Beruflich Dokumente
Kultur Dokumente
HANDOUT INDEX
2004
HO
#
Page
#
Handout Title
Specific Environmental
Issues in the Refining
Industry (12)
12
Pollutants
Refineries
Typical Emissions in
Refineries (44)
13
14
15
16
17
10
11
18
and
Reference Slide
(Title and Presentation
Packet Slide #)
Emissions
from
Handout #1
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Handout # 2
Secondary
StandardNote 2
(Maximum)
10-6g/m3
ppm
Contaminant
Period of
Measurement
Notes
Sulfur Oxides
(as SO2)
80
0.03
"
24 hour average
365
0.14
"
3 hour average
1300
0.5
Particulate
Matter
(PM10)
50
50
4, 5
"
24 hour average
150
150
Particulate
Matter
(PM2.5)
24 hour average
65
65
8, 9
"
15
15
10
Ozone
1 hour average
235
0.12
135
0.12
"
8 hour average
155
0.08
155
0.08
Nitrogen Dioxide
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
1.5
1.5
Notes:
1.
2.
3.
4.
5.
6.
7.
8.
9.
10.
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Revision
Indication
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GR-07
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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Form QUA-10-1
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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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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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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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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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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CAS
Number
(Note 6)
Petrochemical
Organic
Hazardous Air
Pollutants
Petroleum
Refinery
Organic
Hazardous Air
Pollutants
Petroleum Refinery
Process Specific
Hazardous Air
Pollutants (Note
10)
X (Note 7)
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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.
6.
7.
Hazardous air pollutant typically emitted from Fluid Catalytic Cracking units.
8.
9.
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
Reforming
Organics, Inorganics
Reduced Sulfur
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Handout # 4
Pollutants and Emissions from Refineries
Air Pollutant
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)
Carbon Monoxide
Particulate Matter
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)
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Handout # 5
Screen and select appropriate VOC control technologies
Control
Technology
Applicable
Concentration
Range, ppm
Capacity
Range, cfm
Removal
Efficiency
Secondary
Wastes
Advantages
Thermal
Oxidation
100-2000
1000-500,000
95 - 99+ %
Combustion
products
Up to 95 % energy recovery
is possible
Catalytic
Oxidation
100-2000
1000-100,000
90 - 95 %
Combustion
products
Up to 70 % energy recovery
is possible
> 5000
100-20,000
50 - 90 %
Condensate
Carbon
Adsorption
20 - 5000
100-60,000
90 - 98 %
Spent carbon;
Collected
organic
Absorption
500-5000
2000-100,000
95 - 98 %
Wastewater;
Captured
particulate
Condensation
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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
300-2,000
100-300
15-45
6.0-9.0
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
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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
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)
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)
(5)
40 CFR 419 also contains limitations for other refinery categories such as Topping,
Cracking, Petrochemical, and Lube.
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Handout #8
GENERATION OF WASTEWATERS IN THE PETROLEUM REFINING INDUSTRY
Unit Operation
Function
Waste Generated
Desalting
Fractionation: vacuum,
atmospheric flash, distillation
Reforming
Alkylation
Hydrotreating
Polymerization
Isomerization
Dewaxing
Coking
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Function
Waste Generated
Aromatic extraction
Deasphalting
Grease manufacture
Hydrogen manufacture
Storage tanks
Sulfur recovery
Utilities
Marine terminals
General wastewaters
Maintenance
Sources:
Boiler blowdown
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Handout # 9
U.S. REFINERY LISTED HAZARDOUS WASTES
DESIGNATION
K048
K049
K050
K051
K052
K169
K170
K171
K172
F037
F038
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Handout #10
Environmental Reviews and Tools for Process Units Bulletin
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Handout # 11
Example Output Sheet from an Effluent Summary
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Handout # 12
SOURCES OF INFORMATION ON THE INTERNET
Miscellaneous Environmental Sites
SITE NAME/CONTENTS
Government
1
http://www.epa.gov
http://www.epa.gov/oar/oaqps/peg_caa/pegc
aain.html
http://www.epa.gov/enviro/html/ef_overview.
html
U.S.
http://es.epa.gov/oeca/sector/index.html
EPAs
Envirofacts
Warehouse
of
informational databases
petroleum refineries and organic chemical
plants.
http://www.oit.doe.gov/petroleum/profile.shtml
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
http://www.npradc.org
http://www.wef.org
http://www.concawe.be/Content/Default.asp
Concawe
European
Organization
for
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SITE NAME/CONTENTS
Magazines
11
http://www.hydrocarbonprocessing.com
12
http://www.pollutionengineering.com
13
http://www.eponline.com/
Environmental
14
Links
http://www.worldbank.org/nipr/onthenet.htm Excellent,
very
comprehensive
listing
of
http://yosemite.epa.gov/oswer/ceppoweb.n
sf/content/chemicalinfo.htm#envirofacts
O n-L i n e
16
Informational
http://www.refiningonline.com
Resources
Refining
Industry
information
including
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