Proceedings of the First International Conference on Environmental Research and Assessment

Bucharest, Romania, March 23-27, 2003

REMOVAL OF CHROMIUM FROM TANNERY SOLID WASTE1

Cristina MODROGAN, Liliana BOBIRICĂ, Constantin BOBIRICĂ,
Cristina COSTACHE, Rodica STĂNESCU
Politehnica University of Bucharest,
Department of Inorganic Technology and Environmental Protection

ABSTRACT
Romanian tanneries face important financial problems due to internal and external markets. Some of them
store important quantities of solid waste with a chromium high content. These wastes can not be safely
disposed without removal of chromium.
Our study investigated possibilities of chromium removal from solid tannery waste and its recovery as
compounds to be recycled in tanning process. The removal of chromium from sludge was made using
sulphuric acid. The main goal of the research is determination of optimum conditions of obtaining a
chromium low-content sludge that could be safe disposed on land.

Keywords: chromium removal, tanneries, waste management, reuse, safe disposal,

sludge

INTRODUCTION

In tanning industry about 90% of leathers are tanned with chromium salts, even if it can
be performed with different tanning agents.

For a minimum impact to environment, the sound tanning technologies have to consider
low emissions (wastewaters, sludges, solid wastes, gases etc) and recovery and reuse
of chromium. The presence of chromium in primary sludge has to be avoided by
separately collecting of tanning float for an eventually chromium recovery.

Wastewaters and liquors, which have very different compositions, are collected
separately for a proper treatment.

The average values from table 1 and 2 emphasize the importance of separate collection
of wastewaters from different processes. Sulphides presence in the mixed sludge
causes the release of highly toxic hydrogen sulphide gas to the atmosphere. In the
deliming and pickle liquors the sulphides can easily be oxidised with hydrogen peroxide,
sodium metabisulphite or sodium bisulphite, precipitated with iron (II) salts and aeration,
etc.

The content of mixed sludge used by us in the experimental work has a high content of
sulphides and acidulation released important quantities of H2S.

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ISBN: 973-558-077-2: print, on-line, CD-ROM, © 2003 Ars Docendi Publishing House, Bucharest, Romania

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Bucharest, Romania, March 23-27, 2003

Table 1. Averages of loads of emissions to wastewater for the first process units as
percentages of total loads as summary from various references for salted bovine hides
with chrome tanning (IPPC, 2001)
Bovine Wate SS COD BOD TKN S2- Cr Cl-
r
m3/t % % % % % % %
Beamhouse 7-25 ca.80± ca.75±1 ca.75±1 ca.80±5 100 ca.75±5
5 0 0
Tanning 1-3 ca.>5 ca.<10 ca.<10 ca.<5 - ca.70±5 ca.20±5
operations
Post-tanning 4-8 ca.>10 ca.15±5 ca.15±5 ca.>10 - ca.30±5 ca.<5
Finishing 0-1 ca.<5 ca.<5 ca.<5 - - - -

Table 2. Averages of loads of emissions to wastewater for goat skins and ovine skins
from beamhouse, tanyard, post-tanning and finishing operations as percentages of total
loads (IPPC,2001)
Bovine Water SS COD BOD TKN S2- Cr Cl- SO42-
m3/t kg/t kg/t kg/t kg/t kg/t kg/t kg/t kg/t
Beamhouse* 7-25 70-120 120-160 40-60 9-14 4-9 - 120-150 5-20
Tanning 1-3 5-10 10-20 3-7 0-1 - 2-5 20-60 30-50
operations
Post-tanning 4-8 10-20 15-40 5-15 1-2 - 1-2 5-10 10-40
Finishing 0-1 0-5 0-10 0-4 - - - - -
TOTAL 12-37 85-155 145-230 48-86 10-17 4-9 3-7 145-220 45-110
* Soaking to bathing

The wastewater equalization and sedimentation, it results a sludge with high organic
content and variable humidity; the water content has to be remove before sludge
disposal as much as possible in a thickling stage. The chromium content depends on
wastewaters collection and its treatment. If spent liquor from tanning process is mixed
with the rest of wastewaters, the primary sludge will have a high concentration in
chromium (III) in liquid phase. Cr(III) concentration varies as a function of the tanning
method used; tanning may be followed by washing. Also, it could contain high quantities
of sulphides from unhairing process.

Considering the tanneries with a high design capacities but low productions and with
wastewater pre/treatment stations that can not be exploited for sporadic production
(1/10-1/3 of designed capacity), the most applied pretreatment consists of equalization
and homogenization in a settler, sedimentation, discharge in effluent of the supernatant
and sludge evacuation and storage on concrete platforms. A coagulation-flocculation
stage can be adds but the costs are even higher and unaffordable for the tanneries with
financial problems.

