Copper Catalyst Removal from

3
Process Condensate in NH Plants

Stringent effluent discharge regulations under the EPA NPDES permit program have
forced the development of new procedures or the addition of a contaminant removal process
for unrelated routine tasks. During and after the low-temperature shifter guard bed catalyst change,
it is most likely that copper levels are exceeedingly high in the wastewater stream. This article dis-
cusses how a process designed f or copper removal efficiently reduced copper catalyst contamination.

Zoraida R. Diaz
E.I. DuPont de Nemours & Co., Beaumont, TX 77704

Background The LTS-M's effluent is desuperheated by quench-

ing the gas with demineralized water. The condensate
is then separated from the process gas in the raw gas

T
he water-gas shifter system consists of three
vessels, a high-temperature (HTS), low-temper-
ature (LTS-M) and low-temperature guard bed
(LTS-G) that convert CO to CO2 by the reaction with
steam according to the equation
CO + H2O —-> CO2+H2 + heat
The LTS-G and the LTS-M operate using the same
principle and use the same type of catalyst (copper-
based catalyst containing 40-50% copper) although the
LTS-G is approximately half the size of the LTS-M. Its
main function is to prevent all known poisons, espe-
cially sulfur and chloride compounds, from decreasing
the LTS-M's catalyst activity.
The LTS-G can be taken out of service and have the
catalyst changed regularly, while the LTS-M remains
in service. This helps extend the life of the LTS-M
several years and provides an added benefit of addi-
tional CO conversion.
separator. To reuse this condensate, carbon dioxide
(COz), methanol (CH3OH), ammonia (NH3) and small
amounts of amine compounds (RNH2) are removed in
the condensate stripper (Figure 1).
During a catalyst changeout, small quantities of cat-
alyst dust (less than 3% based on catalyst manufactur-
er experience) is generated depending on the catalyst
manufacturer's shipping and handling and on the
method used for catalyst loading. When the vessel is
placed back in service, most of this dust is carried out
of the vessel by the process gas. In the-case of shifter
catalyst, the dust is carried in the gas until it reaches
the raw gas separator, where it drops into the process
condensate and continues its journey to the cooling
tower. Some of it settles in the trays and bottom of the
condensate stripper; the rest ends up in the cooling
tower and eventually into the environment through
continuous blowdown.
EPA's National Pollution Discharge Elimination

AMMONIA TECHNICAL MANUAL 94 1996

 Table 2. Previous Catalyst Change Copper
Table 1. Normal Total Copper Concentrations Contamination

ppmCu Maximum
Raw Water (*) 0.010
Filtered Water 0.005 Raw Gas Separator Effluent 12.00 ppm
Raw Gas Separator Effluent 0.020 Condensate Stripper Effluent 0.70 ppm
Condensate Stripper Effluent 0.070 Cooling Tower Slowdown 0.90 ppm
Ditch 0.050 Ditch (*) 154.0 ppm
Regulated concentration for a 300 to 600 flow is 0.050 to 0.070 ppm.
(*) Water was diverted into storage tanks and processed in order
(*) World average from "Waste Treatment Principles & Design" to meet EPA regulations.
(1985).

System (NPDES) program places limits on several
chemical constituents discharged to the river and cop-
per content in the wastewater discharge to the river is
one of these limits. In previous years, the concentra-
tions of copper in the wastewater discharge to the river
due to a shifter catalyst change met the EPA permit
limits due to use of on-site settling ponds prior to dis-
charge to the Neches River. Presently, EPA and the
state of Texas regulators have eliminated the use of the
on-site settling pond and lowered the copper concen-
tration in our discharge to the river. This change in the
Te Haro
TeRftrar
Figure 1. Process flow diagram.
regulations has required copper catalyst users to
treat/dispose the process condensate differently after
the catalyst change is complete and, in some cases,
modify or change catalyst unloading and loading
methods to prevent catalyst dust from contaminating
the wastewater discharge that is routed to the river.
During routine operation, copper levels in the
process water streams are low and comply with the
regulated limits without a need for any treatment.
Table 1 lists typical copper concentrations in such
streams. Following a prior catalyst change of both the
LTS-G and the LTS-M, coincidental with the environ-
mental regulation changes, copper levels in the water
to be discharged to the river exceeded the regulated
limits. The maximum copper levels observed during
this time are listed in Table 2. These maximum levels
were measured some time after startup, because the
existence of a problem was not immediately apparent.
As can be observed, the copper levels increased to
approximately 10 times the normal levels. To mini-
mize the impact of this contamination, vast quantities
of contaminated water were accumulated in tanks
throughout the plant site. The containment capacity
on-site was less than that needed for which temporary
tanks were rented. Once the contamination source was
identified and all the contaminated water was con-
tained, treatment was required prior to disposal. All
the efforts of identifying, containing, and treating con-

