Santino.diberardino@lneg.pt

MESTRADO INTEGRADO EM ENGENHARIA DA ENERGIA E DO AMBIENTE

Aula N 5

Characterization of Waste and Forest

Biomass. Parameters and Analytical

Techniques

Santino Di Berardino

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Biomass in effluents and waste

• Organic effluents and waste are composed of a wide variety of compounds that remain in water or waste, depending on the use made of it.

• Typically an effluent is considered liquid when its concentration is up to about 1% dry matter.

• In the range of 1 to 20% the effluent is considered to be a slurry or semi-solid residue.

• From 26% of dry matter the residue is considered, technically solid, although it still contains high moisture content.

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Sewage, Sludge and treated effluent

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Suine manure is a slurry

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Tanks for collecting manures

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Solid biomass and collecting trailer

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Source and type of liquid effluents

A number of streams flow into a wastewater collection system making its composition variable:

Domestic sewage,

The infiltration waters from the subsoil that enters, in the non-watertight collectors,

Rainwater from single-unit connections,

industrial effluents collected by the Community drainage network.

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Sampling

The representativity of the sample is an essential element for the characterization of the substrate.

The composition of the sewage is very variable and depends, among other things on the height of collection point.

Therefore, automatic systems are used to collect a sample proportional to the measured flow rate.

The samples frequency may be daily or hourly averaged or specific , according to the case under study.

In case of anaerobic digestion, the collection of temperature data (air and sewage, pH and conductivity are useful values).

The samples are kept cold following defined procedures.

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Sistema de medição e amostragemdo INETI-DER

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13Energia da biomassa

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Biomass Caracterization

Due to the wide variety of compounds present in the sewers, the parameters that are currently determined are not specific but provide a global picture of the contained pollution.

Analytical methods should be simple and economical.

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Parameter for Biological conversion

General characterization: pH, total solids and volatile solids, chemical oxygen demand (COD) and volatile fatty acids (VFAs).

Proximal analysis: water, carbohydrates, crude protein, total fat, gray.

Nutrients and / or inhibitors: total nitrogen and ammoniacalnitrogen, the potential for ammonia inhibition, total phosphorus. Theratio carbon to nitrogen (C: N), sulfur, sodium, potassium and calciumcontent (Macro elements).

Other: content of metals as trace elements for microbial growth oras compounds toxic to man and environment and biodegradablefraction (biomass).

Biodegradable and not biodegradable fraction.

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Parameters usually analyzed in liquid effluents

Total Solids (S.T.) (or DRY matter DM): Volatile Solids (S.V.):

Total Suspended Solids (S.S.T.): Volatile Suspended Solids (S.S.V.):

Chemical Oxygen Demand (COD):

Biochemical Oxygen Demand (CBO): pH:

Total Organic Carbon (TOC)

Nutrients (Nitrogen, Phosphorus, Sulfur):

Fats and oils:

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Additional Parameters

Total and fecal coliforms (contamination)

Micronutrients

Cations and anions

Heavy metals

Organically difficult to biodegrade

Toxicity

Glucose, Starch, pentoses etc..

Tanins etc…

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Thermoquimical conversion

Immediate analysis: total moisture, ash, volatilematter and fixed carbon

Elemental analysis: carbon, hydrogen, nitrogen, sulfur and oxygen

Quality as fuel: lower calorific value

Corrosion characteristics (eg chlorine) and environmental contamination (eg mercury).

Other: Major elements and dash elements

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Total and Volatile Solids (TS and VS)

Expresses the total amount of organic or volatile matter. It is determined by calcination of the sample in a muffle furnace at 550 ° C.

The organic matter of a sample (passes in gas phase) from 550 º C, remaining a mineral residue called Fixed.

Method: APHA-AWWA-WPFC-2540-E

Materials and equipment required:

Capsules

Greenhouse

Muffle

Balance

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Total and Volatile Solids (TS and VS)

Procedure:

• Weigh the capsule (P1)

• Weigh the capsule + sample (P2)

• Dry in the oven for 24 h

• Weigh capsule + dry sample (P3)

• Calcinate in the muffle for 2 h

• Weigh the capsule + the calcined sample (P4)

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Total and Volatile Solids (TS and VS) Cálculations:

•Total solids

– Volatile solids

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Chemical Oxygen Demand CODAPHA-AWWA-WPFC-5220 Method

Indirect measurement of organic matter. It measures the amount

of oxygen needed to oxidize the organic matter of a sample, using

a defined oxidant, and the predetermined temperature and time

of action. Organic Matter (CnH2nOn)+ 2nO2 = nCO2+nH2O

• Materials Needed

• Oven

• Digestion tubes

Volatile Solids VS COD TOC

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Chemical Oxygen Demand COD

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Procedure:

