J. Ind. Eng. Chem., Vol. 13, No. 7, (2007) 1047-1053
REVIEW
Progress on the Preparation of Ultra-pure Hydrogen Peroxide
Guo-Yan Luan*,**,† , Wei-Ping Gao**, and Ping-Jing Yao*
*Department of Chemical Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian
116012, People’s Republic of China
**Department of Chemical Engineering, School of Chemical and Materials Engineering, Jilin Institute of Chemical
Technology, Jilin 132022, People’s Republic of China
Received September 12, 2007; Accepted November 26, 2007
Abstract: Progress on the preparation of ultra-pure hydrogen peroxide is reviewed. The technologies include distillation and relative technologies, combination methods of ion exchange and adsorption resin, membrane separation and relative technologies, crystallization, flocculation, and adding addition agents as so well. Distillation is
reliable and easy to industrialize, while purity of hydrogen peroxide distilled is not high enough. Crystallization,
flocculation, and adding addition agents can only be used as accessory technologies. It is safe for membrane separation, but the life of membrane is short. Ion exchange and adsorption resin processes are simple and the product purity is high, but ion exchange resin is easy to be oxidized. It is the tendency for the preparation of ultra-pure hydrogen peroxide that distillation is used firstly and then the combination of membrane separation technologies or ion exchange and adsorption resin processes are followed.
Keywords: ultra-pure hydrogen peroxide, organic carbon compounds, impurity, purification
Introduction
1)
High purity hydrogen peroxide is one of the key chemicals of ultra large scale integrated circuit, it is mainly
used as cleaning agent, corrosive and wafer etching agent,
the purity of hydrogen peroxide has an impressive effect
on the electronic performances, finished product ratio and
the reliability. The different levels of integrated circuit
have different demands for high purity hydrogen peroxides [1]. High purity hydrogen peroxide may have been
divided into conventional semiconductor grade, electronic
grade, ultra-pure hydrogen peroxide (SEMI-C8, SEMIC12) according to Semiconductor Equipment and Materials Institute (SEMI), which is shown in Table 1.
With the rapid development of electron industry, specially for the highly integration, the demand for the high
purity hydrogen peroxide is increased. The product line
of 0.25, 0.18, and 0.13 µm have become the main manufacture technologies of integrated circuit in china now,
the requirement for high purity agent varied correspond†
To whom all correspondence should be addressed.
(e-mail: deslgy@163.com)
ingly from conventional semiconductor grade and electronic grade to ultra-pure hydrogen peroxide grade. As
the same time, China has become the second integrated
circuit market in the world. The annual consumption for
high purity agents is 60000∼70000 tons. The annual
consumption for the high purity hydrogen peroxide reaches 8000∼10000 tons [2].
Compared with the increment of integrated circuit industry, the production technology of high purity hydrogen peroxide is backward in China. The research of high
purity hydrogen peroxide began in the middle of 1970’s,
the production technology of ultra-pure hydrogen peroxide for 0.2∼0.6 µm chip was stressed in the period of
the Tenth-Five Plan in China. Metal ion impurities of
high purity hydrogen peroxide has reached standard of
SEMI-C8 through key programs of R & D, but particle
amount is beyond of the standard of SEMI-C8. The ultra-pure hydrogen peroxide (SEMI-C12) used for 0.09∼
0.2 µm chip technology still needs import from abroad.
In a word, it is not mature thoroughly for the purifying
technology to remove metal ions, organic carbon compounds and particles from the hydrogen peroxide effectively. The large scale production technology of
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Guo-Yan Luan, Wei-Ping Gao, and Ping-Jing Yao
Table 1. The Standards of Ultra-pure Hydrogen Peroxide for SEMI‐C8 and SEMI‐C12
Years
92
95
98
2001
2004
2007
2010
IC degree
16 M
64 M
256 M
1G
4G
16 G
64 G
Technology level, µm
0.5
0.35
0.25
0.18
0.13
0.10
0.07
Anion impurities, µg/L
200
30
Total Organic Carbon, mg/L
20
10
Metal ion impurities, µg/L
≤1
≤0.1
Particles amount, numbers/mL
(Particle size, µm)
SEMI standards
≤5 (≥0.5)
≤5 (≥0.2)
C8
C12
Table 2. Data of Evaporation and Fractionating for Hydrogen Peroxide Solution
Components
Al
Fe
Zr
Si
Na
3‐
PO4
Crude aqueous hydrogen peroxide solution (µg/L)
120
3
1
10
450
10500
SEMI-C8 and SEMI-C12 is insufficient in China now.
