Академический Документы
Профессиональный Документы
Культура Документы
by Doris Kolb
Illinois Central College
East Peoria, IL 61635
in cooperation with
Kenneth E. Kolb
Bradley University
Peoria. IL 61625
pn:ssim enginrs, ~,specinllyfor airplanec, later made it necessary to extend the octnnt. numtwr scale l~eyonclLOO.) While
the octane numher scale is not a ~ e r f e c means
t
for ratine
t
s~.ule.
gnsolinca qualily, it remains thr singlt: I ~ r s rating
P e t r c h m wfinrrs stmetimes sneak in terms oi-research"
octane number (RON) and sometimes of "motor" octane
number (MON). RON values are ohtained by testing fuel in
a single cylinder engine with variable compression ratio at 6M)
rpm, with inlet air a t 52C and a modest spark advance. MON
values are obtained a t 900 rpm, with inlet air a t 149'C and a
larger spark advance. Before 1973 RON values were the ones
usually quoted to the public, but since 1973 the octane values
posted on station pumps have been RON-MON averages. The
average value better relates to the actual nerformance of the
gasoline in an automobile engine. Concurrently with the introduction of this new average scale. refiners also lowered the
octane quality of their gasolines by about two units. As a result
some motorists began noticing knocking noises in their engines, even though they thought they were using the same
gasoline they had always used.
-
Before 1973
RON
(Advertised)
(MON)
100
94
(94)
(88)
- - -
Premium
Regular
-~
(RON-MON)
average
Since 1973
RON-MON Average
(Posted on pumps)
- - - - --
(97)
~
(91)
95
89
~p
CH:ICH~CH~CH~CH~CH~CH~CH~CH~CH~CH~CH~CH~C
cetane
(cetane no. = 100)
0-methylnaphthalene
(cetane no. = 0)
Just as with the octane scale for gasoline, the cetane numher
of a fuel is determined bv comparing- its performance
in a
.
single cylinder variable compression engine with mixtures of
these reference fuels. The hiaher the octane number of a fuel,
the lower its cetane number will tend to be. A fuel with an
octane number of 80 would have a cetane number of about
20.
~
Boiling
Point ("C)
Carbon Atoms
(approx.range)
1-2%
<30
C,-C4
15-30s
30-200
C,-C,r
5-20%
200-300
CI2-Cq5
kerosene
heater oil
10-40%
300-400
CIS-C~~
Undistilied
>400
gas oil
diesel oil
lubricating oil
residual oil
paraftin wax
>C2$
asohalt [tar)
k
has shown promise as an octane number enhancer, and it is
already being used by several companies with government
appnwal.
Modern Refining Processes
.~
acids.
3) Among the methyl branched compounds, 2-methyl alkanes
4)
Products
natural gas, methane
ethane, propane, butane
liquefied petroleum gas (LPG)
naphtha
straight-run gasoline
TH'
predominate.
Cyelrdkanes present are those predicted by thermodynamics
valalYsL
SOOC
alkanes + alkenes
(kernsene range)
(gasnline range)
The thermal crackine vrocess of the 1920's was lareelv
" - replaced by catalytic p&esses during the 30's and 40's. Today
more than a third of all crude oil is ultimately subjected to
cracking. The catalyst most used today is silica-alumina (Si02,
AI20,), often containing nickel or tungsten and used in the
presence of a hydrogen atmosphere. a he silica-alumina promotes scission of carbon-carbon bonds, preferentially those
near the middle of the chain, since they are weakest. The
process is also called "hydrocracking" because it occurs in a
hydrogen atmosphere, and it is sometimes called "fluid
cracking" when a fluidized catalyst bed is used (the finely
divided solid catalvst being.. k e. ~ in
t a fluid-like state bv the
upward moving stieam of gas). Catalytic cracking occirs a t
a lower temperature (500C) than thermal cracking, and it
Volume 56. Number 7,July 1979 / 467
produces fewer small molecules and much less coke. The addition of Ni or W plus Hz has two advantages: (1) alkenes,
which are gum-formers, are hydrogenated to alkanes, and (2)
sulfur and nitrogen, which are potential air pollutants, are
removed as H2S and NHs.
