POLLUTANTS REMOVAL ONTO NOVEL ACTIVATED CARBONS MADE FROM LIGNOCELLULOSIC PRECURSORS

Introduction
Phenol and mercury are two important toxic materials listed as priority pollutants by the US Environmental Protection Agency (EPA) and also by the EU. Phenol is considered to be very toxic to humans through oral exposure with symptoms including muscle weakness and tremors, loss of coordination, paralysis, convulsions, coma, liver and kidney damage, headache, fainting and other mental disturbances. The ingestion of 1g has been reported to be lethal. Inhalation and dermal exposure to phenol is highly irritating to the skin, eyes, and mucous membranes in humans. Mercury and its compounds act as dangerous and insidious poisons, with the possibility of adsorption not only through the gastrointestinal tract but also through the skin and lungs. After adsorption, mercury circulates in the blood and is stored in the liver, kidneys, brain, spleen and bone, thereby leading to several health problems such as paralysis, serious intestinal and urinary complications, dysfunction of the central nervous system and, in more severe cases of intoxication, death. The soluble compounds of mercury are particularly toxic because their adsorption is very fast. Ingesting a dose of less than 0.5 g can prove to be fatal. The increasing necessity for the reduction of phenol and mercury discharges and the removal of the pollutants from wastewaters before the transport and re-cycling of the latter into the environment requires the need for research and development of better methodologies that can provide effective and total removal from liquid effluents. The use of activated carbons can be considered a costeffective method and seems to have an advantage over the other available methods thanks to the higher removal efficiency and the flexibility of the industrial unit operation. The adsorption of phenol and mercury from dilute aqueous solutions onto new activated carbons was studied. These included activated carbons produced from novel precursors, namely rapeseed, vine shoots and kenaf, and samples oxidised with nitric acid in liquid phase.

From lignocellulosic precursors to activated carbons: The Transformation

HNO3 Oxidation
Rapeseed

CO2 Activation @ 700 and 800C C738 K748 V840 V870

Vine shoots Kenaf

C738Ox K748Ox V840Ox

Hg

Effect of concentration 10-1500mg/L Hg2+ HgCl2 2[HgCl4]

Effect of concentration 0.1-2mM Effect of pH 3-13 Pollutants Removal Phenol

The Carbons Superpowers

Porosity BET DR S ABET (m2g-1) Vs (cm3g-1) Aext (m2g-1) V 0 (cm3g-1) C738 1112 0.52 126 0.47 C738Ox 827 0.35 78 0.35 K748 1021 0.45 84 0.45 K748Ox 962 0.45 20 0.41 V840 856 0.44 26 0.40 V870 1173 0.53 31 0.47 V840Ox 646 0.29 41 0.25 Sample

pzc 9.63 2.32 9.98 2.05 9.71 9.84 2.10

Type I isotherms Microporous solids Pristine carbons with basic properties Oxidation leads to significant changes to acid-base characteristics but only a slight change onto porous structure The use of rapeseed, vine shoots and kenaf as precursors for activated carbon production is very motivating

V870

V840
Arbitrary Units (a.u.)

(002)

(10)
C738 Ox

C738

10

20

30

40
o

50

60

2 ( )

The use of the Carbons Superpower to adsorb mercury and phenols, the bad guys

Hg

Hg(II) species Sample V840 [HgCl4]

2-

pzc 9.71 2.10 9.84 9.71 2.10 9.84 9.71 2.10 9.84

pHinitial Net surface charge Max Ads /mgg + 6 + + 5 + + 3 + 190 89 203 515 103 583 710 1103 895

-1

Sample C738 C738Ox K748 K748Ox

pzc 9.63 2.32 9.98 2.05

pKa pHinitial (phenol) 9.95 7.5

Phenol

V840Ox V870 V840

molecular

Net surface charge ~0 ~0 -

Max Ads/mgg-1 84.1 57.0 82.6 63.1

HgCl2

V840Ox V870 V840

100 90 K748 K748 Ox C738 C738 Ox

100

100 80 60 40 K748 K748 Ox C738 C738 Ox

2 4 6 8 K748 C738

Adsorbed amount (mg/g)

Hg2+

V840Ox V870
3

80 70 60 50 40 30 20 10

60

K748 Ox C738 Ox

1,0

[HgCl4]22

HgCl2
nads (mmol/g) nads (mmol/g)

Hg2+

40

20

20 0

nads (mmol/g)

0 0,0
1

0
0,1 0,2 0,3
3

0,4

0,5

10

12

14

0,5

V870 V840 V840 Ox

Ce (mmol/dm )

pH

0,0
0 2 4 6

0
0 2 4

0
0 2 4 6

Oxidised samples have much less adsorption capacity than the corresponding pristine activated carbon The phenol adsorption for pH less than 10 is independent of the solution pH. On the other hand, for pH values higher than 10 a noteworthy decrease in the phenol removal was observed. Therefore, we can conclude that phenol adsorption occurs via two possible mechanisms being the first one attributed to the adsorption by means of dispersive interactions between the phenol aromatic ring and the activated carbon aromatic structure. In this case the electrostatic interactions dont have a significant role on the adsorption. The second mechanism, which is based on the dispersive attractive forces and the electrostatic repulsion interactions, occurs when phenol is predominantly in the phenolate form and the activated carbon surface is negatively charged.

Ceq (mmol/L)

Ceq (mmol/L)

Ceq (mmol/L)

Adsorption capacity Hg2+ > HgCl2 > [HgCl4]2The maximum adsoprtion capacity values compare quite well with other results published for similar systems The results also indicate that the possible effect of electrostatic interactions is not relevant for the adsorption process and also that the molecular/ionic dimensions and the porosity of the samples are the critical factors for the mercury uptake. The only exception is the adsorption of Hg2+ onto V840Ox where the electrostatic attraction can have a positive influence on the mercury uptake. In this case, the maximum adsorption capacity increases despite the decrease of the apparent BET surface area and of the pore volume

The great final: the SuperCarbon wins Activated carbons from rapeseed, vine shoots and kenaf are promising materials to be used for contaminated water treatment
Acknowledgements The authors are grateful to the Fundao para a Cincia e Tecnologia (Portugal) and the European Regional Development Fund (FEDER) for financial support (Project PTDC/CTM/66552/2006)

T7 ID 151

J.M. Valente Nabais1, C. Laginhas1, P.J.M. Carrott1, M.M. Ribeiro Carrott1, J.A. Gomes1, Suhas1, A. Ramires1, S. Roman2 1Centro de Qumica de vora & Dep. de Qumica, Univ. de vora, Rua Romo Ramalho n 59, 7000-671 vora, Portugal 2Departamento de Fsica Aplicada, Universidad de Extremadura, 06071, Badajoz, Spain E-mail : jvn@uevora.pt
For more details please see Extended Abstract and Journal of Hazardous Materials 167 (2009) 904-910

Phenol Ionisation (%)

80 Phenol Removal (%)