FRATELLI PADOVANI S.R.L.€¦ · Once the substance is identified unambiguously coded sample from FRATELLI PADOVANI S.R.L. with code CI-P-13-10 and your check-in in the first laboratory

ÍNDICE

1. Purpose and Scope __________________________________ 1

2. Sample Identification ________________________________ 1

3. Characterization of substance _________________________ 2

4. Atomic Emission Spectroscopy ________________________ 4

5. RX Difraction _______________________________________ 6

6. Thermal Analysis ____________________________________ 9

7. Analysis of Volatile Organic Compounds (COV´s) _________ 14

Report test results of charcoal

FRATELLI PADOVANI S.R.L.

Prepared by:

Fernando Miguel Naranjo Pérez

FRATELLI PADOVANI

S.R.L.

REPORT TEST RESULTS (Según Reglamento (CE) 1907/2006)

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1. Purpose and Scope

Through this document reports on the results obtained for all analyzes performed on samples

of charcoal contained in facilities of FRATELLI PADOVANI S.R.L. for registration of the

substance according to the following provision:

REGULATION (EC) NO 1907/2006 OF THE EUROPEAN PARLIAMENT AND OF THE COUNCIL OF 18

DECEMBER 2006 CONCERNING THE REGISTRATION, EVALUATION, AUTHORISATION AND

RESTRICTION OF CHEMICALS (REACH).

These analyzes have been sent to different laboratories internationally contrasted to the

request of the Agency and Chemical Preparations (ECHA).

Below are individual results obtained according to the techniques employed.

The analysis has been carried out through complementary techniques, which measure specific

qualitative and quantitative parameters of the constituents of the charcoal, and management

of their atomic structure and its evolution with temperature.

2. Sample Identification

To maintain traceability making process, shipping, and emission analysis of results was carried

out and a control mechanism for identifying the sample unambiguously.

The sample analyzed has an international identification using different encodings such as:

Nº CAS 16291-96-6

Nº EC 240-383-3

Once the substance is identified unambiguously coded sample from FRATELLI PADOVANI S.R.L.

with code CI-P-13-10 and your check-in in the first laboratory 1307055 and the identification

13GE-22 for the second laboratory.

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3. Characterization of substance

3.1 Methodology

This analysis is a characterization of the substance to determine the percentage composition,

this technique is based on the following criteria according to standard methodology.

The equipment used to perform the analysis is an elemental analyzer LECO brand CHNS932

model.

The elemental analysis is a technique that provides the total content of carbon, hydrogen,

nitrogen, and sulfur present in a range of samples of organic and inorganic nature both solid

and liquid.

The technique is based on the complete and instantaneous oxidation of the sample by

combustion in pure oxygen at a temperature of approximately 1000 ° C.

Different combustion products CO2, H2O and N2, are transported by the carrier gas (He) via a

reduction tube and then selectively separated in specific columns to be then thermally

desorbed.

Finally, the gases pass separately by a thermal conductivity detector which gives a signal

proportional to the concentration of each of the individual components of the mixture.

To perform this analysis is used as a standard acetanilide. Once the calibration line three

aliquots were taken between 0.5 and 1.0 milligrams of the previously pulverized and

homogenized sample.

The conditions have been 200mL/min analysis for the carrier gas (He), combustion temperature

1000 ° C and two oxygen dose of 15cc (3s delay) and 5cc (delay 2s), respectively.

To carry out the analysis of moisture, ash and volatile organics equipment and materials used

are:

• CWF1200 Carbolite furnace capable of reaching 1000 ° C

• Balance Ohaus Adventurer Pro Precision Precision AV213C ± 0.0001

• Capsules porcelain and glass desiccator.

The procedure conforms to that described by the UNE-EN-1860-2 by the sample pulverized

charcoal goes undergoing a heating process at different temperatures described in the

standard.

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After each treatment the sample is weighed in the balance of accuracy, to constant weight, and

you get the value of each of the parameters moisture, ash and volatile organics.

The characterization results of the substance.

