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ENVIRONMENTAL ISSUES SECTION

HANDOUT INDEX
2004
HO
#

Page
#

Handout Title

Gasoline Fuel Parameters that Affect


Air Quality

Specific Environmental
Issues in the Refining
Industry (12)

U.S. Primary and Secondary Ambient


Air Quality Standards (40 CFR 50)

Refinery Methods to Address


Air Pollution (38)

U.S. Clean Air Act Hazardous Air


Pollutant List (from UOP Reference
Document GR-07)

Refinery Methods to Address


Air Pollution (43)

12

Pollutants
Refineries

Typical Emissions in
Refineries (44)

13

Screen and select appropriate VOC


control technologies

VOC Control Technologies


(57)

14

Typical Industrial Wastewater Effluent


Limitations

U.S. Effluent Guidelines for


Refineries (91)

15

U.S. Regulatory Effluent Limitations


for Refineries (40 CFR 419 - section
example)

U.S. Effluent Guidelines for


Refineries (91)

16

Generation of Wastewaters in the


Petroleum Refining Industry

Typical Liquid Effluents


Petroleum Refining (92)

17

U.S. Refinery Listed Hazardous Wastes

U.S. Hazardous Waste


Categories (100)

10

UOP Environmental Tools for Process


Units/Environmental Reviews of
Process Units

The "Effluent Summary"


(104)

11

18

Example Output Sheet from an


Effluent Summary

Effluent Summary Tool Main Menu (106)

and

Reference Slide
(Title and Presentation
Packet Slide #)

Emissions

from

SEE GasolineAirQuality.PDF File (1 page)


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ENVIRONMENTAL ISSUES HANDOUT


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Handout #1

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ENVIRONMENTAL ISSUES HANDOUT


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Handout # 2

U.S. Primary and Secondary Ambient Air Quality Standards


Primary StandardNote 1
(Maximum)
10-6g/m3
ppm

Secondary
StandardNote 2
(Maximum)
10-6g/m3
ppm

Contaminant

Period of
Measurement

Notes

Sulfur Oxides
(as SO2)

Annual arithmetic mean

80

0.03

"

24 hour average

365

0.14

"

3 hour average

1300

0.5

Particulate
Matter
(PM10)

Annual arithmetic mean

50

50

4, 5

"

24 hour average

150

150

Particulate
Matter
(PM2.5)

24 hour average

65

65

8, 9

"

Annual arithmetic mean

15

15

10

Ozone

1 hour average

235

0.12

135

0.12

"

8 hour average

155

0.08

155

0.08

Nitrogen Dioxide

Annual arithmetic mean

100

0.053

100

0.053

Carbon
Monoxide

8 hour average

10
(in mg/m3)

10
(in mg/m3)

"

1 hour average

40

35

Lead

Arithmetic mean average


over a calendar quarter

1.5

1.5

Notes:
1.
2.
3.
4.
5.
6.
7.
8.
9.

10.

Primary Standards are to protect the public health.


Secondary Standards are to protect the public welfare and environment.
Value not to be exceeded more than once a year.
Particles with aerodynamic diameter < 10 micrometers.
Once an area has attained this standard, it no longer applies. Area then becomes subject to PM2.5
standard.
Once an area has attained this standard, it no longer applies. Area then becomes subject to the 8-hour
average ozone standard.
Three year average of the annual fourth-highest daily maximum eight-hour concentration.
Particles with aerodynamic diameter < 2.5 micrometers.
Three year average of the 98th percentile of 24-hour concentrations.
Three year average of annual arithmetic mean concentrations.

