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CHEM. R E . CHINESE U. 2006, 2 2 ( 3 ) , 360-363

Indirect Electrochemical Oxidation of 4-Amino-dimethyl-aniline

Hydrochloride *
1. Department

ZHANG Qiang , KANG Bo2 , XU Hong and LIN Hai-bo *

CoUege of Science, Beijing Imtifute of Technology, Beying loooSl, P. R. China ;
2. College of Chemistry, Jilin Universiry , Changchun 130021 , P. R. China

of Chemistry,

Received Dec. IS, 2W5

The indirect electrochemical oxidation of 4-amino-dimethyl-aniline hydrochloride containing Wastewater generated

from vanillin production is presented. Experiments were conducted at a constant current density of 30 mA/cm2 v i a a
TdRu-Ti-Sn ternary oxide coated anode and an undivided reactor. During the various stages of the electrolysis, panunetem such as the v+es of chemical oxygen demand( COD) and total organic carbon( TOC) were determined in
order to evaluate the feasibility of the electrochemical tmatment. The energy consumption and the current efficiency
during the electrolysis were calculated. The present study proves the effectiveness of the electrochemical treatment for
wastewater resulted from vanillin production.

Keywords Electrochemical oxidation; 4-Amino-dimethyl-aniline ; Wastewater treatment ; Vanillin

Article ID 1005-904O( u)o6)-03-360-04

Introduction
4-Amino-dimethyl-aniline hydrochloride is one of
the main components of the wastewater resulted from
vanillin production] which inhibits the normal activity
of the microorganisms of micmbial population, thereby
affecting the biological treatment process of vanillin.
Common treatment processes of wastewater containing
vanillin are complicated[*]. The degradation of 4-amino-dimethyl-aniline is the primary process for the treatment of vanillin.
Electrochemical technology has provided ideal
tools for addressing many environmental problems.
Electrochemical oxidation processes have attracted great
attention because of their versatility that makes the
treatment of liquids, gases and solids possible, their
environmental compatibility, and especially their capability in destructing the toxic and non-biodegradable organic compounds by means of direct or indirect anodic
oxidation. In fact, electrons are the effective substance
in an electrochemical process, which are clean reagents. In recent years, there has been a great demand
for electrochemical methods that have been successfully
applied in the treatment of landfill leachate, tannery
wastes, oil refinery wastewater, textile wastes, etc. [ 3 1 .
In a direct anodic oxidation process, pollutants are

first absorbed on the anode surface and then destroyed

by the anodic electron transferring reaction. In an indirect anodic oxidation process, strong oxidants, such as
hypochlorite , chlorine, ozone and Fenton reagents, are
electrochemically generated. Pollutants are then destroyed in the bulk solution by the oxidation reactions
with the generated oxidants. All of the oxidants are
gentlated in situ and are utilized immediately[41. Chlorides with high concentrations are contained in the
wastewater from vanillin production, 90 there is actual
significance in the study on the degradation of 4-aminodimethyl-aniline hydrochloride via an indirect electrochemical oxidation pmcess.
In this paper are reported COD and TOC removals, the energy consumption, the current efficiency and
the kinetics during the indirect electrochemical oxidation of 4-amino-dimethyl-aniline hydrochloride.

Experimental
1 Equipment
An undivided electrolytic cell( 250 cm3) was assembled to perform the electrochemical oxidation degradation experiments. The anode and cathode were positioned vertically and were parallel to each other. The
anode material was a Ti/Ru-Ti-Sn ternary oxide coated
anode on titanium mesh ( 30 mm x 30 mm x 1.0

Supported by the National Natural Science Foundation of China( No. 20573045).

To whom correspondence should be addressed. E-mail: W 1 0 0 mail. jlu. edu. cn

**

ZHANG Qiang et al.

No. 3

36 1

mm) "I. A titanium mesh ( TA, , 30 mm x 30 mm x

1 . 0 mm) was used as the cathode. Both of the total effective surface areas of the anode and cathode were all
3.0 cm x 3.0 cm. The distance between the electrodes
was 5.0 mm. The electrolyte solution consisted of
100 mg/L 4-amino-dimethyl-aniline hydrochloride and
0.5 moVL Na, SO, as the sustainable electrolyte at
pH =6.38. The current input was controlled by a stabilized DC power supply.

CE =ACOD F V/(8 I At)

where CE is the current efficiency ( % ) ; ACOD =
COD in,tid - COD fid( gO,/L) ; F is the Faraday constant( 26.8 A * h ) ; V is the volume of electrolyte( L) ;
8 is the amount of oxygen formed by 1 Faraday of electric quantity at 100% yield; I is the current( A ) ; and
At is the time of electrolysis( h ) .

