Method to valorize 2G bioethanol waste streams

Abstract

An integrated approach for utilizing waste products of 2G bio-refineries to fractionate the lignin of high purity. The present invention also provides a method of recycling of two waste products (2-G ethanol residue as the substrate (LRBR) and fusel oil/synthetic fusel oil (SFO) as one of the solvent) of the biorefineries in a beneficial manner to fractionate the lignin of high purity. The present method of separating high purity lignin comprises fractioning extractive-free lignin rich residue with a solvent, wherein the solvent is a mixture of SFO/Fusel oil and Formic acid. An optimized ratio of waste fusel oil and formic acid gave more than >85% yields of high purity lignin.

Claims

1. A method for separating high purity lignin from waste streams, the method comprising: i. removing extractives from the waste steam using by hot water treatment at 70-90° C., and repeating the step for 2-5 times; ii. extracting solids obtained in previous step with technical spirit or fusel oil, and repeating the step 1-2 times to obtain extractive-free lignin rich residue; iii. fractioning extractive-free lignin rich residue obtained in previous step with a solvent in high pressure reactor; iv. separating the slurry obtained in previous step into solid and liquid fractions, v. washing the solid fraction with solvent of step (iii), followed by washing with water; and vi. combining the wash from step (v) to liquid fraction and recovering the lignin.

2. The method as claimed in claim 1, wherein the waste steam is a bioethanol residue of the biorefineries and wherein extractive-free lignin rich residue is an extractive-free lignin rich bioethanol residue (LRBR).

3. The method as claimed in claim 1, wherein the organic solvents used in step (iii) is selected from methanol, ethanol, propanol, butanol, acetone, formic acid, acetic acid, propionic acid, synthetic fusel oil (SFO), fusel oil or combination thereof.

4. The method as claimed in claim 3, wherein the synthetic fusel oil comprises iso-amyl alcohol (55%), iso-butyl alcohol (18%), active amyl alcohol (10%), butyl alcohol (5%) propyl alcohol (5%) and Hexanol (2%).

5. The method as claimed in claim 1, wherein the solvent is a mixture of SFO and formic acid.

6. The method as claimed in claim 5, wherein the solvent is a mixture of SFO and formic acid in a ratio of 1:1.

7. The method as claimed in claim 1, wherein the solvent is a mixture of fusel oil and formic acid.

8. The method as claimed in claim 7, wherein the solvent is a mixture of fusel oil and formic acid in a ratio of 1:1.

9. The method as claimed in claim 1, wherein the fractioning in step (iii) is at temperature of 160-200° C. and pressure of 10-12 bar.

10. The method as claimed in claim 1, wherein the method is integrated to a method for production of bioethanol in biorefineries.

Description

DETAILED DESCRIPTION OF THE INVENTION

(1) A more complete understanding of the present invention is available by reference to the following detailed description of aspects and embodiments of the invention. The detailed description of the invention which follows is intended to illustrate but not limit the invention.

(2) The present invention discloses a method to fractionate high purity lignin using bio-ethanol waste streams like fusel oil and lignin rich residues. More particularly the present invention relates to an integrated approach for utilizing waste products of 2G biorefineries to fractionate the lignin of high purity.

(3) In accordance with the present invention, lignin can be fractionated from bio-ethanol waste streams in a two-stage method. The method comprises of the following stages and steps: 1. Extractives Removal Stage: a. The water-soluble extractives are removed with hot water (70-90° C.) and the extraction procedure carried out multiple times (2-5 times); b. The solids recovered from hot-water extractions are further extracted with technical spirit or alternatively with fusel oil for further extractives removal (1-2 times). 2. Lignin Extraction Stage i. The fractionation of extractive-free Lignin Rich Bioethanol Residue (LRBR) is carried out at this stage. a) The industrial grade fusel oil and synthetic fusel oil) were evaluated for lignin solubilization. b) The fractionation of extractive-free LRBR was carried out in a 2.0 L high pressure reactor (HPR) equipped with a temperature controller. The extractive-free sample (50 g, oven dried) was charged in the reactor. The extractive-free sample was treated with different organic solvents, under different temperature and time conditions. c) The fusel oil/Synthetic Fusel Oil combined with formic acid at 1:1 ratio gave highest solubilization. d) Formic acid in combination with individual components of Fusel Oil can also be used for step (c).

(4) Technical spirit is a product stream generated during the distillation process of the fermented broth generated after pretreatment of lignocellulosic biomass, enzymatic saccharification and co-fermentation.