Ultra-pure hydrogen peroxide is manufactured from food
grade or industrial grade hydrogen peroxide with low
purities. In order to eliminate organic, inorganic and particle impurities in the food grade or industrial grade hydrogen peroxide, many purifying technologies were developed, such as distillation, adsorption, ion exchange
resin technology, and membrane separation etc [3]. The
paper focuses on the progress of the preparation of ultra-pure hydrogen peroxide.
The Technologies of the Preparation of
Ultra-pure Hydrogen Peroxide
Distillation and Relative Technologies to Purify Hydrogen Peroxide
Species and quantity of impurities are not same, since
processes and equipment for hydrogen peroxide production are different. The impurities may include organic, inorganic compounds and mechanical impurities etc.
Based on the boiling point of organic compounds is usually higher than solution of hydrogen peroxide and metal
ions are not easy to volatilize, distillation is usually used
for purifying and concentrating hydrogen peroxide.
Shimokawa [4] proposed the method of evaporator,
gas-liquid separator, fractionating distillation for preparation of purified aqueous hydrogen peroxide solution from
a crude aqueous hydrogen peroxide solution. The technology comprises evaporating the crude aqueous hydrogen peroxide solution in an evaporator into vapor with
Purified hydrogen peroxide solution (µg/L)
1
0.5
2
0.2
0.9
20
accompanying liquid in the form of a mist, separating the
vapor from the mist of liquid in a gas liquid separator
and subjecting the vapor to partial condenser.
Partial vapor is condensed to purified hydrogen peroxide solution, the others are transported to fractionating
column in order to upgrade the product solution greatly
relative to the impurity content on the overhead. The
main critical elements are shown in Table 2.
Since gas-liquid is not separated entirely in gas-liquid
separator, metal ion impurities will be introduced into
partial condenser, fractionating distillation in the state of
fine drops of a liquid coming with the vapor of hydrogen
peroxide, hydrogen peroxide can’t reach a higher quality.
It is difficult to reach an ultra-pure grade hydrogen peroxide only by distillation. In general, distillation may be
used as the former purification method, for its process is
reliable and can be scaled up easily.
Inaba’s process for purifying hydrogen peroxide solution
is as follows [5]: hydrogen peroxide solution (concentration 60 %) was diluted to concentration 40 % by ultra water (18 MΩ), the solution was subjected to distillation column made of fluorine plastic. Distillated product (concentration 31 %) drawn from the middle part of distillation
column was with lower contents of total orgnic carbon,
cation ions, anion ions. The total orgnic carbon was reduced from 40 to 5 mg/L, metal ions reached 0.1 µg/L.
3PO4 was reduced from 36000 to 5 µg/L.
Combination Technologies of Ion Exchange Resin and
Adsorption Resin
Ion exchange resin and adsorption resin have extensive
Progress on the Preparation of Ultra-pure Hydrogen Peroxide
1049
Table 3. Devos’s Patnet Data
Items
Na
Ca
Fe
Al
NO3
Cl
Crude aqueous hydrogen peroxide solution (µg/L)
170
14
4
40
5000
170
applied to remove or separate metal ions and organic
compounds [6,7]. In hydrogen peroxide solution, organic, inorganic and mechanical impurities exist in different
shape and form, with electron or not, non-polar or polar,
hydrophilic or hydrophobic. According to these characteristics of impurities, many combination technologies of
ion exchange resin and adsorption resin have been
developed. The product obtained is of high purity. But
this technology falls into troubles for poor anti-oxidation
ability of resin and hydrogen peroxide is easy to decompose. L’Air Liquide [8-12] and MGC [13,14] have
explored extensively in purification technologies of the
hydrogen peroxide.
