Valorization of wastes from pulp and paper industry: effect of …€¦ · The pulp and paper...
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Valorization of wastes from pulp and paper industry: effect of distinct formulations and stabilization conditions in the properties of granules to be used as soil improvers N. Cruz 1 , F. Silva 1 , L. Tarelho 2 , S. Rodrigues 1 1 Department of Chemistry & CESAM University of Aveiro, 3810-193, Aveiro, Portugal 2 Department of Environment and Planning & CESAM, University of Aveiro, 3810-193 Aveiro, Portugal EFFECT OF DISTINCT FORMULATIONS STABILIZATION CONDITIONS INTRODUCTION The energy sector is responsible for the huge amount of biomass ashes produced worldwide every year (currently over 480 million tons/year) being about 70% of these biomass ashes are disposed in landfills [1]. The pulp and paper industry along with wastes derived from heat and power generation, produces other waste materials including effluents and biological sludge from wastewater treatment. Application to soil for pH correction and fertilization has the potential to allow the recycling of large quantities of the materials. However, in general these waste materials cannot be recycled as such or without the processing or pre- treatment of the materials to allow safe and adequate use. The granulation of the materials followed by open air drying and stabilization (with consequent carbonation of the granules (self-hardening)) was proven to be an adequate strategy to prevent dust formation during transportation and application of biomass ash to soils [2], as well as to reduce the immediate reactivity of these waste materials upon application to soil [3]. 13 TH INTERNATIONAL CHEMICAL AND BIOLOGICAL ENGINEERING CONFERENCE AVEIRO, PORTUGAL, 2–4 OCTOBER 2018 REFERENCES [1] Q. Liu, S.C. Chmely, N. Abdoulmoumine, Energy & Fuels, 31 (2017) 3525–36. [2] J. Pesonen, V. Kuokkanen, T. Kuokkanen, M. Illikainen, Journal of Environmental Chemical Engineering, 4 (2016) 4817-4821. [3] N. Cruz, S. Rodrigues, L. Carvalho, A.C. Duarte, E. Pereira, P. Römkens, L. Tarelho, Environmental Science Pollution Research, 24 (2017) 14770–14781. CONCLUSIONS ♦ Distinct formulations allow to obtain products with variable bulk density, organic matter and elemental composition. Stabilization conditions of the granules determine the physical-chemical properties of the materials produced (pH, EC, chloride content and soluble elements). ♦ Granules with longer stabilization time and/or stabilized outdoors presented lower pH, EC, chloride content and soluble elements than the materials stabilized indoors. This will influence the reactivity of the granule products when applied to soil and it will affect the impact that the granules will have on soil properties. ♦ All formulations (BFA 100, BFA_BSE and BFA_CBS) appear to be suitable for the improvement of soils properties, particularly for acidic soils and/ or poor in plant nutrients. Granules that contain higher %wt. of CBS in their formulation can be preferentially used in soils poor in organic matter. ♦ Materials stabilized outdoors can be preferentially used in agricultural/forest/mining soils with potential salinity problems. The low EC and chloride content of these materials can prevent soil salinization problems and potential plant stress problems due to the toxicity induced by chlorides. However, it is necessary to further assess the fate of salts, soluble ions, and chlorides during the stabilization of granules outdoors as it may be necessary to collect and process the treatment of leachates whenever these are formed during this process. ACKNOWLEDGMENTS CESAM Center for Environmental and Marine Studies www.cesam.ua.pt EUROPEAN UNION European Regional Development Fund Fundação para a Ciência e Tecnologia MINISTÉRIO DA CIÊNCIA, TECNOLOGIA E