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New Hampshire
Pollution Prevention Internship Program
Final Report:
Water Reuse / Conservation and Other Projects
Eric Lyons
HADCO Tech Center III
September 3, 1997
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Intern and Facility Information
UNH Intern: Eric Lyons
Work phone #: 508-372-0200 ext. 335
Work email: elyons@hadco.com
Home: (617) 245-4915
100 Myrtle Ave.
Wakefield, MA 01880
Facility: Hadco Corporation
Tech Center Three
46 Rogers Road, P.O. Box 8240
Ward Hill, MA 01835
Contact: David R. Unger, Environmental Health & Safety Manager
Phone #: 508-372-0200 ext. 283
email: dunger @hadco.com
Table of Contents
Page
Executive Summary
4
Introduction
Background
5
5
Figure 1 - Conventional Waste Water Treatment System
Figure 2 - Metal Recovery and Water Reuse System
Figure 3 - Cost Analysis, Before and After Ion Exchange
6
7
9
Internship Objectives
10
Projects
Water Reuse / Conservation
Figure 4 - DEP Line: Present Set-Up
Figure 5 - DEP Line: Proposed Set-Up
Figure 6 - Oxide Line: Present Set-Up
Figure 7 - Oxide Line: Proposed Set-Up
Figure 8 - Impact of changes in Water Consumption and Reuse
10
12
13
15
16
Optimization of Reverse Osmosis Unit
Figure 9 - Pressure Vessel Components
Figure 10 - Reverse Osmosis Unit: Past Set-Up
Figure 11 - Engineering schematic of Reverse Osmosis Unit
Figure 12 - Reverse Osmosis Unit: Present Set-Up
21
23
24
25
28
Investigation into Alternative Methods of Ammonia Emission Reduction
Waste Water Treatment Database
31
References
33
Appendices
Appendix I - Contact List
Appendix II - Production Line Information
Appendix III - Rinse Monitoring Data
Appendix IV -Reverse Osmosis Unit Monitoring Data
Appendix V - Wastewater Treatment Database
20
29
34
37
41
51
66
Executive Summary
Manufacturing facilities of printed circuit boards (PCBs) require large
volumes of high quality water for optimal production levels. Water discharges
can be as high as 500,000 to 1 million gallons per day at some large facilities.
The majority of this water is utilized for rinsing between PCB process steps, as
well as for domestic use. City water, brought in for process use, is of
inconsistent and unacceptable quality that it must be pretreated by techniques
such as softening, deionizing, and demineralizing. Historically, water supplies
have been limitless and industrial consumers could utilize as much as they
needed. However, today water is fast becoming a limited natural resource. Water
prices will continue to rise and limits, if not already in place, will be
imposed on industrial consumers. This has prompted interest by PCB corporations,
equipment vendors, and research foundations into new technologies aimed at
reducing wastewater discharge and increasing water reuse.
The Rio-Grande Technology Foundation, in 1992, awarded Bio-Recovery
Systems, Inc. a grant to develop a near-zero-discharge wastewater treatment
system for the PCB industry. This new treatment system was built in the
beginning of 1993 and was installed at Alternate Circuits Technology (ACT),
presently Hadco Tech Center Three, Inc. (Hadco TC III) during May and June and
was fully operational in July of that year. All targeted specifications for the
initial project were either met or exceeded. Approximately 80% of the water, to
the reuse system, are returned to the rinse operations. The remaining water is
discharged or used for regenerations of the various IX units. The system has now
been in operation for five years and its efficiency has been reduced
significantly.
The purpose of this internship was 1) optimize etcher operation to reduce
or eliminate ammonia emissions and 2) evaluate present water recycling uses in
an effort to maximize recycled water use. This project began with a review of
the system to view any changes or modifications made over the current life span
in order to determine the causes of these deficiencies. An evaluation of the
"wet chemistry" production area was done in order to determine water consumption
and reuse actions currently in place in each production line. The results were
then used to determine the areas which attention would be most beneficial and
accessible to possible change. The possible benefits from pollution prevention
are great. Reducing ammonia emissions will improve etcher operation, reduce
anhydrous ammonia use, and improve the work environment. Although ammonia
emissions are not a problem at this particular facility, other Hadco facilities
could benefit. Improving recycled water use will reduce water treatment and
purchasing costs as well as being a more environmentally conscious operating
procedure. In addition to this an easy to use "point and click" format
wastewater treatment database has been created to aid in department organization
and environmental reporting.
