Marjorie R.
Rover
a,
Alvina
Aui
b,
Mark Mba
Wright
b,
Ryan G.
Smith
a and
Robert C.
Brown
*ab
aBioeconomy Institute, Iowa State University, Ames, IA, USA. E-mail: rcbrown3@iastate.edu; Tel: +1 515 294 7934
bDepartment of Mechanical Engineering, Iowa State University, Ames, IA, USA
First published on 2nd October 2019
Levoglucosan has significant potential in commercial applications for the synthesis of polymers, solvents and pharmaceuticals. It is currently overlooked for commercial applications due to its high cost of synthesis and purification. We have developed a system to produce pure crystals of levoglucosan based on the fast pyrolysis of lignocellulosic biomass. A novel bio-oil recovery system concentrated levoglucosan along with other anhydrosugars, sugars and phenolic compounds in a non-aqueous “heavy ends” fraction. Liquid–liquid water extraction separated sugar-rich solubilized carbohydrates from non-soluble phenolic compounds. The solubilized carbohydrate fraction, contaminated with partially soluble phenolic monomers, was filtered through Sepabeads SP207 adsorption resin to produce clarified juice. The composition of the clarified juice on a dry basis after resin filtration and rotary evaporation was 81.2% sugars, 4.45–4.60% volatile non-sugar, 1.71% carboxylic acids and 12.5–12.6% unidentified compounds, which was sufficiently pure to crystallize the sugars by evaporation. A cold solvent rinse of the crystal mass separated and purified levoglucosan from other sugars. Levoglucosan purity was 102.5% ± 3.109% at the 99% confidence level. Techno-economic analysis of a plant pyrolyzing 250 tonne per day of pretreated biomass to produce cellulosic sugars indicated a minimum selling price (MSP) for pure levoglucosan crystals of $1333 per MT, which is less than one-tenth its current average market price. Operating hours of the plant, fermentable syrup yield and fixed capital are the most significant parameters affecting MSP.
Levoglucosan is conventionally synthesized from D-glucose by attaching the 6-OH group to the anomeric center to form a second ring structure.4 The commonly used synthesis route consists of a series of tedious, time consuming and expensive steps involving the protection of (reactive) hydroxyl groups, activation of the anomeric center in the saccharide, and subsequent removal of the protecting groups.5 Without the use of protecting hydroxyl groups, it is nearly impossible to convert glucose into a 1,6 anhydrosugar derivative without damaging the inner glycosidic bond.5 As a result of these complexities, pure levoglucosan is expensive to synthesize by conventional means, resulting in prices ranging from $10000–50000 per MT.6 This limits its use as a chemical building block for commercially important applications, including the manufacture of plastics, surfactants, explosives, propellants, resins, biodegradable polymers, antiviral agents, and other chiral bioactive natural products.7,8
An alternative pathway for its production exploits the fact that levoglucosan is the major product of the thermal deconstruction of cellulose,9 the most abundant polymer found in nature, occurring primarily as part of lignocellulosic biomass.1 Fast pyrolysis of inexpensive sources of lignocellulosic biomass such as waste wood or crop residues has the potential to produce large quantities of levoglucosan at commercially attractive prices. Two technical challenges, however, must be overcome to advance this opportunity. The first is the presence of alkali and alkaline earth metals (AAEM) in lignocellulosic biomass, which catalyze the fragmentation of pyranose and furanose rings in polysaccharides, shifting selectivity from anhydrosugars to light oxygenated compounds.10 Although washing AAEM from biomass prior to pyrolysis is unlikely to be cost-effective, a simple infusion of dilute mineral acid has been shown to passivate the catalytic activity of AAEM, allowing anhydrosugar yields from both herbaceous and woody biomass to approach those from pure polysaccharides.11
The second challenge is separation and purification of levoglucosan from other products of fast pyrolysis of biomass. Pyrolysis is premised on the deconstruction of biopolymers to molecules small enough to volatilize and escape the reactor in a stream of inert gas followed by condensation to liquids. Although sugars are generally non-volatile, anhydrosugars and xylose from thermal depolymerization of polysaccharides are sufficiently volatile at pyrolysis temperatures (400–600 °C) to vaporize. However, this is also true of light oxygenated compounds (furans, carboxylic acids, aldehydes and ketones) and phenolic compounds that are co-products of the thermal deconstruction of lignocellulosic biomass. Conventionally, these volatile products are condensed together from the pyrolysis stream as a viscous, acidic emulsion containing hundreds of organic compounds known as bio-oil.12 It is difficult to separate and purify levoglucosan from bio-oil13 due to its complex composition. Typical methods of bio-oil separation and purification include liquid chromatography, solvent extraction, centrifugation, and distillation leading to high cost and difficult scale up.14,15
