CASE STUDY 2: LEATHER MANUFACTURE

Company B operates a tannery in south-east Asia processing cattle hides into finished leather,
mainly for side upper leather in shoe manufacture. Treatment of the hides involves a series of
batch operations involving application of a wide range of physical and chemical processes.
Wastewaters discharged contain pollutants from the hides, products from their decomposition,
and chemicals and various spent solutions used for hide preparation and during the tanning
process. Solid wastes and some atmospheric emissions also arise.

The company was required to meet new government standards for discharge of wastewater to the
local watercourse. This necessitated improvements to existing treatment facilities which were
then limited to crude settlement in three lagoons operated in series. Primary sludge produced
was disposed of in liquid form on a large area of surrounding land.

In the light of this situation, the company engaged a local consulting engineering firm to assist
their staff in carrying out a waste audit and waste reduction programme with a view to developing
the best and most cost-effective solution to the waste treatment and disposal problems.

The principal tannery operations carried out, typical of many tanneries throughout the world,
may be summarised as follows.

Pretanning (or Beamhouse) Operations

l soaking of the imported, preserved (wet-salted) hide in water overnight to remove blood,
dung, curing salt and water-soluble and saline-soluble proteins;

l unhairing (complete dissolving of all hair) by immersion in lime and sodium sulphide - and
subsequent reliming;

• trimming and mechanical removal of extraneous tissue from the flesh side of the hides - and
subsequent splitting (lime splitting) of the upper two-thirds grain layer from the lower, less
valuable split layer;

l deliming by treatment with a weak acid (lactic acid) and bating with an enzyme-
based chemical to remove hair remnants and degraded proteins;

l pickling using salt and sulphuric acid solutions to give the required acidity to the skins to
prevent subsequent precipitation of chromium salts on the skin fibres - pickled splits are then
sold to other tanneries for further processing, only the grain layers being tanned and finished
by Company B.

Thus, wastewaters from the beamhouse contain high levels of suspended solids and dissolved
organic matter, curing salt and grease, in addition to unused process chemicals (particularly
sulphides); they will also be alkaline, having a high oxygen demand.

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 Case Study 2: Leather Manufacture

Tanning

Chrome tanning is carried out using chromic sulphate. The tanning process stabilises the
proteineous (collagen) network of the hide. Acidic effluents are produced which contain unused
trivalent chromium salts.

Post-Tanning Operations

These involve:

pressing (samming) to remove moisture;

a second levelling by shaving;

dyeing and softening of the tanned hide with emulsified oils (fatliquoring), preceded by
occasional secondary tanning using synthetic tannins (syntans) and tanning extracts;

drying and final trimming;

surface coating and buffing (finishing)

The following case study describes the waste audit/waste reduction approach taken.

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PHASE 1: PREASSESSMENT

Step 1: Audit Focus and Preparation

It was decided that the study investigations would be carried out by a chemical engineer from the
consulting firm’s staff who had previous experience of carrying out waste audits, assisted by the
tannery’s plant chemist.

Company B’s own laboratory was not equipped to carry out many of the tests normally associated
with wastewater analysis and so arrangements had to be made to deliver samples to a local private
company providing laboratory analytical services.

In view of government pressures, it was decided to concentrate on wastewater discharges arising

from the beamhouse and subsequent tanning operations. However, atmospheric emissions were
also investigated having particular regard to health and safety. Solid waste arisings, in particular
wastewater treatment plant sludges, were also studied.

The waste audit team was keen to gain the support of production personnel in order to ensure
that comprehensive information on all tannery operations could be readily obtained. As a first
step therefore, the study objectives were fully explained to selected staff responsible for the
various production activities.

The investigations were initiated by gathering relevant information from company files. This
preliminary search yielded site and drainage plans, raw material purchase records and water
meter records associated with on-site borehole abstraction.

A preliminary check on water usage was carried out by calculating the water usage per tonne of
wet-salted hide processed. This was found to be 61 m3/tonne. It was noted that this was some
22% higher than the typical average working figure of 50 m3/tonne reported in technical litera-
ture, suggesting that ways of introducing considerable water savings should be possible as a result
of the waste audit/waste reduction study.

Step 2: Listing Unit Operations

The consultant and the plant chemist started the tannery study by walking around the processing
and waste treatment areas, listing all the unit processes and making notes on their function and
use. Help was also sought from various plant operators who were familiar with the day to day
plant operations. The unit operations were listed in Table 1, with processes which did not
produce liquid waste shown in brackets.