AMMONIA TECHNICAL MANUAL 95 1996

tamination resulted in a substantial expense. The need
to remove the copper catalyst contamination was
clearly determined.
Determining Magnitude of Contamination
The copper in the presence of water forms Cu(OH)2
by the following reaction
-------- -> Cu(OH)2
The solubility of Cu(OH)2 in distilled water has been
experimentally determined to be 0.30 ppm. When
other components are present, such as CO2 and NHj,
the solubility increases because of the formation of
soluble copper complexes. In the raw gas separator,
dissolved NH3 will combine with copper to form a cor-
rosive complex which remains dissolved in the con-
densate
NH, + Cu -> Cu-NHj complex
(corrosive agent)
When the NH3 is stripped from the condensate, the
Cu-NH3 complex returns to Cu(OH)2 and some of it
precipitates to maintain the maximum soluble concen-
tration. Since Cu-NH3 complex is more soluble in
water than Cu(OH)2, its removal by mechanical means
is less effective. The presence of CO2 complicates its
removal because the NH3 becomes more soluble.
To understand the possible magnitude of copper con
tamination based on the presence of CO2 and NH3 in
Table 3. Size References
Resin 0.575 mm or 35 mesh
Fine Particulate Matter < 10 microns
Suspended Solids > 0.5 microns
Colloidal Material 0.2 - 0.8 microns
Particulate in Solution < 0.005 microns
AMMONIA TECHNICAL MANUAL
our system, an average of 26 mg of catalyst dust was
added to 300 mL samples from the effluent of the raw
gas separator, stripper and cooling tower basin. After
approximately 10 to 15 min, each sample was filtered
using a 0.45 micron filter to remove the catalyst fines
and any insoluble copper from the samples. This filter
size was chosen because of its availability, and based
on common particle reference (Table 3) it would
assure that the results would mainly consist of dis-
solved copper.
The average results of two similar test runs are listed
in Table 4. The raw gas separator effluent sample,
which contains the highest concentrations of C(>2 and
NH3, had the highest levels of dissolved copper. The
effects of the presence of NH3 and CC«2 was con-
firmed. We concluded that this stream should be
cleaned thoroughly to minimize copper contamination
from migrating into the rest of the process.
The catalyst fines are the known source of the cop-
per, but the total amount of catalyst fines to be
removed and the initial concentration of copper are
unknown since they were not measured during the
many previous catalyst changeouts because there was
no need for it. The possible amount of catalyst dust
generated could be 3% or less of the total catalyst load
(from catalyst manufacture experience), depending on
the catalyst manufacturer handling and on the method
used for catalyst loading.
Table 4. Dissolved Copper Analysis (From Added
Catalyst Fines)
ppmCu
w/o fines w/fines
Raw Gas Separator Effluent 0.14 2.93
Condensate Stripper Effluent 0.03 0.09
Cooling Tower Basin 0.03 0.13
96 1996
Copper Removal Process t•nDCM 43n
1Ib «>*
Design -»•ToFtat»
6tt i 1
Removing the condensate from 1
continuous process Low R*!W mMfym
ToOuföU
T«in
IW Low RiK
*V Temp
sum iteP- f
To treat the condensate, it must be Bad Shifter 1
x- -\
removed from the process and
returned after treatment without
PtaoM«
Good»m«h' J•
1
'i •x//**«
A+—
• ('

