Eucalyptus for the Productions of Cellulose Nanomaterials and - - PowerPoint PPT Presentation

Eucalyptus for the Productions of Cellulose Nanomaterials and Sugar/Biofuel Junyong (J.Y.) Zhu

US Forest Service, Forest Products Laboratory Madison, WI, USA

Mechanical Fibrillation –

Cellulose Nanofibrils (CNF)

Energy cost Less uniform network

5000 nm 100 nm 100 nm

Wang et al. (2012), Cellulose 19(5): 1631-1643

Enzymatic Fractionation –

Cellulose Nanofibrils (CNF) with Sugar

Zhu et al. (2011), Green Chemistry 13(5):1339-1344

100 Nano-fibrillated Cellulose (NFC)

Recalcitrant cellulose (RC) Bleached pulp

60 60 Alkanes

Sugars

41

Enzymatic Fractionation –

Cellulose Nanofibrils (CNF) with Sugar

Zhu et al. (2011), Green Chemistry 13(5):1339-1344

Undeinked Mixed Office Paper

Cellulose Nanofibrils (CNF)

30 60 90 120 150 180 10 20 30 40 50

2.5 5.0 7.5 10.0 12.5 (a) Specific modulus (MNxm/kg)

Grinding time (min)

Specific tensile (kNxm/kg)

Specific tensile Specific modulus

Wang and Zhu (2015), TAPPI J. 14(3):167- 74

30 60 90 120 150 180 210 3 6 9 12 15

MOP y = 0.068x, r

2 = 1.00

BEP y = 0.078x, r

2 = 1.00

Energy (kWh/kg) Time (min)

< 50 kg CNC 100 kg Cellulose

Year Author Acid (wt%) T (°C) Yield (%) 1947 Nickerson & Harble 22 boiling 30-40 1953 Mukherjee & Woods 66 20 low 1998 Dong et al. 64 26-65 <50% 2006 Bondeson et al. 44-65% 40-80 <50% 2010 Hamad & Hu 16-64% 45-85 <40%

CNC Production Kinetics

1 2

d = dt

NC Cel NC

C k C k C 

5 6

d = 1.136 dt

n

X k X k X   

2 3 Cel 4

d = 1.111 1.111 dt

lu NC lu

G k C k C k G       1 3

d

• =( +

)[ (1 )] dt

Cel

Cel Cel

C k k C C   

Wang et al, Ind Eng Chem Res, 53(27):11007-11014, 2014

Centrifuge

Supernatant Cellulosic Solid Residues

(CSR)

Cellulose Nanofibrils I

(CNF-CSR)

Cellulose Nanocrystals

(CNC)

Bleached pulp Acid and sugar stream

Centrifuge

Integrated Production of CNC with CNF – Eucalyptus Pulp

L21 = 228 S = 6.0 CrI = 85.5 L21 = 131 S = 6.8 CrI = 92.3 L21 = 174 S = 7.6 CrI = 87.1

48 52 56 60 64 68 20 40 60 80

Maximal CNC yield

exp

(%)

Sulfuric acid concentration (wt%)

TEM Images of CNF from CSR

CSR

Wang et al., Cellulose, 19(6): 2033-2047, 2012

CNF-CSR Film

Wang et al, ACS Applied Materials and Interfaces, 5(7):2527, 2013

TEM images of CNC

Wang et al., Cellulose, 19(6): 2033-2047, 2012

A Roadside Pile of Douglas-fir Forest Residue

Leu et al, Biomass Bioenergy, 2013, 59:393

SPORL: Sulfite Pretreatment to Overcome the Recalcitrance of Lignocelluloses

Partial delignification without

excessive lignin condensation Lignin sulfonation Hemicellulose degradation Cellulose depolymerization

Sulfite with a base to adjust pH ~ 2

SO2 + Hydroxide

SO2 Steam

2 8 6 4

130 140 170 160 150 180

SPORL

120

pH T(ºC)

