Feedstock Evaluation and Development of Rapid Analytical Methods

Daniel Hayes DIBANET Networking Session Thessalonki 31/10/12

WP2

Task 2.1 Appropriate Feedstock Selection and Analysis

Identify all possible feedstocks for biorefining in Europe and Latin America. Select those most suitable for the DIBANET process. Analyse these feedstocks with wet-chemical methods for their lignocellulosic constituents. UL is responsible for the evaluation of European feedstocks, CTC for sugarcane residues, UNICAMP for other LA biomass.

Task 2.1
Europe (Ireland) Miscanthus Pretreated Miscanthus Cereal straws Waste paper Compost Latin America (Brazil) Sugarcane bagasse Sugarcane trash Coffee husks Banana residues Coconut residues

Short rotation coppices

Animal manures Reed canary grass

Acai residues
Rice husks Sawdust

Green wastes

Soya peel Bamboo

Grass

Feedstock Chemical Evaluation

Important chemical characteristics:

C6 Sugars: Glucose, Galactose, Mannose C5 Sugars: Arabinose, Xylose Lignin content (acid soluble and insoluble) Extractives Ash. Elemental analysis.

Task 2.1 Data Obtained (Wet Chemistry)

Partner UL UL UL UL UL CTC CTC Feedstock Miscanthus Pret. Misc. Straws Papers Others Bagasse Trash Lignin 221 47 33 14 41 80 37 Extractives 257 47 44 19 53 68 37 Ash 243 47 46 13 46 73 37 Sugars 211 47 26 14 24 60 37 Elemental 61 0 15 12 25 0 0

UNIC.
UNIC. UNIC. UNIC.

Coffee husks
Banana Coconut Other

42
81 30 7

102
104 30 7 TOTALS 420 105

102
104 30 7 395 110

42
10 30 7 322 32

0
0 0 0 113 0

UL 356 CTC 96

UNIC. 160
TOTAL 612

243
768

243
748

89
443

0
113

Initial Evaluation (UL) [1]

DIBANET focuses on Miscanthus and waste samples as target feedstocks. Generally waste cardboard/paper samples have the highest cellulose/carb contents and so offer the potential for high LvA yields, this however implies also that the residue for subsequent gasification will be low. Animal Slurries: There is a significant variation between the composition of animal slurries (pig, cattle) but these can offer reasonably attractive carbohydrate contents (up to 50% of dry mass on an extractives free basis). But moisture content is extremely high, hence these feedstocks could probably only act as fillers in a feedstock mix, but there would still be transport problems.

Initial Evaluation (UL) [2]

Spent Mushroom Compost (SMC) is a significant waste resource in Ireland secondary data suggest it has potential for biorefining purposes but our data suggest its carbohydrate content is too low (max 20%, compared to the pre-compost mix of ~50% carbohydrate). Forestry residues (wood and leaves) are suitable for utilisation in the DIBANET process but this will require a significant investment in the infrastructure required for their collection and transport. Sawmill residues are also of value for biorefining but there are other current end-uses for these resources.

Initial Evaluation (UL) [3]

Municipal wastes are predominately composed of waste papers, food waste, garden waste, and waste woods Waste food does not contain sufficient lignocellulosic sugars to warrant its utilisation in the DIBANET process. Garden/green waste contains various types of materials such as grasses, leaves, twigs, and branches. Only the more woody materials have lignocellulosic compositions suitable for the DIBANET process. Garden/green waste taken as a composite (i.e. a sample from a compost pile) does not have a favourable proportion of wood to foliage. Hence, the sourcing of green waste for biorefineries needs to be specifically tailored to highcarbohydrate materials. This may necessitate for separate collection schemes or for processes to sorting the woody material from the total green-waste resource.

Conclusion (UL)
Focus on Miscanthus as a DIBANET feedstock. Also investigate straws and waste papers.

Initial Evaluation (UNICAMP)

A total of 10 different feedstocks were investigated and analysed (wet-chemical methods):

Soy peel, bamboo, banana residues, rice husks, sawdust, acai seeds, elephant grass, coconut residues, coffee residues.

