Accepted Manuscript

Biogas production from tannery solid wastes – Scale-up and cost saving analysis

Caroline Agustini, Marisa da Costa, Mariliz Gutterres

PII: S0959-6526(18)30856-4

DOI: 10.1016/j.jclepro.2018.03.185

Reference: JCLP 12443

To appear in: Journal of Cleaner Production

Received Date: 07 February 2018

Revised Date: 13 March 2018

Accepted Date: 19 March 2018

Please cite this article as: Caroline Agustini, Marisa da Costa, Mariliz Gutterres, Biogas production
from tannery solid wastes – Scale-up and cost saving analysis, Journal of Cleaner Production
(2018), doi: 10.1016/j.jclepro.2018.03.185

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 ACCEPTED MANUSCRIPT

Biogas production from tannery solid wastes – Scale-up and cost saving analysis

Caroline Agustinia,*, Marisa da Costab, Mariliz Gutterresa

aLaboratory for Leather and Environmental Studies – LACOURO, Department of

Chemical Engineering, Federal University of Rio Grande do Sul, Porto Alegre, Brazil
bBacteriology Laboratory, Microbiology Department, Institute of Basic Health Sciences

– ICBS, Federal University of Rio Grande do Sul, Porto Alegre, Brazil

*corresponding author.

E-mail address: agustini@enq.ufrgs.br (C. B. Agustini)

Full postal address: LACOURO – Laboratory for Leather and Environmental Studies,

Department of Chemical Engineering, Federal University of Rio Grande do Sul,

Engenheiro Luiz Englert St., 12204, Porto Alegre, Brazil.

Abstract

This work proposes a laboratory and semi-pilot scales procedure for the evaluation of

biogas production potential and waste biodegradation efficiency from mixtures of solid

wastes from tanneries as well as the evaluation of the energy saving. Leather shavings

and sludge from wastewater treatment plants substrates were considered in the study. A

theoretical model was employed for calculations of the disintegration kinetic constant

(kdis). Biogas yields between 21 and 30 mL/kgVSS, maximum methane content of 59 %

v/v, and a TOC reduction between 68 and 76% were obtained on both scales. A linear

consistency was found in the assessed scale up and a two-fold biodegradation rate to a

five-fold volume of treated waste. In the conditions studied in semi-pilot scale, a

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midsize tannery could reduce 6.8 % of electric and 1.6 % of thermal energy

consumption besides the great cost saving of disposal of this waste.

Keywords: anaerobic digestion, semi-pilot scale, tannery sludge, tannery shavings.

1. Introduction

Bioenergy is one of the most important alternatives to fossil fuels and can

mitigate climate change (Lee, 2017). Renewable energy deriving from biomass sources

has great potential for growth to meet our future energy demands. Biogas is a very

important source of renewable methane. It is produced from anaerobic digestion (AD)

of biomass in the absence of oxygen. Compared to other renewable energy sources such

as wind energy or photovoltaics, biogas is generated independently from weather

phenomena and can be stored, making it available on demand. Furthermore, bio-

methane is a valuable substitute for limited natural gas using the same, already well

established gas distribution system. Additionally, in view of the waste management,

biogas is more favorable than composting, since fossil fuels can be substituted and the

CO2 emissions can be reduced (Gallert et al., 2003). Despite degradation be limited by

recalcitrant biomass (Weiß et al., 2016), lack of inhibitory effect of chromium on AD

was verified (Agustini et al., 2017), still missing alignment gaps focused on scale up

and economic and energetic evaluation.

Raw biogas consists mainly of methane (CH4, 40-75%), with lower heating

value between 15 and 30 MJ/Nm3, and carbon dioxide (CO2, 15-60%). Trace amounts

of other components such as water (H2O, 5-10%), hydrogen sulfide (H2S, 0.005-2%),

siloxanes (0-0.02%), halogenated hydrocarbons (VOC,<0.6%), ammonia (NH3, <1%),

oxygen (O2,0-1%), carbon monoxide (CO, <0.6%) and nitrogen (N2,0-2%) can be

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present and might be inconvenient when not removed (Poeschl et al., 2012; Ryckebosch

et al., 2011; Tippayawong and Thanompongchart, 2010).

