Full Paper

Purification of Phosphoric Acid from Waste Acid Etchant using

Layer Melt Crystallization
By Kwang-Joo Kim*

DOI: 10.1002/ceat.200500383

Spent acid etchant is the corrosive waste coming from the etching process of semiconductor manufacturing plants. This waste
solution consists of phosphoric acid, nitric acid and acetic acid, and includes various toxic metallic impurities. In this work, the
recovery of phosphoric acid from the waste etchant was conducted by removal of metallic impurities, nitric acid, and acetic
acid, using static melt crystallization. The effect of cooling rate, amount of seeds, subcooling, and sweating on the distribution
coefficient was investigated. Nitric acid and acetic acid were successfully removed by single-stage layer crystallization. The
quantity of metallic impurities of the purified phosphoric acid was 1/1000 times smaller than that of the crude etchant.

1 Introduction
Spent etchant is the corrosive waste coming from the etch-
ing process in semiconductor plants. This waste solution
consists of nitric acid, acetic acid, and phosphoric acid, and
includes various toxic metallic impurities due to the reaction
between the acids and metallic elements of the semiconduc-
tor boards, which are composed of several metallic films as
gate electrodes using Al, Al-Ta, poly-Si, and SiNx.
General techniques exist for the treatment of waste acid
mixtures, such as chemical precipitation, neutralization, re-
verse osmosis, catalytic reduction, and incineration [1]. Neu-
tralization is used as the most popular method of treating
waste acid solutions. It requires excessive chemicals until
neutralization is completed with the addition of base and
generates a large amount of neutralization heat. Reverse os-
mosis has also been used to treat or dispose of waste acidic
mixtures, and is adequate for low contaminant levels [2]. Re-
verse osmosis cycles the solution through expensive filtra-
tion systems until the acid concentration of the correspond-
ing stream is reduced to the level where it can be disposed of
by conventional means.
Incineration and catalytic reduction may also be used as
disposal and recovery methods for waste acids [3, 4]. The
acids are converted to SOx and NOx under harsh conditions,
and these are undesirable methods due to the environmen-
tally unfavorable result of the generation of acid rain. De-
spite the extensive literature on the treatment of toxic, cor-
rosive waste, the technical demand for a cost effective and
environmentally prudent method to treat pungent acidic
waste is still increasing.
Melt crystallization has advantages for the production of
highly purified products, such as operation at low tempera-
tures compared to vapor-liquid processes, thus minimizing
decomposition of products, and low energy requirements, re-
± Nitric acid [wt %]
[*] K.-J. Kim (author to whom correspondence should be addressed,
kjkim@hanbat.ac.kr), Crystallization Process & Engineering Laboratory,
Department of Chemical Engineering, Hanbat National University,
SAN 16±1, Dukmyung-Dong, Yuseong-Gu, Daejeon 305±719, Republic
of Korea.
sulting from a low heat of fusion compared with heats of va-
porization. Therefore, a one-stage operation is required to
reach high purities (theoretically only one in simple eutectic
systems), and has been applied to separate close-boiling
isomers, which can be separated practically in no other way
[5±7]. Melt crystallization also has the advantages of needing
no solvents and a reduced environmental hazard compared
to solution crystallization. Melt crystallization is mostly ap-
plied to the separation and purification of organic materials
[8, 9]. Unfortunately, treatment of waste acid etchant has
never been studied by melt crystallization. It is interesting to
explore crystallization to purify phosphoric acid from waste
acid etchant coming from the semiconductor industry.
In this study, the recovery of highly purified phosphoric
acid with negligible metallic content, adaptable to the etch-
ant of semiconductor process, was carried out by static layer
melt crystallization. Optimum conditions were set for sepa-
ration and purification of phosphoric acid from acid etchant.
The operating parameters investigated were cooling rate, de-
gree of super-cooling, and sweating temperature.
2 Experimental
2.1 Materials
The waste etchant used in this work was kindly supplied
by the semiconductor etching process plant. Its composition
is listed in Tab. 1.
Table 1. Composition of waste acid etchant.
Materials Composition
Al [ppb] 124497
Fe [ppb] 550
Na [ppb] 259
Total metallic impurity [ppb] 125307
3.4
Phosphoric acid [wt %] 77.9
Acetic acid [wt %] 5.4
Water [wt %] 13.2

