biomass ash: a past and future raw material for glass-making?...history of biomass ash in glass 1....

Biomass Ash: A Past and Future Raw Material for Glass-Making?

Dr. Daniel J. BackhouseDr. Wei Deng, Adrien Guilbot, Robert Ireson, Martyn Marshall, Prof. Paul A. Bingham

Glassman Europe, Lyon, 17th September 2019

History of Biomass Ash in Glass 1st – 4th Century A.D. Roman Empire produced large amounts of

glassware (Cagno et al., 2012) Primary glass factories produced large quantities of ‘raw glass’

Natron plus lime-rich sand Natron mixture of Na2CO3·10H2O and NaHCO3, small

amounts of NaCl and Na2SO4

Primary sources at Wadi Natrun and al-Barnuj , Egypt (Shortland et al., 2010)

Raw glass exported to secondary glass producers across empire Remelted, worked to produce glass items for local markets

This method of glass production continued after decline of Roman Empire

S. Cagno et al., Evidence of early medieval soda ash glass in the archaeological site of San Genesio (Tuscany), J. Archaol. Sci., 39 (2012), 1540-1552.A. Shortland et al., Natron as a flux in the early vitreous materials industry: sources, beginnings and reasons for decline, J. Archaeol. Sci., 33 (2006), 521-530.

https://en.wikipedia.org/wiki/Roman_glass#/media/File:Munich_Cup_Diatretum_22102016_1.jpg

https://en.wikipedia.org/wiki/Natron#/media/File:Emi_Koussi_crater_natron.jpg

https://en.wikipedia.org/wiki/Roman_glass#/media/File:Munich_Cup_Diatretum_22102016_1.jpg

https://en.wikipedia.org/wiki/Natron#/media/File:Emi_Koussi_crater_natron.jpg

History of Biomass Ash in Glass

A. Shortland et al., Natron as a flux in the early vitreous materials industry: sources, beginnings and reasons for decline, J. Archaeol. Sci., 33 (2006), 521-530.N. Kato, I. Nakai & Y Shindo, Transitions in Islamic plant-ash glass vessels: on-site chemical analyses conducted at the Raya/al-Tur area on the Sinai Peninsula in Egypt, J. Archaeol. Sci., 37 (2010), 1381-1395.K. H. Wedepohl & K. Simon, The chemical composition of medieval wood ash glass from Central Europe, Chemie der Erde, 70 (2010), 89-97.

From 7th – 9th Century A.D., natron availability declined (Shortland et al., 2010) Demand – glass manufacturing, also medicines and

detergents Political – e.g. Persian invasion (619 A.D.), Muslim

conquest (639 – 642 A.D.), Berber invasions (809, 867/868, 871 A.D.), Civil war (811 – 832 A.D.)

By 9th Century, different flux source was required In Levant and Near East, ash from halophytic plants (e.g.

Salicornia and Salsola) used (Kato et al., 2010) In northern Europe, wood ash used (primarily beech (Fagus))

(Wedepohl & Simon, 2010) Production of so-called ‘Waldglas’ (‘Forest Glass’) Carolingian Empire from ca. 800 A.D.

https://ancientglass.wordpress.com/2015/05/13/egyptian-glass-bowl/

Roman Glass in the Corning Museum of Glass vol. 1 # 107 & #109, Fascinating Fragility, Nico Bijnsdorp, P. 401, The Alfred Wolkenberg Collection, Christies’s July 9, 1991 Lot 74, Verres Antiques et De L’Islam, Juin 3 & 4, 1985 Paris, lot 406

https://en.wikipedia.org/wiki/Salicornia#/media/File:Salicornia_depressa_WFNY-049B.jpg

https://www.naturallivingideas.com/wood-ash-uses/

https://ancientglass.wordpress.com/2015/05/13/egyptian-glass-bowl/

https://en.wikipedia.org/wiki/Salicornia#/media/File:Salicornia_depressa_WFNY-049B.jpg

https://www.naturallivingideas.com/wood-ash-uses/

History of Biomass Ash in Glass

K. H. Wedepohl & K. Simon, The chemical composition of medieval wood ash glass from Central Europe, Chemie der Erde, 70 (2010), 89-97.I. J. Merchant, English Medieval glass-making technology : scientific analysis of the evidence., PhD Thesis, University of Sheffield, 1999.