CHEMICAL COMPOSITION OF ALL BIOMASSES ANALYSED BY UNICAMP (%)

BIOMASS SOY BEAN RICE husks SADWUST BAMBOO GRASS COCONUT AA seed BANANA Stalk

TOTAL TOTAL ARABINOSE GALACTOSE RHAMNO GLUCOSE XYLOSE MANOSE SUGARS LIGNIN EXTRACTIVE ASH 4.64 1.70 0.26 0.81 3.56 1.79 0.69 2.89 3.13 0.83 1.23 0.32 1.22 0.71 1.43 1.18 0.92 0.13 0.25 0.06 0.10 0.30 0.17 0.27 35.05 36.17 38.79 44.65 27.52 32.41 8.66 26.83 9.85 16.65 9.72 14.78 16.12 14.37 3.18 6.94 4.31 0.49 0.35 0.07 0.24 0.35 53.59 1.46 57.90 55.98 50.60 61.57 48.84 49.94 67.71 39.56 7.58 23.90 32.87 17.64 15.61 35.87 17.26 10.68 6.81 2.32 8.12 12.62 11.54 1.41 9.5 22.85 4.14 12.5 0.63 2.81 12.66 2.63 0.46 10.33

TOTAL COMP. 77.00 95 92 95 89 90 95 84

BANANA Stem
COFFEE husks

2.37
1.62

0.72
1.54

0.16
0.51

36.32
35.33

5.36
21.89

0.61
1.68

45.53
62.55

8.38
24.46

25.15
4.21

10.30
4.00

90
95

11

Conclusion (UNICAMP)
Three feedstocks were selected for more detailed analysis and evaluation (considering levels of supply, environmental factors, price, and composition)

Banana residues. Coffee Residues. Coconut Residues.

Conclusion (Early Evaluation)

There are a number of viable feedstocks for utilisation in DIBANET. However, secondary analytical data relevant to our needs are severely lacking. There is a clear need for primary wet-chemical analysis in DIBANET. This will also be of value to others in the biorefining industry.

Task 2.1 Detailed Evaluation

Focused on obtaining primary analytical data in the laboratories of UL, CTC, UNICAMP. Analytical methodologies (written at UL) were kept consistent for all partners. Strict quality thresholds placed upon results.

Example: DIBANET WP2 Method

Example: DIBANET WP2 Datasheet

D2.2 - Database
A database containing compositional data of samples analysed by DIBANET partners can be downloaded from the DIABNET website. It contains the results from the wetchemical and/or spectroscopic analysis of 1281 samples from Europe and Latin America.

D2.2 Report: Miscanthus (1)

Miscanthus is a productive energy crop that does not require significant time or expense for maintenance after plantation. It can be productive for up to 20 years without the need for replantation. The lignocellulosic composition of the crop once at full production is highly attractive for use in biorefining technologies. The stem fractions of the plant, when processed in biorefining technologies, will provide higher chemical/biofuel yields than the leaf fractions. This is due to their higher total sugars contents and increased heating values. The lower acid soluble lignin, protein, and extractives contents in the stem sections are also likely to present fewer complications in many conversion processes (e.g. acid and enzymatic hydrolysis).

D2.2 Report: Miscanthus (2)

The total sugars content of the crop in its first year of production is significantly less than in subsequent years. The total biomass yield of the crop is also less in this first year. Given this situation, the commercial harvest of the first year growth of Miscanthus and the subsequent transport of this crop to the biorefinery is not economical and is not advised. Instead, the crop should be cropped after the first year of growth with the biomass either left on the land for soil conditioning or used for other local uses.

D2.2 Report: Miscanthus (3)

The harvest window for Miscanthus is between October and April. Between October and early December a relatively small amount of standing biomass is lost as leaf fall. This period is termed the Early Harvest. Between mid-December and the end of February there is a rapid loss of leaves from the plant. By March the only remaining leaf materials tend to be the sheaths. These are lost from the plant at a much slower rate than the leaf blades. Hence, the loss of standing biomass is much less after March. This period is termed the Late Harvest.

D2.2 Report: Miscanthus (4)

The best time for harvesting Miscanthus will be dependent on how the crop will be processed. The dry biomass yield associated with an Early Harvest can be approximately 30% more than that associated with a Late Harvest. If the maximal biomass yield is the primary desire the crop should be harvested in the Early period. The crop will have a significant amount of moisture (approximately 50% on a wet basis) at this time. An Early harvest will not provide a feedstock suitable for most thermochemical biorefining technologies (e.g. pyrolysis, gasification) since these will require lower moisture contents.

