IWT-TETRA Project Biosorb Vrijdag 26/02/2016
Doel Organische afvalstroom Input? (bv. mest,…)
2
Restconcentratie metalen adsorptie
Metaal+ biokool
Klassieke metaalverwijdering
Effect op kwaliteit?
biokool Milieuvriendelijke regeneratie
Economische evaluatie?
Pyrolyse + activatie
Metaalverontreingde waterstroom
Efficientie?
Gezuiverde stroom
Inhoud 1. Van organisch afval naar biochar via pyrolyse 2. Adsorptiecapaciteit van biochar metalen vergelijking met alternatieve adsorbenten
3
BIOSORB project Pyrolysis of biomass waste into value added products: lab scale approach with pilot scale ambitious? Use of activated carbon. J. Yperman Research group of Applied and Analytical Chemistry University Hasselt Belgium
Pyrolysis?
Heating biomass waste in an oxygen “free” atmosphere up to a moderate temperature (450-550°C):
bio-gas, bio-oil and char Yield, composition and quality of pyrolysis products function of:
Kind of biomass waste
Applied temperature
Reactor concept
Heating rate (slow – fast)
Residence time of gases
Reaction time (short – long)
Used heat transfer medium (direct or sand)
Heat transfer concept: conventional or micro wave
Use of catalyst?
…..
What are the target products?
Activation of char into activated carbon (AC).
Heating char at high temperature (800-950°C) in steam or CO2 atmosphere:
Quality and characteristics of AC is function of:
Final temperature Chemical pre-treatment of char
Application use
Use or not use of catalyst Heating concept: conventional or micro wave
Char characteristics
Used atmosphere: H2O or CO2 Heating time Heating rate
….
Microwave: rotating tube reactor oven (2 L) Pyrolysis of biomass waste under controlled atmosphere, time and temperature.
Production of char Production of AC Regeneration of AC MW approach: faster heating and cooling, direct and uniform heating, transfer of energy not heat, inside heating, easy cleaning and simplicity in operating, ….
Semi lab scale equipment: rotating tube reactor oven Weight: > ½ ton Pyrolysis of biomass waste under controlled atmosphere, time and temperature.
Production of char Production of AC Regeneration of AC Between in set-up: - lab
installation pilot installation Voorstelling Partnerprogramma
Flash co-pyrolysis of biomass: The influence of biopolymers Different combination of willow biomass and biopolymers: polylactic acid (PLA), polyhydrxybutyrate (PHB), corn starch, Biopearls (unknown biopolymer), Easter (syntetic biopolymer, modified PET), Solanyl (starch based) and potato starch Biopolymers can not be mixed with common plastics:
Not possible recycling route => co-pyrolysis Not always biodegradable: not really a “green” waste => composting??? Conclusions: Co-pyrolysis results in improved pyrolysis characteristics + synergetic effect: lower water content and enhanced energy recuperation, In the case of willow/PHB: additional production of pure crystals: crotonic acid (valuable chemical) 29.7g/100g input beside 19.03g of water free biooil (5,52g water) * T. Cornelissen et al. Fuel 87 (2008) 1031-1041 and 2523-2532 and JAAP 85 (2009) 87-97
Activated carbon from co-pyrolysis of particle board (PB) and melamine (urea) formaldehyde (MF) resin: A techno-economic evaluation Different ratios of PB-MF have been pyrolysed and obtained AC are evaluated in view of economic aspects (based on own experimental results and literature data). MF/PB=0/5 breakeven at 1.7 k€/t MF/PB=2/3 breakeven at 2.5k€/t MF/PB=4/1 breakeven at 4.2k€/t
Conclusions: profitable production of AC for a 1t/h process design with assumptions: 1) zero gate fee of MF waste; 2) high content of N in AC; 3) sensitive towards investment cost; production yield and AC selling price. K. Vanreppelen et al. CEJ 172 (2011) 835-846
Characterisation of adsorbents prepared by pyrolysis of sludge and sludge/disposal filter cake mix Industrial sludge waste (S) and S mixed with a disposal filter cake (FC) were fast (F) and slow( S) pyrolysed. Zn and Cu were the target pollutants. Made AC were compared with commercial F400 AC. S and FC were pre-treated (washing) with 0.01 and 1 N HCl to remove high ash content. Different kind of pyrolysis were performed: fast, slow, different T° and different input transfer rate. Conclusions: focus on adsorption of Cu(II) and Zn(II) from aqueous solution at pH=5 on these adsorbents: post treated with 0.01 and 1 N HCl. => A pseudo second order kinetic is followed. => Steady state is reached within 48 h. I. Velghe et al. WR 46 (2012) 2783-2794
Characterisation of adsorbents prepared by pyrolysis of sludge and sludge/disposal filter cake mix Conclusions:
=> Langmuir-Freundlich isotherms model fits the best the adsorption data.
Cation exchange dominate the heavy metal removal mechanism.
No release of other hazardous heavy metals is observed
For Cu(II) adsorption FC addition increased adsorption capacity of slow S adsorbents but NOT fast S adsorbents
Obtained adsorbents performed better than the commercial one. I. Velghe et al. WR 46 (2012) 2783-2794
Characterisation of adsorbents prepared by pyrolysis of sludge and sludge/disposal filter cake mix Conclusions:
Zn(II) adsorption improved for both slow and fast S with FC prediction of adsorption performance of AC is very difficult: NO theoretical base available, experiments still needed. => 1 N HCl treatment no improvement of Zn(II° adsorption => Zn(II) is an endothermic, but spontaneous process => Adsorption capacity increased with enhanced temperature and with lowest initial concentration. => Reuse of adsorbents (1 N washing) is only possible for FS_0.01 and not FSFC_0.01 as they became FS_1 and FSFC_1 (see table 5). I. Velghe et al. WR 46 (2012) 2783-2794
Activated carbon from pyrolysis of brewer’s spent grain (BSG): Production and adsorption properties BSG has high N content => higher added value as AC. AC are produced by own developed reactor oven concept. After pyrolysis, formed char is left in the reactor, One step procedure Phenol was tested as target pollutant at different pH. => AC were again compared with commercial ones: Filltrasorb and Norit.