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 Case Study 2: Leather Manufacture

Table 1: Unit Operations

Soaking
Unhairing and Reliming
(Trimming, Fleshing and Splitting)
Deliming and Sating
Pickling
Chrome Tanning
Pressing
(Shaving)
Secondary Tanning, Dyeing and Fatliquoring
(Drying, Trimming and Sorting)
(Finishing)

As part of the company’s long-term planning, the plant chemist noted that consideration was
being given to moving the hide splitting operations further downstream the process line (after
tanning) in order to improve the accuracy of splitting and hence overall process control, as
commonly practised at other tanneries. The existing arrangement and design of process units,
many of which were relatively old, did not however lend themselves to this change being imple-
mented rapidly.

Step 3: Constructing Process Flow Diagrams

A flow diagram was then prepared to illustrate the interrelationship between the various unit
operations (Figure 1).

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Figure 1: Schematic Diagram of Tannery Operations

INPUTS UNIT PROCESS OUTPUTS

Imported wet-salted
hide Salted Stock

Bactericide , soda ash, Dirt-laden, saline

water liquors

Hydrogen sulphide
Lime, sodium sulphide
water Alkaline waste
waters *

Trimmings and fleshings

Lactic acid, bate,

ammonium
chloride, water

Brine and
Salt, sulphuric acid, acid dilution
water waters

Pickled splits

Chromic sulphate, salt,

syntan, sodium Acidic wastewaters
formate, containing Cr3+
soda ash, bactericide syntan, salts

Press liquors

Tanning extracts,
syntan,dyes, calcium
formate, flour, glue,
titanium dioxide, oil,
water

Surface coatings

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PHASE 2: MATERIAL BALANCE: PROCESS INPUTS AND OUTPUTS

Step 4: Determining Inputs

The audit preparation phase (Step 1) had already highlighted the availability of well-documented
raw material purchasing records. The data produced also proved to be a good check on the raw
material quantities quoted by the plant foremen per unit operation.

The raw material usage data obtained were set out as in Table 2.

Table 2: Annual Consumption of Process Chemicals

Process Chemicals tonnes/annum

Sodium Chloride (other than curing salt 622

present in raw hide)
Hydrated Lime 1,123
Sodium Sulphide (62% Na2S) 445
Sulphuric Acid 166
Soda Ash (anhydrous sodium carbonate) 74
Bate (95% ammonium sulphate, 65
5% enzymes)
Calcium Formate 40
Lactic Acid (38%) 35
Sodium Formate 26
Bactericide 19
Ammonium Chloride 9

Sub-total 2,618

Chemicals Absorbed by the Hide (i)

Tanolin (16% chromium) 760

Syntans A & B 424
Dyes 77
D-l Oil 17
Other Oils 295
Tannin Extracts 190
Soyarich Flour 45
Titanium Dioxide 30
Methyl Cellulose 9
Semi-Sol Glue 17

Sub-total 1,864

Total 4,482

(i) Absorption estimated at 90%, 10% discharged to waste - except for Tanolin, absorption 75%, 25% discharge
to waste

Due to the nature of the raw materials and the well-organised materials storage system which was
found to be in operation, no significant handling losses were occurring.

It was noted that the company incurred no charges for consumption of water drawn from a site
borehole. A separate town water (potable) supply was available for domestic use. Domestic
wastewater passed to the nearby watercourse via a septic tank.

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Case Study 2: Leather Manufacture

Having already tabulated the key production stages (Step 2), raw material usage listed in Table 2
was used to derive average quantities per unit operation throughout the tannery, on both a daily
basis and per tonne of hide processed.

The data compiled were set out in Table 3.