Introduction
Manufacturing facilities of printed circuit boards (PCBs) require large
volumes of high quality water for optimal production levels. Water discharges
can be as high as 500,000 to 1 million gallons per day at some large facilities.
The majority of this water is utilized for rinsing between PCB process steps, as
well as for domestic use. City water, brought in for process use, is of
inconsistent and unacceptable quality that it must be pretreated by techniques
such as softening, deionizing, and demineralizing. Historically, water supplies
have been limitless and industrial consumers could utilize as much as they
needed. However, today water is fast becoming a limited natural resource. Water
prices will continue to rise and limits, if not already in place, will be
imposed on industrial consumers. In addition, the present scenario of water
consumption, that of initial cost, pretreatment, process use, waste treatment,
and discharging is becoming rather costly. This has prompted interest by PCB
corporations, equipment vendors, and research foundations into new technologies
aimed at reducing wastewater discharge and increasing water reuse.
Background
The Rio-Grande Technology Foundation, in 1992, awarded Bio-Recovery Systems,
Inc. a grant to develop a near-zero-discharge wastewater treatment system for
the PCB industry. The grant was given in order to promote environmentally
conscious manufacturing technology in order to reduce hazardous sludge
production, minimize waste water discharge, and investigate the effects of water
reuse on PCB production processes.
In most printed circuit board (PCB) facilities wastewater contains heavy
metal contaminants such as copper, lead, and nickel must be removed prior to
discharge. A flowchart of a conventional wastewater treatment system is shown in
Figure 1. The conventional treatment for this waste water begins with a pH
adjustment to a pH of 9, with the addition of calcium oxide (CaO) and sodium
hydroxide (NaOH), which forms a metal hydroxide precipitate that is removed
through a clarifier. A polymer is added during this process in order to aid in
the flocculation and settling of the metal hydroxides. The precipitate is
removed from the clarifier and sent through a sludge thickener followed by
pressing to remove excess water. The resulting water from this process is laden
with salts, such as calcium, hence is unsuitable for reuse and is discharged.
The hazardous sludge (about 30% solids by weight) is removed periodically for
disposal off site.
The new treatment system, developed by Bio-Recovery Systems, Inc., is
designed primarily to reduce sludge production and excessive water consumption
common to conventional wastewater treatment systems. This system incorporates
ion exchange recovery (IX) units, a deionizing water treatment unit, a reverse
osmosis (RO) unit, as well as an electrowinning unit. A flowchart of the
experimental wastewater reuse wastewater treatment is shown in Figure 2.
Figure 1
Figure 2
The incoming wastewater is pH adjusted to a pH of 4.5 using sulfuric acid
(H2SO4) and sodium hydroxide (NaOH). Since the waste stream is already acidic
(about pH of 4) the chemical usage is minimal. The waste stream then enters the
IX units for heavy metal removal. There are five types of IX units; one specific
for Copper, mixed metals (Copper and Lead), chelated copper, concentrate, and
one for Nickel. Each IX unit contains two columns contain resin beads specific
for the indicated metal recovery. The columns are set up in a lead-lag
orientation so that neither column is overloaded at one time. A regeneration is
done when there is 20% breakthrough (determined by a conductivity controller) of
metal contaminants through the resin. The unit is then placed in a regeneration
mode and is unavailable for normal operation for approximately « hour. This does
not impact the treatment system operation due to buffering tanks, which ensure
available storage capacity. In addition, there are two copper IX units (Sets 1 &
3) due to the large volume of copper contaminated wastewater sent to waste
treatment. The regeneration process utilizes sulfuric acid and methane sulfonic
acid to strip off the metal ions from the resin beads, sodium hydroxide to
reconditioned the resin, and finally DI water to rinse, now RO permeate is used
instead. The metal ion contaminated water resulting from the regeneration is
unsuitable for discharge and is sent to the electrowinning unit. The
electrowinning unit deposits the copper ions onto metal cathodes for recovery
and eventual reuse. During normal operation the metal free effluent from these
units is then fed to the RO unit where the majority of the dissolved salt and
organic matter are rejected. The resulting permeate stream is then stored for
either direct process use or DI treatment followed by process use. A more
detailed description of the RO unit is provided in Optimization of Reverse
Osmosis Unit on page 21. Deionized water is provided by a Point Source Treatment
DeIonizing (PST DI) unit which supplies approximately 5 gpm of DI water
continuously from a city water or RO permeate feed.
