Petroleum Refining Process

Authors: Kraus, Richard S.

in 78. Oil and Natural Gas, Kraus, Richard S., Editor, Encyclopedia of Occupational Health and Safety, Jeanne Mager Stellman, Editor-in-Chief.
International Laor !rgani"ation, #ene$a. % &'((.
General Profile
)etroleum refining egins *ith the distillation, or fractionation, of crude oils into se+arate
h,drocaron grou+s. -he resultant +roducts are directl, related to the characteristics of the crude
oil eing +rocessed. Most of these +roducts of distillation are further con$erted into more useale
+roducts , changing their +h,sical and molecular structures through crac.ing, reforming and
other con$ersion +rocesses. -hese +roducts are suse/uentl, su0ected to $arious treatment and
se+aration +rocesses, such as e1traction, h,drotreating and s*eetening, in order to +roduce
finished +roducts. 2hereas the sim+lest refineries are usuall, limited to atmos+heric and $acuum
distillation, integrated refineries incor+orate fractionation, con$ersion, treatment and lending
*ith luricant, hea$, fuels and as+halt manufacturing3 the, ma, also include +etrochemical
+rocessing.
-he first refiner,, *hich o+ened in (45(, +roduced .erosene , sim+le atmos+heric distillation.
Its ,-+roducts included tar and na+htha. It *as soon disco$ered that high-/ualit, luricating oils
could e +roduced , distilling +etroleum under $acuum. 6o*e$er, for the ne1t 7' ,ears,
.erosene *as the +roduct consumers *anted most. -he t*o most significant e$ents *hich
changed this situation *ere:
the in$ention of the electric light, *hich decreased the demand for .erosene
the in$ention of the internal-comustion engine, *hich created a demand for diesel fuel
and gasoline 8na+htha9.
2ith the ad$ent of mass +roduction and the :irst 2orld 2ar, the numer of gasoline-+o*ered
$ehicles increased dramaticall,, and the demand for gasoline gre* accordingl,. 6o*e$er, onl, a
certain amount of gasoline could e otained from crude oil through atmos+heric and $acuum
distillation +rocesses. -he first thermal crac.ing +rocess *as de$elo+ed in (;(7. -hermal
crac.ing su0ected hea$, fuels to oth +ressure and intense heat, +h,sicall, rea.ing their large
molecules into smaller ones, +roducing additional gasoline and distillate fuels. A so+histicated
form of thermal crac.ing, $isrea.ing, *as de$elo+ed in the late (;7's to +roduce more
desirale and $aluale +roducts.
As higher-com+ression gasoline engines *ere de$elo+ed, there *as a demand for higher-octane
gasoline *ith etter anti-.noc. characteristics. -he introduction of catal,tic crac.ing and +ol,-
meri"ation +rocesses in the mid- to late (;7's met this demand , +ro$iding im+ro$ed gasoline
,ields and higher octane numers. Al.,lation, another catal,tic +rocess, *as de$elo+ed in the
earl, (;<'s to +roduce more high-octane a$iation gasoline and +etrochemical feedstoc.s, the
starting materials, for e1+losi$es and s,nthetic ruer. Suse/uentl,, catal,tic isomeri"ation *as
de$elo+ed to con$ert h,drocarons to +roduce increased /uantities of al.,lation feedstoc.s.
:ollo*ing the Second 2orld 2ar, $arious reforming +rocesses *ere introduced *hich im+ro$ed
gasoline /ualit, and ,ield, and +roduced higher-/ualit, +roducts. Some of these in$ol$ed the use
of catal,sts and=or h,drogen to change molecules and remo$e sul+hur. Im+ro$ed catal,sts, and
+rocess methods such as h,drocrac.ing and reforming, *ere de$elo+ed throughout the (;5's to
increase gasoline ,ields and im+ro$e anti-.noc. characteristics. -hese catal,tic +rocesses also
+roduced molecules *ith a doule ond 8al.enes9, forming the asis of the modern
+etrochemical industr,.
-he numers and t,+es of different +rocesses used in modern refineries de+end +rimaril, on the
nature of the crude feedstoc. and finished +roduct re/uirements. )rocesses are also affected ,
economic factors including crude costs, +roduct $alues, a$ailailit, of utilities and
trans+ortation. -he chronolog, of the introduction of $arious +rocesses is gi$en in tale (.
-ale (. Summar, of the histor, of refining +rocessing
Year Process name Process purpose Process by-products
(45& Atmos+heric distillation )roduce .erosene >a+htha, tar, etc.
(4?' @acuum distillation Luricants 8original9
Crac.ing feedstoc.s 8(;7's9
As+halt, residual
Co.er feedstoc.s
(;(7 -hermal crac.ing Increase gasoline Residual, un.er fuel
(;(5 S*eetening Reduce sul+hur and odour Sul+hur
(;7' -hermal reforming Im+ro$e octane numer Residual
(;7& 6,drogenation Remo$e sul+hur Sul+hur
(;7& Co.ing )roduce gasoline ase stoc.s Co.e
(;77 Sol$ent e1traction Im+ro$e luricant $iscosit,
inde1
Aromatics
(;7A Sol$ent de*a1ing Im+ro$e +our +oint 2a1es
(;7A Catal,tic +ol,meri"ation Im+ro$e gasoline ,ield and
octane numer
)etrochemical
feedstoc.s
(;7? Catal,tic crac.ing 6igher octane gasoline )etrochemical
feedstoc.s
(;7; @isrea.ing Reduce $iscosit, Increased distillate, tar
(;<' Al.,lation Increase gasoline octane and
,ield
6igh-octane a$iation
gasoline
(;<' Isomeri"ation )roduce al.,lation feedstoc. >a+htha
(;<& :luid catal,tic crac.ing Increase gasoline ,ield and
octane
)etrochemical
feedstoc.s
(;A' Beas+halting Increase crac.ing feedstoc. As+halt
(;A& Catal,tic reforming Con$ert lo*-/ualit, na+htha Aromatics
(;A< 6,drodesul+huri"ation Remo$e sul+hur Sul+hur
(;A5 Inhiitor s*eetening Remo$e merca+tan Bisul+hides
(;A? Catal,tic isomeri"ation Con$ert to molecules *ith
high octane numer
Al.,lation feedstoc.s
(;5' 6,drocrac.ing Im+ro$e /ualit, and reduce
sul+hur
Al.,lation feedstoc.s
(;?< Catal,tic de*a1ing Im+ro$e +our +oint 2a1
(;?A Residual h,drocrac.ing Increase gasoline ,ield from
residual
6ea$, residuals

Basic refining processes and operations
)etroleum refining +rocesses and o+erations can e classified into the follo*ing asic areas:
se+aration, con$ersion, treatment, formulating and lending, au1iliar, refining o+erations and
refining non-+rocess o+erations. See figure ( for a sim+lified flo* chart.
:igure (. Refiner, +rocess chart
Separation. Crude oil is +h,sicall, se+arated , fractionation in atmos+heric and $acuum
distillation to*ers, into grou+s of h,drocaron molecules *ith $arious oiling-+oint ranges,
called CfractionsD or CcutsD.
Conversion. Con$ersion +rocesses used to change the si"e and=or structure of h,drocaron
molecules include:
decom+osition 8di$iding9 , h,dro-, thermal and catal,tic crac.ing, co.ing and
$isrea.ing
unification 8comining9 through al.,lation and +ol,meri"ation
alteration 8rearranging9 *ith isomeri"ation and catal,tic reforming
treatment.

Since the eginning of refining, $arious treatment methods ha$e een used to remo$e non-
h,drocarons, im+urities and other constituents that ad$ersel, affect the +erformance +ro+erties
of finished +roducts or reduce the efficienc, of the con$ersion +rocesses. -reatment in$ol$es
oth chemical reactions and +h,sical se+aration, such as dissol$ing, asor+tion or +reci+itation,
using a $ariet, and comination of +rocesses. -reatment methods include remo$ing or se+arating
aromatics and na+hthenes, as *ell as remo$ing im+urities and undesirale contaminants.
S*eetening com+ounds and acids are used to desul+huri"e crude oil efore +rocessing, and to
treat +roducts during and after +rocessing. !ther treatment methods include crude desalting,
chemical s*eetening, acid treating, cla, contacting, h,drodesul+huri"ing, sol$ent refining,
caustic *ashing, h,drotreating, dr,ing, sol$ent e1traction and sol$ent de*a1ing.
Formulating and lending is the +rocess of mi1ing and comining h,drocaron fractions,
additi$es and other com+onents to +roduce finished +roducts *ith s+ecific desired +erformance
+ro+erties.
!u"iliary refining operations. !ther refiner, o+erations *hich are re/uired to su++ort
h,drocaron +rocessing include light ends reco$er,3 sour *ater stri++ing3 solid *aste, *aste
*ater and +rocess *ater treatment and cooling3 h,drogen +roduction3 sul+hur reco$er,3 and acid
and tail gas treatment. !ther +rocess functions are +ro$iding catal,sts, reagents, steam, air,
nitrogen, o1,gen, h,drogen and fuel gases.
#efinery non$process facilities. All refineries ha$e a multitude of facilities, functions, e/ui+ment
and s,stems *hich su++ort the h,drocaron +rocess o+erations. -,+ical su++ort o+erations are
heat and +o*er generation3 +roduct mo$ement3 tan. storage3 shi++ing and handling3 flares and
relief s,stems3 furnaces and heaters3 alarms and sensors3 and sam+ling, testing and ins+ecting.
>on-+rocess facilities and s,stems include firefighting, *ater and +rotection s,stems, noise and
+ollution controls, laoratories, control rooms, *arehouses, maintenance and administrati$e
facilities.
Major Products of Crude Oil Refining
)etroleum refining has e$ol$ed continuousl, in res+onse to changing consumer demand for
etter and different +roducts. -he original +rocess re/uirement *as to +roduce .erosene as a
chea+er and etter source of fuel for lighting than *hale oil. -he de$elo+ment of the internal
comustion engine led to the +roduction of en"ene, gasoline and diesel fuels. -he e$olution of
the air+lane created a need for high-octane a$iation gasoline and 0et fuel, *hich is a so+histicated
form of the original refiner, +roduct, .erosene. )resent-da, refineries +roduce a $ariet, of
+roducts, including man, *hich are used as feedstoc.s for crac.ing +rocesses and luricant
manufacturing, and for the +etrochemical industr,. -hese +roducts can e roadl, classified as
fuels, +etrochemical feedstoc.s, sol$ents, +rocess oils, luricants and s+ecial +roducts such as
*a1, as+halt and co.e. 8See tale &.9
-ale &. )rinci+al +roducts of crude oil refining
6,drocaron gases Eses
Li/uified gases Coo.ing and industrial gas
Motor fuel gas
Illuminating gas
Ammonia
S,nthetic fertili"er
Alcohols
Sol$ents and acetone
)lastici"ers
Resins and fires for +lastics and te1tiles
)aints and $arnish
Chemical industr, feedstoc. Ruer +roducts
Caron lac. )rinting in.s
Ruer industr,
Light distillates
Light na+hthas !lefins
Sol$ents and diluents
E1traction sol$ents
Chemical industr, feedstoc.s
Intermediate na+hthas A$iation and motor gasoline
Br,-cleaning sol$ents
6ea$, na+hthas Militar, 0et fuel
Jet fuel and .erosene
-ractor fuel
#as oil Crac.ing stoc.
6eating oil and diesel fuel
Metallurgical fuel
Asorer oilFen"ene and gasoline reco$er,
6ea$, distillates
-echnical oils -e1tile oils
Medicinal oils and cosmetics
2hite oilFfood industr,
Luricating oils -ransformer and s+indle oils
Motor and engine oils
Machine and com+ressor oils
-urine and h,draulic oils
-ransmission oils
E/ui+ment and cale insulation oils
A1le, gear and steam engine oils
Metal treating, cutting and grinding oils
Guenching and rust inhiitor oils
6eat transfer oils
Luricating greases and com+ounds
)rinting in. oils
)araffin *a1 Ruer industr,
)harmaceuticals and cosmetics
:ood and +a+er industries
Candles and matches
Residues
)etrolatum )etroleum 0ell,
Cosmetics
Rust inhiitors and luricants
Cale coating com+ounds
Residual fuel oil >o. 5 oiler and +rocess fuel oil
As+halts )a$ing as+halt
Roofing materials
As+haltic luricants
Insulating and foundation +rotection
2ater+roof +a+er +roducts
Refiner, ,-+roducts
Co.e Electrodes and fuel
Sul+honates Emulsifiers
Sul+huric acid S,nthetic fertili"er
Sul+hur Chemicals
6,drogen 6,drocaron reformation