Table 3: Chemical Inputs per Tannery Unit Operation

Unit kg/tonne hide kg/tonne kg/d
Operation (at unit operation) wet-salted hide

Soaking
Bactericide 1.6 (i) 1.6 64
Sodium Carbonate 0.8 (i) 0.8 32

Unhairing/Reliming:
Hydrated Lime (unhairing) 48 (i) 48 1,920
Sodium Sulphide (62% Na2S 43 (i) 43 1,720
Hydrated Lime (reliming) 58 (i) 58 2,320

Deliming/Bating:
lactic Acid 5 (ii) 4.3 172
Bate 10 (ii) 8.7 348
Ammonium Chloride 1.3 (ii) 1.1 44

Pickling
Sodium Chloride 60 (ii) 51.9 2,076
Sulphuric Acid 21 (ii) 18.2 728

Chrome Tanning
Tanolin (basic chromic sulphate, 16% Cr3+) 60 (ii) 51.9 2,076
Sodium Chloride 60 (ii) 51.9 2,076
Syntan A 25 (ii) 21.6 864
Sodium Formate 8.9 (ii) 7.7 308
Sodium Carbonate 10 (ii) 8.7 348
Bactericide 1 (ii) 0.9 36
Syntan B 41 (ii) 35.5 1,420

Secondary Tanning Dying

and Fatiquoring:
Dyes 20 (iii) 7.0 280
Calcium Formate 10.3 3.6 145
Syntan B 44 (iii) 15.4 616
Soyarich Flour 16 (iii) 5.6 224
Titanium Dioxide 8 (iii) 2.8 112
Glue/Methyl Cellulose 8 (iii) 2.8 112
Tannin Extracts & Oils 118 (iii) 41.3 1,652

Total 19,693

(i) Based on 40 tonnes wet-salted hide per day

(ii) Based on fleshed, split/trimmed hide, after reliming - 34.6 tonnes per day
(iii) Based on chrome tanned leather, after pressing/shaving - 14.0 tonnes per day

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 Case Study 2: Leather Manufacture

Step 5: Recording Water Usage

The next step was to record the water usage at the tannery and determine how it was used. It was
noted that water obtained by the company from the site borehole was pumped to a covered
storage tank at ground level and then pumped again to a high-level storage tank. Water then
gravitated to the site distribution mains under static head via a water meter, readings for which
were recorded weekly in a log book.

Analysis of these records indicated a daily average total water consumption for the site of 2,450
m3/d. This figure was then broken down into average water usage per tannery unit operation in a
similar manner to that carried out for the process chemicals. Since the tannery wet processes
were all carried out in revolving vessels of known capacity, providing mechanical agitation to
accelerate the wet-chemical operations, batch process water inputs were readily quantifiable.
Rinsewater usage which was continuous for a fixed duration per batch was also known from
previous work carried out by the company. This had involved checking the time taken to fill a
vessel of known volume for a given water valve setting.

The results were summarised as set out in Table 4.

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Case Study 2: Leather Manufacture

Table 4: Water Inputs per Tannery Operation

Unit m3/tonne hide m3/tonne m3 /d

Operation (at unit operation) wet-salted hide

Soaking.-
Prewash 4.3 4.3 172.0
Process Water 1.9 1.9 76.0
Rinse Water 2.1 2.1 84.0

UnhairinglReliming:
Process Water 1.9 76.0
Rinse Water 11.0 440.0
Soak Water (reliming) 1.9 76.0
Rinse Water 2.1 84.0

Deliming/Bating
Pre-rinse 4.2 (ii) 3.635 145.4
Process Water 1.0 (ii) 0.865 34.6
Rinse Water 1.385 (ii) 1.2 48.0

Pickling:
Brine Water 2.49 (ii) 0.215 8.6
Acid Dilution Water 0.84 (ii) 0.073 2.9

Chrome Tanning:
Process Water 0.586 (ii) 0.507 20.3
Rinsing 4.51 (ii) 3.9 156.0

Pressing: 0.202 (ii) 0.175 7.0

Secondary Tanning, Dyeing

and Fatliquoring:
Prerinse 9.15 (iii) 3.2 128.0
Process Water 0.4 (iii) 0.14 5.6
Rinse Water 18.6 (iii) 6.5 260.0
Process Water 0.4 (iii) 0.14 5.6

General floor and Plant Washwater 15.5 620.0

Total - Process Waters 12.115 484.6

- Rinse Waters 33.635 1345.4
- General Washdown 15.500 620.0
- Total 61.250 2,450.O

(i) Based on 40 tonnes wet-salted hide per day

(ii) Based on fleshed, split/trimmed hide, after reliming - 34.6 tonnes per day
(iii) Based on chrome tanned leather, after pressing/shaving - 14.0 tonnes per day

Step 6: Measuring Current Levels of Waste Reuse/Recycling

It was noted that no wastes were reused/recycled at the tannery.

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 Case Study 2: Leather Manufacture

Step 7: Quantifying Process Outputs

The audit team listed ‘the process outputs from each tannery unit operation as set out in Table 5
below.

