hp uiuc part2

72
Biorefinery of municipal and industrial wastes: a new paradigm in waste management leading to biofuels and secondary resources Héctor M. Poggi-Varaldo CINVESTAV-IPN, Dept. Biotechnology and Bioengineering, Environmental Biotechnology R&D Group, Mexico DF, Mexico [email protected] GBPANAT

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Page 1: Hp Uiuc Part2

Biorefinery of municipal and industrial wastes: a new paradigm in

waste management leading to biofuels and secondary resources

Héctor M. Poggi-Varaldo

CINVESTAV-IPN, Dept. Biotechnology and Bioengineering, Environmental Biotechnology R&D

Group, Mexico DF, Mexico [email protected]

GBPANAT

Page 2: Hp Uiuc Part2

Acknowledgements

• Ireri Robles-González, Karla Muñoz-Páez, Alessandro Carmona, Dra. I. Valdez-Vazquez, J. Acevedo-Benítez, Javier, Monserrat from the Environmental Biotechnology R&D Group of CINVESTAV

• Prof. Elvira Ríos-Leal, Mr. Rafael Hernández-Vera, Dr. Fernando Esparza-García, from CINVESTAV

• CINVESTAV for partial financial support

• Dr. Franco Cecchi, Italy; Dr. Richard Sparling, Canada; Dr. Paolo Pavan, Italy

• Agropark

Page 3: Hp Uiuc Part2

Contents

• Notation• Introduction

– Oil and fossile fuels outlook and impact– Hydrogen advantages and production

technologies• Objective• Intermittently-vented SSAH from paper

mill waste • Intermittently-vented SSAH from

organic waste• Semi-continuous acidogenic SSAD• Conclusions and outlook• Biorefinery from organic wastes

Page 4: Hp Uiuc Part2

Notation

BES 2-bromoethanesulfonate A-SSAD acidogenic solid substrate anaerobic

digestionHSP or tt heat shock preatreatmentIV-SSAH intermittently vented and flushed, solid

substrate anaerobic hydrogen generationM-SSAD methanogenic solid substrate anaerobic

digestion PH , Pm maximum amount of accumulated H2 (or

CH4) (mmole/reactor)Ri,H, Ri,m initial rate of H2 (or CH4) accumulation

(mole/(reactor.h))

Page 5: Hp Uiuc Part2

Introduction

GBPANAT

Page 6: Hp Uiuc Part2

World oil production

Duncan and Youngquist, 1998

Panic button

Page 7: Hp Uiuc Part2

World Primary Energy Demand

0

1,000

2,000

3,000

4,000

5,000

6,000

1970 1980 1990 2000 2010 2020 2030

Mto

e

Oil

Natural gas

Coal

Nuclear power

Hydro powerNon-hydro renewables

0

1,000

2,000

3,000

4,000

5,000

6,000

1970 1980 1990 2000 2010 2020 2030

Mto

e

Oil

Natural gas

Coal

Nuclear power

Hydro powerNon-hydro renewables

Priddle, 2002

Page 8: Hp Uiuc Part2

Pollution

Fossil fuel combustion products are causing global problems:

• greenhouse effect,

• ozone layer depletion,

• acid rain

• other pollution effects

Page 9: Hp Uiuc Part2

Renewable energy

• Sustainable and eco-friendly

• Variety of primary energy sources available– solar energy, – wind energy, – hydropower, – geothermal energy, – ocean currents, tidal and

wave energy– biomass

Page 10: Hp Uiuc Part2

Fuel candidates

• None of the new primary energy sources can be used directly as a fuel

• There are many candidates, such as – synthetic gasoline– synthetic natural gas (methane)– Methanol/ethanol – and hydrogen

Page 11: Hp Uiuc Part2

• The fuel of choice must satisfy the following conditions: – Transportation – Versatile – High utilization efficiency– and use should be safe

• In addition, the resulting energy system must be environmentally compatible and economical.

Veziroglu and Barbir, 1992Veziroglu and Barbir, 1992

Page 12: Hp Uiuc Part2

Hydrogen: the best fuel

When we critically look at the fuel options under the criteria given above, it becomes clear that hydrogen appears to be the best fuel

Veziroglu, 1987; Barbir Veziroglu, 1987; Barbir et al.et al., 1990; Veziroglu and Barbir, 1992, 1990; Veziroglu and Barbir, 1992

(Hydrogen experts and advocates say so.....)

