# PROPOSED September 20, 2007

RULE 4661 ORGANIC SOLVENTS (Adopted May 21, 1992; Amended December 17, 1992; Amended December 9, 1999; Amended December 20, 2001; Amended May 16,

2002 ; Amended [ rule adoption date ] ).

1.0 Purpose

The purpose of this rule is to limit the em issions of volatile organic compounds (VOCs) from the use of organic solvents. This rule also specifies the reduction, monitoring, reporting, and disposal requirements.

2.0 Applicability

The provisions of this rule shall apply to any source operation that uses organic solvents unless the source operation is exempted under Section 4.0.

3.0 Definitions

3.1 APCO: as defined in Rule 1020 (Definitions).

3.2 ARB: California Air Resources Board.

3.1 3.3 Baked: heated to a temperature greater than 194 o F for the pu rpose of curing or drying a coating, ink or adhesive. a process whereby the coated object is heated above ambient temperature to a temperatur e at or above 194°F for the purpose of curing or drying.

3.2 3.4 Dissolver: an organic solvent that is a dded to an adhesive, coating, or ink in order to melt or to liquefy solid particles.

3.5 EPA: United States Environmental Protection Agency.

3.3 3.6 Exempt Compounds: all organic compounds not classified as VOC, as listed in the definition of VOC in Rule 1020 (Definitions).

3.4 3.7 Grams of VOC per liter of Material: the weight of VOC per volume of material and is calculated by the following equation:

Grams of VOC per liter of material = Ws – Ww – Wec

Vm

Where: Ws = Weight of volatile compounds, in grams Ww = Weight of water, in grams Wec = Weight of exempt compounds, in grams Vm = Volume of material, in liters.

3.5 3.8 Heat-Cured or Heat-Polymeriz ed: heated to a temperatur e less than or equal to

194 o F for the purpose of curing a coating, ink or adhesive.

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3.9 Normal Business Hours: Monday through Friday, 8:00 am to 5:00 pm.

3.6 3.10 Organic Solvent: the same as “Solvent.”

3.7 3.11 Organic Solvent Cleaning: as defined in Rule 4663 (Organic Solvent Cleaning, Storage, and Disposal).

3.8 3.12 Photochemically Reactive Solvent: any or ganic solvent with an aggregate of

more than 20% of its total volume com posed of chemical compounds classified below or which exceeds any of the fo llowing individual percentage composition limitations referring to the total volume of solvent:

3.8.1 3.12.1 A combination of hydrocarbons, alc ohols, aldehydes, esters, ethers or ketones having an olefinic or cyclool efinic type of unsaturation: five (5) percent; or

3.8.2 3.12.2 A combination of aromatic compounds with eight (8) or more carbon atoms to the molecule except ethyl benzene: eight (8) percent; or

3.8.3 3.12.3 A combination of ethylbenzen e, ketones having branched hydrocarbon structures, or toluene: 20%.

Whenever any organic solvent or any cons tituent of an organic solvent may be

classified from its chemical structure in to more than one (1) of the above groups of organic compounds, it shall be consider ed as a member of the most reactive chemical group, that is, that group having the least allowable percentage of the

total volume of solvents.

3.13 SCAQMD: South Coast Air Qu ality Management District.

3.9 3.14 Solvent: as defined in Rule 4663 (O rganic Solvent Cleaning, Storage, and Disposal).

3.10 3.15 Standard Conditions: as defined in Rule 1020 (Definitions).

3.11 3.16 Thinner or Viscosity Reducer: an organic solvent which is added to an adhesive, coating, or ink to make it more fluid used to dilute coatings to reduce viscosity, color strength, and solids, or to modify drying conditions

.

3.12 3.17 Volatile Organic Compound (VOC): as defined in Rule 1020 (Definitions).

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4.0 Exemptions

The provisions of this rule shall not apply to:

4.1 The manufacture of organic solvents, or the transport of organic solvents or materials containing organic solvents.

4.2 Any source operation that is subject to or specifically exempted by any of the following rules or an EPA approved version of the applicable listed rule :

4.2.1 Rule 4601 (Architectural Coatings),

4.2.2 Until December 31, 2008, Rule 4602 (Motor Vehicle and Mobile Equipment Coating Operations),

4.2.3 Rule 4603 (Surface Coating of Metal Parts and Products),

4.2.4 Rule 4604 (Can and Coil Coating Operations),

4.2.5 Rule 4605 (Aerospace Assembly and Component Coating Operations),

4.2.6 Rule 4606 (Wood Products Co ating Operations),

4.2.7 Rule 4607 (Graphic Arts),

4.2.8 Rule 4610 (Glass Coating Operations),

4.2.9 On and after January 1, 2009, Rule 4612 (Motor Vehicle and Mobile Equipment Coating Operations – Phase II)

4.2.9 4.2.10 Rule 4653 (Adhesives),

4.2.10 4.2.11 Rule 4662 (Organic Solvent Degreasing Operations),

4.2.11 4.2.12 Rule 4684 (Polyester Resin Operations), or

4.2.12 4.2.13 Rule 4691 (Vegetable Oil Processing Operations).