If tanning and unhairing exhaust liquors are mixed with the other wastewaters, the
sludge will can not be safe disposed on soil. This is a residue that is accumulated in
tanyard, most of the time in improper conditions. The humidity and organic content of
this sludge varies with weather conditions, from season to season. Usually microbial
processes could take place at very low rate contributing to air pollution.

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Bucharest, Romania, March 23-27, 2003

Even if the wastewater treatment plants will be rehabilitated and the tanneries will
operate at full capacities, the existing sludges have to be safely disposed. One of the
techniques recommended for small quantities is incineration. It is possible only if there is
a suitable incinerator that is provided with a proper flue gas purification system.

The oldest and most frequently used method for removal of trivalent chromium from
wastewater is the precipitation (Joseph,1985; Marie,1977; Constantin, 1980; Daigle,
1986; Boast, 1988; Santiago, 1993) Research on the efficiency of various alkali such as
sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, calcium carbonate,
basic magnesium carbonate and magnesium oxide, showed that chromium in tanning
liqours can be converted into denser precipitates when less soluble precipitants are
used.

Figure 1. Flow Diagram of chrome recovery by precipitation with sodium

hydroxide/carbonate (Ludvik, 2000)

MATERIAL AND METHODS

This work proposed an approach for removal of chromium from “mixed sludges” and
bring it into an easy chromium recoverable form. It is based on chromium removal from
sludge in sulphuric acid solution, precipitation and solubilisation of chromium hydroxide.

The studied sludge content is highly variable and it is generated through mixing of all
wastewaters and liquors in a tannery from Bucharest. The quantities are moderate
present in the tanyard but an urgent sludge disposal is needed. The sludge treatment
and chromium removal and recovery have to be done with:

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Bucharest, Romania, March 23-27, 2003

• minimum costs;

• minimum volumes of waters discharged in effluents or sewage collecting system;

• low values for content indicators of wastewater discharged.

The proposed scheme for processing the above mentioned particular sludges (call
forward "mixed sludge") is presented in figure 1. The "mixed sludge" is treated with
sulphuric acid solution, filtrated, chromium precipitated with sodium hydroxide solution
and eventually chromium hydroxide separation and its dissolution as chromium sulfate.
Chromium can be recovered from sulfate solution by specialized treatment plant.

The "mixed sludge" was supply by the tannery and it had the following characteristics:

humidity 78.9%

ash 10.2%

chromium (as Cr2O3) 1.1%

Figure 2. Chromium recovery scheme from “mixed sludge”

Cr Removal from Sludge

Chromium is present as Cr(III) in solution and in collagenic structures from sludges

resulted in tanning process. The rate of removal of chromium depends on different
parameters like:

• acid concentration;

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Bucharest, Romania, March 23-27, 2003

• temperature;

• sludge particle granulation;

• mixing;

• age.

The available sludge had a very fine granulation (below 0.1 mm) and it was collected
from five different points of the deposit surface. The sludge was a relatively fresh one
and the difference in properties could be very important in chromium removal process. It
was very difficult to get a representative sample due to the low accessibility on top of
sludge deposit.

The solid particle dimensions can reach 2-3 cm and it could act as a limitation of Cr3+
internal diffusion from collagenic structure when proper conditions are provided. To
ensure a high rate of external diffusion a sufficient mixing rate has to be maintain.

The experimental conditions have been chosen after many preliminary tests which
provided information about parameter ranges to be covered. The experiments have
been done using sulphuric acid with concentration between 5 and 20%, temperature 20,
30 and 40°C, and continuous mixing at a rate of 300 rpm. The temperature was
maintained at a constant level using a water thermostat (GFL-Velp) and the mixing was
achieved using an overhead stirrer (Heidolph RZR2021) for 30 minutes.

The experiments were conducted to determine conditions for a high chromium removal
contacting 10g sludge with 100 ml sulphuric acid solutions. The chromium sulphate
solutions was filtered on low porosity filter paper and analyzed.

Cr(OH)3 Precipitation

The oldest and most frequently used method for removal of trivalent chromium from
wastewater is the precipitation (Joseph,1985; Marie,1977; Constantin, 1980; Daigle,
1986; Boast, 1988; Santiago, 1993) Research on the efficiency of various alkali such as
sodium hydroxide, sodium carbonate, sodium hydrogen carbonate, calcium carbonate,
basic magnesium carbonate and magnesium oxide, showed that chromium in tanning
liqours can be converted into denser precipitates when less soluble precipitants are
used.

Chromium can be recovered from the exhaust liquors by addition of sodium hydroxide
lead to a fast precipitation and voluminous sludge but polyelectrolytes can be added to
facilitate coagulation. The precipitated hydroxide is separated from the supernatant,
which is discharged to the effluent. The precipitate has to be re-dissolved as soon as
possible, because it becomes less soluble with time. The fresh chromium hydroxide
sludge is dissolved in concentrated sulphuric acid to get a chromium sulphate
concentrated solution.