In order to limit the decomposition of hydrogen peroxide, L’Air Liquide Corporation issued many patents
for the purification of hydrogen peroxide solution [8-12],
for example, 30 % hydrogen peroxide solution are introduced into the first column charged with anion-exchange resin with carboxylate ion, and then, in downward mode, into the second column charged with a cation-exchange adsorbents. The result solution is of high
quality, and decomposition of hydrogen peroxide is not
obvious. Na ions reduce from 675 to 0.026 µg/L. In another literature, Ledon [9] proposed that ratio of height to
diameter of resin is 5∼6, the pressure is lower than 5
o
atm, the operation of temperature was limited at -10 C∼
o
+ 10 C. Under this condition, 30 % hydrogen peroxide
solution is continue purified by passing it through the
anion exchange resin column, in turn, the cation-exchange resin column. There is one anion exchange resin
contains carboxylic (CH3COO ) ion at least. In the final,
the metal ion content achieves the very low level in the
product. In another patent [10], they adopted alternative
combination mode the anionic exchange resin column,
the cation exchange resin column, anion exchange resin
column, the cation exchange resin column, in turn, to decrease the danger of the hydrogen peroxide purification
process by increasing the flow speed of 30 % hydrogen
peroxide solution. The product purity in above two patents is equivalent. Devos [11,12] has analyzed the shortcomings of ion exchange technology for purifying hydrogen peroxide solution, and indicated that the hydrogen
peroxide solution will be decomposed when the ion ex-
Purified hydrogen peroxide solution (µg/L)
< 0.1
< 0.1
< 0.1
< 0.1
< 10
< 10
change resin is contacts the hydrogen peroxide in static
state for several dozens minutes. In order to avoid the
shortcomings of the ion exchange resin purification, new
technology is proposed.
Devos [11] explored the purification process, which
combined adsorption resin (XAD4), the anion exchange
resin (IRA958) with the cation exchange resin
(DOWEXC75NGH). In order to reduce the decomposition of hydrogen peroxide in the period of purification, the high speed rinsing water installment and the
temperature examination system were installed. An adsorption resin column, Parallels two anion resin columns,
and a cation resin column to be arranged in the purification series. Moreover, the sodium ion content reduces
from 0.3 mg/L to 0.1 µg/L. In addition, other new technology [12] is proposed that the hydrogen peroxide solution is injected into the resin column at an approximately linear velocity preferably of between 10 and 20
-1
m/h through the funnel distributor locating at the ion exchange column base. It is emphasized that the resin column is compacted substantially for at least half of the purification contacting time, and the ratio of the unfilled
resin column height to the resin column height is less
than 0.1. The purification process is more safely.
The example in the patent [12] is presented that the
aqueous hydrogen peroxide solution passed through the
anion exchange resin column marked DOWEX
MONOSHERE 550A LC NG and the cation exchange
resin column marked DOWEX MONOSHERE 500C
NG. The contrast data are shown in Table 3.
Japan’s MGC Corporation’s Noriyuki Saito [14] adopted purification process with the couple mix columns and
couple adsorption columns (Figure 1).
Dissociable impurities were removed by means of a
mixed ion exchange resins, while undissociable impurities were removed by means of a hydrophilic porous
adsorbent having a specific surface of not less than 1000
2
m /g. The ion exchange resins and the adsorption resin
trademarks are DIAION PA316, DIAION PK228, Wofatit EP63, respectively. The mixing ratio of the cation
exchange resin to the anion exchange resin in the mixed
resin column is determined by their ion exchange
capacity. The high purity product is obtained. Cation
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Guo-Yan Luan, Wei-Ping Gao, and Ping-Jing Yao
1,7 pumps 2,8 heat exchangers 3,6 mixed beds 4,5 adsorbent devices
Figure 1. MGC’s purification process of ion exchange resin.
Figure 2. Tanaka’s integration purification process.
content is lower than 0.1 µg/L, the anion content is lower
than 10 µg/L, total organic carbon content is lower than
10 mg/L.
The purification technology reported by Tanaka [15]
emphasized on monitoring operating condition, controlling the speed of feed strictly (Figure 2). He thought that
the previous purification of aqueous hydrogen peroxide
solution by the column process involved such a problem
that bubbles are formed by autolysis of hydrogen peroxide, and the bubbles sticking to resin circumstances,
thereby decreased purification effects, simultaneously, it
was also disadvantageous to the heat transfer.
Tanaka’s technology [15] proposed that a flow sensor
was used to control the feeding rate of aqueous hydrogen
peroxide solution, in order to monitor the purification
process of the hydrogen peroxide solution through the
resin column (the ion exchange resin, chelate resin or adsorption resin can be used according to the requirement),
the problems of bubble forming, temperature increment,
and product quality fluctuation are avoided in this
technology.