4.3 The spraying or other employment of insecticides, pesticid es or herbicides.

4.4 The employment, application, evaporation, or drying of saturated halogenated hydrocarbons or perchloroethylene.

4.5 The use of any material, in any sour ce operation described in Sections 5.1, 5.2, 5.3, or 5.4 if all of the following conditions are met :

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4.5.1 The volatile content of material consists only of water and organic solvents, and

4.5.2 The organic solvents content comp rises not more than 20 percent by volume of the total volatile content, and

4.5.3 The volatile content is not photochemically reactive, and

4.5.4 The organic solvent does not come into contact with flame.

5.0 Requirements

5.1 Sections 5.2 through 5.7 shall remain in effect until [ 6 months after rule adoption

date ].

5.1 5.2 Solvents Subjected to Heat: An operator shall not discharge into the atmosphere more than 15 pounds of VOC emissions in any one (1) day from any source operation in which any organic solvent or any material c ontaining organicsolvents comes into contact with a flame or is baked, heat-cured, or heatpolymerized in the presence of oxygen, unless the VOC emissions have been reduced through the operation of an APCO- approved VOC emissions control

device system with an overall capture and control efficiency of at least 85 percent by weight . Those portions of any series of source operation designed for processing continuous web, strip, or wire th at emit VOCs in the course of using operations described in this section shal l be collectively subject to compliance

with this section.

5.2 5.3 Photochemically Reactive Solvents: An operator shall not discharge into the atmosphere more than 40 pounds of VOC emissions in any one (1) day from any source operation resulting from conditions other than those described in Section 5.1 for employing or applyi ng any photochemically reac tive solvent, or any material containing such photochemica lly reactive solvent, unless the VOC

emissions have been reduced th rough the operation of an APCO- approved VOC

emissions control device system with an overall capture and control efficiency of at least 85 percent by weight . Emissions resulting fr om baking, heat-curing, or heat-polymerizing, as described in Section 5.1 5.2 of this rule, shall be excluded from determination of complia nce with this section. T hose portions of any series of source operation designed for processing a continuous web, strip, or wire that emit VOCs in the course of using operati ons described in this section shall be collectively subject to compliance with this section.

5.3 5.4 Non-photochemically Reactive Solvents: An operator shall not discharge into the atmosphere more than 3,000 pounds of VOC emissions in any one (1) day from any source operation in which a ny non-photochemically reactive organic solvent or any material containing such a solvent, is employed or applied, unless

VOC emissions have been reduced through the operation of an APCO- approved

VOC emissions control device system with an overall capture and control

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efficiency of at least 85 percent by weight . Emissions resulting from baking, heat-curing, or heat-polymeriz ing, as described in Section 5.1 5.2 of this rule,

shall be excluded from determination of compliance with this section. Those portions of any series of source operat ion designed for processing a continuous web, strip, or wire that emit VOCs in the course of using oper ations described in this section shall be collectively subj ect to compliance with this section.

5.4 5.5 Cleanup: Emissions of VOCs into the atmosphere resulting from cleanup operations utilizing photochemically reactiv e organic solvents, from any source operation described in Sections 5.1, 5.2, or 5.3 5.2, 5.3, or 5.4 shall be included

with other emissions of VOCs from that source operation for determining compliance with this rule.

5.5 5.6 Post Removal Drying: Emi ssions of VOCs into the atmosphere as a result of spontaneously continuing drying of pr oducts for the first 12 hours after their removal from any source opera tion described in Sections 5.1, 5.2, or 5.3 5.2, 5.3,

or 5.4 shall be included with other emissions of VOCs fr om that source operation for determining compliance with this rule.

5.6 5.7 Monitoring: An operator incineratin g, adsorbing, or otherwise processing organic solvents pursuant to this rule sh all provide, properly install and maintain in calibration, in good working order and in operation, devices as specified in the Authority to Construct or the Permit to Op erate, or as specified by the APCO, for indicating temperatures, pressures, rate s of flow or othe r operating conditions necessary to determine the degree and effectiveness of air pollution control the VOC emission control system

.

5.8 On and after [ 6 months and one day after rule adoption date ], from all VOCcontaining materials, equipment, and pro cesses subject to this rule, an operator

shall not emit to the atmo sphere VOCs in excess of 833 pounds VOC per calendar month per facility.