AD is the consequence of a series of metabolic interactions among various

groups of microorganisms: hydrolytic, acidogenic, acetogenic and methanogenic

(Gallert et al., 2003). The process is carried out in digesters that are maintained at

temperatures ranging from 30 to 65°C, where the mesophilic range (30-35 °C) is the

most cost-effective. Co-digestion – the digestion of two or more substrates – is a very

attractive solution for improving the process, as it results in better distribution of

nutrients and trace elements, supporting microbial activity and providing potential for

higher methane yield (Fotidis et al., 2015; Ziganshin et al., 2013).

The leather making process generates substantial quantities of solid waste (cuts

of hides and skins, fats, shavings and trimmings, buffing dust and sludge from

wastewater treatment plants) and wastewater sludge, which in most cases contain

chromium, the main chemical used in the tanning process (Gutterres et al., 2010; Priebe

et al., 2016). These residues are usually disposed of in hazardous industrial landfills,

which are characterized as places of waste confinement where the residues undergo

undesired and uncontrolled biological treatment (C. B. Agustini et al., 2017). As they

are organic matrices, they also correspond to an interesting substrate for the

implementation of AD (Fiore et al., 2016).

Researches carried out on this issue have studied AD of tannery solid waste.

Thermophilic AD of fleshing, hide trimmings and wastewater sludge were investigated

(Zupančič and Jemec, 2010), all with chromium, in 1160 ml vessels; The specific

methane production potential were estimated to be 0.617m3kg-1 of volatile suspended

solids (VSS) for tannery waste sludge, 0.377 m3kg-1 for tannery waste trimmings and

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0.649 m3kg-1 for tannery waste fleshing. Different proportions of waste fleshing and

primary sludge were subjected to mesophilic AD in 100 ml bottles (Thangamani et al.,

2010); VS destruction between 41 and 52%, specific gas production between 0.419 and

0.635 l/g volatile solids feed and methane yield between 71 and 77% were achieved. In

the AD of fleshing and mixtures of primary and secondary sludge in 650 ml bottles (Sri

Bala Kameswari et al., 2011), biogas generated per gram of VS added was on average

410 ml/g. In mesophilic AD of substrates (soybean meal, hydrolyzed collagen, hide

powder and wet-blue leather shaving) containing different concentrations of chromium

in 300 ml bottles (Priebe et al., 2016), the maximum rate of biogas production reached

yield of 162.2 ml/g of VSS and methane fraction of 73.7%. Our previous studies was

focused on prior storage conditions of sludge and in the mesophilic AD of sludge with

shavings in 300 ml bottles; the cumulative biogas production reached yield of 22.5 ml/g

of VSS and sludge kept at ambient conditions showed a significantly higher methane

production (C. B. Agustini et al., 2017).

This research attempts to evaluate the feasibility of the AD of tannery solid

wastes (mixtures of shavings and sludge) in co-digestion processes. The aim of this

work is the assessment of a semi-pilot scale procedure and cost saving analysis for a

reliable and easy to manage evaluation of biogas production potential of complex

substrates such as tannery wastes, not yet found in literature. Assuming solubilization as

the limiting step for AD (Fiore et al., 2016) of the considered wastes, a theoretical

model was proposed and the values of the disintegration kinetic constant (kdis) were

calculated from the experimental data gathered for both scales.