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ENVIRONMENTAL ISSUES HANDOUT


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Revision
Indication

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GR-07

U.S. CLEAN AIR ACT HAZARDOUS


AIR POLLUTANTS

General Reference

Page

1 of 8

HANDOUT # 3
U.S. Clean Air Act Hazardous Air Pollutants
GENERAL EXPLANATORY NOTES:
1. This table is a comprehensive list of all Hazardous Air Pollutants regulated by the U.S. through the
Environmental Protection Agency. Since the Oil Refining and Petrochemical industries are regulated
differently, a different subset of chemicals fall into the hazardous air pollutant area for the two
industries. These are indicated in the three columns on the right side of the table and further described
below:
(a) Petrochemical Organic Hazardous Air Pollutants
This is a list of organic hazardous air pollutants subject to the Maximum Achievable Control
Technology (MACT) for the U.S. Organic Chemical Manufacturing Industry Category. This
basically relates to any process unit which produces a pure organic chemical as its primary product.
Releases are regulated in areas such as Venting , Tankage, Loading, Wastewaters, and Fugitive
emissions.
(b) Petroleum Refinery ORGANIC Hazardous Air Pollutants (Refinery MACT)
This is the list of hazardous air pollutants subject to MACT for the U.S. Petroleum Refining
Industry Category. Regulation controls organic releases from Venting, Tankage, Loading,
Wastewaters, and Fugitive emissions (i.e., similar to petrochemical coverage).
(c) Petroleum Refinery Process-Specific Hazardous Air Pollutants (Refinery MACT2)
(see Note 10)
This list is part of the second phase of Refinery MACT Regulation. This list includes all
hazardous air pollutants from refinery processes that were NOT covered in the first refinery MACT
regulation described in (b) above - namely Catalytic Cracking Units, Reforming Units and Sulfur
Recovery Plants. Pollutants in this list are controlled by limiting surrogate substances as describe
in note 10.

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ENVIRONMENTAL ISSUES HANDOUT


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U.S. Clean Air Act Hazardous Air Pollutants


Chemical Name

Acetaldehyde
Acetamide
Acetonitrile
Acetophenone
2-Acetylaminofluorene
Acrolein
Acrylamide
Acrylic acid
Acrylonitrile
Allyl chloride
4-Aminobiphenyl
Aniline
o-Anisidine
Asbestos
Benzene (including benzene from
gasoline)
Benzidine
Benzotrichloride
Benzyl chloride
Biphenyl
Bis(2-ethylhexyl)phthalate (DEHP)
Bis(chloromethyl)ether
Bromoform
1,3-Butadiene
Calcium cyanamide
Captan
Carbaryl
Carbon disulfide
Carbon tetrachloride
Carbonyl sulfide
Catechol
Chloramben
Chlordane
Chlorine
Chloroacetic acid
2-Chloroacetophenone
Chlorobenzene
Chlorobenzilate
Chloroform

CAS
Number
(Note 6)

Petrochemical
Organic
Hazardous Air
Pollutants

75070
60355
75058
98862
53963
107028
79061
79107
107131
107051
92671
62533
90040
1332214
71432

X
X
X
X

Petroleum
Refinery
Organic
Hazardous Air
Pollutants

Petroleum Refinery
Process Specific
Hazardous Air
Pollutants (Note
10)
X (Note 7)

X
X
X
X
X
X
X

92875
98077
100447
92524
117817
542881
75252
106990
156627
133062
63252
75150
56235
463581
120809
133904
57749
7782505
79118
532274
108907
510156
67663

X
X
X

X
X
X

X (Note 7)

X (Note 9)

X (Note 9)

X
X

X (Notes 7, 8, & 9)

X (Note 8)
X
X
X
X

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ENVIRONMENTAL ISSUES HANDOUT


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U.S. Clean Air Act Hazardous Air Pollutants


Chemical Name

Chloromethyl methyl ether


Chloroprene
Cresols/Cresylic acid (isomers and
mixture)
o-Cresol
m-Cresol
p-Cresol
Cumene
2,4-D, salts and esters
DDE
Diazomethane
Dibenzofurans
1,2-Dibromo-3-chloropropane
Dibutylphthalate
1,4-Dichlorobenzene(p)
3,3-Dichlorobenzidene
Dichloroethyl ether (Bis(2chloroethyl)ether)
1,3-Dichloropropene
Dichlorvos
Diethanolamine
N,N-Diethyl aniline (N,NDimethylaniline)
Diethyl sulfate
3,3-Dimethoxybenzidine
Dimethyl aminoazobenzene
3,3'-Dimethyl benzidine
Dimethyl carbamoyl chloride
Dimethyl formamide
1,1-Dimethyl hydrazine
Dimethyl phthalate
Dimethyl sulfate
4,6-Dinitro-o-cresol, and salts
2,4-Dinitrophenol
2,4-Dinitrotoluene
1,4-Dioxane (1,4-Diethyleneoxide)
1,2-Diphenylhydrazine
Epichlorohydrin (1-Chloro-2,3epoxypropane)
1,2-Epoxybutane
Ethyl acrylate

