Anda di halaman 1dari 13

Activated carbons for water treatment prepared by

phosphoric acid activation of hydrothermally treated

beer waste

Wenming Hao,a Eva Bjrkman,a,b Malte Lilliestrle, b and Niklas Hedin*a

a
Berzelii Centre EXSELENT on Porous Materials and Department of Materials and

Environmental Chemistry, Stockholm University, Stockholm, SE-106 91, Sweden

b
Biokol Lilliestrle & Co KB Sibyllegatan 53, SE-114 43 Stockholm, Sweden

Corresponding author: Tel/Fax +46-8-162417 / +46-8-152187

Email: niklas.hedin@mmk.su.se

1
Supporting information

Activated HTC beer waste

HTC beer waste

4000 3500 3000 2500 2000 1500 1000 500


-1
Wavenumber (cm )

Figure S1. Fourier transform infrared spectra of hydrothermally carbonized (HTC) beer waste

and activated carbon prepared form HTC beer waste

2
0.1
Effect

-0.2

X1 X3 X13 X23 X2 X13 X12 X14 X4 X24

Figure S2. Plot of the effects of the variables (Xn) on the response to BET surface area (Y2) for

the activated carbons prepared by chemical activation of hydrothermally carbonized beer waste

by H3PO4. Interaction effects are double digits.

3
0.10

Effect

-0.04
X3 X23 X13 X4 X24 X2 X12 X14 X1 X34

Figure S3. Plot of the effects of the variables (Xn) on the response to the yield (Y3) for the

activated carbons prepared by chemical activation of hydrothermally carbonized beer waste by

H3PO4. Interaction effects are double digits.

4
a)
3

Effect

-2.5
X3 X1 X2 X13 X12 X23

b)
1.2
Effect

-0.9
X3 X12 X13 X1 X2 X23

Figure S4. Plot of the effects of the variables (Xn) on the response to the median pore size (Y1)

at different N2 flow levels (a, high flow, b, low flow), for the activated carbons prepared by

chemical activation of hydrothermally carbonized beer waste by H3PO4. Interaction effects are

double digits.

5
a)
1.5

Effect

-1.8
X4 X3 X23 X2 X34 X24

b)
2.7
Effect

-1.8
X3 X24 X34 X2 X4 X23

Figure S5. Plot of the effects of the variables (Xn) on the response to the median pore size (Y1)

at different temperature levels (a, high temperature, b, low temperature), for the activated

carbons prepared by chemical activation of hydrothermally carbonized beer waste by H3PO4.

Interaction effects are double digits.

6
a)
1.2

Effect

-0.9
X3 X4 X13 X1 X34 X14

b)
2.5
Effect

-1.8
X3 X14 X1 X34 X13 X4

Figure S6. Plot of the effects of the variables (Xn) on the response to the median pore size (Y1)

at different activation time levels, (a, long time, b, shot time) for the activated carbons prepared

by chemically activation of hydrothermally carbonized beer waste by H3PO4. Interaction effects

are double digits.

7
Table S1. Yield and textual characteristics of activated hydrothermally carbonized beer

waste as determined from nitrogen adsorption data at -196 oC

Activation Activation Concentration Flow rate Surface area Pore volume Median
temperature time of H3PO4 of N2
Yield (m/g) (cm3/g) pore size
(%)
(C) (h) (%) (dm3/h) SBET Sext Vt Vmic (nm)

600 1 40 50 62.3 1039 882 0.737 0.068 2.61


700 1 40 50 58.1 747 562 0.460 0.076 2.95
600 3 40 50 55.0 998 891 0.782 0.048 2.89
700 3 40 50 51.9 1076 812 0,677 0.108 2.61
600 1 85 50 67.0 783 674 0.748 0.047 3.76
700 1 85 50 59.3 773 653 0.703 0.051 3.57
600 3 85 50 61.1 949 796 0.895 0.065 3.75
700 3 85 50 78.9 358 273 0.281 0.036 2.99
600 1 40 100 62.0 941 866 0.653 0.032 2.55
700 1 40 100 60.1 807 417 0.392 0.158 1.50
600 3 40 100 64.2 952 477 0.453 0.192 1.44
700 3 40 100 53.9 942 690 0.560 0.103 1.87
600 1 85 100 59.4 1073 835 0.978 0.101 4.82
700 1 85 100 66.4 586 474 0.476 0.046 3.10
600 3 85 100 75.7 874 714 0.766 0.067 3.39
700 3 85 100 75.8 481 258 0.300 0.090 2.21
650 2 60 75 67.7 861 745 0.793 0.049 3.59
650 2 60 75 57.6 919 833 0.904 0.038 3.80
650 2 60 75 66.1 1042 869 0.896 0.074 3.31

