1981 08-HydrocarbonsProcessing PDF
1981 08-HydrocarbonsProcessing PDF
1981 08-HydrocarbonsProcessing PDF
PROCESSING
A PRIMER FOR ALASKANS
Published by:
Institute of Social and Economic Research
UniversitY of Alaska
Lee Gorsuch, Director
707 "A" Street, Suite 206
Anchorage, Alaska 99501
1981
. , .. <"'7"'
HYOROCARBONS
PROCESSING
.
'
ARLON R. TUSSING
LOIS S. KRAMER
J
Prepared for the Alaska State Legislature
with support from the Joint Gas Pipeline Committee
(Alaska State Legislature) and The Ford Foundation
August 1981
'
PREFACE
Chapter 5 Petrochemicals . . . . . . . . . . . . . . . . . . . 69
Introduction . . . . . . 69
Chemical Industry Structure . 69
Petrochemical Feedstocks . . . . 73
Petrochemical-Product
Groups . . . . . . 77
Final Products . . . . . . . 81
x Contents
Figure 1
Crude-Oil Production and
Consumption of Refined Products By Area, 1979
Production Consumption
(l ,000 barrels) (l ,000 barrels)
Table 2
Assets per Employee for the Fortune 500
(Industry Medians)
Petroleum Food 49,ti88
refining $303,839 Motor Vehicles ti6,039
Mining, crude- Shipbuilding, rail-
oil production 254,336 road & transport
Broadcasting, equipment ti3,9til
motion-picture Rubber and plastic
production and products ti2,563
distribution 108,772 Measuring, sci en-
Tobacco 81,937 tific and photo-
Metal manufact'g 79,868 graphic equipm't ti! ,000
Chemicals 77,947 Aerospace ti0,901
Paper, fiber and Musical instrum'ts,
wood products 76,ltil toys, sporting
Pharmaceuticals 66,5ti3 goods 37,666
Publishing, Electronic appl. 37,59ti
printing 56' 129 Textiles & vinyl
Glass, concrete flooring 26,ti31
abrasives, and Apparel 20,36ti
gypsum 55,668 Leather n. a.
Industrial and Furniture n.a.
farm equipm't 53,361 Jewelry, silver-
Office equipm't, ware n.a.
computers ti9,039
All industries $ 55,505
Table 3
Alaska North Slope Crude Oil Production Forecasts, 1981-2000
(thousands of barrels per day; percentage confidence intervals)
/ I I J, (___,- ,
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I 1
CHAPTER 3
FUNDAMENTALS OF HYDROCARBONS CHEMISTRY
General Introduction.
Fuels refining and petrochemicals manufacturing are
both hydrocarbons-processing industries. They begin with
mixtures of hydrocarbons from crude oil or natural gas as
raw materials, separate them into components, and alter the
molecules in various ways to produce a range of products for
final consumers or for use as inputs to other industries.
The refining and petrochemical industries overlap
technically, using many of the same processes and inter-
mediate products. The chief distinction between them is in
their respective "product slates". The greatest part of
refinery output is made up of liquid hydrocarbon mixtures,
along with certain solid byproducts of fuels refining, such as
asphalt or petroleum coke. While some refinery products
are sold for use as lubricants, solvents, or raw materials for
the petrochemical industry, the main business of the refin-
ing sector is fuels production.
Petrochemicals manufacturing includes practically any
hydrocarbons-processing operation whose principal output is
not liquid hydrocarbon fuels. Petrochemical products may
be liquid, gaseous, or solid: they include synthetic fibers,
plastic, paints and varnishes, resins, food additives, medi-
cines, industrial reagents, and much more.
Composition of Natural Hydrocarbons.
Natural hydrocarbons are complex mixtures of carbon
and hydrogen that are usually found underground in combi-
nation with impurities such as water, sulphur, and carbon
dioxide. Conventionally, hydrocarbons are grouped accord-
ing to the number (n) of carbon atoms (Cn) in each molecule.
However, the variations of hydrocarbon mixtures are vast
and every accumulation of oil and gas is unique.
Table I/ lists the names of some simpler, smaller-
molecule hydrocarbons found in crude-oil and natural-gas
reservoirs, and alludes to the existence of others with
dozens of carbon atoms in each molecule.
Page 26 Hydrocarbons Chemistry
Table 4
Elementary Hydrocarbon Compounds
Chemical Principal
Compound Formula Names
methane CH4 Natural gas.
ethane C2H6 Natural-gas
propane C3Hs liquids (NGL's)
butane C4HJQ or condensate.
pentane C5H12 Pentanes-plus,
hexane CGH14 natural gaso-
heptane C7H16 lines, or
octane CsH1s naphtha.
