## Cover Letter

The submitter is submitting this PMN for a chemical substance that is formed as a byproduct during the etching of copper on printed circuit boards. The submitter will recycle this byproduct and in the recycle commercially useful copper compounds will be produced.. As described in the PMN, this recycling can eliminate potential environmental releases to landfills of copper compounds.

Page 1 NON-CBI SUBMISSION

### 2567ETUP TTM_120330537485116 D34MK9

X

Page 2 NON-CBI SUBMISSION

### X

Page 3 NON-CBI SUBMISSIONLee Wilmot Director, Environmental, Health & SAFETY TTM Technologies, Inc. 5810 Atwater Trail Cumming GA 30040 lee.wilmot@ttmtech.com David Peveler Bergeson & Campbell, P.C. 2200 Pennsylvania Avenue, N.W. Suite 100W Washington DC 20037-1701 dpeveler@lawbc.com 201-690-6438

Lee Wilmot Director, Environmental, Health & SAFETY TTM Technologies, Inc. 5810 Atwater Trail Cumming GA 30040 lee.wilmot@ttmtech.com 678-513-1949



## X X X X

Page 4 NON-CBI SUBMISSION

## X

Copper(2+), tetraammine-, dichloride

10534-87-9 

## X 00091818.DOC 

### Cl2 . Cu H12 N4 See Attachment 001 (TACD.pdf)

TACD.pdf Page 5 NON-CBI SUBMISSIONPage 6 NON-CBI SUBMISSIONPage 7 NON-CBI SUBMISSIONPage 8 NON-CBI SUBMISSIONZinc chloride 7646-85-7 0.5

Arsenous trichloride 7784-34-1 0.06

Page 9 NON-CBI SUBMISSION

### 265000 315000

Raw material for production of copper chemicals 50 25 0 0 100 0 Raw material for the production of animal feed micronutrients. 50 25 0 0 100 0

Page 10 NON-CBI SUBMISSION

## X

275 24 350 

## 1 Chippewa Falls 234 Cashman Drive Chippewa Falls WI 54729

Page 11 NON-CBI SUBMISSIONSee Attachment 003 (00092170.XLSX)

00092170.XLSX Page 12 NON-CBI SUBMISSION1. Pumpimg spent etch

from storage to tank truck Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 1 17 2. Cleaning of etch chamber. Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 2 4

Page 13 NON-CBI SUBMISSION<0.1 kg 0 <0.1 kg In-house waste water treatment plant. 0

Page 14 NON-CBI SUBMISSION

## X

100 24 250 

## 1 Stafford 4 Old Monson Road Stafford CT 06075

Page 15 NON-CBI SUBMISSIONSee Attachment 004 (00092171.XLSX)

00092171.XLSX Page 16 NON-CBI SUBMISSION1. Switching hose from full

storage container to empty storage container. Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 0.2 60 2. Cleaning of etch chamber. Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 2 4

Page 17 NON-CBI SUBMISSION1 0 < 0.1 kg In-house waste water treatment plant. 0

Page 18 NON-CBI SUBMISSION

## X

200 24 350 

## 1 Logan 710 North 600 West Logan UT 84321

Page 19 NON-CBI SUBMISSIONSee Attachment 005 (00091798.XLSX)

00091798.XLSX Page 20 NON-CBI SUBMISSION1. Pumpimg spent etch

from storage to tank truck Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 1 20 2. Cleaning of etch chamber. Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 2 4

Page 21 NON-CBI SUBMISSION1 0 < 0.1 kg In-house waste water treatment 0

Page 22 NON-CBI SUBMISSION

## X

25 24 250 

## 1 San Diego 5037 Ruffner Street San Diego CA 92111

Page 23 NON-CBI SUBMISSIONSee Attachment 006 (00092173.XLSX)

00092173.XLSX Page 24 NON-CBI SUBMISSION1. Switching hose from full

storage container to empty storage container. Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 1 60 2. Cleaning of etch chamber. Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 2 4

Page 25 NON-CBI SUBMISSION1 0 0.1 kg In-house waste water treatment 0

Page 26 NON-CBI SUBMISSION

## X

170 24 250 

## 1 Santa Ana 2630 S. Harbor Blvd Santa Ana CA 92704

Page 27 NON-CBI SUBMISSIONSee Attachment 007 (00092172.XLSX)