ENSINO SUPERIOR Authors acknowledge the financial support of European Commission, and LIFE programme through the project No_Waste - Management of biomass ash and organic waste in the recovery of degraded soils: a pilot project set in Portugal (LIFE14 ENV/PT/000369) and CESAM (Centre for Environmental and Marine Studies). Nuno M. C. Cruz acknowledges financial support from FCT through Ph.D. grant SRFH/BD/115115/2016. OBJECTIVES The main objective of this study is to prepare different formulations of granulated materials to be used as soil improvers, testing three different waste materials from pulp and paper industry: biomass fly ash (BFA), composted biological sludge (CBS), and biological sludge effluent with 2% wt. of solids (BSE). Different formulations and stabilization conditions (indoor and outdoor) were tested, in order to evaluate their influence on the physical-chemical properties and elemental composition of the granules produced. The objectives of this study are directly aligned with two goals of 2030 Agenda for sustainable development: Goal 12.5 – By 2030, substantially reduce waste generation through prevention, reduction, recycling and reuse. Goal 15.3 – By 2030, combat desertification, restore degraded land and soil, including land affected by desertification, drought and floods, and strive to achieve a land degradation neutral world. 0 5 10 15 20 25 30 LOI Al Ca Cl K Na Si Total content by FRX (% wt, d.b.) BFA100_Outdoor BFA100_Indoor S OIL I MPROVER A FTER 7 MONTHS OF STABILIZATION Moisture (%wt.) LOI at 550ºC (%wt.) pH EC (mS cm -1 ) Soluble Cl (% to total) BFA100_Indoor 2.1 7.2 11.1 2.54 25.0 BFA100_Outdoor 11.9 17.3 9.7 0.34 11.8 ♦ Lower values observed for pH, EC and soluble chloride in materials stabilized outdoors are due to the leaching of materials during stabilization process (due to air moisture and raining, thus, promoting a higher carbonation degree), which was further verified by the much higher value of moisture for these granules. ♦ There was a clear impact of leaching during stabilization, at atmospheric conditions and rain, reflected on the reduction of most soluble salts in ash granules. ♦ The elemental composition (minor elements) was quite similar for both materials (not shown). VARIABILITY IN COMPOSITION OF BIOMASS ASH USED IN GRANULATION PROCESS (COLLECTED IN DIFFERENT PERIODS OF THE YEAR) GRANULES WITH BIOLOGICAL SLUDGE (BS) VS. COMPOSTED BIOLOGICAL SLUDGE (CBS) S OIL I MPROVER G RANULES WITH 10%wt. ORGANIC MATERIAL Moisture (%wt.) LOI at 550ºC (%wt.) pH EC (mS cm -1 ) Soluble Cl (% to total) BS 1.5 10.0 7.9 3.9 99.2 CBS 4.4 14.4 9.6 6.6 32.7 ♦ Granules with similar %wt. of organic material presented higher pH and LOI for the mixtures with CBS. Additionally, granules with CBS show a lower dissolution of chloride than granules with BS. The composting process turns the chloride present in the mixture in less soluble forms. CBS at 12%wt. vs. 21%wt ♦ Granules with higher dosage of CBS presented less bulk density. This is due to the lower bulk density of CBS (500 kg m -3 ) relatively to the ash (900 kg m -3 ). ♦ Chloride content is lower for granules with higher dosage of CBS, indicating that in these mixtures the chloride is mostly derived from ash. ♦ Soil improvers with high amount of organic material (CBS 21%wt.) presented an higher solubility ratio for some elements (e.g. Co, Cu, K, Mg, Mo and Na) than granules with only 12%wt. of CBS. This could be related to a high desintegration level of these materials during the leaching tests. S OIL I MPROVER Moisture (%wt.) LOI at 550ºC (%wt.) pH EC (mS cm -1 ) Soluble Cl (% to total) CBS12 4.4 14.4 9.6 6.6 32.7 CBS21 5.6 19.4 9.1 6.8 18.1 EXPERIMENTAL PROCEDURE BIOMASS FLY ASH (BFA) BIOLOGICAL SLUDGE (BS) COMPOSTED BIOLOGICAL SLUDGE (CBS) COMPOSTING PROCESS BIOLOGICAL SLUDGE EFFLUENT (BSE) 