This new treatment system was built in the beginning of 1993 and was installed
at Alternate Circuits Technology (ACT), presently Hadco Tech Center Three, Inc
(Hadco TCIII) during May and June and was fully operational in July of that
year. All targeted specification were either met or exceeded for the initial
project. A cost analysis for the new system is shown in Figure 3. Approximately
80% of the water, to the reuse system, are returned to the rinse operations. The
remaining water is discharged or used for regenerations of the various IX units.
Figure 3
Internship Objectives
The purpose of this internship was 1) optimize etcher operation to reduce or
eliminate ammonia emissions and 2) evaluate present water recycling uses in an
effort to maximize recycled water use. The ammonia emissions, in etcher
operations, were initially approached through two methods. The first is to use a
"low-free ammonia" etchant and control pH with anhydrous ammonia (already on
site). The second is to use a "high-free ammonia" etchant and control pH with
anhydrous hydrochloric acid. The water recycling will be approached through an
evaluation of present applications. This will involve characterization of flows
in and out of the water treatment system and monitoring recycled water use
throughout the facility.
The possible benefits from pollution prevention are great. Reducing
ammonia emissions will improve etcher operation, reduce anhydrous ammonia use,
and improve the work environment. Although ammonia emissions are not a problem
at this particular facility, other Hadco facilities could benefit. Improving
recycled water use will reduce water treatment and purchasing costs, as well as
being a more environmentally conscious operating procedure.
Water Reuse / Conservation
Hadco TC III has been a project test bed for a new wastewater treatment
(WWT) system since 1992. One of the goals of this new system was to reduce water
consumption and increase water reuse. The system has now been in operation for
five years and its efficiency has been reduced significantly.
This project began with a review of the system to view any changes or
modifications made over the current life span in order to determine the causes
of these deficiencies. An evaluation of the "wet chemistry" production area was
done in order to determine water consumption per line. The results were then
used to determine the areas which attention would be most beneficial and
accessible to possible change. A detailed evaluation of the destination of waste
streams entering the WWT system on these production lines was then performed.
This data can be seen in Appendix II. The data provided operational details such
as the frequency of rinsing, dumps, current conservation methods, flow sensors
and restrictors, rinse water type (DI, city water, or RO water) and other
production information. In cases where determining necessary process
information, such as those listed above, became difficult, operators,
environmental control technicians (ECT's), and process engineers were consulted.
When this method failed or was inadequate, plumbing was followed and a stopwatch
employed to gather the necessary information.
Once the above data was collected and evaluated, could recommendations for
water reuse and reduction be made. It was determined that the most accessible
and obvious candidate for water reduction and reuse was the Oxide and Plating
lines.
DEP (Desmear Etch Plate) Line
The purpose of this production line is to deburr and plate the drilled holes
through the circuit board in order to connect and make the various layers
conductive. This line is automated and consists of 28 process tanks, 14 of which
are rinse tanks. Current conservation techniques include solenoid valves to
control water flow and drip times for preprogrammed times. In addition rinse
tanks are paired up in a counter current arrangement. Depending on the PCB
specification at the time there are two procedures. The first is known as single
DEP where the boards travel down the process line once. See Figure 4. The second
process modification is known as double DEP where the boards spend half the time
in the electroless copper bath than the single DEP method. The boards are then
return to rinse tank #16 and travel down the line once again.
Evaluation of this line began with daily monitoring of the rinses to determine
copper concentration (ppm), pH, conductivity (mS/cm), and total dissolved solids
(TDS, g/L). These readings can be seen in Appendix III. The readings were taken
daily over a period of seven weeks. This was done in order to determine a
baseline of the water quality over a length of time sufficient to account for
changes due to chemistry cycles and production fluctuations. Also the reading
were taken on a random schedule on first shift to determine average and maximum
readings. After an evaluation of the collected data the following
recommendations were made.
Proposed Plans:
Counter current tank # 11 to tank #8.
Utilize RO water in tanks 2,3,5,6.
Investigate possible use of dryer effluent to feed tank #11.
Except for two rinse tanks (#8 and #11), all the rinse tanks are paired together
in a counter current arrangement. The results of profiling these tanks for pH,
copper concentration, conductivity, and TDS indicates that the rinse water in
tanks #8 and #11 are of similar quality, only differing significantly in copper
concentration with tank # 11 having a significantly lower Cu concentration than
tank #8. It is desired to feed the effluent from tank #11 to tank #8, therefore
pairing together all the tanks in this line in a counter current arrangement.
See Figure 5.