Beech ash contains CaO, K2O and MgO (Wedepohl & Simon, 2010) CaO/K2O ratio 1:1 – 2:1 in wood, approx. 16:1 in bark

Glasses are (7 – 20 %)K2O·(18 – 25 %)CaO·(49 – 58 %)SiO2 (Wedepohl & Simon, 2010) MgO (3.7 – 4.6 %), P2O5 (2.2 – 5.1 %) and Al2O3 (1.6 – 2.9 %) Fe2O3 (0.5 – 0.9 %) causes yellow-green colouration

Forest glasses known to be produced on a large scale into the 18th

Century (Merchant, 1999) From 18th Century onwards, manufacture declined

Increased demand for glass products (250 tons of wood for 1 ton glass) (Wedepohl & Simon, 2010)

Move to coal-fired furnaces Increased quality/consistency requirement https://www.glasmuseum-lauscha.de/waldglas.html

https://www.glasmuseum-lauscha.de/waldglas.html

Biomass Ash in Glass - Recent Research

T. Lee, R. Othman & F.-Y. Yeoh, Development of photoluminescent glass derived from rice husk, Biom. & Biomen., 59 (2013), 380-392Y. Ruangtaweep, N Srisittipokakun, K. Boonin, P Yasaka & J. Kaewhkao, Characterization of Rice Straw Ash and Utilization in Glass Production, Adv. Mater. Res., 748 (2013), 304-308N. Srisittipokakun, Y. Ruangtaweep, W. Rachniyom, K. Boonin & J. Kaewkhao, CuO, MnO2 and Fe2O3 doped biomass ash as silica source for glass production in Thailand, Res. in Phys., 7 (2017), 3449-3454S. Tuscharoen, J. Kaewkhao, P. Limkitjaroenporn, P. Limsuwan & W. Chewpraditkul, Improvement of BaO:B2O3:Fly ash glasses: Radiation shielding, physical and optical properties, Ann. Nuc. Energy, 49 (2012), 109-113S. R. Teixeira, R. S. Magalhaes, A. Arenales, A. E. Souza, M. Romero & J. M. Rincon, Valorization of sugarcane bagasse ash: Producing glass-ceramic materials, J. Environ. Manage., 134 (2014), 15-19S. R. Teixeira, A. E. Souza, C. L. Carvalho, V. C. S. Reynoso, M. Romero & J. M. Rincon, Characterization of a wollastonite glass-ceramic material prepared using sugar cane bagasse ash (SCBA) as one of the raw materials, Mater. Character., 98 (2014), 209-214.N. Srisittipokakun, K. Kirdsiri, Y. Ruangtaweep, & J. Kaewkhao, Utilization of Pennisetum purpureum ash for use in glass material, Adv. Mater. Res., 770 (2013), 84-87S. Ali & B. Jonson, Preparation of oxynitride glasses from woody biofuel ashes, J. Non-Cryst. Solids, 356 (2010), 2774-2777

Limited research into biomass ash in glass over last 2 - 3 decades Rice Husk Ash (RHA) and Rice Straw Ash (RSA) have received most investigation (Lee et al. 2013,

Ruangtaweep et al. 2013, Srisittipokakun et al. 2017, Tuscharoen et al. 2012) RHA and RSA sources of SiO2 (up to 96% after calcination) Used in photoluminescent glass (Lee et al. 2013), optical glasses (Srisittipokakun et al. 2017) and

glasses for radiation shielding (Tuscharoen et al. 2012) Research into Sugarcane Bagasse Ash (SCBA) as a raw material for glass ceramics (Teixeira et al. 2014a,

Teixeira et al. 2014b) Plant (Pennisetum Purpureum) ash as a raw material in optical glass (Srisittipokakun et al. 2013)

Yellow discolouration Woody ashes in preparation of oxynitride glasses (Ali & Jonson 2010)

Why Biomass Ash?