(5) TABLE-US-00001 TABLE 1 Chemical composition of technical spirit Component Content Ethanol 85.0% Water  5.0% Acetic acid  5.0% Acetaldehyde  5.0%

(6) In another embodiment of the present invention, lignin is fractionated from bio-ethanol waste streams in a two-stage method. The method comprises of the following stages and steps: 1. Extractives Removal Stage: a. The water-soluble extractives are removed with hot water (70-90° C.) and the extraction procedure carried out multiple times (2-5 times). b. The solids recovered from hot-water extractions are further extracted with technical spirit or alternatively with fusel oil for further extractives removal (1-2 times). 2. Lignin Extraction Stage i. The fractionation of extractive-free Lignin Rich Bioethanol Residue (LRBR) is carried out at this stage. a) The industrial grade fusel oil and synthetic fusel oil were evaluated for lignin solubilization. b) The fractionation of extractive-free LRBR was carried out in a 2.0 L high pressure reactor (HPR) equipped with a temperature controller. The extractive-free sample (50 g, oven dried) was charged in the reactor. The extractive-free sample was treated with different organic solvents, under different temperature and time conditions. c) The fusel oil/Synthetic Fusel Oil combined with formic acid at 1:1 ratio gave highest solubilization.

(7) In an embodiment of the present invention, synthetic fusel oil can be used in accordance with the present invention. Synthetic fusel oil comprises iso-amyl alcohol (55%), iso-butyl alcohol (18%), active amyl alcohol (10%), butyl alcohol (5%) propyl alcohol (5%) and Hexanol (2%). In accordance with the present invention, organic solvents used in step (b) of Lignin Extraction Stage include, but are not limited to, methanol, ethanol, propanol, butanol, acetone, formic acid, acetic acid, propionic acid.

(8) In another embodiment of the present invention, yield and purity of lignin is >85% and 99% respectively.

(9) Having described the basic aspects of the present invention, the following non-limiting examples illustrate specific embodiment thereof.

Example-1

(10) Bioethanol Residue Extractives Removal and Composition Analysis

(11) The bioethanol residue obtained after fermentation contained extractives. These extractives include fats, proteins, nonstructural silica and inorganic and organic compounds of lignocellulosic biomass and enzymes, salts, yeast, media components which have been added during the saccharification and fermentation steps. In this invention, extractives were removed at its first step to serve a dual purpose i.e., to get rid of un-necessary burden/load during lignin valorization process and minimize the formation of impurities which might interfere with the product separation/purification procedure.

(12) The water-soluble extractives were removed with hot water (70-90° C.) extraction procedure carried out multiple times (2-3 times) using Soxhlet. The solids recovered after hot-water extractions were then extracted with technical spirit (1-2 times) for further extractives removal (Table 2).

(13) TABLE-US-00002 TABLE 2 Removal of extractives from bioethanol residues Sample Extractives removal (%) Hot water extraction 52.31 Hot water and spirit extraction 92.58

(14) Results indicated that hot water extraction led to only ˜50% removal while hot water plus spirit extraction led to the removal of ˜93% extractives.

(15) The unextracted and extractive free bioethanol residue samples were then washed and air-dried for the composition analysis (Table 3) by NREL LAP (Sluiter et al.; 2008). Sugar and inhibitors concentration in the pretreatment hydrolysate were measured by HPLC (Waters Gesellschaft Gmbg, Austria) using Bio-Rad Aminex HPX-87H column (Bio-Rad, USA) coupled with refractive index (RI) and Photo Diode Array (PDA) detector at a flow rate of 0.6 ml/min at column temperature of 50° C. The mobile phase was 0.005 N H.sub.2SO.sub.4 (Agrawal et al., 2015b).

(16) TABLE-US-00003 TABLE 3 Chemical composition of unextracted and extractive free bioethanol residue Extractives Cellulose Hemicellulose Lignin Ash Sample (%) (%) (%) (%) (%) Bioethanol 21.8 24.8 0.9 32.4 20.8 residue Bioethanol — 28.2 0 46.3 26.4 residue after extraction

(17) The chemical compositions showed that bioethanol residue is composed of high amounts of lignin and ash and contains some un-converted polysaccharides mostly cellulose. Further, the removal of extractives led to the cellulose and lignin enrichment and thus chosen for further study.

Example 2

(18) Lignin Solubilization Using Fusel Oil.

(19) Fusel Oil (waste generated during ethanol distillation) is composed of a mixture of higher alcohols and other organic solvents. The composition of a typical Fusel oil samples is depicted in Table 4.