Table 5: Process Outputs

Unit Operation Wastewater By-Product/ Atmospheric

Waste Reuse Emissions

Soaking Process and

Wash/Rinse
Waters

Unhairing/Reliming Process and Hydrogen Sulphide

Rinse Waters

Trimming, Fleshing and Splitting Trimmings and

Fleshings

Deliming/Bating Process and

Rinse Waters

Pickling Process Brine/

Acid Dilution
Waters

Pickled Hide Storage Pickled Splits

Chrome Tanning Process and

Rinse Waters

Pressing and Shaving Press Liquors Shavings

Secondary Tanning, Dyeing and Process and

Fatliquoring Rinse Waters

Drying, Trimming and Sorting Trimmings

Finishing Solvent Vapours

Final Product Finished Leather

(grain layer)

Action was then taken to quantify these outputs in Steps 8,9 and 10.

Step 8: Accounting for Wastewater

Process wastewater flows were based on totalling up batch water inputs and making allowances
where appropriate for water retention by the hide at each process stage based on percentages
reported in technical literature.

Composite samples of the various discharges were also taken for laboratory analysis.

The results of this exercise were summarised in Table 6.

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Case Study 2: Leather Manufacture

Table 6: Average Flows, Strengths and Pollution Loads of Strong Liquors

Unit Operation flow BOD SS
m3 /d %of pH mg/i kg/d % of mg/l kg/d % of
total total total

Soaking 276 42.1 6.8 2.200 607 19.8 4,400 1,215 30.0
Unhairing 103 15.7 11.5 15,500 1,597 52.0 22,100 2,276 56.1
Reliming 103 15.7 11.7 650 67 2.2 1,650 170 4.2
Delime and Bating 66 10.1 9.5 6,000 396 12.9 2,100 139 3.4
Pickling 37 5.6 2.7 2,900 108 3.5 5,200 192 4.7
Chrome Tan & Press
Liquors 33 5.0 3.6 6.500 215 7.0 1,100 36 0.9
Secondary Tanning,
Dyeing &
Fatliquoring
- 1st dump 19 2.9 4.0 2,000 36 1.2 600 11 0.3
- 2nd dump 19 2.9 3.7 2,200 42 1.4 850 16 0.4

656 100.0 - - 3,070 100.0 - 4,055 100.0

It was decided that having quantified the main, strong-liquor pollution loads per unit operation,
separate quantification of running rinsewater pollution loads per unit operation was not justified
since this would have meant setting up numerous V-notch weirs and many additional sampling
points, thus increasing significantly the time input and analytical work required.

The relatively weak continuous-flow rinse waters were thus monitored using a V-notch weir
located in a common drain within the tannery and combining frequent spot samples to give a
daily composite for the whole tannery. Total rinsewater flow including general floor and plant
washdown was estimated to be 1,944 m3/d with an associated BOD and SS strength of 273 mg/l
and 3% mg/l SS. Corresponding pollution loads (flow x strength) were thus 530 kg BOD/d and
770 kg SS/d.

The overall wastewater flows and BOD and SS strengths and pollution loads were then tabulated
in Table 7.

Table 7: Combined Wastewater Flows, Strengths and Pollution Loads

Wastewater Flow BOD SS

m3/d mg/l kg/d mg/l kg/d

Strong liquors 656 4,680 (i) 3,070 6180 (i) 4,055

Rinse Waters/General 1,944 273 530 396 770

Washdown

Total 2,600 1,430 (i) 3,600 1,950 (i) 4,825

(i) Concentrations calculated from flow/pollution load data

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 Case Study 2: Leather Manufacture

Based on an average 40 tonnes of wet-salted hide processed, it was noted that these overall
figures equate to 65 m3 wastewater/tonne, 90 kg BOD/tonne and 121 kg SS/tonne, ie fairly
typical unit loads compared with average figures for similar tanneries elsewhere but some
20-25% high in terms of wastewater flow.

An assessment was also made of chromium and sulphide pollution loads based on selected
additional wastewater analyses carried out. This yielded pollution loads of 198 kg Cr/d and 412
kg S"/d, equivalent to 4.9 kg Cr/tonne and 10.3 kg S/tonne. Again, it was noted that these loads
were fairly typical in the consultant’s experience even for well operated tanneries, although
somewhat higher (14% and 21% respectively) with respect to figures reported by WHO, 1982.