5.9 In lieu of meeting the VOC emission lim it in Section 5.8, an operator may install and operate a VOC emission control system that meets the following requirements.

5.9.1 The VOC emission control system shall be approved by the APCO.

5.9.2 The VOC emission control system shall have a capture efficiency of at least 90 percent by we ight (90 wt%) and a control efficiency of at least 95

wt%.

5.7 Storage and Disposal of Solv ents: An operator shall st ore or dispose of fresh or spent photochemically reactive solven ts, or any materials containing photochemically reactiv e solvents, solvent

- laden wiping materials such as cloth, paper, etc., i n closed, non

- absorbent and non

- leaking containers. The containers shall

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remain closed at all times except when depositing or re moving the contents of the

containers. Section 5.7 shall remain in effect until November 14, 2002.

5.8 5.10 Organic Solvent Cleaning, Storage, and Disposal Requirements: Effective on and after November 15, 2002, o O perators shall comply with the requirements of Rule 4663 (Organic Solvent Cleaning, Storage, and Disposal) when performing organic solvent cleaning, storage and dis posal of organic solvents and waste solvent materials, coatings, adhesives, ca talysts, and thinners. See Sections 5.0

and 6.0 of Rule 4663 for solvent VOC content limits, work practices, recordkeeping, and testing requirements.

6.0 Administrative Requirements

6.1 Recordkeeping

An operator of any source ope ration subject to this rule shall maintain the records required by Sections 6.1.1 and 6.1.2 for a period of five (5) years. The records shall be made available to the APCO upon request.

6.1.1 Until [ six months after rule adoption date ], T t he records shall identify the organic solvents used in all source operations and shall include the name of each organic solvent, solvent manufacturer’s name, chemical composition, VOC content, vapor pressure, amount used.

6.1.1.1 An operator of a coating oper ation subject to this rule shall maintain daily records.

6.1.1.2 For other operations subject to th is rule, records may be kept on an extended basis, but not to exceed monthly, and shall not exceed a period during which the amount of VOC emissions exceeds the applicable daily VOC emission limits in the rule.

6.1.1.3 Solvent purchase records and ot her such records needed to verify compliance of emission s limits of the rule shall also be kept.

6.1.1.4 Effectiv e on and after November 15, 2002, o O ther such records, including the amount of VOC em issions resulting from organic solvent cleaning opera tions subject to Ru le 4663 utilizing photochemically reactive organic solvents, needed to verify compliance of emission s limits of the rule shall also be kept.

6.1.1.5 Records of the boiling point and amount of waste or spent solvent disposed shall also be ke pt. Section 6.1. 1.5 shall remain in effect until November 14, 2002.

6.1.2 On and after [ six months and one day after rule adoption date ], operators

shall

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6.1.2.1 Materials List: An operator shal l maintain and have available on site, a current list of materials in use which provides all of the data necessary to evaluate compliance including the following information as applicable:

6.1.2.1.1 Specific manufacturer’s name of solvent-containing material, including solvents, catalysts, and thinners.

6.1.2.1.2 VOC content of each solven t-containing material, as used, in g/l or lb/gal.

6.1.2.2 Material Usage Records – An operator shall maintain usage records on a daily basis that in clude the following information:

6.1.2.2.1 Specific material.

6.1.2.2.2 Volume of material used (gallons).

6.1.2.2.3 Specific solvents, catalysts and thinners added to

material.

6.1.2.2.4 Volume of each solvent, catalyst and thinner (gallons)

added.

6.1.2.2.5 When the material is a mixture of different materials that are blended by the operator, the mix ratio of the

batch shall be recorded a nd the VOC content of the

batch shall be calculated and recorded in order to determine compliance with the VOC emission limits.

6.1.3 VOC Emission Control System Records

An operator using a VOC emission control system as a means of complying with this rule shall main tain daily records of key system operating parameters which will demonstrate continuous operation and compliance of the VOC emission c ontrol system during periods of emission-producing activities.

6.1.4 Records Retention

An operator shall retain records required in S ections 6.1.1 through 6.1.3, as applicable, on site for a minimum of five (5) years, make the records available on site during normal busin ess hours to the APCO, ARB, or EPA and submit the records to the APCO, ARB, or EPA upon request.

6.2 Test Methods

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6.2.1 Determination of VOC Content

6.2.1.1 The VOC content of organic solvents shall be determined by using United States Environmental Protection Agency ( EPA ) Test Method 24 or 24A or by using the manufacturer’s product

formulation data and the formula in Section 3.4 3.7

.