Ground Douglas-fir Residue Fractions

I<1/8 3/16<III/1/4 3/8<V<1/2 7/8<IX<1 5/8<VII<3/4

Peterson-Pacific Horizontal Grinder

Sample Bark Klason Lignin Glucan Xylan Mannan G+X+M As harvested 5.9 30.5 38.4 4.4 7.5 50.3 FS-10

screened out fraction I

3.4 29.3 41.0 5.7 9.7 56.4

FS – 10 Chemical Compositions

Scale-up Pretreatment

𝑫𝑰𝑮 = 𝒇 𝜷− 𝑭

𝑺𝑼+ 𝜸 𝑫𝑩 + 𝜹 𝑫𝑪

𝑫𝑩 + 𝑫𝑪 𝒖 𝒖𝑼𝟐𝟓𝟔 = 𝒇𝒚𝒒 −

𝑭 𝑺 ( 𝟐 𝑼𝟐𝟓𝟔 − 𝟐 𝑼𝟐𝟗𝟏) 𝒖𝑼𝟐𝟗𝟏

Maintain same pretreatment severity (CHF): Reaction time at low T can be determined

R = 8.314 J/mole/K, E = 100,000 J/mole

Zhang et al., Process Biochemistry, 49:466, 2014

Optimal Conditions and Inhibitor Formation

Zhang et al., Process Biochemistry, 49:466, 2014

T (°C) Total SO2 (g/L) Time (min) Inhibitor 180 22 26 1.000 173 22 39 0.776 170 22 47 0.694 165 22 75 0.575 155 22 123 0.389 145 22 240 0.258 140 60 50 0.030

SPORL Process Flow - Forest Residue to Ethanol

Forest residue No detoxification No washing Initial pH ~ 2.0 Bisulfite/wood = 6.7%

Steam

Sulfite Solution Size Reduction To wet scrubber

Ethanol

Distillation Separation Purification

Lignosulfonate

Lignin residue Waste water Neutralization Whole slurry Pretreatment 1000 kg FS-10 SO2 = 66 kg Ca(OH)2 = 24 kg Furan = 1.0 g/L

Zhu et al., Bioresour. Technol, 179:390, 2015

FPL Pilot Scale Facility – 390L

Zhu et al., Bioresour. Technol, 179:390, 2015

Overall Mass Balance – FS10

284 L/ton wood @ 42 g/L CTec3 Loading: 35 mL/kg untreated FS-10

1000

Glucan: 410 Mannan: 97 Xylan: 57 Arabinan: 10 Galactan: 20 Lignin: 293

79 (Remaining Liquor)

Glucan: 7 Lignin: 36 Mannan: 16 HMF: 0.2 Xylan: 6 Furfural: 0.5 Arabinan: 1 Acetic acid: 8 Galactan: 4

892 (Wet solids OD weight)

Glucan: 391 Lignin: 222 Mannan: 46 HMF: 0.7 Xylan: 21 Furfural: 2 Arabinan: 3 Acetic acid: 7 Galactan: 11

Ethanol: 224 @ 41.9 g/L

Lignosulfonate: 130 Waste Water Lignin residue

90

Ca(OH)2: 24 SO2: 66

All units: g or kg unless indicated

Zhu et al., Bioresour. Technol, 179:390, 2015

Lignosulfonate as Dispersant for Coal water slurry (CWS)

2 4 8 16 32 64 128 256 1 2 3 4 5 6

Shear rate (1/s) Apparent viscosity of CWS (Pa.s)

Dispersant Dosage (wt%) 0.75 Na-LS Ca-LS FDN

Summary

Total peer reviewed publications ~ 90:

CNC and CNF productions Pretreatment; Scale-up kinetics Fundamentals cellulase interaction with lignocelluloses