'Industrial Decarbonisation & Energy Efficiency Roadmaps to 2050: Glass', Report to Department of Energy and Climate Change and the Department for Business, Innovation and Skills, March 2015.'Options for increased use of ash from biomass combustion and co-firing', IEA Bioenergy, Task 32: Biomass Combustion and Cofiring, Deliverable D7, 2018.

Industrial glass manufacture is: Energy-intensive - 6500 GWh a-1 in UK for furnaces (DECC, 2015) CO2-generating - 2.2 MT in the UK (2012)

IEA report shows increased use of biomass as an energy source in major european economies (IEA, 2018) increased availability of a range of different biomass ashes

Alkali and alkaline-earth content Partial replacement for high-value limestone, soda ash,

dolomite Ashes decarbonised during combustion

Reduced CO2 content vs. limestone, soda ash, dolomite Some ashes have significant K2O contents – mixed-alkali effect to

reduce melting temperatures?

https://www.mottmac.com/article/2282/stevens-croft-biomass-power-station-uk

https://www.mottmac.com/article/2282/stevens-croft-biomass-power-station-uk

Enviroglass 2/BiomAsh Projects Fully-funded (Enviroglass 2 – Innovate UK, BiomAsh – BEIS) UK projects

working with a consortium including Glass Technology Services as well as raw material distributors and biomass power plants

Focus on bringing biomass ashes as raw materials for use in the glass industry Enviroglass 2 – Clear Container, Float, Mineral Wool BiomAsh – Green and amber container glass

Analysis of biomass ashes from 11 UK power plants – 23 ash types in total

Laboratory scale melting of ash-loaded glasses, compared against benchmarks

Composition optimisation to produce an ash-containing low Tm glass Pilot-scale trials using Glass Futures facility

Experimental Work

Clear Container glass samples produced containing range of ashes• Clear Container (CC) Benchmark• CC + 1, 5, 10 wt.% ash (Target benchmark composition)• 1450 °C 4 h for CC• Anneal at 550 °C 1 h for CC

Analysis• Visual Inspection• X-Ray Fluorescence (XRF) spectroscopy• X-Ray Diffraction (XRD)• Batch CO2 reduction calculations

Analysis of Biomass Ashes

Valuable glass-making components CaO, K2O, SiO2, MgO

Component (wt.%) 01FA 10BA 10BAa 12FA 14BA 16BANa2O 1.10 0.49 0.49 1.27 2.07 1.25MgO 2.21 1.34 1.54 4.09 1.51 1.41Al2O3 16.90 0.84 0.86 1.57 8.26 7.16SiO2 37.86 51.85 55.43 8.63 64.81 59.67P2O5 1.60 2.07 1.70 3.09 0.68 0.79SO3 3.17 1.39 0.95 5.22 0.20 0.08Cl 0.21 1.01 0.62 0.51 0.06 0.00

K2O 8.47 24.00 23.81 19.05 3.61 6.12CaO 15.40 15.96 13.61 49.53 12.35 16.68Sc 0.00 0.00 0.00 0.00 0.78 0.00

TiO2 1.15 0.10 0.00 0.27 0.00 0.55V2O5 0.07 0.00 0.00 0.00 0.02 0.02Cr2O3 0.05 0.00 0.02 0.00 0.04 0.06MnO2 0.51 0.08 0.08 2.31 0.20 0.51Fe2O3 10.67 0.82 0.89 3.38 3.90 5.27NiO 0.02 0.00 0.00 0.00 0.21 0.00CuO 0.03 0.00 0.00 0.04 0.98 0.01ZnO 0.11 0.00 0.00 0.44 0.01 0.14Rb2O 0.03 0.00 0.00 0.05 0.00 0.02SrO 0.14 0.06 0.00 0.19 0.04 0.06ZrO2 0.05 0.01 0.00 0.03 0.05 0.03BaO 0.22 0.00 0.00 0.37 0.16 0.13PbO 0.00 0.00 0.00 0.00 0.06 0.00

TOTAL 99.98 100.02 100.00 100.02 99.99 99.95Carbon 6.26 2.08 1.22 22.24 0.24 N.M.