A number of other checks were also made. It was noted that while it was difficult to measure
combined wastewater flows entering the wastewater treatment system, the final lagoon effluent
discharged via a rectangular weir. In order to obtain some cross-check on the combined raw
wastewater flow set out in Table 7, the final effluent flow to the nearby watercourse was moni-
tored using this weir. An average flow over the study period of 2,200 m3/d was recorded.

A limited number of samples of the lagoon effluent were taken and results compared with the raw
wastewater analyses tabulated in Table 7. These indicated pollution load reductions averaging
40% BOD and 70% SS. Based on an average sludge concentration of 6% dry solids, calculations
indicated that the volume of primary sludge generated averaged 56 m3/d. The audit team noted
that while this sludge was periodically being disposed of on surrounding land, this practice would
not be allowed to continue in the future as liquid run-off caused additional pollution problems in
the nearby watercourse, particularly during wet weather.

Step 9: Accounting for Gaseous Emissions

It was decided that consideration of atmospheric pollution issues in the context of this project did
not justify the need for making use of portable gas detection equipment, such facilities in any
case not being readily available. It was also considered that resources required to quantify
gaseous emissions would be out of proportion to the extent of the problems occurring. However,
various useful observations were made during the site survey.

A strong smell of hydrogen sulphide (H2S gas was evident at the primary sedimentation stage of
the wastewater treatment plant. H2S was also evident, although only to a limited extent, within
the tannery processing areas where alkaline beamhouse liquors combined with subsequent acidic
streams within the internal drainage system.

The plant chemist knew that the hydrogen sulphide was a highly-toxic gas having a threshold limit
value (TLV) of 15 mg/m3 (100 ppm by volume) in air. He also knew that the extent to which H2S
could be released from solution to atmosphere was pH dependent, high pHs favouring the
ionised form (HS’) and hence reduced risk of sulphide stripping. He therefore noted that any

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Case Study 2: Leather Manufacture

future wastewater treatment scheme would be best designed to allow pretreatment of alkaline
beamhouse liquors (pH at least 10) before they were allowed to mix with other, acidic waste
flows.

No release of ammonia associated with deliming/bating was apparent but it was noted that release
of some solvent vapours in the working areas associated with leather fmishing could be a potential
health risk to production staff. Discussions with the management subsequently revealed that
plans were already underway to install forced-ventilation equipment to cater for this problem.

Step 10: Accounting for Off-Site Wastes

The only wastes which were recycled were fleshings which were transported to a local rendering
company; these amounted to an average of 9,200 kg/d.

Trimmings and shavings were disposed of to a local municipal landfill site and amounted to
14,600 kg/d.

No sale costs associated with disposal of the fleshings could be readily identified at the time of the
waste audit. It was later established that no charge was levied by the tannery in return for the
rendering company providing transportation facilities at their cost.

Trimmings and shavings were disposed of at an annual cost of US$14,000.

Step 11: Assembling Input and Output Information for Unit Operations

From the information collected the preliminary material balances were started by assembling the
input and output data for the tannery and the wastewater treatment plant. These were tabulated
under Step 12.

Step 12: Deriving a Preliminary Material Balance for Unit Operations

A preliminary material balance of data associated with operations within the tannery was first
drawn up on an overall input/output materials basis. The information was tabulated as set out
below.

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 Case Study 2: Leather Manufacture

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Case Study 2: Leather Manufacture

Inputs kg/d
Cr

Chrome Tanning 332 (a)

(a) Based on 2,076 kg/d Tanolin containing 16% Cr3+

Chrome Tanning

Chrome Tan & Press Liquors 83 (a)

Chrome Leather 249 (b)

Rinsewaters 3 (c)

Total 335

(a) Based on 33 m3/d chrome liquors at 2,500 mg/l Cr3+

(b) Based on 2,076 kg/d Tanolin containing 16% Cr3+ and 75% chrome absorption into hide
(c) Based on 1,944 m3/d rinsewaters containing 1.5 mg/l Cr3+

Inputs m3 /d

Raw Wastewater 2,600

Wastewater Treatment Plant

Outputs m3/d

Primary Effluent 2,200

Primary Sludge 56

Total 2,256

Step 13: Evaluating the Material Balance

The waste audit team were confident that they had obtained an adequate material balance (within
510%) for the tannery as a whole as well as for the specific chromium and sulphide chemicals
used.