A number of chemicals are used in, or formed as a result of, hydrocarbon processing. A
brief description of those which are specifc and pertinent to refning follows:
Sulphur Dioxide
:lue gas from urning high-sul+hur-content fuels usuall, contains high le$els of sul+hur dio1ide,
*hich usuall, is remo$ed , *ater scruing.
Caustics
Caustics are added to desalting *ater to neutrali"e acids and reduce corrosion. Caustics are also
added to desalted crude in order to reduce the amount of corrosi$e chlorides in the to*er
o$erheads. -he, are used in refiner, treating +rocesses to remo$e contaminants from
h,drocaron streams.
Nitrogen oxides and carbon monoxide
:lue gas contains u+ to &'' ++m of nitric o1ide, *hich reacts slo*l, *ith o1,gen to form
nitrogen dio1ide. >itric o1ide is not remo$ed , *ater scruing, and nitrogen dio1ide can
dissol$e in *ater to form nitrous and nitric acid. :lue gas normall, contains onl, a slight amount
of caron mono1ide, unless comustion is anormal.
Hydrogen sulphide
6,drogen sul+hide is found naturall, in most crude oils and is also formed during +rocessing ,
the decom+osition of unstale sul+hur com+ounds. 6,drogen sul+hide is an e1tremel, to1ic,
colourless, flammale gas *hich is hea$ier than air and solule in *ater. It has a rotten egg
odour *hich is discernile at concentrations *ell elo* its $er, lo* e1+osure limit. -his smell
cannot e relied u+on to +ro$ide ade/uate *arning as the senses are almost immediatel,
desensiti"ed u+on e1+osure. S+ecial detectors are re/uired to alert *or.ers to the +resence of
h,drogen sul+hide, and +ro+er res+irator, +rotection should e used in the +resence of the gas.
E1+osure to lo* le$els of h,drogen sul+hide *ill cause irritation, di""iness and headaches, *hile
e1+osure to le$els in e1cess of the +rescried limits *ill cause ner$ous s,stem de+ression and
e$entuall, death.
Sour water
Sour *ater is +rocess *ater *hich contains h,drogen sul+hide, ammonia, +henols, h,drocarons
and lo*-molecular-*eight sul+hur com+ounds. Sour *ater is +roduced , steam stri++ing
h,drocaron fractions during distillation, regenerating catal,st, or steam stri++ing h,drogen
sul+hide during h,drotreating and h,drofinishing. Sour *ater is also generated , the addition of
*ater to +rocesses to asor h,drogen sul+hide and ammonia.
Sulphuric acid and hydrofluoric acid
Sul+huric acid and h,drofluoric acid are used as catal,sts in al.,lation +rocesses. Sul+huric acid
is also used in some of the treatment +rocesses.
Solid catalysts
A numer of different solid catal,sts in man, forms and sha+es, from +ellets to granular eads to
dusts, made of $arious materials and ha$ing $arious com+ositions, are used in refining +rocesses.
E1truded +ellet catal,sts are used in mo$ing and fi1ed ed units, *hile fluid ed +rocesses use
fine, s+herical +articulate catal,sts. Catal,sts used in +rocesses *hich remo$e sul+hur are
im+regnated *ith coalt, nic.el or mol,denum. Crac.ing units use acid-function catal,sts, such
as natural cla,, silica alumina and s,nthetic "eolites. Acid-function catal,sts im+regnated *ith
+latinum or other nole metals are used in isomeri"ation and reforming. Esed catal,sts re/uire
s+ecial handling and +rotection from e1+osures, as the, ma, contain metals, aromatic oils,
carcinogenic +ol,c,clic aromatic com+ounds or other ha"ardous materials, and ma, also e
+,ro+horic.
Fuels
-he +rinci+al fuel +roducts are li/uefied +etroleum gas, gasoline, .erosene, 0et fuel, diesel fuel
and heating oil and residual fuel oils.
%i&uefied petroleum gas '%(G), *hich consists of mi1tures of +araffinic and olefinic
h,drocarons such as +ro+ane and utane, is +roduced for use as a fuel, and is stored and
handled as li/uids under +ressure. L)# has oiling +oints ranging from aout H?< IC to
74+ IC, is colourless, and the $a+ours are hea$ier than air and e1tremel, flammale. -he
im+ortant /ualities from an occu+ational health and safet, +ers+ecti$e of L)#s are $a+our
+ressure and control of contaminants.
Gasoline. -he most im+ortant refiner, +roduct is motor gasoline, a lend of relati$el, lo*-
oiling h,drocaron fractions, including reformate, al.,late, ali+hatic na+htha 8light straight-run
na+htha9, aromatic na+htha 8thermal and catal,tic crac.ed na+htha9 and additi$es. #asoline
lending stoc.s ha$e oiling +oints *hich range from amient tem+eratures to aout &'< IC, and
a flash+oint elo* H<' IC. -he critical /ualities for gasoline are octane numer 8anti-.noc.9,
$olatilit, 8starting and $a+our loc.9 and $a+our +ressure 8en$ironmental control9. Additi$es are
used to enhance gasoline +erformance and +ro$ide +rotection against o1idation and rust
formation. A$iation gasoline is a high-octane +roduct, s+eciall, lended to +erform *ell at high
altitudes.
-etra eth,l lead 8-EL9 and tetra meth,l lead 8-ML9 are gasoline additi$es *hich im+ro$e octane
ratings and anti-.noc. +erformance. In an effort to reduce lead in automoti$e e1haust emissions,
these additi$es are no longer in common use, e1ce+t in a$iation gasoline.
Eth,l tertiar, ut,l ether 8E-JE9, meth,l tertiar, ut,l ether 8M-JE9, tertiar, am,l meth,l ether
8-AME9 and other o1,genated com+ounds are used in lieu of -EL and -ML to im+ro$e
unleaded gasoline anti-.noc. +erformance and reduce caron mono1ide emissions.
*et fuel and +erosene. Kerosene is a mi1ture of +araffins and na+hthenes *ith usuall, less than
&'K aromatics. It has a flash+oint ao$e 74 IC and a oiling range of (5' IC to &44 IC, and is
used for lighting, heating, sol$ents and lending into diesel fuel. Jet fuel is a middle distillate
.erosene +roduct *hose critical /ualities are free"e+oint, flash+oint and smo.e+oint.
Commercial 0et fuel has a oiling range of aout (;( IC to &?< IC, and militar, 0et fuel from AA
IC to &44 IC.
,istillate fuels. Biesel fuels and domestic heating oils are light-coloured mi1tures of +araffins,
na+hthenes and aromatics, and ma, contain moderate /uantities of olefins. Bistillate fuels ha$e
flash+oints ao$e 5' IC and oiling ranges of aout (57 IC to 7?( IC, and are often
h,drodesul+huri"ed for im+ro$ed stailit,. Bistillate fuels are comustile and *hen heated ma,
emit $a+ours *hich can form ignitale mi1tures *ith air. -he desirale /ualities re/uired for
distillate fuels include controlled flash- and +our+oints, clean urning, no de+osit formation in
storage tan.s, and a +ro+er diesel fuel cetane rating for good starting and comustion.
#esidual fuels. Man, shi+s and commercial and industrial facilities use residual fuels or
cominations of residual and distillate fuels, for +o*er, heat and +rocessing. Residual fuels are
dar.- coloured, highl, $iscous li/uid mi1tures of large h,drocaron molecules, *ith flash+oints
ao$e (&( IC and high oiling +oints. -he critical s+ecifications for residual fuels are $iscosit,
and lo* sul+hur content 8for en$ironmental control9.
Health and safety considerations
-he +rimar, safet, ha"ard of L)# and gasoline is fire. -he high $olatilit, and high flammailit,
of the lo*er-oiling-+oint +roducts allo*s $a+ours to e$a+orate readil, into air and form
flammale mi1tures *hich can e easil, ignited. -his is a recogni"ed ha"ard that re/uires
s+ecific storage, containment and handling +recautions, and safet, measures to assure that
releases of $a+ours and sources of ignition are controlled so that fires do not occur. -he less
$olatile fuels, such as .erosene and diesel fuel, should e handled carefull, to +re$ent s+ills and
+ossile ignition, as their $a+ours are also comustile *hen mi1ed *ith air in the flammale
range. 2hen *or.ing in atmos+heres containing fuel $a+ours, concentrations of highl, $olatile,
flammale +roduct $a+ours in air are often restricted to no more than ('K of the lo*er
flammale limits 8L:L9, and concentrations of less $olatile, comustile +roduct $a+ours to no
more than &'K L:L, de+ending on a++licale com+an, and go$ernment regulations, in order to
reduce the ris. of ignition.
Although gasoline $a+our le$els in air mi1tures are t,+icall, maintained elo* ('K of the L:L
for safet, +ur+oses, this concentration is consideral, ao$e the e1+osure limits to e oser$ed
for health reasons. 2hen inhaled, small amounts of gasoline $a+our in air, *ell elo* the lo*er
flammale limit, can cause irritation, headaches and di""iness, *hile inhalation of larger
concentrations can cause loss of consciousness and e$entuall, death. Long-term health effects
ma, also e +ossile. #asoline contains en"ene, for e1am+le, a .no*n carcinogen *ith
allo*ale e1+osure limits of onl, a fe* +arts +er million. -herefore, e$en *or.ing in gasoline
$a+our atmos+heres at le$els elo* ('K L:L re/uires a++ro+riate industrial h,giene
+recautions, such as res+irator, +rotection or local e1haust $entilation.
In the +ast, man, gasolines contained tetra-eth,l or tetra meth,l al., lead anti-.noc. additi$es,
*hich are to1ic and +resent serious lead asor+tion ha"ards , s.in contact or inhalation. -an.s
or $essels *hich contained leaded gasoline at an, time during their use must e $ented,
thoroughl, cleaned, tested *ith a s+ecial Clead-in-airD test de$ice and certified to e lead-free to
assure that *or.ers can enter *ithout using self-contained or su++lied reathing air e/ui+ment,
e$en though o1,gen le$els are normal and the tan.s no* contain unleaded gasoline or other
+roducts.
#aseous +etroleum fractions and the more highl, $olatile fuel +roducts ha$e a mild anaesthetic
effect, generall, in in$erse ratio to molecular *eight. Lo*er-oiling-+oint li/uid fuels, such as
gasoline and .erosene, +roduce a se$ere chemical +neumonitis if inhaled, and should not e
si+honed , mouth or accidentall, ingested. #ases and $a+ours ma, also e +resent in
sufficientl, high concentrations to dis+lace o1,gen 8in the air9 elo* normal reathing le$els.
Maintaining $a+our concentrations elo* the e1+osure limits and o1,gen le$els at normal
reathing ranges, is usuall, accom+lished , +urging or $entilation.
Crac.ed distillates contain small amounts of carcinogenic +ol,c,clic aromatic h,drocarons
8)A6s93 therefore, e1+osure should e limited. Bermatitis ma, also de$elo+ from e1+osure to
gasoline, .erosene and distillate fuels, as the, ha$e a tendenc, to defat the s.in. )re$ention is
accom+lished , use of +ersonal +rotecti$e e/ui+ment, arrier creams or reduced contact and
good h,gienic +ractices, such as *ashing *ith *arm *ater and soa+ instead of cleaning hands
*ith gasoline, .erosene or sol$ents. Some +ersons ha$e s.in sensiti$it, to the d,es used to
colour gasoline and other distillate +roducts.
Residual fuel oils contain traces of metals and ma, ha$e entrained h,drogen sul+hide, *hich is
e1tremel, to1ic. Residual fuels *hich ha$e high crac.ed stoc.s oiling ao$e 7?' IC contain
carcinogenic )A6s. Re+eated e1+osure to residual fuels *ithout a++ro+riate +ersonal +rotection,
should e a$oided, es+eciall, *hen o+ening tan.s and $essels, as h,drogen sul+hide gas ma, e
emitted.
Petrochemical feedstocks
Man, +roducts deri$ed from crude-oil refining, such as eth,lene, +ro+,lene and utadiene, are
olefinic h,drocarons deri$ed from refiner, crac.ing +rocesses, and are intended for use in the
+etrochemical industr, as feedstoc.s for the +roduction of +lastics, ammonia, s,nthetic ruer,
gl,col and so on.
Petroleum solents
A $ariet, of +ure com+ounds, including en"ene, toluene, 1,lene, he1ane and he+tane, *hose
oiling +oints and h,drocaron com+osition are closel, controlled, are +roduced for use as
sol$ents. Sol$ents ma, e classified as aromatic or non-aromatic, de+ending on their
com+osition. -heir use as +aint thinners, dr,-cleaning fluids, degreasers, industrial and +esticide
sol$ents and so on, is generall, determined , their flash+oints, *hich $ar, from *ell elo* H(4
IC to ao$e 5' IC.
-he ha"ards associated *ith sol$ents are similar to those of fuels in that the lo*er flash+oint
sol$ents are flammale and their $a+ours, *hen mi1ed *ith air in the flammale range, are
ignitale. Aromatic sol$ents *ill usuall, ha$e more to1icit, than non-aromatic sol$ents.
Process oils
)rocess oils include the high oiling range, straight run atmos+heric or $acuum distillate streams
and those *hich are +roduced , catal,tic or thermal crac.ing. -hese com+le1 mi1tures, *hich
contain large +araffinic, na+hthenic and aromatic h,drocaron molecules *ith more than (A
caron atoms, are used as feedstoc.s for crac.ing or luricant manufacturing. )rocess oils ha$e
fairl, high $iscosities, oiling +oints ranging from &5' IC to A74 IC, and flash+oints ao$e (&(
IC.
)rocess oils are irritating to the s.in and contain high concentrations of )A6s as *ell as sul+hur,
nitrogen and o1,gen com+ounds. Inhalation of $a+ours and mists should e a$oided, and s.in
e1+osure should e controlled , the use of +ersonal +rotection and good h,gienic +ractices.
!ubricants and greases
Luricating oil ase stoc.s are +roduced , s+ecial refining +rocesses to meet s+ecific consumer
re/uirements. Luricating ase stoc.s are light- to medium-coloured, lo*-$olatile, medium- to
high-$iscous mi1tures of +araffinic, na+hthenic and aromatic oils, *ith oiling ranges from 7?(
IC to A74 IC. Additi$es, such as demulsifiers, anti-o1idants and $iscosit, im+ro$ers, are lended
into the luricating oil ase stoc.s to +ro$ide the characteristics re/uired for motor oils, turine
and h,draulic oils, industrial greases, luricants, gear oils and cutting oils. -he most critical
/ualit, for luricating oil ase stoc. is a high $iscosit, inde1, +ro$iding for less change in
$iscosit, under $ar,ing tem+eratures. -his characteristic ma, e +resent in the crude oil feed
stoc. or attained through the use of $iscosit, inde1 im+ro$er additi$es. Betergents are added to
.ee+ in sus+ension an, sludge formed during the use of the oil.
#reases are mi1tures of luricating oils and metallic soa+s, *ith the addition of s+ecial-+ur+ose
materials such as asestos, gra+hite, mol,denum, silicones and talc to +ro$ide insulation or
luricit,. Cutting and metal-+rocess oils are luricating oils *ith s+ecial additi$es such as
chlorine, sul+hur and fatt,-acid additi$es *hich react under heat to +ro$ide lurication and
+rotection to the cutting tools. Emulsifiers and acteria +re$ention agents are added to *ater-
solule cutting oils.
Although luricating oils , themsel$es are non-irritating and ha$e little to1icit,, ha"ards ma, e
+resented , the additi$es. Esers should consult su++lier material safet, data information to
determine the ha"ards of s+ecific additi$es, luricants, cutting oils and greases. -he +rimar,
luricant ha"ard is dermatitis, *hich can usuall, e controlled , the use of +ersonal +rotecti$e
e/ui+ment together *ith +ro+er h,gienic +ractices. !ccasionall, *or.ers ma, de$elo+ a
sensiti$it, to cutting oils or luricants *hich *ill re/uire reassignment to a 0o *here contact
cannot occur. -here are some concerns aout carcinogenic e1+osure to mists from na+hthenic-
ased cutting and light s+indle oils, *hich can e controlled , sustitution, engineering controls
or +ersonal +rotection. -he ha"ards of e1+osure to grease are similar to those of luricating oil,
*ith the addition of an, ha"ards +resented , the grease materials or additi$es. Most of these
ha"ards are discussed else*here in this Encyclopaedia.
Special products
-a" is used for +rotecting food +roducts3 in coatings3 as an ingredient in other +roducts such as
cosmetics and shoe +olish and for candles.
Sulphur is +roduced as a result of +etroleum refining. It is stored either as a heated, molten li/uid
in closed tan.s or as a solid in containers or outdoors.
Co+e is almost +ure caron, *ith a $ariet, of uses from electrodes to charcoal ri/uettes,
de+ending on its +h,sical characteristics, *hich result from the co.ing +rocess.
!sphalt, *hich is +rimaril, used for +a$ing roads and roofing materials, should e inert to most
chemicals and *eather conditions.
2a1es and as+halts are solid at amient tem+eratures, and higher tem+eratures are needed for
storage, handling and trans+ortation, *ith the resulting ha"ard of urns. )etroleum *a1 is so
highl, refined that it usuall, does not +resent an, ha"ards. S.in contact *ith *a1 can lead to
+lugging of +ores, *hich can e controlled , +ro+er h,gienic +ractices. E1+osure to h,drogen
sul+hide *hen as+halt and molten sul+hur tan.s are o+ened can e controlled , the use of
a++ro+riate engineering controls or res+irator, +rotection. Sul+hur is also readil, ignitale at
ele$ated tem+eratures. As+halt is discussed else*here in the Encyclopaedia.
Petroleum Refining Processes
6,drocaron refining is the use of chemicals, catal,sts, heat and +ressure to se+arate and
comine the asic t,+es of h,drocaron molecules naturall, found in crude oil into grou+s of
similar molecules. -he refining +rocess also rearranges the structures and onding +atterns of the
asic molecules into different, more desirale h,drocaron molecules and com+ounds. -he t,+e
of h,drocaron 8+araffinic, na+hthenic or aromatic9 rather than the s+ecific chemical com+ounds
+resent, is the most significant factor in the refining +rocess.
-hroughout the refiner,, o+erations +rocedures, safe *or. +ractices and the use of a++ro+riate
+ersonal +rotecti$e clothing and e/ui+ment, including a++ro$ed res+irator, +rotection, is needed
for fire, chemical, +articulate, heat and noise e1+osures and during +rocess o+erations, sam+ling,
ins+ection, turnaround and maintenance acti$ities. As most refiner, +rocesses are continuous and
the +rocess streams are contained in enclosed $essels and +i+ing, there is limited +otential for
e1+osure. 6o*e$er, the +otential for fire e1ists ecause e$en though refiner, o+erations are
closed +rocesses, if a lea. or release of h,drocaron li/uid, $a+our or gas occurs, the heaters,
furnaces and heat e1changers throughout the +rocess units are sources of ignition.
Crude oil pretreatment
,esalting
Crude oil often contains *ater, inorganic salts, sus+ended solids and *ater-solule trace metals.
-he first ste+ in the refining +rocess is to remo$e these contaminants , desalting 8deh,dration9
in order to reduce corrosion, +lugging and fouling of e/ui+ment, and to +re$ent +oisoning the
catal,sts in +rocessing units. Chemical desalting, electrostatic se+aration and filtering are three
t,+ical methods of crude-oil desalting. In chemical desalting, *ater and chemical surfactants
8demulsifiers9 are added to the crude oil, heated so that salts and other im+urities dissol$e into
the *ater or attach to the *ater, and are then held in a tan. *here the, settle out. Electrical
desalting a++lies high-$oltage electrostatic charges in order to concentrate sus+ended *ater
gloules in the ottom +ortion of the settling tan.. Surfactants are added onl, *hen the crude oil
has a large amount of sus+ended solids. A third, less common +rocess in$ol$es filtering heated
crude oil using diatomaceous earth as a filtration medium.
In chemical and electrostatic desalting, the crude feedstoc. is heated to et*een 55 IC and (??
IC, to reduce $iscosit, and surface tension for easier mi1ing and se+aration of the *ater. -he
tem+erature is limited , the $a+our +ressure of the crude-oil feedstoc.. Joth methods of
desalting are continuous. Caustic or acid ma, e added to ad0ust the +6 of the *ater *ash, and
ammonia added to reduce corrosion. 2aste *ater, together *ith contaminants, is discharged from
the ottom of the settling tan. to the *aste *ater treatment facilit,. -he desalted crude oil is
continuousl, dra*n from the to+ of the settling tan.s and sent to an atmos+heric crude
distillation 8fractionating9 to*er. 8See figure &.9
:igure &. Besalting 8+re-treatment9 +rocess
Inade/uate desalting causes fouling of heater tues and heat e1changers in all refiner, +rocess
units, restricting +roduct flo* and heat transfer, and resulting in failures due to increased
+ressures and tem+eratures. !$er+ressuring the desalting unit *ill cause failure.
Corrosion, *hich occurs due to the +resence of h,drogen sul+hide, h,drogen chloride,
na+hthenic 8organic9 acids and other contaminants in the crude oil, also causes e/ui+ment failure.
Corrosion occurs *hen neutrali"ed salts 8ammonium chlorides and sul+hides9 are moistened ,
condensed *ater. Jecause desalting is a closed +rocess, there is little +otential for e1+osure to
crude oil or +rocess chemicals, unless a lea. or release occurs. A fire ma, occur as a result of a
lea. in the heaters, allo*ing a release of lo*-oiling-+oint com+onents of crude oil.
-here is the +ossiilit, of e1+osure to ammonia, dr, chemical demulsifiers, caustics and=or acids
during desalting. 2here ele$ated o+erating tem+eratures are used *hen desalting sour crude oils,
h,drogen sul+hide *ill e +resent. Be+ending on the crude feedstoc. and the treatment
chemicals used, the *aste *ater *ill contain $ar,ing amounts of chlorides, sul+hides,
icaronates, ammonia, h,drocarons, +henol and sus+ended solids. If diatomaceous earth is
used in filtration, e1+osures should e minimi"ed or controlled since diatomaceous earth can
contain silica *ith a $er, fine +article si"e, ma.ing it a +otential res+irator, ha"ard.
Crude oil separation processes
-he first ste+ in +etroleum refining is the fractionation of crude oil in atmos+heric and $acuum
distillation to*ers. 6eated crude oil is +h,sicall, se+arated into $arious fractions, or straight-run
cuts, differentiated , s+ecific oiling-+oint ranges and classified, in order of decreasing
$olatilit,, as gases, light distillates, middle distillates, gas oils and residuum. :ractionation *or.s
ecause the gradation in tem+erature from the ottom to the to+ of the distillation to*er causes
the higher-oiling-+oint com+onents to condense first, *hile the lo*er-oiling-+oint fractions
rise higher in the to*er efore the, condense. 2ithin the to*er, the rising $a+ours and the
descending li/uids 8reflu19 mi1 at le$els *here the, ha$e com+ositions in e/uilirium *ith each
other. S+ecial tra,s are located at these le$els 8or stages9 *hich remo$e a fraction of the li/uid
*hich condenses at each le$el. In a t,+ical t*o-stage crude unit, the atmos+heric to*er,
+roducing light fractions and distillate, is immediatel, follo*ed , a $acuum to*er *hich
+rocesses the atmos+heric residuals. After distillation, onl, a fe* h,drocarons are suitale for
use as finished +roducts *ithout further +rocessing.
!tmospheric distillation
In atmos+heric distillation to*ers, the desalted crude feedstoc. is +reheated using reco$ered
+rocess heat. It then flo*s to a direct-fired crude charge heater, *here it is fed into the $ertical
distillation column 0ust ao$e the ottom at +ressures slightl, ao$e atmos+here and at
tem+eratures from 7<7 IC to 7?( IC, to a$oid undesirale thermal crac.ing at higher
tem+eratures. -he lighter 8lo*er oiling +oint9 fractions diffuse into the u++er +art of the to*er,
and are continuousl, dra*n off and directed to other units for further +rocessing, treating,
lending and distriution.
:ractions *ith the lo*est oiling +oints, such as fuel gas and light na+htha, are remo$ed from the
to+ of the to*er , an o$erhead line as $a+ours. >a+htha, or straight-run gasoline, is ta.en from
the u++er section of the to*er as an o$erhead stream. -hese +roducts are used as +etrochemical
and reformer feedstoc.s, gasoline lending stoc.s, sol$ents and L)#s.
Intermediate oiling range fractions, including gas oil, hea$, na+htha and distillates, are
remo$ed from the middle section of the to*er as side streams. -hese are sent to finishing
o+erations for use as .erosene, diesel fuel, fuel oil, 0et fuel, catal,tic crac.er feedstoc. and
lending stoc.s. Some of these li/uid fractions are stri++ed of their lighter ends, *hich are
returned to the to*er as do*nflo*ing reflu1 streams.
-he hea$ier, higher-oiling-+oint fractions 8called residuum, ottoms or to++ed crude9 *hich
condense or remain at the ottom of the to*er, are used for fuel oil, itumen manufacturing or
crac.ing feedstoc., or are directed to a heater and into the $acuum distillation to*er for further
fractionation. 8See figure 7 and figure <.9
:igure 7. Atmos+heric distillation +rocess
:igure <. Schematic of atmos+heric distrillation +rocess
.acuum distillation
@acuum distillation to*ers +ro$ide the reduced +ressure re/uired to +re$ent thermal crac.ing
*hen distilling the residuum, or to++ed crude, from the atmos+heric to*er at higher
tem+eratures. -he internal designs of some $acuum to*ers are different from atmos+heric to*ers
in that random +ac.ing and demister +ads are used instead of tra,s. Larger diameter to*ers ma,
also e used to .ee+ $elocities lo*er. A t,+ical first-+hase $acuum to*er ma, +roduce gas oils,
luricating oil ase stoc.s and hea$, residual for +ro+ane deas+halting. A second-+hase to*er,
o+erating at a lo*er $acuum, distills sur+lus residuum from the atmos+heric to*er *hich is not
used for lue stoc. +rocessing, and sur+lus residuum from the first $acuum to*er not used for
deas+halting.
@acuum to*ers are t,+icall, used to se+arate catal,tic crac.er feedstoc.s from sur+lus residuum.
@acuum to*er ottoms ma, also e sent to a co.er, used as luricant or as+halt stoc. or
desul+huri"ed and lended into lo*-sul+hur fuel oil. 8See figure A and figure 5.9
:igure A. @acuum distillation +rocess
:igure 5. Schematic of $acuum distillation +rocess
,istillation columns
2ithin refineries there are numerous other smaller distillation to*ers, called columns, designed
to se+arate s+ecific and uni/ue +roducts, *hich all *or. on the same +rinci+les as atmos+heric
to*ers. :or e1am+le, a de+ro+ani"er is a small column designed to se+arate +ro+ane from
isoutane and hea$ier com+onents. Another larger column is used to se+arate eth,l en"ene and
1,lene. Small CulerD to*ers, called stri++ers, use steam to remo$e trace amounts of light
+roducts 8gasoline9 from hea$ier +roduct streams.
Control tem+eratures, +ressures and reflu1 must e maintained *ithin o+erating +arameters to
+re$ent thermal crac.ing from ta.ing +lace *ithin distillation to*ers. Relief s,stems are
+ro$ided ecause e1cursions in +ressure, tem+erature or li/uid le$els ma, occur if automatic
control de$ices fail. !+erations are monitored in order to +re$ent crude from entering the
reformer charge. Crude feedstoc.s ma, contain a++reciale amounts of *ater in sus+ension
*hich se+arate during start-u+ and, along *ith *ater remaining in the to*er from steam +urging,
settle in the ottom of the to*er. -his *ater ma, heat to the oiling +oint and create an
instantaneous $a+ori"ation e1+losion u+on contact *ith the oil in the unit.
-he +reheat e1changer, +reheat furnace and ottoms e1changer, atmos+heric to*er and $acuum
furnace, $acuum to*er and o$erhead are susce+tile to corrosion from h,drochloric acid 86Cl9,
h,drogen sul+hide 86&S9, *ater, sul+hur com+ounds and organic acids. 2hen +rocessing sour
crudes, se$ere corrosion can occur in oth atmos+heric and $acuum to*ers *here metal
tem+eratures e1ceed &7& IC, and in furnace tuing. 2et 6&S *ill also cause crac.s in steel.
2hen +rocessing high-nitrogen crudes, nitrogen o1ides, *hich are corrosi$e to steel *hen cooled
to lo* tem+eratures in the +resence of *ater, form in the flue gases of furnaces.
Chemicals are used to control corrosion , h,drochloric acid +roduced in distillation units.
Ammonia ma, e in0ected into the o$erhead stream +rior to initial condensation, and=or an
al.aline solution ma, e carefull, in0ected into the hot crude oil feed. If sufficient *ash *ater is
not in0ected, de+osits of ammonium chloride can form, causing serious corrosion.
Atmos+heric and $acuum distillation are closed +rocesses, and e1+osures are minimal. 2hen
sour 8high sul+hur9 crudes are +rocessed, there ma, e +otential e1+osure to h,drogen sul+hide
in the +reheat e1changer and furnace, to*er flash "one and o$erhead s,stem, $acuum furnace
and to*er, and ottoms e1changer. Crude oils and distillation +roducts all contain high-oiling
aromatic com+ounds, including carcinogenic )A6s. Short-term e1+osure to high concentrations
of na+htha $a+our can result in headaches, nausea and di""iness, and long-term e1+osure can
result in loss of consciousness. Jen"ene is +resent in aromatic na+hthas, and e1+osure must e
limited. -he dehe1ani"er o$erhead ma, contain large amounts of normal he1ane, *hich can
affect the ner$ous s,stem. 6,drogen chloride ma, e +resent in the +reheat e1changer, to*er to+
"ones and o$erheads. 2aste *ater ma, contain *ater-solule sul+hides in high concentrations
and other *ater-solule com+ounds, such as ammonia, chlorides, +henol and merca+tan,
de+ending u+on the crude feedstoc. and the treatment chemicals.
Crude oil conersion processes
Con$ersion +rocesses, such as crac.ing, comining and rearranging, change the si"e and
structure of h,drocaron molecules in order to con$ert fractions into more desirale +roducts.
8See tale 7.9
-ale 7. !$er$ie* of +etroleum refining +rocesses
Process name Action Method Purpose Feedstocs Products
Fractionation processes
Atmos+heric
distillation
Se+aration -hermal Se+arate
fractions
Besalted crude
oil
#as, gas oil,
distillate, residual
@acuum
distillation
Se+aration -hermal Se+arate
*ithout
crac.ing
Atmos+heric
to*er residual
#as oil, lue stoc.,
residual
Con!ersion processes"#ecomposition
Catal,tic
crac.ing
Alteration Catal,tic E+grade
gasoline
#as oil, co.e
distillate
#asoline,
+etrochemical
feedstoc.
Co.ing )ol,meri"atio
n
-hermal Con$ert
$acuum
residuals
Residual, hea$,
oil, tar
>a+htha, gas oil,
co.e
6,drocrac.ing 6,drogenatio
n
Catal,tic Con$ert to
lighter
h,drocaro
#as oil, crac.ed
oil, residuals
Lighter, higher
/ualit, +roducts
ns
6,drogen steam
reforming
Becom+ositio
n
-hermal=catal,t
ic
)roduce
h,drogen
Besul+huri"ed
gas, !& ,steam
6,drogen, C!,C!&
Steam crac.ing Becom+ositio
n
-hermal Crac. large
molecules
Atmos+heric
to*er hea$,
fuel=distillate
Crac.ed na+htha,
co.e, residuals
@isrea.ing Becom+ositio
n
-hermal Reduce
$iscosit,
Atmos+heric
to*er residual
Bistillate, car
Con!ersion processes"$nification
Al.,lation Comining Catal,tic Enite
olefins and
iso+araffins
-o*er
isoutane=crac.
er olefin
Iso-octane 8al.,late9
#rease
com+ounding
Comining -hermal Comine
soa+s and
oils
Lue oil, catt,
acid, al.,metal
Luricating grease
)ol,meri"ation )ol,meri"atio
n
Catal,tic Enite t*o
or more
olefins
Crac.er olefins 6igh octane na+htha,
+etrochemical stoc.s
Con!ersion processes"Alteration%rearrangement
Catal,tic
reforming
Alteration=
deh,drogenati
on
Catal,tic E+grade
lo*-octane
na+htha
Co.er=h,drocra
c.er na+htha
6igh-octane
reformate=aromatic
Isomeri"ation Rearrangeme
nt
Catal,tic Con$ert
straight
chain to
ranch
Jutane, centane,
ce1ane
Isoutane=+entane=he
1ane
&reatment processes
Amine treating -reatment Asor+tion Remo$e
acidic
contaminan
ts
Sour gas,
c,drocarons
*ith C!& and
6&S
Acid-free gases and
li/uid h,drocarons
Besalting 8+re-
treatment9
Beh,dration Asor+tion Remo$e
contaminan
ts
Crude oil Besalted crude oil
Br,ing and
s*eetening
-reatment Asor+tion=ther
mal
Remo$e
6&! and
sul+hur
com+ounds
Li/uid
h,drocaron,
L)#, al.,lated
feedstoc.
S*eet and dr,
h,drocarons
:urfural
e1traction
Sol$ent
e1traction
Asor+tion E+grade
middistillat
e and lues
C,cle oils and
lue feedstoc.s
6igh-/ualit, diesel
and lue oil
6,drodesul+hur
i"ation
-reatment Catal,tic Remo$e
sul+hur,
contaminan
ts
6igh-sul+hur
residual=gas oil
Besul+huri"ed
olefins
6,drotreating 6,drogenatio
n
Catal,tic Remo$e
im+urities=
saturate
h,drocaro
ns
Residuals,
crac.ed
h,drocarons
Crac.er feed,
cistillate, lue
)henol
e1traction
Sol$ent
e1traction
Asor+tion=ther
mal
Im+ro$e
lue
$iscosit,
inde1,
colour
Lue oil ase
stoc.s
6igh-/ualit, lue
oils
Sol$ent
deas+halting
-reatment Asor+tion Remo$e
as+halt
@acuum to*er
residual,
cro+ane
6ea$, lue oil,
cs+halt
Sol$ent
de*a1ing
-reatment Cool=filter Remo$e
*a1 from
lue stoc.s
@acuum to*er
lue oils
Be*a1ed lue ase
stoc.
Sol$ent
e1traction
Sol$ent
e1traction
Asor+tion=
+reci+itation
Se+arate
unsaturated
aromatics
#as oil,
ceformate,
cistillate
6igh-octane gasoline
S*eetening -reatment Catal,tic Remo$e
6&S,
con$ert
merca+tan
Entreated
distillate=gasolin
e
6igh-/ualit,
distillate=gasoline