CAS
Number
(Note 6)

Petrochemical
Organic
Hazardous Air
Pollutants

107302
126998
1319773

Petroleum
Refinery
Organic
Hazardous Air
Pollutants

X
X

95487
108394
106445
98828
94757
3547044
334883
132649
96128
84742
106467
91941
111444

X
X
X
X

X
X
X
X

542756
62737
111422
121697

Petroleum Refinery
Process Specific
Hazardous Air
Pollutants (Note
10)

X (Note 8)
X
X
X

X
X

64675
119904
60117
119937
79447
68122
57147
131113
77781
534521
51285
121142
123911
122667

X
X

X
X
X
X
X
X
X
X
X

106898
106887
140885

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ENVIRONMENTAL ISSUES HANDOUT


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U.S. Clean Air Act Hazardous Air Pollutants


Chemical Name

Ethyl benzene
Ethyl carbamate (Urethane)
Ethyl chloride (Chloroethane)
Ethylene dibromide
(Dibromoethane)
Ethylene dichloride (1,2Dichloroethane)
Ethylene glycol
Ethylene imine (Aziridine)
Ethylene oxide
Ethylene thiourea
Ethylidene dichloride (1,1Dichloroethane)
Formaldehyde
Heptachlor
Hexachlorobenzene
Hexachlorobutadiene
Hexachlorocyclopentadiene
Hexachloroethane
Hexamethylene-1,6-diisocyanate
Hexamethylphosphoramide
Hexane
Hydrazine
Hydrochloric acid
Hydrogen fluoride (Hydrofluoric
acid)
Hydroquinone
Isophorone
Lindane (all isomers)
Maleic anhydride
Methanol
Methoxychlor
Methyl bromide (Bromomethane)
Methyl chloride (Chloromethane)
Methyl chloroform (1,1,1Trichloroethane)
Methyl ethyl ketone (2-Butanone)
Methyl hydrazine
Methyl iodide (Iodomethane)
Methyl isobutyl ketone (Hexone)

CAS
Number
(Note 6)

Petrochemical
Organic
Hazardous Air
Pollutants

Petroleum
Refinery
Organic
Hazardous Air
Pollutants

X
X

100414
51796
75003
106934
107062

Petroleum Refinery
Process Specific
Hazardous Air
Pollutants (Note
10)

107211
151564
75218
96457
75343

50000
76448
118741
87683
77474
67721
822060
680319
110543
302012
7647010
7664393

X
X
X (Notes 7 & 9)

X
X
X
X

X (Notes 7 & 8)
X (Note 8)

123319
78591
58899
108316
67561
72435
74839
74873
71556

X
X
X

X
X

78933
60344

X
X

74884
108101

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ENVIRONMENTAL ISSUES HANDOUT


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U.S. Clean Air Act Hazardous Air Pollutants


Chemical Name

Methyl isocyanate
Methyl methacrylate
Methyl tert butyl ether
4,4-Methylene bis(2-chloroaniline)
Methylene chloride
(Dichloromethane)
Methylene diphenyl diisocyanate
(MDI)
4,4'-Methylenedianiline
Naphthalene
Nitrobenzene
4-Nitrobiphenyl
4-Nitrophenol
2-Nitropropane
N-Nitroso-N-methylurea
N-Nitrosodimethylamine
N-Nitrosomorpholine
Parathion
Pentachloronitrobenzene
(Quintobenzene)
Pentachlorophenol
Phenol
p-Phenylenediamine
Phosgene
Phosphine
Phosphorus
Phthalic anhydride
Polychlorinated biphenyls
(Arochlors)
1,3-Propane sultone
Beta-Propiolactone
Propionaldehyde
Propoxur (Baygon)
Propylene dichloride (1,2Dichloropropane)
Propylene oxide
1,2-Propylenimine (2-Methyl
aziridine)
Quinoline
Quinone
Styrene