Lab scale, pilot scale, pre-commercial scale and biojet for commercial flight

SPORL is robust and efficient Co-products from lignin Enzyme lignin-interactions

Invited as an International Expert by CTBE – at

2014 2nd Generation Ethanol Workshop

Thank you for Attention

Lignosulfonate

Zhu et al., Bioresource Technology, 179:390-397, 2015

Ultrafiltration experiment Sample LS-Ca (%) Sugar (%) Mass (%) Lignin Purity (%) Original 100 100 100 44.5 > 200 kDa 3.9 n/a 2.4 89.1 4-200 kDaa 69.6 7.6 43.2 86.8 < 4 kDa 24.9 84.3 41.5 19.3 GPC (MALS) analysis Sample Mwb Mnc Mw/Mnd 4-200 kDa 23430 12910 1.8 D748 24660 14190 1.7 GPC (UV) analysis 4-200 kDa 2704 1092 2.5 D-748 13113 3293 4.0

Undeinked Mixed Office Paper

Cellulose Nanofibrils (CNF)

Wang and Zhu (2015), TAPPI J. 14(3):167- 74

30 60 90 120 150 180 10 20 30 40 50

2.5 5.0 7.5 10.0 12.5 (a) Specific modulus (MNxm/kg)

Grinding time (min)

Specific tensile (kNxm/kg)

Specific tensile Specific modulus

Model Predictions

48 50 52 54 56 58 60 62 64 66 20 40 60 80 100 20 40 60 80 100

YCNCmax (%) YCSR (%) Acid concentration (wt%)

YCSR YCNCmax T (

• C)

40 50 Measured 60 70 80

Wang et al, Ind Eng Chem Res, 53(27):11007-11014, 2014

Length Weighted Crystal Length

54 56 58 60 62 64 66 100 120 140 160 180 200 220 240 260 280 300

Data y = -15.3x+1130, r

2 = 0.947

L21 (nm) Acid (wt%)

Take Home Messages

We developed a kinetic model to provide good predictions

• f CNC yield, polysaccharide hydrolysis, and sugar

production. CNC yield is dictated by two rate controlling processes: (1) under depolymerization of cellulose (Acid < 58 wt%); (2) sugar degradation (Acid  58 wt%). An acid =58% is the critical concentration for high CNC yield. For a given acid concentration, there is a maximal achievable CNC yield that is almost independent of temperature especially at acid concentration  58 wt%. The required time varies with T CNC morphology, crystal length, surface charge vary with acid concentration. However, CNC crystallinity is not affected.

Sugar Degradation Reaction

𝒆𝑬 𝒆𝒖 = 𝒍𝒆(𝟐 − 𝒀𝑺) 𝒍𝒆 = 𝒇(𝜷𝒆− 𝑭𝒆

𝑺𝑼)

𝑬 = 𝒍𝒆 ∙ 𝒖 𝟐 − 𝟐 − 𝜾 𝑫𝑰𝑮 𝟐 − 𝒇−𝑫𝑰𝑮 − 𝜾 𝒈 ∙ 𝑫𝑰𝑮 (𝟐 − 𝒇−𝒈∙𝑫𝑰𝑮) 𝒀𝑺 = 𝟐 − 𝜾 𝒇−𝑫𝑰𝑮 + 𝜾𝒇−𝒈 𝑫𝑰𝑮

Zhang et al., Process Biochemistry, 49:466, 2014

Substrate Enzymatic Digestibility (SED)

10 20 30 40 50 60 70 80 20 40 60 80 100

Solids (%) 10 15

SED (%) Time (h)

CTec3 Loading: 15 FPU/g glucan

Ethanol Production

Solids Loading: 16.7 wt%

2 4 8 16 32 64 10 20 30 40 50 60 10 20 30 40 50 60

CTec3 (mL/kg FS-10)

35 26

Glucose Ethanol

Ethanol (g/L) Glucose (g/L)

Time (h)

Eliminate Washing by Reducing

Nonproductive Cellulase Binding to Lignin Lan et al. (2013), BioEnergy Research, 6:476-485 Lou et al. (2014), Cellulose, 21:1351 Lou et al. (2013), ChemSumChem, 6:919-927 Zhou et al. (2013), Ind. Eng. Chem. Res, 52:8464 Wang et al. (2013), Biotechnol Biofuels, 6:156 Wang et al.(2013), Biotechnol Biofuels, 6:9

