Journal of Cleaner Production 15 (2007) 920e926

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A clean production process of sodium chlorite from sodium chlorate

Yu Qian*, Yun Chen, Yanbin Jiang, Lijuan Zhang
School of Chemical Engineering, South China University of Technology, Wushan Street, Guangzhou 510640, PR China
Received 17 February 2004; accepted 9 July 2004
Available online 28 December 2005

Abstract

This paper presents a novel cleaner production process for producing sodium chlorite by reducing sodium chlorate with hydrogen peroxide.
In the new process, chlorine dioxide is generated by reducing chlorate ions with hydrogen peroxide in the presence of sulfuric acid: it then reacts
with aqueous sodium hydroxide solution and hydrogen peroxide to produce sodium chlorite. The reaction conditions that were experimentally
investigated included: reaction temperatures, concentrations of sodium chlorate solution, molar ratio of NaClO3:H2SO4:H2O2, and acidity. Waste
acid in the chlorine dioxide generator is dramatically reduced with recycling in the new process. The by-produced sodium sulfate in sulfuric acid
is minimized and reclaimed.
Ó 2005 Elsevier Ltd. All rights reserved.

Keywords: Hydrogen peroxide; Chlorine dioxide; Sodium chlorite; Clean production

1. Introduction high investment and complicated operation, while the

Sodium chlorite is a highly efficient bleaching agent and ox-
idative disinfectant, widely applied in bleaching of textile, fiber,
pulp and paper. It is characteristic of lower harm to fiber. It is
also used to whiten sugar, starch, grease, ointment and wax.
When used in purifying water, little of remained chlorine would
be found. It is also used extensively in sterilization, and deodor-
ization in sewage treatment processes.
Since reaction conditions to produce chlorine dioxide from
sodium chlorite are mild, sodium chlorite is the main feed-
stock chemical for producing chlorine dioxide in mini-type
generators. Chlorine dioxide used in aqueous solution is of
considerable commercial interest in pulp bleaching, water pu-
rification, fat bleaching, medical treatment, sanitation, food
processing, aquiculture, and for the removal of phenols from
industrial wastewater. Chlorine dioxide is generally generated
from sodium chlorite in dilute acid, which is easier than pro-
ducing it from sodium chlorate. Therefore, there is a huge de-
mand to sodium chlorite in the marketplace.
Sodium chlorite is manufactured in two ways: electrolysis
and reduction. The electrolysis method is characteristic of
* Corresponding author. Tel.: þ86 20 87112046; fax: þ86 20 87113735.
E-mail address: ceyuqian@scut.edu.cn (Y. Qian).
reduction method is used in most of the plants to produce
sodium chlorite. Production of sodium chlorite with a reducing
agent consists of two steps: (1) preparation of chlorine dioxide
by reacting sodium chlorate in sulfuric acid, and then (2)
reaction of chlorine dioxide with a reducing agent in sodium
hydroxide solution. The first step is the key to determine
product economics and production technology. In industrial
production, the chlorine dioxide generation is generally
based on the reduction of sodium chlorate by reducing agents
such as sulfur dioxide, hydrochloric acid, sodium chloride,
methanol, and most recently, hydrogen peroxide, at high
acidity [1].
There are a number of conventional chloride-based ap-
proaches to produce chlorine dioxide, named as R2, R3, R5,
and R6 [2]. A typical approach is based on sodium chloride.
The main stoichiometry of the reaction is [3]:
2NaClO3 þ 2NaCl þ 2H2 SO4 / 2ClO2 þ 2Na2 SO4
þ Cl2 þ 2H2 O ð1Þ
One of the disadvantages in using chloride ions as the re-
ducing agent is that, for each mole of chlorine dioxide formed,
half a mole of chlorine gas and 1 mol of sodium sulfate are

