vvEPA
United States
Environmental Protection
Agency
Industrial Environmental Research
Laboratory
Cincinnati OH 45268
Research and Development
EPA-600/S2-81-086 July 1981
Project Summary
Evaluation of Ion Exchange
Technology for Toxic and
Non-Conventional Pollutant
Reduction in Bleach Plant
Effluents
John H Fitch, Jr
This research program was designed
to evaluate the applicability of ion
exchange technology in reducing the
pollutional effects of pulp, paper, and
paperboard bleach plant effluents.
To gain some perspective on the
state-of-the-art concerning ion ex-
change, a literature review was under-
taken to assess the effectiveness of
this technology in reducing toxic and
non-conventional pollutants. This
search revealed that weakly basic ion
exchange resins, based on a phenol-
formaldehyde matrix, are superior in
treating pulp and paper bleach plant
effluents. Additionally, the review
showed that, prior to resin treatment,
it is advantageous to adjust the pH and
pretreat the wastestream. This pre-
treatment step (screening and filtra-
tion) removes macromolecular organics,
which tend to foul the resin irreversibly.
The pH adjustment to pH 2 to 3 has
been found optimal for pollutant re-
moval with this resin type.
Three ion exchange design schemes
have been developed for treating
bleach plant effluents: the Dow process,
the Rohm & Haas process, and the
Billerud Non-polluting Bleach Plant
Concept. Of these systems, only the
Billerud Non-polluting Bleach Plant
Concept has been used on a full-scale
basis in the pulp, paper, and paperboard
industry (see Figure 1). All are struc-
tured with the intent of minimizing
chemical use and pollutant disposal
costs. To this end, ion exchange sys-
tems can be recommended because
process streams can be used to some
extent for eluting pollutants from ion
exchange columns and activating the
columns. Concentrated pollutants
(eluate) can be added to the recovery
system so that a residual does not
result from this treatment.
Batch and pilot plant ion exchange
installations at Billerud Uddeholm AB
(Swedish for Ltd.) in Skoghall, Sweden
were evaluated as a portion of this
project. This assessment was under-
taken to ascertain actual operation
parameters and removal efficiencies,
as well as associated problems and
costs. Analysis was done during this
assessment to determine the removal
effectiveness for 15 volatile com-
pounds, 34 semi-volatile compounds,
13 metals, chemical oxygen demand
(COD), color, chloride, and pH. Effec-
tive removal was noted for color (90
percent), COD (75 percent), chlori-
nated phenolics (90-100 percent),
chlorinated guaiacols (80-90 percent),
and some complexed metals. Addi-
tional amounts of these compounds
were removed during the reactivation
cycle. The Billerud Non-polluting
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Pulp from Screening
Back to
Screening Plant
Fresh Water Intake •
Drum Washing
Filters (Typ J
To Evaporation
and Ftecovery Boiler
The Only Effluent
Decolorized
Demutagenized
BOD - Reduced
Chloride Outlet
BOD7 - 5 kg/metric ton
COD - 15 kg/metric
Color - 4 kg/metric ton
Chlormation Stage
Extraction Stage (First)
Hypochlorite Stage
Chlorine Dioxide Stage (First)
Chlorine Dioxide Stage (Second)
Extraction Stage (Second)
Figure 1. The Billerud non-polluting bleach plant concept
Bleach Plant Concept did not effec-
tively remove resin and fatty acids of
phthalates.
Estimated capital cost for installing
a full-scale plant to treat bleach plant
wastes at a 100,000 metric ton/year
plant (Kappa 35) is $4.78 million.
Operation and maintenance costs are
estimated to be $675,000/year, giving
an annual cost (assuming a ten year
investment at ten percent interest) of
about 1.15 million dollars.
This report was submitted in fulfill-
ment of Contract No. 68-03-2605,
Work Directive No. 6. by the E. C.
Jordan Co. under the sponsorship of
the U.S. Environmental Protection
Agency. This report covers the period
January 24. 1980 to October 1. 1980
and work was completed as of June
25. 1980.
This Project Summary was devel-
oped by EPA's Industrial Environmen-
tal Research Laboratory. Cincinnati,
OH, to announce key findings of the
research project that is fully docu-
mented in a separate report of the
same title (see Project Report ordering
information at back).