2 Reagents
All the chemicals used were of analytical grade.

1 MtialCharacteristics

All the solutions were prepared from double distilled

water.

3 Procedure
All the experiments were conducted at a current
density of 30 &cm* under galvanostatic conditions at
mom temperature [ (25 0.5 ) T 1. The solution was

constantly stirred at 200 r/min with a magnetic stirrer

in order to maintain the uniformity of the electrolyte solution. The COD ( chemical oxygen demand ) values,
the TOC( total organic carbon) values, the cell voltage
and the coulomb consumption were determined and analyzed at the given electrolysis durations ( 1 . 0 , 2 . 0 ,
3 . 0 , 4.Oand5.O h ) .

4 AdyticalMethods
The chemical oxygen demand( COD) values were
determined with a Model 571 COD analyzer( Shanghai,
P. R. China) which was operated at 150 T for 20
min. The total organic carbon( TOC) values were determined with a Model TOC-VCPH TOC analyzer( Shimadzu Co. , Japan. ) , which was operated via the oxidative combustion infrared method at 680 C with a
sample injection amount of 200 pL, an oxygen flow rate
of 12 m u m i n , and a strip time of 3 min. The pH of
the solution was measured with a Model pHS-25 pH
meter ( Shanghai Hongyi Instrumentation Co. , Ltd. ,
P. R. China).
5 Energetic and Economic Balance of the Employed Electrochemical Oxidation

lation :

Results and Discussion

The initial characteristics of the sample are listed
in Table 1. It is known from literature that the initial
pH does not have a significant effect on the degradation
of organic pollutants by the indirect electrochemical oxidation in a range of 3.0-10.0 at the Ti/Ru-Ti-% anodeL6]. Although indirect electrochemical oxidation of
organic compounds was camed out mainly by the Electrogenerated ehlorine/hypochlorite , the production rate
of chlorine/hypochlorite was not affected by the initial
pH condition. Hence, in the present study, the electrochemical degradation experiment for 4-amino-dimethyl-aniline hydrochloride was conducted without pH
adjustments.
Table 1 The initial characteristics of the sample

COD/( mg L - I

PH

6.38

n>C/( mg * L-I )

143.00

38.04

Treatment Efficiency in Terms of COD with

and without Chloride

The present investigation aimed at examining the

influence of chloride ions on the anodic oxidation of
4-amino-dimethyl-aniline hydrochloride in the wastewater from vanillin production. Hence, the experiment
was carried out by adding 8 . 5 mmoVL chloride as an
oxidant to evaluate the degradation efficiency.
Fig. 1 shows the treatment efficiency in terms of
COD removal after 5 h electrolysis at the Ti/Ru-Ti-Sn
anode, under the condition of a current densitv of 30
1601
1

The energy consumption was determined by the

following equation :

W=I.U-At/(ACOD* V010-~)
where W is the energy consumption of degradation per
kilogram of COD( kW h kg-'COD) ; I is the current( A ) ; U is the cell voltage of electrolysis( V ) ; AZ
is the time of electrolysis( h ) ;A ( COD) = COD ,niud COD ( mg/L) ; and V is the volume of an electrolyte
(L).
The current efficiency during the electrochemical
oxidation can be obtained by means of the following re-

40 60

2
3
4
Electrolysis time/ h

COD removal during the electrochemical treatment of the sample without ( a ) and with 8.5
mmd/L chloride( b ) .

CHEM. RES. CHINESE U.

362

mA/cm2 with or without the addition of chloride. The

COD values without( trace a ) and with chloride( trace

b ) decrease from the initial value of 143.00 to 113.00

and 37.00 mg/L at the end of electrolysis, respectively. However, the degradation efficiency in terms of
COD removal is notably high in the case with chloride.
The COD removal rate is 74. 13% under the condition
with chloride, while it is only 22. 38% under the condition without chloride. This result maybe caused by
increasingly oxidizing 4-amino-dimethyl-aniline hydrochloride in the presence of a high chloride concentration, because under constant current electrolysis, chloride with a high concentration may produce an adequate
amount of hypochlorite or chlorine, which favors the
fast indirect oxidation.