0959-6526/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.jclepro.2004.07.008
 Y. Qian et al. / Journal of Cleaner Production 15 (2007) 920e926
produced. In the industry, sodium chlorite has to be used to ab-
sorb chlorine for purifying the product chlorine dioxide.
Solvey and R8 processes are methanol-based production of
chlorine dioxide. Stoichiometry of R8 reaction is as follows
[4,5]:
30NaClO3 þ 7CH3 OH þ 20H2 SO4
/ 30ClO2 þ 10Na3 HðSO4 Þ2 þ 3HCHO þ 26H2 O
þ 4CO2
No chlorine is produced in the methanol-based processes.
However, it is still characteristic of several shortcomings:
 First, methanol is oxidized stepwise to formaldehyde,
formic acid, and carbon dioxide. In commercial genera-
tor, oxidation of formic acid is slow. Formic acid is
thus accumulated as a by-product. The fact that signifi-
cant amounts of formic acid and methanol are found in
solution in the chlorine dioxide absorber indicates that
these chemicals do not react completely but instead
volatize.
 Second, when ClO2 product is used in bleaching, the un-
reacted methanol constitutes a pollution load to the sec-
ondary effluent treatment system of final users.
 Third, the required high acidity for operation produces
waste sodium sesquisulfate, which is of little industrial
use.
 Fourth, methanol as a combustible chemical constitutes
a hazard to operators at the workplace.
When sulfur dioxide based process is adopted, chlorine di-
oxide product is vulnerable to contamination due to the pres-
ence of sulfur dioxide. Chlorine is also found in this process.
Mathieson process and R1 are similar processes. The stoichi-
ometry is:
3NaClO3 þ 4SO2 þ 3H2 O / 2ClO2 þ Na2 SO4 þ 3H2 SO4
þ NaCl
Inadequacies in above-mentioned traditional processes
have led to further research on the hydrogen peroxide-based
process. The main stoichiometry of the reaction using hydro-
gen peroxide as the reducing agent is as follows:
2NaClO3 þ H2 SO4 þ H2 O2 / O2 þ 2ClO2 þ 2H2 O
þ Na2 SO4
There are a number of advantages of a hydrogen peroxide-
based process over the other approaches:
 less salt cake (Na2SO4) produced;
 elimination of an organic reducing agent;
 production of significant amounts of by-product chlorine;
 faster reaction rate.
This process can be easily used in existing facilities as
a substitute and can also increase capacity. When compared
921
with sulfur dioxide and methanol, at the same operating con-
ditions, the hydrogen peroxide-based process has the higher
yield in terms of chlorine dioxide based on the amount of chlo-
rate reacted. Calculated as chlorate transformed, yield of chlo-
rine dioxide in the hydrogen peroxide-based process reaches
more than 95%, while yield of other processes are around
90% [4e6].
The main drawbacks of the above-mentioned processes are
ð2Þ the formation of sodium sulfate as a by-product, which has to
be removed from the reactor, either in the form of a solid salt
cake or as a waste acid. It is hard to find any use of the salt
cake currently and it is normally regarded as an unwanted
by-product. In order to avoid formation of sulfate by-product,
it has been found to be possible to provide all the acid needed
for the chlorine dioxide generation from chloric acid, which
can be prepared electrochemically from sodium chlorate.
Such methods are described in, for example, U.S. Patents
[7e9]. However, it has been found to be difficult to achieve
satisfactory efficiency in production of strong chloric acid,
which is desirable in order to provide efficient chorine dioxide
generation. Twardowski discloses a process in which chlorine
dioxide is generated from sodium chlorate and hydrochloric
acid, in which process the generator liquor is acidified electro-
chemically and recycled back to the reactor [10]. However,
this process necessarily results in co-formation of chlorine,
which is not welcome in modern environmentally friendly
bleaching processes.
There are many U.S. Patents [11e14] disclosing the elec-
trolytic conversion of sodium sulfate into sulfuric acid and
sodium hydroxide. Most of them make use of electrolytic
cells employing diaphragms or ion permeable membranes
to separate the product solutions from the feed solution,
thus avoiding contamination of the products by the feedstock
material.
The objective of the proposed cleaner production process
presented in this paper is to make rational use of resources,
to minimize harm to humankind and the environment, and
for best social benefits in the product manufacture and during
ð3Þ
consumption. The advantages of hydrogen peroxide-based
chlorine dioxide production can be a solid foundation of cleaner
production of sodium chlorite.
The optimal operating conditions and how to make use of
waste acid in reaction system were investigated and are pre-
sented in this paper. In the end of the paper, a novel cleaner
production process for producing sodium chlorite, with mini-
ð4Þ mal resources used and wasted, and maximal economic poten-
tial, is put forward.
2. Reaction mechanism
The following is the basic reaction equation reducing
sodium chlorate with hydrogen peroxide as the reducing agent
in the presence of sulfuric acid [15]:
H2 O2 þ 2ClO þ
3 þ 2H / O2 þ 2ClO2 þ 2H2 O ð5Þ
922 Y. Qian et al. / Journal of Cleaner Production 15 (2007) 920e926
When the concentration of sulfuric acid is higher than
5.5 mol L1, the produced salt is bisulfate. The reaction stoi-
chiometry is:
2NaClO3 þ 2H2 SO4 þ H2 O2 / O2 þ 2ClO2 þ 2H2 O
þ 2NaHSO4
When the concentration of sulfuric acid is between
2.5 mol L1 and 5.5 mol L1, little chlorine is found in the
by-products. Reaction rate and yield are high, while a small
quantity of sodium sesquisulfate is produced. The correspond-
ing reaction stoichiometry is as follows:
6NaClO3 þ 4H2 SO4 þ 3H2 O2 / 3O2 þ 6ClO2 þ 6H2 O
þ 2Na3 HðSO4 Þ2
When the concentration of sulfuric acid is in a range from
1.0 mol L1 to 2.5 mol L1, a high reaction rate is achieved
over other preparation methods, no catalyst is needed. Neutral
salt is produced in this case. The corresponding reaction is:
2NaClO3 þ H2 SO4 þ H2 O2 / O2 þ 2ClO2 þ 2H2 O
þ Na2 SO4
The reaction stoichiometry of chlorine dioxide absorption is:
2ClO2 þ 2NaOH þ H2 O2 / 2NaClO2 þ O2 þ 2H2 O
3. Experimentals and chemical analysis
Experimental facilities were set up to investigate the new
process and conditions of chlorine dioxide generation and
sodium chlorite production. It is shown in Fig. 1. The exper-
imental installation consists of a chlorine dioxide generator,
NaOH+H2O2
air
dilute ClO2
cooling water
absorber ¢ ñ
H2SO4 NaClO3
+H2O2
ClO2 generator
Fig. 1. Lab apparatus for sodium chlorite production from hydrogen peroxide.
several chemical containers in series of absorbers, buffer,
and a vacuum pump. A four-neck round bottle reaction
flask, submerged in a bath of constant temperature, was
used as the reactor to generate chlorine dioxide. Sodium chlo-
rate solution is pre-mixed with hydrogen peroxide. Sulfuric
ð6Þ acid and sodium chlorate with mixed hydrogen peroxide are
added synchronously into the flask at a preset ratio. All of
the ingredients were fed to the reactor very quickly. One
mouth of the flask is for introducing air, while the other mouth
is for withdrawing chlorine dioxide gas from the reactor. The
reactor is operated under 0.5 atm. Ambient air is used to mix
the reaction liquid and to dilute the generated chlorine diox-
ide. The generated chlorine dioxide is introduced to and
absorbed through a series of three absorbers. The mixing
ð7Þ solution of sodium hydroxide and hydrogen peroxide enters
from the top of the absorber, while the product liquid is col-
lected in the bottom of the absorber when reaction is over.
Remnant gas is mostly nitrogen and oxygen; it is pumped
out through a buffer.
Samples of the reactor liquid were taken into a fixed quantify
flask holding cold water after each experiment was completed.
The cold water not only dilutes the sample but also quenches the
ð8Þ reaction. The sample was then neutralized with sodium hydrox-
ide. It was heated to decompose H2O2. The conversion of chlo-
rate does not develop further since there is no acid during the
ð9Þ analysis. The chlorate concentration was determined by iodo-
metric titration. Products, Cl2 and ClO2 were analyzed by titrat-
ing the contents of the KI bubblers at neutral and acidic
conditions with 0.1 N sodium thiosulfate using a single pin Pt
electrode and an Ag/AgCl reference electrode. All analyses
were performed with a Fisher Scientific computer-aided titrim-
eter. Analyses were replicated. Deviation in results is less than
2%, which is considered to be satisfactory. For the detailed ex-
perimental procedures, refer to Ref. [16].
effluent
absorber III
absorber II
gas
water
buffer vacuum pump
NaClO2+NaClO3+NaCl
 Y. Qian et al. / Journal of Cleaner Production 15 (2007) 920e926 923