8
Table S2. Full factorial design matrix for chemical activation of hydrothermally

carbonized beer waste by H3PO4

Median
Flow SBET Yield
Sample Temperature Time Concentration pore size
rate (cm2/g) (%)
(nm)
(X1) (X2) (X3) (X4) (Y1) a (Y2) (Y3)
N1 -1 -1 -1 -1 2.61 1039 62.3
N2 1 -1 -1 -1 2.95 747 58.1
N3 -1 1 -1 -1 2.89 998 55.0
N4 1 1 -1 -1 2.61 1076 51.9
N5 -1 -1 1 -1 3.76 783 67.0
N6 1 -1 1 -1 3.57 773 59.3
N7 -1 1 1 -1 3.75 949 61.1
N8 1 1 1 -1 2.99 358 78.9
N9 -1 -1 -1 1 2.55 941 62.0
N10 1 -1 -1 1 1.50 807 60.1
N11 -1 1 -1 1 1.44 952 64.2
N12 1 1 -1 1 1.87 942 53.9
N13 -1 -1 1 1 4.82 1073 59.4
N14 1 -1 1 1 3.10 586 66.4
N15 -1 1 1 1 3.39 874 75.7
N16 1 1 1 1 2.21 481 75.8
N17 0 0 0 0 3.59 861 67.7
N18 0 0 0 0 3.80 919 57.6
N19 0 0 0 0 3.31 1042 66.1
a
Y1 is the median pore size, below which 50% of the total pore volume is
reached, using a density functional theory model.

9
Table S3. Analysis of variance for the responses (Y1, median pore size; Y2,

BET surface area and Y3, yield) for chemical activation of hydrothermally

carbonized beer waste with H3PO4

Y1 DFa SSb MSc Fd pe SDf


Total 19 182 9.60
Constant 1 169 169
Total Corrected 18 13.1 0.73 0.85
Regression 10 11.1 1.11 4.31 0.025 1.05
Residual 8 2.05 0.26 0.51
Lack of Fit 6 1.93 0.32 5.28 0.168 0.57
Pure Error 2 0.12 0.06 0.25
Y2 DFa SSb MSc Fd pe SDf
Total 19 162 8.52
Constant 1 162 162
Total Corrected 18 0.3 0.02 0.13
Regression 10 0.2 0.02 2.44 0.110 0.15
Residual 8 0.07 0.01 0.09
Lack of Fit 6 0.07 0.01 6.22 0.145 0.11
Pure Error 2 0.004 0.002 0.04
Y3 DFa SSb MSc Fd pe SDf
Total 19 62 3.24
Constant 1 61 61
Total Corrected 18 0.04 0.002 0.05
Regression 10 0.003 0.003 2.47 0.106 0.06
Residual 8 0.01 0.001 0.04
Lack of Fit 6 0.008 0.001 0.94 0.596 0.04
Pure Error 2 0.003 0.001 0.04
a
Degree of freedom. b Sum of the squares. c Mean square value. d
F-
distribution value. e p value. f Standard deviation.

10
A linear form of the Langmuir model was used for the regression analysis. It is expressed by1

Ce C 1
= e+ (1)
qe qm qmK L

where Ce is the concentration at equilibrium, qe is the amount of dye adsorbed by the adsorbent,

qm is the maximum adsorption capacity associated with complete monolayer coverage, and KL is

the equilibrium constant of adsorption.

RL is the dimensionless separation factor, which is an essential characteristic of a Langmuir

isotherm.2

1 (2)
RL=
1 + K LC 0

where KL is the Langmuir constant and C0 is the lowest initial dye concentration. The shape of

the isotherm can be evaluated by RL: unfavorable (RL > 1), linear (RL = 1), favorable (0 < RL <

1), irreversible (RL = 0).

A linear version of the Freundlich isotherm was used for regression analysis:3

1
ln q e = lnC e + ln K F (3)
n

where KF and n are constants, qe is the uptake on the carbon, Ce is the equilibrium concentration

in the aqueous phase.

A linear version of the Temkin equation was used for the regression analysis.4

11
q e = B ln A + B lnC e (4)

where B = RT/b, b is the Temkin constant related to heat of sorption, A is the Temkin isotherm

constant, R is the gas constant, and T is the absolute temperature (K).

Table S4. Langmuir, Freundlich and Temkin

isotherm model constants and correlation

coefficients for adsorption of methylene blue

Isotherm Parameters Values

Langmuir qm (mg/g) 338


KL (L/mg) 0.58
R2 0.99
RL 0.0025

Freundlich KF (mg/g) 183


n 7.82
R2 0.89

Temkin A (L/g) 5475


B (J/mol) 101
R2 0.95

12
Reference

(1) Langmuir, I. The constitution and fundamental properties of solids and liquids. J. Am.
Chem. Sojciedy 1916, 38, 22212295.

(2) Hall, Kenneth, R.; Eagleton, L. C.; Acrivos, A.; Vermeulen, T. Pore- and solid-diffusion
kinetics infixed-bedadsorption under constant-pattern conditions. Ind. Eng. Chem.
Fundam. 1966, 5, 212233.

(3) Freundlich, H. M. F. Over the adsorption in solution. J. Phys. Chem. 1906, 57, 385470.

(4) Temkin, M. J.; Pyzhev, V. Recent modifications to Langmuir isotherms. Acta


Physiochimica URSS 1940, 12, 217222.

13