Iowa State University Capstones, Theses and Retrospective Theses and Dissertations Dissertations 1994 Recovery and purification of lactic acid from fermentation broth by adsorption Roque Lagman Evangelista Iowa State University Follow this and additional works at: https://lib.dr.iastate.edu/rtd Part of the Agriculture Commons, Chemical Engineering Commons, and the Food Science Commons Recommended Citation Evangelista, Roque Lagman, "Recovery and purification of lactic acid from fermentation broth by adsorption " (1994). Retrospective Theses and Dissertations. 11252. https://lib.dr.iastate.edu/rtd/11252 This Dissertation is brought to you for free and open access by the Iowa State University Capstones, Theses and Dissertations at Iowa State University Digital Repository. It has been accepted for inclusion in Retrospective Theses and Dissertations by an authorized administrator of Iowa State University Digital Repository. For more information, please contact [email protected]. INFORMATION TO USERS This manuscript has been reproduced from the microfilm master. UMl films the text directly from the original or copy submitted. Thus, some thesis and dissertation copies are in typewriter face, while others may be from any type of computer printer. The quality of this reproduction is dependent upon the quality of the copy submitted. Broken or indistinct print, colored or poor quality illustrations and photogr^hs, print bleedthrough, substandard margins, and improper alignment can adversely affect reproduction. In the unlikely event that the author did not send UMI a complete manuscript and there are missing pages, these will be noted. Also, if unauthorized copyright material had to be removed, a note will indicate the deletion. Oversize materials (e.g., maps, drawings, charts) are reproduced by sectioning the original, beginning at the upper left-hand comer and continuing from left to right in equal sections with small overlaps. Each original is also photographed in one exposure and is included in reduced form at the back of the book. Photographs included in the original manuscript have been reproduced xerographically in this copy. Higher quality 6" x 9" black and white photographic prints are available for any photographs or illustrations appearing in this copy for an additional charge. Contact UMI directly to order. A Bell & Howell Information Company 300 North Zeeb Road. Ann Arbor, Ml 48106-1346 USA 313/761-4700 800/521-0600 Order Number 9518375 Recovery and purification of lactic acid from fermentation broth by adsorption Evangelista, Roque Lagman, Ph.D. Iowa State University, 1994 UMI 300 N. ZeebRd. Ann Arbor, MI 48106 Recovery and purification of lactic acid from fermentation broth by adsorption by Roque Lagman Evangelista A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of the Requirements for the Degree of DOCTOR OF PHILOSOPHY Department: Food Science and Human Nutrition Major: Food Science and Technology Approved: Signature was redacted for privacy. Signature was redacted for privacy. For the Major Department Signature was redacted for privacy. For the Graduate College Iowa State University Ames, Iowa 1994 ii To my dearest wife, MILA... iii TABLE OF CONTENTS Page LIST OF TABLES v LIST OF FIGURES vi ACKNOWLEDGMENTS x ABSTRACT xi I. INTRODUCTION 1 Research Objectives 2 Explanation of Dissertation Format 3 II. REVIEW OF LITERATURE 4 Properties of Lactic Acid 4 Uses of Lactic Acid 5 Lactic Acid Manufacture 7 Fermentation 7 Recovery and purification processes 9 Filtration, carbon treatment, and evaporation 9 Calcium lactate crystallization 10 Liquid-liquid extraction 10 Esterification and distillation 11 Synthesis 12 Other Processes in Recovery of Lactic Acid 13 Synthetic Adsorbents 14 Functional groups 14 Matrix structure 18 Adsorption of Carboxylic Acid on Basic Sorbents 20 Proposed Processes for Organic Acid Recovery and Purification Using Polymeric Sorbents 23 Adsorption 23 Continuous chromatography 26 Extractive fermentation by using sorbents 27 III. MATERIALS AND METHODS 30 Evaluation of Basic Sorbents 30 Resin preparation 30 Total resin capacity for chloride 32 Analytical methods 32 Preparation of starting lactic acid solutions 33 Batch sorption 33 iv Page Fixed-bed sorption 34 Lactic Acid Recovery From Fermentation Broth 36 Lactic acid recovery scheme 36 Broth preparation 38 Column preparation 38 Broth acidification 39 Column regeneration by using carbonic acid 39 Sorption in weak-base sorbents 41 Broth Pretreatment 42 Browning reaction and activated carbon treatment 42 Broth decolorization by using activated carbon 42 Broth decolorization by using on nonfunctionalized resins 42 IV. RESULTS AND DISCUSSION 44 Evaluation of Selected Basic Sorbents 44 Basic sorbent capacities for HOI 44 Effect of pH on sorption of basic sorbents 46 Fixed-bed sorption 63 Section summary 