D2.2 Report: Miscanthus (5)

An Early harvest is feasible for most hydrolysis biorefining technologies, e.g. DIBANET, providing they do not use pretreatment method that require dry feedstock (e.g. ionic liquids). An Early harvest will remove leaves that would, in a Late harvest, fall to the field. The amount of carbon and nitrogen provided to the soil would therefore be reduced. The removal of leaf material from the land can be addressed with increased fertiliser input.

D2.2 Report: Miscanthus (6)

There are significant changes in lignocellulosic composition of the standing plant over the harvest window. The most important of these are an increase in the glucan and Klason lignin content. On a dry mass per-tonne basis the biomass collected during the Late harvest period is of more value for biorefining processes (hydrolysis and thermochemical) than the biomass collected in the Early harvested period. If a feedstock payment scheme at a biorefinery, using the hydrolysis platform, is based on total sugars content then the Late harvest crop would be worth approximately 10% more per tonne than the Early harvest crop.

Loss of Leaves over Harvest Window

Levulinic Acid Yield per Ha

Database

Sugarcane Residues

Production in Brazil

Sugarcane in Brazil

D2.2: Sugarcane Residues (Bagasse)

D2.2: Sugarcane Residues (Bagasse)

D2.2: Sugarcane Residues

Both sugarcane bagasse and sugarcane trash have sufficient amounts of lignocellulosic sugars to justify their processing in hydrolysis biorefining technologies. The compositions of the bagasse samples that were analysed tended to be more varied than those of the trash samples analysed. Ash, in particular, can vary significantly in bagasse samples. There also seems to be a tendency for the ash contents of bagasse to be higher in some mills. Hence, it is recommended that careful determinations and observations, over a period of time, of the ash contents, associated with the harvesting/milling process of any mill that is being considered for a biorefining scheme, be carried out.

D2.2: Sugarcane Residues (2)

Using the average lignocellulosic compositions of sugarcane bagasse and sugarcane trash determined in DIBANET analyses along with the estimated arisings (165m dry tonnes of bagasse and 128m dry tonnes of straw), the total potential yields possible from processing these feedstocks in representative biorefining technologies were calculated.

102 SAMPLES OF COFFEE - INCLUDED:

Leaves

Husks

Different kinds: - etiopia - rabica -robusta - mundo novo

Grain

Ground coffee
39

SOME HISTOGRAMS FOR COFFEE SAMPLES

40

102 SAMPLES OF BANANA - INCLUDED:

Leaves

Steam

Rhizome

Stalk

Husks

41

SOME HISTOGRAMS FOR BANANA SAMPLES

42

30 SAMPLES OF COCONUT - INCLUDED:

Husks

Fibers

43

SOME HISTOGRAMS FOR COCONUT SAMPLES

44

SOME HISTOGRAMS FOR COCONUT SAMPLES

45

Task 2.2

Development of Lab-Based NIR Calibration Equations Equations will be targeted for at least 5 feedstocks, each, from Europe and Latin America. Europe Latin America UL CTC UNICAMP 1. Miscanthus 1. Bagasse 2. Pret. Misc. 2. Trash 3. Straws 3. Coffee rds. 4. Papers. 4. Banana rds. 5. Global 5. Coconut rds.

Time for Conventional Analysis

Sample as Collected Wet Chopped Sample Dry Sample

Chop sample ~ 10 mins

Air Drying ~ 3+ days

12 10 8 6

Extractives-free sample

Milling + sieving ~ 1 hour

Hydrolysis and Extractives 0 hydrolysate Removal 0 2 4 6 8 10 12 14 16 analysis ~ 3 days Completed ~ 3 days Lignocellulosic
4 2

Analysis

Sample of Appropriate Particle

Dry 47

Sample Preparation

Scans of One Sample

WU Spectra

Important Regression Statistics

R2 for the validation set. RMSEP. RER (range error ratio) = Range/SEP. RER > 15 model is good for quantification. RER 10-15, screening control. RER 5-10, rough sample screening.