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 Full Paper

2.2 Experimental Set-Up ture detected both with without seeds is presented in Fig. 2.
As can be seen, crystallization of phosphoric acid without
The apparatus used is shown in Fig. 1. The crystallizer was seeds is difficult.
a jacketed vessel made of Pyrex glass. Ethanol as coolant
was circulated inside of the annular glass vessel to control
the temperature. The crystallizer was 1000 mm long and had
300
a 30 mm inner diameter. Digital thermocouples were used
to measure the temperature of the melt, the circulating etha-
Without seed
nol, and the cooling surface. The melt temperature in the With seed
vessel was maintained above 10 C to experimentally deter- 280 Equillibrium curve

Temperature(K)
mine the equilibrium temperature of the acidic mixture.
Crystallization operation was started by suddenly cooling
the jacket temperature. The temperature in the crystallizer 260
was controlled by a PID temperature controller with an er-
ror range of ± 0.05 K. A compacted crystalline layer was
formed with needle-like crystals packed in the annular sur-
face. After approaching the specified temperature, residual 240
melt in the vessel was discharged. Additionally, in order to
remove the metallic impurities included in the surface of the
crystal, a partial melting operation was fulfilled. The melted 220
crystal was collected in the bottom of the vessel. Layer crys- 84 85 86 87 88 89 90
tallization was carried out by cooling the wall of the crystalli- Concentration(%)
zer at various cooling rates, which were set to be constant in
Figure 2. Solid-liquid equilibrium curve with nucleation point.
the range 0.01 to 5 K/min.

2.3 Seeding

As phosphoric acid was difficult to crystallize sponta-

Sieve
Figure 1. Experimental Apparatus: 1. Static layer crystallizer; 2. Vessel; 3. Pro-
gramming thermostatic bath with PID controller; 4. Temperature controller.
neously without seeds due to a wide metastable zone width,
seeding was needed to generate nuclei. Seeding was tested
with wet seeds and dry seeds. Wet seeds were found to be
better as a result of being easier to handle and control com-
pared to dry seeds.
Fig. 3 shows examples of photographs of the crystallizer
during crystallization. After seeding in the metsatable zone,
nuclei were formed and grew as needle-like crystals, which
were then packed inside the crystallizer. The packing density
of the crystallizer could be controlled by the cooling temper-
ature and amount of seed. The seed was needle-like with size
of about 10 micron.

A small portion of melted crystal was diluted with ultra- Melt

pure water then analyzed for metallic impurities in the
mother liquor and crystal using ICP-MS (Inductively
th
id
Temperature

Coupled Plasma ± Mass Spectrometer). Potentiometric titra-

w
ne
zo
e

tion was used for analysis of the acid composition.

bl
ta

seeding
as
et

The melting point of phosphoric acid in acid etchant was

M

measured by a Lasentec system and was found to be 9.7 C. Crystal+melt

The Lasentec system is based on measurement of the varia-

tion of the number of particles with elapsed time [10]. The
point of disappearance was measured at various concentra-
tions and saturation temperatures, and was estimated at a
heating rate of 0.1 K/min. The solid-liquid diagram of the Concentration

phosphoric acid and water mixture and nucleation tempera- Figure 3. Photographs of the crystalline layer during crystallization.

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3 Results and Discussion 1.0

0.9
3.1 Separation Processes Nitric acid
0.8 Acetic acid
The waste acid mixture includes nitric acid, 0.7
Metallic elements

acetic acid, and phosphoric acid. Before the re-

moval of metallic compounds from the waste 0.6

etchant, the acetic and nitric acids included 0.5

k
must be separated.
0.4
The removal of acetic acid and nitric acid for
purifying phosphoric acid from waste etchant is 0.3
characterized by the effective distribution coef-
0.2
ficient.
The effective distribution coefficient1) k is de- 0.1

fined by the ratio of mass fractions of impurity 0.0

in the residual xil and in the crystal xic [11]. 0.01 0.1 1 10

xic Cooling rate (K/min)

kˆ …1†
xil Figure 4. Effect of distribution coefficients of impurities on the cooling rate.

An effective distribution coefficient k close to

1 means that in a binary system almost no sepa-
ration occurs, while a k close to 0 means an al- 0.6 14

most perfect separation. Here 0 < k < 1 is an

12
essential condition of purification. Generally, 0.5

the effective distribution coefficient k increases

10
with increasing cooling rate and subcooling be- 0.4

Yield (wt%)
cause they induce a high growth rate and thus 8
cause the entrapment of impurities. Therefore, 0.3
k

the effective distribution coefficient depends on 6

the crystallization conditions. 0.2
Fig. 4 shows the effective distribution coeffi- 4
cients of acids and elemental aluminum against
0.1
cooling rates in the layer melt crystallization. k Yield
2