CAS
Number
(Note 6)

Petrochemical
Organic
Hazardous Air
Pollutants

624839
80626
1634044
101144
75092

X
X
X

101688

101779
91203
98953
92933
100027
79469
684935
62759
59892
56382
82688

X
X
X

Petroleum
Refinery
Organic
Hazardous Air
Pollutants

Petroleum Refinery
Process Specific
Hazardous Air
Pollutants (Note
10)

X (Note 8)

X (Note 7)

X
X

87865
108952
106503
75445
7803512
7723140
85449
1336363

X
X
X
X
X

1120714
57578
123386
114261
78875

X
X
X

75569
75558

91225
106514
100425

X
X

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ENVIRONMENTAL ISSUES HANDOUT


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U.S. Clean Air Act Hazardous Air Pollutants


Chemical Name

CAS
Number
(Note 6)

Styrene oxide
2,3,7,8-Tetrachlorodibenzo-p-dioxin
1,1,2,2-Tetrachloroethane
Tetrachloroethylene
(Perchloroethylene)
Titanium tetrachloride
Toluene
2,4-Toluene diamine
2,4-Toluene diisocyanate
o-Toluidine
Toxaphene (chlorinated camphene)
1,2,4-Trichlorobenzene
1,1,2-Trichloroethane
Trichloroethylene
2,4,5-Trichlorophenol
2,4,6-Trichlorophenol
Triethylamine
Trifluralin
2,2,4-Trimethylpentane
Vinyl acetate
Vinyl bromide
Vinyl chloride
Vinylidene chloride (1,1Dichloroethylene)
Xylenes (isomers and mixture)
o-Xylenes
m-Xylenes
p-Xylenes
Antimony Compounds
Arsenic Compounds (inorganic
including arsine)
Beryllium Compounds
Cadmium Compounds
Chromium Compounds
Cobalt Compounds
Coke Oven Emissions
Cyanide Compounds (NOTE 1)
Glycol ethers (NOTE 2)
Lead Compounds
Manganese Compounds
Mercury Compounds

96093
1746016
79345
127184

Petrochemical
Organic
Hazardous Air
Pollutants

Petroleum
Refinery
Organic
Hazardous Air
Pollutants

Petroleum Refinery
Process Specific
Hazardous Air
Pollutants (Note
10)
X (Note 7,8)

X
X

7550450
108883
95807
584849
95534
8001352
120821
79005
79016
95954
88062
121448
1582098
540841
108054
593602
75014
75354

X
X
X
X

X
X
X
X

X (Notes 7, 8, & 9 )

X (Note 8)

X
X
X

X
X

1330207
95476
108383
106423

X
X
X
X

X
X
X
X

X (Notes 7 & 8)

X (Note 7)
X (Note 7)
X (Note 7)
X (Note 7)
X (Note 7)
X (Note 7)

X (Note 7)
X (Note 7)
X (Note 7)

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ENVIRONMENTAL ISSUES HANDOUT


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U.S. Clean Air Act Hazardous Air Pollutants


Chemical Name

CAS
Number
(Note 6)

Petrochemical
Organic
Hazardous Air
Pollutants

Fine mineral fibers (NOTE 3)


Nickel Compounds
Polycyclic Organic Matter (NOTE
4)
Radionuclides (including radon)
(NOTE 5)
Selenium Compounds

Petroleum
Refinery
Organic
Hazardous Air
Pollutants

Petroleum Refinery
Process Specific
Hazardous Air
Pollutants (Note
10)
X (Note 7)

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ENVIRONMENTAL ISSUES HANDOUT


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TABLE SPECIFIC NOTES:


For all listings above which contain the word 'compounds' and for glycol ethers, the following
applies: Unless otherwise specified, these listings are defined as including any unique chemical
substance that contains the named chemical (i.e., antimony, arsenic, etc.) as part of that
chemical's infrastructure.
1.

X'CN where X = H' or any other group where a formal dissociation may occur. For
example KCN or Ca(CN) 2

2.