Acid sodium pyrophosphate with 0.070 g/L was added
to aqueous hydrogen peroxide solution, in Tanaka’s
example. The mixture was allowed to stand still for 3
days to thereby effect aging, and passed through a filter
of 0.1 µm average pore diameter. The filtered aqueous
hydrogen peroxide solution was purified by sequentially
passing through a cation exchange resin column, a bicarbonate-ion-form anion exchange resin column and a second-stage cation exchange resin column. The sodium
ion, aluminium ion content reduced from 15160 µg/L,
770 µg/L to 0.5 ng/L individually in the product.
German Merck Corporation’s Oeter [16] has reported
recently that the continuous purification process is composed of anion resin, the non-ionic adsorption resin, the
neutral macro porousadsorption resin.
The operation conditions and the resin types used are
provided in this technical example. The organic carbon
content of the purified product reduced from 38 to 2.4
mg/L.
Although many purification technologies of integrated
ion exchange resin and the adsorption resin have been
explored for the requirement of high purity hydrogen
peroxide solution, many problems are encountered in the
purification technologies of integrated ion exchange resin
and the adsorption resin, such as the reliable product
quality, long period production safety, characteristics of
ion exchange resin, the strong oxidation ability and thermal decomposition of hydrogen peroxide etc.
Combination of Membrane Separation and Other
Technologies
Microfiltration, ultrafiltration, nanofiltration, and reverse osmosis are membrane separation technology
which depend on the pressure difference. According to
different size of micro-porous, membrane separation
technology is widely used not only for the removal of
mechanical impurities, but also for the removal of inorganic impurities, organic impurities etc.
Morisaki’s [17] technology included that a raw material
hydrogen peroxide was firstly pumped to an ion exchange column charged by a styrene base gel-type ionexchange resin with strongly acidic groups, then, entered
into a reverse osmosis treatment equipment having a
Progress on the Preparation of Ultra-pure Hydrogen Peroxide
1051
1. pump 2. reverse osmosis unit 3. ion exchange resin unit
Figure 3. Morisaki’s integration purification process.
composite membrane of an aromatic cross-linked polyamide. The permeated aqueous hydrogen peroxide passed
through two ion exchange columns, one was charged by
a styrene base gel-type strongly basic ion-exchange resin,
the other was charged by a styrene base gel type strongly
acidic ion exchange resin. The purified hydrogen peroxide was obtained from above columns. The concentrated aqueous hydrogen peroxide was introduced to the
transition metal scavenging equipment, then recycled to
raw materials hydrogen peroxide reservoir tank. The organic carbon content of the purified product is lower than
10 mg/L, metal ions content is lower than 10 ng/L. The
drawing is shown in Figure 3.
Bianchi [18] has also used the integrated technologies
of reverse osmosis, ion exchange resin and ultrafiltration
for hydrogen peroxide purification. According to the patent, the remarkable advantage of Bianchi’s technologies
is to obtain higher permeate yields compared with the
previous processes. Bianchi’s process includes ultrafiltration, reverse osmosis, and ion exchange resin unit.
The concentrated aqueous hydrogen peroxide coming
from reverse osmosis equipment is used as feed to recycle directly to the industrial distillation unit. So, the
purification is accomplished in the cycle mode. The
membrane separation purification technology is of high
safety, its capacity is easy to enlarge, impurity removing
rate is more higher, but the membrane separation technology exists some shortcomings, such as the high operation pressure and short life time.
Other Technologies
Crystallization Technologies
When the temperature of hydrogen peroxide solution
decreased, the crystals were formed, and the crystals
were collected, washed and melted to obtain high concentration and high purity hydrogen peroxide solution.
The crystallization technology may be used preliminary
method for the purifying and concentrating of raw hydrogen peroxide solution. Different concentrations may
be acquired by adding ultra-pure water. L’Air Liquide
Corporation’s Ledon [19-21] had successively reported
many recrystallization technologies used as pretreatment
step for the purification technology. Recently, Germany’s Nordhoff [22] proposed a crystallization technology
of concentration and purification hydrogen peroxide.
