p090636.eng.txt

INITIAL REVIEW ENGINEERING REPORT 

PMN: 09-0636

Focus Ready Draft 10/19/2009

ENGINEER: Avcin \ DGR

PV (kg/yr): 107,800 YX

SUBMITTER: FUJIFILM Hunt Chemicals USA, Inc.

USE: Chemical intermediate 

OTHER USES: 

MSDS: No Label: No

TLV/PEL:

CRSS :

Chemical Name: Benzenamine, 5-(1,

1-dimethylethyl)-2-[(2-ethylhexyl)thio]-,

4-methylbenzenesulfonate (1:1)

S-H20: 0.0004 g/L @

VP: 1.0E-6 torr @

MW: 465.00 %<500 %<1000

Physical State and Misc CRSS Info:

Neat: Solid Mfg: Solid (wet cake) Proc/Form: NA End Use:

Destroyed. Submitted data: Solid, mp 180 °C, insoluble in water,

solubility 100 g/L in toluene at 50 °C. Estimated data: The PMN

material is a tosylate salt of an amine and is not amenable to

estimation using either EPISuite or ACDLabs. PChem properties

for the free amine and free acid are as follows: Amine: bp

170-174 °C/1.5 torr (measured, ), vp 2.9E-05 torr

(NOMO5), water sol. 0.037 mg/L (EPI, mp entered as 20 °C), LogP

6.95 (EPI). pTSA: mp 104.5 °C (measured), bp 140 °C/20 torr

(measured), vp 2.9E-06 torr (EPI), water sol. 602 g/L (measured),

 LogP -0.62 (EPI). Measured data for pTSA are from Physprop.

The water solubility for the PMN material is estimated to be 0.4

mg/L based on the estimate for the free amine and an observed

10-fold increase in water sol. for various benzenesulfonic acid

salts of aniline derivatives: o-toluidine 16.9 g/L, salt 200

g/L; p-toluidine 6.5 g/L, salt 74 g/L; 2,4,5-trimethylaniline 1.

2 g/L; salt 20.3 g/L; 2-naphthylamine 0.19 g/L, salt 5.9 g/L.

All data are from water sol database (salts) and/or physprop.

Consumer Use: No

SAT (concerns) (10/02/2009):

Related Cases and Related Cases and Misc SAT Info:

Migration to groundwater: Anion rapid; Cation negl

PBT rating: P2B3T2 Anion: P1B1T1; Cation: P2B3T2

Health: 1-2 Dermal, Drinking Water, Inhalation, XB Testing

(Testing desired)

Eco: 3 Water (All releases to water with a CC = 1 ppb), XB

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Testing (Testing desired)

OCCUPATIONAL EXPOSURE RATING: 2-3B

NOTES & KEY ASSUMPTIONS:

Generated by the 06/07/2005 version of ChemSTEER. The technical

contact was called with questions, see contact report for

details. This PMN has a high PB rating (P2B3 for cation), all

release media and exposures were considered. Per

submission/technical contact, all waste expected to go to

off-site incineration. CEB also assessed release to

water/incineration/landfill for container residue due to unknown

drum reconditioner operations, and release to air due to unknown

air pollution control for dust. Inhalation exposures to

particulate and dermal exposures to solids assessed.

Exposure-based criteria evaluated below. There was no MSDS in

the submission (none shown on list of attachments). 

 

 

 

 

 

POLLUTION PREVENTION CONSIDERATIONS:

None provided.

EXPOSURE-BASED REVIEW: Yes (0 criteria met)

1) # of workers exposed: 24 >1000? No

2) >100 workers with >10 mg/day inhalation exposure: No

3) (a) >100 workers w/1-10 mg/day inh. exp. & >100 days/yr: No

 (b) Routine Dermal Cont: >250 workers & >100 days/yr: No

INITIAL REVIEW ENGINEERING REPORT 

PMN: 09-0636

Manufacturing: Batch Production

Number of Sites/ Location: 1

FUJIFILM Hunt Chemicals USA, Inc. Dayton TN 37321

Days/yr: 77

Basis: Submission estimates 1 site, 1,400 kg/bt, 24 hr/bt, 80

bt/yr, 95% PMN in product. ChemSTEER calculates 77 bt/yr for

mass balance.

Process Description: Starting materials charged to reactor ->

PMN formed (liquid) -> Seed crystals added -> Crystallization ->

PMN slurry transferred to second tank for cooling (hard-piped)

-> Centrifuge -> PMN transferred to plastic drums (wet cake,

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95%). (Submission, technical contact)

ENVIRONMENTAL RELEASES ESTIMATE SUMMARY

IRER Note: The daily releases listed for any source below may

coincide with daily releases from the other sources to the same

medium. Water - not expected per submission/technical contact.