Includes moni-and di-ethers of ethylene glycol, diethylene glycol, and triethylene glycol
R-(OCH2CH2) n-OR' where n = 1, 2, or 3 R = alkyl or aryl groups R' = R, H, or
groups which, when removed, yield glycol ethers with the structure: R-(OCH2CH) n-OH.
Polymers are excluded from the glycol category.

3.

Includes mineral fiber emissions from facilities manufacturing or processing glass, rock,
or slag fibers (or other mineral derived fibers) of average diameter 1 micrometer or less.

4.

Includes organic compounds with more than one benzene ring, and which have a boiling
point greater than or equal to 100C.

5.

A type of atom which spontaneously undergoes radioactive decay.

6.

CAS = Chemical Abstract Service

7.

Hazardous air pollutant typically emitted from Fluid Catalytic Cracking units.

8.

Hazardous air pollutant typically emitted from Platforming units.

9.

Hazardous air pollutant typically emitted from sulfur plants.

10.

These substances are regulated by controlling a surrogate, since they are easier and less
expensive to measure and monitor.
Process Unit

HAP

Surrogate

Catalytic Cracking

Metals

Particulate Matter, Nickel

Reforming

Organics, Inorganics

Total Organic Carbon (TOC),


HCl

Sulfur Recovery Units


(SRU)

Reduced Sulfur

SO2, Total Reduced Sulfur

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ENVIRONMENTAL ISSUES HANDOUT


- page 11

Handout # 4
Pollutants and Emissions from Refineries
Air Pollutant

Potential Sources within a Refinery

Hydrocarbon

Loading facilities, turnarounds, sampling storage tanks, wastewater separators, blow-down systems,
catalyst regenerators, pumps, valves, blind changing, cooling towers, vacuum jets, barometric
condensers, air-blowing high pressure equipment handling volatile hydrocarbons, process heaters,
boilers, compressor engines, flanged connections, and spills

Sulfur Oxides
(SO2 , SO3 )

Boilers, process heaters, cracking operations, regenerators, treating units, H2S flares, decoking
operations, sulfur recovery plants.

Nitrous Oxides
(NO, NO2)

Process heaters, boilers, compressor engines, catalyst regenerators, flares

Carbon Monoxide

Catalyst regeneration, decoking, compressor engines, incinerators, boilers, and flares

Particulate Matter

Catalyst regenerators, boilers, process heaters, decoking operations, incinerators, flares

Odors
(e.g., Hydrocarbons, aldehydes,
ammonia, mercaptans, H2S,
sulfides and the like)

Treating units, air-blowing, steam-blowing, drains, tank vents, barometric condenser sumps, wastewater
separators, and biotreatment units

Aldehydes

Catalyst Regenerators

Ammonia (NH3)

Catalyst regenerators and sour water strippers

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ENVIRONMENTAL ISSUES HANDOUT


- page 12

Handout # 5
Screen and select appropriate VOC control technologies
Control
Technology

Applicable
Concentration
Range, ppm

Capacity
Range, cfm

Removal
Efficiency

Secondary
Wastes

Advantages

Limitations and Contraindications

Thermal
Oxidation

100-2000

1000-500,000

95 - 99+ %

Combustion
products

Up to 95 % energy recovery
is possible

Halogenated compounds may require


additional control equipment downstream .
Not recommended for batch operations.

Catalytic
Oxidation

100-2000

1000-100,000

90 - 95 %

Combustion
products

Up to 70 % energy recovery
is possible

Thermal efficiency suffers with swings in


operating conditions. Halogenated
compounds may require additional control
equipment dwonstream. Certain
compounds can poison the catalyst (lead,
arsenic, phosphorus, chlorine, sulfur,
particulate matter)

> 5000

100-20,000

50 - 90 %

Condensate

Product recovery can offset


annual operating costs

Not recommended for material with boiling


points > 100 deg. F. Condensers are subject
to scale buildup, which can cause fouling.

Carbon
Adsorption

20 - 5000

100-60,000

90 - 98 %

Spent carbon;
Collected
organic

Product recovery can offset


annual operating costs. Can
be used as a concentrator I
conjunction with another
type of control device.
Works well with cyclic
processes.