Parameter Units Result

1 Carbon s/s % 69.26 ± 0.33

2 Hyidrogen s/s % 3.631 ± 0.247

3 Nitrogen s/s % 0.546 ± 0.003

4 Sulfur s/s % ND

5 Humidity % 18.26 %

6 Volattile Matter % 14.20 ± 1.10%

7 Ashes % 5.19 ± 1.15 % s/s. Resultado expresado sobre seco

3.2 Conclusions

The results provide a carbon content charcoal médium-low, which allows complete combustion and allows the release of more energy. the sulfur content does not achieve the limit of quantification of the device, which means that charcoal is almost sulfur free, so that the determined amount of this element indicates the coal suitability for human consumption because the volatiles evolved in the combustion of coal will not have a significant content of sulfur derivatives. The rest of parameters are within the normal range, highlighting the low content of ashes,

though the humidity content is relatively high compared to other similar charcoals.

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4. Atomic Emission Spectroscopy

4.1 Methodology

This technique involves conducting a sweep of frequencies of electromagnetic radiation by

atomic emission spectroscopy ICP (inductively coupled plasma) or plasma induced for the

qualitative and quantitative determination of metals.

The objective of this analysis is to determine the presence in values exceeding the legality of

heavy metals, which have a high pollution potential.

For the analysis of elements performed by ICP-MS was made acidic treatment by microwave

digestion and subsequent dissolution in distilled water MilliQ charcoal samples.

The equipment that has conducted analyzes is a brand NexION 300D that has a Perkin Elmer

collision cell / reaction is achieved with significantly reduce interference associated with this

technique.

In the method of analysis have been used both collision modes as reaction to the different

elements for convenience, has been introduced yttrium as internal standard for quantification.

The reagents used for digestion, nitric acid and hydrogen peroxide, are all plus HIPERPUR

quality Brand Sigma Aldrich.

The solutions of the calibration patterns are multicomponent kit of Perkin Elmer

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4.2 Results

Parameter: Metals Unit Results

Be

mg/kg m.s.

ND

B 21.8

P 179.0

Co ND

Sr 74.4

Ag ND

Sn ND

Ba 14.4

Tl ND

Pb ND

Al 9.44

Ti 0.98

V ND

Cr 0.09

Mn 7.51

Fe 58.4

Cu 4.34

Mo 0.81

Cd ND

Sb ND

Ni 0.29

Zn 1.25

As ND

Se ND

m.s. . Result expressed on dry matter (sample dried at 105 ° C)

4.3 Conclusions

Regarding metal analysis review that concentrations for contaminants and heavy metals that

can potentially make the charcoal a hazardous chemical or special consideration are minimized,

since the concentrations of these metals such as arsenic, cadmium, cobalt, tin , Lead, etc..; are

very low or is below the detection limit of the device.

Only Phosphorus and Strontium show values slightly abovee what is usually normal, this may

be due to soil conditions in which stood the wood that has produced coal

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5. RX Difraction

To determine the degree of crystallinity using this microcrystalline powder microscopic

technique.

5.1. Methodology

To perform this analysis used a Bruker D8 ADVANCE diffracting a Bragg-Brentano geometry

and Ge monochromator equipped Ge 200: cooper radiation K1 (λ = 1.5406 Å).

There are 2 types of detectors:

• Scintillation Counter

• Linear Detector VANTEC: with opening swe

The techniques used for this analysis were:

• microcrystalline powder diffraction

• capillary Diffraction (powder or liquid samples)

• temperature chamber experiments: 30-1500 º C and possible treatments: I, air, N2 or vacuum.

The conditions under which the analysis was carried out are:

Measuring Range (º2): 20-70º

º2 Increase: 0.02º

Counting time: 0.5 s

Detector type: linear (Vantec) with opening range of 12º

5.2. Results

To determine the degree of graphitization has been employed Gaussian adjustment of the

reference reflection (002) of graphite, using this method Tagiri [1.2], parameters obtained from

the XRD patterns presented in the following Fig.

In the calculation has been subtracted the contribution caused by air dispersion inherent in the

equipment that is available and which give rise to the downward curve at angles below 20 °.

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The following table presents the data obtained for crystal size and degree of graphitization

achieved through the bands assigned to amorphous carbon.