The melt was cooled from 25 C down to ±35 C

0.0
at a cooling rate of 0.5 K/min. The amount of
0.0
seeds was 0.004 g per gram of melt. Seed with an
average size of 10 micron was fed at ±10 C. The
sweating process was operated at a heating rate
Figure 5. Effect of nitric acid content on the distribution and yield.
of 0.5 K/min from ±35 C to ±10 C after drain-
ing of the residual melt in the vessel. The effec-
tive distribution coefficients of nitric acid, acetic acid, and
metallic elements are in the range 0.08±0.14, 0.1±0.15, and
0.2±0.5, respectively, under the conditions investigated. A
larger distribution coefficient results from a higher cooling
rate, which leads to a higher growth rate. As can be seen, the
distribution coefficient of acid was found to be 0.04 at the
cooling rate of 0.08 K/min, which was equivalent to the crys-
tal growth rate of 10±8 m/s. This means that a greater amount
of acid impurities can be eliminated at lower subcooling and
lower crystal growth rates.
Fig. 5 shows the effect of nitric acid content on the distri-
bution coefficient and yield. The melt was cooled from 25 C
± rates of 0.5 K/min and at above crystallization temperatures
1) List of symbols at the end of the paper.
0
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
Content of Nitric acid in waste etchant(wt%)
to ±35 C at a cooling rate of 0.5 K/min. The amount of seeds
was 0.004 g per gram of melt. Seeds with an average size of
10 micron were fed at ±10 C. The sweating process was op-
erated at a heating rate of 0.5 K/min from ±35 C to ±10 C
after draining of the residual melt in the vessel. The effective
distribution coefficient decreases with increasing amounts of
nitric acid. Acetic acid was not found to affect the distribu-
tion coefficient of metallic elements. This means that nitric
acid dissolves the metallic elements due to being a stronger
acid compared to phosphoric acid and acetic acid.
As a result, crystallization temperatures below ±48 C
were not desirable because acetic acid and nitric acid were
not separated. Phosphoric acid from the waste acid etchant
investigated in this study can be separated below cooling
of ±48 C.

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 Full Paper
3.2 Removal of Metallic Compounds
Impurity behavior depends mainly on the supersaturation
because it affects the nucleation rate as well as the growth
rate. Metallic impurities included in phosphoric acid were
removed by controlling the cooling rate and amount of seeds
in static layer crystallization.
Fig. 6 shows the effect of the cooling rate and amount of
seeds on the distribution coefficient. The melt feed was
85 wt % phosphoric acid and 15 wt % water including
2089 ppb Al, 96 ppb Fe, and 30 ppb Na. The melt was
cooled from 30 C to 5 C at a cooling rate of 0.5 K/min. The
amount of seeds was 0.004 g per gram of melt. The seeds
had an average size of 10 micron and were fed at 18 C. The
sweating process was operated at a heating rate of 0.5 K/min
from 5 C to 25 C after draining of the residual melt in the
vessel. The distribution coefficient of total metallic elements
increases with increasing cooling rate and decreasing
amount of seeds. This means that a greater amount of impu-
rity is removed with lower cooling rates and larger amounts
of seeds.
In static layer crystallization, the cooling rate and amount
of seeds are important parameters to be considered in super-
saturation. Supersaturation is related directly to the metasta-
ble zone width. The metastable zone width DTmax was taken
as the difference between the equilibrium temperature and
the temperature at which nuclei were detected.
Metastable zone widths for saturation temperature and
cooling rate were plotted in log-log coordinates in Fig. 7.
The plots are found to give a good straight line. These results
show that the metastable zone width of the phosphoric acid
increases with the cooling rate for all the experimental con-
ditions explored.
The relationship between metastable zone width DTmax
and cooling rate b is as follows [11, 12]:
1 n
log b = log kn + n log DTmax ± log S (2)
n formed with a feed composition of 85 wt % phos-
1.0
0.001 (kg seed/kg melt)
0.004 (kg seed/ kg melt)
0.8
0.01 (kg seed/kg melt)
0.6
k
0.4
0.2
0.0
0.01 0.1
Cooling rate (K/min)
Figure 6. Effect of cooling rate and seed content on the distribution coefficient.
274 http://www.cet-journal.com  2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
10
1
b (K/min)
0.1
0.01
0.001
0.1 1 10
∆ T max(K)
Figure 7. Plot of cooling rate against metastable zone width.
where kn is a constant related to the nucleation rate and n is
the nucleation order.
The values of the order of nucleation rate n and the con-
stant of nucleation rate kn in Eq. (2) were evaluated by re-
gression analysis from the slopes and intercepts found in
Fig. 7. The order of the nucleation rate is 3.5.
Fig. 8 shows the effect of the amount of seeds on the
metastable zone width and distribution coefficient of total
metallic elements. The melt was cooled from 30 C to 5 C at
a cooling rate of 0.5 K/min. Seed with an average size of
10 micron was fed in melt at 18 C. The sweating process
was operated at a heating rate of 0.5 K/min from 5 C to
25 C after draining of the residual melt in the vessel. The
metastable zone width and distribution coefficient decrease
with increasing amounts of seeds.
Fig. 9 shows the distribution coefficient of the metallic ele-
ments against the fraction of sweating. A crystalline layer
phoric acid and a cooling rate of 0.5 K/min was
used. It was found that the purity of the crystals
had a strong dependence on the amount of
sweating. The distribution coefficient decreased
with an increase in the amount of sweating. The
purity of the crystals increases rapidly until 10 %
sweating. This means that the impurities formed
on growing crystals are mostly located on the sur-
face of the crystalline layer. Impure inclusions
occluded on the outside of the layer are easily
drained away at the beginning of the sweating
operation. This means the crystalline layer be-
gins to be melted from the surface of the layer.
After 20 % sweating, the crystal purity is nearly
constant although the sweating operation is still
in process. This means the impurity inclusions ex-
1 10
ist uniformly in the layer. Increasing the sweating
temperature causes a considerable reduction of
the metallic impurity of the crystals.
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1.0 1.0 Table 2. Separation by multi-stage crystallization.