4. Results and discussions
To determine the optimal reaction conditions and optimal
reaction yield in the chlorine dioxide production process, the
orthogonal design of experiments with factorial analysis was
employed. Five factors and four levels were adopted in the ex-
periments. The five factors investigated were:
A: reaction temperature, which is also the bath temperature
and kept constant during the reaction;
B: concentration of sodium chlorate, calculated as in the
pre-mixed feed solution of sodium chlorate and hydro-
gen peroxide;
C: molar ratio of hydrogen peroxide to sodium chlorate, in
the pre-mixed feed solution;
D: concentration of sulfuric acid, after mixing in the reac-
tor, but prior to the beginning of the reaction;
E: molar ratio of sulfuric acid to sodium chlorate, based
upon the amount of these species fed into the reactor.
Experimental data are shown in Table 1. The last column
shows the conversion rates of sodium chlorate. All conversions
were measured when the reaction had been conducted for 2 h.
After reacting for 2 h, sodium chlorate conversions in most of
experiments were found to reach a constant. Since the efficiency
of reaction of hydrogen peroxide with chlorine dioxide is near
100% in the solution of sodium hydroxide, sodium chlorite
yield is basically the same as the conversion of sodium
chlorate.
A preliminary analysis of the experimental results led to an
understanding that the main factors influencing sodium chlo-
rate conversion are acidity and temperature. Sodium chlorate
concentration, molar ratio of sulfuric acid to sodium chlorate,
and sulfuric acid concentration, are related and vary with each
other.
Sodium chlorate conversion reaches 95e100% under the
following conditions: temperature between 50 and 70  C, sul-
furic acid concentration between 4 mol L1 and 5.5 mol L1,
molar ratio of hydrogen peroxide to sodium chlorate between
0.5:1 and 0.7:1, sodium chlorate concentration between
450 g L1 and 550 g L1, and molar ratio of sulfuric acid to
sodium chlorate between 2.3:1 and 2.5:1, respectively.
Detailed analyses and discussion on the effects of several
main process parameters on the reaction are as follows. In
the experiments, factor E, the molar ratio of sulfuric acid to so-
dium chlorate was documented to be not sensitive to reaction
results, thus, it was maintained at 2.3:1.
4.1. Temperature
When hydrogen peroxide is used as a reducing agent to re-
act with sodium chlorate in sulfuric acid, the rate of chlorine
dioxide formation is 0.65 orders of sodium chlorate, 1.32 or-
ders of hydrogen peroxide concentrations, to contrast to
a 5.21 order of the sulfuric acid. The reaction activation energy
is found to be 90.2 kJ mol1 [17]. These all facilitate the for-
mation of chlorine dioxide. As is shown in Fig. 2 the conver-
sion reaches 78.5% at a temperature of 40  C. It is also shown
in Fig. 2 that sodium chlorate conversion increases as reaction
temperature increases. When temperature, concentration of
sulfuric acid, concentration of sodium chlorate and molar ratio
of hydrogen peroxide to sodium chlorate are 40  C,
6.5 mol L1, 550 g L1 and 0.6:1, respectively, sodium chlo-
rate conversion is 99.6%. When temperature is in the range
of 50e70  C, the highest conversion is nearly 100%. A high
yield is obtained in this temperature range. In case of temper-
atures exceeding 100  C, chlorine dioxide would decompose
and chlorine would be generated.
4.2. Concentration of sulfuric acid
Sulfuric acid is used in production process. The effect of
concentration of sulfuric acid on NaClO3 conversion is shown
in Fig. 3. When the concentration of sulfuric acid is between
1.0 mol L1 and 2.5 mol L1, production rate of chlorine
dioxide is slow compared with the rate at higher acid

