Granted Patent
B2
US 12,492,155 · App. 18/393,900 · Granted Dec 9, 2025
Use of polyamines in the pretreatment of biomass
Inventors:
Ezinne Achinivu (Alexandria, VA); Mood Mohan (Emeryville, CA); Hemant Choudhary (Emeryville, CA); Lalitendu Das (Emeryville, CA); Venkataramana R. Pidatala (Emeryville, CA); Harsha D. Magurudeniya (Newport News, VA); Kaixuan Huang (Albany, CA); John M. Gladden (Alameda, CA); Blake A. Simmons (San Francisco, CA)
Assignees:
THE REGENTS OF THE UNIVERSITY OF CALIFORNIA; NATIONAL TECHNOLOGY & ENGINEERING SOLUTIONS OF SANDIA, LLC
View Patent ↗
Loading inventors, assignments & file history…
Abstract
The present invention provides for a method to deconstruct a biomass: the method comprising: (a) introducing a solvent comprising a polyamine, or a mixture of polyamines, to a biomass to dissolve at least part of solid biomass in the solvent, wherein the polyamine is a Brønsted or Lewis base, and/or the polyamine is a hydrogen bond donor and/or acceptor; (b) optionally introducing an enzyme and/or a microbe to the solubilized biomass mixture such that the enzyme and/or microbe produces a sugar from the solubilized biomass mixture; (c) optionally separating the sugar from the solubilized biomass mixture; and (d) optionally separating the lignan from the solubilized biomass mixture.
Claims (12)
1 . A method to deconstruct a biomass, the method comprising: (a) introducing a solvent comprising a polyamine to a biomass to dissolve at least part of solid biomass in the solvent, wherein the polyamine is a Brønsted or Lewis base, and/or the polyamine is a hydrogen bond donor and/or acceptor; wherein the polyamine lacks an oxygen atom.
2 . The method of claim 1 , further comprising separating the polyamine from the solubilized biomass mixture by distillation.
3 . The method of claim 1 , wherein the polyamine has the chemical structure:
wherein X is C or N; and R 1 , R 2 , R 3 , and R 4 , are each indepedently —H, —NH 2 , alkyl, alkenyl, alkynyl, aryl, alkyl amine, alkenyl amine, alkynyl amine, or aryl amine.
4 . The method of claim 1 wherein the solvent has a viscosity having a value equal to or less than about 50 cP at a temperature of about 90° C.
5 . The method of claim 1 wherein the solvent has a boiling point having a value equal to or less than about 200° C.
6 . The method of claim 1 wherein the polyamine is diamine, triamine, 1,5-diaminopentane, 1,4-diaminobutane, 1,3-diaminopropane, 1,2-diaminoethane, 1,2-diaminopropane, and 1,4-diaminobutane, ethylenediamine (ethane-1,2-diamine), diethylenetriamine, 1,3-diaminopropane (trimethylenediamine), 1,4-diaminobutane (putrescine), 1,5-diaminopentane (cadaverine), 1,2-diaminopropane, spermine (N1, N1′-(butane-1,4-diyl)bis(propane-1,3-diamine)), spermidine (N1-(3-aminopropyl)butane-1,4-diamine), 2,2-dimethyl-1,3-propanediamine, diethylenetriamine, spermine, or a mixture thereof.
7 . The method of claim 1 wherein the polyamine has a longest chain having 2 to 20 nitrogen atoms.
8 . The method of claim 7 wherein the polyamine has a longest chain having 2 to 15 nitrogen atoms.
9 . The method of claim 8 wherein the polyamine has a longest chain having 2 to 10 nitrogen atoms.
10 . The method of claim 9 wherein the polyamine has a longest chain having 2, 3, 4, 5, 6, 7, 8, or 9 nitrogen atoms.
11 . The method of claim 10 wherein the polyamine has a longest chain having 2, 3, or 4 nitrogen atoms.