Lignosulfonate enhance enzymatic hydrolysis

Surfactant to block bound lignin on solid

Eliminate Washing

Lignosulfonate as a Surfactant

Wang et al., Biotechnol Biofuels, 6:9, 2013; 6:156

Process Scale-up: Key Issues

Facility capability

Optimal condition in lab scale: T, t, Chemical dosage Pilot scale facility limitation T < Toptimal

Inhibitors in high solids fermentation

Hemicellulose Dissolution – Lodgepole Pine

Zhou et al., Ind Eng Chem Res, 52:8464. 2013

20 40 60 80 100 120 140 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7

XR

CHF / Min x Mole L

• 1

𝒀𝑺 = 𝟐 − 𝜾 𝒇−𝑫𝑰𝑮 + 𝜾𝒇−𝒈 𝑫𝑰𝑮

Summary

SPORL pretreatment is effective to remove the strong recalcitrance of softwood forest residue. Excellent sugar and ethanol yields at high titer were achieved Co-products from lignin or sugar are the key to make biorefinery economical while still produce a significant amount of biofuel

Mass Distribution and Selectivity

Cheng et al., Biotechnology for Biofuels 8:22, 2015

0-3.2 3.2-4.8 4.8-6.4 6.4-9.5 9.5-12.7 12.7-15.9 15.9-19.1 19.1-22.2 22.2-25.4 25.4-28.6 28.6-31.8 31.8+

4 8 12 16 20 24

Bark mass distribution (%)

0-3.2 3.2-4.8 4.8-6.4 6.4-9.5 9.5-12.7 12.7-15.9 15.9-19.1 19.1-22.2 22.2-25.4 25.4-28.6 28.6-31.8 31.8+

2 4 6 8 10 12 14 16 18

• ven dry mass

Wet mass

Mass distribution (%)

Gaosheng Wang: Tianjin University Science Technol. Wenyuan Zhu: Nanjing Forestry University Hao Liu: South China Univ. Technology Shen Tian: Capital Normal University Xiaolin Lou: Fujian Agr. and Forestry University Zhaojiang Wang: Shangdong Polytechnic Univ. Qianqian Wang: Jiangsu University Xinshu Zhuang: Guangzhou Energy Conv. Inst, CAS Tianqing Lan: Kuming Polytechnique University Hongming Luo: South China Univ. Technology Chao Zhang: Dalian Institute of Chemical Physics Haifeng Zhou: Shangdong University of Science and Technology Shaoyuan Leu: Hongkong Polytechnic University Chuanshuan Hu: South China University of Agriculture Jinlan Cheng: Nanjing Forestry University Wangxia Wang: Nanjing Forestry University Jingzhi Zhang: Beijing University of Chemical Technology Subhash Chandra: Yogi Vemana University, Kadapa, India Liheng Chen: South China University of Technology Xuebing Zhao, Tsinghua University Feng Gu, Nanjing Forestry University Xunjun Pan: University of Wisconsin Bruce Dien: USDA-ARS Rollie Gleisner and Bill Gellies, USFS-FPL Weyerhaeuser, GEVO

Contributors and Collaborators:

Cellulose Nanomaterial Research

Cellulose Nanofibrils (CNF) Zhu et al. (2011), Green Chemistry 13(5):1339-1344 Wang et al. (2015), Cellulose 22:351-361 Wang et al. (2012), Cellulose 19(5): 1631-1643 Hu et al., (2015), Holzforschung DOI: 10.1515/hf-2014-0219 Wang and Zhu (2015), TAPPI J. 14(3):167- 74 Cellulose Nanocrystals (CNC) Wang et al. (2012), Cellulose 19(6): 2033-2047 Wang et al. (2013), ACS Appl. Mater. Interfaces 5:2527-2534 Wang et al. (2104), Ind Eng Chem Res. 53: 11007-11014 Wang et al. (2015), Cellulose 22(3): 1753-1762