2 (ajuste Gaussiano) Lc / nm (tamaño de

cristal) (*)

GD / Grado de

Grafitización(*)

23.45 1.10 16.80

For low order graphitic Systems estimates a value of 20 for GD and a value of 3.5 nm crystal size, below which are considered systems based amorphous disordered graphene planes. Amorphous Carbons [3,4,5].

In addition, broad bands centered around 22 º and 45 º are representative of amorphous

carbonaceous systems. Whose displacement towards lower angles 2θ (about 26.5 ° and 54 °)

and widening are a direct indication of a high degree of disorder of the carbonaceous material

[3.4].

Furthermore, reflections are detected attributable to calcium carbonate and calcium oxalate

monohydrate, as shown in the diffractogram. These reflections have been identified reliably by

PDF II database.

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5.3. Bibliography.

[1] Tagiri, M. (1981). A measurement of the graphitizing degree by the X-ray powder

diffractometer. 1. Japan Assoc. Mineral. Petrol. Econ. Geol., 76: 345-385.

[2] Tagiri, M., Yago, Y., Tanaka, A. (2000). Shuffled-cards structure and different P/T conditions

in the Sanbagawa metamorphic belt, Sakuma-Tenryu area, central Japan. Island Are, 9/2: 188-

203.

[3] A. Cuesta, Factores determinantes de la Reactividad de Fibras de Carbono y otros Materiales

Carbonosos, Tesis Doctoral, Universidad de Oviedo (1994).

[4] N. Iwashita, C.R. Park, H. Fujimoto, M. Shiraishi, M. Inagaki. Specification for a standard

procedure of X-ray diffraction measurements on carbon materials. Carbon 42 (2004) 701-714.

[5] M. Martínez, M. Vivas, S. Marrero, W. Meléndez, G. Garbán, A. Benavides. caracteristicas

morfologicas y cristalográficas del grafito de osumita, venezuela, y su uso como

geotermómetro. Estudios Geol., 59: 267-276 (2003).

PDF II. Base de datos para difracción de rayos X.

CaCO3 Carbonato de Ca: nº ref. 00-024-0027.

CaC2O4.H2O Oxalato de Ca Hidratado: nº ref. 00-020-0231.

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6. Thermal Analysis

This analysis has determined that the different substances are released from charcoal with

increasing temperature.

6.1. Methodology

Determining the presence or absence of hazardous substances in the release of the surface of

charcoal.

This technique is performed by a Differential Thermogravimetry coupling mass spectrometer

identifies substances released.

The technical specifications of the analysis are presented in the following table:

Horno de Grafito

Balanza TG Líneas de Gases Posibilidades

Rango de Temperatura Rangos de medidas

Transportador “Carrier”

1. Acoplamiento Masas

Ar, He, CO2 (con Espectrómetro Quadrupolar

PrismaTM QMS200)

Tª ambiente-1600oC Flujo “Carrier”

Rango rampa de Temperatura

± 200 mg

± 20 mg

Ar: 5.6-280 mL/min He: 0-200 mL/min CO2: 0-200 mL/min

2. Inyección Mezcla de Gases

0 – 99oC/min 3. Generador de humedad controlada (Wetsys)

Rango rampa de Temperatura habitual

Resolución ± 200 mg

Protector

0 - 30 oC/min Ar/He 4. Configuraciones:

Tiempo de enfriamiento

Resolución ± 20 mg

Flujo Protector TGA

45 min a Tª ambiente desde >1600 oC/min

16 mL/min (estándar)

DTA/DSC

The conditions for conducting the analysis are:

• Test Type: TGA / DTA + Bodies

• Treatment and temperature controlled atmosphere: oxidant: CAFE

• Temperature Ramp: 10 ° C / min

• Set Temperature: 900 ° C

• Periods Isothermal: Temperature: 30 ° C every 30 minutes

• Monitoring Gaseous by mass spectrometry

• Relations m / z = N (14), O (16), H2O (18), CO/N2 (28), NO (30), CH3OH (31, 32), O2 (32),

SH2 (34), Cl (35), CO2 (44), NO2 (46), C4H10 (58/59), SO2 (64) C6H6 (77, 78).