Assignments (2)
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Mar 5, 2024
From: CHOUDHARY, HEMANT; GLADDEN, JOHN M.; ACHINIVU, EZINNE; MOHAN, MOOD; MAGURUDENIYA, HARSHA D.; DAS, LALITENDU
To: NATIONAL TECHNOLOGY & ENGINEERING SOLUTIONS OF SANDIA, LLC
Reel/Frame 066655/0933 →
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Mar 5, 2024
From: SIMMONS, BLAKE A.; PIDATALA, VENKATARAMANA R.; HUANG, KAIXUAN
To: THE REGENTS OF THE UNIVERSITY OF CALIFORNIA
Reel/Frame 066656/0305 →
Continuity (3)
Provisional Application
63124660
· Dec 11, 2020
References Cited (114)
US 6177575B1
· Arduengo, III et al.
· 2001
[cited by applicant]
US 7985567B2
· Chou et al.
· 2011
[cited by applicant]
US 8420833B2
· Katz et al.
· 2013
[cited by applicant]
US 8852902B2
· Katz et al.
· 2014
[cited by applicant]
US 9109175B2
· Lee et al.
· 2015
[cited by applicant]
US 9200298B2
· Lee et al.
· 2015
[cited by applicant]
US 9322042B2
· Sapra et al.
· 2016
[cited by applicant]
US 9334514B2
· Fortman et al.
· 2016
[cited by applicant]
US 9376691B2
· Peralta-Yahya et al.
· 2016
[cited by applicant]
US 9376728B2
· Zhang et al.
· 2016
[cited by applicant]
US 9382553B2
· Kirby et al.
· 2016
[cited by applicant]
US 9624482B2
· Sapra et al.
· 2017
[cited by applicant]
US 9631210B2
· Chou et al.
· 2017
[cited by applicant]
US 9725749B2
· Chen et al.
· 2017
[cited by applicant]
US 9765044B2
· Socha et al.
· 2017
[cited by applicant]
US 9803182B2
· Gladden et al.
· 2017
[cited by applicant]
US 9862982B2
· Zhang et al.
· 2018
[cited by applicant]
US 9951345B2
· Steen et al.
· 2018
[cited by applicant]
US 20150094459A1
· Kroon
· 2015
[cited by examiner]
WO 2009006386A2
· 2009
[cited by applicant]
WO 2009006429A1
· 2009
[cited by applicant]
WO 2009006430A1
· 2009
[cited by applicant]
WO 2009134899A2
· 2009
[cited by applicant]
WO 2010124266A2
· 2010
[cited by applicant]
WO 2010127318A2
· 2010
[cited by applicant]
WO 2012050931A2
· 2012
[cited by applicant]
WO 2012058686A2
· 2012
[cited by applicant]
WO 2012064740A1
· 2012
[cited by applicant]
WO 2012071439A1
· 2012
[cited by applicant]
WO 2012135389A2
· 2012
[cited by applicant]
WO 2012151214A1
· 2012
[cited by applicant]
WO 2014093402A2
· 2014
[cited by applicant]
WO 2015013674A2
· 2015
[cited by applicant]
WO 2016070125A1
· 2016
[cited by applicant]
WO 2016105538A1
· 2016
[cited by applicant]
WO 2017087982A2
· 2017
[cited by applicant]
WO 2017091781A1
· 2017
[cited by applicant]
WO 2017214159A1
· 2017
[cited by applicant]
WO 2017214332A1
· 2017
[cited by applicant]
WO 2018200888A1
· 2018
[cited by applicant]
WO 2018119152A1
· 2018
[cited by applicant]
WO 2019050990A1
· 2019
[cited by applicant]
WO WO2020037432A1
· 2020
[cited by examiner]
Eckert et al., “Fast Solvent Screening via Quantum Chemistry: COSMO-RS Approach” AIChE Journal, 2002, 48, 369-385 (2002).
[cited by applicant]
Kurnia et al., “Evaluation of the Conductor-like Screening Model for Real Solvents for the Prediction of the Water Activity Coefficient at Infinite Dilution in lonic Liquids” Ind Eng Chem Res, 53, 12466-12475 (2014).
[cited by applicant]
Grimme et al., “Effect of the damping function in dispersion corrected density functional theory”, J. Comput. Chem., 32, 1456-1465 (2011).
[cited by applicant]
Ding e al., “Theoretical and experimental investigation on dissolution and regeneration of cellulose in ionic liquid” Carbohydr. Polym., 89, 7-16 (2012).
