T H E KECYCLING O F CHKOME TANNING LIQUORS

161

THE RECYCLING OF
CHROME TANNING LIQUORS*
KOREKTPIERCE*"
Sral Tanning Company
Commercial St.
nfanchrster, N . H . 03101
AND
THOMAS

c. 'I'HOKSTENSEN

Thorstensrn Laboratory
66 Littleford Road
Wostforil, A fmsaclrusetts OlS56
ABSTRACT

I n order to decrease the amount of chromium discharged into the

tannery effluent, a recycling system was developed. T h e system is based
on the pumping of the spent chromium solution from hide processors
through a screening system and into a storage tank for equalization.
T h e equalized chrome liquor is used as the pickle liquor. Data are
given on the tanning processes, including material halances and material costs.

---

INTRODUCTION

T h e recycling of chrome tanning liquors is not new. D u r i n g the days of paddle

tannage, it was common practice for tanners to keep the chrome tanning bath ( 1 ).
Either pickled o r hated hides would go through the chrome tanning cycle in approximately 24 to 48 hours. T h e chrome-tanned leather would be pulled; and
the spent solutions analyzed for chrome, salt, and basicity. Additional salt, acid,
and chrome tanning salts ~ . o u l dhe added and the bated stock would be introduced into the tannage.
Under this system, the saving of chrome was considerable. Spent solution
of chrome tanning may contain as much as half of the chromium o r tanning
agent that was used in the original tannage. After the tannage was used from
four to six times, the spent chrome liquor could be used for retanning of splits
or dumped. T h e dumping of the chrome tanning liquor was to prevent the build*The systems described in this paper were the results of developments made in 1972.
Since that time the company has changed its chrome tanning system and is now recycling chrome liquor from drums in a bate, pickle, and tan system. T h e chrome tanning wastes by either approach result in essentially zero chromium discharge.
**Present address: W. 1). I%yron<lo., Williamsport, Md.

162

T H E RECYCLING OF CHROME TANNING LIQUORS

up of sodium sulfate and other material in the chrome tanning bath. W i t h the
passing of chrome tanning from the paddle tannage to drums and hide processors, the concept of recycling of chrome liquors was discarded.
r .

1here is now renewed interest in this approach with the need to decrease
the chromium being discharged in the effluent (2). Several possible methods
are available to the tanner. T h e pH of the effluent niay he raised to above the
precipitation point of the chroinium, and the chrome salts removed by settling.
It has been suggested by several workers that the chrome tanning solutions can
be precipitated separately. T h e hydrated chrome oxide precipitate can then be
redissolved in acid, and the chrome tanning salt reused. T h i s method requires
specialized equipment and handling of the materials.
I n the case of Seal T a n n i n g Company, the Environmental Protection Agency
asked the company to decrease the chromium being discharged into the Merrimack River. A t the time the conipany was tanning in tanning drums, using a
conventional bating, pickling, and tan process. T h e spent chrome liquor was
being dumped on to the floor, through the floor drains, and into the river. It was
imperative that a solution to the chrome discharge be found as quickly as possible.

T h e present report covers only the development of the chrome tan recycling
system. T h e remainder of the wastes are being dumped, untreated, into the river.
M o r e extensive pretreatment will he required on the tannery effluent in the near
future. At present, the company and this laboratory are determining the feasibility
of several possible pretreatment and complete treatment plans.

Theory of Chrome Recycling. I n the paddle tannage system of chrome

tanning and recycling, the n o s t coninion method was to introduce the bated stock
into the spent chrome tanning bath, which was used as a pickle solution. T h e
spent chrome liquor, with a pH of 3% to 4,was refortified with salt and acid
to drop the p H to less than 2, hefore the introduction of the hated stock. T h e
bated hides would then be run in the pickle solution containing approximately
1/3 of the total amount of chrome needed for tannage. After a period of time,
the reniaining chrome tanning material was introduced. T h e tan proceeded for
approximately 21 hours, after which the basification took place and the tan continued through the following day. T h i s resulted in approximately a 48-hour
process.
T h e r e was a certain build-up of salts in the spent chrome liquor as it was
recycled, and this was a function of the liquor ratios used during the tannage.
T h e total amount of water brought in with the bated stock and the total amount
of water lost with the pulling of the chrome tanned sides was approximately
equal. As more chrome tanning salts were added, there was a dilution effect, due
to the addition of water from the bated stock. T h e build-up of salts did not
proceed as a strictly linear function, hut rather has a tendency to level off after
a number of times of reuse.

163

T H E R E C Y C L I S G OF CHROME TANNING LIQUORS

____

IVith the
tide pro-

de c r e a e
methods
m e the
settling.
ions can
then be
requires
Agency
3Ierrisiring a
')r was
It was
I\sibIe.