Not recommended for streams with relative


humidity > 50 %. Ketones, aldehydes, and
esters clog the pores of the carbon,
decreasing system efficiency.

Absorption

500-5000

2000-100,000

95 - 98 %

Wastewater;
Captured
particulate

Product recovery can offset


annual operating costs

Might require exotic scrubbing media.


Design could be difficult in the event of lack
of equilibrium data. Packing is subject to
plugging and fouling if particulates are in the
gas stream. Scale formation from absorbent/
absorber interaction can occur.

Condensation

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ENVIRONMENTAL ISSUES HANDOUT


- page 13

Handout #6
Typical Industrial Wastewater Effluent Limitations

PARAMETER
Bulk Organics
COD
BOD
Oil and Grease/TPH
Physical
TSS
pH
Temperature
Color
Odor
Specific Contaminants
NH3/NO 3
Phosphates
Heavy Metals
Surfactants (Total)
Sulfides
Phenol
Toxic Organics
Cyanide

CONCERN

CONCENTRATION, mg/L

Can be toxic; depletes oxygen


Depletes oxygen in receiving
waters
Damages vegetation and wildlife

300-2,000
100-300

Turbidity; toxic to aquatic life


Acidity or alkalinity is toxic to
aquatic life
Toxic to aquatic life
Aesthetic: destroys algae
Can be toxic to aquatic life and
humans; aesthetic

15-45
6.0-9.0

Toxic to aquatic life;


eutrophication
Eutrophication
Toxic to aquatic life and humans
Toxic to aquatic life and
humans; aesthetic
Toxic to aquatic life and
humans;aesthetic
Toxic to aquatic life and
humans; aesthetic
Toxic to aquatic life and humans
Toxic to aquatic life and humans

15-55

Less than 40 C
2 color units
Site specific
1.0-10
0.2
0.1-5.0
0.5-1.0 total
0.01-0.1
0.1-1.0
1.0 total
0.1

KEY:
TOC = Total Organic Carbon
COD = Chemical Oxygen Demand
BOD = Biochemical Oxygen Demand
TPH = Total Petroleum Hydrocarbons
TSS = Total Suspended Solids

Source: Chemical Engineering Process, August 1995

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ENVIRONMENTAL ISSUES HANDOUT


- page 14

Handout #7
U.S. Regulatory Effluent Limitations for Refineries (40 CFR 419)
EXAMPLE
Effluent Limits for a New Integrated Type Oil Refinery Facility (See Notes 1,2)
Effluent
Characteristic

Maximum for Any One


Day (See Note 4)

BOD5
TSS
COD (See Note 3)
Oil & Grease
Phenolic Compounds
Ammonia as N
Sulfide
Total Chromium
Hexavalent
Chromium
pH

14.7 (41.6)
9.9 (28.1)
104 (295)
4.5 (12.6)
0.105 (0.3)
8.3 (23.4)
0.093 (0.26)
0.22 (0.64)
0.019 (0.052)

Average of Daily Values for Thirty


Consecutive Days Shall Not Exceed
(See Note 4)
7.8
6.3
5.4
2.4
0.51
3.8
0.042
0.13
0.0084

Within range of 6 to 9

(22.1)
(17.9)
(152)
(6.7)
(0.14)
(10.7)
(0.12)
(0.37)
(0.024)

Within range of 6 to 9

Notes:
(1) To obtain actual limitations all values in this table must be multiplied by a subcategory
dependent variable, F; where F is the product of the process factor and the size factor and
the crude throughput (in thousand barrels per day).
(Note: Size factors range from 1.02 to 1.57; Process Factors can range from 0.62 to 4.36.
(2)

Once-through cooling water may be discharged with a total organic carbon (TOC)
concentration not to exceed 5 mg/l.

(3)

In any case in which the applicant can demonstrate that the chloride ion concentration in
the effluent exceeds 1000 mg/l (1000 ppm), the regional administrator may substitute TOC
as a parameter in lieu of COD. Effluent correlating TOC to BOD5. If in the judgement of
the regional administrator, adequate correlation data are not available, the effluent
limitations for TOC shall be established at a ratio of 2.2 to 1 to the applicable effluent
limitation on BOD5.