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• Gas or Gases: Air

• Total flow: 50 mL / min

• Time Temperature maintenance: 0 min

Conducting tests using air greatly complicates the quantification of CO due to the overlap of

the mass 28 from the CO and N2 signals. So your were quantified by difference.

6.2. Results

It keeps track thermogram common chemical species in the release of charcoal. This graph is

shown below.

Water monitoring (H2O). The presence of water in the system below 150-200 ° C indicates

desorption humidity extracted from the surface or pores of larger coal. Moreover, the water

released from the system at higher temperatures is related to adsorbed water or small closed

pores are destroyed or opened during the process of oxidation and molecular water from

surface groups present in the coal-OH type [1.2 ].

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Carbon dioxide monitoring (CO2). The figure presents a common profile of amorphous carbon,

with onset of oxidation temperatures well below normal temperatures and graphites coals

which typically range for the start of oxidation between 500-800 ° C for mineral coals [1.3] and

graphite above 700 °C. [4]. Showing in this sense better properties of oxidation (or

combustion) in comparison to the aforementioned systems.

The graph shown in the following figure shows an exothermic throughout the process, the

process is far below 750 ° C, indicating charcoal combustion [5,6]. In any case, we find typical

temperatures in the DTA curve shown in combustion of graphitic systems, whose maximum is

slightly above 800 ° C [5,6].

During the first stage, up to 100 º C has been detected an artifact that has led to a strong

fluctuation in the signal that is not real, so it is removed. Actual drift of heat flow would be

slightly upward in the first stage, since the water desorption process is slightly exothermic.

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Cuantification:

Masa inicial

(mg)

M final (mg):

cenizas / % peso H2O / mg CO2 / mg

C oxidado a CO2

CO / mg C

oxidado a CO

Masa inicial procedente de cenizas /

mg

21.79 0.75 /

3.44%p/p 2.24 50.94 13.89 11.46 4.91 0.75

CO Quantification was performed and taking all contributions to subtracting it to the obtained

mass loss in TG. Considering the contribution of NOx negligible compared to H2O, CO and CO2.

Besides considering that inorganic matter that makes up the ashes has not been altered in the

process of oxidation.

Considering the appearance of CaCO3 and Ca oxalate monohydrate alone (observed by XRD),

wherein the orientation ratio should be around 30% to 70% carbonate and oxalate, relative to

the intensities obtained (These proportions are not totally quantitative for what should be the

values obtained for orientation, except for the final mass, which is real), whose conversion

after combustion in air ends carbonate CaO + CO2 and CaO + 2CO2 + H2O for oxalate, we can

refine quantifying the data presented in the following table:

Masa inicial

(mg)

M final (mg):

cenizas / %

peso

CO2 procedente

de combustión de CaCo3 +

CaC2O4.H2O / mg

CO2 total /

mg

C oxidado a CO2

H2O procedente de oxalato

/ mg

H2O procedente

de humedad y

carbón

Masa inicial CaCo3 +

CaC2O4.H2O / mg // % peso

22.17 0.75 /

3.44%p/p 0.18 + 0.82 50.94 13.62 0.17 2.07

0.40 +1.37 / 12.52 % p/p

Rest Mass:

Within the masses included in the analysis, the result is shown in the third graph located below,

whose analysis is reported in comparison with monitoring the m / z = 18 corresponding to

water, have resulted in a flat spectrum, with the exception of m / z = 46 (NO2) having a very

small contribution.

Indicating no presence of compounds, or below the detection limit of the mass spectrometer, for this particular case below 0.1% by volume.

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These masses correspond to compounds such as alcohols CH3OH (31), sulphurised SH2 (34) and

SO2 (64), chlorinated Cl (35), hydrocarbons C4H10 (58/59) and aromatics C6H6 (77, 78).

Bibliography

[1] H. Aso, K. Matsuoka, A. Sharma, A. Tomita. Energy and Fuels 18 (2004) 1309-1314.

[2] H. Aso, K. Matsuoka, A. Tomita. Energy and Fuels 17 (2003) 1244-1250.

[3] D. González, O. Altin, S. Eser, A. B. García. Materials Chemistry and Physics 101 (2007) 137-141.