k Composition Crude Step 1 Step 2 Step 3 Step 4

∆Tmax
0.8 0.8 Nitric acid 3.4140 0.4119 ± ± ±
[wt %]

Phosphoric acid 77.9317 86.9987 89.784 89.008 89.726

0.6 0.6 [wt %]
∆ T max (K)

Acetic acid 5.4225 0.5723 ± ± ±

k
[wt %]
0.4 0.4
Water [wt %] 13.2318 12.0171 10.216 10.992 10.274

Operating conditions
0.2 0.2
Crystallization +25 ~ ±35 30~5 35~15 35~15
temperature [C]
0.0 0.0
0.000 0.002 0.004 0.006 0.008 0.010 0.012
Cooling rate 0.5 0.5 0.5 0.5
[K/min]
Seed concentration (kg seed/kg solution)
Amount of seeds 0.004 0.004 0.004 0.004
Figure 8. Effect of seed concentration on the metastable zone width and dis- [g/g]
tribution coefficient. Sweating ±10 25 30 30
temperature [C]

1.0 Sweating rate l 1 1 1

[K/min]
Impurity
Metallic elements
Al
0.8 Al [ppb] 124497.00 20890.70 7845.7 1022.2 194.29
Fe
Na
Fe [ppb] 550.84 96.38 43.12 25.61 22.77

0.6 Na [ppb] 259.27 30.68 12.04 9.20 6.60

Total impurity 125307.11 21017.76 7900.86 1057.01 223.66

k

[ppb]
0.4

0.2 4 Conclusions

In this work, the recovery of phosphoric acid from waste

0.0 acid etchant containing nitric acid, acetic acid, phosphoric
0 5 10 15 20 25 30 35
acid, and metallic elements was successfully conducted using
Sweating ( % ) static layer crystallization. The quantity of metallic impuri-
ties in the purified phosphoric acid was 1/30±1/1000 times
Figure 9. Distribution coefficients of the metallic elements during sweating.
smaller than that included in the crude etchant. Metallic im-
purities were reduced by hundreds of ppb through four-step
3.3 Muli-Step Crystallization layer melt crystallization. This purified phosphoric acid
could be recycled as an etchant in semiconductor process.
Multi-step crystallization processes were used due to their Received: November 25, 2005
difference of composition. Tab. 2 lists results for separation
by multi-stage crystallization with the operating conditions.
The crystallization temperature was set according to the Symbols used
composition of the mixture and productivity.
Acetic acid and nitric acid were perfectly removed during b [K/min] cooling rate
the first step of melt crystallization. The impurity level of k [±] distribution coefficient
the purified crystal was 1/30±1/1000 times smaller than the kn [s±1] constant related to nucleation rate
initial content of the crude etchant. Metallic impurities were n [±] nucleation order
reduced by hundreds of ppb through four-step crystalliza- S [kg/kg K] slope of solubility curve
tion. This purified phosphoric acid could be reused as an DTmax [±] metastable zone width
etchant in semiconductor process. xil [±] mass fraction of impurity in the melt
xic [±] mass fraction of impurity in the crystal

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 Full Paper

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