To overcome problems arising from the condensation of pyrolysis vapors into a single liquid mixture, Pollard et al.16 developed a bio-oil recovery system that separates condensed liquids into fractions with distinct chemical and physical properties.15,16 This is accomplished by carefully controlling coolant temperatures for condensers and electrostatic precipitators used in the bio-oil recovery system. Anhydrosugars and sugars are recovered along with phenolic compounds as high boiling point “heavy ends”. The heavy ends of bio-oil contain very little moisture with most of the water carried to the low boiling point “light ends”. Rover et al.17 have demonstrated that a sugar-rich solution can be recovered from the heavy ends through liquid–liquid extraction using water as the solvent. Stanford et al.18 have successfully removed organic contaminants from this sugar solution using an adsorption resin, SP207, which opens the way to separating and purifying levoglucosan crystals from other pyrolytic sugars.
Techno-economic analysis is a useful tool to evaluate the economic benefits and the costs associated with industrial processes.19 Currently, there are no published studies on the economic feasibility of producing crystallized levoglucosan from fast pyrolysis although previous techno-economic studies on other products of fast pyrolysis using the fractionating condenser system offer a starting point for such an evaluation.20,21
The objective of this research is to evaluate the feasibility of separating, purifying, and crystallizing levoglucosan from bio-oil produced through pyrolysis of lignocellulosic biomass. The process was developed through bench-top experiments with bio-oil produced from a pilot-scale pyrolysis plant. This experimental data was the basis for a discounted cash flow rate of return analysis on the proposed pyrolysis pathway to levoglucosan production.
A sample of the red oak biomass was sent to Celignis Analytical (Limerick, Ireland) for analysis. Total sugars, glucan, xylan, mannan, arbinan, galactan, Klason lignin, acid soluble lignin, extractives, starch and ash were determined. Two replicates were performed for each analysis with averages and standard deviation determined.
GC/FID fitted with a PolyArc (Activated Research Company, Eden Prairie, MN) was used to quantify volatiles in the spent mother liquor after the cold solvent wash and rotary evaporation of the methanol. The GC/FID (Bruker Daltonics, Inc. Fremont, CA) was equipped with a flame ionization detector and fitted with a Zebron ZB-1701 (60 m × 0.25 mm × 0.25 μm film thickness) capillary column (Phenomenex, Torrance, CA). The operating system was a Galaxie Chromatography Data System (version 1.9.302.530) from Bruker Daltonics (Bruker Corporation, Fremont, CA). Helium (99.9995%) was the carrier gas with a constant flow rate of 1.0 mL min−1. Helium make-up was 25 mL min−1, hydrogen flow was at 30 mL with an air flow of 300 mL min−1. The GC oven was programmed to hold for 3 min at 35 °C, ramped at 5 °C min−1 to 280 °C, and held for 4 min for a total of 56.0 min. A sample volume of 1 μL was injected using a Varian CP 8400 (Bruker Daltonics, Inc., Fremont, CA) auto sampler with a split ratio of 1:20. The PolyArc, which enables quantification of chemical compounds without calibration standards, was used to analyze the spent mother liquor after the cold solvent wash and rotary evaporation of the methanol. The internal standards used with the PolyArc were toluene and phenanthrene at 5 wt% each in 95 wt% HPLC grade methanol. The solvent/internal standards solution was mixed with 20 wt% spent mother liquor, which was then analyzed by gas chromatography (GC) (7890B, Agilent Technologies, USA) mass spectroscopy (MS) (5977A, Agilent Technologies, USA) fitted with the same Zebron column and the Bruker 430 GC/FID to identify chemical constituents within the sample. Identification of compounds was accomplished using NIST MS Library Version 2.0. Three trials were performed with averages and standard deviation determined.
