M.

Kolb, Fachhochschule Aalen

Treatment of Industrial Wastewater

1. Chemical Industry
1.1 Biological treatment
Because of the enormous adaptation ability of bacteria biocenosis waste-
water of the chemical industry can often be biologically treated
(aerobically). The following points must however be considered:

- Determination of the BOD5 : N : P ratio

(should be about 100 : 5 : 1)
- Investigations which wastewater streams can be treated
biologically (laboratory scale, pilot plants)
- Investigations which wastewater streams have to be
pretreated (adsorption, extraction, chemical oxidation)
- Excess sludge can not be used for production of biogas?

In few cases the wastewater is treated anaerobically.

Schematic diagramm of the BASF Ludwigshafen wastewater-treatment plant

Daily influx 700.000 m3

BOD5 load 375.000 kg/day
BOD5 removal 97 %
COD removal 89 %
Nitrate removal 98 %

a) Neutralization b) Wastewater pumping station

c) Fine screen d) Activated-sludge treatment
e) Clarification f) High-water pumping station
g) Sludge pumping station h) static thickener
i) Filter press j) Steam generation
k) Two-stage steam turbine l) Generator
m) Fluidized-bed furnace (for sludge) n) Condensation
o) Electrostatic filter p) Wet off-gas treatment
 Special Bioreactors used in chemical industry

 Deep shaft process (ICI)

depth 200 m !

 Bayer Tower Biology (Turmbiologie)

height 30 m

 Tall Bioreactor (Biohochreaktor, Hoechst)

height 20 m

Advantages:
 
O2-Exploitation better
21 % (air)  5 % (off-gas) ; normal activated sludge process: 21 %  16 %

Lesser requirement of area

Closed reactors  no emission of aerosols and odour

The Hoechst tall bioreactor (Biohochreaktor) process
Hoechst tall bioreactor (Biohochreaktor)
1.2 Extraction
 
Examples:
Phenol can be extracted from wastewater with butyl acetate, cumene or
diisopropylether. The remaining concentration is between 20 and 500 mg/l
which is not toxic for the bacteria in the activated sludge tank. Phenol and
the extraction solvent are separated in a following distillation process. The
extraction solvent is reused in the process.

Acetic acid can be extracted with ethyl acetate, again the extraction solvent
is recycled for the process and acetic acid is a valuable substance
1.3 Adsorption
 
(very important also for the purification of drinking water and waste gas)

Adsorption processes are used for waste water generally, but mostly for
individual wastewater streams.
 
Adsorbents:
Activated carbon
Lignite coke
Aluminium oxide
Adsorber resins
Regeneration:
Activated carbon can be thermally reactivated, i. e. the adsorbed substances are
combusted

Lignite coke is burned

Aluminium oxide is thermally regenerated

Adsorber resins can be regenerated with methanol or acetone

Applications:
Aniline is adsorbed from alkaline solutions, desorption by acid solutions

Phenol is adsorbed from acidic solutions, desorption by alkaline solutions

Landfill leachets (Deponie-Sickerwasser) can be treated biologically followed by

ultrafiltration and activated carbon adsorption (for non-biodegradable substances)

Special Application:
Addition of activated carbon into the activated sludge basin  growth
surface for microorganisms causes higher biomass concentration.
1.4 Wastewater incineration (“Abwasserverbrennung”)
Combustion of organic substances, water matrix is simultaneously vaporized

Suitable if:
- substances present are poorly biodegradable or biologically toxic
- high organic load → heat of combustion is sufficient for vaporation of
water
- the wastewater contains a multicomponent mixture in which concentrations
vary in a large amount
- salts shall be recycled
Applications:
-icincineration of wastewater from terephthalic production
-incineration of wastewater which contains lignosulfonic acids
-emulsified organic matter

Problems:
- metal corrosion by acids
-  incrustination by salts
-  flue gas treatment
 
Combination with combustion of waste gases and solids is possible
Wastewater incineration

1 oil burner 2 cumbustion chamber

Clariant AG, Gersthofen plant 3 mix pipe 4 waste heat boiler
5 chimney 6 circulation evaporator
reasonable from ca. 50.000 mg/l 7 condensation tank 8 feed pump
COD, therephthalic acid 9 combustion air fan 10 fuel oil tank
11 fuel oil pump 12 fuel oil preheater
13 wastewater reservoir 14 wastewater pump
(the combustion energy of the
organic compounds meets the a steam 6 bar overpressure b steam 0,9 bar overpressure
c condensate d air
evaporation energy of the water) e fuel oil f wastewater
g sludge
1.5 Wet Oxidation (Nassoxidation)
Oxidation with O2 at higher temperature and higher
pressure, water not vaporized
Often followed by biological treatment

Characteristics:
-    for not degradeable or slowly degradeable or toxic substances
-     for partial streams
-     for high concentrations of contaminants
-     some tolerance for salts and acids
-     corrosion problems (Ti, PTFE)
Low pressure wet oxidation T < 200 °C, p = 5 – 20 bar
At COD > 6.000 mg/l: heat recovery from enthalpy of oxidation is
comparable to the total energy requirement of the process
 
SO32-/HSO3-, phenol, amino- and hydroxyl substituted phenols,
waste water from dye manufacturing
 