A numer of h,drocaron molecules not normall, found in crude oil ut im+ortant to the
refining +rocess are created as a result of con$ersion. !lefins 8al.enes, di-olefins and al.,nes9
are unsaturated chain- or ring-t,+e h,drocaron molecules *ith at least one doule ond. -he,
are usuall, formed , thermal and catal,tic crac.ing and rarel, occur naturall, in un+rocessed
crude oil.
!l+enes are straight-chain molecules *ith the formula Cn6n containing at least one doule ond
8unsaturated9 lin.age in the chain. -he sim+lest al.ene molecule is the mono-olefin eth,lene,
*ith t*o caron atoms, 0oined , a doule ond, and four h,drogen atoms. Bi-olefins
8containing t*o doule onds9, such as (,&-utadiene and (,7-utadiene, and al.,nes 8containing
a tri+le ond9, such as acet,lene, occur in CA and lighter fractions from crac.ing. !lefins are
more reacti$e than +araffins or na+hthenes, and readil, comine *ith other elements such as
h,drogen, chlorine and romine.
Cracking processes
:ollo*ing distillation, suse/uent refiner, +rocesses are used to alter the molecular structures of
the fractions to create more desirale +roducts. !ne of these +rocesses, crac.ing, rea.s 8or
crac.s9 hea$ier, higher-oiling-+oint +etroleum fractions into more $aluale +roducts such as
gaseous h,drocarons, gasoline lending stoc.s, gas oil and fuel oil. Buring the +rocess, some of
the molecules comine 8+ol,meri"e9 to form larger molecules. -he asic t,+es of crac.ing are
thermal crac.ing, catal,tic crac.ing and h,dro-crac.ing.
"hermal cracking processes
-hermal crac.ing +rocesses, de$elo+ed in (;(7, heat distillate fuels and hea$, oils under
+ressure in large drums until the, crac. 8di$ide9 into smaller molecules *ith etter anti-.noc.
characteristics. -his earl, method, *hich +roduced large amounts of solid, un*anted co.e, has
e$ol$ed into modern thermal crac.ing +rocesses including $isrea.ing, steam crac.ing and
co.ing.
.isrea+ing
@isrea.ing is a mild form of thermal crac.ing *hich reduces the +our +oint of *a1, residues
and significantl, lo*ers the $iscosit, of feedstoc. *ithout affecting its oiling-+oint range.
Residual from the atmos+heric distillation to*er is mildl, crac.ed in a heater at atmos+heric
+ressure. It is then /uenched *ith cool gas oil to control o$ercrac.ing, and flashed in a
distillation to*er. -he thermall, crac.ed residue tar, *hich accumulates in the ottom of the
fractionation to*er, is $acuum flashed in a stri++er and the distillate is rec,cled. 8See figure ?.9
:igure ?. @isrea.ing +rocess
Steam crac+ing
Steam crac.ing +roduces olefins , thermall, crac.ing large h,drocaron molecule feedstoc.s at
+ressures slightl, ao$e atmos+heric and at $er, high tem+eratures. Residual from steam
crac.ing is lended into hea$, fuels. >a+htha +roduced from steam crac.ing usuall, contains
en"ene, *hich is e1tracted +rior to h,drotreating.
Co+ing
Co.ing is a se$ere form of thermal crac.ing used to otain straight-run gasoline 8co.er na+htha9
and $arious middle distillate fractions used as catal,tic crac.ing feedstoc.s. -his +rocess so
com+letel, reduces h,drogen from the h,drocaron molecule, that the residue is a form of
almost +ure caron called co+e. -he t*o most common co.ing +rocesses are dela,ed co.ing and
continuous 8contact or fluid9 co.ing, *hich, de+ending u+on the reaction mechanism, time,
tem+erature and the crude feedstoc., +roduce three t,+es of co.eFs+onge, hone,com and
needle co.e. 8See figure 4.9
:igure 4. Co.ing +rocess
,elayed co+ing. In dela,ed co.ing, the feedstoc. is first charged to a fractionator to
se+arate lighter h,drocarons, and then comined *ith hea$, rec,cle oil. -he hea$,
feedstoc. is fed to the co.er furnace and heated to high tem+eratures at lo* +ressures to
+re$ent +remature co.ing in the heater tues, +roducing +artial $a+ori"ation and mild
crac.ing. -he li/uid=$a+our mi1ture is +um+ed from the heater to one or more co.er
drums, *here the hot material is held a++ro1imatel, &< hours 8dela,ed9 at lo* +ressures
until it crac.s into lighter +roducts. After the co.e reaches a +redetermined le$el in one
drum, the flo* is di$erted to another drum to maintain continuous o+eration. @a+our
from the drums is returned to the fractionator to se+arate out gas, na+htha and gas oils,
and to rec,cle hea$ier h,drocarons through the furnace. -he full drum is steamed to
stri+ out uncrac.ed h,drocarons, cooled , *ater in0ection and deco.ed mechanicall,
, an auger rising from the ottom of the drum, or h,draulicall, , fracturing the co.e
ed *ith high-+ressure *ater e0ected from a rotating cutter.
Continuous co+ing. Continuous 8contact or fluid9 co.ing is a mo$ing ed +rocess *hich
o+erates at lo*er +ressures and higher tem+eratures than dela,ed co.ing. In continuous
co.ing, thermal crac.ing occurs , using heat transferred from hot rec,cled co.e
+articles to feedstoc. in a radial mi1er, called a reactor. #ases and $a+ours are ta.en
from the reactor, /uenched to sto+ further reaction and fractionated. -he reacted co.e
enters a surge drum and is lifted to a feeder and classifier *here the larger co.e +articles
are remo$ed. -he remaining co.e is dro++ed into the reactor +reheater for rec,cling *ith
feedstoc.. -he +rocess is automatic in that there is a continuous flo* of co.e and
feedstoc., and co.ing occurs oth in the reactor and in the surge drum.

Health and safety considerations
In co.ing, tem+erature control should e held *ithin a close range, as high tem+eratures *ill
+roduce co.e *hich is too hard to cut out of the drum. Con$ersel,, tem+eratures *hich are too
lo* *ill result in a high as+haltic content slurr,. Should co.ing tem+eratures get out of control,
an e1othermic reaction could occur.
In thermal crac.ing *hen sour crudes are +rocessed, corrosion can occur *here metal
tem+eratures are et*een &7& IC and <4& IC. It a++ears that co.e forms a +rotecti$e la,er on the
metal ao$e <4& IC. 6o*e$er, h,drogen sul+hide corrosion occurs *hen tem+eratures are not
+ro+erl, controlled ao$e <4& IC. -he lo*er +art of the to*er, high tem+erature e1changers,
furnace and soa.ing drums are su0ect to corrosion. Continuous thermal changes cause co.e
drum shells to ulge and crac..
2ater or steam in0ection is used to +re$ent uildu+ of co.e in dela,ed co.er furnace tues. 2ater
must e com+letel, drained from the co.er, so as not to cause an e1+losion u+on recharging *ith
hot co.e. In emergencies, alternate means of egress from the *or.ing +latform on to+ of co.e
drums is needed.
Jurns ma, occur *hen handling hot co.e, from steam in the e$ent of a steam line lea., or from
hot *ater, hot co.e or hot slurr, *hich ma, e e1+elled *hen o+ening co.ers. -he +otential
e1ists for e1+osure to aromatic na+hthas containing en"ene, h,drogen sul+hide and caron
mono1ide gases, and to trace amounts of carcinogenic )A6s associated *ith co.ing o+erations.
2aste sour *ater ma, e highl, al.aline, and contain oil, sul+hides, ammonia and +henol. 2hen
co.e is mo$ed as a slurr,, o1,gen de+letion ma, occur *ithin confined s+aces such as storage
silos, ecause *et caron adsors o1,gen.
Catalytic cracking processes
Catal,tic crac.ing rea.s u+ com+le1 h,drocarons into sim+ler molecules in order to increase
the /ualit, and /uantit, of lighter, more desirale +roducts and decrease the amount of residuals.
6ea$, h,drocarons are e1+osed at high tem+erature and lo* +ressure to catal,sts *hich
+romote chemical reactions. -his +rocess rearranges the molecular structure, con$erting hea$,
h,drocaron feedstoc.s into lighter fractions such as .erosene, gasoline, L)#, heating oil and
+etrochemical feedstoc.s 8see figure ; and figure ('9. Selection of a catal,st de+ends u+on a
comination of the greatest +ossile reacti$it, and the est resistance to attrition. -he catal,sts
used in refiner, crac.ing units are t,+icall, solid materials 8"eolite, aluminium h,drosilicate,
treated entonite cla,, :ullerLs earth, au1ite and silica-alumina9 *hich are in the form of
+o*ders, eads, +ellets or sha+ed materials called e1trudites.
:igure ;. Catal,tic crac.ing +rocess
:igure ('. Schematic of catal,tic crac.ing +rocess
-here are three asic functions in all catal,tic crac.ing +rocesses:
ReactionFfeedstoc. reacts *ith catal,st and crac.s into different h,drocarons.
RegenerationFcatal,st is reacti$ated , urning off co.e.
:ractionationFcrac.ed h,drocaron stream is se+arated into $arious +roducts.

Catal,tic crac.ing +rocesses are $er, fle1ile and o+erating +arameters can e ad0usted to meet
changing +roduct demand. -he three asic t,+es of catal,tic crac.ing +rocesses are:
fluid catal,tic crac.ing 8:CC9
mo$ing ed catal,tic crac.ing
thermofor catal,tic crac.ing 8-CC9.