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2. Materials and Methods

2.1. Biodigestion tests

The tests of batch co-digestion of tannery waste were in two different scales

made of unaltered samples incubated at 35 °C for 150 days:

Laboratory scale: three 300 mL digesters with 226 mL working volume (Fig. 1a)

with 25 mL of sludge (beamhouse + chromium tanning), 1 g of chromium tanned

leather shavings, and 200 ml of nutrient solution (2 g/l of yeast extract, 1 g/l of peptone,

7 g/l of K2HPO4, 3 g/l of KH2PO4);

Semi-pilot scale: three 2.5 L digesters with 1.13 L working volume (Fig. 1b) with

125 mL of sludge (beamhouse + chromium tanning), 5 g of chromium tanned leather

shavings, and 1000 ml of nutrient solution

The leather shavings and the sludge of wastewater treatment (this one also acting

as inoculum) were provided by a tannery which uses chromium as tanning agent. The

ratio of the quantity of sludge/shavings of 25 ml/1 g in the tests was stipulated by local

research carried out with tanneries of the region following the proportional amount of

waste produced. A nutrient solution was employed to ensure favorable conditions for

the growth and metabolism of the microorganisms. The tests were stopped after 150

days.

To analyze all parameters before biodegradation, the same mixtures were

assembled in closed bottles, shaken for 1 h in a Wagner shaker and left to settle for 24 h

at 4 °C until opening and collection of liquid and solid samples. This procedure was

done to prevent sample collection to interfere the biodegradation assays.

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2.2. Biogas monitoring

Biogas volume was measured every 2 days by water displacement with a device

based on the Mariotte principle (C. B. Agustini et al., 2017). The proportion of biogas

components was accessed weekly through a gas chromatograph (GC-2014 Shimadzu)

equipped with a ShinCarbon column (ST 100/120 2 m 1 mmID 1/16” OD Silco) and

TCD detector. Helium (White Martins 5.0) was used as the carrier gas at a flow rate of

10 ml/min. The injector and detector temperatures were held at 200 and 250 °C,

respectively. The oven program was: 40 °C (3 min), ramp at 15 °C/min to 150 °C, and

hold for 0.67 min.

2.3. Monitoring waste biodegradation

Chromium (III) oxide concentrations were determined according ABNT

NBR13341method for residual bath. pH was determined with a Digimed pHmeter (DM-

22). Solid contents (total solids (TS), volatile solids (VS), volatile suspended solids

(VSS), volatile dissolved solids (VDS), humidity and density) were determined with

gravimetric method with the assistance of a digital analytical balance (Edutec

EEQ9003F-B), a drying oven (DeLeo) and a muffle furnace (Quimis Q318M).

Biological oxygen demand (BOD5) was manometrically measured with a VELP

Scientifica BOD Sensor System 6. Total organic carbon (TOC), inorganic carbon (IC)

and total nitrogen (TN) were measured in a total organic carbon analyzer (Shimadzu

TOC-L) equipped with a total nitrogen measuring unit (Shimadzu TNM-L) and 8-port

sampler (Shimadzu OCT-L).

All analyzes (with the exception of VSS) were performed in liquid state of

samples. The sludge and the mixtures of the bioreactors were measured directly as they

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were already in liquid state. As the shavings were solid, they needed to be treated before

analyzes: for TOC, IC, TN and chromium analyses, 1 g of shavings were dissolved in

HCL 50% until total disintegration; for pH measurement 2.5 g of shavings were stirred

for 24 h in 50 mL of distilled water.

A carbon based mass balance was conducted to calculate the percentage of

carbon conversion, taking into account the initial and final TC (converted to moles) and

the carbon that left the system in the biogas (CH4 and CO2, in moles).

2.4. Modelling approach

Solubilization (throughout disintegration and hydrolysis) is generally assumed as

the rate-limiting step during AD of complex substrates. Moreover, disintegration has the

slowest kinetic in the solubilization step and it may be considered as a bottleneck.

Assuming a first order kinetic model, the disintegration rate may be achieved through

the cumulative biogas curve, according to Eq. (1) and (2) (Fiore et al., 2016). All

calculations described were performed by means of Microsoft Excel.

