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New HampshirePollution Prevention Internship ProgramFinal Report:Water Reuse / Conservation and Other ProjectsEric LyonsHADCO Tech Center IIISeptember 3, 1997

Intern and Facility Information

UNH Intern: Eric Lyons Work phone #: 508-372-0200 ext. 335 Work email: elyons@hadco.com

Home: (617) 245-4915100 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 5

Background 5Figure 1 - Conventional Waste Water Treatment System 6Figure 2 - Metal Recovery and Water Reuse System 7Figure 3 - Cost Analysis, Before and After Ion Exchange 9

Internship Objectives 10

ProjectsWater Reuse / Conservation 10

Figure 4 - DEP Line: Present Set-Up 12Figure 5 - DEP Line: Proposed Set-Up 13Figure 6 - Oxide Line: Present Set-Up 15Figure 7 - Oxide Line: Proposed Set-Up 16Figure 8 - Impact of changes in Water Consumption and Reuse 20

Optimization of Reverse Osmosis Unit 21Figure 9 - Pressure Vessel Components 23Figure 10 - Reverse Osmosis Unit: Past Set-Up 24Figure 11 - Engineering schematic of Reverse Osmosis Unit 25Figure 12 - Reverse Osmosis Unit: Present Set-Up 28

Investigation into Alternative Methods of Ammonia Emission Reduction 29

Waste Water Treatment Database 31

References 33

AppendicesAppendix I - Contact List 34

Appendix II - Production Line Information 37Appendix III - Rinse Monitoring Data 41Appendix IV -Reverse Osmosis Unit Monitoring Data 51Appendix V - Wastewater Treatment Database 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 Percent of LineReverse Osmosis Water Use 34%, 26% *Water Reduction 13%, 11% *

* Single DEP, double DEP

Oxide LineThe 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) LineThe 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 DeveloperThe 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 ROSwitch 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 18-20 gpm 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 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 VariablesWater Variables Unit VariablesDate 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 agentNH4Cl Ammonium Chloride, increases copper solubility and etch rateCu2+ Copper ion, oxidizing agentNaClO2 Sodium Chlorite, oxidizing agentNH4CO3 Ammonium Bicarbonate, pH buffer(NH4)3PO4 Ammonium Phosphate, retains solder holesNH4NO3 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+ + 4OH-

Coombs, 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 SelectionsDump LogReverse Osmosis Monitoring SheetChemical / Equipment Maintenance SheetEffluent MonitoringPreventive Maintenance ScheduleQueries / Reports

Dump LogThis 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 SheetThis 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 SheetThis 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 MonitoringThis 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 ScheduleThis log sheet indicates various WWT preventive maintenance action and is

similar to the Chemical / Equipment Maintenance sheet.

Queries / ReportsThis 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 a clean format that can be printed out into hard copies if necessary. Although, time consuming in the data entry aspect, the end result of printable reports, sorting and calculation features saves more time. A hard copy of the Database is shown in Appendix V, note that the RO monitoring Sheet is Appendix IV.

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. WilmotCorporate Safety Health & Environmental Director

HADCO Corporation12A Manor ParkwaySalem, NH 03079PhoneDirect: (603) 896-2424

General: (603) 898-8000Fax: (603) 890-1298

Email: lwilmot@hadco.com

Denise Kilmartin, CSPSr. Safety & Health Specialist

HADCO Corporation7 Manchester RoadDerry, NH 03038

PhoneWork: (603) 896-3204

Fax: (603) 432-2210 x3623Voicemail: (603) 432-2210 x3204

Email: dkilmartin@hadco.com

Ronald P. Blanchetter, MA, CSPSr. Environmental Specialist

HADCO Corporation7 Manchester RoadDerry, NH 03038

PhoneWork: (603) 896-3261

Fax: (603) 896-3623Email: rblanchette1@hadco.com

Marc DuquetteSenior Safety/Environmental Engineer

HADCO CorporationTech Center One7 Manor ParkwaySalem, NH 03079

PhoneWork: (603) 898-8000Direct: (603) 896-2699

Fax: (603) 898-0526Email: mduquette@hadco.com

Ray LetizeDirector of Research

MacDermid Incorporated, Circuit Formation Products245 Freight StreetWaterbury, CT 06702

PhoneWork: (203) 575-5654

Fax: (203) 575-7916Email: rletize@macdermid.com

Charles HullPresident

Separation Engineering IncorporatedEscondido, CA

PhoneWork: (760) 489-0101

Fax: (760) 489-0497

Robert RobinsonSafety / Environmental Specialist

Hadco CorporationTech Center Three46 Rogers Road, P.O. Box 8240Ward Hill, MA 01835

PhoneWork: (508) 372-0200 x335

Fax: (508) 469-7009Email: rrobinson@hadco.com

Frank WereskaFacilities Manager

Hadco CorporationTech Center Three46 Rogers Road, P.O. Box 8240Ward Hill, MA 01835

PhoneWork: (508) 372-0200 x336

Fax: (508) 469-7009Email: fwereska@hadco.com

David R. UngerEnvironmental Health & Safety Manager

Hadco CorporationTech Center Three46 Rogers Road, P.O. Box 8240

Ward Hill, MA 01835

PhoneWork: (508) 372-0200 x283

Fax: (508) 469-7009Email: dunger@hadco.com

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