-- -

' I n the case of the d r u m tannage, a different technique must be used. T h e

spent chrome liquor removed from the drum can be stored in a tank and then
introduced back into tlw d r u m with added salt and acid as part of the pickle
solution. I n this case the dilution effect from the bated stock is more pronounced,
and the build-up of materials becomes considerably less. 1 he quantity of inert
salt build-up can be calculated from the forinula shown in T a b l e I.
r -

TABLE I
BTJILD-I7P OF INERT SALTS

_________
Concentration of S0.i in Spent Solution

stock

The
acid

The
ately
time,
I for
con)our
was
ige.
lint

rly
1ue
lot
ter

SOc from Stock

f so4 in Spent Liquor

Volume of Stock f Spent Liquor

THUS: At 3% so4 used

Percent

At the End of Run No.

so4*

@ 3:1 Liquor Ratio

@ 1:l Liquor Ratio

0.75%

\.cling
I iver.
'L near
I Idity

1rome

- ._
-. --

1.31%

1.74%
2.04%
2.28%
2.4670

1.5 %
2.2S%
2.62%
2.8 %

2.9 96
2.95%

*Calculated from ahove formula.

T h e problem of mechanically handling the spent liquors from drums is much

more complicated than the handling of the spent liquors in paddle tannages. T h e
prohlern of liquor handling is p e a t l y simplified by the use of a hide processor.
A recycling punip ,is part of the regular equipment. T h u s , to remove the spent
liquor froin the tannage, the spent liquor may he pimped directly to any tank
o r piping system as desired.

The Seal Tanning System. T h e spent liquor is pumped directly from the
hide processors through a Hydrasieve, to remove suspended hide particles. After
going through the Hydrasieve, the liquor is pumped t o a storage tank. T h e
storage tanks have suficient volume to hold the discharge from six tannages.
To remake the chrome solution, the spent chrome liquor is used for the pickle
make-up solution as indicated in the forintila ( T a b l e I1 and 'Table 111).
T h e r e is a skim o r overflow provided on the storage tanks to permit drawing
off the accumulatecl grease to he dischatged to the sewer. The grease may he
removed without discharging significant quantities of chroinium tanning salts.
N o t all of the chroiniiini can be recycled since there is more spent liquor discharged than is used in the pickle. W h e n the amount of excess chrome liquor

164

THE RECYCLING OF CHROME TANNING LIQUORS

TABLE 11
H I D E PROCESSOR
W E I G H T : 24,000 Ibs.
LOAD STOCK
Wash 10 minutes @ 75" and 20 minutes at 95F.
Drain to cover stotk.
ADD: 240 Ibs. ammonium sulfate
24 Ibs. bating enzyme.
Drain and wash 30 minutes @ 75F.
DRAIN.
ADD: 800 gals. spent chrome
12 bags (1200 Ibs.) salt - Run 15 minutes.
360 Ibs. sulfuric acid -Run 2 hours.
T u r n steam last % hour. Bring temperature up to 87F.
Take liquor sample.
ADD: 240 Ibs. calcium formate
Run 3 hours.
290 gals. Tekchrome 42-A
N E X T A.M.
Start mixer.
ADD: 260 Ibs. bicarbonate @ 90F. 2 Feeds. 30 minutes
250 gallons.

- Run 1 hour.

TABLE I11
REGULAR PROCEDURE
Formulation : BATE, PICKLE, AND T A N
Basis: 12,000 lbs. lime trimmed stock
Drum: 10 x 10 16 R.P.M.
Wash 10 minutes @ 75" and 20 minutes @ 95F.
Drain to 6" to 8" below gudgeon.
ADD: 0.1% (12 Ibs.) bating enzyme
1% (120 Ibs.) ammonium sulfate Run 5. Stop 1 5 minutes.
Run 5. Stop 15 minutes.
Run 5 minutes.
Wash 30 minutes @ 75F. Drain to 8" below gudgeon.
ADD: 7.5% (900 Ibs.) salt. Run 15 minutes.
1.5% (180 Ibs.) sulfuric acid (dilute to cool). 150 gal.
Run 2 hours.
ADD: 1% (120 Ibs.) calcium formate
. Run '/2 hour. Drain to 14" below gudgeon.
ADD: 145 gals. commercial chrome liquor*
Run 3 hours.
N E X T A.M.
ADD: 180 Ibs. bicarbonate @ 90F. 2 Feeds 30 minutes
130 gal. Run 1 hour.
'1.421 Ibs. CrzOs/gal.

