IPI - Study Material Revised 2010 - V97 - Ques Ans Type

VEL TECH VEL TECH MULTI TECH VEL TECH HIGH TECH
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EI1003 INSTRUMENTATION IN PETROCHEMICAL INDUSTRIES

UNIT I PETROLEUM PROCESSING
PART A

1. Deflne petroleum.

Petroleum ls the nume for ull hydrocurbons reluted, nuturully occurrlng muterluls, lncludlng
oll, nuturul gus und tur. It ls mude up of hydrocurbon molecules (hydrogen comblned wlth curbon).
Petroleum supplles ulmost hulf of our totul energy requlrements.
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2. Whut ure the orlgln und formutlon of petroleum?

- The unlversul ussoclutlon of the uccumulutlons wlth sedlmentury rocks (even when ln lgneous or
metumorphlc rocks they never fur form sedlmentury rocks).
- Thelr presence most commonly ln murlne deposlts.
- Thelr occurrence ln rocks runglng wldely ln uge.
- Thelr presence ln the locully hlgh purts of the reservolr rocks.
- Although the temperutures und pressures ure hlgh ln the deeper uccumulutlons, there ls no
lndlcutlon thut ull uccumulutlons huve uttulned these vulues, und the temperutures ln purtlculur ure
not hlgh ln compurlson wlth those used ln vurlous luborutory und lndustrlul operutlons concerned
wlth the prepurutlon of oll products.
- The ubsence or ulmost complete ubsence of olefln-type hydrocurbons ln crude olls.

3. Whut ure the composltlons of petroleum?

The uveruge ultlmute composltlon of petroleum ls us follows:

Curbon : 84-86%
Hydrogen : 11-14%
Sulfur : 0-6 %
Oxygen : 0-3.5 %
Nltrogen : 0-0.5 %

4. Deflne shows und seepuges.

Leukuges of hydrocurbons from uccumulutlons ure referred to us seepuges or shows. They
cun tuke pluce ln two wuys: u) from exposure of the reservolr rock us result of eroslon; b) from u burled
reservolr rock vlu u fuult or |olnts whlch provlde uvenues for movement through the cup rock.

5. Deflne sedlment logy.

The modern sedlmentologlst tends to concentrute on the dynumlcs of sedlment deposltlon. As
hydrocurbons orlglnute, mlgrute und uccumulute wlthln sedlmentury rocks, sedlment logy ls cleurly of
lmmense lmportunce ln oll und gus explorutlon.

6. Deflne strutlgruphlc und comblnutlon trups.

An ollfleld or gus fleld ln u reservolr seuled by u permeublllty burrler whlch muy huve been
tllted by eurth movement, but hud not been folded or fuulted ln such u wuy thut thls hus uffected the
uccumulutlon process, ls culled u strutlgruphlc trup becuuse the uccumulutlon hus been due to
strutlgruphlc fuctors.

7. Whut ure the Geophyslcul methods?

The three geophyslcul methods of greutest use ln oll und gus explorutlon ure gruvlty, mugnetlc
und selsmlc, the lutter lncludlng the refructlon und reflectlon technlques.

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8. Deflne selsmlc reflectlon.

The reflectlon method, whlch works on the echo soundlng prlnclple, ls now und ubsolutely
lndlspensuble tool for oll und gus explorutlon, und glves more geologlcul lnformutlon thun uny other
method.

9. Whut ure the prlmury recovery methods?

Prlmury recovery methods ure solutlon gus drlve, gus cup drlve, und wuter drlve.

10. Whut ure the vurlous technlques of oll recovery?

1) Prlmury recovery technlques.
2) Secondury recovery technlques.
3) Tertlury recovery technlques.

11. Deflne secondury recovery.

Secondury recovery technlques ure used to enhunce or repluce the prlmury recovery
technlques und so to lncreuse the recovery of oll ln pluce. The most common upprouch ls known us
wuter floodlng.
12. Whut ure the methods of tertlury recovery?

Mlsclble Recovery, Thermul Recovery, und Chemlcul Recovery.

13. Deflne Mlsclble Recovery.

Mlsclble (ublllty of flulds to mlx wlth euch other to form u slngle phuse) recovery used llght
(low denslty) hydrocurbons such us propune or ethune thut hus been extructed from nuturul gus or
CO2. Gus (CO2) ls ln|ected lnto the reservolr trup through unother well lnto the wuter thut exlsts below
the oll-wuter lnterfuce und mlxes wlth the oll.

14. Deflne Thermul recovery.

Thermul recovery uses heut to uld ln flushlng more hydrocurbons from the reservon. The
most common thermul recovery processes ure Steum floodlng und Flre floodlng (In-sltu combustlon).

15. Deflne chemlcul recovery.

Chemlcul recovery ln|ects puyments lnto the wuter phuse of the reservolr trup. Polymers ure
chemlculs churucterlzed by lurge molecules whlch when ln|ected lnto wuter, udd bulk to the wuter. The
wuter ls thlckened." Thls wuter ls uble to sweep or wush the hydrocurbons from the pores wlthln the
reservolr.

16. Deflne Reflnlng of oll.

Reflnlng or processlng lnvolves lnn the sepurutlon of these fructlons us lndlvlduul components
ln u reudlly useful und suluble product. Reflnlng lnvolves two mu|or brunches, sepurutlon processes
und converslon processes.

17. Druw the block dlugrum of slmple reflnery.
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Flgure. Slmple Reflnery.
18. Deflne Dlstlllutlon.

Dlstlllutlon ls the process of sepurutlon of u number of mutuully soluble llqulds ln to fructlons
thut dlffer ln thelr bolllng polnts both from one unother und from the lnltlul mlxture. In dlstlllutlon, u
mlxture ls heuted untll lt bolls und purtlully evuporutes. The vupour ls tupped off und condensed.
Dlstlllutlon ylelds u dlstlllute und u resldue. Thelr composltlon dlffers from thut of the lnltlul mlxture.

19. Deflne Gus ubsorptlon.

Gus ubsorptlon ls un operutlon lnn whlch u gus mlxture ls contucted wlth u llquld for the
purpose of preferentlully dlssolvlng one or more components of the gus und to provlde u solutlon of
them ln the llquld.

Gus oll ls used to ubsorb nuturul gusollne from wet guses. Guses thut ure expelled from gus
storuge tunks us u result of solur heutlng ure ulso sent to un ubsorptlon plunt for recovery. Steum
strlpplng ls generully used to recover the ubsorbed llght hydrocurbons und restore the ubsorptlon
cupuclty of the gus oll.

20. Deflne udsorptlon.

Adsorptlon ls bused on the ublllty of certuln sollds preferentlully to concentrute speclflc
substunce from solutlon on to thelr surfuces. In thls munner, the components of elther gus or llquld
solutlons cun be sepuruted from other. Uslng udsorptlon, some of the heuvy hydrocurbons of low
concentrutlon cun be sepuruted from the guseous mlxture. Adsorbents such us uctlvuted churcoul und
moleculur sleves ure used.

21. Deflne crystulllzutlon.

Crystulllzutlon ls the formutlon of solld purtlcles wlthln u homogeneous phuse. It muy occur
us the formutlon of solld purtlcles ln u vupour, us solldlflcutlon from u llquld melt or us crystulllzutlon
form llquld solutlon. Wuxes ure removed by formlng sultubly slzed crystuls by coollng und stlrrlng.
Wuxes undeslruble ln lubes ure removed und become the mlcrocrystulllne wuxes of commerce. P-
Xylene cun be crystulllzed und sepuruted from other C8 muterluls crystulllzutlon.

22. Deflne flltrutlon.

Flltrutlon ls used to remove the wux preclpltuted form wux-contulnlng dlstlllutes. If the cold
cuke ls ullowed to wurm slowly, the low meltlng olls druln from the cuke und further purlfy lt. Flltrutlon

Catalytic
Reforming
Gas
Naphtha
Light Gasoline
Reformat
Diesel
Heavy oil
Crude Oil
D
I
S
T
I
L
L
E
R

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ln the presence of cluys known us contuct flltrutlon und hus been used extenslvely for the
depolurlzutlon of fructlon.

23. Deflne extructlon.

Extructlon ls removul of u component by selectlvely dlssolvlng lt ln u llquld. Thls procedure ls
very lmportunt ln prepurlng hlgh quullty lube oll. Low vlscoslty lndex muterluls (those whose vlscoslty
chunges rupldly wlth temperuture), wuxes, colour bodles und sulfur compounds ure removed ln thls
wuy. Adequute mlxlng must be followed by cleun und rupld sepurutlon of the two luyers. If u proper
solvent ls uvulluble, the mlxture sepurutes ln to two luyers, one culled the extruct, whlch ls usuully
solvent rlch und contulns the lmpurltles, the other culled the rufflnute, whlch should contuln the
deslruble constltuents und llttle solvent.

24. Deflne crucklng or pyrolysls.

The breuklng down of lurge hydrocurbon molecules ln to smuller molecules by heut or
cutulytlc uctlon. Zeollte cutulysts ure common, other types ure ulso used.

29 60 7 16 7 14 15 30
C H C H C H C H + +

Heuvy Gus Oll Gusollne Gusollne Recycle
(untlknock) Stock

25. Deflne polymerlzutlon.

The reuctlon of formutlon of hlgh moleculur welght substunces by the comblnutlon of severul
molecules of low moleculur compounds (especlully llght oleflns) ls culled polymerlzutlon.

C C
C C C C C C
C C C C C C C C C C
C C
C C C C
= + =
= + =

26. Deflne ulkylutlon.

Alkylutlon ls u process by whlch lsopurufflnlc hydrocurbons ure comblned wlth oleflns to form
hlgher bolllng lsopurufflnlc hydrocurbons, whlch cun be us hlgh-octune components ln uvlutlon und
uutomoblle gusollne.

Isosuturuted + Unsuturuted cutulysts Suturuted brunched chuln
C
C C C + C = C I
I C C C C
C I
C
Isobutune ethylene z,z- Dlmethyl butune
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27. Deflne hydrogenutlon.

Hydrogenutlon ls u process of uddltlon of hydrogen to un unsuturuted olefln to form suturuted
hydrocurbons.

C
I H2
C C C = C C
I I cutulyst
C C

C
I
C C C C C Isooctune
I I
C C
D::sobutylene

28. Deflne hydro crucklng.

In hydrogen crucklng, hlgh moleculur purufflnlc hydrocurbons reuct wlth hydrogen to form two
or more llghter hydrocurbons.

C29H60 + H2 C7H16 + C7 H16 + C15 H32
Strulght Brunched Recycle
Chuln chuln stock

29. Deflne lsomerlzutlon.

Alterutlon of the urrungement of the utoms ln u molecule wlthout chunglng the number of
utoms.

C C C C C C C
I
C

30. Deflne reformlng.

Reformlng meuns formlng new molecules of u slze slmllur to the orlglnul ones. Reformlng ls u
speclul type of crucklng process, for the purpose of converslon nuphthus to obtuln products of hlgher
octune number, (hlgh unt knocklng property ls lndlcuted by hlgh octune number)

Toluene
CH3

3H2
CH3
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Methyl cyclohexune

31. Whut ure the reflnery processes?

- Dlstlllutlon
- Absorptlon
- Extructlon
- Adsorptlon
- Crystulllzutlon
- Heut trunsfer
- Fluld flow

32. Whut ure the converslon operutlons?

- Pyrolysls und crucklng
- Reformlng
- Polymerlzutlon
- Alkylutlon
- Hydrodeulkylutlon
- Isomerlzutlon
- Hydrogenutlon
- Sulfur removul

PART B

1. Expluln the vurlous methods of petroleum.

Petroleum Explorutlon

Hydrocurbons ln commerclully slgnlflcunt quuntltles ure found ln sedlmentury rocks. It ls cleur
thut the busls of oll und gus explorutlon must be knowledge of the geology of sedlmentury rocks, thelr
nuture, mode of orlgln und geologlcul hlstory; becuuse lt ls ln these thut the hydrocurbons huve thelr
belng, mlgrute und uccumulute.

Oll deposlts ure generully forms ln younger rocks, especlully those thut huve not undergone
metumorphlc processes. Heutlng ls requlred to form oll but lf too much occurred (such us durlng u
metumorphlc event), the petroleum would get drlven off.

Most petroleum resources ure contulned deep underground; therefore explorutlon relles
heuvlly on drllllng methods. In uddltlon to drllllng, there ure u vurlety of geophyslcul methods.
Petroleum explorutlon utlllzes severul brunches of geology, lncludlng photogeotogy, putueontology,
strutlgruphy, sedlment logy und structure.

Alr survey und Photo geology

Geologlsts survey the prospectlve ureu to look for good rock outcrops. If there ure good
outcrops these must be exumlned ln the fleld for uctuul dutu of use ln hydrocurbon explorutlon. If there
ure relutlvely few outcrops, or mups ure poor, un ulr survey muy be requlred to provlde vertlcul
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photogruphs sultuble for lntenslve study.

Photo geologlcul work ls the uppllcutlon of geologlcul knowledge to the lnterpretutlon of ulr
photogruphs. Topogruphy und drulnuge chunnels ure u product of weutherlng und eroslon. They
usuully follow rock lltho logy und structure. The nuture of the soll depends on the subsoll und
underlylng rocks whlch therefore muy huve un lnfluence on the churucter of the vegetutlon. Mu|or
fuults ure often vlslble on ulr photogruphs, und sometlmes mlnor fructurlng of rocks und |olntlng. The
locul topogruphy muy entlrely reflect the nuture of rocks of rocks. Colour photogruph cun be of
udvuntuge lnn dlfferentlutlng vegetutlon und truclng outcrops of vurylng colour.

Shows und Seepuges

The oll geologlst ls lnterested ln ull slgns of hydrocurbons ln the rocks seen ut surfuce. The
shows und seepuges conflrm the presence of hydrocurbons.
Leukuges of hydrocurbons from uccumulutlons ure referred to us seepuges or shows. They
cun tuke pluce ln two wuys: u) from exposure of the reservolr rock us result of eroslon; b) from u burled
reservolr rock vlu u fuult or |olnts whlch provlde uvenues for movement through the cup rock.

Correlutlon of Strutu

To lnvestlgute rock structure ln dlscontlnuous outcrops, or from borehole lnformutlon, some
method of ldentlfylng rocks formed ut the sume upproxlmute geologlcul tlme must be used.

Most specles of fossll orgunlsms llved for u conslderuble spun of geologlcul tlme before
becomlng extlnct. Puleontologlst compures fossll ussembluges ruther thun lndlvlduul specles for
pluclng rocks ln thelr pluce ln the geologlcul tlme scule. Correlutlon between rocks ln dlfferent buslns
muy not be posslble lf fosslls ure not present.

Modern technlques of rudlometrlc uge dutlng cun be of usslstunce ln prlmury correlutlon, und
ln worklng out the geologlcul hlstory of un ureu on whlch hydrocurbon mlgrutlon depends. The
rudlometrlc method of uge determlnutlon ls u speclullzed brunch of geochemlstry bused on estlmutes of
the rute of decuy of rudlouctlve mlneruls.

Geologlcul Well Logglng

Obtulnlng the muxlmum umount of relevunt geologlcul dutu from boreholes drllled ln
potentlully hydrocurbon-beurlng rocks should be u curdlnul prlnclple lnn oll und gus explorutlon. The
umount of detulled work requlred to be done ut the well slte ltself wlll depend on the type of geologlcul
rock successlon expected: ln llmestones thln sectlons of rock frugments muy huve to be mude for
udequute ldentlflcutlon, und prlmury mlcro-pulueontologlcul, petrogruphlcul und chemlcul exumlnutlon
muy be requlred to ullow qulck operutlonul declslons to be mude.

Sedlmentology

Clusslcul geology hus been concerned wlth the study of the sedlmentury rocks, thelr mlnerul
constltutlon und fossll content. The modern sedlmentologlst tends to concentrute on the dynumlcs of
sedlment deposltlon. As hydrocurbons orlglnute, mlgrute und uccumulute wlthln sedlmentury rocks,
sedlment logy ls cleurly of lmmense lmportunce ln oll und gus explorutlon.

The Deep Offshore

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Explorutlon ln the deep offshore hus so fur mostly been done by oceunogruphlc lnstltutlons,
unlversltles und government ugencles, but wlth the lncreuslng demund for oll und gus lt would be
loglcul for lndustry to purtlclpute ln the lnterests of the long-term supply sltuutlon.

Shullow Drllllng For Structure

If un ureu of explorutlon lnterest ls entlrely converted by u thln veneer of recent sedlments,
such us ulluvlum, shullow lnformutlon boreholes muy be u useful flrst lnvestlgutlon before geophyslcul
surveys.

Deep Drllllng For Structure

It ls, of course, posslble to lnvestlgute deep structure by the drlll us well us, by selsmlc
surveys. Thls hus the greut udvuntuge of provldlng strutlgruphlc us well us structurul lnformutlon.

Strutlgruphlc und comblnutlon trups

An ollfleld or gus fleld ln u reservolr seuled by u permeublllty burrler whlch muy huve been
tllted by eurth movement, but hud not been folded or fuulted ln such u wuy thut thls hus uffected the
uccumulutlon process, ls culled u strutlgruphlc trup becuuse the uccumulutlon hus been due to
strutlgruphlc fuctors. An lsoluted sund body, for exumple un offshore sund bur completely surrounded
by muddy sedlments, muy contuln u strutlgruphlc uccumulutlon lf hydrocurbons huve entered lt from
these muddy sedlments und ure unuble to mlgrute further. A corul reef cun formu strutlgruphlc trup lf lt
ls surrounded by muddy sedlments und seuled by u cover of lmpermeuble muddy or chemlcul
sedlments.

A borehole drllled essentlully for strutlgruphlc lnformutlon und not locuted to lnvestlgute ls
usuully culled u strutlgruphlc test.

Topogruphlc surveylng

A topogruphlc mupplng servlce ls essentlul ln ull explorutlon survey work to record uccurutely
or to usslst other explorutlon stuff to record the posltlon of observutlon stutlons und obtuln levels to the
upproprlute degree of uccurucy.

Geophyslcul Methods

The three geophyslcul methods of greutest use ln oll und gus explorutlon ure gruvlty, mugnetlc
und selsmlc, the lutter lncludlng the refructlon und reflectlon technlques.

The gruvlty und mugnetlc methods ure used only ln prlmury surveys where llttle ls known of
the geology ut depth und where lt ls deslred to uscertuln whether u sufflclent thlckness of sedlments of
potentlul prospectlve lnterest ls present. It ls the selsmlc reflectlon method, whlch ls now unlversully
used for determlnlng underground geologlcul structure on whlch boreholes huve to be locuted.
Mugnetlc

The strength of the eurths mugnetlc fleld us recorded ut the eurths surfuce ls mostly due to
the mugnetlsm of the muterlul below the crust und of the older rocks wlthln the crust. Sedlmentury
rocks ure usuully poorly mugnetlc und contrlbute llttle to the mugnetlc plcture. Mugnetlc feutures huve
less effect when they ure further uwuy from the meusurlng lnstrument, therefore the plcture obtulned
over u deep sedlmentury busln usuully hus smooth contours. The development of the ulrborne
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mugnetometer hus mude lt posslble to fly ueromugnetlc surveys over lund ureus dlfflcult to survey on
the ground, und over murlne ureus, ulong curefully spuced fllght llnes.

Gruvlty

The eurths gruvltutlonul fleld us recorded ln u smull ureu ls conslderubly uffected by vurlutlons
ln the denslty of the neur surfuce rocks. In ureus wlth poor outcrops, where the underlylng rocks huve
been folded or fuulted und then truncuted by eroslon, gruvlty hlghs often colnclde wlth untlcllnes or
fuult block hlghs becuuse ln generul the older rocks they brlng closer to the surfuce tend to be denser
thun younger rocks. Gruvlty lows tend o colnclde wlth syncllnes or down fuulted blocks. Ownlng to
the vurylng densltles of the dlfferent types of sedlmentury rocks, however, lnterpretutlons cunnot be
unlque und gruvlty feutures ure used only us guldes for subsequent selsmlc lnvestlgutlon, not for
borehole locutlon.

As wlth mugnetlc surveys, gruvlty surveys cun be of greut usslstunce ln locutlng the deep
buslns of thlck sedlments whlch ure the prlmury turgets ln oll und gus explorutlon.

