T. N. Smith et al. / Carbohydrate Research 350 (2012) 6–13
13
reached 1 L, reverse osmosis (RO) purified water (1 L) was added to
the feedstock. The typical rate of the permeate flow when reducing
the volume by 1 L was 48 mL/min. When 2 L of permeate was re-
moved, more RO water (1 L) was added to the feedstock. The typ-
ical rate of permeate flow when removing the second L was 45 mL/
min. This procedure was repeated until a total of 4 L of permeate
was collected and 4 L of RO water had been added to the feedstock.
The typical permeate flow rate when removing the last 1 L was
solution was cooled in an ice bath and the pH adjusted to a con-
stant 9.5 with 45% KOH, then titrated to pH 3.4 with concentrated
hydrochloric acid. The resulting solid monopotassium D-glucarate
(3, 79.6 g, 43% yield) was isolated as described above.
Acknowledgements
This work was funded by USDA Cooperative State Research,
Education and Extension Service award No. 2001-34463-10521
and an EPSCoR Lab Partnership Grant 2000–2003. Special thanks
to Dr. John Vercellotti of V-LABS, Inc. for guidance in developing
the nanofiltration protocol.
4
3 mL/min. The filtration process was continued after the last L
of RO water was added to the feedstock until the permeate flow
slowed to a trickle at which time the filtration was stopped. The fi-
nal volumes of the retentate and permeate were 2.8 L and 5.2 L,
respectively.
References
4
.8. Nitric acid removal by diffusion dialysis
1
2
3
.
.
.
Walaszek, Z.; Szemraj, J.; Hanausek, M.; Adams, A. K.; Sherman, U. Nutr. Res.
1996, 16, 673–681.
Perez, J. L.; Jayaprakasha, G. K.; Yoo, K. S.; Patil, B. S. J. Chromatogr. A 2008, 1190,
The diffusion dialysis system was a Mech-Chem laboratory
scale acid purification unit (Model AP-L05, Mech-Chem Associ-
ates, Inc., Norfolk, MA, USA). The Mech-Chem unit contains two
metering pumps, an acid reclaim pump, and an acid reject pump.
The acid reject pump was set at 30% (pump length) and 30%
pump speed), and the acid reclaim pump was set at 40% (pump
length) and 40% (pump speed), giving a flow through rate of
20 mL/h for the acid reclaim and 112 mL/h for the acid reject.
The system was first primed with RO water according to a stan-
dard setup procedure and then the water was removed from
the acid tank in the unit. The concentrated reaction mixture from
394–397.
Sohst, O.; Tollens, B. Liebigs Ann. Chem. 1888, 245, 1–27.
4. Mehltretter, C. L. U.S. Patent 2,436,659, 1948.
5.
6.
7.
Mehltretter, C. L.; Rist, C. E. J. Agric. Food Chem. 1953, 1, 779–783.
Mustakas, G. C.; Slotter, R. L.; Zipf, R. L. Ind. Eng. Chem. 1954, 46, 427–434.
Mehltretter, C. L.; Alexander, B. H.; Rist, C. E. Ind. Eng. Chem. 1953, 45, 2782–
2784.
(
1
8. Abbadi, A.; Gotlieb, K. F.; Meiberg, J. B. M.; Peters, J. A.; van Bekkum, H. Green
Chem. 1999, 1, 231–235.
9. Korzh, E. N.; Sukhotin, A. M. Zh. Prikl. Khim. 1981, 54, 2404–2407.
1
0. Sukhotin, A. M.; Borshchevskii, A. M.; Korzh, E. N.; Perel’shtein, I. I.; Aref’eva, L.
N.; Kuslyaikin, G. A.; Parushin, E. B. Zashchita Metallov 1982, 18, 268–270.
1. Walaszek, Z. Cancer Lett. 1990, 54, 1–8.
1
1
1
the oxidation of D-glucose reconstituted with water was added to
2. Lampe, J. W.; Li, S. S.; Potter, J. D.; King, I. B. J. Nutr. 2002, 132, 1341–1344.
3. Kiely, D. E.; Chen, L.; Lin, T.-H. J. Am. Chem. Soc. 1994, 116, 571–578.
the acid feedstock tank. The water tank was filled with RO water
and two output streams, an inorganic acid recovery stream (re-
claimed acid stream) and a product recovery stream (product
stream), were collected.