Table 5
Hydrocarbon Boiling Points and Weights
Boiling
Com12ound Formula Tem12erature Pounds/Gallon
Propane C3H8 -44 F 4.2
n-Butane C4H10 310 F 4.9
n-Decane C10H22 3450 F 6.1
H H H
I I
H-C-H H-C-C-H
H H H
Methane (CH4)
HHH
I I I
H-C-C-C-H
I I I
H H H
Propane (C3Hg)
H
H H H H H-C-H
I I
H-C-C-C-C-H H-C-C-C-H
I I II II II
H H H H
Normal or Iso- or
n-butane i-butane
(C4H10) (also C4H 10)
c
c c c
c c
c c
C-C c
Cyclopentane Cyclohexane
(C5H10) (C6H12)
c
C C-CH3
C-C
Methyl
Cyclopentane
(C6H12)
c
c c
II
c c
c
CH3
I
c c c
c c c c
II
c
II
c c c c c
c c c
Toluene Naphthalene
(C6H5CH3) (C10Hg)
H
I
H H H-C-H
H-C C-H
C=C
I I
H H HC=CH
I I
HH
Cyclopentene
(C5Hg)
,' i
/
I ,/
v
CHAPTER 4
FUELS REFINING
The main business of the refining sector is fuels
production. The manufacture of refined fuels begins with
natural hydrocarbon compounds and separates them by dis-
tillation, tears them down, and rebuilds and restructures
their molecules into produce saleable products. Before the
l 900's, a typical refinery just distilled the crude oil into a
series of "cuts" or fractions, which were sold as straight--
run fuels. Today, almost all petroleum products are speci-
ally tailored in their physical and chemical properties and
freedom from impurities to meet exacting market demands,
thus requiring treatment that extends far beyond simple
distillation.
Petroleum Industry Structure.
The refining sector is an integral part of a petroleum
industry made up of thousands of companies that are ex-
ceedingly varied in size, functions, geographical sphere of
operations, and structure.
The major oil companies. "Big Oil" consists of seven,
twelve, sixteen, or twenty "major" or "multinational" corpo-
rations, depending upon the statistical authority. However
many "Sisters" one chooses to count, the major oil compa-
nies are distinguished by both their great size and their
vertical integration: They produce crude oil; own crude-oil
and petroleum-product pipelines, tankers, and barges; refin-
eries; tank farms and terminals; and operate retail outlets.
Many of the majors are engaged in other related businesses,
such as natural-gas production and processing, and petro-
chemicals manufacturing. These major companies vary
greatly in size, and no two of them have the same mix of
functions; some majors are net sellers and others net buyers
of crude oil; some are net sellers of refined products at
wholesale and others net buyers, and in many different
degrees.
In 1979, the top 16 integrated companies produced
about 60 percent of U.S. crude-oil output and accounted for
about 12 million barrels per day (mmb/d) of refining capa-
city, or about two-thirds of the national total. The same
Page 36 Fuels Refining
Table 6
Crude-Oil Distillation
Refining of Petroleum
Distillation. All refinery operations begin with the
distillation of a crude-oil feedstock into petroleum frac-
tions. The crude oil can either be heated through a series of
temperature steps and the vapors condensed at each step, or
a large portion of the crude oil can be vaporized and the
vapor cooled in a series of temperature steps. Either way,
the crude oil is separated into fractions, each composed of
hydrocarbons having similar boiling-points. The boiling
point ranges of the more common products are shown in
Table 7 below.
Table 7
Boiling Ranges and Distillation Products
Table 8
Refinery Processes to Restructure Hydrocarbons
J
GASE fHOM
TOPPlNG "NO -
H
BUTANE - BUfYlE'lt
ALKYLATION "':;"....,
[
Cf\1'CKING UNI! S
CRUC;E OIL
STORAGE L...I
GAS RECOVERY AND
L..J
I '----- T """''"'M'"''""
(/l
" "
~
Oil
-[
FEED PREPARATION
9UTANE 1lPG)
~ euTANE ..>.NO A,00Jf1VE$ IWIA1".lN GA~CUNE
'O
-------- ;:;;
~
AROMATIC TOLUENE
REFORMING EXTRACTION
SENZ ENE il~NZHJ~ !TO PHROCEMICALSI
DESALTING jPLATFORMER)
c.o.,;oc.1 .. f Ll
t:E
LIGHI ANO HEAVY NAPHTH" CASINGHEAO ETC
1Srf!Al0'1I RUN GA$0l tNEI l I MO!C)f\ ,;. ... ,_.,,. INE
KEROSINE
+ t Kt/WSNt "NO .JH ftJE 'Tl
I ......... I ~
T
fl
01snu "HS ('")Oil
~
HfAllNGO.lMJ(JQIE~tL cLIC\
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CO~E
VACUUM
DIS f ILLA TION HA'IY I'- I-
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TRCATn--1r,
;;OlV(N! l OEWA~ING
. O(WAXELJ <.lit CLAY TREATING.