3 cm SAMPLING CAMPAIGNS BFA100_INDOOR 100% wt. ash STABILIZATION OUTDOOR D ISTINCT FORMULATIONS → BFA100: 100% wt. Ash → BFA88_BS12: 88% wt. Ash + 12% wt. BS → BFA68_BS32: 68% wt. Ash + 32% wt. BS → BFA_BSE: 99.5% wt. Ash + 0.5% wt. BSE → BFA88_CBS12: 88% wt. Ash + 12% wt. CBS → BFA79_CBS21: 79% wt. Ash + 21% wt. CBS INDOOR BFA100_OUTDOOR 100% wt. ash 0 5 10 15 20 25 30 35 40 Co Cu K Mg Mo Na % of soluble relatively to total CBS 12% wt. CBS 21% wt. PROPERTIES OF GRANULES OF VARIABLE FORMULATIONS ♦ Granulation process only with water led to a slightly decrease in pH (0.85), and in a subtancial reduction in EC value. ♦ Increment in organic dosage in granulated materials led to a reduction in pH value, due to the neutral pH of BS and CBS. ♦ Granules made with BSE and CBS presented higher contents of LOI than the other granules. Materials with higher %wt. of CBS on their formulation add higher LOI value. ♦ All granulated materials presented similar EC, which was lower than EC in non-granulated ash. ♦ Chloride, potassium and sodium are the most soluble elements in biomass fly ash and in soil improvers (leaching tests according to EN 12457). ♦ Stabilization led to a decrease in soluble content of chloride and calcium for the soil improvers. ♦ Potassium and calcium after stabilization presented a higher solubility than non-granulated fly ash. 0 5 10 15 20 25 LOI (%wt.), pH and EC (mS cm -1 ) LOI pH EC 0 20 40 60 80 Ca Cl K Mg Na % of soluble relatively to total Non-granulated ash BFA100 BFA_BSE BFA88_CBS12 BFA79_CBS21 BFA100_Indoor 0 10 20 30 40 50 Winter Spring Summer 1 Summer 2 Major elements (%wt., d.b.) Ca K Mg Si 0 250 500 750 1000 Winter Spring Summer 1 Summer 2 Minor elements (ppm wt., d.b.) Cr Cu Pb Zn
Transcript of Valorization of wastes from pulp and paper industry: effect of …€¦ · The pulp and paper...
Valorization of wastes from pulp and paper industry: effect of distinct formulations and stabilization conditions in the properties of granules to be used as soil improvers
N. Cruz1, F. Silva1, L. Tarelho2, S. Rodrigues1
1Department of Chemistry & CESAM University of Aveiro, 3810-193, Aveiro, Portugal2Department of Environment and Planning & CESAM, University of Aveiro, 3810-193 Aveiro, Portugal
EFFECT OF DISTINCT FORMULATIONS
STABILIZATION CONDITIONS
INTRODUCTION
The energy sector is responsible for the huge amount of biomass ashes produced worldwide every year (currently over 480million tons/year) being about 70% of these biomass ashes are disposed in landfills [1]. The pulp and paper industry along withwastes derived from heat and power generation, produces other waste materials including effluents and biological sludge fromwastewater treatment. Application to soil for pH correction and fertilization has the potential to allow the recycling of largequantities of the materials. However, in general these waste materials cannot be recycled as such or without the processing or pre-treatment of the materials to allow safe and adequate use. The granulation of the materials followed by open air drying andstabilization (with consequent carbonation of the granules (self-hardening)) was proven to be an adequate strategy to prevent dustformation during transportation and application of biomass ash to soils [2], as well as to reduce the immediate reactivity of thesewaste materials upon application to soil [3].
13TH INTERNATIONAL CHEMICAL AND
BIOLOGICAL ENGINEERING CONFERENCE
AVEIRO, PORTUGAL, 2–4 OCTOBER 2018
REFERENCES
[1] Q. Liu, S.C. Chmely, N. Abdoulmoumine, Energy & Fuels, 31 (2017) 3525–36.
[2] J. Pesonen, V. Kuokkanen, T. Kuokkanen, M. Illikainen, Journal of Environmental Chemical Engineering, 4 (2016) 4817-4821.
[3] N. Cruz, S. Rodrigues, L. Carvalho, A.C. Duarte, E. Pereira, P. Römkens, L. Tarelho, Environmental Science Pollution Research, 24 (2017) 14770–14781.