To inhibition of methanoarchaea

Page 13: Hp Uiuc Part2

Hydrogen

Burning hydrogen produces only water with no CO, CO2, hydrocarbons or fine particles

H2 + 1/2 O2 H2O + 141.9 kJ/kg

Yamin Yamin et al.et al., 2000, 2000

Page 14: Hp Uiuc Part2

Hydrogen production

Hydrogen can be produced

– Chemically or thermo-chemically

– electrochemically

– as a by-product of oil/coal

processing

– by using microorganisms

Page 15: Hp Uiuc Part2

Biological production of hydrogen

Three main systems to obtain hydrogen with microorganisms

– Photochemical from water:• Algae1 • Photosynthetic bacteria2

– Dark fermentation from organic matter 3:• Facultative anaerobes• Obligate anaerobes

– Phototrophic fermentation from organic matter 3:

• Non sulfur purple bacteria

1.- Ike 1.- Ike et al.et al., 1997; 2.- Melis and Happe, 2001; 3.- Nandi and Sengupta, 1998, 1997; 2.- Melis and Happe, 2001; 3.- Nandi and Sengupta, 1998

Page 16: Hp Uiuc Part2

Fermentative hydrogen production 1/2

• Pure cultures – Studies on microbial hydrogen

production has been conducted mostly using pure cultures, either natural or genetically modified

– costly organic substrates

• Disadvantages…– cost, and cost, and cost

Asada Asada et al.et al., 2000; Evvyernie , 2000; Evvyernie et al.et al., 2000, 2001; Fabiano and Perego, 2002, 2000, 2001; Fabiano and Perego, 2002

Page 17: Hp Uiuc Part2

Fermentative hydrogen production 2/2

• Mixed cultures– Hydrogen is a key intermediate in the

anaerobic degradation of organic compounds– In these studies, hydrogen production

resulted from the inhibition of methane fermentation

• Advantages– H2 may be recovered from wastewater or

organic fraction of municipal solid wastes – no aseptic conditions required

Ueno Ueno et al.et al., 1996; Sparling , 1996; Sparling et al.et al., 1997; Lay , 1997; Lay et al.et al., 1999; Mizuno , 1999; Mizuno et al.et al., 2000, 2000

Page 18: Hp Uiuc Part2

Solid substrate anaerobic digestion (to be DASS is better than being SSAD)

• Methanogenic SSAD is an effective way of reclaiming paper mill sludge and other wastes, for obtaining:1 – CH4 as a fuel

– Soil amender or protein enrichments from the digested solids

• Yet, CH4 or CO2 as its combustion product are greenhouse gases2

1.- Poggi-Varaldo 1.- Poggi-Varaldo et al.et al., 1997 a, b, 1999, 2002; 2.- Dickinson and Cicerone, 1986, 1997 a, b, 1999, 2002; 2.- Dickinson and Cicerone, 1986

Page 19: Hp Uiuc Part2

Sparling et al., 1997; Brock ,1997; Chidthaisong & Conrad, 2000; Nagar-Anthal, 1996

Hydrogen and anaerobic digestion

Inhibitor

Methanogenesis

Acidogenesis

Hidrólisis Chemical BES Lumazine Acetylene

Physical or Phys-chem pHThermal treatment

Hydrolysis

Acetate

Polymers(polysaccharides, lipids, proteins)

Monomers(sugars, organic

acids, aminoacids)

Page 20: Hp Uiuc Part2

Important biochemical processes in anaerobic, methanogenic consortia(adapted from Brock and Madigan, 1991).