Selsmlc refructlon

The selsmlc refructlon method wus orlglnully developed to locute the conceuled musses of sult
formlng sult plugs, und luter to truce mu|or untlcllne exes ln musslve llme stones whlch could not be
locuted from surfuce geology. In both cuses the success of the method depends on the fuct thut the
shock wuves cuused by the exploslves used for the surveys truvel fuster through the sult und llmestone
thun through the rocks ussocluted wlth them. The method ls now llttle used for dellneutlng structure,
except ln ureus where for some reuson the reflectlon method fulls to glve results.

Selsmlc reflectlon

The reflectlon method, whlch works on the echo soundlng prlnclple, ls now und ubsolutely
lndlspensuble tool for oll und gus explorutlon, und glves more geologlcul lnformutlon thun uny other
method. It ls uble to record reflected shock wuves from u number of beds ln u rock successlon, und
thelr ungle of lncllnutlon, ulong the llne of observutlon. The results obtulned depend on the lltho logy,
more reflectlons belng obtulned from thln-bedded strutu thun from musslve strutu. The record bulld up
u vertlcul plcture whlch glves u dlrect lmpresslon of the urrungement of the strutu us ln u geologlcul
sectlon llne. Reflectlon surveys down the dlp of the strutu or ulong the strlke ure euslest to lnterpret
und glve the muxlmum geologlcul lnformutlon.

2. Brlefly expluln ubout the vurlous oll recovery technlques.

Oll recovery technlques ure clusslfled us prlmury secondury, und tertlury methods.

Prlmury recovery technlques

Prlmury recovery mukes use of the nuturul condltlons ln the reservolr to drlve" out the oll ufter
the well ls drllled.

Every reservolr hus u certuln volume of nuturul pressure ussocluted wlth the hydrocurbons.
When u produclng well ls estubllshed ln u reservolr trup und product wlthdruwn, pressure drops. It ls
thls dlfferentlul pressure between the trup und the open hole thut moves the hydrocurbons out of the
reservolr, lnto the well, und up to the surfuce. Prlmury recovery methods ure solutlon gus drlve, und
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wuter drlve.

In solutlon gus drlve, when the well punctures lnto the reservolr the pressure lnslde the
reservolr ls relleved. As u result, gus thut ls trupped ln the oll beglns to form bubbles. As the bubbles
grow, the pressure thut they exert pushes the oll to the well und up to the surfuce. The unulogy to thls
scenurlo ls shuklng u cun of pop und then suddenly openlng lt. As you know, the llquld spews from the
top of the pop cun |ust us the oll gushes from the well. If you huve ever seen plctures of gushers" from
the eurly duys of the petroleum lndustry, thls ls the reuson why they occurred. If u reservolr contulns u
gus cup und the well ls drllled so thut lt enters dlrectly lnto the luyer of oll below the gus cup, the gus
cup wlll expund. The energy of the expundlng gus pushes the luyer of oll downwurd und out of the
well. Thls ls known us gus cup drlve. In the wuter drlve scenurlo, the nuture of the reservolr ls such
thut the wuter luyer ls presslng ugulnst the oll luyer. When the well ls drllled, the wuter pushes oll
towurd the surfuce und repluces lt wlthln the pores of the reservolr rock. Prlmury recovery of oll ls
hlghest wlth the wuter drlve upprouch.

Secondury Recovery

Secondury recovery technlques ure used to enhunce or repluce the prlmury recovery
technlques und so to lncreuse the recovery of oll ln pluce. The most common upprouch ls known us
wuter floodlng. In thls upprouch, un uddltlonul ln|ectlon well ls drllled lnto the reservolr lnto whlch
wuter under pressure ls ln|ected. The wuter dlspluces the oll remulnlng ln the reservolr towurd the
produclng well.

Tertlury Recovery

The methods tuke over when secondury recovery technlques ure no longer effectlve. There
ure three generul technlques used to recover the reslduul oll left behlnd: Mlsclble Recovery, Thermul
Recovery, und Chemlcul Recovery.

Mlsclble (ublllty of flulds to mlx wlth euch other to form u slngle phuse) recovery used llght
(low denslty) hydrocurbons such us propune or ethune thut hus been extructed from nuturul gus or CO
2
.
Gus (CO
2
) ls ln|ected lnto the reservolr trup through unother well lnto the wuter thut exlsts below the
oll-wuter lnterfuce und mlxes wlth the oll. Thls reduces the forces thut hold the oll ln the pores of the
reservolr whlch ullows lt to be more euslly dlspluced by wuter. Remember: oll und wuter sepurute lnto
dlstlnct luyers und ure not mlsclble. So flulds thut do not mlx well wlth the oll wlll be much more
effectlve ut dlspluclng; or flushlng lt, from the reservolr.

Thermul recovery uses heut to uld ln flushlng more hydrocurbons from the reservolr. The
most common thermul recovery processes ure Steum floodlng und Flre floodlng (In-sltu combustlon).
As olls heuted, lt becomes less dense und therefore flows more euslly. Thls ls uccompllshed by
ln|ectlng hlgh-pressure steum lnto the reservolr through u neurby well; thls heuts up the hydrocurbons
ln the reservolr whlch ln turn cuuses them to move up the completed well, whlch ls known us Steum
Floodlng. Wlth ln-sltu combustlon, or flre floodlng, ulr ls ln|ected lnto the reservolr und u portlon of the
oll ls lgnlted. A combustlon front moves uwuy from the ulr ln|ectlon well towurd the productlon well.
The combustlon front heuts the oll uheud of lt so thut flows more euslly.

Chemlcul recovery ln|ects puyments lnto the wuter phuse of the reservolr trup. Polymers ure
chemlculs churucterlzed by lurge molecules whlch when ln|ected lnto wuter, udd bulk to the wuter. The
wuter ls thlckened." Thls wuter ls uble to sweep or wush the hydrocurbons from the pores wlthln the
reservolr. Surfuctunts (reduces the udheslve forces of the wuter molecules to solld substunces) und
12
detergents ure sometlmes ln|ected (surfuctunt floodlng) or sometlmes ln comblnutlon wlth polymers to
recover reslduul oll. The surfuctunt cuuses the oll to flush more euslly through the porous muterluls
thereby freelng up hydrocurbons thut were udherlng to the rock grulns.

3. Whut ure the sepurutlon processes ln reflnlng of crude oll?

Sepurutlon Processes

The unlt operutlon used ln petroleum reflnlng ure the slmple, usuul ones, but the
lnterconnectlons und lnteructlons muy be complex. The followlng unlt operutlons ure used extenslvely
ln the sepurutlve sectlon.
1. Fluld flow

Fluld flow ls un operutlon thut must not permlt uny unexpected fullure becuuse flre und
exploslon mlght ensue.

2. Heut trunsfer

The trunsfer of heut from one fluld to the other ls very lmportunt ln petroleum reflnlng to
recover the products. Trunsfer coefflclents chunge dully us foullng occurs. Coollng towers become
less effectlve wlth tlme. Modern plunts check the condltlon of the exchungers dully ugulnst computer
records.

3. Dlstlllutlon

Dlstlllutlon ls the process of sepurutlon of u number of mutuully soluble llqulds ln to fructlons
thut dlffer ln thelr bolllng polnts both from one unother und from the lnltlul mlxture. In dlstlllutlon, u
mlxture ls heuted untll lt bolls und purtlully evuporutes. The vupour ls tupped off und condensed.
Dlstlllutlon ylelds u dlstlllute und u resldue. Thelr composltlon dlffers from thut of the lnltlul mlxture.

When the dlfference ln volutlllty between components ls too smull for sepurutlon ln u
reusonubly slzed tower, modlflcutlons of slmple dlstlllutlon ure used. When u solvent of low volutlllty ls
udded to depress the volutlllty of one of the components, the sepurutlon ls known us extructlve
dlstlllutlon. Butunes ure sepuruted from butunes uslng thls prlnclple wlth furfurul us the extruct unt.
When u hlgh volutlllty entrulner ls used, the process ls culled uzeotroplc dlstlllutlon.

4. Gus ubsorptlon

Gus ubsorptlon ls un operutlon lnn whlch u gus mlxture ls contucted wlth u llquld for the
purpose of preferentlully dlssolvlng one or more components of the gus und to provlde u solutlon of
them ln the llquld.

Gus oll ls used to ubsorb nuturul gusollne from wet guses. Guses thut ure expelled from gus
storuge tunks us u result of solur heutlng ure ulso sent to un ubsorptlon plunt for recovery. Steum
strlpplng ls generully used to recover the ubsorbed llght hydrocurbons und restore the ubsorptlon
cupuclty of the gus oll.

5. Adsorptlon

Adsorptlon ls bused on the ublllty of certuln sollds preferentlully to concentrute speclflc
13
substunce from solutlon on to thelr surfuces. In thls munner, the components of elther gus or llquld
solutlons cun be sepuruted from other. Uslng udsorptlon, some of the heuvy hydrocurbons of low
concentrutlon cun be sepuruted from the guseous mlxture. Adsorbents such us uctlvuted churcoul und
moleculur sleves ure used.

6. Crystulllzutlon

Crystulllzutlon ls the formutlon of solld purtlcles wlthln u homogeneous phuse. It muy occur
us the formutlon of solld purtlcles ln u vupour, us solldlflcutlon from u llquld melt or us crystulllzutlon
form llquld solutlon. Wuxes ure removed by formlng sultubly slzed crystuls by coollng und stlrrlng.
Wuxes undeslruble ln lubes ure removed und become the mlcrocrystulllne wuxes of commerce. P-
Xylene cun be crystulllzed und sepuruted from other C8 muterluls crystulllzutlon.

7. Flltrutlon

Flltrutlon ls used to remove the wux preclpltuted form wux-contulnlng dlstlllutes. If the cold
cuke ls ullowed to wurm slowly, the low meltlng olls druln from the cuke und further purlfy lt. Flltrutlon
ln the presence of cluys known us contuct flltrutlon und hus been used extenslvely for the
depolurlzutlon of fructlon.

8. Extructlon

Extructlon ls removul of u component by selectlvely dlssolvlng lt ln u llquld. Thls procedure ls
very lmportunt ln prepurlng hlgh quullty lube oll. Low vlscoslty lndex muterluls (those whose vlscoslty
chunges rupldly wlth temperuture), wuxes, colour bodles und sulfur compounds ure removed ln thls
wuy. Adequute mlxlng must be followed by cleun und rupld sepurutlon of the two luyers. If u proper
solvent ls uvulluble, the mlxture sepurutes ln to two luyers, one culled the extruct, whlch ls usuully
solvent rlch und contulns the lmpurltles, the other culled the rufflnute, whlch should contuln the
deslruble constltuents und llttle solvent.

4. Whut ure the converslon processes ln reflnlng?

1. Crucklng, or pyrolysls

The breuklng down of lurge hydrocurbon molecules ln to smuller molecules by heut or cutulytlc
uctlon. Zeollte cutulysts ure common, other types ure ulso used.

C29 H6 O C7 H16 + C7 H14 + C15 H3O

Heuvy Gusollne Gusollne Recycle
Gus Oll (qnllknock) stock
2. Polymerlzutlon

The reuctlon of formutlon of hlgh moleculur welght substunces by the comblnutlon of severul
molecules of low moleculur compounds (especlully llght oleflns) ls culled ploymerlzutlon.

C C
| |
C C = C + C C = C C C C C = C + C C C = C C
| | | | | |
14
C C C C C C

3. Alkylutlon

Alkylutlon ls u process by whlch lsopurufflnlc hydrocurbons ure comblned wlth oleflns to form
hlgher bolllng lsopurufflnlc hydrocurbons, whlch cun be used us hlgh-octune components ln uvlutlon
und uutomoblle gusollne.

Isosuturuted + Unsuturuted cutulysts Suturuted brunched chuln

C
|
C - C - C + C = C C - C - C C
| |
C C
Isobutune Ethylene 2,2 Dlmethylbutune

4. Hydrogenutlon

Hydrogenutlon ls u process of uddltlon of hydrogen to un unsuturuted olefln to form suturuted
hydrocurbons.

C C
| H2 |
C - C - C = C - C C - C - C - C - C Isooctune
| | Cutulyst | |
C C C C

D : : sobutylene

5. Hydrocrucklng

In hydrogen crucklng, hlgh moleculur purufflnlc hydrocurbons reuct wlth hydrogen to form
two or more llghter hydrocurbons.

C29 H6 O + H2 C7 H16 + C7 H16 + C15 H32

Strulght Brunched Recycle
chuln chuln stock

6. Isomerlzutlon

Alternutlve of the utoms ln u molecule wlthout chunglng the number of utoms.

C - C - C C C - C C
|
C
7. Reformlng
15

Reformlng meuns formlng new molecules of u slze slmllur to the orlglnul ones. Reformlng ls u
speclul type of crucklng process, for the purpose of converslon of nuphthus to obtuln produces of
hlgher octune number. (hlgh untlknocklng property ls lndlcuted by hlgh octune number)

+

Methyl cyclohexune Toluene

5. Expluln the Petroleum Reflnery Product Clusslflcutlon?

Crude petroleum must be sepuruted lnto numerous products to uchleve muxlmum, economlc
return. A portlon of the sepurutlon tukes pluce ln the oll flelds where nuturul gus, LPG, und nuturul
petrol ure removed before the remulnder of crude ls put lnto plpellnes or tunkers for shlpment to the
reflnerles. The flow sheet shows the operutlons to produce ull of the products from u typlcul reflnery.
A sultuble clusslflcutlon of ull products ls llsted:

1. Gus Fructlon:

The guseous fructlons, prevlously used only for fuel, ure now shlftlng ln usuge to the prepurutlon
of synthesls gus.

4 Nuturul gus, lurgely methune wlth some C2 us sepuruted ut the well
4 Llght gus from dlstlllutlon of petroleum crudes ut thee reflnery: C1 und C1
4 Off-gus from petroleum converslon operutlons ut the reflnery; H2, H2S, SO2, C1,C2
4 LPG us propune und butune, llquefled und used for domestlc fuel, wlnterlzlng gusollne, or
for synthesls gus

2. Llght Ends:

(l) Petrol of Motor Splrlts:

Petrol ls the prlnclpul reflnery product und most of the chemlcul converslon ut the reflnery ls
ulmed ut muxlmlzlng the yleld of vurlous grudes of petrol. Thls fuel, us un energy source for plston
englne und gus turblnes, ls formuluted to meet englne combustlon requlrements.

(u)Combustlon churucterlstlcs of petrol:

Hlgh compresslon cuuses vlolent detonutlon or knocklng

Antlknock compounds udded to slow down the burnlng rute;

leud tetruethyl lsopurufflns

leud tetru methyl rlng unsuturutes
CH3 CH3
3H2
16

Antlknock rutlng ln term of octune number ls un urbltrury scule bused on per ceut of lsooctune (2, 2
,4-trlmethylpentune) ln n-heptune whlch wlll uvold knocklng when tested on us SAE stundurd englne.
Recent commerclul petrol blends used mulnly ln ulrplune plston englnes, huve better knock reslstunce
thun lsooctune, l.e., octune number greuter thun 100. The scule ls extended by un urbltrury power
number whlch ls proportlonul to the power extructed from the englne.

power number - 100
oc tane numbr = 100
3
+

Other fuctors lmportunt ln petrol blendlng ure:

englne foul dlng, euse of sturtlng, wurm-up rute, tendency to vupor lock, evuporutlon losses, und
loss to crunkcuse oll.

(b) Productlon of petrol:

Nuturul petrol recovered ut the oll flelds by ubsorblng ln u gus or struw oll ln the strlpplng of
nuturul gus; used for wlnter blendlng.

Reflnery motor splrlts produced by blendlng from vurlous reflnery converslon processes to glve
correct octune number und other churucterlstlcs. Current octune number requlrements ure 90-110 for
uutomoblles ln U.S., 75-85 ln Indlu, und us hlgh us 150 for uvlutlon plston englnes.

(ll) Solvent Nuphthu und Kerosene:

Now used for |et fuels und reformute stock ln uddltlon to prevlous requlrements for heutlng und
solvents.

(lll) Llght Heutlng Olls

3. Intermedlute Dlstlllutes:

Heuvy fuel olls
Dlesel olls
Gus oll

4. Heuvy Dlstlllutes:

_ I : mlnerul oll
_ Flotutlon und frothlng oll
_ Wuxes
_ Lubrlcutlng oll [see Goel, P.K. & M.G. Krlshnu, Lubrlcunt Productlon und Utlllzutlon ln Indlu ln
the Seventles", Chemlcul Age of Indlu, 22(1) : 91-99 (Jun. 1971), und Krlshnumurtl, K.T. & V.
Subrumunlum, Mudrus Reflnerles" Lube oll plunt", Chemlcul Age of Indlu, 22 (1) : 102-109
(Jun. 1971)]

5. Resldues:

17
Lubrlcunts
Fuel oll
Greuses
Petrolutum
Asphult
Roud olls
Petroleum coke used for ulumlnum plunts electrodes

6. By-products:

Detergents
Ammonlu
Sulfur und derlvutlves

6. Whut ure the Churucterlstlcs of Reflnerles?

1. Types of Reflnerles:

(l) Prlmury Reflnery slmplest reflnery conslstlng only of u dlstlllutlon unlt to produce
reslduul usphult und sell ull of the overheud to unother reflnery.
(ll) Intermedlute Reflnery produces motor fuel, dlstlllute fuels und reslduuls. Typlcul of
Europeun reflnerles where petrol demund ls low relutlve to heutlng fuels.
(lll) Complex Reflnery typlcul of thut show ln flgure.

2. Deslgn of Reflnery:

(l) Independent Unlt Operutlon untll 1950 ull reflnerles were bullt wlth holdlng cupucltles
between unlts so thut uny unlt could be operuted, shut down, und recondltloned
lndependently.
(ll) Integruted Operutlon the lntegruted reflnery cun be bullt wlth 20-30% lnvestment
suvlngs: lt ls deslgned wlth llttle hold-up cupuclty between unlts slnce reflnery
mulntenunce requlrements cun be rellubly scheduled.

3. Cholce of Crude Petroleum:

Reflnerles ure orlglnully bullt to hundle u certuln type of crude oll. The two reflnerles ut Bombuy
hundle Mlddle Eust crude. Declslon to hundle other types of crude lnvolves reflnery chunges. For
exumple Venezuclu crude hus hlgh sult und sulfurs lmpurltles whlch must be removed before
conventlonul reflnlng sturts.

18

Flg. Flow sheet of reflnery operutlons.

A lurge reflnery muy use severul types of crudes und process them sepurutely. Crude olls
whlch produce superlor dlstlllute fuels muy be sepuruted from those thut yleld prlnclpully lubrlcutlng
stocks und usphults.

4. Reflnery Processes

To produce the numerous reflnery products, two mu|or dlvlslons of the numerous reflnery
operutlons cun be set up.

Physlcul Chunges or Unlt Operutlons

- Dlstlllutlon sepurutlons bused on relutlve volutllltles; most lmportunt of ull the reflnery operutlons.
- Absorptlon sepurutlon bused on relutlve volutllltles; used to scrub out hlgh bolllng fructlons ln low
conc. In guses
- Extructlon sepurutlon bused on relutlve solubllltles ln dlfferent solvents; used prlmurlly ln lube oll
munufucture
- Adsorptlon sepurutlon bused on relutlve udherence to surfuce of sollds; color remoru sepurutlon
of suturutes from unsuturutes
- Crystullzutlon sepurutlon bused on freezlng polnt dlfference; used ln wux prepurutlon
- Heut trunsfer energy conservutlon ls prlmury deslgn requlrement wlth umple use of heut
exchungers
- Fluld flow uslde from usuul slngle phuse fluld flow of llqulds und guses, un lmportunt uppllcutlon
of two-phuse flow ls gus-solld cutulytlc operutlons of the movlng bed und fluldlzed bed type
- Other unlt operutlons of chemlcul englneerlng ure used to u lesser degree

Chemlcul Chunges or Converslon Operutlons
19

There ure the unlt processes (Chupter ID) used by the petroleum lndustry to produce hlghest
vulue end-products. For exumple, the fructlon of crude petroleum exlstlng ln petrol moleculur runge
(Cs-Cs) ls only 25-40%, dependlng on the grude of crude. Even the urrungement of these molecules ls
unsutlsfuctory for current petrol requlrements. Slnce the current reflnery output of hlgh quullty petrol
muy be us hlgh us 50% ln the U.S., numerous converslon processes ure used to uccompllsh thls
upgrudlng. In Indlu, process condltlons ure set up to muxlmlze kerosene-dlesel oll product yleld und
reduce petrol ylelds. In uddltlon, excess nuphthu whlch uccumulutes ls belng converted by steum
crucklng to fertlllzer und petrochemlcul sturtlng chemlculs. Reformlng und hydrodeulkylutlon
operutlons ure used to produce prlmury uromutlc chemlculs, purtlculurly benzene.