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Bucharest, Romania, March 23-27, 2003

Chrome recovery by precipitation is a simple and effective process (chromium hydroxide

has a very low solubility product Ksp=6.7x10-31), but special analytical control and
equipment is needed to control the pH value and to dewater the chromium hydroxide
sludge.

The removal of Cr(III) from sludge has to be done with a minimum of reagents (low
content of final discharged wastewater) and a high removal rate. The results of the first
investigation step revealed that the variation of concentration between 5 and 20% of
sulphuric acid does not produce an important increase in removal rate. Therefore, the
solution of chromium sulphate was prepared contacting 60 g sludge with 600 ml 5%
sulphuric acid at 40°C. Afterwards, the system was filtered and in the solution the
chromium hydroxide was precipitated with 20% NaOH solution until pH=7.5 (pH-meter
Sper Scientific). The precipitated hydroxide was separated from the supernatant
(concentration 0.5 mg/l), in the first step, in a settling operation and in the second step
the resulted sludge was doubled centrifugated (centrifuge Hettich Universal 32) and
supernatant removed. The sludge could be utilized to prepared baso-chrome for reusing
in the tanning process. Therefore, chromium hydroxide sludge was weighted (32.5g) and
re-dissolved in 4 ml concentrated sulphuric acid to get a chromium sulphate
concentrated solution (1.26%).

Analytical Methods

Chromium was analyzed as total chromium(VI) using a standard method (STAS 7884-
91). Chromium(III) was oxidized with potassium permanganate in acid solution and
resulted chromium(VI) reacted with diphenylcarbazide resulting a red-violet complex.
Previously the presence of Cr(VI) in sludge has checked. Its concentration was below
method detection limit (0.02mg/l). The red-violet complex was colorimetered at 545 nm
using a spectrophotometer UV-VIS CINTRA 5.

The sludge content in total chromium was determined using the above mentioned
method after digestion in sulphuric acid 96% (ρ=1.84 g/cm3). The water content of
sludge has been determined through heating at 110°C in an oven (Carbolite 303), and
the ash content heating a sample at 1100°C in a furnace (Carbolite).

RESULTS AND CONCLUSIONS

The mixed sludge from the tanyards of some Romanian tanneries, accumulated during
the improper wastewater collection, has to be safe disposed after the removal of as
much as possible chromium(III). The investigation presented in this work emphasized
that the temperature in the range between 20 and 60°C and sulphuric acid concentration
between 2.5 and 20% have not a great influence on chromium removal efficiency (see
figure 2).

Removal efficiency laid in a range between 75 and 90%. Therefore, to be able to reach
low costs in "mixed sludge" treatment, we consider that a 5% sulphuric acid
concentration and 40°C represent reasonable conditions for achieving a satisfactory
removal of chromium. Higher temperatures and sulphuric acid concentrations could
promote the unbinding of the collagen-chromium bonds.

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Bucharest, Romania, March 23-27, 2003

95

Chromium removal efficiency, %

90

85
20 grd C
80 40 grd C

75 60grd C

70

65

60
0 5 10 15 20 25
Acid concentratiion, %

Figure 3. Dependence of chromium removal efficiency on temperature and sulphuric

acid concentration

The final chromium sulphate solution concentration was quite low, but filtering in filter
press are known for giving very good results in water removal. Also the sludge could be
thickled adding polyelectrolites at chromium precipitation stage. Further experimental
works will assess the possibility of chromium concentration in solutions and its recycling.

REFERENCES

Boast D. A., Large scale chrome recovery from chrome wash liquors. J. Amer. Leather
Chemists Assoc., 83, 17-23, (1988).

Constantin J. M. and Stockmann G. B.; Partial replacement of chromium, Technicuir, 14,

49-51, (1980).

Daigle R. P. and Benett D. J., Effluent chrome recovery., J. Amer. Leather Chemists
Assoc., 81, 305-311, (1986).

Integrated Pollution Prevention and Control (IPPC) 2001, Reference Document on Best
Available Techniques for the Tanning of Hides and Skins, European IPPC Bureau,
http://eippcb.jrc.es

Joseph S. and Langerwerf A., Trivalent chromium, a recyclable raw material of the
leather industry: a questionable genotoxic substance, J. Soc. Leather Tech. Chemists,
69, 166 Ludvík J., Chrome management in the tanyard, UNIDO (2000)

Maire M. S., A comparison of tannery chrome recovery systems, J. Amer. Leather

Chemists Assoc., 72, 404-418, (1977).

Santiago C. M., Jr., Isaac D. B., Anglo P. G., Garcia B. M., Silverio C. M., Esguerra R. L.,
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122, 41-58, (1993).-174, (1985).

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