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OSr1u ... , E SOLV~Nf
GAEA$( Gf<t~~f
1: IMPl!f<lfl~~
MANUFACTtJflE
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ro CRAC:ol"'Li
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SOLVENT
EXTRACTION
1>URfUf<A<
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OUO-:S(ll)
Introduction
Table 9
Petrochemical Processes and Market Sectors
Nitrogen
Fertilizers
Pesticides
Petrochemicals Page 71
Table 10
Worldwide Sales of Petrochemicals and Plastics
1980 Sales
Company ($ millions)
Royal Dutch/Shelli 7,633
Exxonl 6,963
Dow Chemica!2 6,882
!CI 4' 105
Union Carbidel,3 3,665
Montedison 3,594
Hoechst4 3,476
BPl 3,394
Veba 3,264
Bayer5 2,943
H H H H H
C=C H-C-C=C-H
H H H
Ethylene (CzH4)
Figure 3
Feedstocks, Primary Petrochemicals, and First Derivatives
NATURAL Methane
GAS
atural-gas
liquids
& LPG
CRUDE
OIL
Petrochemicals Page 81
Table 11
Primary Petrochemicals and Derivatives Considered
For Production in Alaska
Intermediate and
Derivative Product form End-uses
ETHYLENE:
Low-density poly- Resin sold as Film for food wrap,
ethylene (LOPE) pellets, packaged garbage bags; house-
in bags, hoppers, wares, wire & cable
or containers insulation, paper
milk-carton coatings
High-density poly- Same as LOPE Blow-molded articles,
ethylene (HOPE) injection-molded bot-
tles, pipe & films
Ethylene oxide (EO) Gas in water Intermediate for EG
solution
Ethylene glycol (EG) Liquid shipped in Antifreeze, inter-
tanks and drums mediate for polyester
fiber, film, resins
(continued)
Petrochemicals Page 83
Table 11
Primary Petrochemicals and Derivatives Considered
For Production in Alaska (continued)
Intermediate and
Derivative Product form End-uses
ETHYLENE PLUS BENZENE:
E thy !benzene Gas: seldom shipped Intermediate for
styrene monomer
Styrene monomer* Liquid shipped by Intermediate for
pipeline or in tanks polystyrene, syn-
thetic rubber
Polystyrene* Solid sold in pel- Disposable drinking
lets, sheets, and cups, resin for
blocks toys, football he!-
mets, inc.
AMMONIA:
Urea Solid, sold as Nitrogen fertilizers;
prills in bags or intermediate for
in bulk urea & melamine
resins & plastics,
explosives
Acrylonitrile * Liquid shipped in Intermediate for
drums or tanks acrylic resins and
plastics, synthetic
rubber
METHANOL:
Liquid shipped by Direct fuel use,
pipeline or in intermediate for
tanks formaldehyde
Figure 4
Schematic Diagram of the Ethane-to-Ethylene Plant
At Joffre, Alberta
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Page 86 Petrochemicals
00
+NH3
r- cols
00
___t__::.
+oxygen !ethylene +H20r1 ethylene
(catalyst) oxide glycol
I y
di- & tri-
ethylene , __ +alkali ethylene
+hypo- chloro- idvcols
ethyl- chlorousf. h drin
ene acid +alcohols
from ethylene vinyl or alkyl
refin- - - +chlorine ~ dichloride - ...... chloride phenols
ery
gases
or
crack
er
--+bromine
+hydrogen
chloride
ethylene
dibromide
ethyl
chloride
L glycol &
polyglycol
ethers
'"O
(\)
+water
(catalyst) J I ethyl
alcohol
f )I
acetalde-
h de
..+
'"'<
0
()
:r
(\)
+sulfuric- sulfuric +water
acid - esters
3
~-
-
()
llJ
,I
---T V>
+benzene --.. I
ethyl-
benzene I I styrene I poly-
stvrene
Petrochemicals Page 89
Figure 6
Typical Methanol Process
Purge lo furnace
To distilloflon
Crude mathonol
Condenser
11'1-down tank
Separator Converter Redrculator Make-up gas
Converter heat compressor
ex,honger
FIGURE 8
Aromatics Derivatives
Phtha!ic
Exlttlng aromatics anhydride
Refinery
naphthas
Reforming of cyclopentanes,
eye o exanes, an para ms lsophtha!lc
acid
(minor!