Fluid catalytic crac+ing
:luid-ed catal,tic crac.ers ha$e a catal,st section 8riser, reactor and regenerator9 and a
fractionating section, oth o+erating together as an integrated +rocessing unit. -he :CC uses
finel, +o*dered catal,st, sus+ended in oil $a+our or gas, *hich acts as a fluid. Crac.ing ta.es
+lace in the feed +i+e 8riser9 in *hich the mi1ture of catal,st and h,drocarons flo* through the
reactor.
-he :CC +rocess mi1es a +reheated h,drocaron charge *ith hot, regenerated catal,st as it
enters the riser leading to the reactor. -he charge comines *ith rec,cle oil *ithin the riser, is
$a+ori"ed and is raised to reactor tem+erature , the hot catal,st. As the mi1ture tra$els u+ the
reactor, the charge is crac.ed at lo* +ressure. -his crac.ing continues until the oil $a+ours are
se+arated from the catal,st in the reactor c,clones. -he resultant +roduct stream enters a column
*here it is se+arated into fractions, *ith some of the hea$, oil directed ac. into the riser as
rec,cle oil.
S+ent catal,st is regenerated to remo$e co.e *hich collects on the catal,st during the +rocess.
S+ent catal,st flo*s through the catal,st stri++er to the regenerator *here it mi1es *ith
+reheated air, urning off most of the co.e de+osits. :resh catal,st is added and *orn-out
catal,st remo$ed to o+timi"e the crac.ing +rocess.
/oving ed catalytic crac+ing
Mo$ing-ed catal,tic crac.ing is similar to fluid catal,tic crac.ing3 ho*e$er, the catal,st is in
the form of +ellets instead of fine +o*der. -he +ellets mo$e continuousl, , con$e,or or
+neumatic lift tues to a storage ho++er at the to+ of the unit, and then flo* do*n*ard , gra$it,
through the reactor to a regenerator. -he regenerator and ho++er are isolated from the reactor ,
steam seals. -he crac.ed +roduct is se+arated into rec,cle gas, oil, clarified oil, distillate, na+htha
and *et gas.
0hermofor catalytic crac+ing
In thermofor catal,tic crac.ing, the +reheated feedstoc. flo*s , gra$it, through the catal,tic
reactor ed. @a+ours are se+arated from the catal,st and sent to a fractionating to*er. -he s+ent
catal,st is regenerated, cooled and rec,cled, and the flue gas from regeneration is sent to a
caron mono1ide oiler for heat reco$er,.
Health and safety considerations
Regular sam+ling and testing of feedstoc., +roduct and rec,cle streams should e +erformed to
assure that the crac.ing +rocess is *or.ing as intended and that no contaminants ha$e entered
the +rocess stream. Corrosi$es or de+osits in feedstoc. can foul gas com+ressors. 2hen
+rocessing sour crude, corrosion ma, e e1+ected *here tem+eratures are elo*
<4& IC. Corrosion ta.es +lace *here oth li/uid and $a+our +hases e1ist and at areas su0ect to
local cooling, such as no""les and +latform su++orts. 2hen +rocessing high-nitrogen feedstoc.s,
e1+osure to ammonia and c,anide ma, su0ect caron steel e/ui+ment in the :CC o$erhead
s,stem to corrosion, crac.ing or h,drogen listering, *hich can e minimi"ed , *ater *ash or
, corrosion inhiitors. 2ater *ash ma, e used to +rotect o$erhead condensers in the main
column su0ected to fouling from ammonium h,drosul+hide.
Critical e/ui+ment, including +um+s, com+ressors, furnaces and heat e1changers should e
ins+ected. Ins+ections should include chec.ing for lea.s due to erosion or other malfunctions
such as catal,st uildu+ on the e1+anders, co.ing in the o$erhead feeder lines from feedstoc.
residues, and other unusual o+erating conditions.
Li/uid h,drocarons in the catal,st or entering the heated comustion air stream can cause
e1othermic reactions. In some +rocesses, caution must e ta.en to assure that e1+losi$e
concentrations of catal,st dust are not +resent during recharge or dis+osal. 2hen unloading
co.ed catal,st, the +ossiilit, of iron sul+hide fires e1ists. Iron sul+hide *ill ignite
s+ontaneousl, *hen e1+osed to air, and therefore needs to e *etted do*n *ith *ater to +re$ent
it from ecoming a source of ignition for $a+ours. Co.ed catal,st ma, either e cooled to elo*
<; IC efore dum+ing from the reactor, or first dum+ed into containers +urged *ith inert
nitrogen and then cooled efore further handling.
-he +ossiilit, of e1+osure to e1tremel, hot h,drocaron li/uids or $a+ours is +resent during
+rocess sam+ling or if a lea. or release occurs. In addition, e1+osure to carcinogenic )A6s,
aromatic na+htha containing en"ene, sour gas 8fuel gas from +rocesses such as catal,tic
crac.ing and h,drotreating, *hich contains h,drogen sul+hide and caron dio1ide9, h,drogen
sul+hide and=or caron mono1ide gas ma, occur during a release of +roduct or $a+our.
Inad$ertent formation of highl, to1ic nic.el caron,l ma, occur in crac.ing +rocesses that use
nic.el catal,sts *ith resultant +otential for ha"ardous e1+osures.
Catal,st regeneration in$ol$es steam stri++ing and deco.ing, *hich results in +otential e1+osure
to fluid *aste streams *hich ma, contain $ar,ing amounts of sour *ater, h,drocaron, +henol,
ammonia, h,drogen sul+hide, merca+tan and other materials, de+ending u+on the feedstoc.s,
crudes and +rocesses. Safe *or. +ractices and the use of a++ro+riate +ersonal +rotecti$e
e/ui+ment 8))E9 are needed *hen handling s+ent catal,st, recharging catal,st, or if lea.s or
releases occur.
Hydrocracking process
6,drocrac.ing is a t*o-stage +rocess comining catal,tic crac.ing and h,drogenation, *herein
distillate fractions are crac.ed in the +resence of h,drogen and s+ecial catal,sts to +roduce more
desirale +roducts. 6,drocrac.ing has an ad$antage o$er catal,tic crac.ing in that high-sul+hur
feedstoc.s can e +rocessed *ithout +re$ious desul+huri"ation. In the +rocess, hea$, aromatic
feedstoc. is con$erted into lighter +roducts under $er, high +ressures and fairl, high
tem+eratures. 2hen the feedstoc. has a high +araffinic content, the h,drogen +re$ents the
formation of )A6s, reduces tar formation and +re$ents uild-u+ of co.e on the catal,st.
6,drocrac.ing +roduces relati$el, large amounts of isoutane for al.,lation feedstoc.s and also
causes isomeri"ation for +our +oint control and smo.e +oint control, oth of *hich are im+ortant
in high-/ualit, 0et fuel.
In the first stage, feedstoc. is mi1ed *ith rec,cled h,drogen, heated and sent to the +rimar,
reactor, *here a large amount of the feedstoc. is con$erted to middle distillates. Sul+hur and
nitrogen com+ounds are con$erted , a catal,st in the +rimar, stage reactor to h,drogen
sul+hide and ammonia. -he residual is heated and sent to a high-+ressure se+arator, *here
h,drogen-rich gases are remo$ed and rec,cled. -he remaining h,drocarons are stri++ed or
+urified to remo$e the h,drogen sul+hide, ammonia and light gases, *hich are collected in an
accumulator, *here gasoline is se+arated from sour gas.
-he stri++ed li/uid h,drocarons from the +rimar, reactor are mi1ed *ith h,drogen and sent to
the second-stage reactor, *here the, are crac.ed into high-/ualit, gasoline, 0et fuel and distillate
lending stoc.s. -hese +roducts go through a series of high- and lo*-+ressure se+arators to
remo$e gases, *hich are rec,cled. -he li/uid h,drocarons are staili"ed, s+lit and stri++ed, *ith
the light na+htha +roducts from the h,drocrac.er used to lend gasoline *hile the hea$ier
na+hthas are rec,cled or sent to a catal,tic reformer unit. 8See figure ((.9
:igure ((. 6,drocrac.ing +rocess
Health and safety considerations
Ins+ection and testing of safet, relief de$ices are im+ortant due to the $er, high +ressures in this
+rocess. )ro+er +rocess control is needed to +rotect against +lugging reactor eds. Jecause of the
o+erating tem+eratures and +resence of h,drogen, the h,drogen sul+hide content of the feedstoc.
must e strictl, .e+t to a minimum in order to reduce the +ossiilit, of se$ere corrosion.
Corrosion , *et caron dio1ide in areas of condensation must also e considered. 2hen
+rocessing high-nitrogen feedstoc.s, the ammonia and h,drogen sul+hide form ammonium
h,drosul+hide, *hich causes serious corrosion at tem+eratures elo* the *ater de* +oint.
Ammonium h,drosul+hide is also +resent in sour *ater stri++ing. Jecause the h,drocrac.er
o+erates at $er, high +ressures and tem+eratures, control of oth h,drocaron lea.s and
h,drogen releases is im+ortant to +re$ent fires.
Jecause this is a closed +rocess, e1+osures are minimal under normal o+erating conditions.
-here is a +otential for e1+osure to ali+hatic na+htha containing en"ene, carcinogenic )A6s,
h,drocaron gas and $a+our emissions, h,drogen-rich gas and h,drogen sul+hide gas as a result
of high-+ressure lea.s. Large /uantities of caron mono1ide ma, e released during catal,st
regeneration and changeo$er. Catal,st steam stri++ing and regeneration creates *aste streams
containing sour *ater and ammonia. Safe *or. +ractices and a++ro+riate +ersonal +rotecti$e
e/ui+ment are needed *hen handling s+ent catal,st. In some +rocesses, care is needed to assure
that e1+losi$e concentrations of catal,tic dust do not form during recharging. Enloading co.ed
catal,st re/uires s+ecial +recautions to +re$ent iron sul+hideinduced fires. -he co.ed catal,st
should either e cooled to elo* <; IC efore dum+ing, or +laced in nitrogen-inerted containers
until cooled.
Combining processes
-*o comining +rocesses, polymeri1ation and al+ylation, are used to 0oin together small
h,drogen-deficient molecules, called olefins2 reco$ered from thermal and catal,tic crac.ing, in
order to create more desirale gasoline lending stoc.s.
(olymeri1ation
)ol,meri"ation is the +rocess of comining t*o or more unsaturated organic molecules 8olefins9
to form a single, hea$ier molecule *ith the same elements in the same +ro+ortion as the original
molecule. It con$erts gaseous olefins, such as eth,lene, +ro+,lene and ut,lene con$erted ,
thermal and fluid crac.ing units, into hea$ier, more com+le1, higher-octane molecules, including
na+htha and +etrochemical feedstoc.s. -he olefin feedstoc. is +retreated to remo$e sul+hur
com+ounds and other undesirales, and then +assed o$er a +hos+horus catal,st, usuall, a solid
catal,st or li/uid +hos+horic acid, *here an e1othermic +ol,meric reaction occurs. -his re/uires
the use of cooling *ater and the in0ection of cold feedstoc. into the reactor to control
tem+eratures at $arious +ressures. Acid in the li/uids is remo$ed , caustic *ash, the li/uids are
fractionated, and the acid catal,st is rec,cled. -he $a+our is fractionated to remo$e utanes and
neutrali"ed to remo$e traces of acid. 8See figure (&.9
:igure (&. )ol,meri"ation +rocess
Se$ere corrosion, leading to e/ui+ment failure, *ill occur should *ater contact the +hos+horic
acid, such as during *ater *ashing at shutdo*ns. Corrosion ma, also occur in +i+ing manifolds,
reoilers, e1changers and other locations *here acid ma, settle out. -here is a +otential for
e1+osure to caustic *ash 8sodium h,dro1ide9, to +hos+horic acid used in the +rocess or *ashed
out during turnarounds, and to catal,st dust. -he +otential for an uncontrolled e1othermic
reaction e1ists should loss of cooling *ater occur.
!l+ylation
Al.,lation comines the molecules of olefins +roduced from catal,tic crac.ing *ith those of
iso+araffins in order to increase the $olume and octane of gasoline lends. !lefins *ill react *ith
iso+araffins in the +resence of a highl, acti$e catal,st, usuall, sul+huric acid or h,drofluoric acid
8or aluminium chloride9 to create a long-ranched-chain +araffinic molecule, called al+ylate 8iso-
octane9, *ith e1ce+tional anti-.noc. /ualit,. -he al.,late is then se+arated and fractionated. -he
relati$el, lo* reaction tem+eratures of ('IC to (5IC for sul+huric acid, &?IC to 'IC for
h,drofluoric acid 86:9 and 'IC for aluminium chloride, are controlled and maintained ,
refrigeration. 8See figure (7.9
:igure (7. Al.,lation +rocess
Sulphuric acid al+ylation. In cascade-t,+e sul+huric acid al.,lation units, feedstoc.s, including
+ro+,lene, ut,lene, am,lene and fresh isoutane, enter the reactor, *here the, contact the
sul+huric acid catal,st. -he reactor is di$ided into "ones, *ith olefins fed through distriutors to
each "one, and the sul+huric acid and isoutanes flo*ing o$er affles from "one to "one.
Reaction heat is remo$ed , e$a+oration of isoutane. -he isoutane gas is remo$ed from the
to+ of the reactor, cooled and rec,cled, *ith a +ortion directed to the de+ro+ani"er to*er.
Residual from the reactor is settled, and the sul+huric acid is remo$ed from the ottom of the
$essel and recirculated. Caustic and=or *ater scruers are used to remo$e small amounts of acid
from the +rocess stream, *hich then goes to a de-isoutani"er to*er. -he deutani"er isoutane
o$erhead is rec,cled, and the remaining h,drocarons are se+arated in a rerun to*er and=or sent
to lending.
Hydrofluoric acid al+ylation. -here are t*o t,+es of h,drofluoric acid al.,lation +rocesses:
)hilli+s and E!). In the )hilli+s +rocess, olefin and isoutane feedstoc. is dried and fed to a
comination reactor=settler unit. -he h,drocaron from the settling "one is charged to the main
fractionator. -he main fractionator o$erhead goes to a de+ro+ani"er. )ro+ane, *ith trace amounts
of h,drofluoric acid 86:9, goes to an 6: stri++er, and is then catal,ticall, defluorinated, treated
and sent to storage. Isoutane is *ithdra*n from the main fractionator and rec,cled to the
reactor=settler, and al.,late from the ottom of the main fractionator is sent to a s+litter.
-he E!) +rocess uses t*o reactors *ith se+arate settlers. 6alf of the dried feedstoc. is charged
to the first reactor, along *ith rec,cle and ma.e-u+ isoutane, and then to its settler, *here the
acid is rec,cled and the h,drocaron charged to the second reactor. -he other half of the
feedstoc. goes to the second reactor, *ith the settler acid eing rec,cled and the h,drocarons
charged to the main fractionator. Suse/uent +rocessing is similar to )hilli+s in that the o$erhead
from the main fractionator goes to a de+ro+ani"er, isoutane is rec,cled and al.,late is sent to a
s+litter.
Health and safety considerations
Sul+huric acid and h,drofluoric acid are dangerous chemicals, and care during deli$er, and
unloading of acid is essential. -here is a need to maintain sul+huric acid concentrations of 4A to
;AK for good o+eration and to minimi"e corrosion. -o +re$ent corrosion from h,drofluoric acid,
acid concentrations inside the +rocess unit must e maintained ao$e 5AK and moisture elo*
<K. Some corrosion and fouling in sul+huric acid units occurs from the rea.do*n of sul+huric
acid esters, or *here caustic is added for neutrali"ation. -hese esters can e remo$ed , fresh-
acid treating and hot-*ater *ashing.
E+sets can e caused , loss of the coolant *ater needed to maintain +rocess tem+eratures.
)ressure on the cooling *ater and steam side of e1changers should e .e+t elo* the minimum
+ressure on the acid ser$ice side to +re$ent *ater contamination. @ents can e routed to soda ash
scruers to neutrali"e h,drogen fluoride gas or h,drofluoric acid $a+ours efore release. Curs,
drainage and isolation ma, e +ro$ided for +rocess unit containment so that effluent can e
neutrali"ed efore release to the se*er s,stem.
6,drofluoric acid units should e thoroughl, drained and chemicall, cleaned +rior to
turnarounds and entr,, to remo$e all traces of iron fluoride and h,drofluoric acid. :ollo*ing
shutdo*n, *here *ater has een used, the unit should e thoroughl, dried efore h,drofluoric
acid is introduced. Lea.s, s+ills or releases in$ol$ing h,drofluoric acid, or h,drocarons
containing h,drofluoric acid, are e1tremel, ha"ardous. )recautions are necessar, to assure that
e/ui+ment and materials *hich ha$e een in contact *ith acid are handled carefull, and are
thoroughl, cleaned efore the, lea$e the +rocess area or refiner,. Immersion *ash $ats are often
+ro$ided for neutrali"ation of e/ui+ment *hich has come into contact *ith h,drofluoric acid.
-here is a +otential for serious ha"ardous and to1ic e1+osures should lea.s, s+ills or releases
occur. Birect contact *ith sul+huric or h,drofluoric acid *ill cause se$ere s.in and e,e damage,
and inhalation of acid mists or h,drocaron $a+ours containing acid *ill cause se$ere irritation
and damage to the res+irator, s,stem. S+ecial +recautionar, emergenc, +re+aredness measures
should e used, and +rotection should e +ro$ided that is a++ro+riate to the +otential ha"ard and
areas +ossil, affected. Safe *or. +ractices and a++ro+riate s.in and res+irator, +ersonal
+rotecti$e e/ui+ment are needed *here +otential e1+osures to h,drofluoric and sul+huric acids
during normal o+erations e1ist, such as reading gauges, ins+ecting and +rocess sam+ling, as *ell
as during emergenc, res+onse, maintenance and turnaround acti$ities. )rocedures should e in
+lace to assure that +rotecti$e e/ui+ment and clothing *orn in sul+huric or h,drofluoric acid
acti$ities, including chemical +rotecti$e suits, head and shoe co$erings, glo$es, face and e,e
+rotection and res+irator, +rotecti$e e/ui+ment, are thoroughl, cleaned and decontaminated
efore reissue.
#earranging processes
Catalytic reforming and isomeri1ation are +rocesses *hich rearrange h,drocaron molecules to
+roduce +roducts *ith different characteristics. After crac.ing, some gasoline streams, although
of the correct molecular si"e, re/uire further +rocessing to im+ro$e their +erformance, ecause
the, are deficient in some /ualities, such as octane numer or sul+hur content. 6,drogen 8steam9
reforming +roduces additional h,drogen for use in h,drogenation +rocessing.
Catalytic reforming
Catal,tic reforming +rocesses con$ert lo*-octane hea$, na+hthas into aromatic h,drocarons for
+etrochemical feedstoc.s and high-octane gasoline com+onents, called reformates2 , molecular
rearrangement or deh,drogenation. Be+ending on the feedstoc. and catal,sts, reformates can e
+roduced *ith $er, high concentrations of toluene, en"ene, 1,lene and other aromatics useful in
gasoline lending and +etrochemical +rocessing. 6,drogen, a significant ,-+roduct, is se+arated
from the reformate for rec,cling and use in other +rocesses. -he resultant +roduct de+ends on
reactor tem+erature and +ressure, the catal,st used and the h,drogen rec,cle rate. Some catal,tic
reformers o+erate at lo* +ressure and others at high +ressure. Some catal,tic reforming s,stems
continuousl, regenerate the catal,st, some facilities regenerate all of the reactors during
turnarounds, and others ta.e one reactor at a time off stream for catal,st regeneration.
In catal,tic reforming, na+htha feedstoc. is +retreated *ith h,drogen to remo$e contaminants
such as chlorine, sul+hur and nitrogen com+ounds, *hich could +oison the catal,st. -he +roduct
is flashed and fractionated in to*ers *here the remaining contaminants and gases are remo$ed.
-he desul+huri"ed na+htha feedstoc. is sent to the catal,tic reformer, *here it is heated to a
$a+our and +assed through a reactor *ith a stationar, ed of i-metallic or metallic catal,st
containing a small amount of +latinum, mol,denum, rhenium or other nole metals. -he t*o
+rimar, reactions *hich occur are +roduction of high-octane aromatics , remo$ing h,drogen
from the feedstoc. molecules, and the con$ersion of normal +araffins to ranched-chain or
iso+araffins.
In +latforming, another catal,tic reforming +rocess, feedstoc. *hich has not een
h,drodesul+huri"ed is comined *ith rec,cle gas and first +assed o$er a less e1+ensi$e catal,st.
An, remaining im+urities are con$erted to h,drogen sul+hide and ammonia, and remo$ed efore
the stream +asses o$er the +latinum catal,st. 6,drogen-rich $a+our is recirculated to inhiit
reactions *hich ma, +oison the catal,st. -he reactor out+ut is se+arated into li/uid reformate,
*hich is sent to a stri++ing to*er, and gas, *hich is com+ressed and rec,cled. 8See figure (<.9
:igure (<. Catal,tic reforming +rocess
!+erating +rocedures are needed to control hot s+ots during start-u+. Care must e ta.en not to
rea. or crush the catal,st *hen loading the eds, as small fines *ill +lug u+ the reformer
screens. )recautions against dust *hen regenerating or re+lacing catal,st are needed. Small
emissions of caron mono1ide and h,drogen sul+hide ma, occur during regeneration of catal,st.
2ater *ash should e considered *here staili"er fouling has occurred in reformers due to the
formation of ammonium chloride and iron salts. Ammonium chloride ma, form in +retreater
e1changers and cause corrosion and fouling. 6,drogen chloride, from the h,drogenation of
chlorine com+ounds, ma, form acids or ammonium chloride salt. -he +otential e1ists for
e1+osure to ali+hatic and aromatic na+hthas, h,drogen-rich +rocess gas, h,drogen sul+hide and
en"ene should a lea. or release occur.
3someri1ation
Isomeri"ation con$erts n-utane, n-+entane and n-he1ane into their res+ecti$e iso-+araffins.
Some of the normal straight-chain +araffin com+onents of light straight-run na+htha are lo* in
octane. -hese can e con$erted to high-octane, ranched-chain isomers , rearranging the onds
et*een atoms, *ithout changing the numer or .inds of atoms. Isomeri"ation is similar to
catal,tic reforming in that the h,drocaron molecules are rearranged, ut unli.e catal,tic
reforming, isomeri"ation 0ust con$erts normal +araffins to iso-+araffins. Isomeri"ation uses a
different catal,st than catal,tic reforming.
-he t*o distinct isomeri"ation +rocesses are utane 8C<9 and +entane=he1ane. 8CA=C59.
Jutane 8C<9 isomeri"ation +roduces feedstoc. for al.,lation. A lo*er-tem+erature +rocess uses
highl, acti$e aluminium chloride or h,drogen chloride catal,st *ithout fired heaters, to
isomeri"e n-utane. -he treated and +reheated feedstoc. is added to the rec,cle stream, mi1ed
*ith 6Cl and +assed through the reactor 8see figure (A9.
:igure (A. C< isomeri"ation
)entane=he1ane isomeri"ation is used to increase the octane numer , con$erting n-+entane and
n-he1ane. In a t,+ical +entane=he1ane isomeri"ation +rocess, dried and desul+huri"ed feedstoc.
is mi1ed *ith a small amount of organic chloride and rec,cled h,drogen, and heated to reactor
tem+erature. It is then +assed o$er su++orted-metal catal,st in the first reactor, *here en"ene
and olefins are h,drogenated. -he feed ne1t goes to the isomeri"ation reactor, *here the
+araffins are catal,ticall, isomeri"ed to iso+araffins, cooled and +assed to a se+arator. Se+arator
gas and h,drogen, *ith ma.e-u+ h,drogen, is rec,cled. -he li/uid is neutrali"ed *ith al.aline
materials and sent to a stri++er column, *here h,drogen chloride is reco$ered and rec,cled. 8See
figure (5.9
:igure (5. Isomeri"ation +rocess
If the feedstoc. is not com+letel, dried and desul+huri"ed, the +otential e1ists for acid formation,
leading to catal,st +oisoning and metal corrosion. 2ater or steam must not e allo*ed to enter
areas *here h,drogen chloride is +resent. )recautions are needed to +re$ent 6Cl from entering
se*ers and drains. -here is a +otential for e1+osure to iso+entane and ali+hatic na+htha $a+ours
and li/uid, as *ell as to h,drogen-rich +rocess gas, h,drochloric acid and h,drogen chloride, and
to dust *hen solid catal,st is used.
Hydrogen production $steam reforming%
6igh-+urit, h,drogen 8;A to ;;K9 is needed for h,drodesul+huri"ation, h,drogenation,
h,drocrac.ing and +etrochemical +rocesses. If not enough h,drogen is +roduced as ,-+roducts
of refiner, +rocesses to meet the total refiner, demand, the manufacture of additional h,drogen
is re/uired.
In h,drogen steam reforming, desul+huri"ed gases are mi1ed *ith su+erheated steam and
reformed in tues containing a nic.el ase catal,st. -he reformed gas, *hich consists of steam,
h,drogen, caron mono1ide and caron dio1ide, is cooled and +assed through con$erters *here
the caron mono1ide reacts *ith steam to form h,drogen and caron dio1ide. -he caron
dio1ide is scrued *ith amine solutions and $ented to the atmos+here *hen the solutions are
reacti$ated , heating. An, caron mono1ide remaining in the +roduct stream is con$erted to
methane. 8See figure (?.9
:igure (?. Steam reforming +rocess
Ins+ections and testing must e conducted *here the +ossiilit, e1ists for $al$e failure due to
contaminants in the h,drogen. Carr,o$er from caustic scruers to +re$ent corrosion in
+reheaters must e controlled and chlorides from the feedstoc. or steam s,stem +re$ented from
entering reformer tues and contaminating the catal,st. E1+osures can result from contamination
of condensate , +rocess materials such as caustics and amine com+ounds, and from e1cess
h,drogen, caron mono1ide and caron dio1ide. -he +otential e1ists for urns from hot gases
and su+erheated steam should a release occur.
&iscellaneous refinery processes
%uricant ase stoc+ and 4a" processes
Luricating oils and *a1es are refined from $arious fractions of atmos+heric and $acuum
distillation. 2ith the in$ention of $acuum distillation, it *as disco$ered that the *a1, residuum
made a etter luricant than an, of the animal fats that *ere then in use, *hich *as the
eginning of modern h,drocaron luricant refining technolog,, *hose +rimar, o0ecti$e is to
remo$e undesirale +roducts, such as as+halts, sul+honated aromatics and +araffinic and iso-
+araffinic *a1es from the residual fractions in order to +roduce high-/ualit, luricants. -his is
done , a series of +rocesses including de-as+halting, sol$ent e1traction and se+aration and
treatment +rocesses such as de*a1ing and h,drofinishing. 8See figure (49
:igure (4. Luricating oil M *a1 manufacturing +rocess
In e1traction +rocessing, reduced crude from the $acuum unit is +ro+ane de-as+halted and
comined *ith straight-run luricating-oil feedstoc., +reheated and sol$ent e1tracted to +roduce
a feedstoc. called raffinate. In a t,+ical e1traction +rocess *hich uses +henol as the sol$ent, the
feedstoc. is mi1ed *ith +henol in the treating section at tem+eratures elo* &'< IC. )henol is
then se+arated from the raffinate and rec,cled. -he raffinate ma, then e su0ected to another
e1traction +rocess *hich uses furfural to se+arate aromatic com+ounds from non-aromatic
h,drocarons, +roducing a lighter-coloured raffinate *ith im+ro$ed $iscosit, inde1 and
o1idation and thermal stailit,.
Be*a1ed raffinate ma, also e su0ect to further +rocessing to im+ro$e the /ualities of the ase
stoc.. Cla, adsorents are used to remo$e dar.-coloured, unstale molecules from luricating-
oil ase stoc.s. An alternate +rocess, lue h,drofinishing, +asses hot de*a1ed raffinate and
h,drogen through a catal,st that slightl, changes the molecular structure, resulting in a lighter-
coloured oil *ith im+ro$ed characteristics. -he treated lue oil ase stoc.s are then mi1ed and=or
com+ounded *ith additi$es to meet the re/uired +h,sical and chemical characteristics of motor
oils, industrial luricants and metal-*or.ing oils.
-he t*o distinct t,+es of *a1 deri$ed from crude oil are +araffin *a1, +roduced from distillate
stoc.s, and microcr,stalline *a1, manufactured from residual stoc.s. Raffinate from the
e1traction unit contains a considerale amount of *a1, *hich can e remo$ed , sol$ent
e1traction and cr,stalli"ation. -he raffinate is mi1ed *ith a sol$ent, such as +ro+ane, meth,l
eth,l .etone 8MEK9 and toluene mi1ture or meth,l isout,l .etone 8MIJK9, and +recooled in
heat e1changers. -he cr,stalli"ation tem+erature is attained , the e$a+oration of the +ro+ane in
the chiller and filter feed tan.s. -he *a1 is continuousl, remo$ed , filters and cold sol$ent
*ashed to reco$er retained oil. -he sol$ent is reco$ered from the de*a1ed raffinate , flashing
and steam stri++ing, and rec,cled.
-he *a1 is heated *ith hot sol$ent, chilled, filtered and gi$en a final *ash to remo$e all traces of
oil. Jefore the *a1 is used, it ma, e h,dro-finished to im+ro$e its odour and eliminate all traces
of aromatics so the *a1 can e used in food +rocessing. -he de*a1ed raffinate, *hich contains
small amounts of +araffins, na+hthenes and some aromatics, ma, e further +rocessed for use as
luricating-oil ase stoc.s.
Control of treater tem+erature is im+ortant to +re$ent corrosion from +henol. 2a1 can clog se*er
or oil drainage s,stems and interfere *ith *aste *ater treatment. -he +otential e1ists for
e1+osure to +rocess sol$ents such as +henol, +ro+ane, a meth,l eth,l .etone and toluene mi1ture
or meth,l isout,l .etone. Inhalation of h,drocaron gases and $a+ours, aromatic na+htha
containing en"ene, h,drogen sul+hide and h,drogen-rich +rocess gas is a ha"ard.
!sphalt processing
After +rimar, distillation o+erations, as+halt is a +ortion of residual matter *hich re/uires further
+rocessing to im+art characteristics re/uired , its final use. As+halt for roofing materials is
+roduced , air lo*ing. Residual is heated in a +i+e still almost u+ to its flash+oint and charged
to a lo*ing to*er *here hot air is in0ected for a +redetermined +eriod of time. -he deh,drogen
ation of the as+halt forms h,drogen sul+hide, and the o1idation creates sul+hur dio1ide. Steam is
used to lan.et the to+ of the to*er to entrain the contaminants, and is +assed through a scruer
to condense the h,drocarons.
@acuum distillation is generall, used to +roduce road tar as+halt. -he residual is heated and
charged to a column *here $acuum is a++lied to +re$ent crac.ing.
Condensed steam from the $arious as+halt +rocesses *ill contain trace amounts of h,drocarons.
An, disru+tion of the $acuum can result in the entr, of atmos+heric air and suse/uent fire. In
as+halt +roduction, raising the tem+erature of the $acuum to*er ottom to im+ro$e efficienc,
can generate methane , thermal crac.ing. -his creates $a+ours in as+halt storage tan.s *hich
are in the flammale range, ut not detectale , flash testing. Air lo*ing can create some
+ol,nuclear aromatics 8i.e., )A6s9. Condensed steam from the air lo*ing as+halt +rocess ma,
also contain $arious contaminants.
Hydrocarbon sweetening and treating processes
Man, +roducts, such as thermal na+hthas from $isrea.ing, co.ing or thermal crac.ing, and
high-sul+hur na+hthas and distillates from crude-oil distillation, re/uire treating in order to e
used in gasoline and fuel oil lends. Bistillation +roducts, including .erosene and other
distillates, ma, contain trace amounts of aromatics, and na+hthenes and luricating-oil ase
stoc.s ma, contain *a1. -hese undesirales are remo$ed either at intermediate refining stages or
0ust +rior to sending +roducts to lending and storage, , refining +rocesses such as sol$ent
e1traction and sol$ent de*a1ing. A $ariet, of intermediate and finished +roducts, including
middle distillates, gasoline, .erosene, 0et fuel and sour gases need to e dried and s*eetened.
-reating is +erformed either at an intermediate stage in the refining +rocess or 0ust efore
sending finished +roducts to lending and storage. -reating remo$es contaminants from oil, such
as organic com+ounds containing sul+hur, nitrogen and o1,gen, dissol$ed metals, inorganic salts
and solule salts dissol$ed in emulsified *ater. -reating materials include acids, sol$ents, al.alis
and o1idi"ing and adsor+tion agents. Acid treatments are used to im+ro$e the odour, colour and
other +ro+erties of lue ase stoc.s, to +re$ent corrosion and catal,st contamination, and to
im+ro$e +roduct stailit,. 6,drogen sul+hide *hich is remo$ed from Cdr,D sour gas , an
asoring agent 8diethanolamine9 is flared, used as a fuel or con$erted to sul+hur. -he t,+e of
treatment and agents de+ends on the crude feedstoc., intermediate +rocesses and end-+roduct
s+ecifications.
Solent treatment processes
Solvent e"traction se+arates aromatics, na+hthenes and im+urities from +roduct streams ,
dissol$ing or +reci+itation. Sol$ent e1traction +re$ents corrosion, +rotects catal,st in suse/uent
+rocesses and im+ro$es finished +roducts , remo$ing unsaturated, aromatic h,drocarons from
luricant and grease ase stoc.s.
-he feedstoc. is dried and su0ected to continuous countercurrent sol$ent treatment. In one
+rocess, feedstoc. is *ashed *ith a li/uid in *hich the sustances to e remo$ed are more
solule than in the desired resultant +roduct. In another +rocess, selected sol$ents are added,
causing im+urities to +reci+itate out of the +roduct. -he sol$ent is se+arated from the +roduct
stream , heating, e$a+oration or fractionation, *ith residual trace amounts suse/uentl,
remo$ed from the raffinate , steam stri++ing or $acuum flashing. Electric +reci+itation ma, e
used for se+aration of inorganic com+ounds. -he sol$ent is then regenerated to e used again in
the +rocess.
-,+ical chemicals used in the e1traction +rocess include a *ide $ariet, of acids, al.alis and
sol$ents, including +henol and furfural, as *ell as o1idi"ing agents and adsor+tion agents. In the
adsor+tion +rocess, highl, +orous solid materials collect li/uid molecules on their surfaces. -he
selection of s+ecific +rocesses and chemical agents de+ends on the nature of the feedstoc. eing
treated, the contaminants +resent and the finished +roduct re/uirements. 8See figure (;.9
:igure (;. Sol$ent e1traction +rocess
Solvent de4a"ing remo$es *a1 from either distillate or residual ase stoc.s, and ma, e a++lied
at an, stage in the refining +rocess. In sol$ent de*a1ing, *a1, feedstoc.s are chilled , heat
e1changer and refrigeration, and sol$ent is added to hel+ de$elo+ cr,stals that are remo$ed ,
$acuum filtration. -he de*a1ed oil and sol$ent are flashed and stri++ed, and the *a1 +asses
through a *ater settler, sol$ent fractionator and flash to*er. 8See figure &'.9
:igure &'. Sol$ent de*a1ing +rocess
Solvent de$asphalting se+arates hea$, oil fractions to +roduce hea$, luricating oil, catal,tic
crac.ing feedstoc. and as+halt. :eedstoc. and li/uid +ro+ane 8or he1ane9 are +um+ed to an
e1traction to*er at +recisel, controlled mi1tures, tem+eratures and +ressures. Se+aration occurs
in a rotating-disc contactor, ased on differences in soluilit,. -he +roducts are then e$a+orated
and steam stri++ed to reco$er +ro+ane for rec,cle. Sol$ent de-as+halting also remo$es sul+hur
and nitrogen com+ounds, metals, caron residues and +araffins from feedstoc.. 8See figure &(.9
:igure &(. Sol$ent de-as+halting +rocess
Health and safety considerations.
In sol$ent de*a1ing, disru+tion of the $acuum *ill create a +otential fire ha"ard , allo*ing air
to enter the unit. -he +otential e1ists for e1+osure to de*a1ing sol$ent $a+ours, a mi1ture of
MEK and toluene. Although sol$ent e1traction is a closed +rocess, there is +otential e1+osure to
carcinogenic )A6s in the +rocess oils and to e1traction sol$ents such as +henol, furfural, gl,col,
MEK, amines and other +rocess chemicals during handling and o+erations.
Be-as+halting re/uires e1act tem+erature and +ressure control to a$oid u+set. In addition,
moisture, e1cess sol$ent or a dro+ in o+erating tem+erature ma, cause foaming *hich affects the
+roduct tem+erature control and ma, create an u+set. Contact *ith hot oil streams *ill cause s.in
urns. -he +otential e1ists for e1+osure to hot oil streams containing carcinogenic +ol,c,clic
aromatic com+ounds, li/uefied +ro+ane and +ro+ane $a+ours, h,drogen sul+hide and sul+hur
dio1ide.
Hydrotreating processes
6,drotreating is used to remo$e aout ;'K of contaminants, including nitrogen, sul+hur, metals
and unsaturated h,drocarons 8olefins9, from li/uid +etroleum fractions such as straight-run
gasoline. 6,drotreating is similar to h,drocrac.ing in that oth the h,drogen and the catal,st are
used to enrich the h,drogen content of the olefin feedstoc.. 6o*e$er, the degree of saturation is
not as great as that achie$ed in h,drocrac.ing. -,+icall,, h,drotreating is done +rior to +rocesses
such as catal,tic reforming, so that the catal,st is not contaminated , untreated feedstoc..
6,drotreating is also used efore catal,tic crac.ing to reduce sul+hur and im+ro$e +roduct
,ields, and to u+grade middle distillate +etroleum fractions into finished .erosene, diesel fuel
and heating fuel oils.
6,drotreating +rocesses differ de+ending u+on the feedstoc.s and catal,sts.
6,drodesul+huri"ation remo$es sul+hur from .erosene, reduces aromatics and gum-forming
characteristics, and saturates an, olefins. 6,droforming is a deh,drogenation +rocess used to
reco$er e1cess h,drogen and +roduce high-octane gasoline. 6,drotreated +roducts are lended
or used as catal,tic reforming feedstoc..
In catalytic hydrodesulphuri1ation, the feedstoc. is de-aerated, mi1ed *ith h,drogen, +reheated
and charged under high +ressure through a fi1ed-ed catal,tic reactor. -he h,drogen is se+arated
and rec,cled and the +roduct staili"ed in a stri++er column *here the light ends are remo$ed.
Buring this +rocess, sul+hur and nitrogen com+ounds +resent in the feedstoc. are con$erted to
h,drogen sul+hide 86&S9 and ammonia 8>679. Residual h,drogen sul+hide and ammonia are
remo$ed either , steam stri++ing, , a comination high- and lo*-+ressure se+arator or ,
amine *ash *hich reco$ers h,drogen sul+hide in a highl, concentrated stream suitale for
con$ersion into elemental sul+hur. 8See figure && and figure &7.9
:igure &&. 6,drodesul+huri"ation +rocess
:igure &7. Schematic of h,drodesul+huri"ation +rocess
In h,drotreating, the h,drogen sul+hide content of the feedstoc. must e strictl, controlled to a
minimum to reduce corrosion. 6,drogen chloride ma, form and condense as h,drochloric acid
in the lo*er-tem+erature +ortions of the unit. Ammonium h,drosul+hide ma, form in high-
tem+erature, high-+ressure units. In the e$ent of a release, there is a +otential for e1+osure to
aromatic na+htha $a+ours *hich contain en"ene, h,drogen sul+hide or h,drogen gas, or to
ammonia should a sour *ater lea. or s+ill occur. )henol ma, also e +resent if high-oiling-
+oint feedstoc.s are +rocessed.
E1cessi$e contact time and=or tem+erature *ill create co.ing in the unit. )recautions need to e
ta.en *hen unloading co.ed catal,st from the unit to +re$ent iron sul+hide fires. -he co.ed
catal,st should e cooled to elo* <; IC efore remo$al, or dum+ed into nitrogen-inerted ins
*here it can e cooled efore further handling. S+ecial anti-foam additi$es ma, e used to
+re$ent catal,st +oisoning from silicone carr,o$er in co.er feedstoc..
'ther sweetening and treating processes
-reatment, dr,ing and s*eetening +rocesses are used to remo$e im+urities from lending stoc.s.
8See figure &<.9
:igure &<. S*eetening M treating +rocesses
S*eetening +rocesses use air or o1,gen. If e1cess o1,gen enters these +rocesses, it is +ossile
for a fire to occur in the settler due to the generation of static electricit,. -here is a +otential for
e1+osure to h,drogen sul+hide, sul+hur dio1ide, caustic 8sodium h,dro1ide9, s+ent caustic, s+ent
catal,st 8Mero19, catal,st dust and s*eetening agents 8sodium caronate and sodium
icaronate9.
!mine 'acid gas treatment) plants
Sour gas 8fuel gas from +rocesses such as catal,tic crac.ing and h,drotreating, *hich contains
h,drogen sul+hide and caron dio1ide9 must e treated efore it can e used as refiner, fuel.
Amine +lants remo$e acid contaminants from sour gas and h,drocaron streams. In amine
+lants, gas and li/uid h,drocaron streams containing caron dio1ide and=or h,drogen sul+hide
are charged to a gas asor+tion to*er or li/uid contactor, *here the acid contaminants are
asored , counterflo*ing amine solutionsFmonoethanolamine 8MEA9, diethanolamine
8BEA9 or meth,ldiethanolamine 8MBEA9. -he stri++ed gas or li/uid is remo$ed o$erhead, and
the amine is sent to a regenerator. In the regenerator, the acidic com+onents are stri++ed , heat
and reoiling action, and dis+osed of, *hile the amine is rec,cled.
In order to minimi"e corrosion, +ro+er o+erating +ractices should e estalished, and regenerator
ottom and reoiler tem+eratures need to e controlled. !1,gen should e .e+t out of the s,stem
to +re$ent amine o1idation. -here is +otential for e1+osure to amine com+ounds 8i.e., MEA,
BEA, MBEA9, h,drogen sul+hide and caron dio1ide.
S4eetening and drying
S*eetening 8merca+tan remo$al9 treats sul+hur com+ounds 8h,drogen sul+hide, thio+hene and
merca+tan9 to im+ro$e colour, odour and o1idation stailit,, and reduces concentrations of
caron dio1ide in gasoline. Some merca+tans are remo$ed , ha$ing the +roduct ma.e contact
*ith *ater-solule chemicals 8e.g., sul+huric acid9 that react *ith the merca+tans. Caustic li/uid
8sodium h,dro1ide9, amine com+ounds 8diethanolamine9 or fi1ed-ed catal,st s*eetening ma,
e used to con$ert merca+tans to less o0ectionale disul+hides.
)roduct dr,ing 8*ater remo$al9 is accom+lished , *ater asor+tion, *ith or *ithout adsor+tion
agents. Some +rocesses simultaneousl, dr, and s*eeten , adsor+tion on molecular sie$es.
Sulphur recovery
Sul+hur reco$er, remo$es h,drogen sul+hide from sour gases and h,drocaron streams. -he
Clause +rocess con$erts h,drogen sul+hide to elemental sul+hur through the use of thermal and
catal,tic reactions. After urning h,drogen sul+hide under controlled conditions, .noc.out +ots
remo$e *ater and h,drocarons from feed-gas streams, *hich are then e1+osed to a catal,st to
reco$er additional sul+hur. -he sul+hur $a+our from urning and con$ersion is condensed and
reco$ered.
0ail gas treatment
Joth o1idation and reduction are used to treat tail gas from sul+hur reco$er, units, de+ending on
the com+osition of the gas and on refiner, economics. !1idation +rocesses urn tail gas to
con$ert all sul+hur com+ounds to sul+hur dio1ide, and reduction +rocesses con$ert sul+hur
com+ounds to h,drogen sul+hide.
Hydrogen sulphide scruing
6,drogen sul+hide scruing is a +rimar, h,drocaron feedstoc. treating +rocess used to
+re$ent catal,st +oisoning. Be+ending on the feedstoc. and the nature of the contaminants,
desul+huri"ation methods *ill $ar, from amient-tem+erature-acti$ated charcoal asor+tion to
high-tem+erature catal,tic h,drogenation follo*ed , "inc o1ide treating.
Sat and unsat gas plants
:eedstoc.s from $arious refiner, units are sent to gas treating +lants, *here utanes and utenes
are remo$ed for use as al.,lation feedstoc., hea$ier com+onents are sent to gasoline lending,
+ro+ane is reco$ered for L)# and +ro+,lene is remo$ed for use in +etrochemicals.
Sat gas plants se+arate com+onents from refiner, gases, including utanes for al.,lation,
+entanes for gasoline lending, L)#s for fuel and ethane for +etrochemicals. -here are t*o
different sat gas +rocesses: asor+tion-fractionation or straight fractionation. In asor+tion-
fractionation, gases and li/uids from $arious units are fed to an asorer=de-ethani"er *here C&
and lighter fractions are se+arated , lean-oil asor+tion and remo$ed for use as fuel gas or
+etrochemical feed. -he remaining hea$ier fractions are stri++ed and sent to a deutani"er, and
the lean oil is rec,cled ac. to the asorer=de-ethani"er. C7=C< is se+arated from +entanes in the
deutani"er, scrued to remo$e h,drogen sul+hide, and fed to a s+litter to se+arate +ro+ane and
utane. -he asor+tion stage is eliminated in fractionation +lants. Sat gas +rocesses de+end on
feedstoc. and +roduct demand.
Corrosion occurs from the +resence of h,drogen sul+hide, caron dio1ide and other com+ounds
as a result of +rior treating. Streams containing ammonia should e dried efore +rocessing.
Anti-fouling additi$es are used in asor+tion oil to +rotect heat e1changers. Corrosion inhiitors
are used to control corrosion in o$erhead s,stems. -he +otential e1ists for e1+osure to h,drogen
sul+hide, caron dio1ide, sodium h,dro1ide, MEA, BEA and MBEA to e carried o$er from
+rior treating.
5nsat gas plants reco$er light h,drocarons from *et gas streams from catal,tic crac.ers and
dela,ed co.er o$erhead accumulators or fractionation recei$ers. In a t,+ical +rocess, *et gases
are com+ressed and treated *ith amine to remo$e h,drogen sul+hide either efore or after
entering a fractionating asorer, *here the, mi1 into a concurrent flo* of deutani"ed gasoline.
-he light fractions are se+arated , heat in a reoiler, *ith the offgas sent to a s+onge asorer
and the ottoms sent to a deutani"er. A +ortion of the deutani"ed h,drocaron is rec,cled, and
the alance goes to a s+litter for se+aration. !$erhead gases go to a de+ro+ani"er for use as
al.,lation unit feedstoc.. 8See figure &A.9
:igure &A. Ensat gas +lant +rocess
Corrosion can occur from moist h,drogen sul+hide and c,anides in unsat gas +lants *hich
handle :CC feedstoc.s. Corrosion from h,drogen sul+hide and de+osits in the high-+ressure
sections of gas com+ressors from ammonium com+ounds is +ossile *hen feedstoc.s are from
the dela,ed co.er or the -CC. -he +otential e1ists for e1+osure to h,drogen sul+hide and to
amine com+ounds such as MEA, BEA and MBEA.
(asoline) distillate fuel and lubricant base stock blending processes
Jlending is the +h,sical mi1ture of a numer of different li/uid h,drocaron fractions to +roduce
finished +roducts *ith s+ecific desired characteristics. )roducts can e lended in-line through a
manifold s,stem or atch lended in tan.s and $essels. In-line lending of gasoline, distillates,
0et fuel and luricant ase stoc.s is accom+lished , in0ecting +ro+ortionate amounts of each
com+onent into the main stream *here turulence +romotes thorough mi1ing.
#asolines are lends of reformates, al.,lates, straight-run gasoline, thermal and
catal,ticall, crac.ed gasolines, co.er gasoline, utane and a++ro+riate additi$es.
:uel oil and diesel fuel are lends of distillates and c,cle oils, and 0et fuel ma, e
straight-run distillate or lended *ith na+htha.
Luricating oils are lends of refined ase stoc.s
As+halt is lended from $arious residual stoc.s de+ending on its intended use.