Table 1
Sodium chlorate conversion in perpendicular experimentation
Level combination A (  C) B (g NaClO3 L1) C (mol H2O2/ D (mol H2SO4 L1) E (mol H2SO4: NaClO3
mol NaClO3) mol NaClO3) conversion (%)
A1B1C1D2E1 40 400 0.5:1 4 2.0:1 85.8
A1B2C2D3E2 40 450 0.6:1 5 2.3:1 97.9
A1B3C3D4E3 40 550 0.7:1 5.5 2.5:1 99.6
A1B4C4D1E4 40 650 0.9:1 3 3.0:1 27.2
A2B1C2D4E4 50 400 0.6:1 5.5 3.0:1 99.6
A2B2C1D1E3 50 450 0.5:1 3 2.5:1 63.1
A2B3C4D2E2 50 550 0.9:1 4 2.3:1 98.5
A2B4C3D3E1 50 650 0.7:1 5 2.0:1 99.9
A3B1C3D1E2 60 400 0.7:1 3 2.3:1 95.3
A3B2C4D4E1 60 450 0.9:1 5.5 2.0:1 99.8
A3B3C1D3E4 60 550 0.5:1 5 3.0:1 95.7
A3B4C2D2E3 60 650 0.6:1 4 2.5:1 95.5
A4B1C4D3E3 70 400 0.9:1 5 2.5:1 86.5
A4B2C3D2E4 70 450 0.7:1 4 3.0:1 99.1
A4B3C2D1E1 70 550 0.6:1 3 2.0:1 79.4
A4B4C1D4E2 70 650 0.5:1 5.5 2.3:1 95.6
924 Y. Qian et al. / Journal of Cleaner Production 15 (2007) 920e926