The DEP line currently employs city water for all rinses. In an effort to
increase water reuse, it is desired to utilize DI water, from the RO unit, in
several rinse tanks where applicable. The water quality of tanks 2,3,5,6 is of
relatively good quality (not heavily loaded, just above city water quality) that
the use of DI water use looks feasible. The only constraint will possibly be
higher flow rates to compensate for the lack of buffering capacity present in
the RO water. Again, this will optimize water reuse and utilize the abundant
amounts of DI water available from waste treatment. Investigation of the board
dryer effluent quality and flow rate will determine possible use as feed for
tank #11. Initial sampling indicates that the use of this effluent will be
possible. After three weeks of sampling and monitoring it was determined that
the dryer effluent was near equivalent to the city water feed differing only in
an elevated copper concentration. The only draw back to the use of this effluent
to feed into tank #11 is the infrequent use of the unit. Further study of
operational frequency is recommended. Present observations indicate this to be a
feasible option.
Figure 4
Figure 5
These plans eliminate 4-5 gpm of water from the line while increasing RO water
use resulting in a cost savings of 767 $/year.
Benefit
Reverse Osmosis Water Use
Water Reduction
Percent of Line
34%, 26% *
13%, 11% *
* Single DEP, double DEP
Oxide Line
The purpose of this production line is to clean and roughen the inner layer
surfaces in order to promote the adhesion of dielectric material and lamination
(sandwiching of inner layers into circuit board). This line consists of 16
process tanks, 7 of which are rinse tanks. Current conservation measures include
the use of solenoid valves to control water flow as well as counter current
rinse tank arrangements. As with the DEP line the water was monitored in order
to determine copper concentrations (ppm), pH, conductivity (mS/cm), and total
dissolved solids (TDS, g/L). These readings can be seen in Appendix III. The
readings were taken by the same method employed on the DEP line rinse
evaluation. After an evaluation of the collected data the following
recommendations were made. See Figure 6.
Proposed Plans:
Employ RO water in tanks 2 and 3.
Reduce observed flow rates to design specifications
The Oxide originally utilized DI water and city water for the rinse
compositions. With the successful implementation of the new WWT system RO water
was utilized in tanks 2 and 3. See Figure 7. However, due to insufficient
buffering capacity and an increase in inner layer rejection this action was
terminated and switched back to the original configuration. An evaluation and
subsequent improvement in RO water quality have allowed for this action to be
reversed. Also observation of the flow rate indicted that they were well above
(2 to 3 times higher) design specifications. The flow rates were subsequently
reduced to proper process specifications. This plan eliminates excess water use
and reduce the water consumption by the line by 40% resulting in a cost savings
of 10328 $/year.
Figure 6
Figure 7
DES (Develop Etch Strip) Line
The purpose of this production line is to perform several inner layer
process steps. It first develops the exposed resist (a polymer) thereby
hardening the circuit pattern. The excess copper is then etched away. The final
step is the removal (stripping away) of the photo resist. Flow rates were easily
determined by three flow meters for each of the rinse feed. The entire line
consumes about 8 gpm and is active for approximately 16 hours.
Proposed Plans:
Switch line to RO water.
Switch cooling water to from city to RO water.
The DES line currently utilizes city water for the spray rinses. It is
proposed to employ RO water for all of the three rinses. The cooling system for
this line currently utilizes city water in a closed loop system (opening only to
release overflow to city sewer). If the need to utilize more RO water becomes
apparent, then the application for cooling water could easily be accomplished.
Benefits include the addition of temped water to the RO storage tank. There are
concerns as to the availability of that quantity of water from the RO unit.
Other lines could be completely converted over to RO unit whereas this line may
be difficult due to its high water consumption. If supplying the entire line
with RO water is not achievable, then a possible reduction in the flow rates (of
city water) could be considered. Other options include the use of RO water on a
portion of the line. Even minute decreases in each of the three rinses would
have a significant effect on the daily water consumption due to the constant
operation of the line. The alternate plan, that or reduce city water flow rates,
eliminates approximately 1.5 gpm resulting in a cost savings of 2203 $/year.
Hyoki (Inner Layer Preclean Unit)
The Hyoki lines are inner layer preclean units, which remove dirt and debris
from the inner layers prior to entering the photo department. It is here that
the inner layers are coated with a photo resist and exposed to a circuit
pattern. Initially there was one unit in operation. However, with the addition
of a second unit there is concern that wastewater treatment will be overwhelmed.
In order to reduce the amount of wastewater and reduce water consumption it is
necessary to determine the operational water flow rates. The new unit has a
specified operational flow rate of 7 gpm, however this may change from actual
operational requirements. A flow meter regulating the city water feed was read
flow beyond 7 gpm.