‒ 𝑘𝑑𝑖𝑠𝑡 (1)
𝐵(𝑡) = 𝐵𝑝𝑜𝑡(1 ‒ 𝑒 )
TC 𝑅𝑇
𝐵𝑝𝑜𝑡 = (2)
𝑀𝐶 𝑃

where:

𝐵(𝑡) represents the cumulative biogas/methane production at a given time [L];

𝐵𝑝𝑜𝑡 is the biogas potential yield of the substrate, calculated on the assumption of ideal

gas [L];

𝑘𝑑𝑖𝑠 is the first order disintegration rate [day-1];

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𝑡 is the time [day];

TC is the total carbon [g];

𝑀𝐶 is the molar mass of carbon [g/mol];

𝑅 is the universal gas constant [atm mL/mol K];

𝑇 is the temperature [K];

𝑃 is the pressure [atm].

2.5. Statistical and economic analyses

Statistical analysis was performed using Microsoft Excel (version 2012)

software for Windows. Results are presented as the mean ± standard deviation.

Statistical significance values for the means were evaluated using one-way ANOVA

(test-F of analysis of variance). Differences were accepted as significant when the p-

value was < 0.01.

Economic analysis was performed evaluating the cost saving from the

production of biogas from the co-digestion of all shavings and sludge generated by a

midsize tannery (on semi-pilot scale) and the cost of disposal of such waste. The values

were estimated by local research carried out with midsize tanneries operating in Brazil

to obtain data of average production of residues.

3. Results and Discussion

3.1. Waste characterization

Table 1 presents the tanning agent (chromium), pH, TOC, TC (TOC + IC), TN,

humidity, density, TS and VS contents of the raw sludge and the raw leather shavings.

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Both waste exhibited high VS/TS values and organic carbon contents (TOC/TC)

above 35%. The sludge exhibited basic pH values and low concentration of chromium

as expected (Gutterres and Mella, 2015), as during the process of transforming of hides

into leathers there is a great absorption of the chromium by the hide, so that little

quantity of chromium remains in the wastewater and consequently little quantity of

chromium remains in the sludge. The shavings exhibited acid pH values and high

concentration of chromium as expected (Piccin et al., 2016), confirming the high

absorption of chromium in the leather tanning process. These concentrations of

chromium in these waste did not show any toxicity for theirs anaerobic co-digestion,

both in this study and in previous ones (C. B. Agustini et al., 2017; Priebe et al., 2016;

Sri Bala Kameswari et al., 2011; Thangamani et al., 2010; Zupančič and Jemec, 2010).

The C:N ratios (TC/TN) of shavings (TC/TN = 2.8) and of sludge (TC/TN = 1.8)

(Table 1) are very far to the optimum range of 20–30 for AD (Adu-Gyamfi et al., 2012).

Even with these low values of C:N ratio, the biodigestion fully establish, which leads

the degradation to occur satisfactorily without the addition of any carbon-rich substrate.

3.2 Biogas production and composition

The daily evolution and the composition of the biogas produced in both scales

are shown in Fig. 2. The three laboratory scale replicates returned a biogas cumulative

production of 20.94 ± 4.39 mL/gVSS added (average value on three replicates ±

standard deviation) (Fig. 3), a methane cumulative production of 9.42 ± 2.06 mL

CH4/gVSS added, with a subsequent maximum methane content of 59.3 ± 1.1% b.v. (by

volume). With reference to the semi-pilot scale, the three replicates returned a biogas

cumulative production of 29.91 ± 2.51 mL/gVSS added (Fig. 3), a methane cumulative

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production of 11.50 ± 1.22 mL CH4/gVSS added, with a subsequent maximum methane

content of 59.1 ± 0.1% b.v. (by volume).

The analysis of the results of the obtained cumulative productions of biogas and

methane of both scales by means of the statistic inference of variance (test F with 0.05

significance level), showed no significant differences (Fbiogas (17.62) and Fmethane (0.06)

< Fcrit (18.51)), hence the digestion may be considered linear in the assessed scale up, as

expected. These results in overall demonstrated that disintegration was the limiting step

of the process, as proven by other studies (Fiore et al., 2016).