100 100

90 90
NaClO3 conversion,

NaClO3 conversion,
80 80

70 70

60 60

50 50
40 50 60 70 80 0.5 0.6 0.7 0.8 0.9
T, ºC CH2O2 :CNaClO3 , mol: mol
Fig. 2. Effect of temperature on NaClO3 conversion, CNaClO3 ¼ 400 g L1 , Fig. 4. Effect of CH2 O2 : CNaClO3 on NaClO3 conversion, T ¼ 70  C,
CH2 SO4 ¼ 4 mol L1 , CH2 O2 : CNaClO3 ¼ 0:6:1. CNaClO3 ¼ 400 g L1 , CH2 SO4 ¼ 5 mol L1 .

concentrations. The reaction liquid becomes yellow, half an

hour after the beginning of the reaction because generated
chlorine dioxide dissolves in it. Under such conditions, the
yield of chlorine dioxide will reach 30e40%. When the con-
centration of sulfuric acid is in a range of 4e5.5 mol L1, so-
dium chlorate conversion exceeds 95% without any catalyst.
Alkali metal sulfates are not found in the reaction process.
The higher the concentration of sulfuric acid is, the faster
the reaction rate is, and the higher sodium chlorate conversion
is. However, if the concentration of sulfuric acid is too high,
equipment is easily corroded.
4.3. Sodium chlorate concentration, reaction material
proportions
Concentration of sodium chlorate is between 400 g L1 and
650 g L1 in the experiment. Effect of the concentration on the
reaction rate is not significant. The best molar ratio of sulfuric
100
80
NaClO3 conversion,
acid to sodium chlorate is found to be 2.3. When its ratio is
higher, reaction rate decreases on the contrary. Fig. 4 shows
the effect of the ratio of hydrogen peroxide to sodium chlorate
on sodium chlorate conversion. The stoichiometric coefficient
of hydrogen peroxide to sodium chlorate is 1:2, while the best
molar ratio in actual reaction is found between 0.5 and 0.7.
When their ratio increases, NaClO3 conversion decreases.
However, hydrogen peroxide should be excessive 5e15% be-
cause hydrogen peroxide decomposes in reaction process and
impurity in feedstock of sodium chlorate consumes part of
hydrogen peroxide.
5. A clean production process of sodium chlorite
As the price of hydrogen peroxide decreases sharply in the
marketplace, the hydrogen peroxide-based approach becomes
the most promising approach to realize the cleaner production
process of sodium chlorite.
Firstly, efficiency of the hydrogen peroxide-based process
is high. The conversion ratio of the key component of materi-
als sodium chlorate is high. Compared with other process in
which chlorine gas might be produced [18e21], there are
few exhaust gases found in this hydrogen peroxide-based pro-
cess. It is a good method for production of sodium chlorite in

60 high purity and high yield. Another advantage is that there are
fewer reaction steps in the new process, which means fewer
impurities are produced. Other processes that use sulfur diox-
40
ide, sodium chloride, hydrochloric acid or methanol as reduc-
ing agents produce one or more unwanted contaminated
20
material such as chlorine, sulfur dioxide, methanol, formalde-
hyde and formic acid.
Secondly, the theoretical consumption of acid in the hydro-
0 gen peroxide-based process is low. In almost all of the other
3 4 5 6 7
processes for producing chlorine dioxide and further to sodium
H2SO4, M
chlorite, reduction of sodium chlorate has to be in acidic con-
Fig. 3. Effect of reaction acidity on NaClO3 conversion, T ¼ 40  C, ditions. The acid used is usually sulfuric acid. Theoretical con-
CNaClO3 ¼ 500 g L1 , CH2 O2 : CNaClO3 ¼ 0:6:1. sumption of acid in R2 and R3 processes, which use sodium
 Y. Qian et al. / Journal of Cleaner Production 15 (2007) 920e926 925