3 The Formation of Stable Compounds

The following conditions ( initial pH = 6. 38, a
chloride concentration of 8. 5 mmoVL, and a current
density of 30 rnA/cm2 ) were maintained during 5 h
continuous electrolysis at the Ti/Ru-Ti-% anode. Total
organic carbon( TOC) analysis can be used to quantify
all the weight fractions of total petroleum hydrocarbons
(THP) and can be performed quickly and easily on
site. The determination of TOC values is a gross measure of all forms of organic carbon including petroleum
hydrocarbons and natural matter"].
Trace b in Fig. 2 shows the relatively efficient mineralization of 4-amino-dimethyl-aniline hydrochloride
up to 5 h. The TOC value reduces fmm an initial value
of 38.04 mg/L to 22. 80 mg/L at the end of the electrolysis. The TOC removal rate is 40.06% , which is
less than the COD removal. The evolution of strongly
oxidized species during this indirect electrochemical
degradation is reflected by the concomitant decrease of
the COD/TOC ratio from 3 . 7 6 to 1.61 ( trace a ) ,
which indicates that stable compounds were formed.
However, such stable compounds will be degraded with
the elongation of the electrolysis time according to the
160 1

40

20
0

Fig.2

v-

3
Electrolysis time/h
2

-Y
4

The values d the ratio d COD to Toc(0)

rutd TOC(Q)vs. the time of iadirect electrochemical oxidation.

VOl. 22

declination of COD and TOC values.

These observations suggest the following sequence
for the process:

cI,/oc1-

Organic compounds -Intermediate

products + CO,

+ H,O

(F-t)
C1,/OcI -

-CO,

stable

+ H,O

Because of the presence of chloride, active chloro

species ( C1,/OC1- ) are generated first in the indirect
oxidation process :
2C1 - - - L I Z+ 2e
(1)
C1, +H,O-+HOCl+H' +C1(2)
HOCI-H + + OC1(3)
The organic compounds( pollutants) are then destroyed in the bulk solution by the active chloro species
and further degrade to other organic intermediate products.
4 The Kinetics of Reaction
In an indirect electrochemical oxidation process,
the COD removal rate is proportional to the total concentration of the organic compounds( pollutants) and to
the concentration of chlorine or hypochlorite because
the indirect oxidation is mediated by chlorine or hypochlorite. Therefore, the kinetics for COD .removal is
- d[ COD]/dt= k[ COD] [ C12]
(4)
where [COD] is the concentration of the organic compound( mg/L) ; t is the time of reaction( s ) ; k is the
rate constant( L * mol-' * s - ' ) ; and [ Cl,] is the concentration of chloride( mg/L).
Electrochemical treatment involves the application
of an electrical current to the effluent, to convert chloride to chlorine and hypochlorite. Chlorine and hypochlorite can oxidize the organic compounds and then
can be reduced to a chloride. The process is repeated
in a catalytic fashion. Therefore, the concentration of
chlorine or hypochlorite during the electrolysis is assumed to be a constant and so eq. ( 4 ) can be written
as a pseudo first-order kinetic equation :
- d[ COD]/dt = - k'[ COD]
(5)
where [COD] is the concentration of the organic compounds( mg/L) ; t is the time of reaction( s) ; and k' is
the rate constant ( s - ' ) .
'The logarithmic plots of the COD concentration
show the plot of the rate expression:
In[COD],/[COD],,=
-k't
or
In c,/co = - k ' t
(6)
where [ COD], or c, is the COD value at time t
( mg/L) ; [ COD 3, or co is the initial COD value
(mg/L) ; t is the time of reaction( s) ; and k' is the
rate constant ( s - ' ) .

ZHANG Qiang et al.

No. 3

363

Table 2 displays the rate constant ( k' ) and the

corresponding y2 values for COD removal.
Table 2 Summary of the electrochemical treatment d the initial sample
Charge paseed

'

( Ah * kg - COD)
5.09 10'

Initial COD/

'

Final COD/

( mg * L - ) ( mg L - )
143
37

Kinetica
Rate constant k'( a - I )
2.93x10-~

Conclusion
The study shows that the proposed indirect electrochemical oxidation process of 4-amino-dimethyl-aniline hydrochloride-containing wastewater generated
from vanillin production is effective. At a constant current density of 30 mA/cm2 via the Ti/Ru-Ti-% ternary
oxide coated anode and an undivided reactor, the electrolysis has been carried out for 5 h , the COD and TOC
removal rates are 74. 13% and 40.06% , respectively,
and the COD/TOC ratio decreases from 3.76 to 1.61,
which indicates the stable compounds have been
formed, but such stable compounds will be degraded
with the elongation of electrolysis time according to the
declination of COD and TOC values. Hence, it is feasible for wastewater from vanillin production to be trea-

Current elhiency
7'

(%

0.9778

27.40

Cell voltage/V
3.41

Energy consumption/

(kWh kg-' COD)

122.60

ted by electrochemical methods.

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