3870 basic

165

T H E RECYCLING OF CHROME T A N N I N G LIQUORS

reaches nearly a tankfull, the following procedure is followed :

1. T h e grease is skimmed off.

T h e pH is raised to 10.0 with soda ash and sodium hydroxide.

2.
3.
4.
5.

T h e precipitated chromium Iiydroxide is settled.

T h e supernatant liquid is drawn off and discharged.
T h e chromium hydroxide sludge is dissolved in sulfuric acid and added
to the spent liquor for recycling.
T h e presence of chrome tanning salts during the pickling operation did not
cause any difficulty or significant variation in the quality of tlie leather o r the
,stratigraphic distribution of the clirorne during the tannage. I he practical experience from paddle tatinages w o i i l ~ lindicate that the method can be used with
little difficulty.
T h e work of Thorstrn>en and Osugi ( 3 , 1) on the penetration of pickled
acids and chrome in the simultaneous chrome tanning/pickling operation has
shown that the fixation of the chrome is a function of the pH in the stock. T h e
chrome will penetrate following tlie pickle acid in accordance with the limits
of pH of the system.
T h e saving in chrome would amount to approximately 19 gallons per batch ;
based on a price of 80$ per gallon this is $ 1 5 ~ f o rchrome tanning salt (Tables
IV and V ) .
T h e savings in sodium chloride is 600 pounds of salt per 24,000 pounds of
limed weight. At 24 per pound (delivered to the tannery) the savings are $12
per batch. T h e total savings then would be $15 plus $12, o r $27 per 24,000
pounds of limed weight. 'I'he daily saving would then be approximately $108
per day (based on 4 batches per day) or about $30,000 per year.

TABLE IV
MATERIALS USED 24,000 LRS. LIMED STOCK
IIide
Processor
Ammonium sulfate
Rating enzyme
Spent chrome liquor
Salt
&SO4
Calcium formate
Commercial chrome liquor
Bicarbonate

240
24
800
1200
360
240
290
180

Ibs.
Ibs.
gal.
ihs.
Ibs.
Ihs.
gal.
Ibs.

c,ooo LHS. 0
Saving 6.6% on Chromium Tanning Materials
Saving 33% on Salt

Two
Drums

240 Ibs.
24 Ibs.
1800 Ihs.
360 Ibs.
240 Ibs.
290 gal.
180 Ibs.

Ilide Processor
Saving Chrome
240 Ibs.
24 Ihs.
24 Ihs. CrzOa
1200 Ibs.
360 Ibs.
240 lbs.
290 gal.
180 Ibs.

STOCK
19 gal. chrome liquor
600 Ibs. NaCl

166

THE RECYCLING O F CHI<OME TANNING LIQUORS

-

TABLE: V
ANALYSIS OF S P E N T SOLUTIONS

-Sample: 4 Batches Chrome Coinporite

Unfiltered
Suspended Solids

6.194 mg./l.

CrzOs

0.348%
0.029 Ibs./gal.

Salt

4.83 g./100 ml.

Filtered

Suqwntled Solids

5.692 mg./l.

CrzO:i

0.352%
0.030 Ibs./gal.

Salt

4.87 g./lOO ml.

0.405 Ibs./gal.

___

After working with the system for some time, it was decided that the quantity
of chrome to be used in the tannage shoiild not he decreased in accordance with
the quantity used in the pickle. T h i s resulted in an increase in the chronie fixed
by the leather with no change in the quantity of the material used,
I t was found that in discharging the chrome liquor from the processors it was
best not to run the hide processors to extreme dryness. The chrorne liquor should
be pumped out well, tvith the leather lying in a static condition. T h i s method
a v o i d d the mill grain effcct. 'I'he system h i l s worked very well, and this company has heen producing leather on this hasia for over eieht months.
Stratigraphic analyses of the clirome leather produced shows good, even penetration in both tannages (?'able V I ) . W e are well satisfied with the quality
of the leather.

TAHI,IC \'I
STRATIGRAI'HIC ANALYSIS - c/o CrzOs
(Hide Substance Basis)
Layer
(Number)

Recycle System

Regular System

4.97
3.19
3.69
3.91
3.94
3.97
4.27

2.85
4.06
3.76
4.39
2.68
4.13
4.40

Grain
2
3
4
5
6

Flesh

THE KECYCLINC O F CHROME TANNING LIQUORS

167

Some additional savings could he obtained if sump pumps were arranged with
the machine and the floor drains, hut w e have not gone into this additional complication since the quantity of chrome discharge is now within the acceptable
limits.
ACKNOWLEDGMENTS

T h e authors would like to thank Fred Severance of Seal T a n n i n g Company

for his help and encouragement on this project, and also Julian Agoos of Seal
Tanning for his permission to puhlish this work.
REFERENCES
1. OFlaherty, F.
Roddy, W. T . ,
2. Hauck, R. A.
3. Osugi, T . , and
4. Osugi, T., and

Chemistry and Technology of Leather, Vol. 11, p. 260 (OFlaherty, F.,

and Lollar, R. M., Editors), Reinhold Publishing Corp., N e w York, 1958.
J A L C A , 67, 422 (1972).
Thorstensen, T. C. J d L C A , 64, 357 (1969).
Thorstensen, T . C. JALCA, 65, 594 (1970).