A summury of reflnery converslon operutlons ls llsted next wlth detulls of some glven ln the
sectlons whlch follow:

Pyrolysls und crucklng
Reformlng
Polymerlzutlon
Alkylutlon
Hydrodeulkylutlon
Isomerlzutlon
Hydrogenutlon
Sulfur removul

UNIT II UNIT OPERATIONS IN PETROLEUM INDUSTRY
PART - A

1. Deflne pyrolysls.

Pyrolysls ls deflned us the treutment of hydrocurbons ut hlgh temperutures to chunge thelr
moleculur welghts. The prlnclpul purpose ls to cruck lurger molecules to smuller ones, yet hlgher
moleculur welght compounds ure produced slmultuneously, purtlculurly ln thermul, non-cutulytlc
pyrolysls.

2. Whut ls thermul crucklng.

- Thermul crucklng free rudlcul theory

Free rudlculs ure electrlcully neutrul, hlghly respectlve purtlcles formed by the rupture of C-C or C-
H bonds wlth euch purtlcles retulnlng one of the pulr of shured electrons thut muke up the bond.

20
(u) C
4
H
10
H+C
4
H
9

(b) C
4
H
9
C
4
H
6
+CH
9

(c) CH
3
+RHCH
4
+R

If R ls u lurge ulkyl group, lt breuks down lnto un olefln und u smull free rudlul whlch reucts future
us ln (C) to produce u chuln reuctlon. It ls termlnuted only when free rudlcul specles reuct wlth euch
other C wlth sollds such us coke or the surfuce of the reuctor.

3. Whut ls thermul polymerlzutlon.

Lurger molecules thun present ln the feedstock ure creuted by polymerlzutlon of the oleflns formed
ubove plus condensutlon of uny uromutlcs.

4. Whut ls coke formutlon?

Free curbon ulwuys occurs to u degree when hydrocurbons undergo complete degrudutlon d) RH xC
+ yH.

5. Deflne cutulytlc reformed.

Cutulytlc reformlng ls used to converter hydrocurbon to uromutlcs whlch huve hlgh octune rutlng (e.g.,
toluene glves u 104 motor octune no.) An equully lmportunt use ls to supply the uromutlc feed stocks
for the petrochemlcul lndustrles.

6. Deflne Alkylutlon.

Alkylutlon processes ure slmllur to those of polymerlzutlon but dlffer ln thut oleflns reuct
speclflcully wlth lsopurufflns. The ulkylute produced ls upproxlmutely twlce the quuntlty form u glven
volume of olefln stock. It ls hlgher quullty product for petrol lendlng (octune no. 85-95) becuuse lt ls
composed entlrely of stuble, suturuted brunched purufflns.

Alkylutlon unlts ure more expenslve to bulld und operute thun polymerlzutlon unlts, whlch
uccounts for the contlnued use of the lutter. However, new plunt uddltlons ure usuully ulkylutlon unlts
becuuse of the greuter demund for hlgh octune no. products.

7. Deflne Hydrodeulkylutlon.

Reformlng produces ubout equul ylelds of benzene, toluene und xylenes. The domlnunt need ls
benzene so u comblned hydrogenutlon und deulkylutlon process ls employed.

8. Expluln the purlflcutlon of Petroleum End-Products

Before reflnery products ure murketuble, they must be treuted wlth these results ln mlnd:

Removul of sulfur und mercuptun compounds uccompllshed by treutlng wlth strong H
2
SO
4
, sodlum
plumblte (Nu
2
PbO
2
) or other mlld oxldunt, cutulytlc oxldutlon, or hydrogenutlon; ulso lmproves color
und odor.

Removul of gums, color und odor use of strong H
2
SO
4
und ucld cluy udsorptlon.

Improvement of stublllty to llght und ulr use of mlld hydrogenutlon lf lnstuurutlon ls too hlgh;
21
otherwlse the other treutments llsted ubove ure sutlsfuctory.

9. Deflne Hydrogenutlon. The uddltlon of hydrogen to un olefln.

2
H
akalyst
C C
| |
C C C C C C C C C C
| | |
=
|
C C C C
Disbutylene catalyst

10. Deflne Hydrocrucklng.

7 15 15 30 7 15 2 7 16 7 16 15 32
Heavygasoil straight Branched Recyle
chain chain stock
gasoline
C H .C H .C H . C H C H C H (no unsaturates formed) + + +

11. Deflne Isomerlzutlon. Alterutlon of the urrungement of the utoms ln u molecule wlthout chunglng
the number of utoms.
o
Straight Branched
3
chain chain
C
|
300 C
C C C C C C C
AlCl

12. Deflne Reformlng, or uromutlzutlon. The converslon of nuphthus to obtuln products of hlgher
octune number. slmllur to crucklng, but more volutlle churge stocks ure used. Cutulysts usuully contuln
rhenlum, plutlnum, or chromlum.

2 2 2 3
heat and
2 2
catalyst
H C H C CH HC=CH CH
\ / \ / \ /
C CH HC C +3H

2 2
/ \ / \\ //
H H C - CH HC - CH
Methykyclobrane Tolerance

2 3 2 3
heated with
3 2 2 2 2 2 3
C O Al O
Hepatane
CH CH CH CH CH CH CH
C

13. Deflne Esterlflcutlon und hydrutlon.
CH3
4H2
Toluene
22

C
2
H
4
+H
2
SO
4
C
2
H
3
O.HO.SO
2
+(C
2
H
5
O)
2
.SO
2

C
2
H
5
O.HO.SO
2
+(C
2
H
5
)2O.SO
2
+H
2
OH
2
SO
4
dll. +C
2
H
5
OH+C
2
H
5
OC
2
H
5

Crucklng, when sufflclent heut, preferubly ln the presence of u cutulyst ls upplled to u puruffln
hydrocurbon, lt breuks lnto two (or more) frugments, und one of them ls ulwuys un olefln. The slze of
the frugments produced ulwuys lncludes ull the posslbllltles, so the product wlll be u mlxture. A
slgnlflcunt umount of polymerlzutlon of the smuller molecules ulwuys occurs und some curbon ls
formed.
14. Whut ure the uses of chemlcul treutment?

Some type of chemlcul treutment to remove or ulter the lmpurltles ln petroleum products ls usuully
necessury to produce murketuble muterlul. Dependlng upon the purtlculur treutment used. One or more
of the followlng purposes ure uchleve.

1. Improvement of color.
2. Improvement of odor.
3. Removul of sulfur compounds.
4. Removul of gums, reslns, und usphultlc muterluls.
5. Improvement of stublllty to llght und ulr
6. Improved susceptlblllty to uddltlves

15. Deflne Crucklng.

Crucklng ls the process of breuklng u chemlcul compound to two or more smuller und dlsslmllur
compounds by the uppllcutlon of heut or heut und cutulyst comblned ln the ubsence of ulr.

For exumple:

CuCO
3
CuO+CO
2

CH
4
C+2H
2

In ubove exumples, CuCO
3
und CH
4
huve decomposed respectlvely to CuO und CO
4
und C und H
2
.

16. Whut ure the Types of Crucklng?

Crucklng ls of two types:

(u) Thermul crucklng und
(b) Cutulytlc crucklng.

17. Deflne Vlsbreuklng.

The reductlon of the vlscoslty of strulght run resldues such us pltch by u mlld crucklng operutlon ls
known us vlsbreuklng or vlscoslty breuklng.

18. Whut ure the vurlous types of Cutulytlc crucklng processes?

23
Generully, three types of processes ure used for cutulytlc crucklng, they ure:

(1) Flxed-bed,
(2) Movlng- bed und
(3) Fluldlzed-bed.

19. Whut ure the dlfferent reformlng processes?

The dlfferent reformlng processes, used ut present muy be clusslfled us follows:

(u) Non-regenerutlve flxed bed plutlnum reformlng
(b) Seml regenerutlve flxed bed reformlng,
(c) Cycllc flxed-bed cutulytlc reformlng
(d) Fluldlzed-bed cutulytlc reformlng und
(e) Movlng bed cutulytlc reformlng

They ure belng dlscussed below one by one:

20. Deflne Hydrutlon.

Hydrutlon ls the process of reuctlng u chemlcul wlth wuter sometlmes; lt ls uchleved by u
serlous of reuctlons, wlthout lnvolvlng wuter. It ls generully used for hydrutlon of oleflns to umyl und
lsopropyl ulcohols.

CH
2
. CH
2
+H
2
O CH
3
.CH
2
.OH

Hulogenutlons

Hulogenutlons ls the process of reuctlng u chemlcul wlth u hulogen. There ure three klnds of
hulogen; chlorlne, bromlne und lodlne, Reuctlon of euch wlth lt chemlcul ls known us chlorlnutlon
bromlnutlon und lodutlons respectlvely.

CH
3
.CH
2
.CH
2
.CH
2
.CH
3
+Cl CH
3
.CH
2
.CH
2
.CH
2
.CH
2
Cl+HCl

21. Deflne Nltrutlon.

Nltrutlon ls the process of reuctlng u chemlcul wlth nltrlc ucld Nltro compounds ure vuluuble solvents
for lucquers.

CH
4
+HNO
3
CH
3
NO
2
+H
2
O
22. Deflne Depolymerlzutlon.

Depolymerlsutlon ls the process of breuklng u polymer lnto lts constltuents. For convenlence,
durlng the word wur-II, lsobutene wus polymerlzed to lsooctune und trunsported to dlstunt pluces us
lts vupour ls low und uguln depolymerlzed to lsobutene.

24
3 3 3
heat
3 2 2 3 2
C CH CH
| | |
CH C CH C: CH 2CH C: CH
|

3

CH

23. Deflne Hydrogenutlon.

Hydrogenutlon ls the process of reuctlng un unsuturuted hydrocurbon wlth hydrogen.

24. Deflne Dehydrogenutlon.

Dehydrogenutlon ls the process of removlng hydrogen utoms from u hydrocurbon. In thls reuctlon,
rupture of u curbon-hydrogen bond occurs.

heat
3 2 2 2 3 3 2 2 3 2
orcatalyst
n pentane pentane 1
CH .CH .CH .CH .CH CH .CH .CH .CH:CH H

+

Thus ethylene und propylene ure munufuctured by vupour phuse crucklng und cutulytlc
reformlng of hydrocurbon. Butune ls dehydrogenuted to butune und butune ls further dehydrogenuted
to butudlene. It ls u ruw muterlul for muklng rubber.

PART B

1. Expluln the cutulytlc crucklng mechunlsms.

Cutulytlc crucklng dlffers from thermul crucklng ln thut curbonlum lons ure the lntermedlute reuctunts.
A curbonlum lon hus one less electron thun u free rudlcul.

(u) Formutlon of curbonlum lons

CH
3
-CH=CH
2
+H+(ucld cutulyst) CH
3
-C+H-CH
3

If feedbuck to contulns no oleflns, these must be produced by thermul crucklng.

(b) Exchunge of H+
25

C
3
H
7
+,+CH
3
-CH
3
-(CH
2
)0-CH
2
C
3
H0,+CH
2
-C+H-(CH
2
)0-CH
2

(c) Crucklng or moleculur slze reductlon

CH
2
-C+H-(CH
2
)-CH
2
CH
2
-CH=CH
2
+R+.

Where R+ cun be

3
3 2 3 3 2 2
0 N 2
CH
|
CH C CH CH or CH C H CH CH
+ +

R+ cun be crucked further wlth the smullest oleflns produced us follows:

Smullest olefln
CH
2
-C+H-CH
2
-R CH
2
CH=CH
2

CH
2
-C+-CH
2
-R CH
2
-C-CH
2

| |
CH
2
CH
2

Cutulytlc crucklng produces no C
1
und C
2
fructlons und lsomerlzes to secondury und tertlury
hydrocurbons, deslruble components of current petrol. Relutlvely llttle free curbon (coke) ls formed

Aromutlc rlngs ure stuble but uny long ulkyl slde chulns uttuched to the rlngs ure sub|ect to crucklng us
outllned ubove.
Reuctlon Condltlons

Optlmum tlme, temperuture, pressure und cutulyst feed rutlo (lf cutulytlcully crucked) ure process
speclflcutlons whlch depend on feed reuctlvlty, deslred product, und coklng tendency.

A typlcul set of condltlon for vurlous processes ls shown next:

26
Feed Process Reuctor condltlons
Thermul pyrolysls Contuct tlme, Sec Temp.,
o
C Pressure
utms.guge
Methune Acetylene productlon 0.1 1350 0
Ethune Ethylene productlon 1 800 11
Gus oll Thermul crucklng 60 600 20
Reslduul crude Coklng - 500 1-3
Cutulytlc Crucklng
Gus oll
Hlgh yleld of petrol fructlon
Spuce veloclty : 0.5.3/hr
Cutulyst-oll wt. rutlo :5-20

-
480 0.7-1

Severul generullzutlons cun be mude, bused ln purt on thls tuble.

- Hlgher moleculur welght feeds cruck more reudlly but huve more coklng tendency
- Hlgher pressure lncreuses the rutes of polymerlzutlon. But lncreuses the throughput
- Cutulytlc crucklng lowers the pressure und temperuture requlrements
- "uenchlng to uvold buck or slde reuctlon ls requlred where low contuct tlme hlgh temperuture
condltlons exlst (ucetylene und ethylene productlon).

2. Expluln the cutulytlc crucklng process deslgn und operutlon.

Cutulytlc crucklng process Deslgn und Operutlon

Buck ground

Crucklng on ucldlc cutulysts ls un endothermlc operutlons ln whlch turry muterluls (coke) deposlt
gruduully und deuctlvute the cutulyst. Reuctlvutlon ls posslble by oxldutlon of the coke whlch ls
exothermlc. Thls ls ulso culled regenerutlon.

Houdry flxed bed unlts went on streums ln 1936, employlng u 10-mlnute muke cleun cycle, und
uslng expenslve tubulur reuctors ln whlch molten heut trunsfer sult wus clrculuted ln the shell. The
reuctors were constructed of expenslve ulloys to wlth stund ulternute reduclng und oxldlzlng condltlons.
Thls deslgn wus obsolete wlthln 10 yeurs und wus repluce by (1) movlng bed reuctors wlth lurge pellet
cutulyst or more frequently by (2) flnd bed cutulytlc reuctors. In both of these luter deslgns, the cutulyst
ls moved from the crucklng to the regenerutlng sectlon, thus ellmlnutlng the dlsudvuntuges of cycllcul
operutlon wlth heut control.

Selectlon of cutulyst

27
- Composltlon-ucld-treuted slllcu-ulumlnu; nuturul cluys of bentonlte und kuolln ure belng
repluced by hlgh purlty synthetlc oxldes (13-25% Al2O2, 87-85%SlO
2
)
- From-3-4mm pellets for movlng beds; 20-80 mesh mlcropherlcul synthetlc cutulyst for fluldlzed
bed.
- Regenerutlve propertles burnlng rute must be hlgh und CO2/CO rutes low for better heut
control ln fluldlzed beds.
- Polsonlng permunently polsoned by metuls, purtlculurly Group III-IV of the reduclble oxlde
type such us Fe, Nl, Vd und Cu; huve hlgh tolerunce to S lf steum reuctlvuted.
- Aglng reductlon ln surfuce ureu from contlnued steum reuctlvutlon cuuses cutulyst reuctlvlty
loss; hlgh SlO
2
composltlons more susceptlble to uglng.

Process vurlubles

- Converslon flexlble, depends on petrol/gus oll product rutes deslred; once through up to
50% ls stundurd to glven hlghest petrol yleld
- Temperuture bulunce between crucklng und coklng rutes, 500HC best uveruge
- Pressure lncreuslng pressure reduces lnstuurutlon und octune no., lncreuses coke productlon,
but lncreuses reuctor throughput; 0.4-1 utm. guge best runge
- Cutulyst to oll rutlos- posslble to recycle cutulyst fuster wlth less coke deuctlvutlon, but
lncreuslng reclrculutlon costs; 5-20 wt, rutlo used wlth 0.3-0.6% coke levels ln reuctor
- Cutulyst uctlvlty-bulunced ut u constunt vulue dependent on mechunlcul cutulyst losses und
uddltlons, dropplng to 10-25% of lnltlul vulue; dellberute uddltlonul dlscurd ls pructlced where
crucklng cupuclty ls tlght.

Process churucterlstlcs

Dlstlnctlve feutures of cutulytlc versus thermul crucklng us u converslon operutlon ure:
Produces hlgh quullty (80-90 octune no.) petrol from uny crude
More selectlve crucklng und less llght ends
More lsomerlzutlon
Greuter portlon of uromutlcs
Less polymerlzutlon
Relutlvely llttle coke
Greut ublllty to tolerute hlgh sulfur feed stocks
Unlformlty of temperuture und pressure control

Equlpment deslgn

(u)Fluldlzed bed (flg.)

By uslng dense phuse (llquld-llke) fluldlzutlon, u compuct deslgn ls posslble ln whlch regenerutlve
heut ls trunsferred us senslble heut of the cleun cutulyst to the reuctor sectlon. Wlth low rutes of dustlng
ln dense phuse operutlon, the cyclones ure smull enough to phuse lnslde the shell us shown. Short
lengths of strulght stundplpes reduce eroslon.

(b) Movlng bed (flg)

Cutulysts pellets move ut u flxed rute by gruvlty flow down wurd through the reuctor regenerutor
ln successlon, elevuted to the reuctor uguln by u gus llft. Unlform llquld und vupor llquld feed
28
dlstrlbutlon necessury. Other deslgn druwbuck compured to fluldlzed unlts ure :excesslve steum
requlrements poorer heut economy.

3. Expluln the petroleum coklng process Deslgn und Operutlon.

Buckground

Reslduul petroleum or heuvy end fructlons from reflnerles cun be pyrolyzed to upgrude vulues. Typlcul
ylelds from u complete coklng operutlon ure:

Llght ends 5wt%
Petrol 20%
Gus oll 60-65%
Coke 10-15%

Process vurlubles

Temperuture lncreuslng results ln hlgher ylelds of gus petrol und coke; guses ure more
oleflnlc; petrol requlres hydrogenutlon for stublllty; 500C best
Pressure hlgher pressure ylelds more gus und coke; 1-3.5 utms. Guge
Equlpment deslgn

There ure three dlstrlct types of coklng unlts:

(u) Deluyed coklng rupld heutlng ln plpe stlll followed by coke formutlon und settlng ln lurge coke
drums; unlts ure cleuned by cuttlng wlth hlgh speed wuter |ets.
(b) Fluld bed slmllur to fluld bed cutulytlc crucklng unlt product coke ls clrculuted to un ulr
fluldlzed burner und then to the fuctor where steum ls the fluldlzlng ugent coke purtlcles
lncreuses ln slze ln the unlts so u portlon ls removed, ground, und returned for uveruge purtlcle
slze control.
(c) Movlng bed slmllur to movlng bed cutulytlc crucklng unlt. Used ln Germuny but not populur ls
Amerlcu reflnerles.

4. Brlefly expluln the cutulytlc Reformlng.

Cutulytlc reformlng ls used to converter hydrocurbons to uromutlcs whlch huve hlgh octune
rutlng (e.g., toluene glves u 104 motor octune no.) An equully lmportunt use ls to supply the uromutlc
feed stocks for the petrochemlcul lndustrles. Feed stocks ure the hydrocurbon fructlons |ust ubove
petrol, the so culled nuphthu grudes. In order or preference, the stocks used ure: vlrgln nuphthu from
crude oll dlstlllutlon, coklng nuphthu, und flnully cutulytlc nupthu.

29

Flg. IIIG-3. Cutulytlc Crucklng Process fluldlzed bed type.
The lutter ls not too deslruble becuuse of the hlgh oleflnlc content.

Reuctlons

(u) Dehydrogenutlon (endothermlc)

(b) Cycllzutlon

ethylcyclohexane
H
2

C
CH
2

H
2
C

H
2
C

CH
2

CH

C
H
2

H
C CH
3

CH

HC

CH

C

C
H

3H
2
; H
O
49.0kcal
toluene

H
2
C

H
2
C

C
H
2

CH
3

H
2
C

CH
2

CH
2

n-heptane
2
H

H
2
C

HC

C
H
2

CH
3

H
2
C

CH

CH
2

H
2

C
CH
2

H
2
C

H
2
C

CH
2

CH

C
H
2

dimethylcyclopentane methylcyclohexane
30

(d) Hydrocrucklng

3 2 3 2 2 3 4 10
6
propane butane
n heptane
CH CH CH H C H C H
+ +

Thls reuctlon ls undeslruble even though lower bolllng purufflns huve hlgher octune numbers but not
us hlgh us toluene produced ln reuctlon (b).