Pfe-herfer
Sumo

CM*•t
interruptions to the main process. Hm* t
The best location for intercepting the MMmmi OlvBraton ir
condensate is at the exit of the raw PMMWt s \
/Dfwraton\
gas separator because it eliminates " " I
y 7' \ *i Tmto j
contamination of additional vessels
and because of piping and space
MnwiffMl
NMWrä
\

CM•tag
T«MBf
/

.
v_y
BteMdawm
availability. The full flow is routed
through the copper removal system Figure 2. Final location of all interceptions.
and returned to the process at the
inlet of the stripper preheater (see
Figure 1).
Additional polishing must be con-
sidered due to the presence of CO2
and NH3 and the effects on copper
concentration and copper complex
formation when removed in the
stripper, as explained earlier. Also, a
backup system should be available
as a contingency against any unex-
pected failure of the copper removal
facilities. For both of these, addition-
al process tie-ins for diversion and
additional processing must be com-
pleted. The location of these tie-ins
were selected based on accessibility
and safety. Figure 2 displays the
final location of all interceptions.

Removing the Catalyst Fines

Figure 3. Filter vendor recommended a configuration consisting of
. , . ,, --. . , ... three filters in series..
A highly efficient catalyst fines
removal system, located upstream of the stripper inlet, designed based on particle-size analysis, copper solu-
is imperative to minimize or eliminate: (1) tray plug- bility data and speculation. The only known parame-
gage; (2) concentration of the soluble Cu-NH3 com- ters were flows, pressures, and temperatures.
plex. Although there are several methods for removing
Without the knowledge of the total quantity of fines contaminants from water (resins, filters, membranes,
to be removed and the copper concentration in the cyclones, etc.) factors such as cost, availability and
process condensate, the removal facilities were efficiency dictated the method selected. Because the

AMMONIA TECHNICAL MANUAL 97 1996

quantity of fines to be processed was unknown, and
there is NH^ and €(>> present in the condensate and
the bulk of the contamination to be removed is undis-
solved, filtration was selected.
The configuration of a filter system depends on flow
and the filter element used, bag or cartridge. Several
cartridges are required for the same flow as one bag.
Either element would work for this application, so the
choice was dependent on time required to change, ease
of changing, and cost.
Table 5. Particle-Size Distribution Analysis
Above 124 micron 54.1%
124 to 50 micron 13.0%
50 to 10 micron 24.2%
10 to 2.8 micron 7.0%
Below 2.8 micron 1.7%
Determining filter size requirements
The catalyst dust sample was generated from stable
reduced catalyst that was supplied by the catalyst man-
ufacturer. The catalyst was in the form of pellets
which were pulverized to obtain the catalyst dust. A
particle-size distribution analysis was completed and
results are listed in Table 5. The main concern was the
smaller particle size (less than 2.8 micron) which
would be more difficult to remove.
Based on these results, the filter vendor recommend-
ed a configuration which consisted of three filter sets
in series, each removing a different particle-size range
(Figure 3). The first set would remove particles greater
than or equal to 150 micron. The second would take
care of the particles greater than or equal to 50 micron
and the third set would remove those that were greater
than 1 micron. Any catalyst dust that was smaller than
1 micron would have to be removed separately, with
the dissolved copper.
Removing dissolved copper
The filtration system, even with the smallest mesh
AMMONIA TECHNICAL MANUAL
1
RTTOj 1
TYnHn lalvmr *
1-3 micron
Export tagfitere
TMMT
L_
Figure 4. Treated condensate using a 1-3 micron
bag of precipitated copper compounds..
bag (1 micron) will not remove the dissolved copper
(Table 3). It was expected that the maximum dissolved
copper concentration would be similar to the soluble
concentration which was established to be 0.30 ppm.
This concentration would exceed the maximum per-
mitted levels; therefore, the dissolved copper had to be
removed. Again, many alternatives were evaluated,
but the one selected was copper precipitation using a
chemical manufactured by Betz: Betz 1744 (sodium
trithiocarbonate) and a static mixer with final filtration
of the copper precipitate using the smallest filter bag
size available.
The sodium trithiocarbonate precipitates metals
according to the following increasing solubility series:
Cu < Ni < Co < Pb < Zn < Mn < Fe (least reactive
with steel). The precipitation of copper with sodium
trithiocarbonate proceeds according to the following
reaction
Cu(OH)2 + Na.CS, CuCS3 + 2NaOH
Betz 1744 directly precipitates sequestered, com-
plexed and chelated copper in water by feeding a 30: 1
(Na2CS3:Cu) ratio. A static mixer was installed down-
stream of the feed point to assure complete mixing and
98 1996
precipitate formation. Treated condensate was filtered
using a 1-3 micron bag for the removal of the precipi- Table 7. Copper Removal Program Results
tated copper compounds (Figure 4).
Sodium trithiocarbonate oxidizes with chlorine to
form carbonates and sulfates. For this reason, the con-
densate stream from the final filtration was discharged Max. Cu raw gas
into the cooling tower to eliminate the potential for eparator effluent 90.00 ppm
discharging high concentrations of sodium trithiocar- Cu in stripper effluent
bonate to the river. No changes to the cooling tower at above max. 0.44 ppm
chemical treatment program were required. Cu to cooling tower at above max.0.02 ppm
To confirm effectiveness of the treatment, Betz con-
ducted a series of tests designed to model the copper Max. Cu cone, to
removal from the stripper effluent using Betz 1744. cooling tower (Normal 0.07 ppm) 0.07 ppm
Copper concentrations higher than the solubility con- Avg. Cu concentration
centration were used for these tests to assure that the to cooling tower 0.04 ppm
desired effectiveness was achieved for the worse-case
Total copper to raw
Table 6. Metal Removal with Precipitation (Betz's gas separator (meas.) 30.5 Ibs (13.8 kg)
1,744 Bench Tests) Total copper removed 28.13 Ibs (12.8 kg)
(Equiv. to 70.3 Ib (31.9 kg) fines or 0.14% of charge was dust)