Additi$es are often mi1ed into gasoline and motor fuels during or after lending to +ro$ide
s+ecific +ro+erties not inherent in +etroleum h,drocarons. -hese additi$es include octane
enhancers, anti-.noc. agents, anti-o1idants, gum inhiitors, foam inhiitors, rust inhiitors,
carurettor 8caron9 cleaners, detergents for in0ector cleaning, diesel odouri"ers, colour d,es,
distillate anti-static, gasoline o1idi"ers such as methanol, ethanol and meth,l tertiar, ut,l ether,
metal deacti$ators and others.
Jatch and in-line lending o+erations re/uire strict controls to maintain desired +roduct /ualit,.
S+ills should e cleaned and lea.s re+aired to a$oid sli+s and falls. Additi$es in drums and ags
need to e handled +ro+erl, to a$oid strain and e1+osure. -he +otential for contacting ha"ardous
additi$es, chemicals, en"ene and other materials e1ists during lending, and a++ro+riate
engineering controls, +ersonal +rotecti$e e/ui+ment and +ro+er h,giene are needed to minimi"e
e1+osures.
Au'iliary Refinery Operations
Au1iliar, o+erations su++orting refiner, +rocesses include those *hich +ro$ide +rocess heat and
cooling3 +ro$ide +ressure relief3 control air emissions3 collect and treat *aste *ater3 +ro$ide
utilities such as +o*er, steam, air and +lant gases3 and +um+, store, treat and cool +rocess *ater.
*aste water treatment
Refiner, *aste *ater includes condensed steam, stri++ing *ater, s+ent caustic solutions, cooling
to*er and oiler lo*do*n, *ash *ater, al.aline and acid *aste neutrali"ation *ater and other
+rocess-associated *ater. 2aste *ater t,+icall, contains h,drocarons, dissol$ed materials,
sus+ended solids, +henols, ammonia, sul+hides and other com+ounds. 2aste *ater treatment is
used for +rocess *ater, runoff *ater and se*erage *ater +rior to their discharge. -hese
treatments ma, re/uire +ermits, or there must e rec,cling.
-he +otential e1ists for fire should $a+ours from *aste *ater containing h,drocarons reach a
source of ignition during the treatment +rocess. -he +otential e1ists for e1+osure to the $arious
chemicals and *aste +roducts during +rocess sam+ling, ins+ection, maintenance and
turnarounds.
(retreatment
)retreatment is the initial se+aration of h,drocarons and solids from *aste *ater. A)I
se+arators, interce+tor +lates and settling +onds are used to remo$e sus+ended h,drocarons, oil,
sludge and solids , gra$it, se+aration, s.imming and filtration. Acidic *aste *ater is
neutrali"ed *ith ammonia, lime or soda ash. Al.aline *aste *ater is treated *ith sul+huric acid,
h,drochloric acid, caron dio1ide-rich flue gas or sul+hur. Some oil-in-*ater emulsions are first
heated to hel+ se+arate the oil and the *ater. #ra$it, se+aration de+ends on the different s+ecific
gra$ities of *ater and immiscile oil gloules, *hich allo*s free oil to e s.immed off the
surface of the *aste *ater.
Sour 4ater stripping
2ater containing sul+hides, called sour *ater, is +roduced in catal,tic crac.ing and h,dro-
treating +rocesses, and *hene$er steam is condensed in the +resence of gases containing
h,drogen sul+hide.
Stri++ing is used on *aste *ater containing sul+hides and=or ammonia, and sol$ent e1traction is
used to remo$e +henols from *aste *ater. 2aste *ater *hich is to e rec,cled ma, re/uire
cooling to remo$e heat and=or o1idation , s+ra,ing or air stri++ing to remo$e an, remaining
+henols, nitrates and ammonia.
Secondary treatment
:ollo*ing +retreatment, sus+ended solids are remo$ed , sedimentation or air flotation. 2aste
*ater *ith lo* le$els of solids is screened or filtered, and flocculation agents ma, e added to
hel+ se+aration. Materials *ith high adsor+tion characteristics are used in fi1ed-ed filters or
added to the *aste *ater to form a slurr, *hich is remo$ed , sedimentation or filtration.
Secondar, treatment +rocesses iologicall, degrade and o1idi"e solule organic matter , the
use of acti$ated sludge, unaerated or aerated lagoons, tric.ling filter methods or anaeroic
treatments. Additional treatment methods are used to remo$e oils and chemicals from *aste
*ater.
0ertiary treatment
-ertiar, treatments remo$e s+ecific +ollutants in order to meet regulator, discharge
re/uirements. -hese treatments include chlorination, o"onation, ion e1change, re$erse osmosis,
acti$ated caron adsor+tion, and others. Com+ressed o1,gen ma, e diffused into *aste *ater
streams to o1idi"e certain chemicals or to satisf, regulator, o1,gen content re/uirements.
Cooling towers
Cooling to*ers remo$e heat from +rocess *ater , e$a+oration and latent heat transfer et*een
hot *ater and air. -he t*o t,+es of to*ers are counterflo* and crossflo*.
In counterflo* cooling, hot +rocess *ater is +um+ed to the u++ermost +lenum and
allo*ed to fall through the to*er. >umerous slats, or s+ra, no""les, are located
throughout the length of the to*er to dis+erse the *ater flo* and hel+ in cooling.
Simultaneousl,, air enters at the to*er ottom, creating a concurrent flo* of air against
the *ater. Induced draft to*ers ha$e the fans at the air outlet. :orced draft to*ers ha$e
the fans or lo*ers at the air inlet.
Crossflo* to*ers introduce airflo* at right angles to the *ater flo* throughout the
structure.