Colourants Fe2O3 (SO3, carbon), MnO2


K2O 8.47 24.00 23.81 19.05 3.61 6.12CaO 15.40 15.96 13.61 49.53 12.35 16.68Sc 0.00 0.00 0.00 0.00 0.78 0.00


TOTAL 99.98 100.02 100.00 100.02 99.99 99.95Carbon 6.26 2.08 1.22 22.24 0.24 N.M.



Colourants Fe2O3 (SO3, carbon), MnO2

Problematic components Cl, NiO, PbO, carbon


K2O 8.47 24.00 23.81 19.05 3.61 6.12CaO 15.40 15.96 13.61 49.53 12.35 16.68Sc 0.00 0.00 0.00 0.00 0.78 0.00


TOTAL 99.98 100.02 100.00 100.02 99.99 99.95Carbon 6.26 2.08 1.22 22.24 0.24 N.M.

mm

q

q

k kh

mmh h

k

mkh

k

qm k

m mh

qkh k

mm

hh

k


m – mullite q – quartz h – haematite, Fe2O3 k - KAlSi2O6 c – cristobalite mi – microcline, KAlSi3O8 kc – K2Ca(CO3)2ns – Na3Fe(SO4)3 ca – calcite cp – H2Ca(P2O7) np – Na2CaP4O12 an – anorthite, CaAl2Si2O8

q

c

qmi

mi c

q

q

q

kc nscans

cp

q

cp ns

cakcns

np kcca

npkccp

cpcp

cp

ca np caq

cpnp

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kcnp

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cacpnp

cacp

ns qkc

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ca qkcnp

cakcnp

qan

anmian

qan

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qan q

anqan q q q q q

q q q

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anancaan

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Clear Container Biomass Ash Glasses - Visual Inspection

Biomass Ash 01FA 10BA 10BAa 12FA 16BA

Benchmark

1 wt. %

5 wt. %

10 wt. %

X-Ray Fluorescence (XRF) SpectroscopyComponent CC Nominal CC Analysed CC10BA1a CC10BA5a CC10BA10a CC16BA1 CC16BA5 CC16BA10

SiO2 72.00 72.89 71.79 72.25 73.01 72.38 73.31 73.79Al2O3 1.48 1.27 1.28 1.45 1.16 1.30 1.37 1.34K2O 0.56 0.43 0.65 1.55 2.68 0.42 0.49 0.58CaO 11.25 12.23 12.44 12.14 11.69 12.01 11.54 11.10MgO 1.06 0.43 0.96 0.99 1.03 0.92 0.50 0.17MnO 0.00 0.00 0.00 0.01 0.01 0.01 0.02 0.03Na2O 13.30 12.46 12.42 10.96 9.78 12.45 12.09 12.04P2O5 0.00 0.00 0.00 0.07 0.18 0.00 0.00 0.00SO3 0.25 0.11 0.20 0.18 0.13 0.22 0.17 0.18SrO 0.00 0.00 0.02 0.01 0.02 0.01 0.01 0.01

Fe2O3 0.05 0.04 0.07 0.20 0.15 0.12 0.30 0.55TiO2 0.03 0.15 0.11 0.14 0.12 0.12 0.16 0.16

Cr2O3 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00BaO 0.01 0.00 0.02 0.03 0.02 0.03 0.01 0.02ZnO 0.00 0.00 0.02 0.01 0.02 0.01 0.02 0.02ZrO2 0.00 0.00 0.01 0.01 0.01 0.01 0.01 0.00Total 99.99 100.00 100.00 100.00 100.00 100.00 100.00 100.00