(20) TABLE-US-00004 TABLE 4 Chemical composition of Fusel oil (obtained from ethanol production unit) Content S.No. Component (%, v/v) 1 Iso-amyl alcohol 55 2 Iso-butyl alcohol 18 3 Active amyl alcohol (2-methyl-1-butanol) 10 4 Butyl alcohol 5 5 Propyl alcohol 5 6 Hexanol 2 7 Others (including mixture of methanol, ethanol, 5 acids, water, metal salts, etc.)

(21) The industrial grade fusel oil and synthetic fusel oil or (blend prepared in laboratory by mixing its individual components i.e., iso-amyl alcohol (55%), iso-butyl alcohol (18%), active amyl alcohol (10%), butyl alcohol (5%) propyl alcohol (5%) and Hexanol (2%) named as SFO) were evaluated for lignin solubilization. Various other combinations with formic acid or ethanol were also tested (Table 5). Study was carried out in a 2.0 L high pressure reactor (HPR) (Amar Equipments, Mumbai India) equipped with temperature controller. Extractive-free bioethanol residue at 10% loading was taken as the substrate and all the experiments were conducted under similar conditions (temperature 160° C., residence time 60 min).

(22) The slurry obtained after treatment was centrifuged to separate the solids and liquids. Solids were washed first with the same solvent used for fractionation and then with water. The wash was combined with the filtrate/liquid. The solids obtained were kept for drying while the liquid fraction was concentrated using the vacuum evaporator (R-205, Büchi, Bern, Switzerland). Mass balance was done for both the fractions after oven-drying. Moisture content of samples was determined according to NREL LAP, using an infrared drier from. Lignin solubilization was calculated using following formula:

(23) $\mathrm{Lignin}\mathrm{solubilization}=\frac{\mathrm{Weight}\mathrm{of}\mathrm{residue}\mathrm{loaded}\left(g\right)-\mathrm{Weight}\mathrm{of}\mathrm{solid}\mathrm{obtained}\left(g\right)}{\mathrm{Weight}\mathrm{of}\mathrm{residue}\mathrm{loaded}\left(g\right)}\times 100$
where, ‘weight’ refers to the oven-dry weight (ODW) i.e., the weight after moisture correction.

(24) TABLE-US-00005 TABLE 5 Lignin solubilization yields with Fusel oil and other synthetic blends. Pressure Solubilization S.No. Solvent (Bar) (%) Remarks 1 Iso-amyl alcohol 11 10.3 Poor solubilization 2 Iso-butyl alcohol 10 7.8 Poor solubilization 3 SFO 10 22.2 Optimum solubilization 4 Fusel Oil 12 26.8 Optimum solubilization 5 SFO:Ethanol (1:1) 15 28.5 Optimum solubilization 6 Fusel oil:Ethanol (1:1) 17 32.7 Optimum solubilization 7 SFO:Formic acid (1:1) 11 36.4 High solubilization with low ash 8 Fusel Oil:Formic acid (1:1) 12 41.2 High solubilization with low ash (*SFO means synthetic blend of iso-amyl alcohol (55%), iso-butyl alcohol (18%), active amyl alcohol (10%), butyl alcohol (5%) propyl alcohol (5%) and Hexanol (2 %)).

(25) The fusel oil/SFO combined with formic acid at 1:1 ratio gave highest solubilization. Fusel oil plus formic acid was found to be promising with 41% lignin solubilization followed by SFO plus formic acid with 36.7% solubilization. Fusel oil thus found to have tremendous potential for applications in lignin solubilization and valorization processes.

Example 3

(26) Temperature Optimization for Lignin Recovery

(27) Reaction was optimized at different temperatures (120-200° C.) using fusel oil:formic acid (1:1) at 10% loading for a residence period of 1 h (Table 6). Lignin recovery and purity was estimated by compositional analysis according to the methods above.

(28) TABLE-US-00006 TABLE 6 Optimization of temperature for maximum recovery of lignin Composition (%) Lignin HPR Treatments (Solubilized Lignin Phase) Recovery Temperature Cellulose Lignin Ash (%) 120° C./1 Hour 6.7 55.5 0.9 49.8 140° C./1 Hour 5.4 61.7 0.8 57.3 160° C./1 Hour 2.2 77.6 0.1 80.0 180° C./1 Hour 0.1 84.3 0.06 86.1 190° C./2 Hour 0.0 71.1 0.09 52.2 200° C./1 Hour 0.0 68.3 0.5 50.0

(29) Based on compositional analysis, optimum temperature was found to be 180° C. with 86.1% lignin recovery and >99% purity.