Recirculated cooling *ater must e treated to remo$e im+urities and an, dissol$ed
h,drocarons. Im+urities in cooling *ater can corrode and foul +i+ing and heat e1changers, scale
from dissol$ed salts can de+osit on +i+es, and *ooden cooling to*ers can e damaged , micro-
organisms.
Cooling to*er *ater can e contaminated , +rocess materials and ,-+roducts, including
sul+hur dio1ide, h,drogen sul+hide and caron dio1ide, *ith resultant e1+osures. -here is
+otential for e1+osure to *ater treatment chemicals or to h,drogen sul+hide *hen *aste *ater is
treated in con0unction *ith cooling to*ers. Jecause the *ater is saturated *ith o1,gen from
eing cooled *ith air, the chances for corrosion are intensified. !ne means of corrosion
+re$ention is the addition of a material to the cooling *ater *hich forms a +rotecti$e film on
+i+es and other metal surfaces.
2hen cooling *ater is contaminated , h,drocarons, flammale $a+ours can e$a+orate into the
discharge air. If a source of ignition or lightning is +resent, fires ma, start. :ire ha"ards e1ist
*hen there are relati$el, dr, areas in induced-draft cooling to*ers of comustile construction.
Loss of +o*er to cooling to*er fans or *ater +um+s can create serious conse/uences in +rocess
o+erations.
Steam generation
Steam is +roduced through heater and oiler o+erations in central steam generation +lants and at
$arious +rocess units, using heat from flue gas or other sources. Steam generation s,stems
include:
heaters 8furnaces9, *ith their urners and a comustion air s,stem
draft or +ressure s,stems to remo$e flue gas from the furnace, soot lo*ers, and
com+ressed air s,stems *hich seal o+enings to +re$ent flue gas from esca+ing
oilers, consisting of a numer of tues *hich carr, the *ater=steam mi1ture through the
furnace +ro$iding for ma1imum heat transfer 8these tues run et*een steam distriution
drums at the to+ of the oiler, and *ater collecting drums at the ottom of the oiler9
steam drums to collect steam and direct it to the su+erheater efore it enters the steam
distriution s,stem.