Removal efficiency 92.2%

Ambient Temps. High Temp.
ppmCu 2.1 to <0.05 0.67to<0.05
Raw gas separator treatment sys. 4 d in service
ppmFe 0.14 to <0.05 0.16to<0.05
Stripper effluent treatment sys. 2 d in service
ppmZn 2.4to<0.01 0.89to<0.01
Filter Bag
Change Freq.
High Temp. = 75°C
No.of Bags First 2 h Total
1-3 micron 66 3 times(*)15 times(*)
Once on cooling tower
50 micron 40 5 times 10 times
scenario. Results were as expected, and high copper 150 microns 59 5 times 15 times
removal effectiveness was demonstrated (Table 6).
This process would remove the dissolved copper to Total Used 165 bags
acceptable levels.
filtration system. This permitted some contaminated
Results water to continue to the stripper, but a portion of the
flow was diverted from the stripper effluent to a hold-
After completing the LTS-G catalyst unloading and ing tank. The chemical/filtration system was in service
loading, the copper removal facilities were placed in and managed to clean the condensate to the appropri-
service. Within the first five minutes after placing the ate levels. The bulk of fines was removed within the
LTS-G back on-line, the filtration system at the raw first two hours. Table 7 summarizes the results.
gas separator effluent had reached its maximum pres- The several gallons of contaminated water that had
sure drop of 40 psi (276 KPa); the filters were been diverted to the holding tank was tested and the
plugged. The bags were immediately changed, while copper concentration was found to be below the nor
some of the flow was bypassing the raw gas separator mal levels. The tank contents was slowly discharged to

AMMONIA TECHNICAL MANUAL 99 1996

the river. Within several days, the project was consid-
ered successfully completed. The plant continued run-
ning at normal rates throughout the entire procedure,
DISCUSSION
Gerardo Nunez, Pequiven: Do you have condensation
inside of LTS bed? Are you worried about condensa-
tion inside the LTS bed?
Diaz: There isn't any; we watch it. We quench it (the
gas). We measure the dew point and make sure that the
AMMONIA TECHNICAL MANUAL
and there were no copper excursions or environmental
upsets,
gas doesn't reach the dew point. That's how we assure
we don't have any condensation. The main portion of
the water that makes up process condensation comes
from the quenching after the shifters. That's where the
bulk of the water comes from.
100 1996