Acid content of the mother liquor (prior to crystallization) was determined by ion-exchange chromatography (IC). Acetic, formic, glycolytic, and propionic acids were quantified using a Dionex ICS3000 (Thermo Scientific®, Sunnyvale, CA) equipped with a conductivity detector and an Anion Micromembrane Suppressor AMMS-ICE300. The regenerate for the suppressor was 5 mM tetrabutylammonia hydroxide (TBAOH) at 4–5 mL min−1 flowrate. The eluent was 1.0 mM heptaflourobutyric acid with an IonPac® ICE-AS1 4 × 50 mm guard column and IonPac® ICE-AS1 4 × 250 mm analytical column. The flow rate was 0.120 mL min−1 at 19 °C. The software was Dionex Chromeleon (Thermo Scientific®, Sunnyvale, CA) version 6.8. Samples of mother liquor (prior to crystallization) were prepared using 6 mL deionized water and 1.5 mL methanol. All samples were filtered with a Whatman® 0.45 μL Glass Microfiber (Thermo Scientific® Hanover Park, IL) syringe filter prior to IC analysis. Samples were analyzed in duplicate with averages and standard deviations determined.24
Autothermal pyrolysis uses air at low equivalence ratio to support partial oxidation of pyrolysis products for the purpose of supplying the enthalpy for pyrolysis.25 There are four main advantages of autothermal pyrolysis: firstly, air-blown operation eliminates the need for inert gases to fluidize the bed and removes ancillary heat transfer equipment from the system, which simplify reactor design. Secondly, biomass feed rate is several times higher than for conventional pyrolysis, depending upon reactor size, resulting in significant process intensification. Lastly, capital costs are reduced about 25%. These advantages increase sugar productivity and reduce capital costs in the economic analysis.
Aspen Plus 10™ was employed to build the process model and obtain mass and energy balances for levoglucosan crystals production from red oak. It includes unit operations for biomass preparation including drying and grinding; autothermal pyrolysis; product fractionation and recovery; and sugar crystallization and purification. Both the mass and energy balance of each unit operation and operating conditions were employed to select and size process equipment in the analysis, while cost of equipment was estimated using Aspen Process Economic Analyzer (APEA). Additionally, project installation factors were obtained from Peters et al.27
Fig. 3 shows a block diagram of the process design with the key material and energy streams tabulated in Table 1. Red oak at 50 wt% moisture content and >10 mm average particle diameter is pretreated prior to pyrolysis, which includes grinding to particles of approximately 3 mm size, and infusion of 0.4 wt% sulfuric acid solution into the biomass at a 1:1 mass ratio to passivate inorganic materials in the biomass for the purpose of enhancing sugar production during pyrolysis.28 for the purpose of enhancing sugar production during pyrolysis. The biomass is then dried to a moisture content below 10 wt%. The biomass is dried with heat from burning tail gas (light ends vapor and non-condensable gases) from the pyrolysis process. The pretreated and dried biomass feeds into the pyrolysis section with 7 wt% moisture content and 3 mm particle diameter. To attain autothermal processing of biomass, the pyrolysis reactor is fluidized with air at an equivalence ratio of 0.1, temperature of 500 °C, and atmospheric pressure.25 Other than the autothermal reactor, most of the design of the pyrolysis plant is based on work by the National Renewable Energy Laboratory (NREL). The NREL design represents a 2000 metric tonne per day fluidized bed reactor. For this study, plant size was scaled down to 250 metric tonne per day of capacity while the autothermal reactor was assumed to process five times more feedstock than a similar-sized conventional pyrolysis reactor.25
