
• Est. Priority Date: 12/29/2000
• Status: Expired due to Term

• Current Assignee: Chempolis Oy
• Original Assignee: Chempolis Oy
• Inventors: Anttila, Juha, Rousu, Päivi, Tanskanen, Juha, Rousu, Pasi, Rousu, Esa
• Primary Examiner(s): Manoharan, Virginia
• Application Number:
  US10/465,955
• Publication Number:
  US 20040040830A1
• Time in Patent Office: 1,390 Days
• Field of Search: 203/1, 203/62, 203 75- 80, 203 14- 17, 159/47.3, 159/901, 159/DIG.20, 162/16, 162/38, 162/76, 549/490, 562/608, 562/609
• US Class Current: 203/62
• CPC Class Codes: D21C 11/0014 Combination of various pulping processes with one or several recovery systems (cross-recovery)
• CPC Class Codes: D21C 11/10 Concentrating spent liquor by evaporation evaporators B01D
• CPC Class Codes: D21C 3/04 with acids, acid salts or acid anhydrides D21C3/003 and D21C3/222 take precedence
• CPC Class Codes: D21C 3/20 with organic solvents or in solvent environment
• CPC Class Codes: Y10S 159/20 Additive
• CPC Class Codes: Y10S 159/901 Promoting circulation

Abstract

The invention relates to a process for recovering and producing chemicals in a pulp production process where organic chemicals, such as formic acid and acetic acid, are used as cooking chemicals. The process of the invention is based on regeneration of cooking acids and formation of additional cooking acids and furfural by evaporating the cooking liquor and then separating acetic acid, formic acid, furfural and water. The separation is preferably carried out by distillation using the furfural formed in the process as a distilling aid in the distillation.

Claims

1. A process for recovering formic acid, acetic acid and furfural and simultaneously forming same in a pulp production process where an acid mixture containing mainly formic acid and acetic acid is used as a cooking liquor, the cooking liquor is separated from the pulp, the pulp is washed, and the cooking liquor is subjected to a recovery phase, wherein the recovery phase comprises

a) evaporating the used cooking liquor obtained from the separation of cooking liquor and pulp and including an organic substance and/or a chemically bound organic acids, wherein the evaporation yields as condensate a concentrated acid mixture which contains formic acid and acetic acid and is at least partly returned to the cooking, and as a first evaporation residue an evaporation concentrate, where acetic acid, formic acid and furfural have formed in the evaporation from the organic substance included in the used cooking liquor and/or from the chemically bound acids included therein,

b) separating the evaporation concentrate into a volatile part and a second evaporation residue,

c) separating the volatile part of the evaporation concentrate obtained in step (b) and/or part of the condensate obtained in step (a) into four fractions comprising a mixture of acetic acid and formic acid, water, furfural and acetic acid by distillation, which comprises an azeotropic-extractive distillation phase by utilizing the furfural formed and recovered in the process as a distillation aid, wherein the azeotropic-extractive distillation phase comprises

introducing the volatile part of the evaporation concentrate obtained in step (b) and/or the condensate obtained in step (a) and including acetic acid, formic acid, furfural and water feedstream into a first distillation column and recovering a mixture of furfural and water as the top product of the distillation and a concentrated mixture of acetic acid and formic acid containing also water and furfural as the bottom product of the distillation, followed by separating the top product of the distillation to recover water and furfural and distilling the bottom product of the distillation to recover a mixture of acetic acid and formic acid, water, furfural and acetic acid, and,

d) returning the mixture of formic acid and acetic acid obtained from the distillation to cooking, returning at least part of furfural to the distillation of step (c), recovering the rest of furfural and acetic acid and returning water to pulp washing.