Proposed Plans: Determine the necessary water flow rate for operation and reduce
water consumption if possible.
As with the DES line, this line is operate almost continuously for 16 hours.
Investigation into the design specifications for feed flow rate is ongoing. The
elimination of 1 gpm of city water feed would result in a cost savings of 2938
$/year.
Etcher/Board Developer
The board developer and board etcher process the actual circuit boards.
Once the inner layers are combined into a board, called an out layer. Several
process steps necessitate that the circuit pattern be placed on the outer layer.
This process is similar to the pattern print process for inner layers described
above on the DES line. The only difference there being two units for this
process step. Each unit consumes approximately 5 gpm of city water feed for
rinsing and 1gpm for cooling water while in operation, about 5 hours per day.
Proposed Plans:
Switch rinse water from city to RO
Switch cooling water to from city to RO water
Currently, both these units utilize city water. It is of interest to link these
units together with RO feed water for their respective rinses and cooling water
flows. Benefits include the availability to heat RO water and return it to the
RO storage tank.
A summary of all changes and their water consumption and economic impact is
shown on the next page. A graphical representation of these changes is shown in
Figure 8.
Water Consumption / Reuse Summary
Figure 8
Optimization of Reverse Osmosis Unit
There are two major methods, reverse osmosis and ion exchange, for water
purification for PCB manufacturing. Hadco TC III posses both these systems in
order to pretreat incoming city water and to treat waste water for reuse or
discharge.
Osmosis is the process by which pure water and a saline solution are separated
by a semipermeable membrane. The pure water naturally diffuses across this
membrane diluting the saline solution with the effective pressure difference,
across the membrane, defined as the osmostic pressure. Reverse osmosis is the
opposite process in which pressure (200 to 600 psig), is applied on the feed
water (saline solution) and forced through a semipermeable membrane. This
membrane has a porosity specific for water and rejects dissolved salts, organic
matter, and small particulate matter. The membrane separates the feed water into
two streams, a permeate stream, which is relatively pure water, and a
concentrate stream which contains the majority of the contaminants. The
hydraulic split of these two streams is determined by the feed water makeup. In
most RO systems this split is about 90% permeate with a balance of concentrate.
Another parameter, which gauges the RO unit efficiency, is the salt rejection.
The RO process removes 90 to 98 percent of the contaminants listed above, as
well as all organic molecules with a molecular weight above 200. Water quality
is measured either by conductivity (mS/cm) or total dissolved solids (TDS, g/L).
The purer the water, the lower the conductivity which is directly related to
TDS. Good quality DI water has conductivity reading below 10 mS/cm. The
resulting permeate, which contains small amounts of contaminants, facilitates
further purification by a deionizing water treatment system or activated carbon
filtration and direct process reuse. The PST DI unit at Hadco TC III has the
capability to process both city water or RO water (permeate) for shop use.
As stated in the Introduction, a full-scale reverse osmosis (RO) unit was
installed to process the metal free effluent from the ion exchange recovery
units. The unit was designed by Separation Engineering, Inc. (SEI) to process
the following feed water quality.
Reverse Osmosis Feed Stream
Flow
pH
6
Temperature
60-90 deg. F
Cu
0-0.5 ppm
Pb
0-0.5 ppm
Ni
0-0.5 ppm
Cl
150-850 ppm
Sulfate
500-3000 ppm
Organics
10-100 ppm
TDS
18-20 gpm
500-5000 ppm
Note: TDS is Total Dissolved Solids. Organic is defined as
small chain molecules (mostly carboxylic acid) with a molecular weight of 500.
The RO unit is composed of six pressure vessels (V-5 through V-10); each is
approximately 5 inches in diameter and 20 feet six inches in length. Each vessel
contains six cylindrically wound filter units each 4 inches in diameter and 40
inches in length. These units are connect by small permeate collection
connections between membranes and two larger collection conduits inserted into
each end of the pressure vessel. A diagram of a pressure vessel end is shown in
Figure 9. A feed pump sends feed water, at 40 psig, from tank D09 through a
backwash filter screen to remove large particulate matter. A chemical pump also
is turned on to pump a scale inhibitor to prevent scale formation inside the
membrane structure. Next, the water enters the main feed water pump which
pressurizes the feed up to 600 psig, followed by a throttle valve which reduces
the operating pressure to 450 psig. The actual feed pressure depends on the feed
water chemistry and can vary between 100 to 300 psig. The design specifications
for the reverse osmosis process indicate a feed pressure of 200 to 600 psig. The
unit is configured in a 2-2-1 arrangement to optimize hydraulic flow, see Figure
10. In this configuration the feed water enters vessels five and six in
parallel, followed by vessels seven and eight in parallel, then followed by
vessel nine and ten in series. The feed water entering each subsequent vessel is
the concentrate of the preceding vessel. The feed flow rate is to be maintained
between 18-20 gpm, with a permeate flow rate of approximately 18 gpm and balance
concentrate flow. The permeate from vessels 5 through 9 are collected to form
the "pure" water from the unit which is then stored temporarily in tank D10. The
main RO storage tank, D11, draws from D10 when needed in order to maintain
level. See Figure 11.