Introduction
Concern in recent years for the effects
of toxic, mutagenic, and colored wastes
has sparked research that hassoughtto
devise safe means of disposing with
these wastes. These wastes have been
shown to be major contributors of color,
COD, toxicity and mutagenicity to the
effluent from pulp, paper and paper-
board industry bleach plants. The report
discusses ion exchange technologies
investigated for treating pulp, paper,
and paperboard bleach plant waste-
streams.
This study includes a summation of
both recent literature, and lab and pilot
scale work. An m-depth analysis was
undertaken to assess the usability of
this technology as operated at the
Billerud Uddeholm AB mill in Skoghall,
Sweden.
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The research reported in the literature
concerns many different wastewaters
containing differing concentrations of
pollutants Various ion exchange and
adsorption resins were tested in many
different configurations. Some research
was found which went beyond lab scale
testing to actual pilot plant testing at
pulp, paper, and paperboard mills
These plants make use of different
resins and treatment configurations,
but perform the same treatment steps.
The initial step involves a pretreatment
operation (screening and/or single or
dual media filtration) which reduces the
concentration of large particles (mac-
romolecules), whether organic or in-
organic. These solids may foul the resin
columns, in some cases irreversibly, so
that effective treatment is not possible
Another important part of the pretreat-
ment program is pH adjustment. The pH
must be adjusted until the pollutants are
in a form such that they can be removed
by the resin used. The optimal pH varies
with the resins, but is usually on the
acid side (pH 2 to 4) for pulp and paper
wastes. In the next step, the waste-
stream is passed through the resin
column (or columns if a series or parallel
operation is used) until breakthrough
capacity is reached. Breakthrough ca-
pacity is dictated by the overall removal
efficiency desired When the resin has
absorbed as much of the pollutants as it
can, the column must be removed from
service and eluted. During the elution
cycle, the wastewater can be fed to
backup columns, stored, or sewered.
During the elution cycle the exchanged
pollutants are removed from the satu-
rated resin co-lumn m a concentrated
form. The resins currently used in the
pulp, paper, and paperboard industry
require caustic solutions for elution.
Some columns can be eluted with
caustic streams found in the pulp mill.
This reduces costs, as virgin chemicals
need not be purchased. Once eluted, the
resins must be activated. For treatment
of bleachery wastes, this is best done
with an acid stream in the mill, again
reducing costs. Care must be taken
during the elution and activation
processes to insure that the resin is not
oxidized or otherwise damaged which
will reduce its useful life. The literature
reports that resins can be used for 3 to
12 months without losing substantial
capacity In these studies, different
types of resins and elution/activation
chemicals were used for removing
different waste components (i.e., de-
colonzation vs. deionization). Billerud
Uddeholm AB has successfully used the
Diamond Shamrock resin, developed
especially for their process, for fourteen
months without oxidation or damage
and expects the resin will be useful for
two years once the system is completely
optimized. Generally the high capacity
resins, though efficient pollutant re-
movers, have a very short life and are
susceptible to oxidation, while low
capacity resins resist oxidation and
have a longer useful life
After activation, the column can be
put back into service for another treat-
ment cycle. Initially, a new resin may
have a large removal capacity, but this
will dimmish after a few treatment
cycles. Additional capacity will be lost
slowly until the resin must be replaced.
Research and pilot scale studies in
the pulp, paper, and paperboard industry
have shown that it is possible to add the
eluted wastestream, which contains the
concentrated pollutants, to the black
liquor stream, which is normally con-
centrated and burned in recovery boilers.
The heat generated is captured as
steam and used in generating power
and in other mill processes. The resulting
slag is made up of inorganic chemicals
from the black liquor stream. Most of
these chemicals are components of the
cooking liquors and have been washed
from the pulp after the digestion process.
Additional inorganic chemicals in this
slag may be from chemicals used in the
mill, residual inorganics from the fiber
furnish, or inorganics eluted from the
resin columns. Chloride is the inorganic
in this slag of most concern to research-
ers, as large concentrations can accel-
erate corrosion in the boilers If an ion
exchange treatment system is operated
carefully, inorganic chlorides are not
picked up by the exchangers and, there-
fore, do not find their way to the recovery
system.