14. Werpy, T.; Petersen, G. Top Value Added Chemicals from Biomass, Volume 1:
Results of Screening for Potential Candidates from Sugars and Synthesis Gas.
1
1
5. Mehltretter, C. L.; Rist, C. E.; Alexander, B. H. U.S. Patent 2,472,168, 1949.
6. Thaburet, J.-F.; Merbouh, N.; Ibert, M.; Marsais, F.; Queguiner, G. Carbohydr. Res.
4
.9. Monopotassium D-glucarate isolation from an oxidation
2001, 330, 21–29.
where nitric acid was evaporatively removed at reduced
pressure with heat
1
7. Merbouh, N.; Thaburet, J.-F.; Ibert, M.; Marsais, F.; Bobbitt, J. M. Carbohydr. Res.
2001, 336, 75–78.
1
1
8. Merbouh, N.; Bobbitt, J. M.; Brückner, C. J. Carbohydr. Chem. 2002, 21, 65–77.
9. Schroeder, W. A.; Hicks, P. M.; McFarlan, S. C.; Abraham, T. W. U.S. Patent
The pH of the concentrated reaction mixture from the oxidation
7,326,549 B2, 2008.
of
D-glucose (4:1 molar ratio of nitric acid to
D-glucose) reconsti-
20. Moon, T. S.; Yoon, S.-H.; Lanza, A. M.; Roy-Mayhew, J. D.; Prather, K. L. Appl.
Environ. Microbiol. 2009, 75, 589–595.
tuted with water (370 mL) was adjusted to a constant pH of 9.5
with 45% KOH. The solution was cooled in an ice bath and titrated
to pH 3.4 with concentrated hydrochloric acid. A precipitate was
formed when the solution pH dropped below 5. The mixture was
cooled and held at 5 °C for 4 h and the precipitate then isolated
by filtration. The resulting solid cake was washed with cold water
and dried at reduced pressure for 18 h to give solid monopotassi-
2
1. Denton, T. T.; Hardcastle, K. I.; Dowd, M. K.; Kiely, D. E. Carbohydr. Res. 2011,
46, 2551–2557.
2. Kiely, D. E.; Hash, Sr. Kirk R. U.S. Patent 7,692,041 B2, 2010.
3
2
23. Cotton, F. A.; Wilkinson, G. W. Advanced Inorganic Chemistry, 2nd ed.;
Interscience: New York, 1966. pp 341–353.
2
2
4. Kiely, D. E.; Carter, A.; Shrout, D. P. U.S. Patent 5,599,977, 1997.
5. Xi, H.; Gao, Z.; Wang, J. Ind. Eng. Chem. Res. 2009, 48, 10425–10430.
26. Joshi, S. R.; Kataria, K. L.; Sawant, S. B.; Joshi, J. B. Ind. Eng. Chem. Res. 2005, 44,
25–333.
3
um
D
-glucarate (3), 83.2 g (45% yield from 134.3 g of dextrose).
2
2
7. Blake, J. D.; Clarke, M. L.; Richards, G. N. J. Chromatogr. 1987, 398, 265–277.
8. Mills, H. C. M.; M. Sc. Thesis, The University of Waikato, 2007.
4
.10. Monopotassium
D
-glucarate isolation after nitrate
29. Davey, C.-L.; M. Sc. Thesis, The University of Waikato, 2008.
3
0. Cantrell, C. E.; Kiely, D. E.; Abruscato, G. J.; Riordan, J. M. J. Org. Chem. 1977, 42,
562–3567.
1. Kiely, D. E.; Ponder, G. U.S. Patent 6,049,004, 2000.
removal by nanofiltration
3
3
The retentate stream from the nanofiltration system was con-
centrated to an approximate volume of 300 mL. The concentrated
32. Bailey, D. E. U.S. Patent 5,264,123, 1993.
3. Olsen, D. R. and Bailey, D. E. U.S. Patent, 5,562,828, 1996.
3