ID | Name | Description | Temperature (°C) | Pressure (Pa) | Mass flow (tonne per day) |
---|---|---|---|---|---|
0 | BIOMASS | Biomass feedstock (50% moisture) | 25 | 101325 | 500 |
1 | CRYSTALS | Crystalized levoglucosan product | 25 | 101325 | 6.6 |
2 | H2SO4 | Sulfuric acid reactant | 25 | 101325 | 8.0 |
3 | NG | Natural gas for drying | 40 | 101325 | 0.0 |
4 | PHENOLS | Phenolic oil product | 25 | 101325 | 80.9 |
5 | PLCHAR1 | Biochar product | 25 | 101325 | 32.7 |
6 | PLCLGAS | Clean pyrolysis vapors without solids | 500 | 101325 | 239 |
7 | PLFEED3M | Biomass feedstocks (3 mm-diameter) sized | 101 | 101325 | 272 |
8 | PLNCG | Pyrolysis non-condensable gases | 18 | 101325 | 54.0 |
9 | PLRECYCL | Pyrolysis gas recycle stream | 200 | 101325 | 317 |
10 | PLSF12 | Heavy and light ends | 103 | 101325 | 155 |
11 | PLVAPORS | Pyrolysis vapors (with solids) | 500 | 101325 | 272 |
12 | SF3–5 | Pyrolysis tail gas | 120 | 101325 | 28.6 |
13 | SYRUP | Spent mother liquor product | 25 | 101325 | 39.8 |
Pyrolysis vapors exiting the reactor progress through two gas cyclones in series to remove biochar, which is sold as co-product. The cyclones collectively recover up to 99% of solids from the gas flow. Pyrolysis vapors enter the bio-oil recovery section, which fractionates and condenses the vapors into heavy ends and light ends. The heavy ends feed into the sugar recovery section that includes liquid–liquid extraction of sugars; resin removal of phenolic contaminants from the sugar solution; and crystallization and methanol rinsing. The final products from the heavy ends include levoglucosan crystals, fermentable syrup (spent mother liquor), and phenolic oil.
Liquid–liquid extraction contacts the heavy ends with water at a 1:1 ratio followed by separation into a water-soluble fraction (sugar-rich solution) and water-insoluble fraction (phenolic oil). The sugar-rich solution goes to a resin purification unit to remove contaminants followed by an evaporation/crystallization unit (modeled as a yield reactor) where crystals of mixed sugars are obtained. The design specification for this analysis is 2.75 wt% levoglucosan crystal yield from red oak, which is based on the experimental results described in this paper. Finally, 99% of the crystals are recovered as a pure stream in a separator unit. The remaining water-soluble sugars leave as spent mother liquor, which is sold as fermentable syrup.
The economic feasibility of this process is evaluated using a multi-year discounted cash flow rate of return (DCFROR) analysis. A financial spreadsheet that accounts for the biorefinery plant life of 10 years, 8% loan interest rate and a 10-year payback period and other financial assumptions was used to compute the minimum levoglucosan crystals selling price (MSP). The financial assumptions are tabulated in Table 2. All costs are reported in 2015$ basis.
Parameter | Assumptions |
---|---|
Equity | 40% |
Plant life | 10 years |
Construction period | 1 year |
Depreciation period | 7 years, 200 DDB |
Working capital | 5% of FCI |
Plant salvage value | 0 |
Revenue & cost during startup (% of normal) | Revenue: 50% |
Variable costs: 75% | |
Fixed costs: 100% | |
Interest rate for financing | 8% annually |
Internal rate of return | 10% |
The annual fixed operating cost of the biorefinery consists of cost of labor, overhead, maintenance and insurance. Overhead costs are 90% of the cost of labor, cost for maintenance is 3% of Inside Battery Limits (ISBL) and insurance is 0.7% of the Fixed Capital Investment. Labor cost is based on a modified analysis of a previous NREL study29 and is based on the number of employees and their salary rates. The breakdown of the labor cost is tabulated in Table 3.