Both batch (full-scale) and pilot
(continuously operating, microprocessor-
controlled) systems of the Billerud Non-
polluting Bleach Plant Concept have
been instituted at the Billerud Uddeholm
AB plant in Skoghall, Sweden. These
systems were chosen to evaluate the
feasibility of ion exchange for treatment
of pulp, paper, and paperboard bleachery
wastestreams Construction of a full-
scale continuous ion exchange treat-
ment system of the Billerud Non-
polluting Bleach Plant Concept has
been completed and began operating on
12/10/80. Currently, the system is
being fine-tuned to gam optimal per-
formance of the plant.
Initially, samples were obtained and
analyzed (following EPA screening
protocol) to estimate the concentration
ranges, to establish the spiking levels
for surrogate compounds, to check the
overall sampling and analysis scheme
and to make final the list of compounds
to be checked during this analysis. Tests
were made for the volatile and semi-
volatile compounds found previously in
tests of pulp, paper,, and paperboard
wastes Compounds detected were
placed on the list, which included
metals and several conventional pollu-
tants, of those to be checked during this
study (see Table 1) Once these tests
were performed and the procedures set,
the detailed assessment of the batch
and pilot plant was begun
The ion exchange process consists of
dual columns in series in which the first,
or primary, is the roughing unit and the
second is the scavenger. At break-
through, the roughing unit is eluted and
activated and becomes the secondary
unit while the scavenging unit becomes
the roughing unit
During the sampling phase of this
study, parameters in the bleach plant
were monitored. Bleach plant production
was low initially, but normal for most of
the sampling program.
The sampling programs were designed
to determine how effectively the Dia-
mond Shamrock resin could remove
different compounds during different
modes of operation (see Table 2 for a
summary of these programs). Initially,
pollutant reduction was assessed for
the entire ion exchange plant during
normal operation. Later the treatment
cycle was extended and the effectiveness
of treatment with lengthened cycle
times was determined In addition,
sampling was also done so that the
removals taking place in the first and
second columns during one treatment
cycle could be assessed. In one final
test, the removal effectiveness of one
column was followed throughout an
entire cycle. Note that this is through
two breakthrough cycles, since the
column starts in the second position and
is transferred to the first position after
the initial breakthrough
Conclusions
The batch and pilot scale ion exchange
plants at Billerud Uddeholm AB in
Skoghall effectively remove color, COD,
chlorinated phenols, chlorinated guaia-
cols and some complexed metals (Table
3) These treatment plants do not remove
resin and fatty acids and'phthalates.
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Table 1. Compounds Studied at Billerud Uddeholm AB
Methylene chloride
Trichlorofluoromethane
1,1 -Dichloroethane
Chloroform
1,2-Dichloroethane
1,2 -Dichloroethane
1,1,1 -Trichloroethane
Bromodichloromethane
Tnchloroe th y/en e
Semi-
Phenol
Isophorone
Naphthalene
Hexachlorobutadiene
2,4-Dichlorophenol
2,4,6-Trichlorophenol
2.3,5- Trichlorophenol
Diethyl phthalate
Trichloroguaiacol
4-Bromophenyl phenyl ether
Tetrachloroguaiacol
Pentachlorophenol
Phenanthrene/Anthracene
Dibutyl phthalate
Heptadecanoic acid
Fluoranthene
Linoleic acid !C18:2)
Linolenic acid fC 18:3)
Oleic acid (C18:1)
Metals
Sb - Antimony
As - Arsenic
Be - Beryllium
Cd - Cadmium
Cr - Chromium
Cu - Copper
Other
COD - chemical oxygen demand
Chloride
Volatile Organic Compounds
Dibromochloromethane
Benzene
1,1,2,2-Tetrachloroethane
Tetrachloroethylene
Toluene
Chlorobenzene
Ethylbenzene
Volatile Organic Compounds
Pyrene
Pimaric acid
Sandracopimaric acid
Isopimanc acid
Dehydroabietic acid
Abietic acid
Heneicosanoic acid (C21:0)
Chrysene
Chlorodehydroabietic acid
flsomer A)
bis (2-Ethylhexyl) phthalate
Chlorodehydroabietic acid
(Isomer B)
Dichlorodehydroabietic acid
(unknown isomer)
Dioctyl phthalate
Neoabietic acid
9,10-Dichlorostearic acid
Pb - Lead
Ni - Nickel
Se - Selenium
Ag - Silver
Ti - Thallium
Zn - Zinc
Hg - Mercury
Color
pH
Volatile
d4-1,4-Dichloroethane
d6-Benzene
d8- Toluene
Surrogate Compounds
Semi-Volatile
Pentafluorophenol
d8-Naphthalene
d35-Stearic acid
Inorganic chloride is removed initially
but drops off shortly after the cycle
starts.