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 Case Study 2: Leather Manufacture

The material balance for the wastewater treatment plant was also considered reasonable taking
into account that some water seepage was possibly occurring through the base of the crude
lagoons, thus contributing to the 13% difference between inflow and total outflows recorded.

Step 14: Refining the Material Balance

It was considered that the material balance information obtained was sufficient to meet immedi-
ate requirements but that it would be useful to carry out a further waste audit once any waste
reduction measures had been implemented.

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PHASE 3: SYNTHESIS

Step 15: Examining Obvious Waste Reduction Measures

It was noted that the rinsewater usage following unhairing was appreciable, amounting to some
18% of the total water usage throughout the tannery.

It was considered that significant savings could be achieved at this stage by changing from a 4-
hour running rinse to a two-stage batch wash operation, each of 20-25 minutes duration. It was
anticipated following a short-term trial that it should be possible to achieve a consistent 60%
reduction in rinsewater usage, that is, from 440 m3/d to 176 m3/d.

The audit team also realised that considerable water wastage was taking place by tannery staff
leaving numerous hoses running in between general floor and equipment washdown operations.
On the basis of an average of 15 hoses in continuous use, it was estimated that water passing to
drain surplus to actual requirements could be as much as 136 m3/d, some 5% of the total waste-
water flow. Recommendations were therefore made for the fitting of pistol-grip self-closing
valves on all hoses in use throughout the tannery.

Thus, it was concluded that total wastewater flows could be reduced from 2,600 m3/d to 2,200
m3/d, reducing the wastewater production to a more respectable 55 m3/tonne wet-salted hide
processed.

Step 16: Targetting and Characterizing Problem Wastes

a) Sulphide Liquors
As indicated in Step 9, it was evident that pretreatment of all sulphide-containing liquors was
needed before they became mixed with other acidic flows; the possibility also existed of at
least partial recycle of fine-screened sulphide liquors in subsequent unhairmg operations.

The management favoured a flexible approach with the treatment system designed to handle
the total daily sulphide liquor flow if required, conscious that sulphide liquor recycle would
probably require a higher level of surveillance of the efficiency of the unhairing operation
which might not be readily achieved on a consistent basis in practice.

The audit team then proceeded to draw up design flow and strength data for the pretreatment
of sulphide-bearing waste streams; and also for the subsequent combined wastewater treat-
ment facility required to meet the government’s new discharge requirements.

Sulphide-bearing liquors were taken as being all the process and rinsewaters associated with
the unhairing process and all wastewater associated with deliming/bating other than the final
rinse. The resultant average design flow and sulphide load assessed were as shown in Table 8.

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 Case Study 2: Leather Manufacture

Table 8: Characteristics of Sulphide-Bearing Wastewater’s

Parameter Actual Design

Flow 590 m3/d * 600 m3/d

Sulphide 412 kg/d (700 mg/l) 420 kg/d (700 mg/l - ave.)
600 kg/d (1,000 mg/l - max.)

* assuming unhairing-stage rinsing carried out on a 2-stage batch basis to reduce water usage (equivalent
to 27% of total wastewater flows following instigation of water saving)

An assessment was made of the likely BOD reduction due to oxidation of sulphide. The
theoretical oxygen uptake rate due to oxidation of sulphide was taken as 0.75-2.0 kg O2/kg S"
depending on the ratio of the thiosulphate:sulphate oxidation products. Taking an average
1.4 kg O2/kg S” and a 97% S” reduction (down to 20 mg/l S”), this gave a BOD reduction of
560 kg/d.

With reference to Table 7, the combined wastewater BOD load can be expected to reduce
from 3,600 kg/d to 3,040 kg/d, equivalent to 1,380 mg/l BOD in a reduced flow of 2,200 m3/d.
Regarding the effect on suspended solids loads as a result of fine-screening of sulphide
liquors, actual removals were difficult to predict accurately without further test work. As a
conservative approach therefore, it was decided that the calculated total SS load of 4,825 kg/d
(Table 7) should be carried forward as a design SS load for sizing and budgetary costing of the
combined wastewater treatment plant; this gave a concentration of 2,190 mg/l SS at the
predicted future reduced flow.

b) Chrome Liquors
The audit team considered the possibility of recovering chrome from the chrome-bearing
liquors by fine screening, addition of sodium carbonate to precipitate chrome hydroxide (at
pH 8-8.5), filter-plate pressing of the resultant sludge and then conversion of the chrome
precipitate to soluble chromic sulphate using sulphuric acid.