Compared with the former crystallization technology, its
characteristics may be scaled up and produced in continuous manner. The high concentrated hydrogen peroxide was obtained and total organic carbon of hydrogen
peroxide reduced to 4 from 40 mg/L, simultaneously,
Sn, Ni, PO43- reduced to 20 µg/L, 1 mg/L, 2 mg/L respectively.
Flocculation Technologies
Tanaka [23] has made great improvement on study of
purification technologies. It is discovered that it is diffi-1
cult to reduce the silicon ion content to 1 µg/L by using
the strong acid cation exchange resin to remove metal
cation ion impurity, except for Na, K, and Ca ions.
Moreover, reproducibility of experiment results is poor.
The reason is that silicon oxide may be existed in the
soluble silicon and the insoluble silicon (suspension particles and colloid) in the hydrogen peroxide solution, so,
Tanaka proposed that firstly, sodium pyrophosphate or
methyl ethylidene phosphoric acid were added in hydrogen peroxide solution to form flocculant, secondly, the
hydrogen peroxide solution was filtrated to remove solid
impurities by 0.1 µm filter membrane, thirdly, the fluorine ion exchange resin was used to remove soluble sili-
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Guo-Yan Luan, Wei-Ping Gao, and Ping-Jing Yao
con of the above hydrogen peroxide solution. The silicon
impurities reduced from 2 µg/L to 50 ng/L in purified hydrogen peroxide solution.
Reagents Combination Technology
Chiharu [24] proposed that pyrophosphoric acid or the
its salt with 0.1∼8 mg/L was added to raw aqueous hydrogen peroxide solution, then the hydrogen peroxide
solution passed through the anion exchange resin
column. The purifying effect is remarkable. The experiment results showed aluminum ion content reduced from
80 to 0.05 µg/L in the purified aqueous hydrogen peroxide solution. The purifying data of other metal ions
was not described in the patent.
Tokai Denka Kogyo Kabushiki Kaisha company’s
Watanabe [25] put forward a more convenient and safe
purification method. Firstly, the chelating agent was prepared by alkali metal salts such as HEDTA, EDTA etc.
Then, the adsorption is performed by pouring an aqueous
solution of the above chelating agents into a column
charged with anion exchange resin (Amberlite IRA-900).
After hydrogen peroxide was disposed by the above resin, the Fe, Ni, Cr ion content decreased to 1 µg/L.
The metal ions are removed effectively and safely. The
subsequent adsorption resin column is not needed. The
purification may be carried at room temperature. The results will not deteriorate after the resin repeated for 40
times.
Dhalluin [26] added macroligands to the aqueous solution of hydrogen peroxide. The macroligands may be
comprised at least one carboxylic, sulphonic, phosphonic
or nitrogen-containing functional group, such as 4-vinylpyridine homopolymer, acrylic phosphate copolymer
which molecule weight is greater than 500000. The macroligands were mixed with aqueous solution of hydrogen
peroxide to adsorb metal ions, then the mixture was
forced through an ultrafiltration membrane, thereby, producing a purified permeate, which Fe, Al ions contents
decreased remarkably. Simultaneously, the purification
process may be combined with ion exchange resin exchange, distillation or reverse osmosis.
Auxiliary reagents technologies play main role in the
purifying aqueous hydrogen peroxide solution for reducing decomposition of the above solution, stabilization
of process and removal of special ions. But new polluting
sources are introduced through adding the new reagents,
which resulted in the increment of purification capacity.
When the purification process is scaled up, the production costs will be enlarged inevitably.
Conclusions and Perspective
With the rapid growth of demand for ultra-pure hydro-
gen peroxide, the purifying technologies of hydrogen
peroxide are more and more focused. The ion exchange
resin and the adsorption resin purification technology has
advantages of simple process, the mild operation conditions and high purity, but it also has some shortcomings, such as the life time of the resin is short, the ion
exchange resin is easy to be oxidated or polluted, the organic epoxide or the peroxide formed after the carbon
skeleton of ion exchange resin was oxidated, which is
dangerous for purifying process.
With the fast development of materials science, it is
possible to provide new ion exchange resin and reverse
osmosis membrane with long life time. Integrated method of membrane separation or ion exchange and adsorption resin process for purifying distilled hydrogen peroxide is the tendency of the preparation of ultra-pure hydrogen peroxide.
Acknowledgments
This study was supported financially by the Science
and Technology Committee of Jilin Province (NO.
19990110).
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