00092172.XLSX Page 28 NON-CBI SUBMISSION1. Switching hose from full

storage container to empty storage container. Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 1 250 2. Cleaning of etch chambers. Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 2 4

Page 29 NON-CBI SUBMISSION1 0 0.1 kg In-house waste water treatment 0

Page 30 NON-CBI SUBMISSION

## X

200 24 250 

## 1 Santa Clara 407 Mathew St. Santa Clara CA 95050

Page 31 NON-CBI SUBMISSIONSee Attachment 008 (00091797.XLSX)

00091797.XLSX Page 32 NON-CBI SUBMISSION1. Switching hose from full

storage container to empty storage container. Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 0.2 227 2. Cleaning of etch chamber. Safety glasses with splash shields or goggles and chemical resistant gloves. Liquid, 40% 1 2 4

Page 33 NON-CBI SUBMISSION1 0 0.1 kg In-house waste water treatment 0

Page 34 NON-CBI SUBMISSION

### 1

See Attachment 011 (Phibro-Tech.pdf)

Phibro-Tech.pdf Copper Recovery from Spent Ammoniacal Etchant via the Caustic Boilout Process The recycling process of spent ammoniacal etchant is described as follows: The spent etchant obtained from customers is stored in either 55 gallon drums or in bulk storage tanks depending upon whether it was returned fromprinted circuit board manufacturers in drums or tanker trucks. The spent etchant is then transferred from a storage tank to one of two vessels which are known as ‘reactor tanks.’ Caustic soda and heat are added. The ensuing chemical reaction is allowed to proceed for approximately 12-15 hours. During the reaction, copper oxide precipitates out of the spent etchant/caustic soda mixture and ammonia gas is generated. At the end of the reaction, the copper oxide is allowed to settle and the liquid remaining in the reactor tank is pumped into another vessel for treatment and disposal as a process wastewater. The copper oxide remaining in the reactor tank is washed and discharged to a filter press for final processing. The copper oxide is the first end-product of the process that uses spent etchant as an ingredient. The ammonia gas generated in the reactor tanks flows to a scrubber in which the ammonia gas is reacted with hydrochloric acid scrubbing liquid to produce ammonium chloride. That reaction occurs throughout the twelve plus hour process as the ammonia gas is being generated. The ammonium chloride produced in the scrub tanks is the second end-product of the above described process that uses spent etchant as an ingredient.
Page 35 NON-CBI SUBMISSIONP10SB1(a)(4)1 Part II, Section B, 1(a)(4). Operation Site Locations

Phibro-Tech Santa Fe Springs, CA

Page 36 NON-CBI SUBMISSIONA 1 1 250 See MSDS 40

None

Page 37 NON-CBI SUBMISSION

### 1

See Attachment 012 (Micronutrients.pdf)

Micronutrients.pdf See continuation page. id: <P10SB1(b)2>

Page 38 NON-CBI SUBMISSIONP10SB1(b)2 Part II, Section B, 1(b). Optional Text Description

There are two types of spent etching solutions from printed circuit board manufacturing operations: an acidic cupric chloride solution (CuCl2/HCl), and an alkaline cuprammine chloride solution (Cu(NH3)4Cl2). Tribasic copper chloride is generated by neutralization of either one of these two solutions (acidic pathway or alkaline pathway), or by combination of these two solutions, a self-neutralization reaction. In the acidic pathway, the cupric chloride solution can be neutralized with caustic soda, or ammonia, lime, or other base. In the alkaline pathway, cuprammine chloride solution can be neutralized with HCl or other available acidic solutions (eq. 8). 2 [Cu(NH3)4Cl2] + 5 HCl + 3 H2O Cu2(OH)3Cl + 8 NH4Cl (eq. 8) More efficiently, the two spent etching solutions are combined under mild acidic conditions, one neutralizing the other, to produce higher yield of basic copper chloride (eq. 9). 3 [Cu(NH3)4Cl2] + 5 CuCl2 + 12 H2O 4 Cu2(OH)3Cl + 12 NH4Cl (eq. 9) Seeding is introduced during crystallization. The production is operated continuously under well-defined conditions (pH, feeding rate, concentrations, temperature, etc.). Product with good particle size is produced and can be easily separated from background salt and other impurities in the mother liquor. After simple rinse with water and drying, pure, free-flowing, non-dusty green crystalline solid with typical particle size of 30 ~ 100 micron is obtained. The product from this process is predominantly atacamite and paratacamite, the stable crystal forms of basic copper chloride – and is called alpha basic copper chloride for simplicity. Careful control of process conditions to favor the alpha polymorphs results in a product that remains free flowing over extended storage times, thus avoiding caking as occurs with both copper sulfate and the botallackite crystal form - also called beta basic copper chloride.