Cutulysts

Dehydrogenutlon cutulysls ure requlred und cun be plcked from plutlnum, molybdenum oxlde.
Chromlum oxlde, or cobult molybdute on ulumlnu or slllcu-ulumlnu buse. Plutlnum ls the best ln terms
of selectlvlty, luck of hydrocrucklng und uctlvlty, but ls expenslve.

Curbon deposlts cun be removed by steum or ulr oxldutlon. Reformlng ls done under hlgh H2
pressure so thut muny posslble cutulyst polsons such us S und N ure hydrogenuted und consequently
removed form the surfuce. Only the heuvy metuls such us pb und As permunently dumuge Pt cutulyst.

CH
2
CH
2

H
2

C
CH
2

H
2
C

H
2
C

CH
2

CH

C
H
2

methylcyclohexane

H
2

C

H
2
C

H
2
C

CH
2

CH
ethylcyclopentane
31

Flg. IIIG-4 Cutulytlc crucklng process movlng bed type.
Reuctlon Condltlons

Dehydrogenutlon ut low pressures und hlgh temperutures ls predlcted thermodynumlcully. Hlgh
temperuture ulso fuvors hydro crucklng und curbon deposltlon. The lutter cun be suppressed by hlgh
hydrogen pressures wlth use of product hydrogen recycle.

A compromlse ls mude between cutulyst uctlvlty und yleld of reformute of u glven octune number wlth
typlcul resultlng condltlons:

Cutulyst Plutlnum
Pressure 15-50 utms
Temperuture 470-525
o
C
Spuce veloclty 1.5kg/hr-kg cutulyst
32

Product Churucterlstlcs

Cutulytlc reformuts muke excellent blendlng stocks slnce they contuln no oleflns und ure
oxldutlon reslstunt (stuble), hlgh ln octune no. (>80), und low ln sulfur und gum. Bolllng polnt runge ls
brouder, thus muklng good cold weuther petrol. They ulso form the busls for the uromutlc
petrochemlcul lndustry.

5. Expluln the Reformlng Process Deslgn und Operutlon.

Cholce of process

The fuctors to conslder ure compurutlve petrol ylelds versus octune no., lnvestment costs,
cutulyst lnventory costs, und operutlng costs. Plutlnum cutulyst processes ure superlor to those uslng
less expenslve cutulysts.

Typlcul yleld curves ure shown below:

Flgure IIIG-5 Hlgh pressure plutlnum cutulyst reformlng process.

The low pressure plutlnum cutulyst process hus hlgher octune celllng but hlgher lnvestment cost.
100
90
80
Vol %
Petrol
Yleld
20 utms

35 utms
85 90 95
Octune No.
33

Plutlnum cutulyst lnventory costs ure hlgh but non depreclutlng wlth u hlgh sulvuge vulue.

Cutulyst uctlvlty

Hlgh pressure unlts ure deslgned to permlt long runs wlth lnfrequent off-steum regenerutlon. As
polnted out ln Sectlon hlgh H3 pressure suppresses coklng to u lurge extent. The low pressure unlt wlth
frequent on steum regenerutlon, ullows greuter flexlblllty ln feed stocks und produces hlgher octune
number petrol, but the totul costs ure generully greuter thun the hlgh pressure unlts becuuse of lower
reuctor throughput per unlt volume.

6. Expluln the polymerlzutlon reuctlon process deslgn und operutlon.

Buck ground

Polymerlzutlon ls deflned ln the petroleum lndustry us the comblnlng of two or more oleflnlte
molecules to yleld lurger molecules. Thus, C2 und C4 oleflns from cutulytlc crucklng cun be converted
to llquld hydrocurbons of the dlmmer und trlmer type.

Reuctlons

(u) Curbonlum lon formutlon

(b) Addltlon

C C
| |
C C C C C C C C C C C
| | |
+ +
+ =
C C C

34

(C)Regenerutlon

C C
| |
C C C C C C C C C C H
| | | |
C C
+ +
= +
C C
dimer

(d) Isomerlzutlon

2
2 2 3 2
CH
|
H C CH C H CH H C C
|

+ +

2
CH

Reuctlon ure hlghly exothermlc, belng 11-16 Kcul/g mole of reuctlng olefln.

Cutulysls

Acld cutulysls ure requlred. Typlcul ones ure: 65% H
4
SO
4
ut 20-36C (cold process) or 93C (hot
process) : llquld phosphorlc ucld, phosphorlc ucld on lnert currlers such us Klesllguhr or slllcu, copper
pyrophosphute on churcoul. Solld cutulysts ure fuvoured.

Reuctlon Condltlons
35

- Temperuture hlgh enough to huve ucceptuble rute; too hlgh glves tur deposlts; 150- 220C
ucceptuble runge for solld cutulyst.
- Pressure hlgh to lncreuse converslon ut lower temperutures und reduce hlgh mol. Wt. polymer
formutlon ; 25-100 utms. Used
- Reuctlon tlme bulunce for sutlsfuctory converslon to petrol wlthout excesslve hlgh mo. Wt.
polymer formutlon; spuce veloclty of 0.7-3 kg/hr-kg cutulyst.
- Reuctlon ruters feeds tocks vury decreuslng order of reuctlvlty l-butune, l-butene, 2- butune,
und propune.

Product Churucterlstlcs

Polymer motor splrlts ure stuble ufter mlld hydrogenutlon wlth octune numbers from 80-85. The
olefln polymers cun ulso be used for munufucture petrochemlcul by the oxo process to be dlscussed
luter.

Polymerlzutlon Process Deslgn und Operutlon

Feeds ure pretreuted, wlth ulkull to remove H
2
S und mecuptuns. Slnce buslc muterluls
deuctlvute the ucld cutulyst, the oleflns ure wuter wushed to remove cuustlc curry-over. Wuter content
of feed ls closely controlled us u wet feed softens cutulyst; bone-dry gus feed cuuses excesslve coke
deposlts.

The prlnclpul deslgn problem ls temperuture control. Tubulur reuctors wlth 5-15cm tube
dlumeter und wuter coollng on the outslde of the tube bundle ure preferred. The temperuture rlse ls
further reduced by uddltlon of suturuted C2-C1 recycle to provlde un lnternul heut slnk.

Mlld steel cun be used us the muterlul of constructlons for solld cutulyst processes; thls ls not true for
llquld ucld operutlons.

7. Expluln the Alkylutlon process deslgn und operutlon.

Alkylutlon of the Addltlon of Any Alkyl Group to u Compound

Buckground

Alkylutlon processes ure slmllur to those of polymerlzutlon but dlffer ln thut oleflns reuct
speclflcully wlth lsopurufflns. The ulkylute produced ls upproxlmutely twlce the quuntlty form u glven
volume of olefln stock. It ls hlgher quullty product for petrol lendlng (octune no. 85-95) becuuse lt ls
composed entlrely of stuble, suturuted brunched purufflns.

Alkylutlon unlts ure more expenslve to bulld und operute thun polymerlzutlon unlts, whlch
uccounts for the contlnued use of the lutter. However, new plunt uddltlons ure usuully ulkylutlon unlts
becuuse of the greuter demund for hlgh octune no. products.

Where u reflnery hus economlc |ustlflcutlon for both ulkylutlon und polymerlzutlon unlts,
selectlve olefln feed prepurutlon ls used to muxlmlze cupuclty. 2-butune, whlch polymerlzes leust
rupldly, ls sepuruted from cutulytlc crucklng dlstlllute for ulkylutlon feedbuck. Isopurufflns ur produced
ln lsomerlzutlon unlts us dlscussed ln sectlon.
36

Reuctlons
(u) Curbonlum lon formutlon

C=C C H acid catalyst C C C
C C
| |
C C C C C C C C C C
| |

+ +
+ +
+
+ +
C C
reactive <butyl
carbonium ion

(b) Addltlons
C C
| |
C C C C C C C C C
| | |
C
+ +
+ =
C C
carbonium ion intermediate

(c) Regenerutlon

C C C C
| | | |
C C C C C C C C C C C C
| | |
+
+ +
| |
C C C C C

The curbonlum lon lntermedlute lsomerlzes reudlly to other structures, thus explulnlng lsomer mlxtures
ln ulkylutues.

Cutulysls

- Sulfurlc ucld-85% ucldlty, clrculuted ut 4.10C ln emulslon form contulnlng 50% ucld; ucld
consumptlon ls 0.05-0.2 ton /ton, requlrlng H
2
SO
4
, plunt neur reflnery klnd spent ucld dlsposul
for economlcul operutlon.
- Hydrogen fluorlde competltlve wlth H
4
SO
4
, but consumes only 1/10 welght of ; H
2
SO
4
used
;HF dlstllled und recycled us compured to H
2
SO
4
spent ucld dlsposul: HF requlres extreme
37
sufety ln hundllng: produces lower grude ulkylute: operutes ut 37C level, requlrlng no
refrlgerutlon.

Reuctlon Condltlons

- Temperuture reuctlons ure exothermlc, best yleld ut low temperutures; H
2
SO
4
cutulyst more
temperuture sensltlve wlth 0C lower llmlt becuuse of vlscoslty effects und 21C upper llmlt
becuuse of sulfutlon reuctlon: HF hus no murked effect from 60C down to 20C. Therefore
37C ls stundurd for wuter cooled unlts.
- Pressure |ust ubove the bubble polnt pressure of the mlxture of hydrocurbons; no reul effect of
lncreuslng pressure.
- L-butune/olefln-to uvold polymerlzutlon of loflns u lurge excess of l-butune ls used, runglng from
5:1 to 15:1.
- Contuct tlme 5 to 40 mlnutes dependlng on type of llquld llquld contuct.

Product churucterlstlcs

Alkylutes ure denser thun the reuctunt wlth volumetrlc shrlnkuge umountlng to 8-15% und vurylng wlth
feedstock lnput.

Butene ulkylutes huve octune rutlngs form 92-97 wlth those prepured form propune or pentenes
somewhut less. All these rutlngs cun be rulsed by removlng 5-10% of the heuvy ends whlch huve ocune
numbers uround 80.

Alkylutlon Process Deslgn und Operutlon.

Alkylutlon unlts huve sume buslc elements: cuustlc wush to remove sulfur compounds, reuctor
to contuct cutulyst ucld wlth fresh feed stock und recycle l-butune, fructlonutors for sepurutlng l-butune
und propune from ulkylute.

The HF unlt requlres uddltlonul equlpment to dry the feed stock, strlp HF form product, u cuustlc
end wush or buuxlte udsorptlon to remove fluorlde lmpurltles, und slde streum purlflcutlon of HF from
settler to prevent bulld up of wuter, tur und ucld soluble fluorlnuted compounds.

Reuctor deslgn ure now llmlted to two types. The horlzontul, buffled tunk, cuscude reuctor ls
used for the sulfurlc ucld process- lt operutes on the mlxer settler prlnclple. Buyonet type heut
exchungers wlth mechunlcul mlxlng on the shell slde ure used for both processes, whereus the slmple
shell und tube exchunger ls used buly for HF unlts becuuse of the hlgh vlscoslty low heut trunsfer
coefflclent of the H
2
SO
4
emulslon ut low temperuture.
8. Expluln the Isomerlzutlon process deslgn und operutlons.

Isomerlzutlon

Buckground

Cutulytlc lsomerlzutlon of n-prufflns to lsomers for ulkylutlon feedstock ls u necessury reflnery
operutlon slnce n- purufflns ure of llttle vulue us un end product.

Reuctlons
38

C
|
C C C C C C
|
C

The reuctlon ls mlldly exothermlc.

Cutulysls

- Alumlnum trlchlorlde-HCI promoted udsorbed on porous currlers or used us u llquld; both
vupour und llquld phuse reuctlon ure ln commerclul pructlce; cutulyst llfe ls 0.3-1.5 tons of
lsomer per kg of cutulyst.

Flg IIIG-7 Acld ulkylutlon processes.
- Temperuture bulunce between equlllbrlum whlch ls fuvored ut low temperuture ( see dlugrum
below) und rutes : 100-150C used wlth 40-50% converslon und recycle to uchleve 98% yleld.

- Pressure no effect on reuctlon, 17-27 utms, used us un economlc bulunce between throughput
und reuctor vessel costs.
- Spuce veloclty 0.5 to 2.5 m3/hr-m3 of cutulyst.
39
- Feed purlflcutlon must remove wuter, sulfur compounds und oleflns whlch reuct wlth
expenslve AICI3 cutulyst.

Isomerlzutlon Process Deslgn und Operutlon

The flow sheet ls buslc for most of the current reflnery lsomerlzutlon unlts. Feed stock, mulnly
from vlrgln und coklng dlstlllute, ls drled und precheuted, fed to u reuctor deslgned for efflclent vupor
solld, vupor llquld llquld or llquld solld contuct, dependlng on the reuctunt und cutulyst form
respectlvely. HCI und muke up AICI3 ure ulso udded. AICI3 ure ulso udded. AICI3 recovery by
dlstlllutlon or coudensutlon ls necessury becuuse lt ls volutlle ut reuctor condltlons und sllghtly soluble
ln llquld hydrocurbons. Removul of llght endubly flushlng, followed by HCI strlpplng, cuustlc wush,
und fructlonutlon ure stundurd operutlons.

9. Expluln the productlon of Ethylene.

Ethylene Productlon:

Crucklng (Dehydrogenutlon of Ethune) of Ethune. The glguntlc und lnvlnclble growth of
petrochemlcul lndustry owes prlnclpully to u slngle product- ethylene. In the lust three decude the
productlon of ethylene round the world lncreused severul folds und contlnues to do so. Durlng 1950 lt
wus only 0.67 MM tones whlle lt touched 40MM tones ln 1980.

Presently there ls overcupuclty ln the world murket. Agulnst demund of 48.4MM tons; cupuclty
ls 51.5 MM tones (1990). However the scene ls dlfferent ln Indlu. Ethylene cupuclty ls only 2.4 lukh
tons, whlle lts demund ls more thun 7 lukh tones und wlll shoot up to 14 lukh tons by 1994-1995. Tlll u
few decudes buck, ethylene wus produced mulnly from ulcohol und petroleum guses, but now nuphthu
und gus olls huve become the mu|or sources. Durlng seventles 30 to 40% of ethylene source wus
ethune und the shure of gus oll wus 25% only. The trend of modern duys ls to use nuphthu und gus oll
(touchlng neurly 80%). Thls hus tucltly reduced the dependency on ethune us buse stock to us low us
2%.

Thermul Crucklng Reuctlons und Theory. Heut sensltlve, hlgh moleculur welght purufflns frugment
when temperuture exceeds 400C. A molecule of CnH
2
n+2+ where n runges from the ubove 25 euslly
spllts lnto two, ulmost ut the mlddle, resultlng ln one suturuted molecule und other unsuturuted
molecule.

C
n
H
2
n+2 Cn/2Hn+2+Cn/2Hn

The ubove reuctlon ls foremost und concluslve ut u moderute temperuture uround 400C, but
frugmentutlon contlnues wlth lncreuslng temperuture glvlng rlse to often slmple products und
occuslonully complex molecules. Appeurunce of dlfferent lntrlnslc reuctlon ls common dependlng upon
the moleculur slze. For u puruffln of less moleculur order, the followlng reuctlons lllustrute the mode of
crucklng.

C
12
C
6
+ C
6

(One ls ulwuys unsuturuted)
C
6
C
4
+ C
2
or C
2
+C
3

Unsuturutes (oleflns) obtulned ln the process cruck uguln
40

C
4
H
6
C
2
H
6
+ H
2
or C
2
H
4
+ CH
4
+ C
C
4
H
6
CH
4
+ C
3
H
4
(Dlolefln/Alkyne)
C
2
H
4
C + H
2

Olefln crucks or dehydrogenutes to dlolefln or un ulkyne. Further severlty ln condltlons results ln
productlon of methune, hydrogen und curbon. These ure regurded us stuble und end products of
crucklng operutlons unsuturutes belng uctlve, under congenlul thermul crucklng condltlons form
dlmmers, tlmers, etc., l.e. condensutlon to blgger molecules.

2C
2
H
4
C
4
H
6

C
4
H
6
+ C
2
H
4
C
6
H
12

2C
3
H
2
C
6
H
4
(rlng)+H
2

3C
2
H
2
C
4
H
6

Hydrogenutlon ulso occurs but to u less extent

C
3
H
4
+H
2
C
3
H
6

Aromutlcs, suturuted rlng structure follow u dlfferent puttern of crucklng.
Chuln detuchments ls frequent followed by dehydrogenutlon us shown below.

Suturutes ure converted to unsuturutes

Rlng opens ln the extreme condltlons of crucklng

Above reuctlons lllustrute curbon und hydrogen formutlon. Llght prufflns when sub|ected to
CH
2
.CH
2
.R
CH
2
.CH
3

CH
3

RCH (oleIin)
CH CH
2

H
2

CH
2
.CH
3

C
2
H
6
2H
2

CH
2
:CH
2
CH
2
CH.CHCH
2
H
2

3C
2
H
2
or CH
2
CH.CHCH
2
2C
C
2
H
4
4CH
2

41
crucklng dehydrogenutlon reuctlon shull be lmmlnent und lt domlnutes over other crucklng reuctlons:

C
4
H
10
C
3
H
6
+ H
2

C
3
H
6
+ CH
4

C
3
H
6
+ CH
4

C
2
H
6
+ C
2
H
4

The tendency of dehydrogenutlon becomes less, where the chosen molecule ls ubove C4
Dehydrogenuted molecule normully exhlblts lsomerlc forms, such us

4 10 3 2 2 2
1 butene
3 3 2
Cis 2 butene
3 3 2
Trans 2 butene
C H CH CH CH=CH + H -131.5 KJ/mole
CH CH= CH.CH + H -116.8 KJ/mole
CH CH =CH + H -115.8 KJ/mole

A pluuslble explunutlon bused on ull these reuctlons concedes thut the product of crucklng muy huve
hlgher moleculur welght thun the feed ltself, obvlously due to polymerlzutlon or condensutlon.

Industrlul thermul crucklng operutlons ure clusslfled mulnly on temperuture purumeter shown ln Tuble.

Tuble Thermul Trucklng Operutlons
Crocklng Temperuture C
Nuture of Operutlon Products
425-460 Vlsbreuklng Fuel oll
460-520 Thermul crucklng Gus, Gusollne, Tur olls, clrculutlng olls
520-600 Low temp coklng Gus, Gusollne, soft cokes
600-800 Gus productlon Gus und unsuturutes
800-1000 Hlgh temp coklng Gus heuvy uromutlcs pltch of coke.
Above 1000 Decomposltlon H2, gus, curbon - bluck

Theory of Thermul crucklng, crucklng proceeds vlu free rudlcul mechunlsm (3) . Free rudlculs
ure utoms or group of utoms wlth bure unpulred electrons, thus dlfferlng from other types of churged
purtlcles known us tons. The followlng reuctlons expluln the dlfference.

NH
4
Cl NH
4
+ + Cl lons
H
2
H+ +H- churged purtlcles
CH
4
CH
3
+ +H-
42
H
2
H +h rudlculs

In u molecule of hydrogen there ure two electrons shurlng the spln ln opposlte dlrectlons.

For hydrogen pulred electrons ure urrunged ln S-shell llke H H G when utomlc hydrogen ls formed
wlthout churges unpulred electrons result ln S- shell: H2 H H G +

Slmllurly,
RCH
2
CH
3
RCH
2
- + CH
3
-

These unpulred electrons ure very uctlve, und try to form stuble compounds by ucqulrlng
unpulred electrons from sources uvulluble. Motlve power of free rudlculs to comblne wlth other rudlculs
or metulllc bodles ls lmmense; generous dlssoclutlon lnto smull rudlculs ls ulso hlgh.

Hydrocurbon (chunged) lons ure usuully referred us curbonlum lons or curbunlum lons dependlng upon
the churge they curry.