[cited by applicant]
Mohan et al., “Solubility of glucose in tetrabutylammonium bromide based deep eutectic solvents: Experimental and molecular dynamic simulations” Fluid Phase Equilibria, 448, 168-177 (2017).
[cited by applicant]
Guo et al., “Probing anion-cellulose interactions in imidazolium-based room temperature ionic liquids: a density functional study” Carbohydr. Res., 345, 2201-2205 (2010).
[cited by applicant]
Espinosa et al., “Hydrogen bond strengths revealed by topological analyses of experimentally observed electron densities” Chem. Phys. Lett., 285, 170-173 (1998).
[cited by applicant]
Lu et al., “Multiwfn: A Multifunctional Wavefunction Analyze” J. Comput. Chem., 33, 580-592 (2012).
[cited by applicant]
Humphrey et al., “VMD: Visual molecular dynamics”, J Mol Graph, 14, 33-8, 27 (1996).
[cited by applicant]
Loschen et al., “COSMOquick: A Novel Interface for Fast σ-Profile Composition and Its Application to COSMO-RS Solvent Screening Using Multiple Reference Solvents” Ind Eng Chem Res, 51, 14303-14308 (2012).
[cited by applicant]
Niederquell et al., “New prediction methods for solubility parameters based on molecular sigma profiles using pharmaceutical materials” Int. J. Pharm., 546, 137-144 (2018).
[cited by applicant]
Yu et al., “Selective Separation of Wood Components Based on Hansen's Theory of Solubility” Ind Eng Chem Res, 50, 7513-7519 (2011).
[cited by applicant]
Yao et al., “Insights of Ethanol Organosolv Pretreatment on Lignin Properties of Broussonetia papyrifera” ACS Sustain. Chem. Eng., 6, 14767-14773 (2018).
[cited by applicant]
Sluiter et al., “Determination of Structural Carbohydrates and Lignin in Biomass” NREL, TP-510-42618 (2008).
[cited by applicant]
Greaves et al. “Protic lonic Liquids: Properties and Applications” Chem. Rev. 108(1):206-237 (2008).
[cited by applicant]
Vanholme et al., “Lignin Biosynthesis and Structure”, Plant Physiol., 153, 895-905 (2010).
[cited by applicant]
Galbe et al., “Pretreatment for biorefneries: a review of common methods for efcient utilisation of lignocellulosic materials”, Biotechnol Biofuels, 12, 294 (2019), 26 pages.
[cited by applicant]
Chang, “Harnessing energy from plant biomass” Curr. Opin. Chem. Biol., 11, 677-684 (2007).
[cited by applicant]
Rodionova et al., “Biofuel production: Challenges and opportunities” Int. J. Hydrogen Energy, 42, 8450-8461 (2017).
[cited by applicant]
Achinivu et al., “Lignin extraction from biomass with protic ionic liquids”, Green Chem., 16, 1114-1119 (2014).
[cited by applicant]
Upton et al., “Strategies for the Conversion of Lignin to High-Value Polymeric Materials: Review and Perspective” Chem. Rev., 116, 2275-2306 (2016).
[cited by applicant]
Kumar et al., “Methods for Pretreatment of Lignocellulosic Biomass for Efficient Hydrolysis and Biofuel Production” Ind Eng Chem Res, 48, 3713-3729 (2009).
[cited by applicant]
Kautto et al., “Economic analysis of an organosolv process for bioethanol production” BioRes, 9, 6041-6072 (2014).
[cited by applicant]
Zhang et al., “Organosolv Pretreatment of Plant Biomass for Enhanced Enzymatic Saccharification ” Green Chem., 18, 360-381 (2016).
[cited by applicant]
Borand et al., “Effects of organosolv pretreatment conditions for lignocellulosic biomass in biorefinery applications: A review” J. Renewable Sustainable Energy, 10, 033104 (2018).
[cited by applicant]
Zhao et al., “Evaluation of the mass transfer effects on delignification kinetics of atmospheric acetic acid fractionation of sugarcane bagasse with a shrinking-layer model” Biofuels, Bioprod. Bioref., 11, 567-590 (2017…
[cited by applicant]
Chen et al. “Distillable lonic Liquids: reversible Amide O Alkylation”, Angewandte Comm. 52:13392-13396 (2013).