UL Misc. Glucose Models

Glucose DS and WU Models

50

50

Predicted GLU_SRS (WU Model) (%)

Predicted GLU_SRS (DT Model) (%)

45

45

40

40

35

35

30

30

25 25 30 35 40 45 50 Reference GLU_SRS (DS Samples of All Varieties) (%)

25 25 30 35 40 45 50 Reference GLU_SRS (DS Samples of All Varieties) (%)

UL Misc. Xylose Models

UL KL Models (Gig)

Miscanthus Models - Summary

DS
Glucose Xylose Rhamnose Mannose Arabinose Galactose Total Sugars KL ASL Ash EXTR_PD Nitrogen Moisture A A B C B C A A A A B A -

DU
B A B C B C B A B B B C -

WU
A A C C B C A B B B C C A

RMSEPWU
1.26% 0.53% 0.06% 0.07% 0.27% 0.12% 1.21% 0.93% 0.42% 0.93% 1.38% 0.28% 2.52%

RERWU
16.20 17.05 8.38 5.52 11.04 7.97 18.59 10.86 10.62 10.66 7.83 6.84 23.80

Pretreated Miscanthus

Click to edit Master text styles

Second level
Third level

Fourth level Fifth level

UNICAMP Lignin Models-DS

Y TL Sample Pre-

Set1 B+C
B C COC. B+C+COC. B+C

Treatment2 2d+OSC
2d+OSC 1d(25) 2d(1) 2d(25) 2d+OSC 2d+OSC 1d(25) 2d(1) 2d(25)

Range NIR NIR NIR NIR NIR Full NIR NIR NIR NIR

Matrix

LV 2 3 6 4 7 3 3 5 4 5

Outli er 3 4 2 3 1 5 2 5

R2

RMSE

89x4200 64x2800 42X2800 30X2800 134X2800 89x4200 64x2800 42X2800 30X2800 134X2800

Cal 0.96
0.96 0.88 0.91 0.94 0.93 0.96 0.90 0.90 0.94

Val 0.95
0.93 0.85 0.94 0.91 0.92 0.92 0.91 0.91 0.90

SEC 1.193
0.883 1.62 1.03 1.55 1.379 0.779 1.28 1.00 1.531

SEP 1.278
1.142 1.80 0.92 1.96 1.489 1.186 1.27 0.96 1.988

RE 6.90 7.80 7.00 4.00 10.00 10.80 11.20 6.00 4.00 12.50

KL B C COC. B+C+COC

B+C: pooled datset (banana a and coffee); B: banana alone;C: coffee; COC: coconut; B+C+Coc.: banana+coffee+coconut. 3: The asterisks indicates statistically significant difference (* p < 0.05) between RMSEP and RMSEC.

UNICAMP Lignin Models-DU

Y TL Sample Set1 B C COC. PreTreatment2 SNV+DT(2) SNV+1d(1) 2d(1) Range NIR NIR NIR Matrix 55X2800 60x2800 LV 9 7 5 Outli er 3 5 4 R2 Cal 0.88 0.97 0.97 Val 0.86 0.90 0.97 RMSE SEC 1.513 SEP 1.872 RE 14.00 8.00 2.00

0.700* 1.831* 0.55 0.56

30x2800
55X2800 60x2800 30x2800 55X2800 60x2800 30x2800 52x2800

B
KL C

SNV+DT(2)
SNV+1d(1)

NIR
NIR

9
7

4
5

0.86
0.97

0.84
0.90

1.480
0.714

1.811
1.693

16.00
9.00

COC.
ASL B

2d(1)
SNV+1d

NIR
NIR

5
8

4
5

0.98
0.97

0.96
0.96

0.67
0.170

0.47
0.181

3.00
6.00

C
COC. AIR B C

SNV+1d(1)
2d(1) SNV+1d(1) SNV+1d(1)

NIR
NIR NIR NIR

4
3 9

5
2 2 5

0.80
0.89 0.95 0.97

0.73
0.85 0.94 0.90

0.085
0.118 1.039

0.105
0.121 1.227

2.00
8.00 10.00 9.00

60x2800 30x2800

0.743* 1.835*

COC.