-he most +otentiall, ha"ardous o+eration in steam generation is heater start-u+. A flammale
mi1ture of gas and air can uild u+ as a result of loss of flame at one or more urners during
light-off. S+ecific start-u+ +rocedures are re/uired for each different t,+e of unit, including
+urging efore light-off and emergenc, +rocedures in the e$ent of misfire or loss of urner
flame. If feed*ater runs lo* and oilers are dr,, the tues *ill o$erheat and fail. E1cess *ater
*ill e carried o$er into the steam distriution s,stem, causing damage to the turines. Joilers
should ha$e continuous or intermittent lo*do*n s,stems to remo$e *ater from steam drums
and to limit uild-u+ of scale on turine lades and su+erheater tues. Care must e ta.en not to
o$erheat the su+erheater during start-u+ and shut do*n. Alternate fuel sources should e
+ro$ided in e$ent of loss of fuel gas due to refiner, unit shutdo*n or emergenc,.
Heater fuel
An, one or an, comination of fuels, including refiner, gas, natural gas, fuel oil and +o*dered
coal ma, e used in heaters. Refiner, off-gas is collected from +rocess units and comined *ith
natural gas and L)# in a fuel gas alance drum. -he alance drum +ro$ides constant s,stem
+ressure, fairl, stale J-E 8energ,9 content fuel and automatic se+aration of sus+ended li/uids
in gas $a+ours, and +re$ents carr,o$er of large slugs of condensate into the distriution s,stem.
:uel oil is t,+icall, a mi1 of refiner, crude oil and straight-run and crac.ed residues, lended
*ith other +roducts. -he fuel oil s,stem deli$ers fuel to +rocess unit heaters and steam
generators at re/uired tem+eratures and +ressures. -he fuel oil is heated to +um+ing tem+erature,
suc.ed through a coarse suction strainer, +um+ed to a tem+erature-control heater and then
through a fine mesh strainer efore eing urned. Knoc.out +ots, +ro$ided at +rocess units, are
used to remo$e li/uids from fuel gas efore urning.
In one e1am+le of +rocess unit heat generation, caron mono1ide 8C!9 oilers reco$er heat in
catal,tic crac.ing units as caron mono1ide in flue gas is urned to com+lete comustion. In
other +rocesses, *aste heat reco$er, units use heat from the flue gas to ma.e steam.
Steam distriution
Steam t,+icall, is generated , heaters and oilers comined into one unit. Steam lea$es the
oilers at the highest +ressure re/uired , the +rocess units or the electrical generator. -he steam
+ressure is then reduced in turines *hich dri$e +rocess +um+s and com+ressors. 2hen refiner,
steam is also used to dri$e steam turine generators to +roduce electricit,, the steam must e
+roduced at much higher +ressure than re/uired for +rocess steam. -he steam distriution s,stem
consists of $al$es, fittings, +i+ing and connections *hich are suitale for the +ressure of the
steam trans+orted. Most steam used in the refiner, is condensed to *ater in heat e1changers and
reused as oiler feed*ater, or discharged to *aste *ater treatment.
Steam feed4ater
:eed*ater su++l, is an im+ortant +art of steam generation. -here must al*a,s e as man,
+ounds of *ater entering the steam generation s,stem as there are +ounds of steam lea$ing it.
2ater used in steam generation must e free of contaminants, including minerals and dissol$ed
im+urities, *hich can damage the s,stem or affect the o+eration. Sus+ended materials such as
silt, se*age and oil, *hich form scale and sludge, are coagulated or filtered out of the *ater.
Bissol$ed gases, +articularl, caron dio1ide and o1,gen *hich cause oiler corrosion, are
remo$ed , de-aeration and treatment. Bissol$ed minerals such as metallic salts, calcium and
caronates, *hich cause scale, corrosion and turine lade de+osits, are treated *ith lime or soda
ash to +reci+itate them out of the *ater. Be+ending on its characteristics, ra* oiler feed*ater
ma, e treated , clarification, sedimentation, filtration, ion e1change, de-aeration and internal
treatment. Recirculated cooling *ater must also e treated to remo$e h,drocarons and other
contaminants.
Process heaters) heat exchangers and coolers
)rocess heaters and heat e1changers +reheat feedstoc.s in distillation to*ers and in refiner,
+rocesses to reaction tem+eratures. -he ma0or +ortion of heat +ro$ided to +rocess units comes
from fired heaters found on crude and reformer +reheater units, co.er heaters and large-column
reoilers, *hich are fueled , refiner, or natural gas, distillate and residual oils. 6eaters are
usuall, designed for s+ecific +rocess o+erations, and most are either c,lindrical $ertical or o1-
t,+e designs. 6eat e1changers use either steam or hot h,drocaron, transferred from some other
section of the +rocess, for heat in+ut.
6eat is also remo$ed from some +rocesses , air and *ater e1changers, fin fans, gas and li/uid
coolers and o$erhead condensers, or , transferring the heat to other s,stems. -he asic
mechanical $a+our com+ression refrigeration s,stem is designed to ser$e one or more +rocess
units, and includes an e$a+orator, com+ressor, condenser, controls and +i+ing. Common coolants
are *ater, alcohol=*ater mi1ture or $arious gl,col solutions.
A means of +ro$iding ade/uate draft or steam +urging is re/uired to reduce the chance of
e1+losions *hen lighting fires in heater furnaces. S+ecific start-u+ and emergenc, +rocedures are
re/uired for each t,+e of unit. If fire im+inges on fin fans, failure could occur due to o$erheating.
If flammale +roduct esca+es from a heat e1changer or cooler due to a lea., a fire could occur.
Care must e ta.en to assure that all +ressure is remo$ed from heater tues efore remo$ing an,
header or fitting +lugs. Consideration should e gi$en to +ro$iding for +ressure relief in heat
e1changer +i+ing s,stems in the e$ent the, are loc.ed off *hile full of li/uid. If controls fail,
$ariations of tem+erature and +ressure could occur on either side of the heat e1changer. If heat
e1changer tues fail and +rocess +ressure is greater than heater +ressure, +roduct could enter the
heater *ith do*nstream conse/uences. If the +ressure is less, the heater stream could enter into
the +rocess fluid stream. If loss of circulation occurs in li/uid or gas coolers, increased +roduct
tem+erature could affect do*nstream o+erations, re/uiring +ressure relief.
Be+ending on the fuel, +rocess o+eration and unit design, there is a +otential for e1+osure to
h,drogen sul+hide, caron mono1ide, h,drocarons, steam oiler feed*ater sludge and *ater
treatment chemicals. S.in contact *ith oiler lo*do*n *hich ma, contain +henolic com+ounds
should e a$oided. E1+osure to radiant heat, su+erheated steam and hot h,drocarons is +ossile.
Pressure relief and flare systems
Engineering controls *hich are incor+orated into +rocesses include reducing flammale $a+our
concentrations , $entilation, dilution and inerting. )ressuri"ation is used to maintain control
rooms ao$e atmos+heric +ressure in order to reduce the +ossiilit, of $a+ours entering. )ressure
relief s,stems are +ro$ided to control $a+ours and li/uids *hich are released , +ressure-
relie$ing de$ices and lo*do*ns. )ressure relief is an automatic, +lanned release *hen
o+erating +ressure reaches a +redetermined le$el. Jlo*do*n usuall, refers to the intentional
release of material, such as lo*do*ns from +rocess unit start-u+s, furnace lo*do*ns,
shutdo*ns and emergencies. @a+our de+ressuring is the ra+id remo$al of $a+ours from +ressure
$essels in case of emergenc,. -his ma, e accom+lished , the use of a ru+ture disc, usuall, set
at a higher +ressure than the relief $al$e.
Safety relief valves
Safet, relief $al$es, used to control air, steam, gas and h,drocaron $a+our and li/uid +ressures,
o+en in +ro+ortion to the increase in +ressure o$er the normal o+erating +ressure. Safet, $al$es,
designed +rimaril, to release high $olumes of steam, usuall, +o+ o+en to full ca+acit,. -he
o$er+ressure needed to o+en li/uid relief $al$es, *here large-$olume discharge is not re/uired,
increases as the $al$e lifts due to increased s+ring resistance. )ilot-o+erated safet, release
$al$es, *ith u+ to si1 times the ca+acit, of normal relief $al$es, are used *here tighter sealing
and larger-$olume discharges are re/uired. >on-$olatile li/uids are usuall, +um+ed to oil=*ater
se+aration and reco$er, s,stems, and $olatile li/uids are sent to units o+erating at a lo*er
+ressure.
Flares
A t,+ical closed +ressure-release and flare s,stem includes relief $al$es and lines from +rocess
units for collection of discharges, .noc.out drums to se+arate $a+ours and li/uids, seals and=or
+urge gas for flashac. +rotection and a flare and igniter s,stem, *hich comusts $a+ours if
discharge direct to the atmos+here is not +ermitted. Steam ma, e in0ected into the flare ti+ to
reduce $isile smo.e.
Li/uids should not e allo*ed to discharge to a $a+our dis+osal s,stem. :lare .noc.out drums
and flares need to e large enough to handle emergenc, lo*do*ns, and drums re/uire relief in
e$ent of o$er+ressure. )ro$ide +ressure relief $al$es *here the +otential e1ists for o$er+ressure
in refiner, +rocesses, such as due to the follo*ing causes:
loss of cooling *ater, +ossil, resulting in a greatl, increased +ressure dro+ in
condensers, in turn increasing the +ressure in the +rocess unit
ra+id $a+ori"ation and +ressure increase from in0ection of a lo*er-oiling-+oint li/uid,
including *ater, into a +rocess $essel o+erating at higher tem+eratures
e1+ansion of $a+our and resultant o$er+ressure due to o$erheated +rocess steam,
malfunctioning heaters or fire
failure of automatic controls, closed outlets, heat e1changer failure, etc.
internal e1+losion, chemical reaction, thermal e1+ansion, accumulated gases, etc.
loss of reflu1, causing a +ressure rise in distillation to*ers.
Jecause the /uantit, of reflu1 affects the $olume of $a+ours lea$ing the distillation to*er, loss of
$olume causes a +ressure dro+ in condensers and a +ressure rise in distillation to*ers.
Maintenance is im+ortant ecause $al$es are re/uired to function +ro+erl,. Common $al$e
o+erating +rolems include:
failure to o+en at set +ressure due to +lugging of the $al$e inlet or outlet or , corrosion,
+re$enting +ro+er o+eration of the disc holder and guides
failure to reseat after +o++ing o+en due to fouling, corrosion or de+osits on the seat or
mo$ing +arts, or , solids in the gas stream cutting the $al$e disc
chattering and +remature o+ening, due to o+erating +ressure eing too close to the $al$e
set +oint.

+tilities
-ater. Be+ending on location and communit, resources, refineries ma, dra* u+on +ulic *ater
su++lies for drin.ing and +rocess *ater or ma, ha$e to +um+ and treat their o*n +otale *ater.
-reatment ma, include a *ide range of re/uirements, from desalting to filtration, chlorination
and testing.
Se4age. Also, de+ending on a$ailailit, of communit, or +ri$ate offsite treatment +lants,
refineries ma, ha$e to +ro$ide for the +ermitting, collection, treatment and discharge of their
sanitar, *aste.
Electric po4er. Refineries either recei$e electricit, from outside sources or +roduce their o*n,
using electric generators dri$en , steam turines or gas engines. Areas are classified *ith regard
to the t,+e of electrical +rotection re/uired to +re$ent a s+ar. from igniting $a+ours or contain an
e1+losion *ithin electrical e/ui+ment. Electrical sustations, *hich are normall, located in non-
classified areas, a*a, from sources of flammale h,drocaron $a+our or cooling to*er *ater
s+ra,, contain transformers, circuit rea.ers and feed circuit s*itches. Sustations feed +o*er to
distriution stations *ithin the +rocess unit areas. Bistriution stations can e located in
classified areas, +ro$ided that electrical classification re/uirements are met. Bistriution stations
t,+icall, use a li/uid-filled transformer +ro$ided *ith an oil-filled or air-rea. disconnect
de$ice.
>ormal electrical safet, +recautions, including dr, footing, Chigh $oltageD *arning signs and
guarding should e im+lemented to +rotect against electrocution. Em+lo,ees should e familiar
*ith refiner, electrical safe *or. +rocedures. Loc.out=tagout and other a++ro+riate safe *or.
+ractices should e im+lemented to +re$ent energi"ing *hile *or. is eing +erformed on high-
$oltage electrical e/ui+ment. 6a"ardous e1+osures ma, occur *hen *or.ing around
transformers and s*itches *hich contain a dielectric fluid re/uiring s+ecial handling +recautions.
-hese su0ects are discussed more full, else*here in this Encyclopaedia.
"urbine) gas and air compressor operations
!ir and gas compressors
Refiner, e1haust $entilation and air su++l, s,stems are designed to ca+ture or dilute gases,
fumes, dusts and $a+ours *hich ma, contaminate *or.ing s+aces or the outside atmos+here.
Ca+tured contaminants are reclaimed if feasile, or directed to dis+osal s,stems after eing
cleaned or urned. Air su++l, s,stems include com+ressors, coolers, air recei$ers, air dr,ers,
controls and distriution +i+ing. Jlo*ers are also used to +ro$ide air to certain +rocesses. )lant
air is +ro$ided for the o+eration of air-+o*ered tools, catal,st regeneration, +rocess heaters,
steam-air deco.ing, sour *ater o1idation, gasoline s*eetening, as+halt lo*ing and other uses.
Instrument air is +ro$ided for use in +neumatic instruments and controls, air motors and +urge
connections. )lant gas, such as nitrogen, is +ro$ided for inerting $essels and other uses. Joth
reci+rocating and centrifugal com+ressors are used for gas and com+ressed air.
Air com+ressors should e located so that the suction does not ta.e in flammale $a+ours or
corrosi$e gases. -here is a +otential for fire should a lea. occur in gas com+ressors. Knoc.out
drums are needed to +re$ent li/uid surges from entering gas com+ressors. If gases are
contaminated *ith solid materials, strainers are needed. :ailure of automatic com+ressor controls
*ill affect +rocesses. If ma1imum +ressure could +otentiall, e greater than com+ressor or
+rocess e/ui+ment design +ressure, +ressure relief should e +ro$ided. #uarding is needed for
e1+osed mo$ing +arts on com+ressors. Com+ressor uildings should e +ro+erl, electricall,
classified, and +ro$isions made for +ro+er $entilation.
2here +lant air is used as ac.-u+ to instrument air, interconnections must e u+stream of the
instrument air dr,ing s,stem to +re$ent contamination of instruments *ith moisture. Alternate
sources of instrument air su++l,, such as use of nitrogen, ma, e needed in the e$ent of +o*er
outages or com+ressor failure. A++l, a++ro+riate safeguards so that gas, +lant air and instrument
air are not used as the source for reathing or for +ressuring +otale *ater s,stems.
0urines
-urines are usuall, gas or steam +o*ered and are used to dri$e +um+s, com+ressors, lo*ers
and other refiner, +rocess e/ui+ment. Steam enters turines at high tem+eratures and +ressures,
e1+anding across and dri$ing rotating lades *hile directed , fi1ed lades.
Steam turines used for e1haust o+erating under $acuum need a safet, relief $al$e on the
discharge side for +rotection and to maintain steam in e$ent of $acuum failure. 2here ma1imum
o+erating +ressure could e greater than design +ressure, steam turines need relief de$ices.
Consideration should e gi$en to +ro$iding go$ernors and o$ers+eed-control de$ices on turines.
Pumps) Piping and ,ales
Centrifugal and +ositi$e dis+lacement 8reci+rocating9 +um+s are used to mo$e h,drocarons,
+rocess *ater, fire *ater and *aste *ater throughout the refiner,. )um+s are dri$en , electric
motors, steam turines or internal comustion engines.
)rocess and utilit, +i+ing s,stems distriute h,drocarons, steam, *ater and other +roducts
throughout the facilit,. -he, are si"ed and constructed of materials de+endent on the t,+e of
ser$ice, +ressure, tem+erature and nature of the +roducts. -here are $ent, drain and sam+le
connections on +i+ing, as *ell as +ro$isions for lan.ing. Bifferent t,+es of $al$es, including
gate $al$es, ,+ass $al$es, gloe and all $al$es, +lug $al$es, loc. and leed $al$es and chec.
$al$es are used, de+ending on their o+erating +ur+ose. -hese $al$es can e o+erated manuall, or
automaticall,.
@al$es and instrumentation *hich re/uire ser$icing or other *or. should e accessile at grade
le$el or from an o+erating +latform. Remote-controlled $al$es, fire $al$es and isolation $al$es
ma, e used to limit the loss of +roduct at +um+ suction lines in the e$ent of lea.age or fire.
!+erating $ent and drain connections ma, e +ro$ided *ith doule loc. $al$es, or a loc.
$al$e and +lug or lind flange for +rotection against releases. Be+ending on the +roduct and
ser$ice, ac.flo* +re$ention from the discharge line ma, e needed. )ro$isions ma, e made
for +i+eline e1+ansion, mo$ement and tem+erature changes to a$oid ru+ture. )um+s o+erated
*ith reduced or no flo* can o$erheat and ru+ture. -he failure of automatic +um+ controls could
cause a de$iation in +rocess +ressure and tem+erature. )ressure relief in the discharge +i+ing
should e +ro$ided *here +um+s can e o$er+ressured.
"ank storage
Atmos+heric storage tan.s and +ressure storage tan.s are used throughout the refiner, for
storage of crudes, intermediate h,drocarons 8those used for +rocessing9 and finished +roducts,
oth li/uids and gases. -an.s are also +ro$ided for fire *ater, +rocess and treatment *ater, acids,
air and h,drogen, additi$es and other chemicals. -he t,+e, construction, ca+acit, and location of
tan.s de+ends on their use and the nature, $a+our +ressure, flash+oints and +our +oints of the
materials stored. Man, t,+es of tan.s are used in refineries, the sim+lest eing ao$e-ground,
cone-roof tan.s for storage of comustile 8non-$olatile9 li/uids such as diesel fuels, fuel oils
and luricating oils. !+en-to+ and co$ered 8internal9 floating-roof tan.s, *hich store flammale
8$olatile9 li/uids such as gasoline and crude oil, restrict the amount of s+ace et*een the to+ of
the +roduct and the tan. roof in order to maintain a $a+our-rich atmos+here to +reclude ignition.
-he +otential for fire e1ists if h,drocaron storage tan.s are o$erfilled or de$elo+ lea.s *hich
allo* li/uid and $a+ours to esca+e and reach sources of ignition. Refineries should estalish
manual gauging and +roduct recei+t +rocedures to control o$erfills or +ro$ide automatic
o$erflo* control and signaling s,stems on tan.s. -an.s ma, e e/ui++ed *ith fi1ed or semi-
fi1ed foam-*ater fire +rotection s,stems. Remote-controlled $al$es, isolation $al$es and fire
$al$es ma, e +ro$ided at tan.s for +um+-out or closure in the e$ent of a fire inside the tan. or
in the tan. di.e or storage area. -an. $enting, cleaning and confined-s+ace entr, +rogrammes are
used to control *or. inside tan.s, and hot *or. +ermit s,stems are used to control sources of
ignition in and around storage tan.s.
Handling) shipping and transportation
Loading gases and li/uid h,drocarons into +i+elines, tan. cars, tan. truc.s and marine $essels
and arges for trans+ort to terminals and consumers is the final refiner, o+eration. )roduct
characteristics, distriution needs, shi++ing re/uirements, fire +re$ention, and en$ironmental
+rotection and o+erating criteria are im+ortant *hen designing marine doc.s, loading rac.s and
+i+eline manifolds. !+erating +rocedures need to e estalished and agreed to , the shi++er and
recei$er, and communications maintained during +roduct transfer. -an. truc.s and rail tan. cars
ma, e either to+ or ottom loaded. Loading and unloading li/uefied +etroleum gas 8L)#9
re/uires s+ecial considerations o$er and ao$e those for li/uid h,drocarons. 2here re/uired,
$a+our reco$er, s,stems should e +ro$ided at loading rac.s and marine doc.s.
Safe *or. +ractices and a++ro+riate +ersonal +rotecti$e e/ui+ment ma, e needed *hen loading
or unloading, cleaning u+ s+ills or lea.s, or *hen gauging, ins+ecting, sam+ling or +erforming
maintenance acti$ities on loading facilities or $a+our reco$er, s,stems. Beli$er, should e
sto++ed or di$erted in the e$ent of an emergenc, such as a tan. truc. or tan. car com+artment
o$erfill.
A numer of different ha"ardous and to1ic chemicals are used in refineries, $ar,ing from small
amounts of test reagents used in laoratories to large /uantities of sul+huric acid and
h,drofluoric acids used in al.aline +rocessing. -hese chemicals need to e recei$ed, stored and
handled +ro+erl,. Chemical manufacturers +ro$ide material safet, information *hich can e
used , refineries to de$elo+ safet, +rocedures, engineering controls, +ersonal +rotection
re/uirements and emergenc, res+onse +rocedures for handling chemicals.
-he nature of the ha"ard at loading and unloading facilities de+ends u+on the +roducts eing
loaded and the +roducts +re$iousl, trans+orted in the tan. car, tan. truc. or marine $essel.
Jonding e/uali"es the electrical charge et*een the loading rac. and the tan. truc. or tan. car.
#rounding +re$ents the flo* of stra, currents at truc. and rail loading facilities. Insulating
flanges are used on marine doc. +i+ing connections to +re$ent static electricit, uild-u+ and
discharges. :lame arrestors are installed in loading rac. and marine $a+our reco$er, lines to
+re$ent flashac.. 2here s*itch loading is +ermitted, safe +rocedures should e estalished and
follo*ed.
Automatic or manual shutoff s,stems at su++l, headers should e +ro$ided at to+- and ottom-
loading rac.s and marine doc.s in the e$ent of lea.s or o$erfills. Anti-fall +rotection, such as
hand rails, ma, e needed for doc.s and to+-loading rac.s. Brainage and reco$er, s,stems ma,
e +ro$ided at loading rac.s for storm drainage, at doc.s and to handle s+ills and lea.s.
)recautions are needed at L)#-loading facilities so as not to o$erload or o$er+ressuri"e tan. cars
and truc.s.
Refinery (upport Acti!ities and Facilities
A numer of different facilities, acti$ities and +rogrammes, each of *hich has its o*n s+ecific
safet, and health re/uirements, are needed to su++ort refiner, +rocesses de+ending on the
refiner,Ls location and a$ailale resources.
-dministratie actiities
A *ide $ariet, of administrati$e su++ort acti$ities, de+ending on the refining com+an,Ls
+hiloso+h, and the a$ailailit, of communit, ser$ices, are re/uired to assure continued
o+eration of a refiner,. -he function *hich controls oil mo$ements into, *ithin and out from the
refiner, is uni/ue to refineries. -he administrati$e functions can e ro.en do*n as follo*s. -he
da,-to-da, o+eration of the +rocess units is the o+erations function. Another function is
res+onsile for assuring that arrangements ha$e een made for a continuous su++l, of crude oil.
!ther functional acti$ities include medical ser$ices 8oth emergenc, and continuing health care9,
food ser$ice, engineering ser$ices, 0anitorial ser$ices and routine administrati$e and management
functions common to most industries, such as accounting, +urchasing, human relations and so
on. -he refiner, training function is res+onsile for su+er$isor and em+lo,ee s.ills and crafts
training including initial, refresher and remedial training, and for em+lo,ee and contractor
orientation and training in emergenc, res+onse and safe *or. +ractices and +rocedures.
Construction and maintenance
-he continued safe o+eration of refineries de+ends u+on the estalishment and im+lementation
of +rogrammes and +rocedures for regular maintenance and +re$enti$e maintenance, and
assuring re+lacement *hen necessar,. 0urnarounds, *herein the entire refiner, or entire +rocess
units *ill e shut do*n for total e/ui+ment o$erall and re+lacement at one time, is a t,+e of
+re$enti$e maintenance +rogramme uni/ue to the +rocess industr,. Mechanical integrit,
acti$ities, such as ins+ection, re+air, testing and certification of $al$es and relief de$ices, *hich
are +art of the +rocess safet, management +rogramme, are im+ortant to the continued safe
o+eration of a refiner,, as are maintenance *or. orders for the continued effecti$eness of the
refiner, Cmanagement of changeD +rogramme. 2or. +ermit +rogrammes control hot *or. and
safe *or., such as isolation and loc.out, and entr, into confined s+aces. Maintenance and
instrumentation sho+s ha$e +ur+oses *hich include:
delicate and +recise *or. to test, maintain and calirate refiner, +rocess controls,
instruments and com+uters
*elding
e/ui+ment re+air and o$erhaul
$ehicle maintenance
car+entr, and so on.