[4] J. Rodríguez-Mirasol, T. Cordero, J. J. Rodríguez. Carbon 34 (1996) 43-52.

[5] M. V. Nel, C. A. Strydom, H. H. Schobert, J. Paul Beukes, J. R. Bunt. Fuel Processing

Technology 92 (2011) 1042-1051.

[6] J.A. Turner, K.M. Thomas. Thermochimica Acta 294 (1997) 51-56.

[7] N. Raje, D. A. Aacherekar, A.V.R. Reddy. Thermochimica Acta 496 (2009) 143–150.

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7. Analysis of Volatile Organic Compounds (COV´s)

7.1 Methodology

This analysis consists in a characterization of the substances identified in the volatile matter in

the charcoal.

This technique is based on an analysis by gas chromatography detector coupled with flow

injection (FID). The methodology we have:

• A known amount of sample is extracted with a given volume of solvent.

• The extract was analyzed by gas chromatography with FID detector (flame ionization).

• The chromatographic separation was performed with a column of Phenyl Methyl

Siloxane 5% and the compounds were confirmed and quantified skilled in another

column of polyethylene glycol.

As an aside, note that the laboratory is accredited by ENAC for this methodology in charcoal

tubes, very similar matrix to the samples analyzed.

The compounds tested in the sweep are:

1,1,1-tricloroetano acetato de butilo cloroformo metil n-butil cetona

1,2-dicloroetileno acetato de etoxi propilo dibromoclorometano metil terc-butil éter

1,2,4- triclorobenceno acetato de i-butilo diclorobencenos metilpropilcetona

1,2-dicloropropano acetato de i-propilo diclorometano metilsobutilcetona

1,3,5-trimetilbenceno acetato de metilo diisobutilcetona n- propanol

1,2,3-trimetilbenceno acetato de n-amilo diacetato alcohol naftaleno

1,2,4-trimetilbenceno acetato de n-propilo dimetilformamida n-butanol

1-etoxi-2-propanol acetato de sec-butilo dodecano (c12) n-butil glicidil eter

1-metoxi-2-propanol acetato de vinilo decano (c10) n-octano

1-hexeno acetona epiclorhidrina n-heptano

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2,2,4-trimetilpentano acetonitrilo estireno n-nonano

2-(2-butoxietoxi)-etanol acrilato de etilo etanol n-pentano

2-butoxietanol acrilato de metilo eter etilico oxido de propileno

2-etiltolueno acrilato de n-butilo etil tert-butil eter piridina

2-etoxietanol acrilonitrilo etilbenceno sec-butanol

2-metoxietanol alcohol isoamílico h.c. alifaticos > nc9 tetracloroeteno

3-etiltolueno a-metilestireno h.c. alifaticos <= nc9 (execpto

nc6)

tetracloruro de carbono

3-metil pentano a-pineno h.c. aromaticos >= nc9 tetradecano (c14)

4-etiltolueno benceno h.c. totales (expresados nc6) tetrahidrofurano

4-vinil-1-ciclohexeno b-pineno hexano tolueno

5-metil 2-hexanona bromodiclorometano isobutanol tricloroeteno

3,4-viniltolueno bromoformo isopropanol xilenos (sumatorio)

acetato de 1-metoxi 2-

propilo

ciclohexano isopropilbenceno cot como n-hexano

acetato de 2-etoxietilo ciclohexanol limoneno

acetato de 2-metoxietilo ciclohexanona metil etilcetona

acetato de 2-nbutoxietilo ciclopentano metil isopropil cetona

acetato de etilo clorobenceno metil n-amil cetona

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7.2 Results

Parameter Units Results

Barrido COV´s µg/g < 10

If the result does not show any other substance identified in the above table means that have

not been detected during the analysis.

Fernando Miguel Naranjo Pérez

Lcdo. en CC. Químicas

Dtor. Tco. Cohexiona Consultores

Badajoz November 18th, 2013

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FRATELLI PADOVANI S.R.L.€¦ · Once the substance is identified unambiguously coded sample from FRATELLI PADOVANI S.R.L. with code CI-P-13-10 and your check-in in the first laboratory