Zinc and copper are removed through
complexation and chelation processes
Cadmium and nickel appear to be re-
moved effectively in the second column,
but are virtually untouched in the first
Chlorinated phenols and guaiacols are
removed more efficiently toward the
end of the treatment cycle, a phenome-
non most likely caused by the loss of
ionic character at low pH and the subse-
quent interaction with compounds al-
ready removed
Extended contact time yielded no
benefits. Effective removal was lost
rapidly and a considerable number of
pollutants passed through the columns.
Generally, the first column removed
compounds with high charge densities
and allowed others to pass onto the
second column. This column became
saturated with weakly bound compounds,
which were eluted by the wastestream
when this column was transferred to
the first position, thereby showing a
pollutant increase across the column.
The projected capital cost for a full-
scale ion exchange plant to treat flows
from a 100,000 metric ton/yr. bleach
plant bleaching pulp with a Kappa
number of 35 is $4 78 million The
annual operation costs are estimated to
be between $513,000 and $564,000
(depending on the resin life). Mainte-
nance costs are $83,000/yr, labor costs
are $51,000/yr.
Design of an ion exchange adsorption
system is complicated by a number of
factors but if these complications can be
overcome, and the initial capital cost
accepted, this system may be economi-
cally superior to other technologies
currently available.
Recommendations
A verification program, which would
assess full-scale operation parameters,
capital costs, and operation and mainte-
nance costs, should be established once
the full-scale plant at B.illerud Uddeholm
AB is optimized and operated for a
period of time.
Additional work is recommended to
obtain data usable to calculate a mass
balance through this system for all
compounds tested. This would lead to a
higher confidence level in the figures
denoting removal effectiveness. A mobile
pilot plant setup in this country maybe a
desirable aid in this study. The plant
could be set up at any industrial location
to assess the usability of ion exchange
treatment for any industrial polluter.
It may be desirable to inject known
concentrations of pollutants into this
pilot scale system and monitor the
removal efficiency of various resins in
different configurations at different
resin ages. These data would be very
useful in assessing the effectiveness of
different resins in different configura-
tions. As an example, it is postulated
that use of a strong base ion exchange
resin after weak base ion exchange
would remove resin and fatty acids (pH
reversal would be necessary between
these operations). The effectiveness
and economics of this system should be
assessed to determine its usability for
cleaning bleach plant wastes.
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Table 2. Summary of Sampling Programs
Program Plant Sampled Sampling Time
Operation
Mode Sample Type
Purpose of Program
Screening
1
2
3
4
5
6
batch plant
batch plant
batch plant
pilot plant
pilot plant
pilot plant
pilot plant
2/13/80
2/26/80 (2 hr)
3/4/80 (9 hr)
3/4/80 (5'/2 hr)
3/5/80 (8 hr)
3/5/80 (4 hr)
3/6/80 (6 hr)
normal
normal
normal
normal
normal
normal
extended
grab
manual composite
and grab
manual composite
manual composite
manual composite
series of manual
composites
series of manaul
composites
Finalize analysis methods and determine
pollutant types and concentrations
Determine removal efficiency and
efficiency reduction through cycle
Determine average removal efficiencies
through cycle
Determine average removal efficiencies
through cycle
Determine average removal efficiencies
through cycle
Determine a single columns' removal
efficiency through a cycle and the strong
eluate pollutant content
Determine removals when cycle is ex-
tended beyond optimal
Table 3.