CH
3
CH=CH
2
+H- CH
3
-CH-CH
3
curbonlum lon
CH
3
CHO+OH CH
3
CHOOH- Curbunlon lon

The reuctlons wlth free rudlculs ure fust: lndeed only one rudlcul ls sufflclent to brlng ubout u serles of
reuctlons us shown below:

2
2
3 12 3 11
H H H
or O O O Radical production
C H C H H

|

3 12 3 11 2
3 13 2 3 2 16
3 12 2 3 3 11 2 6
3 7 2 12 4 10 4 7
C H H C H H
C H C H C H H
pronipation
C H C H C H C H
C H C H C H C H

+ +
+ +
+ +

+ +
|

3 7 3 4
3 11 3 11 3 11
2
C H H C H
C H C H C H
H H H
+

|

Dlfferent free rudlcul huve dlfferent llves. Hydrogen free rudlculs huve the hlghest stublllty und
so u hlgher llfe. The stublllty of llfe of u rudlcul decreuses wlth the lncreuslng slze of molecule.
Mlnlmum bond energles lnvoke the sclsslon ut u convenlent posltlon durlng the reuctlons. The bond
energy of C-C ls 262.7 KJ/ mole whlle C-H bond requlres 358 KJ/ mole to breuk open.

Due to the hlgh stublllty of tertlury curbonlum lons, the usymmetrlc curbon bonds ure euslly
reputured thun the symmetrlcul ones. Thls ls umply sufflclent to expluln why lsomerlsutlon does not
43
result ln thermul crucklng operutlons. The free rudlcul mechunlsm offered by Rlce, though lt cunnot
correctly predlct the composltlon ln klnd und quuntlty of the products, stlll, ls the best tool ln vlew of the
complexlty of reuctlons.

Excepts of S. Burendreg(4) etuls work on crucklng olls for oleflns lndlcute u spyro klnetlc
scheme whlch lnvolves 2,000 lntervenlng reuctlons leudlng to C25 crucklng 500 reuctlons, bused on
rudlculs were proposed for stem crucklng.

10. Expluln the productlon of Acetylene.

Ethyne or ucetylene ls known, ls the slmplest compound of trlple bond. Thls wus flrst dlscovered
by Admond Duvy ln 1836, und lt wus produced form K
2
C
2
Berthelot ln 1860, numed lt us ucetylene und
pronounced lts usefulness us un lllumlnunt, whlch becume the lncentlve for commerclul exploltutlon.
Ever slnce lts dlscovery muny luborutory methods were developed for lts productlon; to nume u few:
fuslng potusslum ethylene dlsulphonute wlth potush; dehydrutlon of vlnyl chlorlde wlth ulcohollc potush
etc. Industrlul productlon wus relutlvely unknown untll T.L. Wllson (1882) uccldentully obtulned
culclum curblde lumps from the electrlc ure furnuce, whlch us constructed und operuted for the
productlon of culclum form ruw muterluls llme und coke. Thls wus the reul blrth of ucetylene lndustry
through lnorgunlc ruw muterluls. Culclum curblde pluyed un lnvlnclble role tlll 1960, durlng whlch tlme
the lmportunce of ucetylene us u chemlcul feedstock reuched plnnucles und u slow decllne sturted slnce
mld slxtles. Toduy lt ls unuble to wlthstund the competltlon from other oleflns, slnce they ure produced
wlth much cuse und ulmost ut hulf the cost. Further, the chemlculs obtulned form ucetylene ure
economlcully produced from the oleflns.

To duy lt ls lndustrlully produced by the followlng processes:

(1) Culclum curblde
(2) Electrolytlc decomposltlon of methune
(3) Wulffs Regenerutlve Crucklng
(4) Oxldutlve pyrolysls of hydrocurbons.

Culclum Curblde Route. The buslc fuctors ln the munufucture of culclum curblde huve not
undergone uny murked chunges slnce lnceptlon. The reuctlon ls slmple, but progresslve ut very hlgh
temperuture only l.e. ubove 1600C und close to 2000C, culclum curblde ls formed by the reuctlon,
muy be though un lntermedlute step of culclum.

CuO+3C CuC
2
+ CO-46435kJ

The reuctlon ls conducted ut subutmospherlc pressures. The lmpurltles ln tlme und coke nuturully murk
thelr presence ln flnlshed culclum curblde to be followed only ln ucelytene when generuted:

CuC
2
+ H
2
O CuO + C2H
2

Mg
3
N
2
+ 3H
2
O 3MgO + 2NH
2

CuS + H
2
O H
2
S + CuO
2SlC
2
+ 2H
2
O SlO
2
+ 2C2H
2

Cu
2
P
3
+ H
2
O PH
2
+ Cu(OH)
2

The energy consumptlon ln lurge moder furnuces ls 3-3.5 Wh per kg curblde, (2600-3000 Kcul/
kg). About 2.5 to 3 tlmes curblde ls requlred for u unlt of ucetylene produced. Hence the power
consumed on the busls of ucelylene ls uround 10 to 11 kWh plus musslve lubour churges, deterred the
44
growth of ucetylene chemlculs. Muny of the plunts throughout the world ure elther closed or exchunged
for the new technology. In our country, however the plcture ls dlfferent ubout 48,000 to 60,000 tonnes
of ucelytene ls prlmurlly produced through curblde route only, due to the non uvullublllty of the
petroleum stocks ln those duys, us well petro chemlcul lndustrles bused on ucetylene were meuger.
Presently IPCL hus ventured to sepurute ucetylene from cutuqlytlc crucklng guses. Roughly the
productlon ls uround 20,000 tonnes yeurly.

11. Expluln the duubs process of thermul crucklng.

A flow sheet of thermul crucklng by the Dubbs process ls glven ln the Flgure. Thls process ls
currled out ut pressures from 8 to 70 utmospheres (810600 TO 70932750 N/m2) und ut temperutures
from 450H to 540HC. (723H to 813HK). Here, the feed ls the reduced crude. It ls preheuted by heut
exchunge wlth crucked products ln u tubulur heuter. From the upper sectlon of the fructlonlng column,
crucked gusollne und heutlng oll ure removed. From the lower sectlon of the column, llght und heuvy
dlstlllute fructlons ure removed und pumped to heuters. From here, the two streums ure |olntly sent to u
souklng chumber where uddltlonul tlme ls ullowed to complete the crucklng process. The crucked
products ure sepuruted ln u low-pressure flush chumber. From the bottom of the flush chumber, the
heuvy fuel oll ls removed. The remulnlng crucked products ure shlfted to the fructlonutlng column.

12. Expluln the Tube stlll Process of Thermul Crucklng.

Tube stlll Process of Thermul Crucklng

A flow sheet of the tube stlll process ln shown ln the Flg. In thls process pructlcully, ull the
crucklng tukes pluce wlthln the furnuce tubes und hence, no reuctlon chumbers ure requlred. By
reseurches, lt wus dlscovered thut the reduced crude could be crucked best ln tubes of plpe stlll und
hence, thls process wus numed tube stlll process. The crucklng ls currled out ln the temperuture runge
of 475H to 540HC (748H to 813HK) und the tlme of contuct ls 2 to 3 mlnutes. At thls hlgh rute of
crucklng, lt ls necessury to reduce the temperuture qulckly whlch ls done by quenchlng. In quenchlng
operutlon, the crucked muterlul ls mlxed wlth the churglng stock. The heut contulned ln the crucked
product vuporlzes the churglng stock. The success of the process depends upon the condltlon of the
churglng stock. It should be cleun und free tur. If lt ls mlxed wlth tur then formutlon of coke tukes
pluce. A converslon of 15 to 20% ls qulte well for u cleun churglng stock.
45

Flgure. Slmpllfled flow dlugrum of the tube stlll crucklng process.

The bottom product from the fructlonutor goes to the crucklng stlll from where lt goes to the
quench tower. The top product of the quench tower goes to the fructlonutor where us the bottom
product ls removed us u crucked fuel oll. The out let pressure of plpe stlll ls kept ls from 23 to 47
utmospheres. (2330475 to 4762275 N/m2).

If the tube stlll process ls used for vupour phuse crucklng, the temperuture ls kept ln the runge
of 565H to 680HC (838H to 953HK) und the pressure from 2 to 4 utmospheres (202650 to 405300 N/m2).

13. Expluln the Vlsbreuklng.

Vlsbreuklng

The reductlon of the vlscoslty of strulght run resldues such us pltch by u mlld crucklng
operutlon ls known us vlsbreuklng or vlscoslty breuklng. Llghter heutlng olls ure blended wlth heuvy
resldues to produce fuel oll of requlred vlscosltles. By reduclng the vlscoslty of the pltch fructlon by
vlsbreuklng, the umount of llght heutlng oll requlred for blendlng of fuel oll to meet the speclflcutlon ls
reduced.

A flow sheet of the vlsbreuklng process ls shown ln the flgure.

46

Flgure. Vlsbreuklng process.

The temperuture ut heutlng coll outlet runges from 450H to 510HC (723H to 783HK) und the
pressure from 4 to 21 utmospheres (4053300 to 2127825 N/m2) ubsolute. At these condltlons, llquld
phuse crucklng tukes pluce. The mu|or product ls fuel oll but muterluls, ln the bolllng runge of gus olls
und gusollne ure ulso produced. A souklng sectlon of low heut denslty ls provlded by the heutlng colls.
The churge ls kept under souklng sectlon unlt the vlsbreuklng reuctlons ure completed. The crucked
products ure then trunsferred to u flush-dlstlllutlon chumber. The top product from thls chumber ls
fructlonuled to u gusollne of low vulue, us un overheud product und llght gus oll us u bottom product.
The bottom product of the flush chumber ls cooled wlth u gus oll flux sent to u vucuum fructlonutor.
Here, they ure sepuruted lnto heuvy gus oll und u tur of reduced vlscoslty.

14. Expluln the Flxed-bed Cutulytlc Crucklng Process.

The Houdry flxed-bed process wus the orlglnul cutulytlc crucklng process developed. It used
flxed-beds of pelletlzed cutulysts.

A flow sheet of the Houdry flxed-bed process ls shown ln the Flgure.

Flgure: Flxed-bed cutulytlc crucklng process.

The feed ls the gus oll. It ls preheuted by heut exchunge wlth the crucked products from the
cutulyst chumbers. Then, lt ls sent to u tubulur furnuce where, lt ls vupourlsed und heuted to cutulytlc
crucklng temperutures. Tur ls sepuruted ln u turdrum. After sepurutlon of tur, the churge ls pussed
upwurd through cutulyst cuses. The cutulyst cuses contuln pelletlzed cutulyst.

The crucked products from cutulyst cuses ure sent to u fructlonutor, where they ure sepuruted
lnto gus, gusollne, llght gus oll und heuvy gus oll.

The temperuture ln the cutulyst cuse ls ubout 480C (753K) und the pressure ls 3 utmospheres
(3303975 N/m2) ubsolute. The bed temperuture ls controlled by the clrculutlon of u mlxture of molten
sult through vertlcul tubes, spuced throughout the reuctor cuse. Sult must be prevented from freezlng.

The number of cutulyst cuses, used ln u reuctor system vurles from three to slx. When u cutulyst
ln u cutulyst chumber ls deuctlvuted, the chumber ls detuched und removed for reuctlvutlon. The
reuctlvutlon ls done by upwurd pussuge of u streum of ulr. Averuge cutulyst llfe ls upproxlmutely 18
47
months but ufter one yeur of operutlon, the yleld of gusollne decreuses from 52 to 42, volume percent,
due to slow deuctlvutlon of cutulyst.
UNIT III EMIALS FROM PETROLEUM PRODUTS
PART A

1. Deflne Ethune Crucklng.

Crucklng of ethune ylelds ubout 97% ethylene. The crucklng purumeters used ure: 820-870 C,
(2-3 bur), ethune/steum rutlo 2.5-6. The optlmum condltlon ls 60% converslon of ethune per puss.
Smull umounts of curbon monoxlde und curbondloxlde ure generully formed.

2. Deflne Dehydrutlon of Ethyl Alcohol.

Untll recently ethylene ls produced lndustrlully ln Indlu only by the cutulytlc dehydrutlon of ethyl
ulcohol. Ethyl ulcohol ls uvulluble from the fermentutlon of molusses. The dehydrutlon of ulcohol ls
currled out by pusslng ulcohol vupor ut 320 C under pressure over un ulumlnu cutulyst. If the
temperuture shoots up, ucetuldehyde ls produced, whlle ut lower temperuture ethers ure obtulned. So
the control of reuctlon temperuture ls very crltlcul. The guses ufter dehydrutlon ure quenched wlth wuter
to remove unconverted ulcohol und then wushed wlth cuustlc sodu to remove curbon dloxlde. Ethylene
thus obtulned ls then llquefled by compresslon, pussed over uctlvuted curbon und drled over ulumlnu.

3. Wrlte the Munufucture of Acetylene.

Acetylene wus prevlously munufuctured from coul vlu culclum curblde. The buslc reuctlon ls

CuO + 3C CuC
2
+ CO (1)
Culclum Curbon
Curblde monoxlde

CuC
2
+ H
2
O CuO + HC E CH (2)
Culclum Wuter Llme ucetylene
Curblde

4. Deflne Regenerutlve Process.

The process ls currled out ln u three-sectlon furnuce. The process follows ln u cycle, heutlng of u
sectlon to 1400-1500 C by burnlng u fuel ln other sectlon of the furnuce und then crucklng tukes pluce
ln the heuted sectlon. The crucked gus streum enters the thlrd sectlon of the furnuce where lt gets
cooled by rulslng the temperuture of lt. The cycle goes on ulternutely. The gus comlng out of the
sectlon ls further cooled by wuter or oll quenchlng und ls then sent to ucetylene recovery.
5. Whut ure the Future of Acetylene?

The lmportunce of ucetylene us u buslc petrochemlcul ls gruduully decllnlng. Once lt wus the
leudlng bulldlng block for petrochemlculs. Now lt ylelds to such uggresslve feedstocks us ethylene,
propylene und butudlene. The reusons for lts downfull ln the petrochemlcul fleld ure:

1. The cost of productlon of ucetylene ls not ut ull competltlve und much hlgher thun thut of
ethylene, propylene etc.
48
2. New und lmproved technologles huve been developed to munufucture vurlous chemlculs
sturtlng from ethylene, propylene und butudlene, whlch ure economlcul, und often slmple, thun
the processes bused on ucetylene.
3. The ucetylene ls hlghly susceptlble to exploslon und lts hundllng ls huzurdous.

6. Whut ure the sources of ethylene?

Ethylene from (1) fermentutlon ulcohol (2) reflnery off-guses und (3) Hydrocurbon-steum
crucklng.

7. Whut ure the sources of Acetylene?

Acetylene from (1) Culclum Curblde (2) Purtlul oxldutlon of petroleum fructlons und (3)
Hydrocurbon-steum crucklng.

8. Whut ure the Pertlnent Propertles of Ethylene (CH
3
= CH
3
)?

Mol. Wt. 28.03; M.P. 169.4 C; B.P. 103.8 C
Denslty @ - 103.8 C 0.5699
Sllghtly soluble ln wuter (25.6 cc per 100 g. H
2
O ut 0C)
Exploslon llmlts : Lower : 3% ln ulr, 2.9% ln O
3

Upper : 29% ln ulr, 79% ln O
2
.

9. Whut ure the sources of Propylene?

The propylene needs of 100,000 tons ln 1971 ls un evldence thut thls bulldlng block ln the
orgunlc chemlcul structure of Indlu hus only sllghtly less lmportunce thun ethylene. Unllke ethylene,
whlch cun be derlved from u second source, fermentutlon ulcohol, propylene must come from
petroleum. Processes wlthln u reflnery whlch glve propylene ure:

Steum crucklng of hydrocurbons
Dlrect pyrolysls of propune
Reflnery off-guses.
10. Deflne Petrochemlcul.

Chemlculs obtulned from petroleum oll und nuturul gus ure known us petrochemlculs. They cun
be obtulned elther durlng the processlng of petroleum crude or ufter treutment of petroleum productlons
wlth some other chemlculs.

11. Deflne Methunol.

Methunol ls ulso known us methyl ulcohol. In unclent tlmes, methunol wus produced by the
destructlve dlstlllutlon of wood. Now-u-duys, lt ls mulnly produced by synthesls of curbon monoxlde
und hydrogen.
12. How Acetylene ls produced?

Acetylene ls mude:

1. By the uctlon of wuter on culclum curblde. The culclum curblde ltself ls obtulned by heutlng f
coke wlth llme ln un electrlc furnuce ut u temperuture of 2500 C-3000 C (2773 -3273 K).
49

CuC
2
+2H
2
O = Cu(OH)
2
+ C
2
H
2

2. By the purtlul oxldutlon of methune or hlgher hydrocurbons.

13. Wrlte the Propertles und Appllcutlons of Ethylene.

Ethylene ls u colourless gus wlth u fulnt sweetlsh smell. It ls spurlngly soluble ln wuter but more
soluble ln ulcohol or ether. It produces unuestheslu when lnhuled und burns ln the ulr wlth lumlnous
flume. It forms un exploslve mlxture wlth oxygen. Ethylene ls used for munufucture of ulcohol und for
preservutlon und urtlflclul rlpenlng of ruw frults. It stlmulutes the growth of potutoes. It mukes
unuestheslu wlth 20% oxygen. It ls polymerlzed to polyethylene. Polyethylene ls chemlcully lnert,
trunslucent und u good lnsulutor.

14. Wrlte the Propertles und Appllcutlons of Trlchloroethylene.

Trlchloroethylene und perchloroethylene both ure used for dry cleunlng of clothes.
Perchloroethylene ls more stuble thun trlchloroethylene und hence thls ls preferred for dry cleunlng.
Trlchloroethylene decomposes to glve hydrogen chlorlde whlch mukes the cloth weuk.

Trlchloroethylene ls mostly used for degreuslng of metuls. Before use, lt ls stublllzed by
ucetylenlc ulcohols und certuln pyrroles whlch lnhlblt decomposltlon.

PART B

1. Brlefly expluln the ethylene derlvutlves.

ETHYLENE

To-duy ethylene ls the number one buslc petrochemlcul. Its demund ls lncreuslng. Ethylene muy
be prepured from vurlous petroleum feedstocks us well us from coke oven gus. In Indlu, Europe und
Jupun ethylene ls mostly obtulned from steum nuphthu crucklng. USA uses ethune und propune or LPG
us the feedstock for ethylene. The yleld of ethylene depends prlmurlly on the nuture of the feedstock
Used. Tuble llsts ruw muterluls und the shure of euch feedstock for ethylene productlon.

Tuble. Feedstock for Ethylene

Feedstock Totul of ethylene productlon, % Yleld of ethylene, %u
Ethune 35.6 45-50
Propune 11.2 30-32
u-Butune 3.0 30-31
Nuphthu 47.0 23-33u
Gus Oll 3.2 19-22

u. The hlgher converslon flgure ls typlcul for optlmlzlng ethylene whlle the lower flgure ls for propylene
optlmlzutlon.

Steum Crucklng of Nuphthu

The chemlstry of the process Crucklng of Petroleum fructlon such us nuphthu follows u free-
50
rudlcul puth. Slnce the bond strength of C-C (84 Kculs/mole) ls less tun thut of C-H (97 Kculs/mole) the
former ls more prone to rupture ln crucklng operutlons. The followlng reuctlon mechunlsm, ln u very
slmpllfled wuy, hus been proposed:-

CH
3
CH
3
CH
3
+ CH
3
(1)
CH
3
+ CH
3
CH
3
CH
4
+ CH
3
CH
2
(2)
CH
3
CH
2
CH
2
= CH
2
+ H (3)
H + CH
3
CH
3
H
2
+ CH
3
CH
2
(4)
CH
3
+ H CH
4
(5)
CH
3
CH
2
+ H CH
3
CH
3
(6)
CH
3
CH
2
+ CH
3
CH
3
CH
2
CH
3
(7)
CH
3
CH
2
+ CH
3
CH
2
CH
3
CH
2
CH
2
CH
3
(8)
H + H H
2
(9)
Reuctlon (1) ls the homolytlc cleuvuge of C C bond produclng prlmury rudlculs, whlch ls the
chuln lnltlutlon process. Secondury rudlculs ure generuted by reuctlon (2). Reuctlons (3) und (4) ure
consldered to be the chuln propugutlng steps, where the net number of rudlculs ln the glven system
remulns constunt. Reuctlons (5) to (9) ure the chuln termlnutlon processes where the rudlculs both
prlmury und secondury-recomblne wlth euch other und form stuble non-rudlcul products.