Despite the cumulative production of biogas and methane showed no significant

differences between the scales, it has been observed (Fig. 3) that the log phase was

twice higher for the semi-pilot scale (slope of 0.4862) (Yadav et al., 2017) compared to

laboratory scale (slope of 0.2375), and also faster, ending 20 days earlier. This result

demonstrates that even though the carbon consumption yield was equal in both scales,

the speed at which it occurred was twice higher in the semi-pilot scale. This result

indicates that a higher concentration of solids, found in the semi-pilot scale, favors the

speed of AD.

3.3. Waste destruction

Table 2 presents the tanning agent (chromium), pH, BOD, TOC, TC (TOC +

IC), TN, VDS and VSS contents of mixtures (sludge + shavings + nutrient solution)

before and after DA process in laboratory and semi-pilot scales.

The initial and final chromium concentration appeared very low, even with the

high percentage of chromium of the shavings. The three laboratory scale replicates

returned a reduction of chromium of 0.48 ± 0.06 ppm (13%) (average value on three

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replicates ± standard deviation). The three semi-pilot scale replicates returned a

reduction of chromium of 1.15 ± 0.01 ppm (32%) (average value on three replicates ±

standard deviation). The reduction of chromium concentration of both scales by means

of the statistic inference of variance (test F with 0.05 significance level), showed no

significant differences (FChromium (0.44) < Fcrit (18.51)). Hence the low chromium

concentration throughout the process showed no influence on AD and the shavings may

have acted as chromium adsorbent (Mella et al., 2017).

The initial and final pH check did not highlight critical situations such as the

irreversible deviation of pH value toward acidic conditions, even with the low pH of the

shavings. The initial and final pH remained constant around 7.4.

The dissolved BOD greatly reduced in both scales. The three laboratory scale

replicates returned a reduction of BOD of 950 ± 23 ppm (47%) (average value on three

replicates ± standard deviation). The three semi-pilot scale replicates returned a

reduction of BOD of 1,020 ± 10 ppm (50%) (average value on three replicates ±

standard deviation). The analysis of the results of the obtained reduction of BOD of

both scales by means of the statistic inference of variance (test F with 0.05 significance

level), showed no significant differences (FBOD (0.78) < Fcrit (18.51)). BOD is related to

many parameters related to biodegradable matter, so that no difference between the

BOD reductions in both scales was detected.

The dissolved TOC greatly reduced in both scales. The three laboratory scale

replicates returned a reduction of dissolved TOC of 792 ± 7 ppm (68%) (average value

on three replicates ± standard deviation). The three semi-pilot scale replicates returned a

reduction of dissolved TOC of 886 ± 14 ppm (76%) (average value on three replicates ±

standard deviation). The analysis of the results of the obtained reduction of dissolved

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TOC of both scales by means of the statistic inference of variance (test F with 0.05

significance level), showed significant differences (FTOC (6.17) > Fcrit (5.99)), hence the

digestion conduced in semi-pilot scale was more effective in the destruction of organic

carbon.

The dissolved TC remained practically constant, with little variation in both

scales. The three laboratory scale replicates returned a slight increase of dissolved TC of

24 ± 7 ppm (2%) (average value on three replicates ± standard deviation). The three

semi-pilot scale replicates returned a slight reduction of dissolved TC of 45 ± 15 ppm

(3%) (average value on three replicates ± standard deviation). The analysis of the results

of the obtained reduction of dissolved TC of both scales by means of the statistic

inference of variance (test F with 0.05 significance level), showed no significant

differences (FTC (2.98) < Fcrit (5.99)). As there was a great reduction of TOC, the TC

remained constant because concomitantly there was an increase in IC, characteristic of

the AD.

A balance that involves TC was carried out for the mixtures in bioreactors in

order to compare the amount of initial carbon with the amount of carbon that was

converted to methane or carbon dioxide. The results are detailed in Table 3. It can be

confirmed that the AD process performed in the semi-pilot scale was more efficient,

converting 35 % of carbon from the waste to CH4 and CO2, than the process in

laboratory scale that converted only 26 %.