2d(1)

NIR

0.96

0.91

0.65

0.91

4.00

UNICAMP Lignin Models-WU

Y TL C COC. KL B C COC. ASL B C COC. AIR B 2d(1) 2d(25) 1d(7) 2d(1) 2d(25) 1d(7) SNV+1d 2d(25) 1d(7) NIR NIR NIR NIR NIR NIR NIR NIR NIR Sample Set1 B PreTreatment2 1d(7) Range NIR Matrix LV 8 6 5 7 6 4 7 5 6 8 62x4200 64x2800 30X2800 62x2800 Outli er 5 5 2 4 5 2 3 5 3 5 R2 Cal 0.89 0.95 0.96 0.85 0.96 0.81 0.82 0.80 0.92 0.89 Val 0.74 0.80 0.84 0.76 0.90 0.80 0.81 0.76 0.84 0.75 RMSE SEC 1.452 SEP 1.916 RE 15.00 11.00 8.00 17.00 9.00 9.00 16.00 16.00 9.00 16.00

0.903* 2.450* 0.858* 1.939* 1.590 0.790 1.842 0.362 0.440 1.772 1.779 1.973 0.424 0.591

42X2800
30X2800 62x2800 42X2800 30X2800 62x2800 42X2800 30X2800

0.082* 0.136* 1.470 1.788

C
COC.

2d(1)
2d(25)

NIR
NIR

7
7

5
3

0.98
0.93

0.89
0.92

0.587* 1.914*
1.13 1.30

10.00
5.50

UNICAMP Ash and Extractives Models-DS

Y

Sample
Set1 B+C

PreTreatment2 2d+SNV

Range NIR

Matrix
205x2800 103x4200 102X2800 30X2800 233X2800 205x2800 103x2800 102X2800 30X2800

LV 7

Outli er 2

R2
Cal 0.83 Val 0.80

RMSE
SEC 0.526 SEP 0.556

RE 22.00

ASH

B
C COC. B+C+COC. B+C Extr. B C COC. B+C+COC.

2d
1d(25) 2d(1) 2d(25) 2d+SNV 2d 1d(25) 2d(1) 2d(25)

Full
NIR NIR NIR NIR NIR NIR NIR NIR

7
7 4 6 7 6 6 2 7

2
5 1 5 1 5 3 4

0.76
0.73 0.86 0.80 0.81 0.86 0.80 0.84 0.82

0.70
0.60 0.86 0.75 0.79 0.86 0.75 0.84 0.81

0.559
0.22* 0.34 0.587 0.947 0.794 1.08 0.88 1.04

0.711
0.39* 0.40 0.619 1.063 0.985 1.22 0.84 1.25

18.00
20.00 20.00 22.00 11.00 12.00 12.00 8.00 13.00

233X2800

UNICAMP Sugar Models-DS

Y GLUC. Sample Set1 B C COC. B C COC. B C COC. B C COC. B C COC. MAN. B C COC. TS B C COC. EMSC SNV+1d(1) NIR NIR 41X2800 30X2800 7 7 5 2 0.75 0.95 0.72 0.94 4.40 1.41 4.06 2.05 13.00 5.50 SNV+1d(1) SNV+1d(1) NIR NIR 41X2800 30X2800 7 6 4 3 0.89 0.52 0.75 0.53 1.574 0.16 1.676 0.10 22.00 16.00 PreTreatment2 2d(25) SNV+1d(1) EMSC SNV+1d(1) 2d(25) 2d(1) SNV+1d(1) SNV+1d(1) 2d(25) 2d(1) Range NIR NIR NIR NIR NIR NIR NIR NIR NIR NIR Matrix LV 7 4 7 5 5 5 7 7 5 3 Outli er 2 2 5 2 5 2 2 3 5 3 R2 Cal 0.78 0.92 0.95 0.88 0.87 0.91 0.94 0.79 0.87 0.90 Val 0.70 0.82 0.80 0.82 0.83 0.85 0.86 0.72 0.86 0.83 RMSE SEC SEP 1.99 1.13 0.723 0.94 0.443 0.06* 0.053 0.01 0.479 0.15 2.22 1.25 0.780 1.44 0.476 0.14* 0.055 0.04 0.582 0.17 RE 14.00 5.00 16.00 11.00 15.00 10.00 8.00 12.00 12.00 7.00 41X2800 30X2800 41X2800 30X2800 41X2800 30X2800 41X2800 30X2800 41X2800 30X2800

XYL.
GALA. RHAM ARAB.