Construction and maintenance safet, and health relies on some of the follo*ing +rogrammes.
3solation
-he safe maintenance, re+air and re+lacement of e/ui+ment *ithin +rocess units often re/uires
the isolation of tan.s, $essels and lines in order to +reclude the +ossiilit, of flammale li/uids
or $a+ours entering an area *here hot *or. is eing +erformed. Isolation is normall, attained ,
disconnecting and closing off all of the +i+ing leading to or from a $essel3 linding or lan.ing
the +i+e at a connection near the tan. or $essel3 or closing a doule set of loc. $al$es on the
+i+ing, if +ro$ided, and o+ening a leeder $al$e et*een the t*o closed $al$es.
%oc+out6tagout
Loc.out and tagout +rogrammes +re$ent the inad$ertent acti$ation of electrical, mechanical,
h,draulic or +neumaticall, energi"ed e/ui+ment during re+air or maintenance. All electricall,
+o*ered e/ui+ment should ha$e its circuit rea.er or main s*itch loc.ed or tagged out and
tested to assure non-o+erailit,, +rior to starting *or.. Mechanical h,draulic and +neumatic
e/ui+ment should e de-energi"ed and ha$e its +o*er source loc.ed or tagged out +rior to
starting *or.. @al$e closing lines *hich are eing *or.ed on, or *hich are isolated, should also
e loc.ed out or tagged to +re$ent unauthori"ed o+ening.
/etallurgy
Metallurg, is used to assure the continued strength and integrit, of lines, $essels, tan.s and
reactors *hich are su0ect to corrosion from the acids, corrosi$es, sour *ater, and gases and
other chemicals created , and used in +rocessing crude oil. >on-destructi$e testing methods are
em+lo,ed throughout the refiner, to detect e1cessi$e corrosion and *ear efore failure occurs.
)ro+er safet, +recautions are re/uired to +re$ent e1cessi$e e1+osures to *or.ers *ho are
handling or are e1+osed to radioacti$e testing e/ui+ment, d,es and chemicals.
*arehouses
2arehouses store not onl, the +arts, materials and e/ui+ment needed for continued refiner,
o+erations, ut also store +ac.aged chemicals and additi$es that are used in maintenance,
+rocessing and lending. 2arehouses ma, also maintain su++lies of re/uired +ersonal +rotecti$e
clothing and e/ui+ment including hard hats, glo$es, a+rons, e,e and face +rotection, res+irator,
+rotection, safet, and im+er$ious foot*ear, flame-resistant clothing and acid-+rotecti$e clothing.
)ro+er storage and se+aration of flammale and comustile li/uids and ha"ardous chemicals is
needed to +re$ent s+ills, fires and mi1ing of incom+atile +roducts.
!aboratories
Laoratories are res+onsile for determining the $alues and consistenc, of the crude oils +rior to
+rocessing, as *ell as +erforming the testing re/uired for finished +roduct /ualit, control.
Laorator, +ersonnel should e trained to recogni"e the ha"ards inherent in the handling and
mi1ing of to1ic chemicals and flammale li/uids, and +ro$ide +rotection for themsel$es and
others.
Safety and enironmental and occupational hygiene
!ther im+ortant refiner, su++ort acti$ities are safet,, fire +re$ention and +rotection,
en$ironmental +rotection and industrial h,giene. -hese ma, e +ro$ided as se+arate functions or
integrated into the refiner, o+erations. Safet,, emergenc, +re+aredness and res+onse, and fire
+re$ention and +rotection acti$ities are often the res+onsiilit, of the same function *ithin a
refiner,.
-he safet, function +artici+ates in +rocess safet, management +rogrammes as +art of the design
re$ie*, +re-construction and construction re$ie* and +re-start-u+ re$ie* teams. Safet, often
assists in the contractor /ualification +rocess, re$ie*s contractor acti$ities and in$estigates
incidents in$ol$ing em+lo,ees and contractors. Safet, +ersonnel ma, e res+onsile for
o$erseeing +ermit-re/uired acti$ities such as confined s+ace entr, and hot *or., and for
chec.ing the a$ailailit, and readiness of +ortale fire e1tinguishers, decontamination facilities,
safet, sho*ers, e,e *ash stations, fi1ed detection de$ices and alarms, and emergenc, self-
contained reathing a++aratus +laced at strategic locations in e$ent of a to1ic gas release.
Safety programmes. -he refiner, safet, function usuall, has res+onsiilit, for the de$elo+ment
and administration of $arious safet, and incident +re$ention +rogrammes, including, ut not
limited to, the follo*ing:
design construction and +re-start-u+ safet, re$ie*s
accident, incident and near miss in$estigation and re+orting
emergenc, +re+aredness +lans and res+onse +rogrammes
contractor safet, +rogramme
safe *or. +ractices and +rocedures
loc.out=tagout
confined and inert s+ace entr,
scaffolding
electrical safet,, e/ui+ment grounding and fault +rotection +rogramme
machine guarding
safet, signs and notices
hot *or., safe *or. and entr, +ermit s,stems.

Fire rigades. Refiner, fire rigades and emergenc, res+onders ma, e full-time rigade
memers3 designated refiner, em+lo,ees, such as o+erators and maintenance +ersonnel *ho are
trained and assigned to res+ond in addition to their regular duties3 or a comination of oth.
Jesides fires, rigades traditionall, res+ond to other refiner, incidents such as acid or gas
releases, rescue from $essels or tan.s, s+ills and so on. -he fire +rotection function ma, e
res+onsile for the ins+ection and testing of fire detectors and signals, and fi1ed and +ortale fire
+rotection s,stems and e/ui+ment, including fire truc.s, fire +um+s, fire *ater lines, h,drants,
hoses and no""les.
Refiner, firefighting differs from normal firefighting ecause rather than e1tinguishment, it is
often +referale to allo* certain fires to continue to urn. In addition, each t,+e of h,drocaron
li/uid, gas and $a+our has uni/ue fire chemistr, characteristics *hich must e thoroughl,
understood in order to est control their fires. :or e1am+le, e1tinguishment of a h,drocaron
$a+our fire *ithout first sto++ing the $a+our release, *ould onl, create a continued $a+our gas
cloud *ith the +roailit, of re-ignition and e1+losion. :ires in tan.s containing crude oil and
hea$, residuals need to e handled *ith s+ecific firefighting techni/ues to a$oid the +ossiilit,
of an e1+losion or tan. oil-o$er.
6,drocaron fires are often e1tinguished , sto++ing the flo* of +roduct and allo*ing the fire to
urn out *hile a++l,ing cooling *ater to +rotect ad0acent e/ui+ment, tan.s and $essels from heat
e1+osures. Man, fi1ed fire +rotection s,stems are designed *ith this s+ecific +ur+ose. :ighting
fires in +rocess units under +ressure re/uires s+ecial consideration and training, +articularl,
*hen catal,sts such as h,drofluoric acid are in$ol$ed. S+ecial firefighting chemicals, such as dr,
+o*der and foam-*ater solutions, ma, e used to e1tinguish h,drocaron fires and control
$a+our emissions.
Emergency preparedness. Refineries need to de$elo+ and im+lement emergenc, res+onse +lans
for a numer of different +otential situations, including e1+losions, fires, releases and rescues.
-he emergenc, +lans should include the use of outside assistance, including contractors,
go$ernmental and mutual aid as *ell as a$ailailit, of s+ecial su++lies and e/ui+ment, such as
firefighting foam and s+ill containment and adsor+tion materials.
Gas and vapour testing
#as, +articulate and $a+our monitoring, sam+ling and testing in refineries is conducted to assure
that *or. can e +erformed safel, and +rocesses can e o+erated *ithout to1ic or ha"ardous
e1+osures, e1+losions or fires. Atmos+heric testing is conducted using a $ariet, of instruments
and techni/ues to measure o1,gen content, h,drocaron $a+ours and gases, and to determine
ha"ardous and to1ic e1+osure le$els. Instruments must e +ro+erl, calirated and ad0usted +rior
to use, , /ualified +ersons, to assure de+endale and accurate measurements. Be+ending on the
*or. location, +otential ha"ards and t,+e of *or. eing +erformed, testing, sam+ling and
monitoring ma, e conducted +rior to the start of *or., or at s+ecified inter$als during *or., or
continuousl, throughout the course of *or..
2hen estalishing refiner, +rocedures for sam+ling and testing flammale, inert and to1ic
atmos+heres, the use of +ersonal +rotecti$e e/ui+ment, including a++ro+riate res+irator,
+rotection, should e considered. It should e noted that canister-t,+e res+irators are unsuitale
for o1,gen-deficient atmos+heres. -esting re/uirements should de+end u+on the degree of
ha"ard *hich *ould e +resent in the e$ent of instrument failure.
-esting of the follo*ing sustances ma, e +erformed using +ortale e/ui+ment or fi1ed
instrumentation:
O"ygen. Comustile gas meters *or. , urning a minute sam+le of the atmos+here eing
tested. In order to otain an accurate comustile gas reading, a minimum of ('K and a
ma1imum of &AK o1,gen must e +resent in the atmos+here. -he amount of o1,gen +resent in
the atmos+here is determined , using an o1,gen meter +rior to, or simultaneousl, *ith, using
the comustile gas meter. -esting for o1,gen is essential *hen *or.ing in confined or enclosed
s+aces, as entr, *ithout res+irator, +rotection 8+ro$ided that there are no to1ic e1+osures9
re/uires normal reathing-air o1,gen concentrations of a++ro1imatel, &(K. !1,gen meters are
also used to measure the amount of o1,gen +resent in inerted s+aces, to assure that there is not
enough +resent to su++ort comustion during hot *or. or other o+erations.
Hydrocaron vapours and gases. C6ot *or.D is *or. *hich creates a source of ignition, such as
*elding, cutting, grinding, last cleaning, o+erating an internal comustion engine and so on, in
an area *here the +otential for e1+osure to flammale $a+ours and gases e1ists. In order to
conduct hot *or. safel,, instruments .no*n as comustile gas meters are used to test the
atmos+here for h,drocaron $a+ours. 6,drocaron $a+ours or gases *ill urn onl, *hen mi1ed
*ith air 8o1,gen9 in certain +ro+ortions and ignited. If there is not enough $a+our in the air, the
mi1ture is said to e Ctoo lean to urnD, and if there is too much $a+our 8too little o1,gen9, the
mi1ture is Ctoo rich to urnD. -he limiting +ro+ortions are called the Cu++er and lo*er flammale
limitsD and are e1+ressed as a +ercentage of $olume of $a+our in air. Each h,drocaron molecule
or mi1ture has different flammailit, limits, t,+icall, ranging from aout ( to ('K $a+our in air.
#asoline $a+our, for e1am+le, has a lo*er flammale limit of (.<K and an u++er flammale
limit of ?.5 +er cent.
0o"ic atmospheres. S+ecial instruments are used to measure the le$els of to1ic and ha"ardous
gases, $a+ours and +articulates *hich ma, e +resent in the atmos+here *here +eo+le are
*or.ing. -hese measurements are used to determine the le$el and t,+e of +rotection needed,
*hich ma, $ar, from com+lete $entilation and re+lacement of the atmos+here to the use of
res+irator, and +ersonal +rotecti$e e/ui+ment , +eo+le *or.ing in the area. E1am+les of
ha"ardous and to1ic e1+osures *hich ma, e found in refineries include asestos, en"ene,
h,drogen sul+hide, chlorine, caron dio1ide, sul+huric and h,drofluoric acids, amines, +henol
and others.
Health and safety programmes
-he asis for refiner, industrial h,giene is an administrati$e and engineering controls
+rogramme co$ering facilit, e1+osures to to1ic and ha"ardous chemicals, laorator, safet, and
h,giene, ergonomics and medical sur$eillance.
Regulator, agencies and com+anies estalish e1+osure limitations for $arious to1ic and
ha"ardous chemicals. -he occu+ational h,giene function conducts monitoring and sam+ling to
measure em+lo,ee e1+osure to ha"ardous and to1ic chemicals and sustances. Industrial
h,gienists ma, de$elo+ or recommend engineering controls, +re$enti$e *or. +ractices, +roduct
sustitution, +ersonal +rotecti$e clothing and e/ui+ment or alternate measures of +rotection or
reducing e1+osure.
/edical programmes. Refineries t,+icall, re/uire +re+lacement and +eriodic medical
e1aminations to determine the em+lo,eeLs ailit, to initiall, and suse/uentl, +erform the *or.,
and assure that the continued *or. re/uirements and e1+osures *ill not endanger the em+lo,eeLs
health or safet,.
(ersonal protection. )ersonal +rotection +rogrammes should co$er t,+ical refiner, e1+osures,
such as noise, asestos, insulation, ha"ardous *aste, h,drogen sul+hide, en"ene and +rocess
chemicals including caustics, h,drogen fluoride, sul+huric acid and so on. Industrial h,giene
ma, designate the a++ro+riate +ersonal +rotecti$e e/ui+ment to e used for $arious e1+osures,
including negati$e +ressure and air-su++lied res+irators and hearing, e,e and s.in +rotection.
(roduct safety. )roduct safet, a*areness co$ers .no*ing aout the ha"ards of chemicals and
materials to *hich the +otential for e1+osure e1ists in the *or.+lace, and *hat actions to ta.e in
the e$ent e1+osure , ingestion, inhalation or s.in contact occurs. -o1icological studies of crude
oil, refiner, streams, +rocess chemicals, finished +roducts and +ro+osed ne* +roducts are
conducted to determine the +otential effects of e1+osure on oth em+lo,ees and consumers. -he
data are used to de$elo+ health information concerning +ermissile limits of e1+osure or
acce+tale amounts of ha"ardous materials in +roducts. -his information is t,+icall, distriuted
, material safet, data sheets 8MSBSs9 or similar documents, and em+lo,ees are trained or
educated in the ha"ards of the materials in the *or.+lace.
.nironmental Protection
En$ironmental +rotection is an im+ortant consideration in refiner, o+erations ecause of
regulator, com+liance re/uirements and a need for conser$ation as oil +rices and costs escalate.
!il refineries +roduce a *ide range of air and *ater emissions that can e ha"ardous to the
en$ironment. Some of these are contaminants in the original crude oil, *hile others are a result
of refiner, +rocesses and o+erations. Air emissions include h,drogen sul+hide, sul+hur dio1ide,
nitrogen o1ides and caron mono1ide 8see tale &9. 2aste *ater t,+icall, contains h,drocarons,
dissol$ed materials, sus+ended solids, +henols, ammonia, sul+hides, acids, al.alis and other
contaminants. -here is also the ris. of accidental s+ills and lea.s of a *ide range of flammale
and=or to1ic chemicals.
Controls estalished to contain li/uid and $a+our releases and reduce o+erating costs include the
follo*ing:
Energy conservation. Controls include steam lea. control and condensate reco$er,
+rogrammes to conser$e energ, and increase efficienc,.
-ater pollution. Controls include *aste *ater treatment in A)I se+arators and suse/uent
treatment facilities, storm *ater collection, retainment and treatment and s+ill +re$ention
containment and control +rogrammes.
!ir pollution. Since refineries o+erate continuousl,, lea. detection, +articularl, at $al$es
and +i+e connections, is im+ortant. Controls include reducing h,drocaron $a+our
emissions and releases to the atmos+here, refiner, $al$e and fitting tightness
+rogrammes, floating roof tan. seals and $a+our containment +rogrammes, and $a+our
reco$er, for loading and unloading facilities and for $enting tan.s and $essels.
Ground pollution. )re$enting oil s+illage from +olluting soil and contaminating ground
*ater is accom+lished , the use of di.es and the +ro$iding of drainage to s+ecified,
+rotected containment areas. Contamination from s+illage inside di.e areas ma, e
+re$ented , the use of secondar, containment measures, such as im+er$ious +lastic or
cla, di.e liners.
Spill response. Refineries should de$elo+ and im+lement +rogrammes to res+ond to s+ills
of crude oil, chemicals and finished +roducts, on oth land and *ater. -hese +rogrammes
ma, rel, on trained em+lo,ees or outside agencies and contractors to res+ond to the
emergenc,. -he t,+e, amount needed and a$ailailit, of s+ill clean-u+ and restoration
su++lies and e/ui+ment, either on site or on call, should e included in the +re+aredness
+lan.