Table 2 sulfate at crystallization was analyzed by using an ion chro-

Material balance of the proposed process of sodium chlorite production (1 mol matogram. It was found that existing species of the acid salt
NaClO3 base), mole
cake depend upon the content of sulfuric acid, sodium sulfate
Theoretical Actual and operational temperatures. Waste acid is condensed during
ClO2 generation crystallization to form acid salt cake, which is at lowest acid-
NaClO3 1 1 ity. The filtrate is recycled to the chlorine dioxide generator.
H2SO4 0.5 0.7
H2O2 0.5 0.6
The utilization ratio of sulfuric acid is around 70% by recy-
ClO2 1 1 cling waste acid in the experimental system. Introducing
water or other reaction materials to the mix with acid crys-
ClO2 absorption
NaOH 1 1 tallization and ion exchanging Hþ from acid salt cake were
ClO2 1 1 the next step of investigation to recycle waste acid.
H2O2 0.5 0.6 The crystallized sulfate was dissolved and fed to the ano-
NaClO2 1 0.98 lyte compartment of the electrolytic cell. Then, an acid en-
riched reaction solution, which can be recirculated to the
chlorine dioxide generator, was produced. In the cathode com-
chloride as a reducing agent, is 1 mol sulfuric acid for 1 mol of partment sodium hydroxide is formed. Thus, with this process,
chlorine dioxide according to Eq. (1). Whereas, acid consump- it is possible to develop the sodium sulfate solution into two
tion in the hydrogen peroxide-based process are 0.5 mol ac- useful streams, one being the enriched acid solution which is
cording to Eq. (4), which is exactly a half of the former. It brought back into the chlorine dioxide generator, and the other
cuts down the load of waste acid recycle from the headstream. being sodium hydroxide which is brought back into the chlo-
A materials balance is shown in Table 2 of the proposed pro- rine dioxide absorber. By this method the alkali metal added to
cess of sodium chlorite production based on 1 mol of NaClO3 the chlorine dioxide generator is withdrawn as a useful chem-
feedstock. For the best efficiency of oxidation of NaClO3, ex- ical instead of as a waste by-product. The method is performed
perimentally optimized process conditions have been re- substantially without removing any sulfate from the system.
searched and listed in Table 2. In comparison with the other Thereby the whole cleaner production system is integrated.
conventional approaches, this process is characteristic of reac- The cleaner production of sodium chlorite from the hydro-
tions that have optimal atom economy and which also use less gen peroxide-based two-stage process is proposed according
acid. to the production flow sheet presented in Fig. 5.
According to the basic kinetics study [16], the reaction rate The major units of the process mass flows based on the pro-
of ClO2 is experimentally determined as the following duction of 100 kg product of sodium chlorite are presented.
equation: The reagents, including sodium chlorate, hydrogen peroxide
  and sulfuric acid are proportionately added into the chlorine
4:5 1=2
R ¼ 812 expð  43240=RTÞ ClO
3 ½H2 SO4  ½H2 O2  ð10Þ dioxide generator. The sulfuric acid solution is a mixture of

in which the order of sulfuric acid is much larger than the or-
der of other reagents. Increasing concentration of sulfuric acid 40.8KgO2
will clearly reduce the reaction time and make the best use of 45kg
23kgH2O2
the sodium chlorate, which is the most expensive reagent in NaOH
ClO2absorber