Page 39 NON-CBI SUBMISSIONP10SB1(a)(4)2 Part II, Section B, 1(a)(4). Operation Site Locations

Micronutrients Indianapolis, IN

Page 40 NON-CBI SUBMISSIONA 1 1 250 See MSDS 40

Page 41 NON-CBI SUBMISSIONThe PMN substance is the result of a research project to develop a process to reclaim the copper from byproducts of the manufacturing of printed

circuit boards. The project resulted in the development of dicopper chloride trihydroxide crystals. Because of their neutrality, insolubility in water and high copper content, these crystals were studied as a potential source of nutritional copper in animal diets. A proprietary process has been refined for using two types of spent etching solutions (material used in manufacturing electronic printed wiring boards). These spent etchants can be reacted to produce a copper crystal matching the desired basic copper chloride formula. As a result, the spent etchants from printed wiring boards that were once considered waste could now be recycled to make trace mineral copper.

Page 42 NON-CBI SUBMISSION001 PMN Substance Structure TACD.pdf Pt.I, Sec.B, 1e. 1 002 CAS Registry File 00091818.DOC Pt.I, Sec.B, 1c. 1 003 Process Description 00092170.XLSX Pt.2, Sec.A, 1d. 1 004 Process Description 00092171.XLSX Pt.2, Sec.A, 1d. (#2) 1 005 Process Description 00091798.XLSX Pt.2, Sec.A, 1d. (#3) 1 006 Process Description 00092173.XLSX Pt.2, Sec.A, 1d. (#4) 1 007 Process Description 00092172.XLSX Pt.2, Sec.A, 1d. (#5) 1 008 Process Description 00091797.XLSX Pt.2, Sec.A, 1d. (#6) 1 009 MSDS 00092200.PDF 7 010 Waste Water Treatment Process 00092196.PDF 1 011 Process Description Phibro-Tech.pdf Pt.2, Sec.B, 1a. 1 012 Process Description Micronutrients.pdf Pt.2, Sec.B, 1a. (#2) 1

Page 43 NON-CBI SUBMISSION

## X Measured

>400 Measured 25

Page 44 NON-CBI SUBMISSION

## ATTACHMENT HEADER SHEET Attachment Number 001 Attachment Name PMN Substance Structure 

## Associated PMN Section Number

Pt.I, Sec.B, 1e. Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 002 Attachment Name CAS Registry File 

## Associated PMN Section Number

Pt.I, Sec.B, 1c. Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 003 Attachment Name Process Description 

## Associated PMN Section Number

Pt.2, Sec.A, 1d. Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 004 Attachment Name Process Description 

## Associated PMN Section Number

Pt.2, Sec.A, 1d. (#2) Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 005 Attachment Name Process Description 

## Associated PMN Section Number

Pt.2, Sec.A, 1d. (#3) Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 006 Attachment Name Process Description 

## Associated PMN Section Number

Pt.2, Sec.A, 1d. (#4) Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 007 Attachment Name Process Description 

## Associated PMN Section Number

Pt.2, Sec.A, 1d. (#5) Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 008 Attachment Name Process Description 

## Associated PMN Section Number

Pt.2, Sec.A, 1d. (#6) Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 009 Attachment Name MSDS 

## Associated PMN Section Number

N/A Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 010 Attachment Name Waste Water Treatment Process 

## Associated PMN Section Number

N/A Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 011 Attachment Name Process Description 

## Associated PMN Section Number

Pt.2, Sec.B, 1a. Does not contain CBI 

## Report Number TTM_120330537485116

## ATTACHMENT HEADER SHEET Attachment Number 012 Attachment Name Process Description 

## Associated PMN Section Number

Pt.2, Sec.B, 1a. (#2) Does not contain CBI 

## Report Number TTM_120330537485116