CONCLUSIONS♦ Distinct formulations allow to obtain products with variable bulk density, organic matter and elemental composition. Stabilization conditions of the
granules determine the physical-chemical properties of the materials produced (pH, EC, chloride content and soluble elements).
♦ Granules with longer stabilization time and/or stabilized outdoors presented lower pH, EC, chloride content and soluble elements than the materialsstabilized indoors. This will influence the reactivity of the granule products when applied to soil and it will affect the impact that the granules will haveon soil properties.
♦ All formulations (BFA 100, BFA_BSE and BFA_CBS) appear to be suitable for the improvement of soils properties, particularly for acidic soils and/ orpoor in plant nutrients. Granules that contain higher %wt. of CBS in their formulation can be preferentially used in soils poor in organic matter.
♦ Materials stabilized outdoors can be preferentially used in agricultural/forest/mining soils with potential salinity problems. The low EC and chloridecontent of these materials can prevent soil salinization problems and potential plant stress problems due to the toxicity induced by chlorides. However,it is necessary to further assess the fate of salts, soluble ions, and chlorides during the stabilization of granules outdoors as it may be necessary tocollect and process the treatment of leachates whenever these are formed during this process.
ACKNOWLEDGMENTS
CESAM Center for Environmental and Marine Studies
www.cesam.ua.pt
EUROPEAN UNION
European Regional
Development Fund
Fundação para a Ciência e TecnologiaMINISTÉRIO DA CIÊNCIA, TECNOLOGIA E ENSINO SUPERIOR
Authors acknowledge the financial support of European Commission, and LIFE
programme through the project No_Waste - Management of biomass ash and organic
waste in the recovery of degraded soils: a pilot project set in Portugal (LIFE14
ENV/PT/000369) and CESAM (Centre for Environmental and Marine Studies).
Nuno M. C. Cruz acknowledges financial support from FCT through Ph.D. grant
SRFH/BD/115115/2016.
OBJECTIVES
The main objective of this study is to prepare different formulations of granulated materials to be used as soil improvers, testingthree different waste materials from pulp and paper industry: biomass fly ash (BFA), composted biological sludge (CBS), andbiological sludge effluent with 2% wt. of solids (BSE). Different formulations and stabilization conditions (indoor and outdoor) weretested, in order to evaluate their influence on the physical-chemical properties and elemental composition of the granules produced.
The objectives of this study are directly aligned with two goals of 2030 Agenda for sustainable development:
Goal 12.5 – By 2030, substantially reduce waste generation through prevention, reduction, recycling andreuse.
Goal 15.3 – By 2030, combat desertification, restore degraded land and soil, including land affected bydesertification, drought and floods, and strive to achieve a land degradation neutral world.
0
5
10
15
20
25
30
LOI Al Ca Cl K Na SiTota
l co
nte
nt
by F
RX (
% w
t, d
.b.)
BFA100_Outdoor BFA100_Indoor
SOIL
IMPROVER
AFTER 7 MONTHS OF STABILIZATION
Moisture(%wt.)
LOI at 550ºC (%wt.)
pHEC
(mS cm-1)Soluble Cl
(% to total)
BFA100_Indoor 2.1 7.2 11.1 2.54 25.0
BFA100_Outdoor 11.9 17.3 9.7 0.34 11.8
♦ Lower values observed for pH, EC and soluble chloride in materials stabilizedoutdoors are due to the leaching of materials during stabilization process (dueto air moisture and raining, thus, promoting a higher carbonation degree),which was further verified by the much higher value of moisture for thesegranules.
♦ There was a clear impact of leaching during stabilization, atatmospheric conditions and rain, reflected on the reduction ofmost soluble salts in ash granules.
♦ The elemental composition (minor elements) was quite similarfor both materials (not shown).
VARIABILITY IN COMPOSITION OF BIOMASS ASH USED IN GRANULATION PROCESS
(COLLECTED IN DIFFERENT PERIODS OF THE YEAR)
GRANULES WITH BIOLOGICAL SLUDGE (BS) VS. COMPOSTED BIOLOGICAL SLUDGE (CBS)
SOIL
IMPROVER
GRANULES WITH 10%wt. ORGANIC MATERIAL
Moisture(%wt.)