Although thermal cracking is no longer important for
making gasoline, a type of severe thermal cracking called
"steam cracking" is the major process for producing the alkene
petrochemicals-ethene, propene, and the hutenes. The use
of steam in this high temperature (about 800C) process reduces the partial pressureof the hydrocarhons in the system,
which favors a greater yield of gaseous products, the volatile
alkenes, s n d also reduces coke formation
Catalytic Reforming
T h e catalytic reforming process can convert a 6-9 carbon
naphtha fraction of modest octane numher (about 60) to
material of very high octane (10&110). This dramatic increase
in octane numher results from the conversion of alkanes and
cycloalkanes to aromatic compounds (benzene and alkylbenzenes) all of which have octane numhers ereater than 100.
The product, called reformate, often contaiis more than 60%
aromatics. In the following example
and
~~~~
cat.
CH3CHzCH2CH2CH2CH2CH3
swoc
CGHSCH~
n-heptane
toluene
(octane no. = 103)
(octane no. = 0)
normal heotane is converted to toluene. resultine in a oheuomenal increase of 103 octane units. he major Ltalys't for
catalytic reforming is platinum on silica-alumina. One popular
trade-marked process is called Platforming. The operation
is also called "hydroforming", since it is carried out in an atmosphere of hydrogen. Many of the newer catalyst systems
are bimetallic. containing
- in addition to platinum a metal such
as rhenium, which promotes aromatization of cyclohexanes
to henzene. Typically a catalytic reformer operates around
500'C and 20 atm. With appropriate regeneration the platinum catalyst can he used for a decade or longer. This process
was first commercialized durine World War I1 to make high
octane fuel fur airplanes. It also provided toluene for making
trinitrotoluene ('I'N'I'Jex~losives.S i t r e 1952 ref8,rmute has
become the major source df henzene, toluene, and the xylenes
(BTX) for the chemical industry, although this,represents a
3mall use as compared with gasoline. (The original commercial
source for these aromatics was coal tar, which can supply only
about 10%of the current demand.
Besides producing high octane gasoline and BTX petrochemicals, catalytic reforming also produces large amounts
of by-product hydrogen. The rapid growth of the ammonia
fertilizer business during the 1950's was the direct result of
this process. Needing to find a use for all their by-product
hydrogen, refiners started building plants to combine it with
nitrogen from the air to make ammonia by the Haber process.
H,C=CH-CH,
CH,-
'i H
CH,
CH
N2
Polymerization
Another way to produce gasoline from smaller molecules
is to polymerize an alkene such as propene. Perhaps oligomerize is a more accurate term. since the ~ r o d u c t are
s dimers.
trimers, and tetramers rather than longchain polymers. l he
formation of the propene trimer is shown here
acid eat.
CH:,-TH-CH,-
FH
CH CH
= -CH3
+ 3Hz %
2NH3
IW'C
lsomerization
The isomerization process converts straight chain hydrocarbons to hranched mixtures. Although isomerization is a
highly important reaction in refining processes (such as catalytic cracking and reforming), as a separate process isomerization is of minor importance in a modern oil refinery.
Probably its main use today is for converting n-butane to
isohutane, which is reacted with an alkene in the alkylation
process.
4lkylation
T h e alkylation process, although not as important as catllytic cracking or reforming, is a useful process for converting
Coal
Hydroelectric
Nuclear
References
Henrrln..I.."WhntDlmd AreOcfanes?."l'hcrn Tech. 6. I 6 (19761.
Hmmfeheek. R. .I.. "l'cfn,leum Pn~~erring-Principlesand Ajlplicatii~nr."McCraw-Hill,
NPWY m k . 1959.
H I L w ~1;.
. I). Ib.'d!irrI."Mndarn Pelrulerrm Terhnol~,gy:4rhcd.. Halrfed Pre\r..I<>hn
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"Kirk-Othmer Encyd<>pPdia,XChemieal'Pechn,,L~pu.'?nded..+,hn
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Vol. IS.
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S~>illane.
I. ..I.,rnd L.c,llin. H. P. I~d,tr,rsI."Helininr:Pelroleumfor Chomicalr."ACS ad^
vnnees in Chemistry Series. NII. 97.Al'S. Washingtun. 1971).
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1. 1859-1899.Nwlhvertern llniuersity I'rerr. Evanrlcri. 1969.
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