Terephthalic
acid
Cyclohexane
Air
Cyclohexanol,
cydohexanone
Hydroxyl' Phosgene
amine, acid
Toluene
diisocyanate
Adipic
acid
Acid
Hexamethylene- Bisphenol
diamine Sulfonation & alkali fusion
Propylene
tetramer
Dodecyl-
Polymers ben:zene
Figure 9
Dow-Shell Petrochemical Project
PHASE I PHASE II
polyethyl
ene 400
ethylene
oxide&:
ethylene alpha
ethane ethylene glycol olefins
1 200 600 ,,... 400
ethylene
propane 1 200 ethylene
butanes oxide&:
pentanes ex ort ethylene
naehtha I
benzene
970
glycol
600
ethylene
coal tmethano di-
4 000 ex ort chloride
chlorine 1- 700
salt and
caustic
soda
1,150
Page 94 Petrochemicals
Table ll
Projected Utility Requirements: Dow-Shell Project
Electricity 75 mw 245 mw
Steam 350 ton/hr 615 tons/hr
Nitrogen 2,000 SCFM 3,500 SCFM
Air 7,500 SCFM 9,000 SCFM
Potable Water 300 GPM 500 GPM
Demineralized Water 2,500 GPM 4,600 GPM
Cooling Make-Up Water 8,000 GPM 12,000 GPM
water 16 miles from the Kenai River, but found that an air-
cooling system was less expensive. Because of the choice of
air-cooling, the Pac-Alaska plant, if constructed, will re-
quire only about one percent of the water now used by the
much smaller Phillips LNG plant.
Energy requirements. Both the chemical and refining
sectors are substantial users of energy for boiler and process
fuel, refrigeration, pumps and compressors, etc., in addition
to their feedstock requirements. The chemical industry
consumes more than one third of the energy used by all
manufacturing industries in the United States. Because it is
a significant cost factor, plants are carefully designed to
use energy synergistically and are often located in places
where fuel is relatively cheap.
Illustrations.
Natural gas is interchangeable with fuel oil in most of
its end uses. Because more than half of the natural gas
Page 122 Economics and Alaska Outlook
Figure 9
Netback Value of Prudhoe Bay Natural Gas
Natural-Gas
Lower-48 Markets Pipeline Prudhoe Bay
Natural-gas value
($5.00 per mmbtu) less pipeline
Netback gas value
equals the transportation
($1.00 per mmbtu)
oil price cost ($4.00
($30.00 per barrel) per mmbtu)
Figure 10
Value vs. Opportunity Cost at Cook Inlet
Cook Inlet
netback value of
petrochemicals
per mmbtu) ($8.00 er mmbtu)
Page 126 Economics and Alaska Outlook
Figure 11
Methane-to-Methanol Price Determination
I Ceiling price
($2.00 e r mmbtu)
plus me thanol
manufacturing
cost ($2.50)
f
plus pipe line North Slope meth-
tr a nsporta ti on anol opportunity
cost (= $1.00 cost to "Exxon"
pe r mmbtu (= $4.50 per mm-
of me thane) btu of me thane )
Cook Inlet
W'
Economies of Scale
"Economies of scale" are another factor that combines
with transportation economics, feedstock prices, and rela-
tive construction costs to influence owner decisions where
to locate various kinds of industrial facilities. The term
refers to the tendency of larger machines, plants, firms, and
industries to have lower average unit costs of production,
processing, or transportation than smaller units of the same
kind. Several elementary physical principles contribute to
technical economies of scale in the equipment and plants
used for petroleum refining, pipeline transportation, and
petrochemicals manufacturing. Three of most important of
these principles are as follows:
The amount of steel in a pipe increases
roughly in proportion to its diameter; but the
volume of fluid it can contain increases with its
cross-sectional area (which is proportional to the
square of its diameter) and, because the amount
of friction depends on the inner surface area
(which is directly proportional to the diameter
rather than to the cross-sectional area) the flu-
ids-carrying capacity of the pipe increases more
than proportionally to the square of its diameter.
Page 132 Economics and Alaska Outlook