Gibbs freeenergy

(kJ/reaction)

No Type of reaction Reaction

Go a G' b

1 Fermentation ofcarbohydrates fobutyrate

Glucose + 2H2O -> 2H2 +Butyrate + 2HCO3- +

3H+-135 -284

2 Fermentation ofcarbohydrates toacetate

Glucose + 4H2O -> 4H2 +2Acetate + 2HCO3- +

4H+-207 -319

3 Anaerobic oxidation ofbutyrate (syntrophy) c

Butyrate + 2H2O -> 2H2 +2Acetate + H+ +48.2 -17.6

4 Anaerobic oxidation ofpropionate (syntrophy)d

Propionate + 3H2O -> 3H2 +Acetate + HCO3- + H+ +76.2 -5.5

5 Hydrogenotrophicmethanogenesis

4H2 +HCO3- + H+ -> CH4 + 3H2O -136 -3.2

6 Acetogenesis fromCO2 and hydrogen

4H2 + 2HCO3- + H+ -> Acetate + 4H2O -105 -7.1

7 Sulfate reduction 4H2 + SO4-2 -> HS- + 3 H2O + OH- NA e -165

Notes: a standard conditions: soluble species 1M, gas species 1 ata pressure; b conditionsprevailing in anaerobic ecosystems, i.e., [organic acids] = 1 mM, pH = 7, [HCO3

-] = 20 mM,[Glucose] = 10 mM, and the partial pressures of H2 and CH4 are 10-4 and 0.6 ata, respectively.Negative values of the Gibbs free energy indicate a spontanous, feasible thermodynamicprocess (exoergonic) whereas positive values indicate an impossible process(endoergonic); c typically effected by Syntrophomonas genera; d typically carried out bySyntrophobacter species; e Not available.

To Merits

To IV-SSAH OFMSW

To metabolites A-SSAD

Page 21: Hp Uiuc Part2

Inhibiting methanoarchaea in methanogenic solid substrate

anaerobic digesters

Hydrogen might be produced from organic wastes using microorganisms from M-SSAD, suppressing the activity of hydrogenotrophic methanogens with inhibitors such as:– chemicals: 2-bromoethanesulfonate (BES),

acetylene, lumazine– heat-shock pretreatment (HSP)– acidogenic environment (low pH)

Sparling and Daniels, 1987; Sparling Sparling and Daniels, 1987; Sparling et al.et al., 1997; Valdez-Vázquez , 1997; Valdez-Vázquez et alet al., 2003., 2003

Page 22: Hp Uiuc Part2

Solid waste in Mexico

• Municipal solid waste: 53 000 tonne/day

• Industrial solid waste: 370 000 tonne/day

• Pulp and paper industry solid waste:

500 000 tonne/year

• Dumping sites, few landfills

CNICP(1993), Poggi-Varaldo CNICP(1993), Poggi-Varaldo et al.et al. (1997a) (1997a)

Page 23: Hp Uiuc Part2

Pulp and paper industry

• It ranks second in the list of industrial polluters in Mexico

• An important proportion of the solid waste stream is dumped in sites which do not meet actual sanitary landfill design standards and environmental regulations

Page 24: Hp Uiuc Part2

Objectives

GBPANAT

Page 25: Hp Uiuc Part2

To review the research efforts of our

Group on biological hydrogen production. This review concentrates on four areas:

(i) the study of batch, repeated fermentation of paper mill waste,

(ii) batch, repeated fermentation of the organic fraction of municipal solid wastes (OFMSW), and

(iii) the semi-continuous, acidogenic fermentation (A-SSAD) of the OFMSW

(iv) development of the concept of Biorefinery of Solid Wastes

To A-SSAD

Page 26: Hp Uiuc Part2

Intermittently-vented SSAH from paper

mill waste

GBPANAT

Page 27: Hp Uiuc Part2

Objectives

• To determine the effect of the inhibitor of methanogenesis, i.e., acetylene (non specific), bromoethanesulphonate (BES), and oxygen on batch fermentation of paper mill waste

• To evaluate the influence of venting and flushing with inert gas the headspace of reactors

Response variables:• maximum hydrogen production PH,max (mmole

H2/reactor),

• initial rate of hydrogen generation Ri,H in each cycle of incubation (mmole H2/ (reactor.h))

Page 28: Hp Uiuc Part2

1.- Poggi-Varaldo et al., 1997 a, 1999; 2.- Valdez-Vázquez, 2003; 3.- Sparling and Daniels, 1987

Waste office paper with 25% w/w dry

matter content (80 g)

glass juice bottlesAnaerobic glove box…

BES (25 mM) orAcetylene ( 1% v/v)3

250ml250ml

250ml

Mesophilic, continuous

M-SSAD Reactors1,2

These were autoclaved and stored until used

20 g of inoculum

flushed with N2. Incubation at

37°C. paper

paperpaper

H2

Organic acidsand

solvents

Page 29: Hp Uiuc Part2

1.- Poggi-Varaldo et al., 1997 a, 1999; 2.- Valdez-Vázquez, 2003; 3.- Sparling and Daniels, 1987

Waste office paper with 25% w/w

dry matter content (80 g)

Recycled glass juice bottles

In the anaerobic glove box

BES (25 mM) orAcetylene ( 1% v/v)3

Mesophilic, continuous

M-SSAD Reactors1,2

These were autoclaved and

stored until used.