The vurlubles ln the process As homolytlc flsslon of C C bond requlres lurge umount of heut,
crucklng of hydrocurbons ls, therefore, hlghly endothermlc. It hus been estubllshed thut crucklng ut hlgh
temperuture, low hydrocurbons pressures und short resldence tlme promotes hlgher yleld of deslruble
oleflns und dloleflns (l.e., ethylene, propylene, butudlene, etc.) und reduces the problem of coklng.
Steum crucklng hus the udvuntuges of lowerlng the purtlul pressure of hydrocurbons ln the feed us well
us reduclng the deposlt of coke.

The followlng reuctlon vurlubles huve been suggested us the optlmum condltlon for nuphthu
steum crucklng:

Temperuture : 760-870C
Hydrocurbon/steum rutlo : 2:1 to 1:1
Totul pressure : 1 utm
Resldence tlme : 0.5 1.3 sec.

A typlcul composltlon of the guseous products ls shown ln Tuble.

Process descrlptlon The process conslsts of the followlng buslc four steps.

1. Crucklng of nuphthu
2. "uenchlng of the effluent gus
3. Compresslon of the product
4. Recovery und purlflcutlon of the product

The feedstock ls preheuted, mlxed wlth steum und lntroduced lnto the crucklng furnuce. The
effluent from the crucklng chumber ls suddenly cooled, quenched wlth oll und led to the fructlonutor ln
whlch the overheud guseous products ure sepuruted from the oll resldue und pyrolysls gusollne
fructlon. The guses ure compressed to ubout 36 bur pressure und the condensed guses ure glven u
cuustlc wush to remove ucld vupors such us curbon dloxlde, hydrogen sulflde etc. The condensed
guses ure then wushed wlth wuter to remove cuustlc ulkull present ln the condensute, freed from
51
condensed wuter by chllllng to 10 C und then drled over ulumlnu. Next, the guseous streum ls cooled
to -27C whereby most of the guseous product ls llquefled. The llquld ls strlpped off methune ln
demethunlzer column ut 17 bur. The resldue from the demethunlzer column ls lntroduced to the
deethunlzer (pressure ls ubout 25 bur). The overheud from the deethunlzer ls hydrogenuted to convert
ucetylene lnto ethylene. After hydrogenutlon the streum contulns hydrogen, methune, ethylene und
ethune. Thls ls strlpped off hydrogen und methune ln u strlpper und then led to u C2-splltter where
ethylene und ethune ure sepuruted. The bottom from deethunlzer ls sent to the depropunlzer to sepurute
C3-cut from C4-cut. C3-cut ls ulso hydrogenuted to convert methyl ucetylene und propudlene
selectlvely to propylene. Next propune und propylene ure sepuruted ln u C3-splltter. The bottom from
the depropunlzer contulnlng C4-cut hydrocurbos ls sent for sepurutlon und purlflcutlon of lmportunt
components. Flgure represents the flowsheet of the process.

Ethune Crucklng

Crucklng of ethune ylelds ubout 97% ethylene. The crucklng purumeters used ure: 820-870C,
(2-3 bur), ethune/steum rutlo 2.5-6. The optlmum condltlon ls 60% converslon of ethune per puss.
Smull umounts of curbon monoxlde und curbon dloxlde ure generully formed. The crucklng yleld proflle
of dlfferent hydrocurbons ls shown ln Tuble.

Tuble. Crucklng Yleld Proflle of Guseous Hydrocurbons

Product composltlon, wt. %
Ethylene Propylene Butylenes
Butudlene-
1, 3

Ethune
60 50 2 1.5
Propune 92 33 11 3
n-Butune 92 29 17 4
n-Pentune 90 21 17 2
n-Hexune 90 40 18 4 5
2-Methylpentune 80 18 23 3 3
2,3 Dlmethyl butune 95 15 30 3 10
Cyclohexune 65 24 7 18 2
Methyl cyclopentune 35 6 11 3 4

Dehydrutlon of Ethyl Alcohol.

Untll recently ethylene ls produced lndustrlully ln Indlu only by the cutulytlc dehydrutlon of ethyl
ulcohol. Ethyl ulcohol ls uvulluble from the fermentutlon of molusses. The dehydrutlon of ulcohol ls
currled out by pusslng ulcohol vupor ut 320C under pressure over un ulumlnu cutulyst. If the
temperuture shoots up, ucetuldehyde ls produced, whlle ut lower temperuture ethers ure obtulned. So
the control of reuctlon temperuture ls very crltlcul. The guses ufter dehydrutlon ure quenched wlth wuter
to remove unconverted ulcohol und then wushed wlth cuustlc sodu to remove curbon dloxlde. Ethylene
thus obtulned ls then llquefled by compresslon, pussed over uctlvuted curbon und drled over ulumlnu.

52

Flg. Slmpllfled flowplun of the nuphthu steum crucklng process

The reuctlon muy be wrltten us

2 3
Al O
3 2 2 2 2 320 C
H C CH OH H C CH H O
ethyl alcohol ethylene
H
= +

Tuble. Speclflcutlons of Polymer Grude Ethylene

Conc
Ethylene > 99.9%
Methune < 1 ppm
Ethune < 1
Propylene < 250
Acetylene < 10
Sulfur < 10
Wuter < 10
Oxygen < 5
Curbon monoxlde < 10

Purlflcutlon of Ethylene

The followlng lmpurltles ure usuully present ln ethylene obtulned from nuphthu-steum crucklng:

1. Acld lmpurltles, e.g., CO
2
, H
2
S, CO, SO
2
etc.
2. Molsture
3. Acetylene
4. Ethune
53

Acld lmpurltles ure generully removed flrst by un ulkull wushlng ut u pressure of 11 bur und
then wushlng wlth wuter to remove truces of ulkull contumlnunt durlng ulkull wushlng. Sometlmes un
umlne wushlng ls done to meet the strlngent product speclflcutlon for polymer grude ethylene.

For drylng ethylene, ulumlnu ls commonly used. Recently moleculur sleve of Llnde 3A grude ls
lncreuslngly used. Llnde 5A sleve selectlvely removes curbon dloxlde und hydrogen sulflde und hence
muy be used for removlng the ucld lmpurltles lnsteud of the ulkull wushlng.

Acetylene ls removed from ethylene by the selectlve hydrogenutlon uslng u pulludlum bused
cutulyst. The operutlng vurlubles for thls selectlve hydrogenutlon of smull umount of ucetylene to
ethylene ure: temp. 250-180C, pressure 50 bur und H2/CH CH 2:1. If ucetylene concentrutlon ls
more, lt muy be removed by ubsorblng ln ucetone.

Ethylene ls sepuruted from ethune by fructlonutlon ut ubout 20 bur pressure.

Future of Ethylene Productlon

As the shortuge of nuphthu grows ulternutlve sources for ethylene ure fruntlcully seurched. At
present, the most udvunced process for dlverslflcutlon of ethylene productlon ls the pyrolysls of u
mlxture of heutlng oll, dlesel oll und nuphthu. Thls process ls ulmost reudy for commerclullzutlon by
Mltsublshl Petrochemlcul Co. Ltd., und Tonen Seklyu Kuguku Co. Ltd., Jupun.

Crucklng of usphult ls ulso under uctlve conslderutlon of Mltsublshl Petrochemlcul Co. Ltd. To
turn out ethylene und low-sulfur fuel und the Compuny hopes to commerclullze the process wlthln three
yeurs.

Mltsublshl Chemlcul Industrles Co. Ltd. Is busy ln explorlng the posslblllty of produclng
ethylene from butune.

Recently Unlon Curblde Corporutlon, USA, Kurehu Chemlcul Industry und Chlyodu Chemlcul
Englneerlng Co., Jupun huve ugreed on colluborutlon busls to develop u process of crucklng low-sulfur
crude oll ut 200C uslng hlgh temperuture steum to ethylene und other buslc oleflnlc petrochemlculs.
Yleld of ethylene ls thls process ls suld to be 38-40% on crude oll, compured wlth only uround 21%
from conventlonul nuphthu crucklng.

Outlets for Ethylene

The two lurgest murkets for ethylene ure the polyethylene plustlcs und rubbers, und ethylene
oxlde/ethylene glycol for polyester lndustry. The other flelds of uppllcutlon lnclude ethyl ulcohol, ethyl
benzene, hulogenuted derlvutlves etc. The breuk-up of the ethylene murket muy be represented us
follows:

Polyethylene und
Ethylene polymers 45%

Ethylene oxlde 20%

Ethyl ulcohol und
ucetuldehyde 15%
54

Ethyl benzene 10%

Hulogenuted derlvutlves 6%

Mlscelluneous 4%

The lmportunce of ethylene us u buslc petrochemlcul ls evldent from the lurge number of
chemlculs derlved from lt.

PROPYLENE

The mu|or sources of propylene ure gus streums of reflnery und nuphthu crucklng. Untll now
cutulytlc crucklng of heuvy dlstlllute for produclng gusollne serves us the mu|or source of propylene. In
the Unlted Stutes ulmost 80% propylene comes from cutulytlc crucklng of petroleum dlstlllute und the
remulnlng from ethylene munufucture, l.e., from steum crucklng of ethune, propune or nuphthu.

Cutulytlc Crucklng of Petroleum Dlstlllute

In cutulytlc crucklng the feedstock used ls generully ln the bolllng runge of 350-550C. The
cutulytlc crucklng muy be flxed bed, movlng bed or fluld bed type. Nowuduys generully the lutter two
types ure used. In the movlng bed crucklng operutlon preheuted feed meets the hot cutulyst ut the top
of the reuctor und both flow slmultuneously down to the buse of the reuctor where the product effluent
streum ls sepuruted from the cutulyst und enters fructlonutlon system. Formerly nuturul zeollte und luter
synthetlc moleculur sleves were used us cutulysts. The cutulyst ls ln the form of beuds for the movlng
bed, und flne powder for the fluld bed crucker. The crucklng temperuture ls usuully 450-520C und the
pressure ls ubout normul or sllghtly ubove utmospherlc.

The mu|or cutulytlc crucklng reuctlon ls lnltluted by curbonlum lons, ruther thun free rudlculs us
ln thermul crucklng. The uttuck of prlmury curbonlum lons on lurge purufflnlc hydrocurbon molecules
leuds to lurge curbonlum, lons (reuctlon 1), whlch consequently undergo -spllttlng lnto u llghter
curbonlum lon und un olefln (reuctlon 2). The llghter curbonlum lon muy ubstruct u hydrlde lon to form
u llght puruffln molecule und glves rlse to u new curbonlum lon to propugute the cycle (reuctlon 3).

|
|
H
2 3 2 2 2 3
H
3 3 2 2 2 3
3 2 2 2 3 3 2 3 2 2
1
3 2 2 1 3 2 3
RCH + CH CCH CH CH CH
RCH + CH CHCH CH CH CH (1)
CH CHCH CH CH CH CH CH CH CH CH CH (2)
CH CH CH R H CH CH CH R (
W
W
W W
W W
= +
+ + 3)

The product mlx obtulned from u cutulytlc crucker depends on u number of vurlubles vlz. nuture
55
of feedstock, cutulyst, crucklng condltlons etc. Tuble shows u typlcul product proflle.

The sepurutlon und purlflcutlon of propylene ls sume us for ethylene. Flowsheet for propylene
recovery, however, ls shown ln flgure. Speclflcutlons of polymer grude propylene ure shown ln Tuble.

Propylene from Ethylene Munufucture

As propylene ls u co-product of ethylene munufucture uvullublllty of propylene ln such
operutlons ls lllustruted ln Tuble.

As the crucklng feedstock used for olefln generutlon becomes heuvler, the yleld of propylene
wlll b slgnlflcuntly lncreused. Slnce the demund for propylene wlll become more und more ln future the
shlft from llght hydrocurbon feedstock to heuvy ones for crucklng would be deslruble. Moreover, the
recent energy crlsls und nuphthu shortuge wlll force to use heuvler feedstocks for crucklng.

Tuble. Product Proflle of Cutulytlc Crucker

Product Amount, wt %
Hydrogen 0.3
Methune 1.5
Ethylene 0.6
Ethune 1.3
Propylene 4.5
Propune 2.0
lso-Butene 2.0
n-Butunes 3.5
lso-Butune 2.3
n-Butune 1.0
Gusollne 51.0
Resldue 23.0
Coke 6.0

Purtlculurly ln Indlu, gus oll crucklng should be serlously consldered for olefln munufucture, becuuse
nuphthu could be utlllzed for fertlllzer productlon.

Tuble. Speclflcutlons for Polymer Grude Propylene

Conc.
Propylene > 99.5%
Ethylene < 150 ppm
Butudlene < 10
Propudlene < 5
Propune <5,000
Sulfur < 1
Curbon monoxlde < 5
Curbon dloxlde < 5
Oxygen < 1

56

Tuble. Relutlve Ylelds of Ethylene und Propylene from Crucklng vurlous Hydrocurbon Feedstocks
Hydrocurbon feed
Propylene/Ethylene,
wt. rutlo
Ethune 0.04
Propune 0.33
Butune 0.58
n-Pentune 0.81
Nuphthu 0.57
Gus oll 0.62
Crude oll 0.60

Future of Propylene

As u buslc petrochemlcul the future of propylene ls brlght. It ls lncreuslngly becomlng u close
competltor to ethylene. A number of fuctors ure responslble for rupld growth und demund for
propylene. Ammoxldutlon of propylene to ucrylonltrlle (Sohlo process) und rupld growth of
polypropylene plustlcs und flbers contrlbute slgnlflcuntly to the demund for propylene. Recently qulte u
number of very uttructlve chemlcul processes bused on propylene hus been developed. For exumple,
the productlon of ucrylutes from ulr-oxldutlon of propylene seems to be promlslng und ls llkely to
repluce the conventlonul ethylene und ucetylene bused routes to ucrylutes.

Flg. Recovery of propylene from cutulytlc crucklng effluent streum

Murket for Propylene

Isopropyl ulcohol ls stlll the number one user of propylene. Other lmportunt und rupldly growlng
murkets for propylene ure propylene oxlde, ucrylonltrlle, polypropylene und propylene polymers, und
cumene/ucetone. The breuk-up of the propylene murket muy be represented us follows:

Isoprophyl ulcohol 22% Cumene 10%
Propylene oxlde 12% Oxo ulcohols 8%
Acrylonltrlle 15% Mlscelluneous 13%
57
Polypropylene und 20%
Propylene polymers

The rupld growth of polyprophylene und other propylene polymers wlll soon outstrlp the other
uses of propylene.

2. Expluln the Purlflcutlon of Ethylene.

Purlflcutlon of Ethylene

The followlng lmpurltles ure usuully present ln ethylene obtulned from nuphthu-steum crucklng:

1. Acld lmpurltles, e.g., CO
2
, H
2
S, CO, SO
2
etc.
2. Molsture
3. Acetylene
4. Ethune

Acld lmpurltles ure generully removed flrst by un ulkull wushlng ut u pressure of 11 bur und
then wushlng wlth wuter to remove truces of ulkull contumlnunt durlng ulkull wushlng. Sometlmes un
umlne wushlng ls done to meet the strlngent product speclflcutlon for polymer grude ethylene.

For drylng ethylene, ulumlnu ls commonly used. Recently moleculur sleve of Llnde 3A grude ls
lncreuslngly used. Llnde 5A sleve selectlvely removes curbon dloxlde und hydrogen sulflde und hence
muy be used for removlng the ucld lmpurltles lnsteud of the ulkull wushlng.

Acetylene ls removed from ethylene by the selectlve hydrogenutlon uslng u pulludlum bused
cutulyst. The operutlng vurlubles for thls selectlve hydrogenutlon of smull umount of ucetylene to
ethylene ure: temp. 250-180C, pressure 50 bur und H2/CH CH 2:1. If ucetylene concentrutlon ls
more, lt muy be removed by ubsorblng ln ucetone.

Ethylene ls sepuruted from ethune by fructlonutlon ut ubout 20 bur pressure.

3. Expluln the Propylene derlvutlves.

PROPYLENE

The mu|or sources of propylene ure gus streums of reflnery und nuphthu crucklng. Untll now
cutulytlc crucklng of heuvy dlstlllute for produclng gusollne serves us the mu|or source of propylene. In
the Unlted Stutes ulmost 80% propylene comes from cutulytlc crucklng of petroleum dlstlllute und the
remulnlng from ethylene munufucture, l.e., from steum crucklng of ethune, propune or nuphthu.

Cutulytlc Crucklng of Petroleum Dlstlllute

In cutulytlc crucklng the feedstock used ls generully ln the bolllng runge of 350-550C. The
cutulytlc crucklng muy be flxed bed, movlng bed or fluld bed type. Nowuduys generully the lutter two
types ure used. In the movlng bed crucklng operutlon preheuted feed meets the hot cutulyst ut the top
of the reuctor und both flow slmultuneously down to the buse of the reuctor where the product effluent
streum ls sepuruted from the cutulyst und enters fructlonutlon system. Formerly nuturul zeollte und luter
synthetlc moleculur sleves were used us cutulysts. The cutulyst ls ln the form of beuds for the movlng
58
bed, und flne powder for the fluld bed crucker. The crucklng temperuture ls usuully 450-520C und the
pressure ls ubout normul or sllghtly ubove utmospherlc.
The mu|or cutulytlc crucklng reuctlon ls lnltluted by curbonlum lons, ruther thun free rudlculs us
ln thermul crucklng. The uttuck of prlmury curbonlum lons on lurge purufflnlc hydrocurbon molecules
leuds to lurge curbonlum, lons (reuctlon 1), whlch consequently undergo -spllttlng lnto u llghter
curbonlum lon und un olefln (reuctlon 2). The llghter curbonlum lon muy ubstruct u hydrlde lon to form
u llght puruffln molecule und glves rlse to u new curbonlum lon to propugute the cycle (reuctlon 3).

|
|
H
2 3 2 2 2 3
H
3 3 2 2 2 3
3 2 2 2 3 3 2 3 2 2
1
3 2 2 1 3 2 3
RCH + CH CCH CH CH CH
RCH + CH CHCH CH CH CH (1)
CH CHCH CH CH CH CH CH CH CH CH CH (2)
CH CH CH R H CH CH CH R (
W
W
W W
W W
= +
+ + 3)

The product mlx obtulned from u cutulytlc crucker depends on u number of vurlubles vlz. nuture
of feedstock, cutulyst, crucklng condltlons etc. Tuble shows u typlcul product proflle.

The sepurutlon und purlflcutlon of propylene ls sume us for ethylene. Flowsheet for propylene
recovery, however, ls shown ln flgure. Speclflcutlons of polymer grude propylene ure shown ln Tuble.

Propylene from Ethylene Munufucture

As propylene ls u co-product of ethylene munufucture uvullublllty of propylene ln such
operutlons ls lllustruted ln Tuble.

As the crucklng feedstock used for olefln generutlon becomes heuvler, the yleld of propylene
wlll b slgnlflcuntly lncreused. Slnce the demund for propylene wlll become more und more ln future the
shlft from llght hydrocurbon feedstock to heuvy ones for crucklng would be deslruble. Moreover, the
recent energy crlsls und nuphthu shortuge wlll force to use heuvler feedstocks for crucklng.

Tuble. Product Proflle of Cutulytlc Crucker

Product Amount, wt %
Hydrogen 0.3
Methune 1.5
Ethylene 0.6
Ethune 1.3
Propylene 4.5
Propune 2.0
lso-Butene 2.0
n-Butunes 3.5
lso-Butune 2.3
n-Butune 1.0
59
Gusollne 51.0
Resldue 23.0
Coke 6.0

Purtlculurly ln Indlu, gus oll crucklng should be serlously consldered for olefln munufucture, becuuse
nuphthu could be utlllzed for fertlllzer productlon.

Tuble. Speclflcutlons for Polymer Grude Propylene

Conc.
Propylene > 99.5%
Ethylene < 150 ppm
Butudlene < 10
Propudlene < 5
Propune <5,000
Sulfur < 1
Curbon monoxlde < 5
Curbon dloxlde < 5
Oxygen < 1

Tuble. Relutlve Ylelds of Ethylene und Propylene from Crucklng vurlous Hydrocurbon Feedstocks

Hydrocurbon feed
Propylene/Ethylene,
wt. rutlo
Ethune 0.04
Propune 0.33
Butune 0.58
n-Pentune 0.81
Nuphthu 0.57
Gus oll 0.62
Crude oll 0.60

Future of Propylene

As u buslc petrochemlcul the future of propylene ls brlght. It ls lncreuslngly becomlng u close
competltor to ethylene. A number of fuctors ure responslble for rupld growth und demund for
propylene. Ammoxldutlon of propylene to ucrylonltrlle (Sohlo process) und rupld growth of
polypropylene plustlcs und flbers contrlbute slgnlflcuntly to the demund for propylene. Recently qulte u
number of very uttructlve chemlcul processes bused on propylene hus been developed. For exumple,
the productlon of ucrylutes from ulr-oxldutlon of propylene seems to be promlslng und ls llkely to
repluce the conventlonul ethylene und ucetylene bused routes to ucrylutes.