the reaction. Thus, the concentration of sulfuric acid is kept NaOH

at high level in the chlorine dioxide generation process. In other make up
industrialized processes such as the methanol-based process, 76.3kg ClO2
120kg NaClO3 100 kg
much higher acidity is required for good reaction conditions.
ClO2 NaClO2
Recycling of waste acid is critical to the realization of cleaner 23kgH2O2 generator 254kgH2SO4
production of sodium chlorite in the hydrogen peroxide-based 79kg
two-stage process. Components in the waste acid are mainly 78kg Na2SO4 fresh H2SO4
sodium sulfate and sulfuric acid. A little sodium chlorate and NaClO3
+ 196kg H2SO4
chlorine dioxide may also exist. Mixtures of sodium sulfate Water Filtration
and sulfuric acid in different levels of acidity in turn forms and washing Waste acid
acid salt cakes: sodium sulfate Na2SO4, sodium sesquisulfate recycle
Na3H(SO4)2 (1.5Na2SO4 þ 0.5H2SO4), and sodium bisulfate 78kg Na2SO4
NaHSO4 (0.5Na2SO4 þ 0.5H2SO4), according to the increase
of acidity. Different acid salt cake may decompose into sul- Electrolytic cell
53kg Electrolytic acid
fate containing some different sulfuric acid. Reaction effi- H2
ciency and sulfuric acid consumption should be considered
comprehensively to optimize the recycling of the waste 44kg NaOH
acid. In our investigation, in order to condense waste acid Fig. 5. The proposed clean production process of sodium chlorite (100 kg
to crystallization, acidity was determined. The content of NaClO2 product base).
926 Y. Qian et al. / Journal of Cleaner Production 15 (2007) 920e926
a make-up oil of vitriol and recycled waste acid. Reaction
liquid is boiled to generate chlorine dioxide under sub-
atmospheric pressure. The generator effluent is a solution of
mainly sodium sulfate in sulfuric acid. The slurry from the
chlorine dioxide generator is filtered to obtain the crystal of
the acid salt cake. A flow of water or sodium chlorate solution
is used to wash the crystals prior to being recycled as sulfuric
acid. Then, the filtrate and wash liquid are mixed into sulfuric
acid stream. A majority of crystals are sodium sulfate, which
is then electrolyzed to sulfuric acid and sodium hydroxide.
This low concentration stream of sulfuric acid, which is mixed
with other acidic steams, is recycled into the chlorine dioxide
generator. The electrolytic sodium hydroxide and hydrogen
peroxide solution are mixed for absorbing chlorine dioxide
as they pass through the chlorine dioxide absorber. Sodium
chlorite is generated. Cheap salt cake can be electrolyzed to
the corresponding acid and alkali, which are consumed in
the system. There is scarcely any waste produced in the whole
system. Process characteristics are highly beneficial to realize
cleaner production of sodium chlorite.
6. Conclusions
Laboratory experiments were performed to investigate
a new cleaner production process for producing sodium chlo-
rite. Operating conditions were explored. Feasible and optimal
operating conditions investigated included: reaction tempera-
tures, concentrations of sulfuric acid, molar ratio of hydrogen
peroxide to sodium chlorate, concentration of sodium chlorite
solution, and molar ratio of sulfuric acid to sodium chlorate.
Sodium chlorate conversion to sodium chlorite of 95e100%
was achieved. The main factors such as concentration of sul-
furic acid and temperature influencing on reaction process
were documented.
An integrated process flow sheet is proposed. Waste mini-
mization is taken into consideration in this work. The reaction
rate is fast and material conversion efficiencies are high. Con-
sequently the pollution burden is much lower in this process
compared with the old method. These characteristics establish
a solid foundation for realizing a cleaner production process
for producing sodium chlorite. By recycling waste acid pro-
duced in the chlorine dioxide generator and washing acidic
salt cake, the sulfuric acid is fully reclaimed; by electrolyzing
the cheap sodium sulfate one can obtain and reuse the resultant
sulfuric acid and sodium hydroxide. By synthesizing a series
of unit operations, filtration, washing, electro analysis and ab-
sorption, a cleaner production process of sodium chlorite pro-
duction were documented and presented.
Acknowledgments
Financial supports to this work from the Excellent Young
Scientist Fund of China (20225620), China Natural Science
Fund (20376025, 20536020), and the Outstanding Young
Professor Award from Guangdong Province Bureau of Educa-
tion are gratefully acknowledged.
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Yu Qian is a professor in the School of Chemical Engineering at South China
University of Technology, Guangzhou, China. He is engaged in recent years on
a number of chemicals and chemical process development projects, including
clean fuels, clean oxidation agents. He holds a PhD degree in chemical
engineering from Tsinghua University, in Beijing, China. He was then a post-
doctoral fellow at the Norwegian Institute of Technology, in Trondheim,
Norway; Research associate at the University of British Columbia, in Vancou-
ver, Canada, before joining the South China University of Technology.