The dissolved TN greatly increased in both scales, as expected (Guštin and

Marinšek-Logar, 2011), as it remains usually in the form of ammonium. In nitrogen-rich

waste, such as the present tannery waste, the high concentration of nitrogen remaining

after the AD process suggest the destination of this residue for fertilizers component a

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promising alternative. The three laboratory scale replicates returned an increase of

dissolved TN of 955 ± 4 ppm (57%) (average value on three replicates ± standard

deviation). The three semi-pilot scale replicates returned an increase of dissolved TN of

863 ± 9 ppm (42%) (average value on three replicates ± standard deviation). The

analysis of the results of the obtained reduction of dissolved TN of both scales by means

of the statistic inference of variance (test F with 0.05 significance level), showed

significant differences (FTN (12.73) > Fcrit (5.99)). This result is contrary to the result

obtained for TOC reduction, where the semi-pilot scale replicates returned a

significantly greater TOC reduction than the laboratory scale replicates. This higher

concentration increase of TN in laboratory scale assays may be influenced by the

smaller volume of this scale, where volume reduction due to the biogas output was more

representative. However, TN variation is not directly linked to degradation, so that even

so semi-pilot scale was more effective in waste destruction than laboratory scale.

Through VDS and VSS parameters, it is possible to monitor the step of

hydrolysis, which transforms complex organic suspended compounds in simpler organic

soluble compounds. VDS remained practically constant, with little variation in both

scales. The three laboratory scale replicates returned a slight reduction of VDS of 2 ±

0.7 % (average value on three replicates ± standard deviation). The three semi-pilot

scale replicates returned a slight increase of VDS of 1 ± 0.8 % (average value on three

replicates ± standard deviation). The analysis of the results of the obtained variation of

VDS of both scales by means of the statistic inference of variance (test F with 0.05

significance level), showed no significant differences (FVDS (0.32) < Fcrit (5.99)). VDS is

related to the total mass of volatile organic matter, not only carbon. So even though

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dissolved TOC was reduced, organic nitrogen compounds increased in concentration

and, thus, VDS remained practically constant.

VSS reduced in both scales. The three laboratory scale replicates returned a

reduction of VSS of 60 ± 1.1 % (average value on three replicates ± standard deviation).

The three semi-pilot scale replicates returned a reduction of VSS of 33 ± 1.0 % (average

value on three replicates ± standard deviation). The analysis of the results of the

obtained variation of VSS of both scales by means of the statistic inference of variance

(test F with 0.05 significance level), showed significant differences (FVSS (42.28) > Fcrit

(5.99)). In the same way as the results obtained for TN reduction, this result is contrary

to the result obtained for TOC reduction, where the semi-pilot scale replicates returned a

significantly greater TOC reduction than the laboratory scale replicates. This reinforces

that laboratory scale was more sensitive to volume variation and that VSS, as VDS, is

not only related to organic carbon, so that organic suspended nitrogen influenced this

result.

3.4. Model results

The theoretical cumulative production of biogas (𝐵𝑝𝑜𝑡), calculated from the TC

feed in each scale (Eq. 2) are 1.021 L for laboratory scale and 5.105 L for semi-pilot

scale. The first order disintegration rate (𝑘𝑑𝑖𝑠) obtained from the values of accumulated

biogas production are 0.0023 day-1 for laboratory scale and 0.0043 day-1 for semi-pilot

scale.

The model (Eq. 1) (Fiore et al., 2016), based on the values of kdis, employed as a

control tool appeared adequate for the evaluation of the scale-up of the AD process, as it

corroborates with the results for production of biogas and methane and reduction of

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organic carbon. Other authors also found a first-order rate for the disintegration of

residues (Polizzi et al., 2017). It was confirmed that the disintegration rate for the semi-

pilot scale (5 times more mass of waste) was twice higher than for laboratory scale,

showing a better energy efficiency of the process in semi-pilot scale.