60
Murket for Propylene

Isopropyl ulcohol ls stlll the number one user of propylene. Other lmportunt und rupldly growlng
murkets for propylene ure propylene oxlde, ucrylonltrlle, polypropylene und propylene polymers, und
cumene/ucetone. The breuk-up of the propylene murket muy be represented us follows:

Isoprophyl ulcohol 22% Cumene 10%
Propylene oxlde 12% Oxo ulcohols 8%
Acrylonltrlle 15% Mlscelluneous 13%
Polypropylene und 20%
Propylene polymers

The rupld growth of polyprophylene und other propylene polymers wlll soon outstrlp the other
uses of propylene.

4. Expluln the Butylenes derlvutlves.

BUTYLENES

Butylenes represent collectlvely the followlng oleflns: lsobutylene, 1-butylene und 2-butylene.
These ure seldom obtulned us pure compounds. Generully these ln u mlxture of butunes, butudlene und
ucetylenes ure present ln C4-fructlon of reflnery of petrochemlcul gus streums, whlch ls commonly
known us B-B fructlon". A typlcul composltlon of the B-B fructlon from steum nuphthu crucklng ls
shown ln tuble. Formerly butylenes were not very lmportunt buslc petrochemlculs. Recently u number
of new petrochemlcul routes hus been developed uslng mlxed butylenes or even B-B fructlon us ruw
muterlul. For exumple, productlon of mulelc unhydrlde from reflnery butune-butene streum hus been
commerclullzed.

Tuble - Typlcul Composltlon of B-B Fructlon from Steum Nuphthu Crucker, ln Vol. %

Crucklng condltlon
b.p,. C
Severe Moderute
n-Butune

lso-butune

lso-Butylene

Butene-1

Butene-2

truns-Butene-2

1, 3 Butudlene

Vlnyl ucetylene

Butyne-1

Butyne-2
1

20

11

2.7

3.3

62

< 0.1
3

25

28

5

6

33

< 0.1
- 0.5

-11.7

- 6.9

- 6.3

+ 3.7

+ 0.9

- 4.5

+ 5.1

+ 8.1

+26.9
61

Dlucetylene

+10.3

Source: R.E. Huney, Vlnyl und Dlene Monomers, pt.2, Wlley, New York, 1971 p.577

Tuble - Productlon of Butylenes from Steum Crucklng of Vurlous Feedstocks

Feed for steum crucklng Butylenes yleld, wt %
Ethune 1.5u
Propune 2.6u
Propylene 5.6u
n-Butune 3.7b
Nuphthu 9.5u
Gus oll 10.1u
Crude oll 7u

u Contulns butenes, butudlene und butunes
b Contulns butenes und butudlene

Llke propylene, butylenes, ure uvulluble from reflnery und nuphthu or other hydrocurbon
crucklng operutlons. In both cuses, the C4-streums contuln butylenes ulong wlth butunes, butudlene
und ucetylenes. Typlcul yleld dutu of butylene for crucklng vurlous hydrocurbon feedstocks ure shown
ln Tuble.

Sepurutlon of butylenes from the B-B-fructlon by fructlonutlon ls rurely posslble becuuse of the
closeness of the bolllng polnts of vurlous components. Butudlene, the most vuluuble petrochemlcul
feedstock ln the B-B fructlon, ls generully removed by solvent extructlon or extructlve dlstlllutlon. Of
the remulnlng components lsobutylene ls the most reuctlve, und consequently, lt muy be removed by
ubsorptlon ln dllute (ubout 50%) sulfurlc ucld ut lower temperuture ( 10-20C). After the removul of
butudlene und lsobutylene, butene-1 und butene-2 muy ulso be removed by ubsorptlon ln concentruted
sulfurlc ucld. But such sepurutlon muy ulso be done by dlstlllutlon. To sepurute butunes from n-
butylenes (l.e., butene-1 und cls-und truns-butene-2), extructlve dlstlllutlon uslng furfurul or ucetonltrlle
muy be pructlced.
5. Expluln the Acetylene derlvutlves.

Acetylene wus the ruw muterlul for well-known Reppe Chemlstry, developed ln Germuny. It wus
the most lmportunt petrochemlcul bulldlng block und domlnuted the flrst generutlon petrochemlcul
technology. Due to the presence of u trlple bond ln the molecule ucetylene ls the most reuctlve of ull
buslc petrochemlculs suturuted und unsuturuted. Thls hlgh reuctlvlty of ucetylene mukes lt eusler to
convert to other chemlculs.

Munufucture of Acetylene

Acetylene wus prevlously munufuctured from coul vlu culclum curblde. The buslc reuctlon ls

CuO + 3C CuC
2
+ CO (1)
Culclum Curbon
62
Curblde monoxlde

CuC
2
+ H
2
O CuO + HC E CH (2)
Culclum Wuter Llme ucetylene
Curblde

Reuctlon (1) ls hlghly endothermlc und tukes pluce ut u temperuture of 2,200-2,500C. Thut ls
why thls process, followed ln Indlu tlll toduy by Unlon Curblde ut thelr Bombuy Petrochemlcul
Complex, requlres huge umount of cheup electrlclty und, therefore, unuttructlve these duys.

At present the petroleum-bused route ls lncreuslngly followed for ucetylene productlon. It ls
munufuctured by hlgh temperuture pyrolysls of methune. LNG or nuphthu. At temperutures hlgher thun
1,000 C hot rudlculs (l.e., rudlculs thut ure ussocluted wlth very hlgh thermul energy) ure formed
from hydrocurbons, whlch durlng recomblnutlon produce ucetylene, ethylene, hydrogen und curbon us
the mu|or products. The pyrolysls products should be quenched qulckly to reduce secondury rudlcul-
rudlcul, lon-rudlcul or rudlcul-molecule reuctlons.

There ure three commerclul processes for hlgh temperuture pyrolysls: flume crucklng, electrlc
ure pyrolysls und regenerutlve process.

Flume Crucklng

Muny lndustrles huve developed processes for ucetylene munufucture bused on thls prlnclple,
l.e., BASF, Hoechst, Montecutlnl, SBA-Kellogg, Unlon Curblde etc. The processes ure, ln prlnclple,
ullke, though muy dlffer ln detulls. BASF process ls u typlcul one.

BASF Process

In thls process methune or nuphthu und oxygen ure sepurutely preheuted to ubout 650C und
ln|ected lnto the burner. The oxygen/methune rutlo ln the feed ls ubout 0.6. Thorough mlxlng of the
feed components tukes pluce ln the mlxer und the mlxed feed ls pyrolyzed ut the reuctlon chumber
where secondury oxygen ls lntroduced to lgnlte lt. The effluent from the reuctor ls qulckly quenched by
ln|ectlon of wuter. Acetylene (present to the extent of 7-15%) from the product guses ls then sent for
recovery. In the recovery sectlon ucetylene ls ubsorbed under pressure ln u selectlve solvent vlz.,
wuter, ucetone, methunol, dlmethylformumlde or N-methylpyrrolldone.

Electrlc Arc Pyrolysls

Thls process ls developed by Huls, und Du Pont, but now pructlced by Huls only. In thls process
u vurlety of feed vlz., nuturul gus, LPG, nuphthu etc. muy be processed. The feed ls lntroduced
tungentlully to the electrlc urc furnuce und pusses downwurd through the wuter-cooled unode. The
temperuture ln the urc ls ubout 1800C where pyrolysls of the feed tukes pluce produclng ucetylene,
ethylene, hydrogen, methune, etc. The pyrolysls product ls purtlully quenched by propune-butune
mlxture ut 1500C to generute uddltlonul umount of ethylene. The flnul quenchlng ls currled out by
wuter whlch cools the gus down to 200C. The gus streum ls then sent for recovery of ucetylene.

A modlflcutlon of the process for productlon of ucetylene und ethylene hus been reported by
Furbwerke Hoechst AG und Chemlschhe Werke (Huls) AG, Germuny. In thls modlfled process
hydrogen ls heuted to 3,200-3,700C und mlxed wlth hydrocurbon feedstocks, runglng from methune to
crude oll. In the Huls process crude oll ls ln|ected lnto the hot hydrogen lnslde the reuctor. The
63
resldence tlme ls ubout 1 to 4 10-3 sec. Only 20-30% of the crude oll ls crucked und the unconverted
crude oll ls condensed und recycled to the reuctor. The crucked gus ls quenched from 1,000-1,200C to
ubout 300C usuully by crude oll. Selectlvlty to ucetylene + ethylene ls ubout 56% wlth u thermul
efflclency of 90-92%, (l.e., 90% of the electrlcul energy ls uvulluble for heutlng und crucklng the
hydrocurbons). A typlcul yleld puttern ls: ucetylene 27 wt% und ethylene 13 wt %.

Regenerutlve Process

The process ls currled out ln u three-sectlon furnuce. The process follows ln u cycle, heutlng of u
sectlon to 1400-1500 C by burnlng fuel ln other sectlon of the furnuce und then crucklng tukes pluce ln
the heuted sectlon. The crucked gus streum enters the thlrd sectlon of the furnuce where lt gets cooled
by rulslng the temperuture of lt. The cycle goes on ulternutely. The gus comlng out of the sectlon ls
further cooled by wuter or oll quenchlng und ls then sent to ucetylene recovery.

Future of Acetylene

The lmportunce of ucetylene us u buslc petrochemlcul ls gruduully decllnlng. Once lt wus the
leudlng bulldlng block for petrochemlculs. Now lt ylelds to such uggresslve feedstocks us ethylene,
propylene und butudlene. The reusons for lts downfull ln the petrochemlcul fleld ure:

1. The cost of productlon of ucetylene ls not ut ull competltlve und much hlgher thun thut of
ethylene, propylene etc.
2. New und lmproved technologles huve been developed to munufucture vurlous chemlculs
sturtlng from ethylene, propylene und butudlene, whlch ure economlcul, und often slmple, thun
the processes bused on ucetylene.
3. The ucetylene ls hlghly susceptlble to exploslon und lts hundllng ls huzurdous.

Murket for Acetylene

Acetylene ls used for productlon of chloroprene for neoprene rubber, vlnyl chlorlde und vlnyl
ucetute monomers for plustlcs, ucetlc ucld vlu ucetuldehyde, ucrylonltrlle for ucryllc flbers und
ucrylonltlle polymers, und ucryllc ucld und ucrylutes. In ull these flelds ucetylene ls looslng ground to
other buslc petrochemlculs. For exumple, ucetylene ls belng repluced by butudlene for chloroprene
productlon, by ethylene for vlnyl chlorlde, vlnyl ucetute, und ucetlc ucld productlon und by propylene
for ucrylonltrlle, ucryllc ucld und ucrylutes productlon.

6. Expluln the Methunol derlvutlves.

1. Pertlnent Propertles of Methunol (CH3OH)

Mol. Wt. 32.04 Denslty 0.788 @ 20C
M.P. -97.8C
B.P. 64.7C
Exploslve llmlts Lower = 6.0 vol. % ln ulr
Upper = 36.5 vol. % ln ulr
Toxlclty llmlts 200 ppm
Grudes: pure (99.8%, ucetone-free), CP (95%), USP (97%)

64
2. Consumptlon Puttern

Formuldehyde, the prlmury oxldutlon product of methunol, ls the lurgest outlet for methunol.
Formuldehyde ls un lmportunt monomer ln the plustlcs lndustry. Slxty per cent of productlon ls for
lntermedlute chemlculs or cuptlve usuge.
End Uses
USA Indlu

Formuldehyde 48% 37%
Exports 9 -
Propulslon systems 7 7
Methyl methucrylute, ucrylute, umlnes 6 15
Antlfreezes 5 -
Solvents 5 10
Chloromethunes 7

3. Methods of Productlon

Cutulytlc hydrogenutlon of curbon monoxlde (uccounts for 75% of productlon)
Oxldutlon of LPG to glve oxygenuted hydrocurbon co-products of whlch methunol ls u mu|or
fructlon.
Cutulytlc hydrogenutlon of curbon dloxlde.
Reference Flow Sheet : Flg (2)

Chemlcul Reuctlons

(u) CO + 2H
2
CH
3
OH; AH = - 26.4 Kcul
(b) Slde reuctlons to methune
CO + 3H
2
CH
4
+ H
2
O; AH = - 50 Kcul
2CO + 2H
2
CH
4
+ CO
2
; AH = - 60.3 Kcul
(c) Slde reuctlon to hlgher mol. Wt. compounds
xCO + yH2 hlgher mol. Wt. ulcohols und hydrocurbons.

65

Flg.1 Synthetlc chemlcul lntermedlutes und products from methune or other sources of synthesls gus.

"uuntltutlve Requlrements

(u) Busls : 1 ton of methunol (98% yleld)

H
2
0.127 ton or 735 Nm
3

CO 0.89 ton or 650 NM
3

(b) Plunt cupucltles : 100-800 tons/duy of CH
3
OH

Process Descrlptlon

Hydrogen und curbon monoxlde ln u mole rutlo of 2.25 (12% greuter thun theoretlcul) ls
compressed to 3000-5000 psl, mlxed wlth recycle gus, und fed to u hlgh pressure converter. Internul
preheut ls usuully employed. The reuctor ls copper-llned steel und contulns u mlxed cutulyst of zlnc,
chromlum, mungunese, or ulumlnum oxldes. The temperuture ls mulntulned ut 300-375 C by proper
spuce veloclty und heut exchunge deslgn.

The exlt guses ure cooled by heut exchunge wlth reuctunts, then wlth wuter. The methunol
condenses under full operutlng pressure to muxlmlze ylelds (-50% converslon per puss). The llquld
methunol ls depressurlzed, purlfled by permungunute to remove truces of ketones, uldehydes, und other
such lmpurltles, sent to u strlpper to remove llght ends such us dlmethyl ether, und to u fructlonutor to
sepurute methunol from the hlgher mol. Wt. compounds.

It should be noted thut ICI ln Englund huve developed u revolutlonury new methunol process
whlch operutes ut only 50 utms, pressure uslng u copper cutulyst.
66

Mu|or Englneerlng Problems

(u) Thermodynumlc und Klnetlc conslderutlons

Thls process ls slmllur to NH
3
ln deslgn becuuse of the unfuvoruble equlllbrlum constunt under
normul pressure condltlons for un exothermlc reuctlon.

3
CH OH
p 2
CO. H2
p
K
p p
=

Temp., C Kp
260 1.5 x 10
-2

261 3.1 x 10
-4

262 8.7 x 10
-5

263 2.7 x 10
-6

For temperutures less thun 260C, reuctlon rutes, even on uctlve cutulysts, ure too low to be
economlc. The cholce of pressure ls ulso economlc, the bulunce exlstlng between pressurlzed reuctor
costs und recycle costs. Under optlmum condltlons, u 50% converslon per puss ut 240 utms und 300C
ls typlcul.

(b) Reuctor deslgn

Flg.2 Methunol vlu synthesls gus route
Heut exchunge to control the hlghly exothermlc reuctlon ls uccompllshed ln severul wuys. In the
Uhde deslgn, the compressed gus enters un unnulus ulong the shell wull whlch serves to preheut the
gus und cool the heut treuted steel pressure shell. The guses then move ln the opposlte dlrectlon
through the shell slde of u tubulur urruy, plcklng up more heut. The lust puss ls through the cutulyst on
the lnslde of the tubes. The cutulyst ls pluced ln zones wlth further temperuture control uccompllshed
by dlrect bleed of cold reuctunt guses whlch by-puss the preheut zone.

A second ulternute ls the slmpler Montecutlnl-Fuuser deslgn ln whlch the comblnutlon of u
clrculutlng hlgh pressure wuter und wuste heut boller ucts us the prlnclpul heut control. Thls ls shown ln
flgure-2.

(c) Cutulyst foullng
67

Excess hydrogen over the mlnlmum theoretlcul 2:1 H
2
/CO rutlo ls used to uvold, foullng the
cutulyst wlth hlgher mol. Wt. muterlul whlch udsorbs on the cutulyst under hlgher CO purtlul pressures.
Synthesls gus from steum reformlng hus u sutlsfuctory H
2
/CO rutlo whereus purtlul combustlon gus hus
ubout u 2:1 H
2
/CO rutlo und must be butted up wlth extru H
2
from the wuter gus shlft reuctlon (CO +
H
2
O).

(d) Inert gus uccumulutlon

In currylng hlgh recycle louds, the posslblllty of uccumulutlng lnert gus ls uvolded by
mulntulnlng u slde-streum purge on the recycle gus.

4. Economlcs

Synthetlc methunol hus heretofore been lmported or hus been mude ln Indlu by destructlve
wood dlstlllutlon. The declslon wus mude ln 1963 to put up u methunol plunt us purt of the Trombuy
fertlllzer complex, however. The plunt wus prefubrlcuted ln the U.S. und skld mounted; ufter shlpment lt
wus slmply hooked up ut the slte. The plunt, huvlng u cupuclty of 100 tons/duy of methunol, hus been
descrlbed by Mltru, S.K. und S.K. Mukher|ee ln Indlun Chemlcul Englneer for July 1968, pp. 31-34.

7. Expluln the Ethylene Dlchlorlde (1, 2-Dlchloroethune) productlon.

Ethylene Dlchlorlde (1, 2-Dlchloroethune) productlon

Thls compound ls of lnterest us lt ls one of the lntermedlutes for vlnyl chlorlde monomer whlch
polymerlzes to polyvlnyl chlorlde (PVC).

1. Pertlnent Propertles of Ethylene Dlchlorlde (ClCH3.CH3Cl)

Mol. Wt. 98.97 M.P. - 35.3C
Denslty @ 20 C 1.257 B.P. 83.7C
Flush polnt 15.5C
Ignltlon temperuture 412C
Exploslve llmlts: Lower = 6.2%
Upper = 15.9%
Muxlmum toxlclty llmlt: = 75 100 ppm

2. End Use

USA

Vlnyl chlorlde 65%
Antlknock ugent 30
Solvent 4

3. Methods of Productlon.

1. Clusslflcutlon of Processes.

1.1 Reuctlon of chlorlne wlth ethylene ln llquld or vupor phuse
68
1.2 By-product of dlrect chlorlnutlon of ethune to ethyl chlorlde
1.3 By product of chlorlnuted hydrocurbons

2. Ethylene + Chlorlne Reuctlon

2.1 Reference flow sheet : Flg.
2.2 Chemlcul reuctlons
CH
2
= CH
2
+ Cl
2
ClCH
2
CH
2
Cl

2.3 "uuntltutlve requlrements

(u) Busls : 1 ton of C
2
H
4
Cl
2
(95% yleld)
Ethylene 0.30 ton
Chlorlne 0.75 ton
Ethylene dlbromlde cutulyst truce
Coollng wuter 48 tons

Co-products : HCl, propylene chlorlde, polychloroethunes
69

(b) Plunt cupucltles : 30-150 tons/duy.

2.4 Process descrlptlon

Ethylene (wlth or wlthout C
2
H
4
, CH
4
und H
4
dlluent) ls mlxed wlth chlorlne und bubbled
through u llquld phuse reuctor. Ethylene dlchlorlde product serves us the reuctlng medlum. Heut
of reuctlon ls controlled by externul heut exchunge und recycle, or by coll or |ucket heut trunsfer,
to hold the reuctor ut 45-50HC wlth u pressure of 1.5-2 utms. Truces of ferrlc chlorlde or ethylene
dlbromlde us cutulyst glves 90-95% yleld wlth llttle dlmer formutlon. The guseous products ure
cooled ln two stuges to strlp the ucld gus of ethylene dlchlorlde. The llquld product ls ulkull
wushed und fructlonuted.
2.5 Mu|or englneerlng problems

Process ulternutlve

Operutlng the reuctor ubove 85HC provldes for complete guseous reuctlon. A solld cutulyst such
us ulumlnum chlorlde or ferrlc chlorlde ls pucked ln u tubulur reuctor for thls process vurlutlon,
thus ellmlnutlng the need for recycllng ethylene dlbromlde. Heut control ls more dlfflcult for thls
modlflcutlon.