Pollutant
A verage Pollutant Reduction (Percent) During Samp/ing Programs
Batch Plant
Pilot plant
Screening Program 1 Program 2 Program 3 Program 4 Program 5* Program 6
Volatile Organics
Methylene chloride
1,1 -dich/oroethane
Chloroform
Bromodichloromethane
Trichloroethy/ene
Benzene
Tetrachloroethy/ene
Toluene
Chlorobenzene
Semi- Volatile Organics
Phenol
Hexachlorobutadiene
2,4-dichlorophenol
2.4,6-trichlorophenol
2,3,5- tnchlorophenol
Diethyl phthalate
Trichloroguaiacol
4-bromophenyl phenyl ether
Tetrachloroguaiacol
Pentachlorophenol
Dibutyl phthalate
Heptadecanoic acid
Dehydroabietic acid
Hemeicosanoic acid (C21:0)
Chlorodehydroabietic acid
(Isomer A)
bis(2-ethylhexyl)phthalate
Chlorodehydroabietic acid
(Isomer B)
Dichlorodehydroabietic acid
(unknown isomer)
Dioctyl phthalate
9,10-dichlorostearic acid
ND
+
50
42
+
WO
ND
100
24
98
98
ND
100
ND
WO
ND
14
8
ND
ND
ND
ND
ND
ND
ND
ND
ND
35
65
13
+
ND
ND
ND
100
99
100
ND
88
ND
82
ND
+
74
85
+
16
6
+
ND
58
ND
9
51
+
13
+
45
ND
ND
ND
100
99
100
ND
97
ND
89
ND
53
21
87
ND
57
95
38
32
ND
30
WO
ND
34
56
+
33
100
+
ND
ND
ND
100
94
WO
ND
89
ND
78
ND
6
+
-v-
100
ND
+
78
ND
31
100
+
42
ND
ND
ND
100
88
100
ND
78
ND
82
ND
48
ND
+
86
ND
+
41
ND
5
61
11
40
ND
ND
98
62
100
ND
81
ND
79
ND
71
+
29
35
ND
ND
ND
35
26
+
ND
ND
ND
WO
93
ND
ND
91
ND
92
ND
+
77
61
WO
61
62
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Table 3.
{continued)
Batch Plant
Pilot plant
Pollutant
Metals
Sb
As
Be
Cd
Cr
Cu
Pb
Ni
Se
Ag
Ti
Zn
Hg
Other
COD
Color
Chloride
pH change
Screening
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
NS
Program 1
+
+
NS
38
18
60
33
4
+
+
NS
61
54
66
77
18
3.4-6.7
Program 2
+
+
NS
42
5
24
75
+
+
+
70
51
+
65
69
13
3.4-6.2
Program 3
NS
63
NS
WO
59
72
67
83
2O
62
+
31
57
67
90
+
3.3-2.8
Program 4
NS
67
NS
WO
47
82
50
+
33
17
39
94
38
77
90
+
3.2-2.5
Program 5*
NS
70
NS
79
42
75
+
43
7
31
45
15
37
68
85
+
3. 4 -2. 93
Program 6
NS
50
NS
WO
24
82
50
74
33
50
40
39
60
75
90
+
3.2-2.9
Notes: See Table 2 for a description of the sampling programs.
*Due to the organization of Program 5. adequate samples were not taken to determine the average overall removal efficiency
without a small incurred error.
. _ , Component Concentration in Column #1 Feed- Comp. Cone, in Col. #2 Discharge
Overall Percent Removal = - - - - -
+ Increase Noted
ND - not detected
NS - not sampled
Compounds were removed from this table if they were not detected during these analyses.
James H. Fitch. Jr. is with Edward C. Jordan Co., Inc, Portland, ME 04112.
Michael R. Strutz and Donald L. Wilson are the EPA Project Officers (see
belowj.
The complete report, entitled "Evaluation of Ion Exchange Technology for Toxic
and Non-Conventional Pollutant Reduction in Bleach Plant Effluents," (Order
No. PB 81-208 175; Cost. $21.50, subject to change) will be available only
from
National Technical Information Service
5285 Port Royal Road
Spring field, VA 22161
Telephone: 703-487-4650
The EPA Project Officers can be contacted at
Industrial Environmental Research Laboratory
U.S. Environmental Protection Agency
Cincinnati, OH 45268
1 US GOVERNMENT PRINTING OFFICE 1961 -757-01Z/7Z59
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