6.2.1.2 Exempt halogenated VOCs shall be determined by using the California Air Resources Board ( ARB ) Test Method 432 or South Coast Air Quality Management District ( SCAQMD ) Test

Method 303.

6.2.2 Determination of Overall Capture and Control Efficiency of VOC

Emission Control Devices

6.2.2.1 The capture efficiency of each collection device shall be demonstrated according to the EPA’s document “Guidelines for Determining Capture Efficiency,” dated January 9, 1995. An equivalent alternate test method may be u sed provided it has been approved by the EPA, ARB and the APCO. The capture efficiency of a VOC emission control system’s collection device(s) shall be determined according to EPA’s “Guidelines for Determining Capture Effi ciency,” January 9, 1995 and 40 CFR 51, Appendix M, Test Methods 204-204F, as applicable, or any other method approved by EPA, ARB, and the APCO.

6.2.2.2 The control efficiency of the VOC emission control system’s

control device and the emissions of VOCs, measured and

calculated as carbon

, shall be determined by using EPA Methods 2, 2A, or 2D for measuring flow rates and EPA Test Method 25, 25A,

or 25B , as applicable for measuring total gaseous organic

concentrations at the inlet an d outlet of the control device . EPA

Test Method 18 or ARB Method 422 sha ll be used to determine the emissions of exempt co mpounds. The control efficiency of the VOC emission control system’s control device shall be calculated by using the follo wing equation:

CE CONTROL = [1 – ( VOC OUT / VOC IN )] x 100%

Where:

CE CONTROL = Control Efficiency, in percent

VOC IN = VOC content, in grams/liter, less exempt compounds and water, into the control device

VOC OUT = VOC content, in grams/liter, less exempt compounds and water, out of the control device.

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6.2.2.3 The ove rall capture and control effici ency shall be calculated by using the following equation For VOC emission control systems that consist of a single VOC em ission collection device connected to a single VOC emission control device, the overall capture and control efficiency shall be cal culated by using the following equation :

CE CAPTURE AND CONTROL = [ CE CAPTURE x CE CONTROL ] / 100 %

Where:

CE CAPTURE AND CONTROL = Overall Capture and Control Efficiency, in percent

CE CAPTURE = Capture Efficiency of the collection device, in percent, as determined in

Section 6.2.2.1

CE CONTROL = Control Efficiency of the control device, in percent, as determined in

Section 6.2.2.2.

6.2.3 Determination of VOC Emissions

6.2.3.1 The emissions of VOCs, measured and calculated as carbon, shall be determined by using EPA Test Method 25, 25A, or 25B, as applicable. EPA Test Met hod 18 or ARB Method 422 shall be used to determine the emissions of exempt compounds.

6.2.3.1 6.2.3.2 Total VOC emissions per day shall be determined for each source operation by using the following equation:

454 1001

1 1 / %)/( x E

Total ⎥ ⎦ ⎤ ⎢ ⎣ ⎡ ⎟ ⎠ ⎞ ⎜ ⎝ ⎛

− + ⎟ ⎠ ⎞ ⎜ ⎝ ⎛

= 

# ∑∑

= = CE VLVL n

m mm k

i ii

Where:

E Total = Total VOC emissions, in pounds per day

L i = Liters per day used of th e “i”th organic solvent that

is uncontrolled

V i = Grams of VOC per liter of material of the “i”th organic solvent that is uncontrolled

L

m = Liters per day used of the “m”th organic solvent

that is controlled

V

m = Grams of VOC per liter of material of the “m”th organic solvent that is controlled CE = Overall capture and control efficiency of the control device, in percent, as determined in Section 6.2.2.3.

6.2.4 Determination of Boiling Point and Vapor Pressure

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6.2.4.1 The boiling point of organic solvents shall be determined by using either the manufacturer’s pr oduct formulation data or from

p ublications such as Perry’s Chemical Engineer’s Handbook, CRC Handbook of Chemistry and Physics, Lange’s Handbook of Chemistry, or other District ap proved sources. Section 6.2.4.1 shall remain in effect until November 14, 2002.

6.2.4.2 The vapor pressure of organic solvents sh all be determined by using ASTM Method D2879 or from publications such as Perry’s Chemical Engineer’s Ha ndbook, CRC Handbook of Chemistry and Physics, and Lange’s Handbook of Chemistry.

6.2.5 6.2.4 Multiple Methods of Determination

VOC emissions and overall capture and control efficiency determined to exceed any limits established by this ru le through the use of any of the

above-referenced test methods and /or equations shall constitute a violation

of the rule.

7.0 Compliance Schedu le

All rule provisions remain in effect on and after December 20, 2001, unless otherwise

indicated.

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