The ability to reuses water at this facility depends on the efficient
functioning of this unit. Once areas for water reuse were determined (see Water
Reuse / Conservation) the source of this water was observed through initial
monitoring of feed, permeate, and concentrate streams, to become steadily less
pure. Contact was made with Charles Hull at Separation Engineering Incorporated
(SEI), the RO vendor, to discuss possible actions to remedy the situation. It
was suggested and agreed that a full profile of the unit be done. This entailed
monitoring feed, permeate, and concentrate samples from each vessel. The
following tables lists the data collected.
Reverse Osmosis Profiling Variables
Water Variables
Unit Variables
Date
Pre-filter pressure (PI-100)
Time
Post filter pressure (PI-101)
RO Feed*
Feed temperature (TI-102)
V-5 through V-9 concentrate* Feed pressure
(PI-103)
V-10 & V-9 recirculation*
V-10 Feed pressure (PI-107)
V-5 through V-9 permeate*
Concentrate feed pressure (PI-108)
V-9 recycle flow (FI-105)
V-10 recycle flow (FI-106)
Total concentrate flow (FI-109)
Total permeate flow (FI-110)
Permeate Conductivity (CI-111A)
Concentrate Conductivity (CI-111B)
Figure 9
Figure 10
Figure 11
Monitoring of the RO unit began in late June and has been ongoing. The collected
data is shown in Appendix III. This profiling of the RO unit was paramount in
determining which membranes had failed in which vessels. After several weeks of
data collection it was clear that the membranes in vessels 5 & 6 were the cause
of most of the deterioration. These two membranes receive the fresh feed and
should provide the purest permeate. In mid July a major malfunction of the unit
occurred, causing a severe pressure drop (over 100 psig) and degraded water
quality. It was decided to dissect the first two pressure vessels, 5 &6, and to
visually inspect the membranes and find the cause of the malfunction. The
results indicated heavy sedimentation of small particulate matter, which
resulted in membrane damage in the lead membranes of both vessels. The structure
of each membrane includes heavy plastic ends to keep the membrane bound. The
ends of the lag membranes, of these two vessels, had been crushed and misshapen.
This is most likely due to the constant pressurization and depressurization,
caused by noncontinuous use, which literally slams the membranes (in a 6-member
chain), down the vessel into the vessel end caps. Subsequently, these two
membranes were replaced. The cause of the malfunction was determined to be a
ruptured permeate collection conduit (inserted into each end of the pressure
vessel) which resulted in the significant pressure drop and adverse system
performance. Once repairs were completed, the water quality was observed to
improve significantly. The operating pressure increased from an average of 250
psig to over 300 psig.
Upon further discussion of system performance and the malfunction with
SEI, it was agreed to replace the first four pressure vessels (V-5 through V-8)
with more efficient membranes. In addition, the permeate from vessels 9 & 10
were recycled back to the feed tank (D09). The RO water is now composed of the
permeate from vessels 5 through 8. The present RO unit configuration is shown in
Figure12 on page 28. SEI also requested that four selected membranes be sent to
them for examination. Once this overhaul was complete the water quality and
efficiency from the unit increase dramatically. This coupled with the
implementation of RO water use on the board etcher and developer significantly
increased the operating time of the unit. The following page details the RO unit
over this past year, provided reuse data, and economic projections for savings.
RO Summary Data and Cost Savings
Figure 12
In conclusion, the monitoring and subsequent refit of the RO unit has
dramatically increased permeate quality to acceptable levels (well below city
water quality). Average permeate conductivity reading have been reduced by 61%
and daily RO water output has increased by 114%. The key to maintaining and
improving this performance is continued RO unit operation. The longer the unit
operates per day the more consistent the RO water quality becomes. The proposed
changes in the preceding section if implemented will provide the necessary feed
to achieve this goal.