- 20 mL of sample

- 30 mL of sulfuric acid (acid medium) with silver sulfate (catalyst)

- 10 mL of potassium dichromate (oxidizing agent)

- 1 microdose of mercury sulphate (eliminate interference of chlorides)

- 2 hours of digestion at 150 ° C

- Determination with iron sulphate and mercury by the addition of ferro-

- Preparation of titrant and white

Chemical Oxygen Demand COD

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Chemical Oxygen Demand COD

Calculations:

V

T x ) V- (V x 0008 = (ppm) /LO mg CQO, 10

2

V1 = Volume spent of iron and ammonium sulphate used for determination

V0 = Volume spent of iron and ammonium sulphate used for determination of the white

T = Normality of iron and ammonium sulphate used for determination

V = Sample volume

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Total Organic Carbon (TOC)

Total amount of carbon in an organic compound. The amount of carbon

dioxide that is generated when the organic matter is oxidized in an oven

under established conditions is measured.

Method -APHA-AWWA-WPFC- 5310-B

•Analisator SHIMADZU TOC –

5050A

Volatile Solids VS COD TOC

Organic Matter (CnH2nOn)+ 2nO2 = nCO2+nH2O

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Total Organic Carbon (TOC)

Background:A known amount of sample is injected into a high temperature furnace in the presence of a catalyst. The organic carbon forms carbon dioxide, which diffuses through a membrane into an indicator solution. The color change of the indicator, evaluated by infrared photometry, allows detection of the quantities.

• Procedure:

• Filter the sample with 0.45 mm filter

• Dilute

• Injected into the system

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Volatile Fatty Acids (VFA)

They are organic biomolecules of lipid nature formed by a short linear hydrocarbon chain at the end of which there is a carboxyl group.

Instrument - Gas Chromatograph SHIMADZU GC-2010

Reagents: Phenol or Ac. Piválico, as internal standard

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Typical composition of sewage

PARÂMETRO TIPO DE SÓLIDOMineral Orgânico Total

Sólidos Suspensos Totais 25 65 90Sólidos Suspensos Decantáveis 15 39 54Sólidos Susp. não Decantáveis 10 26 36Sólidos Dissolvidos 80 80 160CBO5 --- --- 54CQO --- --- 115Azoto total --- --- 12,5Fósforo total --- --- 2,4Coliformes Fecais (NPM/hab/dia) --- --- 2,4 x 1010

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Suspended, colloidal and dissolved substances

The pollutants present in the sewage can be classifiedaccording to their size into:

Decanting suspended solids Average diameter = 0.02mm

Colloidal solids 0.0002 mm <Mean diameter <0.02mm

Dissolved solids Mean diameter <0.0002 mm

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Parameters analyzed in solid wastes

They are the same as in the liquid samples, but a leaching pretreatment is performed.

ST (%)

SV (%)

SFT (%)

pH

Semisolid sample

Lixiviação

5g:50mL

agua M RO

2h

N-amoniacal

Alcalinidade

Amostra

lixiviada

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2

3

45 6

7

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9

1 10

2

3

45 6

7

8

9

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Filtro0,22 µm

AGV

Amostra

filtrada

Filtro 0,47 µm

TOC

Amostra

filtrada

CQO

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Composition of some wastes

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Concentrations for discharge sewage in water body

PARAMETRO (DL 74/90) (Directiva 91/271/CEE)

Zonas sensíveis

Valor

(mg/l)

Valor

(mg/l)

percentagem

de Redução

mínima (%)

CBO5 40 25 70-90

CQO 150 125 75

S.S.T. 60 30 90-70

Ntot. 15 6 70-80

Ptot 10-3* 2 80

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Characteristics of sludge

Sludge "is the concentrated waste that results from the treatment of the sewage in the WWTP. It contains 60-90% of the pollution withdrawn into the sewer.

Anaerobic digestion was developed for the treatment of this residue. Then used for other similar waste.

in a WWTP two types of sludge are generated: primary sludge: 2.5-3.5% of the sewage volume. secondary sludge: 1.5-25%

The sludge from a conventional WWTP can vary between 4 and 7% of the volume of the sewage, depending on the treatment system and the operating conditions.

Sludge, although compact and dark in appearance, contains a lot of water. Solid content: only 3 - 5% ST.