20 g of inoculum

Venting and flushing with N2.

Incubation at 37°C.

Organic acids

H2

Glass juice bottles with waste

office paper

Hydrogen production

Page 30: Hp Uiuc Part2

Effect of 1% acetylene on CH4 and H2 production:Preliminary experiments

• A batch minireactor exposed to air at the start-up and spiked with acetylene.

Hollow squares: CH4 ; Black squares: H2

• In an non-exposed, non-inhibited batch minireactor

Hollow circles: CH4 ; Black circles: H2

0

2

4

6

8

10

12

0 500 1000 1500

Time(h)

H2

or

CH 4

accu

mu

lati

on

(m

mo

le/r

eacto

r)

Acetylene

0

2

4

6

8

10

12

0 500 1000 1500

Time(h)

H2

or

CH 4

accu

mu

lati

on

(m

mo

le/r

eacto

r)

Acetylene CH4, non-inhibited culture

CH4, inhibited culture

H2, inhibited culture

Acetylene

Page 31: Hp Uiuc Part2

• Acetylene was a very effective inhibitor of the methanogenesis and facilitated the hydrogen accumulation

• Exposure of batch minireactors to air had a slight inhibitory effect on the methanogenic microflora. The effect was reversible:

it has been reported that methanogenic Archaea in anaerobic, methanogenic consortia can tolerate the exposure to O2,1

and the protective effect increased with increasing concentrations of sucrose.2

1.- Estrada-Vázquez 1.- Estrada-Vázquez et al.et al., 2001, 2002; 2.- Estrada-Vázquez , 2001, 2002; 2.- Estrada-Vázquez et al., et al., 20032003

Page 32: Hp Uiuc Part2

Intermittently vented solid substrate anaerobic hydrogen generation (IV-SSAH)

• Hollow circles: CH4 from non-inhibited minireactors• Black circles: H2 from minireactors spiked with BES• Black triangles: H2 from minireactors spiked with acetylene

0

3

6

9

12

15

18

0 1000 2000 3000 4000 5000

Time (hour)

CH

4 o

r H

2 (m

mo

le/r

eact

or) N2

N2

N2

Page 33: Hp Uiuc Part2

Hydrogen and methane accumulation and initial rates of hydrogen andmethane production in batch minireactors loaded with anaerobic solidinoculum plus paper waste substrate.

Cycle of incubation1 2 3 TotalParamete

r C2H2 a BES b C2H2

a BES b C2H2 a BES b C2H2

a BES b

PH c 17±1.2 14.4±1.4 11.1±1.0 9.6±0.8 5.9±0.7 5.2±0.4 34.0±1.7 29.2±1.6

Ri,H*10-3 d

[r, P(F)] e10.6±0.8

[0.96;10-5]9.6±0.9

[ 0.95; 10-4]9.1±0.4

[0.98; 10-6]8.0±0.3

[0.98; 10-6 ]6.7±0.2

[0.99; 10-6]5.4±0.4

[0.98; 10-5]NA f NA f

Pm g 12.1± 0.8 h < 0.2 < 0.2 12.1± 0.8 h

Ri,m *10-3 i

[r, P(F)] j17.3±1.2 h

[0.99; 2*10-4]--- --- NA f

Notes: a acetylene; b bromoethanesulfonate; c maximum amount of hydrogen accumulated atthe end of the incubation period (mmole H2/reactor) in inhibited minireactors, the methaneproduction was null; d initial rate of hydrogen accumulation (mmole H2/(reactor.h)); e

correlation coefficient and probability of the F statistics for the regression of the initial rateof H2 (significance level of the regression); f

not applicable; g maximum amounto of methaneaccumulated at the end of the incubation period (mmole CH4/reactor) in non-inhibitedminireactors, the hydrogen production was null; h the methanogenic batch reactor was notspiked with acetylene or BES (that is, it was not inhibited); i initial rate of methaneaccumulation (mmole CH4/(reactor.h)); j correlation coefficient and probability of thestatistics F for the regression of the initial rate of CH4 (significance level of the regression).