Position | Salary ($ per year) | Number of employees |
---|---|---|
Maintenance supervisor | 54900 | 1 |
Maintenance technician | 38500 | 8 |
Lab manager | 53900 | 1 |
Lab technician | 38500 | 1 |
Shift supervisor | 46200 | 5 |
Shift operators | 38500 | 5 |
Yard employees | 27000 | 2 |
Variable operating cost assumptions are listed in Table 4. These include feedstock cost, process water, utility costs, and by-product credits. Previous studies have reported that feedstock cost at the plant gate vary from $30–$60 per MT.30,31 In this study, feedstock cost is assumed to be $41 per MT, which is comparable and within the range of previous studies. The cost of solids handling is assumed to be $8 per MT as suggested in a recent NREL study.32 Additionally, the fermentable syrup credit of $406 per MT assumed in this study is based on a previous economic analysis of cellulosic ethanol from lignocellulosic biomass and adjusted for inflation.34 Both phenolic oils and biochar are valued at $50 per MT, which assumes no valorization beyond their use as boiler fuel. Based on previous studies, the cost of electricity is reported to vary from $0.06–$0.23 kW−1 h−1.33,34 We assumed the cost of electricity to be 6.7′ kW−1 h−1. Lastly, the methanol used to recover levoglucosan crystals has a market cost ranging between $310 and $850 per MT.35 This study assumes a cost of $500 per MT. The methanol recovery rate is assumed to be 99%.36 We estimate the methanol recovery cost to be $7 per MT of methanol based on work by Shahandeh et al.37 This cost includes the annualized capital and operating costs of the distillation process.
Parameter | Flows (daily) | Price |
---|---|---|
Red oak (dry) | 250 MT | $41 per MT |
Solids handling | 50 MT | $8 per MT |
Process water | 95 MT | $0.2 per MT |
Methanol | 0.285 MT | $500 per MT |
Electricity | 18000 MJ (4990 kWh) | $0.0186 per MJ ($0.067 kW−1 h−1) |
Co-products | ||
Syrup (dry basis) | 39.8 MT | −$406 per MT |
Phenolic oil | 80.9 MT | −$50 per MT |
Biochar (ash-free) | 32.7 MT | −$50 per MT |
Red oak lignocellulosic component | Dry matter (%) |
---|---|
Total sugars | 58.6 ± 0.43 |
Glucan | 40.0 ± 0.22 |
Xylan | 15.7 ± 0.23 |
Mannan | 1.30 ± 0.34 |
Arabinan | 0.34 ± 0.01 |
Galactan | 0.92 ± 0.01 |
Klason lignin | 20.3 ± 0.33 |
Acid soluble lignin | 2.95 ± 0.03 |
Extractives | 6.85 ± 0.07 |
Ash | 0.40 ± 0.07 |
Total | 89.1 |
Water extraction of the heavy ends produced a sugar-rich, water-soluble fraction and a phenolic-rich, water insoluble fraction. The yields of these products on a moisture-free basis and their carbon contents are given in Table 6. The yield of water-soluble fraction from the heavy ends was 48.1 wt% and contained 48.5 wt% carbon. The yield of sugar from water extraction of heavy ends was 10.9 wt% and consisted mostly of levoglucosan (7.47 wt%) with smaller amounts of cellobiosan, xylose, galactose, and mannose. The yield of the water-insoluble fraction was 51.9 wt% and contained 72.6 wt% carbon.
Yield (wt%) | |
---|---|
Water-soluble fraction | 48.1 |
Levoglucosan | 7.47 ± 0.033 |
Cellobiosan | 1.25 ± 0.327 |
Xylose | 1.34 ± 0.053 |
Galactose | 0.725 ± 0.011 |
Mannose | 0.105 ± 0.001 |
Total sugar | 10.89 ± 0.123 |
Water-insoluble fraction | 51.9 |
Carbon content of water extracted fractions of heavy ends | Carbon content (wt%) |
---|---|
Water-soluble fraction | 48.5 ± 0.313 |
Water-insoluble fraction | 72.6 ± 0.158 |
The compositions of the mother liquor before and after recovery of crystalized levoglucosan are shown in Table 7. Total sugar content of the mother liquor prior to crystallization was 81.2 wt% db. Levoglucosan was the most abundant sugar at 44.7 wt% db of the mother liquor before crystallization followed by mannose and cellobiosan at 12.8 and 11.7 wt% db, respectively. Xylose and galactose were present at 9.31 wt% db and 2.72 wt% db, respectively.