LOI at 550ºC (%wt.)
pHEC
(mS cm-1)Soluble Cl
(% to total)
BS 1.5 10.0 7.9 3.9 99.2
CBS 4.4 14.4 9.6 6.6 32.7
♦ Granules with similar %wt. of organic material presented higher pH andLOI for the mixtures with CBS. Additionally, granules with CBS show alower dissolution of chloride than granules with BS. The compostingprocess turns the chloride present in the mixture in less soluble forms.
CBS at 12%wt. vs. 21%wt
♦ Granules with higher dosage of CBS presented less bulk density. This isdue to the lower bulk density of CBS (500 kg m-3) relatively to the ash(900 kg m-3).
♦ Chloride content is lower for granules with higher dosage of CBS,indicating that in these mixtures the chloride is mostly derived from ash.
♦ Soil improvers with high amount of organic material (CBS21%wt.) presented an higher solubility ratio for some elements(e.g. Co, Cu, K, Mg, Mo and Na) than granules with only 12%wt.of CBS. This could be related to a high desintegration level ofthese materials during the leaching tests.
SOIL
IMPROVER
Moisture(%wt.)
LOI at 550ºC (%wt.)
pHEC
(mS cm-1)Soluble Cl
(% to total)
CBS12 4.4 14.4 9.6 6.6 32.7
CBS21 5.6 19.4 9.1 6.8 18.1
EXPERIMENTAL PROCEDURE
BIOMASS FLY ASH
(BFA)
BIOLOGICAL SLUDGE
(BS)COMPOSTED BIOLOGICAL
SLUDGE (CBS)
COMPOSTING
PROCESS
BIOLOGICAL SLUDGE
EFFLUENT (BSE)
3 cm
SAMPLING
CAMPAIGNS
BFA100_INDOOR
100% wt. ash
STABILIZATION
OU
TD
OO
R
DISTINCT FORMULATIONS
→ BFA100: 100% wt. Ash
→ BFA88_BS12: 88% wt. Ash + 12% wt. BS
→ BFA68_BS32: 68% wt. Ash + 32% wt. BS
→ BFA_BSE: 99.5% wt. Ash + 0.5% wt. BSE
→ BFA88_CBS12: 88% wt. Ash + 12% wt. CBS
→ BFA79_CBS21: 79% wt. Ash + 21% wt. CBS
IND
OO
R
BFA100_OUTDOOR
100% wt. ash
0
5
10
15
20
25
30
35
40
Co Cu K Mg Mo Na
% o
f so
luble
rela
tively
to t
ota
lCBS 12% wt. CBS 21% wt.
PROPERTIES OF GRANULES OF VARIABLE FORMULATIONS
♦ Granulation process only with water led to a slightly decrease in pH(0.85), and in a subtancial reduction in EC value.
♦ Increment in organic dosage in granulated materials led to areduction in pH value, due to the neutral pH of BS and CBS.
♦ Granules made with BSE and CBS presented higher contents of LOIthan the other granules. Materials with higher %wt. of CBS on theirformulation add higher LOI value.
♦ All granulated materials presented similar EC, which was lower thanEC in non-granulated ash.
♦ Chloride, potassium and sodium are the most soluble elements inbiomass fly ash and in soil improvers (leaching tests according to EN12457).
♦ Stabilization led to a decrease in soluble content of chloride andcalcium for the soil improvers.
♦ Potassium and calcium after stabilization presented a higher solubilitythan non-granulated fly ash.
0
5
10
15
20
25
LO
I (%
wt.),
pH
and E
C (
mS c
m-1)
LOI pH EC
0
20
40
60
80
Ca Cl K Mg Na
% o
f so
luble
rela
tively
to t
ota
l
Non-granulated ash BFA100
BFA_BSE BFA88_CBS12
BFA79_CBS21 BFA100_Indoor
0
10
20
30
40
50
Winter Spring Summer 1 Summer 2
Majo
r ele
ments
(%
wt.,
d.b
.)
Ca K Mg Si
0
250
500
750
1000
Winter Spring Summer 1 Summer 2
Min
or
ele
ments
(ppm
wt., d.b
.)
Cr Cu Pb Zn