Parameter

Page 34: Hp Uiuc Part2

IV-SSAH 1/2

• The plateau and initial rates of H2 accumulation decreased in each subsequent cycle of incubation

• Yet, the total cumulative H2 harvested in the three cycles was nearly double than that in the first cycle alone

• The total H2 accumulated in the batch minireactors spiked with acetylene was slightly better than that corresponding to the minireactors spiked with BES

Page 35: Hp Uiuc Part2

IV-SSAH 2/2

Venting and flushing the headspace with N2 would have released the product inhibition effected by the H2 on the activity of some fermentative microorganisms in the consortia (for instance, syntrophic bacteria)

Brock and Madigan, 1991Brock and Madigan, 1991

Page 36: Hp Uiuc Part2

Organic acids

• Another cause contributing to the biochemical inhibition might be the accumulation of organic acids

• A conservatively low estimate of butyric (HBu) and acetic acid (HAc) final concentrations can be made based on the biochemical equations 1 and 2 in the latter Table

To Table Biochemical Reactions

Page 37: Hp Uiuc Part2

Organic acids We made the following simplifying

assumptions: – 95% of the paper is degradable cellulose– cellulose is approximately equal to glucose– half of the consumed substrate is fermented

according to Eq 1 and the other half to Eq. 2

– the H2 harvested is directly related to consumed substrate

Page 38: Hp Uiuc Part2

Organic acids

Final concentration of short chain volatile organic acids approx.

• 6 800 mg HAc/kg wet basis (34 000 mg HAc/kg dry initial substrate)

• 6 000 mg HBu/kg wet basis (25 000 HBu/kg dry inittal substrate)

can be expected in the solid phase at the end of the 3rd cycle

Page 39: Hp Uiuc Part2

IV-SSAH merits with respect to other biological alternatives

I. More cost-effective than processes working with pure microbial strains

II. More attractive than processes that ferment soluble carbohydrates to H2

III. No light is needed as compared to photobiological H2 production

IV. The inhibitor used (acetylene) is a cheap gas that will exit the bioreactor with the H2-rich gas stream

Page 40: Hp Uiuc Part2

However…

I. The kinetics of H2 accumulation is slower than reported rates for liquid fermentation processes

II. There is a potential for lower H2 yields than those of processes using pure cultures

III. There is an upper limit for the amount of H2 that can be obtained via anaerobic fermentation of carbohydrates To table Biochem. Reactions

Page 41: Hp Uiuc Part2

Intermittently-

vented SSAH from

organic waste

GBPANAT

Page 42: Hp Uiuc Part2

Objectives To determine the effect of:

– origin of inocula (from meso- and thermophilic methanogenic SSAD reactors; M and T, respectively),

– inhibition of the methanogenesis (acetylene and heat shock pretreatment, Ac or tt, respectively), and

– incubation temperature (37 oC and 55 oC, M and T, respectively)

on batch fermentation of organic fraction of municipal solid waste

Response variables: • maximum hydrogen production PH,max (mmole H2/reactor),• initial rate of hydrogen generation Ri,H (mmole H2/(reactor.h)),• lag time, and • accumulation of organic acids and solvents

Page 43: Hp Uiuc Part2

1.- Poggi-Varaldo et al., 1997 a, 1999; 2.- Valdez-Vázquez, 2003; 3.- Sparling and Daniels, 1987

Organic fraction of MSW

with 25% w/w dry matter content (80 g)

glass juice bottlesAnaerobic glove box…

Heat-shock pretreatmentor Acetylene ( 1% v/v)3

250ml250ml

250ml

Meso- and thermophilic continuous

M-SSAD Reactors1,2

These were autoclaved and stored until used

20 g of inoculum

flushed with N2. Incubation at 37°C or 55oC.