Investigation into Alternative Methods of Ammonia Emission Reduction
The primary source of ammonia emissions from PCB manufacturers is due to board
etching, which utilizes ammonia based etches. Hadco is one of the largest PCB
manufacturers in the United States with facilities located in New Hampshire,
Massachusetts, New York, California, and internationally in Malaysia. In 1994,
Hadco was responsible for 35% of the ammonia emissions in New Hampshire. With
the corporation continually expanding there is mounting concern about these
emissions. It is in the interest of the corporation to investigate methods for
ammonia emission reduction.
Ammonia is employed due to its excellent ability to convert elemental copper to
cupric ions. The following table describes the components of most ammonia based
etches.
Components of Ammonia Based Etches
NH4OH Ammonium Hydroxide, complexing agent
NH4Cl
Ammonium Chloride, increases copper solubility and etch rate
Cu2+
Copper ion, oxidizing agent
NaClO2
Sodium Chlorite, oxidizing agent
NH4CO3
Ammonium Bicarbonate, pH buffer
(NH4)3PO4
Ammonium Phosphate, retains solder holes
NH4NO3
Ammonium Nitrate, increases etch rate
The etching process proceeds according to the following mechanism.
Cu + Cu(NH3)42+ Þ 2Cu(NH3)4+
4Cu(NH3)2+ + 8NH3 + O2 + 2H2O Þ 4Cu(NH3)42+ + 4OHCoombs, Clyde F. Jr., Printed Circuits Handbook, 4th edit., chap. 21, section
4.1.1, McGraw-Hill, New York, New York, 1996.
The ammonia etcher (Chemcut Etcher System CS 2000) at Hadco TCIII utilizes an
alkaline ammoniacal etchant (MacDermid Ultra Etch FL) and anhydrous ammonia for
pH control. The etching rate is pH dependent which is a function of the ammonia
/ chloride ratio present in the etch. Originally, there were two board etchers,
which would have allowed one for experimentation. However, the second etcher was
removed which has put any experimentation in jeopardy due to the production
constraints on the remaining etcher.
The ammonia emission, in etcher operations, was initially to be approached
through two methods. The first is to use a "low-free ammonia" etchant and
control pH with anhydrous ammonia (already on site). The second is to use a
"high-free ammonia" etchant and control pH with anhydrous hydrochloric acid.
Contact was made with Ray Letize, Director of Research at MacDermid Incorporated
Circuit Formation Products, to discuss options for emission reduction. The use
of anhydrous hydrochloric acid would theoretically adjust the ammonia / chloride
ratio by increasing the chloride concentration instead of the traditional
ammonia addition for pH control. However, the use of this approach was not
advised due to the exothermic formation of ammonium chloride. Another concern
was precipitation of copper hydride at the acid / base interface. Instead, it
was proposed to utilize a dilute hydrochloric acid solution. The prescence of
water will act as a heat sink for any ammonium chloride reactions and reduce
possible clogging. This project is in the very early stages. It is proposed to
have MacDermid perform initial lab experiments to determine interface effects,
heat of reactions, as well as etch rates.
Following the successful completion of this step, the second etcher at Hadco
TCIII will be set up in the WWT area for a pilot study. Other Hadco facilities
have shown interest and plan to supply "dummy" boards for testing as well as
there own suggestions.
If successful, any results gained from this project will greatly benefit
all Hadco facilities in addition to the PCB industry in general. As ammonia
emissions limits become stricter and with continued production increases
throughout Hadco facilities, this project and similar ones will gain more
attention and focus in the near future.
Wastewater Treatment Database
The current status of documentation in the Wastewater Treatment (WWT) department
involves many logs books and manuals. Papers are easily removed and can be
misplaced in such a cluttered and corrosive environment. Another drawback from
this system is the difficulty and time consuming process searching for
information.
This can result in premature chemical dumping, lack of equipment maintenance,
and difficulty in compiling environmental reporting data. Therefore, an easy to
use "point and click" format database has been created. The database and
supporting file were created using Microsoft software. Microsoft Access as the
main interface program with log and data sheets was then created within Access
or Excel. All files are stored in a clearly labeled folder on the facilities
network. The Environmental Controls Technician (ECT) can now access the main
menu and can navigate to the following areas.
Database Selections
Dump Log
Reverse Osmosis Monitoring Sheet
Chemical / Equipment Maintenance Sheet
Effluent Monitoring
Preventive Maintenance Schedule
Queries / Reports
Dump Log
This log tracks the dumping of chemical baths throughout the "wet
chemistry" production areas. The log includes date, shift, tankID, volume
dumped, technician, line name, tank name. In addition to performing the function
of the paper-based logbook, the electronic log can perform sorts, queries, and
reports for environmental reporting purposes.