AOX decreases, COD decreases, BOD5 increases
 
High pressure wet oxidation T > 200 °C, p > 20 bar
At COD > 50.000 mg/l: heat recovery from enthalpy of oxidation
is comparable to the total energy requirement of the process
 
wet oxidation plant
T = 300 °C, p = 120 bar
1.6 Oxidation with H2O2, H2O2/UV, O3
Often followed by biological treatment
 
H2O2:
hardening plants, tanneries
Selfdecomposition, catalyzed by heavy metal ions is unfavourable
 
H2O2/Fe2+ (Fenton’s reagent):
H2O2  HO+ + HO-
Fe2+ + HO-  Fe3+ + HO·
HO· + H+ + e-  H2O

from oxidized substances

 
Best results at pH 3
Neutralization leeds to sludge formation
O3, O3/UV:
two mechanisms:
 
so called direct oxidation under acidic conditions, slow process
– can be accelerated by UV-rays
O3 + hν  O· + O2
O· + H2 O  H2 O2
H2O2 + hν  2 HO·
 
alkaline oxidation takes place also via the intermediate
formation of hydroxyl radicals
O3 + HO-  HO2- + O2
HO2- + O3  ·O2- + O2 + HO·
H2O + O3 + ·O2-  HO- + 2 O2 + HO·
 
Organic halogen compounds are dehalogenated, but formation
of new organic halogen compounds from inorganic halides is
possible
2. Breweries, tanneries, papermills, creameries, food- production

Wastewater can be treated biologically (aerob) but BOD5 : N : P-ratio has

to be checked.
 
 
Danger:
Wastewater can cause the formation of bulking sludge (Blähschlamm).
The extent of activated sludge flocs is diminished relative to filament-like
organisms
 
 Microscopic pictures of activated sludge

many filament-like
strong bacteria bacteria bulking
flocs (90x) sludge, slow
sedimentation (115x)

Sphaerotilus natans, Vorticella spec.

filament-like (230 x)
Bacteria (1150x)
3. Anaerobic treatment of wastewater

Sugar industry, starch industry, yeast manufacture, alcohol destillation

BOD5-concentration > 2000 mg/l

Compare anaerobic treatment of sludge in municipal wastewater

treatment

Subsequent aerobically biological purification is necessary

Anaerobic degradation of organic substances to biogas

P roteins, C arbohyd rates, F ats

H y d rolyses
(facu ltative
an aerobic b acteria )
A m ino acids, S ugar, G lycerole, F atty acid s

F orm ation of acids

(facu ltative
a n aerobic b a cteria )

H P O 42- H 2 /C O 2 P rop ion ic acid

N H 4+/N H 3 A cetic acid
B u tyric acid
H 2S A lk oh oles
F o rm ation of acetic acid
(acetogen ic ba cteria)
H 2 /C O 2
A cetic acid

F orm a tion of m eth ane

(m eth ano genic b acteria)
~ 70 % C H 4 , ~ 30% C O 2
Advantages:

•No energy for supplying the process with air

•Energy rich biogas is formed
•Less production of sludge (ca. 10 % compared with aerobic
degradation)
  
Disadvantage:

•Residence time longer (> 2 days)  not for treatment of municipal

wastewater
 Two-stage anaerobic fluidized-bed
Carbon balances in the (A) aerobic and
reactor for treating wastewater from
(B) anaerobic microbial degradation of
baker’s yeast manufacture by Gist
organic compounds
Brocades, Delft, Holland
pilot plant for anaerobic treatment of textile waste water (right)
and aerobic treatment of municipal + textile waste water (left)
Aalen-Unterkochen
4. Electroplating industry
 
Many electroplating facilities
 
After electroplating the workpiece has to be cleaned from the adhesive solution;
by this washing process wastewater occurs
 
wastewater contains toxic components: cyanide (CN -), chromate (CrO42-), Metal-
ions and slowly biodegradeable organic components (EDTA)
 
Special treatment of wastewater is necessary
separated facilities for treatment of chromate, cyanide and acidic bathes
former: wastewater from flow-basin was led directly into the detoxification
plants, today it is led into ion-exchange facilities and reused in the flow-basins
cation-exchanger anion-exchanger

 Polymer resin -SO3- H+ Polymer resin N OH

-

After regeneration of the ion-exchanger (HCl, NaOH) the concentrated

solutions are detoxified
 Cyanide:

CN- + OCl- + H2O  Cl-CN + 2OH- (pH = 10 – 12)

toxic
 
Cl-CN + 2OH-  OCN- + Cl- + H2O
 
Disadvantage: chlorinated compounds are formed (AOX) with organic additives
of the bathes
 
Therefore: oxidation with H2O2/UV, O3, H2SO5, H2O2/H2SO5
 
Chromate:
 
Cr2O72- + 3 HSO3- + 8H+  2Cr3+ + 3HSO4- + 4 H2O (pH ~ 2,5)

Metal ions:
 
Me2+ + 2OH-  Me(OH)2 
Me3+ + 3OH-­  Me(OH)3   
Precipitation with polymers containing –SH-groups or Na2S also possible
Sludge:
 
Filter press, hazardous waste site
 
 
Newer developments:
 
Recycling of metal ions:
electrolytic deposition after
-         reverse osmose
-         electrodialysys
-         ion-exchanger