H2

Organic acidsSolvents

Page 44: Hp Uiuc Part2

H2 production for batch solid substrate anaerobic hydrogen production with intermittent ventingand flushing of the headspace fed with organic fraction of municipal solid waste

Incubation Cycle

1 2 3 4

Minireactor a

PH,max b PH,max PH,max PH,max

Overall H2

production

4

1,,

jjmaxHP

M-tt-M 10.17 ± 4.45 c 5.21 ± 0.51 3.07 ± 1.02 2.58 ± 0.60 21.03 ± 5.38

T-tt-M 11.89 ± 1.90 4.95 ± 0.26 2.46 ± 0.57 1.89 ± 1.62 21.20 ± 0.03

M-tt-T 0.67 ± 0.67 2.23 ± 1.03 1.80 ± 0.59 0.01 ± 0.01 4.71 ± 1.13

T-tt-T 0.34 ± 0.34 3.05 ± 3.05 1.21 ± 1.21 0.11 ± 0.11 4.71± 4.02

M-Ac-M 8.01 ± 3.55 5.39 ± 1.32 2.25 ± 0.23 1.77 ± 1.77 17.42 ± 6.86

T-Ac-M 10.19 ± 2.00 7.24 ± 0.89 3.02 ± 0.52 1.08 ± 0.50 21.53 ± 3.16

M-Ac-T 5.82 ± 4.51 3.76 ± 0.83 2.37 ± 1.09 0.10 ± 0.10 12.05 ± 6.53

T-Ac-T 3.85 ± 2.87 5.88 ± 1.22 1.62 ± 0.37 0.00 ± 0.00 11.35 ± 4.46

Notes: a for the codes of minireactors, see section Experimental Design, Second Experiment above; b

maximum hydrogen production in the incubation cycle in mmole H2/reactor; c average plus minus standarddeviation of two replicates

Page 45: Hp Uiuc Part2

0

4

8

12

16

0 100 200 300 400 500 600 700 800

Time (h)

H2 p

rod

uct

ion

(mm

ol H

2/m

ini-

reac

tor)

M-tt-M M-tt-T T-tt-M T-tt-T

0

4

8

12

16

0 100 200 300 400 500 600 700 800

Time (h)

H2 p

rod

ucti

on

(mm

ole

s H

2/m

ini-

reacto

r)

M-Ac-M M-Ac-T T-Ac-M T-Ac-T

Kinetics of H2 production from organic fraction of municipal solid waste fermentation by anaerobic consortia:First cycle of incubation

(a) heat-shock pretreated mini-reactors; (b) mini-reactors treated with acetylene; M mesophilic; T thermophilic.

Page 46: Hp Uiuc Part2

0

4

8

12

H2 p

rod

uct

ion

(m

mo

l H2/m

ini-

reac

tor)

0

100

200

300

400

500

Lag

tim

e (

h)

0

10

20

30

40

H2 p

rod

uct

ion

rat

e (m

mo

l H2/(

min

i-re

acto

r h

))

0

4000

8000

12000

16000

Met

abo

lites

acc

um

ula

tio

n(m

g C

OD

/kg

wet

bas

is)

VOA

Solvents

Main effect of inhibition treatment on performance of first cycle of incubation

tt: heat-shock pretreatment; Ac: acetylene; VOA volatile organic acids (sum of acetate, butyrate and propionate); solvents sum of acetone and ethanol

Page 47: Hp Uiuc Part2

0

4

8

12

H2 p

rod

uct

ion

(mm

ol H

2/m

ini-

reac

tor)

0

100

200

300

400

500

600

Lag

tim

e (h

)

0

10

20

30

40

H2 p

rod

cuti

on

rat

e(m

mo

l H2/(

min

i-re

acto

r h

))

0

4000

8000

12000

16000

Met

abo

lites

acc

um

ula

tio

n(m

g C

OD

/kg

we

t b

as

is)

VOA

Solvents

Main effect of incubation temperature on performance of first cycle of incubation

M: mesophilic incubation; T: thermophilic incubation; VOA volatile organic acids (sum of acetate, butyrate and propionate); solvents sum of acetone and ethanol

Page 48: Hp Uiuc Part2

Semi-continuous

acidogenic SSAD

GBPANAT

Page 49: Hp Uiuc Part2

Objectives

To evaluate the effect of the temperature regime (meso- and thermophilic ) on semi-continuous acidogenic SSAD of organic fraction of municipal solid waste