Incineration - all process wastes to off-site incineration (RCRA

incinerator or kiln, 99.99% eff.) per submission/technical

contact. Landfill - not expected per submission/technical

contact. Air - assessed per EPA/OPPT Dust Model.

Air or Incineration

Output 2: 7.0E+0 kg/site-day over 77 days/yr from 1 site

or 5.4E+2 kg/yr

to: Air or off-site incineration

from: Loading Solid Product into Transport Containers

basis: User-Defined Loss Rate Model. EPA/OPPT Dust Emissions

from Transferring Solids Model (revised Nov 2006) estimates 0.5%

of the quantity transferred is released to water, incineration,

land or air. Technical contact indicates all waste from the

process is sent to off-site incineration (RCRA incinerator or

kiln, 99.99% eff.). CEB assesses release to air or incineration

(i.e., if PMN dust is captured it will be sent to incineration).

 Note dust release may be mitigated by transfer as wet

centrifuge cake rather than as a dry solid.

Incineration

Conservative: 2.8E+1 kg/site-day over 77 days/yr from 1 site

or 2.2E+3 kg/yr

to: Off-site incineration (technical contact)

from: Equipment Cleaning Losses of Liquids from Multiple Vessels

basis: EPA/OPPT Multiple Process Vessel Residual Model, CEB

standard 2% residual. Multiple vessels containing PMN: Reactor

D, Reactor F, Centrifuge. Technical contact indicates all waste

from the process is sent to off-site incineration (RCRA

incinerator or kiln, 99.99% eff.).

Incineration

Output 2: 7.2E+1 kg/site-day over 77 days/yr from 1 site

or 5.5E+3 kg/yr

to: Off-site incineration (Submission)

from: Centrifuge Mother Liquor Discharge

basis: User-Defined Loss Rate Model. Submission estimates 72

kg/bt (~5%) released from spent mother liquor to off-site

incineration (RCRA incinerator or kiln, 99.99% eff.).

RELEASE TOTAL

8.2E+3 kg/yr - all sites

OCCUPATIONAL EXPOSURES ESTIMATE SUMMARY

Tot. # of workers exposed via assessed routes: 12

Basis: Submission estimates 12 workers exposed to wet solid that

is 95% PMN.

Inhalation:

Potential inhalation exposure assessed due to chance of airborn

PMN (submission indicates that air purifying respirator is

called for)

Exposure to Particulate (Class I)

Upper Bound: 1.4E+2 mg/day over 77 days/yr

Number of workers (all sites) with inhalation exposure: 12

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Basis: Loading Solid Product into Transport Containers; OSHA

PNOR PEL-Limiting Model.

NOTE: The respirator class is: I. Particulate (including solid

or liquid droplets).

INHALATION MONITORING DATA REVIEW

1) Uncertainty (estimate based on model, regulatory limit,

 or data not specific to industry): Yes

2)a) Exposure level > 1 mg/day? Yes

 OR

 b) Hazard Rating for health of 2 or greater? 1-2 No

Inhalation Monitoring Data Desired? Yes (both criteria met)

Dermal:

Exposure to Solid at 95.00% concentration

High End: 2.9E+3 mg/day over 77 days/yr

Number of workers (all sites) with dermal exposure: 12

Basis: Loading Solid Product into Transport Containers; EPA/OPPT

Direct 2-Hand Dermal Contact with Solids Model.

INITIAL REVIEW ENGINEERING REPORT 

PMN: 09-0636

Use: Intermediate for 

Number of Sites/ Location: 1

FUJIFILM Hunt Chemicals USA, Inc. Dayton TN 37321

Days/yr: 77

Basis: Submission indicates 1 Use batch per Mfg batch, 1 site, 1,

400 kg/bt, 24 hr/bt, 80 bt/yr, 95% PMN in raw material.

ChemSTEER calculates 77 bt/yr for mass balance.

Process Description: PMN in plastic drums (wet solid, 95%) ->

PMN and other materials charged to reactor -> PMN reacted to

form (PMN destroyed). (Submission, technical contact,

CRSS)

ENVIRONMENTAL RELEASES ESTIMATE SUMMARY

IRER Note: The daily releases listed for any source below may

coincide with daily releases from the other sources to the same

medium. Water - not expected per submission/technical contact,

but assessed for container residue due to uncertainty.

Incineration - all process wastes to off-site incineration (RCRA

incinerator or kiln, 99.99% eff.) per submission/technical

contact. Landfill - not expected per submission/technical

contact, but assessed for container residue due to uncertainty

(note drinking water concern, non-negligible migration for

anion). Air - assessed per EPA/OPPT Dust Model.