The longer the steam activation, the higher the burn off value or thus the lower the AC yield. K. Vanreppelen et al. Waste M & R 32(7) (2014) 634-645
Activated carbon from pyrolysis of brewer’s spent grain (BSG): Production and adsorption properties Conclusions: AC yields between 16-24%.
N-content of AC between 2,1-3,8%. BSG-AC higher adsorption rate than commercial ones (benefit in continuous adsorption set-up), but somewhat lower adsorption capacity. Best operating pH is around 8 (at higher pH phenolate-ion is formed). Techno-economic model calculation (even in a pessimistic scenario) demonstrates encouraging results for profitable AC production. K. Vanreppelen et al. Waste M & R 32(7) (2014) 634-645
Inhoud 1. Van organisch afval naar biochar via pyrolyse 2. Adsorptiecapaciteit van biochar metalen vergelijking met alternatieve adsorbenten
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Schudproeven
Metex DLS (Desotec)
Adsorptie
Adsorptie
Schudproeven/batch
Schudproeven OF continue proeven
Synthetisch afvalwater Synthetisch
afvalwater
Ionenuitwisseling
Ionenuitwisseling
Metex DLS Biochar (Desotec)
Restfractie algen Biochar (Eco Treasures)
Restfractie TP207 algen (Eco Treasures) (Lanxess)
TP207 Metalclean (Lanxess) (Brenntag)
Precipitatie
Brenntafloc (Brenntag)
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BATCH: Schudproeven • Testcondities o
2u schudden bij 120 rpm
o
concentratie: 200 mg metaal/l
o
1 – 10 g adsorbent
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Verwijderingsefficiëntie metaalverwijderingsefficiëntie (mg/g)
Verwijderingsefficiëntie 71,9 80
70 60 50
40,21
37,65
40
22,84
30 20 10 0 Metex DLS
Biochar
TP207
Algen
Verwijderingscapaciteit uitgezet in (mg/g) berekend met de testresultaten van 1g adsorbens, ionenwisselaar of 1 ml precipitant
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Verwijderingsefficiëntie
Verwijderingscapaciteit uitgezet in (mg/g) en (mmol/g) berekend met de testresultaten van 1g adsorbens, ionenwisselaar of 1 ml precipitant
20
Techno-economische analyse Economische analyse voor Metex DLS, biochar en TP 207
Kostprijs
€/kg
Metex DLS
3,4
Biochar*
1,23
TP207
7,27 *300% Geschatte productiekost
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Techno-economische analyse Economische analyse
metaalverwijdering per euro (g/€)
30,61
22
35 30 25 20
11,83
15
9,89
10 5 0 Metex DLS
Biochar
TP207
Continue proeven Metex DLS (Desotec)
Adsorptie
Schudproeven OF continue proeven
Synthetisch afvalwater
Restfractie algen (Eco Treasures)
Ionenuitwisseling
23
Biochar
TP207 (Lanxess)
CONTINU: Kolomexperimenten • Hoogte kolom:
± 20 cm
• Binnendiameter: 1 cm
• Inhoud:
± 15 ml
• Debiet:
1ml/min
• Metalen: Zn2+ , Cu2+ , Cr3+ , Cd2+, Ni2+, Pb2+ (200 mg/L) 24
CONTINU Metex DLS (Desotec)
Adsorptie
Schudproeven OF continue proeven
Synthetisch afvalwater
Restfractie algen (Eco Treasures)
Ionenuitwisseling
25
Biochar
TP207 (Lanxess)
CONTINU Cu
100 90 80 70 60 50 40 30 20 10 0
koperverwijdering (%)
loodverwijdering (%)
Pb
0 50 100 150 200 behandelde hoeveelheid afvalwater (mL) METEX
TP207
Analoog voor Zn
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Bio
100 90 80 70 60 50 40 30 20 10 0 0
50
100
150
200
behandelde hoeveelheid afvalwater (mL) METEX
TP207
BIO
Analoog voor Cd en Ni
CONTINU Verwijdering uit 150 mL water METEX
TP207
biochar
11,0% 35,5%
62,6%
13,0%
28,8% 16,0%
6,7% 12,0% 10,1%
7,9%
8,0%
4,3%
16,3%
6,4% 5,5% 4,4%
Zn2+
27
Cu2+
12,3%
5,2%
Cr3+
Cd2+
Ni2+
10,0%
9,7%
Pb2+
14,4%
Niet verwijderd
CONTINU 31,56
verwijderingsefficiëntie (mg/g)
35
28,31
30
25,34 21,9
25 20
16,56
15 10 5
0
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Enkelvoudige kolomtesten
Geschakelde kolomtesten
METEX biochar TP207 MTP BTP
CONTINU metaalverwijdering per euro (g/€)
Economische analyse
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61,8
70 60 50 40 30 20
4,87
4,34
4,1
11,08
METEX biochar TP207 MTP BTP
10 0
Enkelvoudige kolomtesten
geschakelde kolomtesten
Lab4U: Afvalwaterzuivering
[email protected] TANC: Pyrolyse
[email protected] ME: Techno - Economische analyse
[email protected]
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