67 Recovery of Lactic Acid from Fermentation Broth 68 Broth acidification 68 Column regeneration by using carbonic acid 70 Recovery of lactic acid from acidified broth by using basic sorbents 76 Riedel-de-Haen Vl-15 column 76 Dowex MWA-1 column 78 Amberlite IRA 35 column 86 Section summary 89 Broth Pretreatment 90 Browning and activated carbon treatment 90 Broth pretreatment by using nonfunctionalized resins 98 Section summary 106 Proposed Lactic Acid Recovery and Purification Scheme 110 V. GENERAL SUMMARY AND CONCLUSIONS 114 VI. RECOMMENDATIONS 117 REFERENCES 118 APPENDIX 122 V LIST OF TABLES Page Table 2.1. Physical properties of lactic acid 5 Table 3.1. Properties of selected basic adsorbents 31 Table 3.2. Composition of model lactic acid broth 38 Table 3.3. Nonfunctlonalized polymeric sorbents 43 Table 4.1. Capacities of sorbents for HOI 45 Table 4.2. Calculated values of the Langmuir model parameters and resin capacities 59 vi LIST OF FIGURES Page Figure 2.1. Models of (a) L-(+)-, and (b) D-(-)-lactic acid 4 Figure 2.2. Composition of aqueous lactic acid in equilibrium 6 Figure 2.3. Chemical structures of ion exchange resins 15 Figure 2.4. Chemical structures of weak-base resins 16 Figure 2.5. Chemical structures of weak-base resins with tertiary amine functionality 17 Figure 2.6. Chemical structures of strong-base anion exchangers 19 Figure 3.1. Set-up for fixed-bed sorption experiments 35 Figure 3.2. Scheme for lactic acid recovery and purification 37 Figure 3.3. Set-up for carbonic acid regeneration 40 Figure 4.1. Composite sorption isotherms of lactic acid in Reillex 425 47 Figure 4.2. Composite sorption isotherms of lactic acid in Riedel-de- Haen VI-15 48 Figure 4.3. Composite sorption isotherms of lactic acid in Dowex MWA-1 50 Figure 4.4. Composite sorption isotherms of lactic acid in Dowex XUS 40283 51 Figure 4.5. Composite sorption isotherms of lactic acid in Dowex XUS 43432 52 Figure 4.6. Composite sorption isotherms of lactic acid in Dowex WGR-2 53 Figure 4.7. Composite sorption isotherms of lactic acid in Dowex XUS 40196 54 vii Page Figure 4.8. Composite sorption isotherms of lactic acid in Amberlite IRA 958 55 Figure 4.9. Composite sorption isotherms of lactic acid in (a) weak-base, and (b) moderate-base sorbents 58 Figure 4.10. Composite sorption isotherms of lactic acid in Dowex XUS 40196 and Amberlite IRA 958 at (a) pHs < 3, and (b) pHs >6 62 Figure 4.11. Breakthrough profiles of lactic acid feed (60 mg/mL) at different pHs 64 Figure 4.12. Effect of pH on saturation capacity for lactic acid in (a) weak-base, (b) moderate-base, and (c) strong-base sorbents 66 Figure 4.13. Elution profile of model broth on Duolite 464 column 69 Figure 4.14. Chromatogram of (a) model lactic acid broth, and (b) Duolite C-464 column-acidified model lactic acid broth 72 Figure 4.15. pH profiles of acidified effluent of lactate (pH 6.5) from Duolite C-464 after regenerating with HCI and H2CO3 74 Figure 4.16. pH profiles of acidified model broth from (a) Duolite C-464, and (b) Amberlite IRC-50 after H2SO4 and HgCOg regeneration 75 Figure 4.17. Effluent profile for VI-15 column 77 Figure 4.18. Chromatogram of lactic acid eluted by methanol from VI-15 column 79 Figure 4.19. Chromatogram of NaOH rinse of VI-15 column after methanol elution 80 Figure 4.20. Effluent profile for MWA-1 column 81 Figure 4.21. Chromatogram of lactic acid eluted by methanol from MWA-1 column 83 viii Page Figure 4.22. Effluent profile for MWA-1 column with NH4OH as desorbent 84 Figure 4.23. Chromatogram of lactic acid eluted by 5% NH4OH from MWA-1 column 85 Figure 4.24. Effluent profile for IRA-35 column with methanol as desorbent 87 Figure 4.25. Chromatogram of lactic acid eluted by methanol from IRA-35 column 87 Figure 4.26. Modified scheme for lactic acid recovery and purification 90 Figure 4.27. Chromatograms of model lactic acid broth (pH 10) (a) before, and (b) after heating for 5 h 93 Figure 4.28. Chromatograms of model lactic acid broth (pH 4.5) (a) before, and (b) after heating for 5 h 95 Figure 4.29. Effluent profiles of (a) unheated lactic acid broth (pH 4.5), and browned broths at (b) pH 4.5 and (c) pH 5.3 on activated carbon column 97 Figure 4.30. Chromatograms of unheated broth effluent from activated carbon column 98 Figure 4.31. Chromatograms of browned broth (pH 4.5) effluent from activated carbon column 99 Figure 4.32. Chromatograms of browned broth (pH 10) effluent from activated carbon column 100 Figure 4.33. Effluent profiles of model lactic acid broth in (a) Duolite S-761, (b) Diaion HP-2MG, and (c) Amberlite XAD 16 columns 101 Figure 4.34. Chromatograms of model lactic acid broth (a) before, and (b) after passing through Amberlite XAD 16 column 103 Figure 4.35. Chromatograms of model lactic acid broth (a) before, and (b) after passing through Diaion HP-2MG column 104 ix Page Figure 4.36.