Constituent | Mother liquor before crystallization | Mother liquor after crystallization |
---|---|---|
wt% (db) | wt% (db) | |
Levoglucosan | 44.7 ± 0.044 | 33.7 ± 0.078 |
Mannose | 12.8 ± 0.064 | 16.3 ± 0.103 |
Cellobiosan | 11.7 ± 0.060 | 16.5 ± 0.060 |
Xylose | 9.31 ± 0.019 | 11.8 ± 0.064 |
Galactose | 2.72 ± 0.004 | 2.99 ± 0.043 |
Total sugar content | 81.2 ± 0.038 | 81.3 ± 0.070 |
Other compounds (by difference) | 18.8 | 19.2 ± 0.100 |
Total | 100 | 100 |
After removal of crystals, levoglucosan concentration in the spent mother liquor was 33.7 wt% db. Thus, only 24.8% of the levoglucosan in the mother liquor was recovered by the one-stage crystallization process employed in this laboratory study. Multi-stage crystallization, as regularly practiced in industry, is expected to significantly increase the recovery of crystallized levoglucosan although it is difficult to quantify. The purity of these levoglucosan crystals was 102.5% ± 3.109% at the 99% confidence level. Purity likely could be increased to over 99.99% by utilizing resin columns in series versus one pass through the resin employed in this study.
Cellobiosan, xylose, galactose, and mannose increased in the spent mother liquor, as expected, but slightly more than anticipated. This is thought to be attributed to the loss of volatiles during the repeated handling of the sample throughout crystal removal and rotary evaporation of the solvent.
Volatile compounds other than anhydrosugars in the spent mother liquor were quantified by GC/PolyArc/FID and ranged from 4.45–4.60 wt% db. Carboxylic acid content was 1.71 wt% db and consisted of glycolic and formic acids. These relatively low concentrations is attributed to the unique bio-oil collection system, which collected most of the light oxygenated compounds (carboxylic acids, ketones, aldehydes, alcohols) in condensers downstream of the point where heavy ends were collected.
As detailed in Table 1 of the Methodologies section, the plant yields 6.6 MTPD of levoglucosan crystals. Co-products include 80.9 MTPD of phenolic oil, 39.8 MTPD of fermentable syrup, and 32.7 MTPD of biochar, which provide annual operating credits of $1.33 MM, $5.29 MM, and $0.538 MM. Annual net operating cost for the plant is $2.88 MM. The fixed operating costs, which include cost for insurance, maintenance and overhead, is $2.44 MM; labor cost is $0.93 MM; and variable operating costs is $3.66 MM on an annual basis.
The contributions of various operating costs and credits to the MSP are summarized in Fig. 5. Gross operating cost is $4500 per MT of levoglucosan crystals. Feedstock dominates operating costs, representing 33% of the gross operating cost. Fermentable syrup, phenolic oil and biochar provide credits equal to 70% of the gross operating costs. These credits reduce the minimum selling price (MSP) of levoglucosan from $4500 per MT to $1333 per MT. This price is much lower than the current market price for levoglucosan crystals synthesized from glucose, which ranges between $10000–50000 per MT.6
Fig. 5 Operating costs ($ per MT of levoglucosan) in the production of crystalline levoglucosan from lignocellulosic biomass. |
Sensitivity analysis was also conducted to determine the most significant operating parameters on the MSP. The results of the analysis are illustrated in Fig. 6. Operating hours, followed by fermentable syrup yield and fixed capital are the three most significant parameters affecting the MSP, while phenolic oil yield, phenolic oil credit and biochar yield affect the MSP of anhydrosugar crystals the least. Increasing fermentable syrup yield or operating cost by 20% can reduce MSP by 37%, while a 20% decrease in fixed capital from $18 MM to $14 MM can reduce MSP by 37%. Improving methanol recovery by 20% would reduce MSP by 27%. On the other hand, a 20% increase in yields of either phenolic oil or biochar will only reduce the MSP by 8% and 4%, respectively.
This journal is © The Royal Society of Chemistry 2019 |