(4)

Units are in pounds per thousand barrels of feedstock


( metric: kilograms per thousand cubic meters of feedstock)

(5)

40 CFR 419 also contains limitations for other refinery categories such as Topping,
Cracking, Petrochemical, and Lube.

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ENVIRONMENTAL ISSUES HANDOUT


- page 15

Handout #8
GENERATION OF WASTEWATERS IN THE PETROLEUM REFINING INDUSTRY
Unit Operation

Function

Waste Generated

Desalting

Reduce inorganic salts and


suspended solids in crude to prevent
fouling of equipment; remove
inorganic impurities that poison
catalysts

Desalting sludge; desalter brine

Fractionation: vacuum,
atmospheric flash, distillation

Separate constituents of crude oil

Wastewater from overhead


accumulators; discharge from oil
sampling lines; oil emulsions from
condensers; barometric condenser
water

Cracking: catalytic, visbreaking,


thermal, hydrocracking

Convert heavy oil fractions into


lighter oil fractions

Wastewater from overhead


accumulators and steam strippers

Reforming

Convert naphthas to finished high


octane gasoline

Waste water from overhead


accumulators on stripper towers

Alkylation

Convert gaseous hydrocarbons to


high-octane fuel

Wastewater from overhead


accumulators in fractionation
section; alkylation reactor; caustic
wash

Hydrotreating

Wastewater from overhead


Saturate olefins and remove
contaminants such as sulfur, nitrogen accumulators on fractionators and
steam strippers; sour water stripper
and oxygen compounds
bottoms

Polymerization

Convert olefins to high-octane


gasoline

Wastewater from caustic scrubbers


and pretreatment washwater towers

Isomerization

Convert light gasoline materials into


high-octane isomers for fuel

Wastewater from leaks and spills

Solvent refining and extraction of


oil stocks

Obtain lube oil fractions and


aromatics from feedstocks
containing hydrocarbons and
undesirable materials

Wastewater from bottom of


fractionation towers

Dewaxing

Remove wax from lube oil stocks to


produce products with low pour
points and to recover wax for further
processing

Wastewater from leaks and spills

Coking

Convert heavy oil fractions into


lighter oil fractions and into solid
petroleum coke

Cutting water blowdown;


fractionation section overhead
accumulator waters

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GENERATION OF WASTEWATERS IN THE PETROLEUM REFINING INDUSTRY


Unit Operation

Function

Waste Generated

Aromatic extraction

Recovery of benzene, toluene, and


xylene from gasoline stocks

Wastewater from overhead


accumulator on stripping towers and
condensers

Deasphalting

Separate asphalts or resins from


vacuum distillation residuals;
recover paraffinic catalytic cracking
stock from distillation residuals

Sour water from overhead


condensers on steam strippers; spills

Drying and sweetening

Remove sulfur compounds; improve


color, odor; oxidation stability;
inhibitor response; remove water,
carbon dioxide, and other impurities

Spent caustic; wastewater from water


washing of treated product;
regeneration of treating solution

Grease manufacture

Produce wide range of lubricating


greases

Wastewater from leaks and washing


of batch process units

Lubricating oil finishing

Produce motor oils and lubricating


greases

Wastewater from rinses and clay


treatment; sludge from sampling;
leaks

Hydrogen manufacture

Produce hydrogen needed for


refining processes

Wastewater from desulfurization unit

Storage tanks

Storage of crude oil, intermediates,


and final products

Settled water and sludge from tank


bottoms and cleaning

Sulfur recovery

Removal of sulfur compounds from Spent caustics; spent amine solution;


hydrocarbon streams and recovery of spent Stretford solution
sulfur product

Blending and packaging

Produce and package final products

Wastewater from tank wash; vessel


cleaning water

Cooling water system

Heat exchanger operation

Blowdown from cooling tower


systems; once-through cooling water

Surface and storm water collection Treatment of storm and surface


drainage

Wastewater from storm and surface


drainage

Utilities

Steam and electricity generation

Marine terminals

Load and unload marine vessels with Ballast water


crude oil and refined products

General wastewaters

Maintenance

Sources:

Boiler blowdown

Wash water; pump gland water;


leaks and spills on every operation

Jacobs Engineering Company, Assessment of Hazardous Waste Management, 1967


Jones, H. R. Pollution Control
Gloyna and Ford, Characteristics and Pollutional Problems

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Handout # 9
U.S. REFINERY LISTED HAZARDOUS WASTES
DESIGNATION

HAZARDOUS WASTE DESCRIPTION

K048

Dissolved Air Flotation float

K049

Slop oil emulsion solids

K050

Heat Exchanger bundle cleaning sludge

K051

API Separator sludge

K052

Tank bottoms (leaded)

K169

Crude oil storage tank sediments

K170

Clarified slurry oil tank sediments and/or in-line filter/separation solids

K171

Spent hydrotreating catalyst

K172

Spent hydrorefining catalyst

F037

Primary sludge from gravity separation of process wastewaters and oily


cooling wastewaters

F038

Secondary sludge from physical and/or chemical separation of process


wastewaters and oily cooling wastewaters

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ENVIRONMENTAL ISSUES HANDOUT


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Handout #10
Environmental Reviews and Tools for Process Units Bulletin

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ENVIRONMENTAL ISSUES HANDOUT


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Handout # 11
Example Output Sheet from an Effluent Summary

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ENVIRONMENTAL ISSUES HANDOUT


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Handout # 12
SOURCES OF INFORMATION ON THE INTERNET
Miscellaneous Environmental Sites

INTERNET SITE (URL)

SITE NAME/CONTENTS

Government
1

http://www.epa.gov

U.S. Environmental Protection Agency;


Very comprehensive!

http://www.epa.gov/oar/oaqps/peg_caa/pegc
aain.html

Plain English Guide to the Clean Air Act

http://www.epa.gov/enviro/html/ef_overview.
html

U.S.

http://es.epa.gov/oeca/sector/index.html

Notebooks on major industrial groups including

EPAs

Envirofacts

Warehouse

of

informational databases
petroleum refineries and organic chemical
plants.

http://www.oit.doe.gov/petroleum/profile.shtml

Energy & Environmental Profile of the U.S.


Petroleum Refining Industry , by the U.S.
Department of Energy (DOE)

O r g a n i z a t i o n s,

A s s o c i a t i o n s, I n s t i t u t e s

http://www.api.org

American Petroleum Institute

http://www.npradc.org

National Petrochemical and Refiners Association

http://www.wef.org

Water Environment Federation

http://www.concawe.be/Content/Default.asp

Concawe

European

Organization

for

Environmental, Health, and Safety concerning


crude oil refining & distribution of refinery
products.
10

http://lnweb18.worldbank.org/essd/envext.ns World Bank Pollution Management Guidelines


f/51ByDocName/PollutionPreventionandAba
tementHandbookProjectGuidelines

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ENVIRONMENTAL ISSUES HANDOUT


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INTERNET SITE (URL)

SITE NAME/CONTENTS

Magazines
11

http://www.hydrocarbonprocessing.com

Hydrocarbon Processing Magazine

12

http://www.pollutionengineering.com

Pollution Engineering Magazine

13

http://www.eponline.com/

Environmental Protection Magazine

Environmental
14

Links

http://www.worldbank.org/nipr/onthenet.htm Excellent,

very

comprehensive

listing

of

environmental links on the internet.


15

http://yosemite.epa.gov/oswer/ceppoweb.n
sf/content/chemicalinfo.htm#envirofacts
O n-L i n e

16

EPA Chemicals Info Links

Informational

http://www.refiningonline.com

Resources

Refining

Industry

information

including

engineering, software, catalyst and chemicals,


equipment, and consultants. Also includes a Q
and A section.
17

18

http://www.epa.gov/OCEPAterms
http://web.umr.edu/~aeg/arco/arco.html
http://www.etd.ameslab.gov/etd/library/a
cronyms/acronym.html

http://www.epa.gov/air/oaqps/eog/course
_listing.html#web

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Abbreviations/Acronyms/Terms

U.S. EPA Training Courses on Air Pollution


Control

ENVIRONMENTAL ISSUES HANDOUT


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