Microsoft Word master thesis report fina doc

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ENVIRONMENTAL REVIEW
OF PETROLEUM INDUSTRY 
EFFLUENTS ANALYSIS
C l a i r e F a u s t i n e
Master of Science Thesis
Stockholm 2008

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Claire Faustine 
Master of Science Thesis 
STOCKHOLM 2008 
E
NVIRONMENTAL REVIEW OF 
PETROLEUM INDUSTRY
 
E
FFLUENTS ANALYSIS
 
 
 
S
UPERVISORS
: 
L
ENNART 
N
ILSON
, I
NDUSTRIAL 
E
COLOGY 
A
LAIN 
M
ORVAN
,
 
A
XENS 
IFP 
 
E
XAMINER
: 
L
ENNART 
N
ILSON
, I
NDUSTRIAL 
E
COLOGY
PRESENTED AT
 
INDUSTRIAL ECOLOGY 
ROYAL INSTITUTE OF TECHNOLOGY

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TRITA-IM 2008:39 
ISSN 1402-7615 
Industrial Ecology, 
Royal Institute of Technology 
www.ima.kth.se 

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Abstract 
The present report deals with environmental issues in refineries and petrochemical processes. 
More precisely gaseous, liquid and solid effluents from processes are analysed qualitatively 
and quantitatively when possible. Techniques to treat these effluents are reviewed or proposed 
when lacking and methods to do not produce these effluents are envisaged.
In the part A of the report general effluents that are released from all types of processes are 
studied. These effluents include fugitive emissions, flue gases from process heaters, 
blowdown systems emissions and wastewaters. Fugitive emissions, one of the greatest 
sources of VOCs can be qualified and quantified by the average emission factor approach and 
reduced thanks to the implementation of an LDAR program. Flue gases from process heaters, 
which are a major source of NOx, SOx and particulate matters can be characterized with 
emission factors and several techniques exist to treat or prevent these emissions. Concerning 
blowdown systems emissions, which are difficult to quantify, methods to minimize these 
emissions are given. Finally, wastewaters treatment in petroleum industry is shortly described 
before best management practices and pollution prevention methods are enounced. 
In the part B of the report four families of processes are studied: naphtha hydrotreatment, 
naphtha isomerization, catalytic reforming and hydrogenation in olefin plants. Each of these 
processes is firstly described, the process flow diagram is explained and continuous and 
intermittent effluents are characterized. In addition to general effluents dealt with in part A, it 
has been found that processes can produce other effluents such as dioxins in isomerization or 
catalytic reforming units or green oils during catalyst regeneration operations.

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ii
List of Tables 
 
Table A-2-1: Comparison of available techniques for NOx control for process heaters 
Table A-2-2: Comparison of SOx-removal techniques 
Table B-1-1: Typical properties of crude oil distillation naphtha 
Table B-1-2: Typical properties of naphtha hydrotreating products 
Table B-2-1: Typical properties of isomerisation naphtha feed 
Table B-3-1: Typical properties of two charges for catalytic reforming unit 
Table B-4-1: Typical composition of a raw C
3
cut entering a selective hydrogenation unit 
Table B-4-2: Compounds possibly present in catalyst regeneration effluents 
Table B-4-3: Gaseous effluents during catalyst regeneration in C
3
selective hydrogenation 
Table B-4-4: Gaseous effluents during catalyst oxidation in C
4
selective hydrogenation 
Table B-4-5: Gaseous effluents during catalyst regeneration in GHU first reactor 
Table B-4-6: Gaseous effluents during catalyst regeneration in GHU first reactor 
Table B-4-7: Gaseous effluent during catalyst sulfurization in GHU 

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iii
List of Figures 
Figure A-2-1: Settling chamber
Figure A-2-2: Baffle chamber 
Figure A-2-3: Cyclone 
Figure A-2-4: Baghouse 
Figure A-2-5: Wet scrubber 
Figure A-4-1: Sour waters stripping system 
Figure B-1-1: Naphtha hydrotreating process flow diagram 
Figure B-1-2: Influents/effluents scheme for naphtha hydrotreating unit in normal operations 
Figure B-1-3: Influents/effluents scheme for naphtha hydrotreating unit during catalyst 
sulfiding 
Figure B-1-4: Influents/effluents scheme for naphtha hydrotreating unit during catalysts 
regeneration 
Figure B-2-1: Simplified process flow diagram for isomerization with chlorinated Pt/Al
2
O
3
catalyst 
Figure B-2-2: IPSORB
®
isomerization process 
Figure B-2-3: HEXORB
®
isomerization process 
Figure B-2-4: Influents/effluents scheme for naphtha isomerisation unit in normal operations 
Figure B-2-5: Influents/effluents scheme for naphtha isomerisation unit during dryers 
regeneration 
Figure B-2-6: 2,3,7,8-Tetrachlordibenzodioxin 
Figure B-3-1: Simplified scheme of semi-regenerative process for catalytic reforming
Figure B-3-2: Continuous catalyst regeneration reforming 
Figure B-3-4: Influents/effluents scheme for catalytic reforming reaction section 
Figure B-3-5: Simplified process flow diagram for CCR regeneration section 
Figure B-3-6: Influents/effluents scheme for catalytic reforming in regeneration section 
Figure B-4-1: Flow sheet of the C
3
selective hydrogenation process 
Figure B-4-2: Flow sheet of the C
4
selective hydrogenation process 
Figure B-4-3: Flow sheet of the gasoline hydrogenation process 
Figure B-4-5: Influents/effluents scheme for C
3
selective hydrogenation during normal 
operations 
Figure B-4-6: Influents/effluents scheme for C
4
selective hydrogenation during normal 
operations 
Figure B-4-7: Influents/effluents scheme for gasoline hydrogenation during normal operations 
Figure B-4-8: Influents/effluents scheme for C
3
selective hydrogenation during catalyst 
reduction or reactivation 
Figure B-4-9 Influents/effluents scheme for C
4
selective hydrogenation during catalyst 
reduction, reactivation or stripping 

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iv
List of Acronyms 
API-
American Petroleum Institute 
BOOS- 
Burner Out Of Service 
CCR-
Continuous Catalytic Reforming 
CO-
Carbon 
Monoxide 
CO
2
-
Carbon 
Dioxide 
DMDS- Dimethyl 
Disulfur 
EPA-
United States Environmental Protection Agency 
ETBE-
Ethyl Tertiary-Butyl Ether 
FCC-
Fluid Catalytic Cracking 
FG-
Fuel 
Gas 
FGR-
Flue Gas Recirculation 
FO-
Fuel 
Oil 
GHU-
Gasoline Hydrogenation Unit 
HAP-
Hazardous Air Pollutant 
HC-
Hydrocarbon 
LDAR- 
Leak Detection And Repair
LEA-
Low Excess Air 
LNB-
Low NO
x
Burner 
LPG-
Liquefied Petroleum Gas 
MA-
Methyl 
Acetylene 
MTBE- 
Methyl Tertiary-Butyl Ether 
NO
x
-
Nitrogen 
Oxide 
NO
2
-
Nitrogen 
dioxide 
OFA-
Over Fire Air 
PD-
Propadiene 
PCDD- Polychlorodibenzo-p-dioxin 
PCDF-
Polychlorodibenzo-p-furan 
PM-