Discussions with the management revealed that this possibility had been considered in the past
but was not favoured on overall technical and cost grounds unless the benefits of economy of
scale could be introduced by providing a centralised chrome recovery plant to serve all
tanneries in the local area. While some preliminary discussions had been held through the
national tannery association, such a scheme was not foreseen at this stage.

It was agreed therefore that for the present, the design of a new wastewater treatment plant
should assume that chrome would be precipitated and disposed of off-site as part of the
primary sludge generated.

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Case Study 2: Leather Manufacture

Step 17: Segregation

In order to segregate sulphide liquors for separate ‘pretreatment, it was decided to divert existing
drainage outlets in the unhairing area to a batch treatment plant located within the existing
tannery process building.

Treated flows would then be combined with all other wastewaters at a new treatment plant
located close to the existing settlement lagoon facility.

Step 18: Developing Long-Term Waste Reduction Options

The waste audit consultant was responsible for drawing up outline proposals for the required new
wastewater treatment facilities.

Consideration was given to available methods of sulphide treatment. These included:

l acidification to pH 2-3 and aeration, with absorption of the resultant hydrogen sulphide gas in
caustic soda solution within packed-tower scrubbers prior to discharge of the resultant liquor
to drain or reuse;

l precipitation with ferrous or ferric salts;

l oxidation using chlorine or hydrogen peroxide;

l oxidation using aeration with a manganese catalyst.

The latter method was considered the most technically satisfactory and cost-effective solution
following line screening. This view was supported by reference to available information sources
concerning operational experience elsewhere.

It was decided to divert existing drainage outlets in the unhairing area to a mechanical self-
cleaning screen (1 mm) located in a modified floor channel, the upper end being designed to
convey screenings to an adjacent skip.

Screened flows would then gravitate to a submersible pumping station to lift flows into one of two
batch-treatment oxidation tanks, one to be used for treatment and the other to be available for
receiving the next batch of liquor. A diffused-air system, using non-clog coarse-bubble diffusers,
was selected to provide mixing and aeration in each tank and a facility for dosing a solution of
manganese sulphate catalyst was incorporated.

The main treatment plant for pretreated sulphide liquors combined with all other wastewater
flows involved the following features:

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 Case Study 2: Leather Manufacture

l flow/pollution load balancing incorporating coarse-bubble aeration/mixing;

l pH correction (if required), chemical flocculation with alum and polyelectrolyte and subse-
quent primary settlement;

l extended aeration treatment using low-speed mechanical surface aerators (sized to provide a
robust biological system capable of withstanding fluctuating loads);

l batch storage/thickening of mixed primary and surplus secondary sludges prior to pumping to
drying beds and subsequent disposal of sludge cake to landfill.

Provision for iron salt dosing to the sludge storage/thickening tank was incorporated to precipi-
tate any sulphide formed as a result of anaerobic activity within the tank and hence to minimise
odour problems occurring.

A schematic diagram of the proposed treatment plant was compiled as illustrated in Figure 2.

Step 19: Environmental and Economic Evaluation of Waste Reduction

Options

Company B was placed in a position of having to upgrade its wastewater treatment system in
order to comply with new discharge standards imposed by the government, part of a new empha-
sis on the need to control pollution of the environment.

The new effluent discharge standards laid down were 40 mg/l BOD and 60 mg/l SS. Hence,
provision of a new treatment facility designed to meet these standards consistently was expected
to improve the quality of the local watercourse substantially.

There was a clear need to minimise capital and operating costs of the treatment scheme to ensure
the overall financial viability of the company’s operations. Therefore, in preparing outline designs
for budgetary purposes, particular attention was paid to providing a plant which would be robust
and relatively simple to operate.

The cost of the treatment scheme drawn up was estimated at US$500,000 including contingencies
and design/construction supervision fees. This reflected a conservative approach to the sizing of
the activated sludge process, particularly in terms of aeration capacity. It also took into account
the availability of two redundant water storage vessels suitable for use as sulphide-liquor treat-
ment tanks.

This approach was adopted to provide some flexibility over the mode of operation of the plant
with a view to minimising operating costs - it would allow the primary settlement stage to operate
without addition of chemical flocculants if desired, with consequent higher strength effluent

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 Final Effluent To
Watercourse

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