X-Ray Diffraction

All glasses are X-ray amorphous

5 15 25 35 45 55 65 75°2θ

CC16BA1CC16BA5CC16BA10

5 15 25 35 45 55 65 75°2θ

CC10BA1aCC10BA5aCC10BA10a

Batch CO2 reduction - 16BA glasses

Soda Ash Limestone Dolomite Total

CC16BA1Reduction in Raw Material (wt.%) 0.10 0.14 0.20 0.44CO2 reduction (wt.%) 0.04 0.06 0.05 0.15CO2 reduction per tonne (kg) 0.42 0.62 0.48 1.51



Total CO2 in benchmark batchRaw Material wt. % of Batch CO2 (wt%) CO2 per tonne batch (kg)

Soda Ash 18.32 7.61 76.07Limestone 14.62 6.43 64.29Dolomite 4.08 0.97 9.74

Total 37.02 15.01 150.09

Sample Reduction in CO2 compared to Benchmark (%)CC16BA1 1.00CC16BA5 3.91CC16BA10 7.53

Batch CO2 reduction - 10BA glasses

Soda Ash Limestone Dolomite Total

CC10BA1aReduction in Raw Material (wt.%) 0.45 0.36 -0.28 0.53CO2 reduction (wt.%) 0.19 0.16 -0.07 0.28CO2 reduction per tonne (kg) 1.87 1.58 -0.67 2.78

CC10BA5aReduction in Raw Material (wt.%) 2.11 0.99 -0.06 3.04CO2 reduction (wt.%) 0.88 0.44 -0.01 1.30CO2 reduction per tonne (kg) 8.76 4.35 -0.14 12.97

CC10BA10aReduction in Raw Material (wt.%) 4.05 1.79 0.23 6.07CO2 reduction (wt.%) 1.68 0.79 0.05 2.52CO2 reduction per tonne (kg) 16.82 7.87 0.55 25.24

Total CO2 in benchmark batchRaw Material wt. % of Batch CO2 (wt%) CO2 per tonne batch (kg)

Soda Ash 18.32 7.61 76.07Limestone 14.62 6.43 64.29Dolomite 4.08 0.97 9.74

Total 37.02 15.01 150.09

Sample Reduction in CO2 compared to Benchmark (%)CC10BA1a 1.85CC10BA5a 8.64CC10BA10a 16.81

BiomAsh Project - Green and Amber

Green glass Amber glassWe can prepare glasses in our lab by using current ashes from biomass plant:

Without treatment, up to 23 wt.% biomass ash can be added into modified green/amber glass without impact on glass redox status and colour in lab.

With treatment, up to 25 wt.% biomass ash can be added into modified without colouraffects in lab (even higher in green/amber)

Conclusions and Further Work

A. Fluegel: "Glass Viscosity Calculation Based on a Global Statistical Modeling Approach"; Glass Technol.: Europ. J. Glass Sci. Technol. A, vol. 48, 2007, no. 1, p 13-30.

Biomass ash glasses have been known for > 1200 years Environmental and economic factors require changes in glass

manufacturing Biomass ashes offer reduced CO2 batches, potential for reduced melting

temperatures and lower energy demand Presence of transition metals, particularly Fe, causes colouration in clear

glasses 10 wt.% ash loading with no appreciable colour change demonstrated

Reformulated biomass ash batches show clear reduction of batch CO2

25 kg te-1 (16 %) reduction for Clear Container High ash-loadings (> 23 wt.%) possible for green/amber glass Low melting temperature formulations are being targeted

Mixed-alkali effect

Acknowledgments

Enviroglass 2/BiomAsh Consortium

Funding Body

Contributors: Dr Wei Deng (SHU), Martyn Marshall (GTS), Dr Feroz Kabir (SHU), Alex Wardlow(GTS), Adam Jackson (GTS)Supervision: Prof. Paul A. Bingham (SHU), Robert Ireson (GTS)

No Copyright Intended

biomass ash: a past and future raw material for glass-making?...history of biomass ash in glass 1....

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