Reverse Osmosis Monitoring Sheet
This sheet is a completely record of the operational performance of the RO
unit. Readings are taken every shift and entered. Then the sheet automatically
calculates efficiencies and performs sorting functions.
Chemical / Equipment Maintenance Sheet
This sheet is a compilation of many logs of information into a
comprehensive data sheet. The various actions are listed vertically with dates
listed horizontally. When an action is completed the technician enters a "C" for
completed and their initials. This set up has the added advantage of allowing
one to view the maintenance actions of the entire facility.
Effluent Monitoring
This sheet simply displays the copper, lead, and nickel concentration, as
well, as the daily effluent discharge from the facility in graphical form. This
enables the composition and amount of effluent to be viewed over time.
Preventive Maintenance Schedule
This log sheet indicates various WWT preventive maintenance action and is
similar to the Chemical / Equipment Maintenance sheet.
Queries / Reports
This pertains to the Microsoft Access logs incorporated in the WWT
database.
Various queries have been programmed to show the date of the last dump of each
tank, the monthly and yearly volumes dump. In addition, profession reports have
been created from these queries, which are automatically updated upon data
entry.
This system presents the above data in
out into hard copies if necessary. Although,
aspect, the end result of printable reports,
saves more time. A hard copy of the Database
the RO monitoring Sheet is Appendix IV.
a clean format that can be printed
time consuming in the data entry
sorting and calculation features
is shown in Appendix V, note that
References
1.
Coombs, Clyde F. Jr., Printed Circuits Handbook, 4th edit., McGraw-Hill,
New York, New York, 1996.
2.
Horsea, J.M., Development of Environmentally Conscious Manufacturing
Technology, Near Zero Discharge of Water and Waste in Printed Circuit Board
Manufacturing; Submitted to Rio Grande Technological Foundation, November 19,
1993.
Appendix I -Contact List
Lee R. Wilmot
Corporate Safety Health & Environmental Director
HADCO Corporation
12A Manor Parkway
Salem, NH 03079
Phone
Direct: (603) 896-2424
General: (603) 898-8000
Fax: (603) 890-1298
Email: lwilmot@hadco.com
Denise Kilmartin, CSP
Sr. Safety & Health Specialist
HADCO Corporation
7 Manchester Road
Derry, NH 03038
Phone
Work: (603) 896-3204
Fax: (603) 432-2210 x3623
Voicemail: (603) 432-2210 x3204
Email: dkilmartin@hadco.com
Ronald P. Blanchetter, MA, CSP
Sr. Environmental Specialist
HADCO Corporation
7 Manchester Road
Derry, NH 03038
Phone
Work: (603) 896-3261
Fax: (603) 896-3623
Email: rblanchette1@hadco.com
Marc Duquette
Senior Safety/Environmental Engineer
HADCO Corporation
Tech Center One
7 Manor Parkway
Salem, NH 03079
Phone
Work: (603) 898-8000
Direct: (603) 896-2699
Fax: (603) 898-0526
Email: mduquette@hadco.com
Ray Letize
Director of Research
MacDermid Incorporated, Circuit Formation Products
245 Freight Street
Waterbury, CT 06702
Phone
Work: (203) 575-5654
Fax: (203) 575-7916
Email: rletize@macdermid.com
Charles Hull
President
Separation Engineering Incorporated
Escondido, CA
Phone
Work: (760) 489-0101
Fax: (760) 489-0497
Robert Robinson
Safety / Environmental Specialist
Hadco Corporation
Tech Center Three
46 Rogers Road, P.O. Box 8240
Ward Hill, MA 01835
Phone
Work: (508) 372-0200 x335
Fax: (508) 469-7009
Email: rrobinson@hadco.com
Frank Wereska
Facilities Manager
Hadco Corporation
Tech Center Three
46 Rogers Road, P.O. Box 8240
Ward Hill, MA 01835
Phone
Work: (508) 372-0200 x336
Fax: (508) 469-7009
Email: fwereska@hadco.com
David R. Unger
Environmental Health & Safety Manager
Hadco Corporation
Tech Center Three
46 Rogers Road, P.O. Box 8240
Ward Hill, MA 01835
Phone
Work: (508) 372-0200 x283
Fax: (508) 469-7009
Email: dunger@hadco.com
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matthew