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Wastewater Treatment Plant

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Composition of sludgeTipo de lama TS (% ) Dry matter

(g/inh./day)Volume

(l.inhabit./day)

Primary sludge not thickenedPrimary sludge thickened

0,2 - 24 - 10

55 1,10,2-0,5

Settled Activated sludge (organicload average)

0,5 – 1,5 35 0,7-1,1

Slkudge from secondarydecantation (High rate tricklingfilters)

0,5-1 20 0-4-0,7

Mixed Sludge (Primary +Secondary)

3-5 86 1,8-2,4

Thickened mixed Sludge 5 - 10 86 0,9-1,2

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Sludge Problem

In addition to biodegradable organic matter andnutrients content, dangerous contaminants (sewage) arepresent in the sludge in a concentrated form such as:

heavy metals,

organic chemical compounds

pathogenic compounds,

due to industrial effluent connections in domesticcollection networks. These compounds interfere with theanaerobic digestion process, creating inhibition andmalfunction and conditioning their final disposal.

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Animal CBO5 CQO CBO/CQO Ntot C/N Nam P(P2 O5)

K(K2O)

Chicken 3,46 9,8 0,35 0,74 - 0,26 0,60 0,30

Swine 3,1 6,4 0,48 0,51 20 0,24 0,42 0,40

Milk cow 1,15 9,8 0,11 0,23 30 0,23 0,01 0,02

Cows 1,61 9,42 0,17 0,32 25 0,11 0,18 0,23

Agrochemical waste chemical composition

(Kg/100 Kg animal weight

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ResidueVolume of residues

(m3/day)

Organic Matter

(ton/day)

Pig manure 50 000 750

Cattle manure 20 000 2 300

Chicken manure 60 000 400

TOTAL 130 000 3450

Agro-livestock waste: quantities

The energy potential of these wastes is important and it is possibleto produce about 2000 MWh / day by applying anaerobic digestion

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• Agro-livestock waste in addition to biodegradableorganic matter contains micro and macronutrients, suitable for agricultural fertilization.

• However in an agro-livestock farm it is advisableto separate the effluents from the disinfectionand watch over the rations rich in copper oranabolic.

Agro-livestock waste: Fertilization

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Animal Ca Hg Zn Cu Fe Mn Na K P S N

Chicken - - - - - - - - - - -

Swine 4,9 0,79 0,06 0,015 0,27 - - - - 1,43 -

Milk cow 2,53 1,0 - - 0,036 - - 4,53 0,9 0,453 5,07

Cows 2,56 1,7 0,045 0,006 4,09 0,51 1,05 4,62 - - -

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Concentration of inorganic compounds (g/l)

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Lignocellulosic materials

If the biomass to be degraded comes from energy crops, the number of parameters to be analyzed increase.

Lignocellulosic materials represent the most expressive fraction of the plant biomass, the largest organic decomposing biosphere source.

They consist of three main fractions which, together, account for more than 90% of the total dry mass:

cellulose, hemicellulose and lignin.

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cellulose, hemicellulose and lignin

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celulose

Cellulose, the most abundant constituent of the plant cell wall, is a homo-polysaccharide consisting of D-glucose units linked together by β (1 → 4) glycosidic bonds, having a degree of polymerization up to 10,000.

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Hemicelulose

It is a heteropolysaccharide complex composed of D-glucose, D-galactose, D-mannose, D-xylose, L-arabinose, D-glucuronicacid and 4-O-methyl-glucuronic acid. It is branched, has a degree of polymerization of less than 200 and can beacetylated.

In coniferous woods (softwoods), galactoglucomananas and arabinoglucuronoxilanes are the main hemicellulosicconstituents.

On the other hand, 4-Ometil-glucuronoxilanas and glucomananas are the main polysaccharides found in thehemicellulose of hardwoods.

Grass, on the other hand, present to glucuronoarabinoxilanasas main hemicellulosic constituents (4-7).

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lignin

Lignin is a complex macromolecule formed by the radical polymerization of phenyl propane units (p-coumaryl alcohol, coniferyl alcohol and synapyl alcohol).

It is the most abundant non-polysaccharide fraction of lignocellulose. It involves cellulosic microfibrils, providing protection from chemical and / or biological degradation, and can form covalent bonds with hemicellulose. While the cellular walls of grasses have the lowest lignin contents, those of softwoods are the richest in this component (5)

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Substrates usable

From the technological point of view, the sugars contained in the cellulosic (glucose) and hemicellulosic (xylose, arabinose, glucose, mannose and galactose) fractions represent the substrates that can be used for fermentative ethanol production.

However, as shown in the Figure, the intimate association between the three main fractions (cellulose, hemicellulose and lignin) is such that it is difficult to recover the constituent sugars in the form of high purity monomers (8)

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Arquitecturo of cell walls

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Fiber Biodegradation