Response variables:• hydrogen percentage in biogas, • biogas productivity,

• H2 yield (NmL H2/gVSrem),

• organic acids and solvents concentrations in spent solids

Page 50: Hp Uiuc Part2

1.- Poggi-Varaldo et al., 1997 a, 1999; 2.- Valdez-Vázquez, 2003; 3.- Sparling and Daniels, 1987

Organic fraction of MSW

with 35% w/w dry matter content

Mesophilic, continuous

A-SSAD Reactors1,2

Biogas H2

Spent solids: Organic acidsand solvents

Thermophilic continuous

A-SSAD Reactors1,2

Biogas H2

Spent solids: Organic acidsand solvents

Page 51: Hp Uiuc Part2

Reactors setup for semi-continuous hydrogen production

Page 52: Hp Uiuc Part2

0

1000

2000

3000

4000

0 10 20 30 40 50

T ime (days)

Bio

ga

s p

rod

uc

tiv

iy (

Nm

L/(

kg

d))

0

100

200

300

400

500

Hy

dro

ge

n y

ield

(m

L H 2

/ g

VS

rem

)

Typical performances of acidogenic, semi-continuous reactors fed with the organic fraction of municipal solid

waste

Black symbols: biogas productivity; hollow symbols: H2 yield; squares: Thermophilic reactor 1; circles: Mesophilic reactor 1. The methane contents in both reactors were less than 0.5%.

Thermophilic A-SSAD

Mesophilic A-SSAD

Page 53: Hp Uiuc Part2

2

4

6

8

10

0 10 20 30 40 50

T ime (days)

pH

Evolution of pH in acidogenic semi-continuous reactors fed with the organic fraction of municipal

solid waste Black symbols: Thermophilic reactor 1; hollow symbols: Mesophilic reactor 1

Thermophilic A-SSAD

Mesophilic A-SSAD

Page 54: Hp Uiuc Part2

0

3600

7200

10800

14400

18000

T hermophilic Me sophilic

Pro

du

ct

dis

trib

uti

on

(m

g C

OD

/kg

wet

bas

is)

Acetone Ethanol Acetate Propionate Butyrate

Average distribution of volatile organic acids and solvents in the spent solids of the acidogenic, solid substrate reactors fed with the organic fraction of

municipal solid wasteHAc

HAc

HBu

HBu

To Table

Page 55: Hp Uiuc Part2

Comparison of biological hydrogen production from organic fraction of municipal solid waste by anaerobic

culturesSubstrate Seed

Temperature

(ºC)pH

H2

(% v/v)

Cultivation

method

H2

yield aRef

Cabbage 37 55 62

Carrot 37 47 71

Rice

Pretreated

digested sludge b

37

No

control46

Batch

96

[20]

OFMSW c

Pretreated

digested sludge b

and H2-producing

bacteria

37 5.2 60 Batch 180 [21]

37 5.5 d 42 eSemi-

continuous165 f

OFMSW cAnaerobic

digestates55 6.4 g 58 h

Semi-

continuous360 i

This

study

Notes: a NmL/g VS; b inoculum boiled at 100 oC/15 min; c OFMSW: organic fraction ofmunicipal solid waste; d 5.5 0.1; e 42 3; f 165 15; g 6.4 0.2; h 58 3; i 360 48. d,e,f

average and standard deviations of duplicate reactors; g,h,i average and standarddeviations of triplicate reactors.

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Conclusions

GBPANAT

To Conclusions A-SSAD

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Preliminary experiments:

• Similar final H2 productions were obtained for reactors spiked with acetylene and BES, although a slightly lower for the minireactors spiked with BES

• O2 as methanogenic inhibitor was not successful

• Acetylene and BES OK. Acetylene has a lower cost than BES and does not accumulate in the solid materials

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IV-SSAH from paper mill waste:

– Plateaux and initial rates of H2 accumulation decreased in each subsequent incubation cycle

– Total cumulative H2 harvested in the three-cycle incubation was double than that in the first cycle alone (17 and 34 mmole/bottle)

– Kinetics of H2 accumulation is very slow

– Acetylene and BES work OK as inhibitors of methanogenesis. Acetylene has a lower cost than BES and does not accumulate in the solid materials