2. A process according to claim 1, wherein the evaporation step (a) is carried out to a dry solids content of 20 to 85%.

3. A process according to claim 2 wherein the evaporation step is carried out to a dry solids content of 40 to 80%.

4. A process according to claim 1, wherein the evaporation step (a) is carried out at a temperature of 60 to 180°

C. at overpressure or at low pressure.

5. A process according to claim 4, wherein the evaporation step (a) is carried out in one or more phases, of which at least one is carried out at a temperature higher than 100°

C.

6. A process according to claim 1, wherein the evaporation concentrate further comprises xylose, wherein the formation of formic acid, acetic acid and furfural is monitored by measuring the xylose content of the evaporation concentrate.

7. A process according to claim 6, wherein the evaporation is continued until the evaporation concentrate does not substantially contain xylose.

8. A process according to claim 1, wherein the process also includes, before the separation step (b), step (a1) where the evaporation concentrate obtained from step (a) is reacted at an elevated temperature without evaporation, as a result of which more formic acid, acetic acid and furfural are formed in the evaporation concentrate.

9. A process according to claim 8, wherein the temperature is 50 to 250°

C.

10. A process according to claim 8, wherein the reaction time is 0.5 min to 24 h.

11. A process according to claim 8, wherein the evaporation concentrate further comprises xylose, wherein the formation of formic acid, acetic acid and furfural is monitored by measuring the xylose content of the evaporation concentrate.

12. A process according to claim 11, wherein the reaction is continued until the reaction mixture does not substantially contain xylose.

13. A process according to claim 8, wherein the process also includes, before step (a1), step (a0) where water or diluted acid solution is added to the evaporation concentrate.

14. A process according to claim 13, wherein the diluted acid solution is wash acid mixture obtained from pulp washing.

15. A process according to claim 14, wherein the wash acid mixture is concentrated wash acid mixture.

16. A process according to claim 1, wherein the separation of step (b) is carried out by drying, which yields as volatile component a mixture which contains water, formic acid, acetic acid and furfural and is introduced into the distillation step (c), and lignin as drying residue.

17. A process according to claim 16, wherein the lignin residue obtained from drying is cooled down and granulated.

18. A process according to claim 16, wherein drying is carried out at a temperature of 40 to 170°

C.

19. A process according to claim 16, wherein the drying time is 0.5 min to 24 h.

20. A process according to claim 16, wherein drying is carried out to a dry solids content of 75 to 99% of the drying residue.

21. A process according to claim 20, wherein drying is carried out to a dry solids content of 85 to 97% of the drying residue.

22. A process according to claim 16, wherein after the drying step the process also comprises step (b2) where water or diluted acid solution is added to the drying residue and the mixture thus obtained is dried and/or re-evaporated.

23. A process according to claim 22, wherein the diluted acid solution is a wash acid mixture obtained from pulp washing.

24. A process according to claim 23, wherein the wash acid mixture is a concentrated wash acid mixture.

25. A process according to claim 1, wherein separation of the top product of the distillation is performed by decanting.

26. A process according to claim 1, wherein part or all of the bottom product from the first distillation phase is introduced into a second distillation phase where a mixture of formic acid and acetic acid, which is returned to cooking, is obtained as the top product of distillation and a furfural-containing mixture as the bottom product.

27. A process according to claim 26, wherein the bottom product also contains acetic acid.

28. A process according to claim 27, wherein the bottom product obtained from the second distillation phase and containing acetic acid and furfural is introduced into a third distillation phase, from which acetic acid is obtained as the top product and furfural as the bottom product.

29. A process according to claim 1, further comprising second and third distillation phases, wherein a stream of at least part of the furfural separated as the top product of the first distillation phase and/or of the furfural obtained as the bottom product from the second or third distillation phase is returned to the first distillation column and the rest is recovered.

30. A process according to claim 29, wherein the returned furfural stream is introduced into the first distillation column above the feed stream containing water, formic acid, acetic acid and furfural.

31. A process according to claim 1, wherein water from separation of the top product is returned to pulp washing.

32. A process according to claim 1, wherein the process also comprises a pre-concentration step before the evaporation phase of step (a).