[cited by applicant]
King et al. “Distillable Acid-Base Conjugate lonic Liquids for Cellulose Dissolution and Processing”, Angewandte Comm. 50:6301-6305 (2011).
[cited by applicant]
Vijayaraghavan et al. “CO2-based Alkyl Carbamate Ionic Liquids as Distillable Extraction Solvents”, ACS Sustainable Chem. Engin. 2:31724-1728 (2014).
[cited by applicant]
Idris et al. “Distillable Protic lonic Liquids for Keratin Dissolution and Recovery”, ACS Sustainable Chem. Engin. 2:1888-1894 (2014).
[cited by applicant]
Chen et al., “A comparison of several organosolv pretreatments for improving the enzymatic hydrolysis of wheat straw: Substrate digestibility, fermentability and structural features” Appl. Energy, 150, 224-232 (2015).
[cited by applicant]
Cheng et al, “Using Solubility Parameter Analysis to Understand Delignification of Poplar and Rice Straw with Catalyzed Organosolv Fractionation Processes” BioRes, 14, 486-499 (2019).
[cited by applicant]
Zhao et al., “Organosolv pretreatment of lignocellulosic biomass for enzymatic hydrolysis” Appl. Microbiol. Biotechnol., 82, 815-827 (2009).
[cited by applicant]
Qin et al., “Optimization of ethylenediamine pretreatment and enzymatic hydrolysis to produce fermentable sugars from corn stover” Ind. Crops Prod., 102, 51-57 (2017).
[cited by applicant]
Cheng et al., “Lignocellulosic biomass delignification using aqueous alcohol solutions with the catalysis of acidic ionic liquids: A comparison study of solvents” Bioresour. Technol., 249, 969-975 (2018).
[cited by applicant]
Sun et al. “One-pot integrated biofuel production using low-cost biocompatible protic ionic liquids”, Green Chem. 19(13):3152-3163 (2017).
[cited by applicant]
Ye et al., “Application of solubility parameter theory to organosolv extraction of lignin from enzymatically hydrolyzed cornstalks” Bioresources, 9, 3417-3427 (2014).
[cited by applicant]
Quesada-Medina et al., “Organosolv extraction of lignin from hydrolyzed almond shells and application of the d-value theory” Bioresour. Technol., 101, 8252-8260 (2010).
[cited by applicant]
Soh et al., “Green Solvents in Biomass Processing” ACS Sustain. Chem. Eng., 4, 5821-5837 (2016).
[cited by applicant]
Kwok et al., “Pretreatment Efficacy and Lignin Solubility of Organic Solvents on Juvenile Slash Pine Chips for Lignin Value Prior to Pulping” Bommarius, BioRes, 14, 5988-6003 (2019).
[cited by applicant]
Novo et al., “Hansen Solubility Parameters: A Tool for Solvent Selection for Organosolv Delignification” Ind Eng Chem Res, 58, 14520-14527 (2019).
[cited by applicant]
Balaji et al., “COSMO-RS Based Predictions for the Extraction of Lignin from Lignocellulosic Biomass Using Ionic Liquids: Effect of Cation and Anion Combination” J. Solution Chem., 41, 1610-1630 (2012).
[cited by applicant]
Casas et al., “Comparison of lignin and cellulose solubilities in ionic liquids by COSMO-RS analysis and experimental validation” Ind. Crops Prod., 37, 155-163 (2012).
[cited by applicant]
Casas et al., “Relation between differential solubility of cellulose and lignin in ionic liquids and activity coefficients” RSC advances, 3, 3453-3460 (2013).
[cited by applicant]
Zhang et al., “Genomic and phenotypic diversity of carbapenemase-producing enterobacteriaceae isolates from bacteremia in china: A multicenter epidemiological, microbiological, and genetic study” ACS Sustain. Chem. Eng.…
[cited by applicant]
Zhang et al., “A DFT study on lignin dissolution in imidazolium-based ionic liquids”, Rsc Advances, 7, 12670-12681 (2017).
[cited by applicant]
Ji et al., “Mechanism of Lignin Dissolution and Regeneration in lonic Liquid” Energy Fuels, 26, 6393-6403 (2012).