UNICAMP Sugar Models-WU

Y
GLUC.

Sample Set1
B

PreTreatment2
SNV+DT
1d(1) EMSC SNV+1d(1) 2d(25) 2d(25) 2d(25) 2d(1)

Range
NIR
NIR NIR NIR NIR NIR NIR NIR

Matrix
41X2800

LV
9
5

Outli er
3
3

R2 Cal
0.81
0.92

Val
0.77
0.88

RMSE SEC SEP

1.399
1.030

RE
10.00
7.00

C
COC. XYL. B C COC. GALA. B C COC. RHAM B C COC. ARAB B C COC. MAN. B C COC. TS B C COC.

1.547
1.768

30X2800
41X2800 30X2800 41X2800 30X2800 41X2800

5 7 6 6 1

3 3 4 2 1

0.90 0.91 0.95 0.77 0.91

0.85 0.88 0.80 0.70 0.60

0.80* 0.192 0.06* 0.054 0.014

1.34* 0.294 0.12* 0.106 0.015

12.00 9.00 11.00 6.50 5.00

30X2800

2d(25) 2d(1) 2d(25) 2d(1) 2d(25) SNV+dt(2)

NIR NIR NIR NIR NIR NIR

41X2800 30X2800 41X2800 30X2800 41X2800 30X2800

4 1 4 3 6 4

4 1 4 4 4 2

0.73 0.92 0.72 0.98 0.82 0.96

0.70 0.71 0.71 0.77 0.76 0.90

0.589 0.12* 0.370 0.031* 1.975* 1.40

0.971 0.31* 0.476 0.103* 3.085* 2.52

20.00 11.50 25.00 19.00 9.00 5.00

Banana Residues

Coffee Residues

Coconut Residues

Banana+ Coffee + Coconut (pooled set)

Sugarcane Trash (KL)

DS (ALL) WU (ALL)

R2 = 0.90 RMSECV = 0.30%

R2 = 0.87 RMSECV = 0.35%

Sugarcane Trash (Extractives)

DS (ALL) WU (ALL)

R2 = 0.87 RMSECV = 0.63%

R2 = 0.85 RMSECV = 0.69%

Sugarcane Trash (Ash)

DS (ALL) WU (ALL)

R2 = 0.84 RMSECV = 0.50%

R2 = 0.88 RMSECV = 0.44%

Sugarcane Bagasse (KL)

WU (ALL)

WU (Low Ash)

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Second level
Third level

Fourth level Fifth level

R2 = 0.80 RMSECV = 0.46%

R2 = 0.72 RMSECV = 0.50%

Ash Variability According to Mill

Task 2.2: Spectra Collected

Partner UL Miscanthus 562 492 759 1,884 3,697 DS DG DU WU TOTAL

Pret. Misc.
Straw Papers Global (excl. above) CTC Bagasse Bagasse (online system) Trash UNICAMP Banana Residues Coffee Residues Coconut Residues TOTAL

94
78 60 310 404 74 206 204 60 2,052

78 60 404 74 216 243 90 1,657

117 90 606 249 111 186 198 90 2,406

606 249 111 186 198 90 3,324

94
273 210 310 2,020 498 370 794 843 330 9,439

D2.3 - BACI
(1) Wet Chemical Analysis:

Sugars Ash

Lignin (Klason and acid soluble) Extractives (ethanol and water) Elemental

More planned in mid-term.

Accuracy of DIBANET methods has been identified as superior to other competing companies and the literature. Company will offer guarantees on precision of analysis.

D2.3 - BACI
(2) NIR Analysis.

D2.3 Markets for Company

1.

Biorefining Companies
Biorefining database has been prepared. BACI has identified 115 companies that are developing technologies and facilities for the commercial production of second-generation biofuels from lignocellulosic biomass. Also numerous other companies that invest in biorefining projects, and examples include BIOeCON, BP, Cargill, Chevron, Honda, Khosla Ventures, Mitsubishi, Petrobras, Shell, Total SA, Toyota, and UOP.

D2.3 Markets for Company

D2.3: Markets for BACI

2. Farmers and consumers of energy crops (particularly Miscanthus) 3. Energy crop breeders. 4. Waste service providers and waste producers. 5. Scientific researchers.