3.4. Energy valorization

Taking into account the biogas cumulative production per initial mass of VSS

added, a preliminary evaluation of the potential energetic valorization of the biogas

generated by the tannery waste was calculated (Table 4), assuming a average calorific

value for biogas of 6 kWh/m3 (Bond and Templeton, 2011), a 35 % conversion from

primary to electric energy production and 42 % conversion from primary to thermal

energy conversion (Ruffino et al., 2015).

Extrapolating the values of biogas production per kgVSS of waste in a semi-pilot

scale to a real tannery (calculations are detailed in Table 5), a reduction of 7 % of

electric or 2 % of thermal energy consumption can be achieved if all shavings and

sludge produced be co-digested. Besides this energy cost saving, there is a great

reduction in the cost of disposal of this waste – 46% in terms of electric consumption

and 24 % in terms of thermal consumption –, assuming that the digested product of DA

would still be destined for some noble purpose such as fertilizers, proving the

competitiveness of AD of tannery solid waste rather than disposing it in landfills.

4. Conclusions

Renewable energy deriving from tannery wastes sources has great potential for

growth to meet our future energy demands and there are still missing alignment gaps

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focused on scale up and economic and energetic evaluation. The procedure allowed

comparison of AD of mixtures of shavings and sludge from tanneries in laboratory and

semi-pilot scales. The results exhibited a linear consistency in cumulative biogas and

methane production and two-fold biodegradation rate to five-fold volume of treated

waste. The 70 % of TOC reduction demonstrated that the substrates may be considered

interesting matrices in co-digestion processes. AD appeared feasible as a reduction of

6.8 % of electric and of 1.6 % of thermal energy consumption are estimated for a

midsize tannery that co-digest all solid waste generated, besides the great cost saving of

disposal of this waste.

Acknowledgements

This study was supported by CNPq (Edital UNIVERSAL – MCTI/CNPq Nº 14/2013),

FAPERGS (Edital FAPERGS/CAPES 17/2012) and FINEP (Edital MCTI/FINEP CT-

HIDRO 01/2013).

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 Table 1

Leather shavings and sludge from wastewater treatment characterization.

Humidity Density TS (%) (g/g of VS (%) (g/g

Waste Chromium pH TOC TC TN
(%) (g/ml) waste) of TS)

Beamhouse +

Chromium 2.5 mg/l 7.80 1,362 ppm 3,767 ppm 2,114 ppm 97.3 1.07 2.7 98.1

sludge

Chromium
7.79%
tanned leather 4.03 38.1 % (g/g) 38.3 % (g/g) 13.6 % (g/g) 26.2 0.17 73.8 94.0
(g/g)
shavings

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Table 2

Comparison of the waste parameters obtained from the two tested scales of AD.

Initial Final

Both scales* Laboratory Semi-pilot

Chromium (ppm) 3.7 ± 0.6 3.2 ± 0.6 < 2.5

pH 7.3 ± 0.002 7.7 ± 0.08 7.3 ± 0.11

BOD (ppm) 2,040 ± 110 1,090 ± 65 1,010 ± 10

TOC (ppm) 1,165 ± 29 374 ± 22 279 ± 2

TC (ppm) 1,310 ± 28 1,334 ± 21 1,266 ± 6

TN (ppm) 609 ± 7 1,565 ± 4 1,473 ± 13

VDS (%) 25 ± 0.4 23 ± 1.5 26 ± 3.0

VSS (%) 63 ± 1.3 3 ± 1.2 30 ± 0.9

*The initial parameters were the same in both scales because the components ratio was

identical.

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Table 3

Carbon-based mass balance from the two tested scales of AD.

Scale Initial C amount (g) Initial C (moles) C (moles) CH4 C (moles) CO2 C conversion

Laboratory 0.48 0.04 0.01 0.004 26%

Semi-pilot 2.39 0.20 0.04 0.03 35%

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Table 4

Preliminary evaluation of the potential energetic valorization of the biogas generated by

the tannery solid waste.