[cited by applicant]
Thielemans et al., “Lignin Esters for Use in Unsaturated Thermosets: Lignin Modification and Solubility Modeling” and R. P. Wool, Biomacromolecules, 6, 1895-1905 (2005).
[cited by applicant]
Hoy, “Solubility Parameter as a Design Parameter for Water Borne Polymers and Coatings” Journal of Coated Fabrics, 19, 53-67 (1989).
[cited by applicant]
Mohan et al., “Multiscale modelling strategies and experimental insights for the solvation of cellulose and hemicellulose in ionic liquids” Mol. Phys., 116, 1-21 (2018).
[cited by applicant]
Kahlen et al., “Modelling cellulose solubilities in ionic liquids using COSMO-RS” Green Chemistry, 12, 2172-2181 (2010).
[cited by applicant]
Liu et al., “Predictive screening of ionic liquids for dissolving cellulose and experimental verification” Green Chemistry, 18, 6246-6254 (2016).
[cited by applicant]
Liu et al., “Enhanced Enzymatic Hydrolysis and Lignin Extraction of Wheat Straw by Triethylbenzyl Ammonium Chloride/Lactic Acid-Based Deep Eutectic Solvent Pretreatment”, ACS Omega, 4, 19829-19839 (2019).
[cited by applicant]
Song et al., “Effect of Liquid Viscosity on the Liquid Phase Mass Transfer Coefficient of Packing” Energy Procedia, 63, 1268-1286 (2014).
[cited by applicant]
Song et al., “Effect of Liquid Viscosity on Mass Transfer Area and Liquid Film Mass Transfer Coefficient for GT-Optimpak 250Y” Energy Procedia, 114, 2713-2727 (2017).
[cited by applicant]
Zhao et al., “Evaluation of the mass transfer effects on delignification kinetics of atmospheric acetic acid fractionation of sugarcane bagasse with a shrinkinglayer model” Bioresour. Technol., 261, 52-61 (2018).
[cited by applicant]
Simão et al., “Heterogeneous studies in pulping of wood: Modelling mass transfer of dissolved lignin”, Chemical Engineering Journal, 170, 264-269 (2011).
[cited by applicant]
Hartono et al., “Density, viscosity, and excess properties of aqueous solution of diethylenetriamine (DETA)” The Journal of Chemical Thermodynamics, 41, 973-979 (2009).
[cited by applicant]
Padmanabhan et al., “Delignification of miscanthus using ethylenediamine (EDA) with or without ammonia and subsequent enzymatic hydrolysis to sugars”, 3 Biotech, 6, 23 (2016), 10 pages.
[cited by applicant]
Popelier, “Characterization of a Dihydrogen Bond on the Basis of the Electron Density”, J. Phys. Chem. A, 102, 1873-1878 (1998).
[cited by applicant]
Hanwell et al., “Avogadro: an advanced semantic chemical editor, visualization, and analysis platform” J. Cheminform., 2012, 4, 17 (2012), 17 pages.
[cited by applicant]
Mohan et al., “Solid Liquid Equilibrium of Cellobiose, Sucrose, and Maltose Monohydrate in Ionic Liquids: Experimental and Quantum Chemical Insights” Journal of Chemical & Engineering Data, 61, 2923-2932 (2016).
[cited by applicant]
Gonzalez-Miquel et al., “Excess Enthalpy of Monoethanolamine + Ionic Liquid Mixtures: How Good are COSMO-RS Predictions?” J. Phys. Chem. B, 118, 11512-11522 (2014).
[cited by applicant]
Mohan et al., “Solubility of glucose, xylose, fructose and galactose in ionic liquids: Experimental and theoretical studies using a continuum solvation model”, Fluid Phase Equilib., 395, 33-43 (2015).
[cited by applicant]
Anantharaj et al., “COSMO-RS-Based Screening of Ionic Liquids as Green Solvents in Denitrification Studies” Ind Eng Chem Res, 49, 8705-8725 (2010).
[cited by applicant]
Li et al., “Effects of thermal pretreatment on acidification phase during two-phase batch anaerobic digestion of kitchen waste” Renew. Energy, 77, 550-557 (2015).
[cited by applicant]