D2.3: Business Plan Objectives

Secure the Irish market for the analysis of lignocellulosic materials in the short-term. To obtain the necessary licenses to allow for the importation of biomass samples from outside the country. To utilise the equipment and laboratory space of UL in the short to mid-term. Continue to improve NIR models. Continue and strengthen EU/LA ties: Develop a working relationship with DIBANET partners CTC and UNICAMP allowing for their NIR models to be used, under license, at BACI. CTC may also form a spin-out company that could offer DIBANET analytical services.

BACI Prices
Constituent(s) Price for 1 Sample (incl. ref) Price per Extra Sample Bulk, Round (/ sample) Moisture Content Sample Preparation Wet-Chemical Analysis Ethanol-Extractives Water-Extractives Water+Ethanol Extraction Ash Lignocellulosic sugars KL, ASL, AIR, AIA Sugars, KL, ASL, AIR, AIA
This cost is included in the price for the relevant methods in BACI

Microbac ($/sample)

80 150 150 150 200 80 550 275 (no AIR, AIA) 825 (no AIR,AIA) N/A N/A N/A N/A N/A N/A N/A N/A N/A

70

70

70

220 220 330 50 515 350 575 250 250 300 200 250 300 200 250 200

150 150 200 50 300 200 350 -

160 160 220 50 340 230 395 150 175 200 125 150 175 125 175 125

NIR Analysis
Wet unchopped (WU Model) Wet unchopped (DU Model) Wet unchopped (DS Model) Wet chopped (WU Model) Wet chopped (DU Model) Wet chopped (DS Model) Dry chopped (DU Model) Dry chopped (DS Model) Dry Sieved (DS Model)

Task 2.2: Other Outputs (1)

Discrimination between samples

Have developed NIR models to differentiate Miscanthus samples on the basis of:
Early/Late Harvest.

Variety (giganteus or other).

Plant fraction (e.g. stems, internodes, leaves). Stand age (1st year of growth or later).

Task 2.2: Other Outputs (2)

Where available, NIR tools will also analyse process outputs of WP3.

Chemometric models have been developed for:

Acid hydrolysis residues.

Pretreated samples (Miscanthus, bagasse).

Analytical hydrolysates (WP2) (UV). Hydrolysates from WP3 reactor (UV).

Task 2.2: Reactor Yields N = 188 R2 (CV) = 0.962

Task 2.2: Hydrolysate Analysis N = 201 R2 (CV) = 0.955

Task 2.3 Transfer of Methods to an Online NIR Facility

Bagasse NIR Analysis

Cane NIR Analysis

Task 2.3
Transfer of Methods to an Online NIR Facility

Objectives:

(1) Install online NIR equipment at a Brazilian sugar-mill.

Status: An older NIR model has been operational at a sugar mill in Quata, Sao Paulo. Its performance was monitored Nov-Dec 2011.

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T2.3
(1) Install online NIR equipment at a Brazilian sugar-mill.

Status (Contd): Following failure of the Quata system it was decided that an improved sample presentation method and a more modern device would be needed. The ProFOSS system:

Diode array detection (no moving parts). Analysis over 1100-1650nm. Capable of operating in industrial environments. Was installed in Aug 2012.

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LAB

ONLINE

D2.4

Report on Potential Markets for The FOSS Systems Following DIBANET Development This report will examine under which conditions the online device (BAS or a variant of it) will be attractive for biomass analysis and will examine the market for this in the EU and LA. Status: Ongoing. Planned for Month 38, expected completion Month 42 (due to delays in setting up and validating the online NIR system). On advice of FOSS this report will also include market evaluations for lab-based NIR systems. E.g. an NIR/DIBANET-model package that would allow biorefinery operators to characterise biomass in an at-line (rather than online) basis.

Conclusions
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A large number of samples have been analysed to high accuracy via wet-chemical methods. Data available on DIBANET analytical database. The state of the art in NIR analysis of lignocellulosic feedstocks has been advanced by allowing accurate predictions for wet heterogeneous biomass. A spin-out company offering biomass analytical services is being developed. The use of NIRS as an online analysis tool for biorefineries is being demonstrated. Strong EU-LA links have been developed and will be maintained.

Thank You!!!
daniel.hayes@ul.ie www.carbolea.ul.ie