Received February 25, 1974 ; revised, February, 1976.

DISCUSSION

MR. RAYMOND
A. HAIJCK(Geo. Moser Leather Company; then at Tanners
Council Laboratory) : T o m , I would like to thank you for bringing us a practical
paper. T h e work presented today demonstrates again that recycling is practical
as a means of reducing chrome in the prime tan effluent. Previously w e have had
reports on recycling chrome in the paddle and in the d r u m system. T h e current
success in the hide processor certainly indicates that the recycle can be attained
in normal tannery processes regardless of the equipment being used for chrome
tannage.
I n addition to reducing the chrome in the effluent, the results suggest that
the step can save money on tanning material costs without adverse effect on
leather quality. T o m , could you give us an overall estimate of the efficiency of
this system?

c.

Jv?

DR. r H O M A S
THOKSTENSEN :
are using approximately 1600 pounds
of C r 2 0 , per day. W i t h o u t any recycling, w e would be dumping about 320 lhs.
Cr,O, per day. W i t h the present recycling w e are dumping about 12 pounds
of Cr,O,, per day.
MK. ALREKT
S. J A n l I S O N (Seton Leather Company) : T o m , did you check
your chrome in the total tannery efluent after this recycling?
r .

DK.THOMAS
C. TIIOKSTENSEN:
1 his is very difficult to do in this tannery
due to the multiple sewer discharges in the old textile mill building which this
tannery uses. T h e r e is no comiion discharge. However, we can estimate that
figure based on the tannery use of 600,OO gallons of water per day. T h i s means

that with a loss of 12 pounds of C r 2 O 9per day o r 8 pounds of chromium, w e are

down to 1.6 tng. chroniium/liter.
MR. S I a n r u N I ) PANZEK
(Rohson-1,ang 1,eathers 1,td.) : Did you sccure any
analytical data on formates in the 1 ecycled liquors?
nil. 'rHOhIAS C. pI'IfOiISTl?NSi?N : $Vc did not analyze for formates. Similar
principles of huildup to a stahle level should result, and a saving in formate used
could he possible.
MIL SIGMUND ~ ' A N Z E K : W i l l the increase in formate level cause any diffiC U I tp ?

DR. THOMAS
C. THOI<STENSEN:
I do not espect any difficulty, and we have
not seen any practical difficulties in the tannery operations or leather quality.
MK. PANZEK
: Are many unfinished leathers marketed ?
nit. 'rHOKsTENsEN : hIIost of the leather is niade from heavy steerhides and
marketed as finished side leather.

MR. PANZEK:
H a v e you observed any darkening

of the blue stock as you con-

tinue recycling?

DK.THOKSTENSEN
: No, w e did not see any change as we entered the recycling
process. All tanning is now I u n on recycled liquors without any periodic dumping
of liquors. Even so, the blue color still seems entirely normal.
MR. PANZEK:
W h a t about the chrome you precipitate?
DK. THORSTENSEN
: 'This precipitated chroine is not reused.
MK. PANZER:
W e have been experimenting with a similar recycle system.
W e make a wide variety of unfinished leathers. W e have observed a darkening
of the color, hich plays havoc with our colors.
I)IL THWSTENSEN
: 'This has not been our experience. 'l'he chrome tanned
stock in this tannery is not significantly darker than the chrome tanned stock you
see in other tanneries, in m y opinion.

MR. SATYENDRA
M. D E (Chestnut Operating Company) : LVe have been
working on chrome recycling. I n suede leather we found color darkening after
tannage. Have you tried suede leathers?
DR. rrHORSTENSEN: W e have not seen this color darkening. T h e tannery
does not make suede leather.
O n e possible cause of color darkening could be fat huildup in the chrome tanning liquors. T h i s would be accentuated in suede leather. Since w e do draw off
the accumulated grease, we may be avoiding this prohlem.
MR. DE: We thought of that also.
~ I KRAYMOND
.
A. H A u C h : 7'11ank you, 'l'oni, for a very interesting practical
paper.