Water or Incineration or Landfill

Output 2: 1.4E+1 kg/site-day over 77 days/yr from 1 site

or 1.1E+3 kg/yr

to: Uncertain

from: Cleaning Solid/ Powder Residuals from Containers Used to

Transport the Raw Material

basis: EPA/OPPT Solid Residuals in Transport Containers Model,

CEB standard 1% residual. Technical contact indicates wet solid

PMN stored in plastic drums, which could be reused in the

process and are sent to a drum reconditioner at end of life.

CEB assesses release to water, incineration, or landfill based

on uncertainty (drum| reconditioner operations unknown).

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Air or Incineration

Output 2: 7.0E+0 kg/site-day over 77 days/yr from 1 site

or 5.4E+2 kg/yr

to: Air or off-site incineration

from: Unloading Solid Raw Material from Transport Containers

basis: User-Defined Loss Rate Model. EPA/OPPT Dust Emissions

from Transferring Solids Model (revised Nov 2006) estimates 0.5%

of the quantity transferred is released to water, incineration,

land or air. Technical contact indicates all waste from the

process is sent to off-site incineration (RCRA incinerator or

kiln, 99.99% eff.). CEB assesses release to air or incineration

(i.e., if PMN dust is captured it will be sent to incineration).

 Note dust release may be mitigated by transfer as wet solid

rather than as a dry solid.

RELEASE TOTAL

1.6E+3 kg/yr - all sites

OCCUPATIONAL EXPOSURES ESTIMATE SUMMARY

Tot. # of workers exposed via assessed routes: 12

Basis: Submission estimates 12 workers exposed to wet solid that

is 95% PMN.

Inhalation:

Potential inhalation exposure assessed due to chance of airborn

PMN (submission indicates that air purifying respirator is

called for)

Exposure to Particulate (Class I)

Upper Bound: 1.4E+2 mg/day over 77 days/yr

Number of workers (all sites) with inhalation exposure: 12

Basis: Unloading Solid Raw Material from Transport Containers;

OSHA PNOR PEL-Limiting Model.

NOTE: The respirator class is: I. Particulate (including solid

or liquid droplets).

INHALATION MONITORING DATA REVIEW

1) Uncertainty (estimate based on model, regulatory limit,

 or data not specific to industry): Yes

2)a) Exposure level > 1 mg/day? Yes

 OR

 b) Hazard Rating for health of 2 or greater? 1-2 No

Inhalation Monitoring Data Desired? Yes (both criteria met)

Dermal:

Exposure to Solid at 95.00% concentration

High End: 2.9E+3 mg/day over 77 days/yr

Number of workers (all sites) with dermal exposure: 12

Basis: Unloading Solid Raw Material from Transport Containers;

EPA/OPPT Direct 2-Hand Dermal Contact with Solids Model.



MEMORANDUM of TELEPHONE CONVERSATION

CALL BY: Dan Roper

Organization: ERG, for EPA/OPPT/CEB

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CALL TO: Larry McDermott

Organization: Fujifilm Hunt Chemicals USA, Inc.

Date: 10/13/2009

Time: 10:20 am

Phone: 423-285-1031

Concerning what TSCA ?

PMN: 09-0636

 Q1: Is there a difference between BEHTA-pTSA and

BEHTA*pTSA (- vs. *)? A1: No, same chemical (PMN), our

terminology is still in flux. /// Q2: The description on p. 8

states the PMN is formed in Reactor E, but the diagram on p. 8a

indicates some of the reactants are added to Reactor D.

Clarify? A2: The PMN is formed in Reactor D. We've been

revising the process , and neither the description nor the

diagram are the final version. /// Q3: Are the seed crystals

added to Reactor D or F? A3: Reactor D. Reactor F will only be

used for cooling. /// Q4: Are the transfers between reactors

manual or piped? A4: All the connections and transfers between

vessels are piped. PMN is only transferred manually as the wet

cake from the centrifuge. /// Q5: What type of containers are

used to store the wet cake and how are they cleaned/disposed of?

 A5: Plastic drums, they may be reused several times, they are

sent to a drum reconditioner at end of life. /// Q6: Does the

PMN completely react in the use? A6: Yes the PMN is just the

salt form of and is easily disassociated. /// Q7: Are

all wastes incinerated or do you send any waste streams to WWT?

A7: All waste is incinerated off site. Don't have an on-site

WWTP and don't discharge to POTW. Do send non-hazardous waste

from other processes at plant to off-site, non-hazardous WWTP,

but nothing is sent from this process to the non-hazardous WWTP.

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