Laboratory Semi-pilot

Biogas cumulative volume (mL/gVSS) 20.94 29.91

Primary energy production (kWh/kgVSS) 12.56 17.95

Gross electric energy production (kWh/kgVSS) 4.40 6.28

Gross thermal energy production (kWh/kgVSS) 5.28 7.54

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Table 5

Evaluation of the potential energy saving by exploitation of tannery solid wastes

through biogas.

Waste produced
Hides processed 10,000
Weight of shavings produced (kg) 5,000
Weight of volatile matter in shavings produced (kgVSS) 4,700
Volume of shavings produced (m3) 30
Weight of sludge produced (kg) 100,000
Weight of volatile matter in sludge produced (kgVSS) 98,000
Volume of sludge produced (m ) 3 90
Weight of total waste produced (kg) 107,400
Volume of total waste produced (m3) 120
Cost of landfill disposal (US$/m3) 50
Cost of landfill disposal of total waste produced (US$) 6,000
Energy consumption
Electric consumption of an average tannery (MWh) 100
Cost of electric energy (US$/MWh) 130
Cost of electric energy consumption (US$) 13,000
Thermal consumption of an average tannery (MWh) 500
Cost of thermal energy (US$/MWh) 50
Cost of thermal consumption of an average tannery (US$) 25,000
Total cost of energy consumption (US$) 38,000
Biogas/energy potential production from waste
Biogas generated in a semi-pilot scale (m3/kgVSS) 3,222
Primary energy potential production (kWh/kgVSS) 19,332
Gross electric energy potential production (kWh/kgVSS) 6,766
Gross thermal energy potential production (kWh/kgVSS) 8.119
Consumption reduction
Percentage reduction in electric consumption (%) 7
Percentage reduction in thermal consumption (%) 2
Percentage reduction in waste disposal cost in terms of electric 46
consumption (%)
Percentage reduction in waste disposal cost in terms of thermal 24
consumption (%)
*The values were estimated by local research carried out with the tanneries of the
region.
** Monthly average values of a midsize tannery operating in Brazil.

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(a) (b)
Valve for pressure relief and
measurement of the volume of biogas

Septum valve for sample collection

9.5 cm

for composition analysis

Cover

Laboratory Semi-pilot
scale scale
23 cm

300 mL 2.5 L
Glass cylinder

5 cm 14 cm

Fig 1. Bioreactors design and dimensions scheme in (a) laboratory and (b) semi-pilot

scales.

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Laboratory scale: 300 mL

Percentage of gases
100% O2 N2 14
90%

Biogas (mL)
12
80%
70% 10
60% 8
50%
40% 6
30% 4
20%
2
10%
0% Days 0
0 20 40 60 80 100 120 140 160
Days

Semi-pilot scale: 2.5 L

Percentage of gases

100% O2 N2 160
90% 140

Biogas (mL)
80%
120
70%
60% 100
50% 80
40% 60
30%
40
20%
10% 20
0% Days 0
0 20 40 60 80 100 120 140 160
Days

Fig 2. Mean biogas composition and daily production during the tests in laboratory and

semi-pilot scales.

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Semi-pilot scale - 2.5 L Laboratory scale - 300 mL

35
Cumulative biogas/initial VSS (mL/g)

30

25

20
m = 0.4862
15

10
m = 0.2375
5

0
Days
0 50 100 150

Fig 3. Cumulative biogas production gathered from laboratory and semi-pilot scale tests

with indication of the slope of each log phase.

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Highlights

 Anaerobic co-digestion of shavings and sludge from tanneries

 Modeling and comparing digestion in two different scales
 Cost saving analysis for biogas from tannery solid waste instead of their disposal
 Linear consistency in biogas production in laboratory and semi-pilot scales
 Two-fold biodegradation rate to a five-fold volume of digested waste