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IV-SSAH from organic fraction of municipal solid waste:

– Acetylene was more effective than HSP – Incubation at 37 oC gave the highest hydrogen

accumulation in the batch reactors

– Origin of inocula did not have a significant effect on hydrogen production

– Units with thermophilic inocula that were treated with HSP and thermophilic incubation gave the poorest hydrogen production in the first cycle, but interestingly, they somewhat improved the hydrogen production in the subsequent cycles

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Semi-continuous acidogenic SSAD of organic fraction of municipal solid waste:

– Higher percentage of H2 in the biogas of thermophilic reactors than that in mesophilic ones (60 and 43%, respectively)

– Hydrogen yield of the thermophilic A-SSAD was significantly higher than that of the mesophilic reactors (470 versus 150 NmL/gVS)

– Higher concentrations of volatile organic acids in the spent solids of the thermophilic reactors than in the corresponding solids of the mesophilic units

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• Our results point out to a feasible strategy for obtaining higher H2 yields from the fermentation of industrial and municipal solid wastes, and a possible combination of waste treatment processes A-SSAD and M-SSAD

• Useful products of this approach would be– H2– organic acids and solvents– CH4

– and anaerobic digestates that could be used as soil amenders or protein enrichments for animal feed

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Lo que vendrá (Tango, Astor Piazzolla)

Biorefinery from

organic solid wastes

Cuando el destino nos alcance…

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Organicsolid

waste

H2

IV-SSAH or

A-SSAD

Spent solids

Extracts

Photo-heterotrophic fermentation

Microbial fuel cells Electricity

Downstream processing

AcidsSolvents

M-SSAD

CH4Animal feed

Fertil-izer

Adapted from Poggi-Varaldo, H.M. (2006)

CH4

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Sustainable development in Mexico City =Biorefinery of solid wastes

1 ton OFMSW

•47 kW-h biohydrogen

•1050 kW-h methane

•50 to100 kg of organic acids and solvents

•600 kg fertilizer

Recyclables

0.3 ton

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Biofuels from food or from wastes?

In the world in which we live, each year millions of people die from the lack of food.

However, none dies for not having a car to drive.

Carlos Escamilla-Alvarado, Mexico, 2008

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First International Congress of Biotechnology

and Bioengineering

1ICBB

Mexico City, Mexico, CINVESTAV

Novembre 5-7, 2008

[email protected]

Page 67: Hp Uiuc Part2

3rd International Meeting on Environmental Biotechnology and

Engineering

3IMEBE

Palma de Mallorca, Baleares Islands, Spain

September 2008

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Subjects:Microbial Ecology Molecular Biology Applications

Soil Remediation Environmental Risk Assesm.

Groundwater remediation Sustainable Development

Phytoremediation Wastewater Treatment

Solid and Hazardous Wastes Process Modelling and Control

Environmental Chemistry Atmospheric pollution

Information:

[email protected]

[email protected]

www.cinvestav.mx/2IMEBE

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Questions

and

Uncertainties

GBPANAT

[email protected]

Page 70: Hp Uiuc Part2

Shadow

I am just the shadowof my echo.I go back and treasuremy yesterday,and I abhor of tomorrowand its treachery.Yet, I fade away, prisoner of a perverse gameof blind mirrorsand blind doors.Now, I am justa shiverof the echo of my shadow.

Sombra

Soy tan solo la sombra de mi eco.Regreso y me abrazoa aquel mi ayer,y abjuro horrorizdodel mañana y sustraiciones.Sin embargo, desaparezcoprisionero de un perversojuego de espejos ciegos y puertas falsas.Ahora, soy tan soloun temblor del ecode mi sombra.

HMP-V, Mexico, 2006

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Despedida FarewellMe miro al espejo I look at myself in the

mirror

y sólo veo but I can only see

la desnuda pared a mis espaldas. the bare wall behind me.

Me estremezco y me pregunto: I shiver and mutter:

¿quién llorará nuestras derrotas? Who will cry for our defeats?

¿quién soñará nuestros sueños? Who will dream our dreams?

¿quién peleará nuestras batallas? Who will fight our battles?

¿quién ganará nuestras victorias? Who will win our victories?

HMP-V, March 2003