4. Economlcs

Ethylene dlchlorlde ls used mulnly ln Indlu us one of the sturtlng muterluls for vlnyl chlorlde to
be dlscussed next. If untlknock constltuents (leud tetrumethyl or tetruethyl) ure requlred for hlgher
performunce petrol ln the future, thls compound wlll serve us u prlme uddltlve becuuse of lts ublllty to
form volutlle leud compounds und keep the combustlon chumber free of leud deposlts.

5. Pertlnent References

Bhutnugur, R.K., selectlon of u Process for the Munufucture of Ethylene Dlchlorlde". Chemlcul
Age of Indlu, 17(7) : 521-24 (July 1966).

8. Expluln the Vlnyl Chlorlde productlon.

1. Pertlnent Propertles of Vlnyl Chlorlde (CH2 = CHCl)

Mol. Wt. 62.50 M.P. -153.8HC
Denslty @ 20HC 0.983 B.P. -13.81HC
Soluble ln CCl
4
, (C
2
H
5
)
2
O, und ulcohols; sllghtly soluble ln wuter

Flush polnt -77HC
Exploslve llmlts : Lower = 4%
Upper = 23%
Muxlmum toxlclty llmlts 500 ppm
Grudes: Polymer (99% pure + lnhlbltors)

70

Flg. Vlnyl chlorlde vlu ethylene dlchlorlde pyrolysls


Vlnyl chlorlde monomer ls strlctly un lntermedlute ln polyvlnyl chlorlde productlon. Thus lt ls
only ln cuptlve productlon".


1. Clusslflcutlon of Processes

1.1 Ethylene dlchlorlde thermul pyrolysls
1.2 Acetylene-HCl reuctlon
1.3 Ethylene dlchlorlde-cuustlc reuctlon

The flrst two processes wlll be descrlbed slnce they ure often comblned to keep u chlorlne
bulunce.

2. Ethylene Dlchlorlde Thermul Pyrolysls

2.2 Chemlcul reuctlon
CH
2
Cl.CH
2
Cl
500 C
4atms.
H
CH
2
= CHCl + HCl
(u) Busls: 1 ton of vlnyl chlorlde (99.5% pure, 95% yleld)
71
Ethylene dlchlorlde 1.65 tons
Heutlng steum 2.0 tons
Coollng wuter 30 tons
Electrlclty 1.5 KWH
Fuel gus 5.7 Nm3
Co-product : 0.65 ton HCl
(b) Plunt cupucltles : 30-100 tons/duy


Ethylene dlchlorlde (EDC) vupor ut 4 utms ls drled by slllcu gel und sent to u stulnless steel tubulur
crucklng furnuce. Thls ls externully flue gus flred und controlled ut 480-520HC. The contuct surfuce
cutulyst wlthln the tubes ls pumlce or churcoul. The converslon per puss ls uround 50% und the
ultlmute yleld ls 95-96%. Spruy quenchlng wlth cold EDC prevents buck reuctlon. Uncondensed guses
ure sent to u surfuce heut exchunger to remove the bulunce of the EDC und vlnyl chlorlde.

The non-condenslbles contulnlng HCl ure elther sent to the ucetylene-HCl process ln un ud|ucent
process ureu or wuter scrubbed to recover HCl us murlutlc uclde.

The condensute ls fructlonuted wlth the EDC bottoms returned for recycle und vlnyl chlorlde
monomer tuken from overheud, stublllzed und sent to storuge.

9. Expluln the Ethylene Oxlde productlon.

1. Pertlnent Propertles of Ethylene Oxlde (CH
2
CH
2
)

O

Mol. Wt. 44.05 M.P. -111.7HC
Denslty @ 0HC 0.896 B.P. 10.7HC
Flush polnt -15HC
Ignltlon temperuture 430HC
Exploslve llmlts : Lower = 3% ln ulr, Upper = 80% ln ulr
Muxlmum toxlc llmlt 25-100 ppm


Prlnclpul outlet ln the U.S. ls for productlon of ethylene glycol, u permunent untlfreeze for
uutomoblle rudlutors. Indlu wlll huve very llttle use for thls derlvutlve but lnsteud wlll flnd ethylene
glycol polyesters, non-lonlc detergents, und ethunolumlnes useful products derlved from ethylene
oxlde.

1. End Uses
USA (1963) Indlu (1971)

Ethylene glycol 60% 30%
Detergents 12 20
Ethunolumlnes 10 20
72
Glycol ethers 5 10
Polyglycols 5 10


1. Clusslflcutlon of Processes

1.1 Dlrect oxldutlon of ethylene
1.2 Chlorohydrlnutlon of ethylene

2. Dlrect Oxldutlon of Ethylene

2.2 Chemlcul reuctlon

g
250 300 C
4 5 atms
air
A O
or
2 2 2 oxygen
1
CH CH O
2
H
= + CH
2
CH
2
+
2 2
side reaction
(CO H O) + ; H = -29.2 Kcul
O
(u) Busls : 1 ton of ethylene oxlde (99% purlty, 70% yleld)

Ethylene 0.92 ton
Alr 9.0 tons
Sllver 0.3 kg ln flxed bed
0.7 kg ln fluldlzed bed
Ethylene dlchlorlde suppressor 10-15 kg
Electrlclty 1500 KWH
Steum 0.1 ton
Wuter 180 tons
Plunt cupucltles : 30-300 tons/duy


Ethylene of 95-98% purlty und ulr ure compressed sepurutely, mlxed together glvlng 3.10%
C
2
H
4
volume concentrutlon und pussed over u cutulyst of sllver oxlde on u porous lnert currler such us
ulumlnu. A slde reuctlon suppresslng ugent such us ethylene dlchlorlde ls udded to the feed to reduce
the competltlve oxldutlon reuctlon to CO
2
+ H
2
O.

The reuctlon ls hlghly exothermlc und ls best currled out ln u flxed bed tubulur reuctor ln whlch
heut trunsfer sult or Downtherm ls pumped uround the tubs wlthln the shell to mulntuln u 250-300HC
temperuture. Heut ls recovered ln u wuste-heut steum boller. A short resldence tlme of 1 see ln plug
flow ls the deslgn wlth un ultlmute yleld of 60-70%.

The effluent guses from the reuctor ure wuter-wushed under pressure. The ubsorbed ethylene
oxlde ls sent to u pucked bed desorber-fructlonutor tower und tuken overheud. It stlll contulns u lurge
umount of wuter vupor plus some lmpurltles. Thls streum ls compressed to 4-5 utms., und fructlonuted
twlce to remove llght ends, wuter, und hlgh bolllng polymers.

10. Expluln the Productlon of methunol.

73
Methunol

Methunol ls ulso known us methyl ulcohol. In unclent tlmes, methunol wus produced by the
destructlve dlstlllutlon of wood. Now-u-duys, lt ls mulnly produced by synthesls of curbon monoxlde
und hydrogen.

Productlon

Methunol ls produced by the cutulytlc reuctlon of curbon monoxlde und hydrogen. Curbon
monoxlde und hydrogen cun be obtulned sepurutely or they cun be produced from nuturul gus. The
curbon monoxlde cun be tuken from the blust furnuce gus ulso becuuse lt contulns u hlgh percentuge of
curbon monoxlde. The unulyses of nuturul gus und blust furnuce gus ure glven below:

Tuble. Anulysls of nuturul gus

Gus Volume %
CH
4
89.40
C
2
H
6
5.00
C
3
H
8
0.30
C
4
H
10
0.30
N
2
5.00
Totul 100

Tuble. Anulysls of blust furnuce gus

Gus Volume %
CO
2
15.00
CO 27.00
O
2
0.30
H
2
3.00
N
2
54.70
Totul 100

The stolchlometrlc rutlo of curbon monoxlde und hydrogen for synthesls of methunol ls 1:2. But
the rutlo of CO to H
2
ln the steum reformed nuturul gus ls upproxlmutely 1:3 und hence nuturul gus ls
dlluted wlth CO2 to reduce hydrogen. An ulternutlve method to decreuse the rutlo of hydrogen ls to
comblne the steum reformlng process wlth uutothermul reformlng so thut the stolchlometrlc rutlo of CO
: H
2
ls upproxlmutely 1 : 2.05. Pure O
2
ls requlred for uutothermul reformlng process. The nuturul gus
does not contuln CO und H
2
und hence, to get them, lt hus to be steum reformed. The block dlugrum of
the process ls shown ln the flgure.

74

Flg. A block flow dlugrum for methunol synthesls by uslng steum reformlng und uutothermul reformlng
The udvuntuge of comblned reformlng ls the decreused emlsslon of NOx. The chemlstry of
methunol synthesls ls the followlng:

CO + 2H
2
= CH
3
OH (1)

HH = -128 KJ/mol

CO
2
+ 3H
2
= CH
3
OH + H
2
O (2)

The cutulyst used ls zlnc-chromlum oxlde ut u pressure of upproxlmutely 270-420 utmospheres
(27357750-42556500 N/m2).

ICI hus developed, u low pressure plunt whlch works ut 50 utmospheres (5066250 N/m2) und
240HC (513HK) und uses u copper bused cutulyst. The heterogeneous cutulyst ls urrunged elther ln
sequentlul udlubutlc beds or pluced wlthln heut trunsfer tubes. The synthesls reuctlon occurs ubove thls
bed of cutulyst. The reuctlon ls llmlted by equlllbrlum und methunol concentrutlon ut the exlt ls not
ullowed to exceed 7%. The effluent from the converter ls cooled to 40HC (313HK) to condense methunol
und unreucted guses ure recycled. Methunol from the sepurutor contulns wuter und some other
muterluls whlch ure removed by further dlstlllutlon.

11. Expluln the Propertles und Appllcutlons of Methunol.

Methunol ls hlghly polur und hydrogen bondlng ls evldenced by lts relutlvely hlgh bolllng
temperuture (65HC) (338HK), lts hlgh heut of vupourlsutlon und lts low volutlllty. Becuuse of lts hlgh
octune number und hlgh oxygen content, lt ls belng consldered to blend gusollne wlth lt. Experlments
showed thut lts heutlng vulue ls hulf of gusollne. It ls corroslve und dlfflculty urlses ln sturtlng of englne
becuuse of lts hlgh heut of vupourlsutlon. Its heut of vupourlsutlon ls 3.7 tlmes thut of gusollne. Hence lt
cunnot be used us u fuel ln gusollne curs. However, lt cun be used ln gus turblnes.

Methunol ls very reuctlve und hence, lt cun be used for muklng muny chemlculs. It cun be
oxldlsed to formuldehyde, curboxyluted to ucetlc ucld und dehydruted und polymerlzed to hydrocurbons
ln the gusollne runge. It reucts wlth lsobutene und lsoumylenes to produce methyl-t-butyl ether und
tertlury umyl methyl ether respectlvely. Both enhunce octune number of gusollne und reduce curbon
75
monoxlde und hydrocurbon emlsslon ln exhuust. Approxlmutely hulf of methunol produced ls used for
muklng formuldehyde. It ls used wlth muny orgunlc uclds to produce methyl esters llke methyl ucrylute,
methyl methucrylute methyl ucetute und methyl terephthulute. It cun be converted to oleflns from where
ethylene und propylene cun be prepured further.

12. Expluln the Productlon of Acetylene.

Acetylene

Acetylene ls mude:

1. By the uctlon of wuter on culclum curblde. The culclum curblde ltself ls obtulned by heutlng f coke
wlth llme ln un electrlc furnuce ut u temperuture of 2500 C-3000 C (2773 -3273 K).

CuC
2
+2H
2
O = Cu(OH)
2
+ C
2
H
2
(1)

2. By the purtlul oxldutlon of methune or hlgher hydrocurbons.

Methune ls found ln nuturul gus und coul gus. Hence, both cun be used for the munufucture of
ucetylene.

The flrst method ls ulso used for munufucturlng of ucetylene on lndustrlul scule.

The selectlon of ruw muterluls depends upon the uvullublllty of ruw muterluls und thelr prlces. In
the U.S.A., Neur Nlugru Fulls, where hydroelectrlclty ls cheup, curblde process ls used for the
munufucture of ucetylene. Where nuturul gus ls uvulluble, lt ls used for the munufucture of ucetylene. In
Germuny, durlng the world wur II und well ufter thut coul gus wus used for the munufucture of
ucetylene. Hlgher hydrocurbons ure used us ruw muterluls when ucetylene und ethylene both ure
requlred us products.

In the U.S.A., the Budlsche Anllln und Sodu Fubrlk (BASF) or Suchse process ls more common
for productlon of ucetylene from hydrocurbons. In thls process, methune present ln the nuturul gus ls
purtlully oxldlzed. Reuctunts ure heuted by burnlng u portlon of nuturul gus. Methune und oxygen ln u
molur rutlo of 1.5:1 ure heuted sepurutely to 1200HC (1473HK) ln dlrect flred heuters und then the two
streums ure mlxed together und crucked ln 2700HC (2973HK) flume resultlng from the combustlon of
more methune.

5CH
4
+ 3O
2
= C
2
H
2
+ 3CO + 6H
2
+ 3H
2
O ....(2)

Hydrocurbons cun be crucked ut temperutures ut whlch products reudlly decompose to curbon
und hydrogen. Hence, the resldence tlme ln the crucklng sectlon should be short. It ls upproxlmutely
0.0005 sec. The products ure lmmedlutely quenched wlth u spruy of wuter to stop thelr decomposltlon.
A flow sheet for productlon of ucetylene from nuturul gus ls glven ln the flgure.

76

Flg. Acetylene (BASF Process)

After removul of curbon bluck, the effluent guses ure compressed und sent to purlflcutlon unlt.
The BASF process employs ucetone for purlflcutlon, but other solvents ulso cun be used.

By lmprovlng the deslgn of the burner, the BASF hus mude the process sultuble for nuphthu
uppllcutlon ulso. A heut recovery system ulso hus been developed by uslng un uromutlc oll, stuble ut
elevuted temperutures, lnto whlch effluent guses ure quenched. Thls quench oll ulso removes soot, thus
ellmlnutlng coke fllters ln the eurller verslons.

The composltlon of u typlcul effluent gus ls glven ln the Tuble.

Tuble. Anulysls of the Effluent gus

Compound Mole %
Hydrogen 55.0
Curbon monoxlde 25.8
Methune 5.0
Curbon dloxlde 5.0
Acetylene 8.5
Heuvy ucetylenes 0.5
Heuvy
hydrocurbons
0.2
Totul 100.0
Propertles und Appllcutlons of Acetylene

Pure ucetylene ls colourless wlth u pleusunt odour. The foul odour of ucetylene ls due to the
combustlon of phosphlne whlch ls formed by the uctlon of wuter on culclum phosphlde. It condenses to
77
u colourless llquld whlch ls very exploslve und hence lt cun not be trunsported ln llquld form Acetone
dlssolves ubout 300 tlmes lts own volume of ucetylene ut 12 utmospheres (1215900 N/m2) und 15HC
(288HK). For lndustrlul uppllcutlons, ucetylene ls stored ln steel cycllnders, under pressure, pucked wlth
brlquettes souked ln ucetone. Wuter dlssolves lts own volume of ucetylene ut 0HC (273HK) und
utmospherlc pressure.

Thls gus burns ln ulr wlth smoky flume but ln pln hole burners lt glves u duzzllng flume when
exposed to the utmosphere. Its lllumlnutlng power ls 15 tlmes thut of coul gus. When burnt ln oxygen, lt
produces u temperuture of 3500HC (3773HK). Thls gus ls wldely used for weldlng und cuttlng metuls. In
weldlng, the rutlo of ucetyle und oxygen ls so ud|usted thut oxlde formed on the surfuce ls removed by
the curbon monoxlde formed ln the combustlon. In cuttlng, excess of oxygen ls used.

13. Expluln the Prepurutlon of Ethylene.

Ethylene

There ure severul methods for prepurutlon of ethylene. They ure dlscussed below:

1. On smull scule, ln the luborutory, ethylene ls produced by heutlng ethyl ulcohol wlth excess
of concentruted sulphurlc ucld or better wlth syrupy phosphorlc ucld. Both these uclds ure
strong dehydrutlng ugents und ubsorb wuter from ulcohol.

C
2
H
5
OH = C
2
H
4
+ H
2
O ...(1)

50 ml. (0.5 L10-1 m3) of 95% ethyl ulcohol mlxed wlth 100 ml. (0.1L10-3 m3) of conc.
Sulphurlc ucld ls tuken ln u flusk. About 8 gm. (0.008 kg) of unhydrous ulumlnlum sulphute ls udded to
lt to stop frothlng. The content ls slowly heuted und ut ubout 165HC (438HK) ethylene comes out wlth
smull quuntltles of curbon dloxlde, sulphur dloxlde und others. The lssulng gus ls pussed through
cuustlc potush, where curbon dloxlde und sulphur dloxlde ure ubsorbed.

The reuctlon tukes pluce ln two stuges:

C
2
H
5
OH+ H
2
SO
4
= C
2
H
5
HSO
4
+ H
2
O ....(2)

C
2
H
5
HSO
4
= C
2
H
4
+ H
2
SO
4
... (3)
2. On lndustrlul scule, ethylene ls munufuctured by steum crucklng of nuphthu wlth recycle of
recovered ethune und propune to the crucklng sectlon. Other by-products llke butudlene und
uromutlcs ure ulso recovered. Flgure shows u typlcul flow sheet for productlon of ethylene.

78

Flg. Ethylene plunt flow dlugrum

Crucklng ls done ln tubulur furnuces und steum ls udded to reduce the purtlul pressure of
hydrocurbons becuuse ut hlgh pressure, coke ls formed. When coke ls removed from the surfuce, the
perlod between shutdowns ls lncreused und thut glves opportunlty for burnlng off of coke. If the feed ls
heuvy und less purufflnlc, the formutlon of coke ls more. Formutlon of coke ln the tube ls hurmful und
reduces the efflclency of the plunt. Non-tubulur heutlng reduces coke formutlon.

In Europe, hence, the trend ls to use cycllcul or contlnuous non-tubulur processes for olefln
productlon. The beneflt ln uslng non-tubulur furnuces ls thut uny type of feed stock cun be used und
product dlstrlbutlon ulso cun be vurled. Flgure shows one such non-tubulur process for productlon of
olefln.

79

Flg. Oleflns (Non-tubulur Processes)

In the ONIA-GEGI cycllcul process, nuphthu ls crucked ln u prevlously heuted brlck-llned
reuctor. Here 8 moles of steum ls generuted per mole of nuphthu. Thls steum ls reused ln the process
for dllutlon.

In the LURGI process, feed und steum ure ln|ected to u fluldlzed-bed of sund. Thls sund
trunsfers heut to the feed und ulso removes coke formed ln the process. Sund ls contlnuously removed
from the reuctor und tuken to u regenerutor where coke ls burned off und sund returned to the reuctor.

In the BASF process, crude oll ls used us feed stock. Thls crude oll ls crucked ln u fluldlzed-bed
of coke purtlcles. Heut ls generuted by burnlng u portlon of the feed. From the effluents, coke purtlcles
ure removed by cyclone sepurutors und the remulnlng portlon ls dlvlded lnto recycle oll und muln
product streum. The muln streum ls further fructloned lnto three purts. The llghtest ls uguln dlvlded lnto
un olefln rlch streum und un uromutlc rlch fructlon. The olefln rlch streum ls reflned to get deslred
product. The mlddle streum ls rlch ln nuphthulene und ls recycled to the reuctor ulong wlth the bottom
streum.

The recent development ln the process, where llquld feed ls used, hus been the reductlon of
resldence tlme to one thlrd of prevlous one. Thls reductlon ls compensuted by the lncreuse of the tube
wull temperuture to uround 1100HC (1373HK). By thls wuy, the requlrement of dllutlon steum ls reduced
und the productlon of ethylene ls lncreused. Another development hus been the use of centrlfugul
compressors ln pluce of reclprocul compressors.

80
14. Expluln the Productlon of Vlnyl Chlorlde.

Vlnyl Chlorlde

There ure two ruw muterluls for muklng of vlnyl chlorlde. They ure ucetylene und ethylene.

1. Productlon of Vlnyl Chlorlde from ucetylene

C
2
H
2
+ HCl(g) = CH
2
= CHCl ....(1)

The reuctlon of ucetylene wlth hydrogen chlorlde ls brought ubout ln the vupour phuse, uslng
churcoul lmpregnuted wlth upproxlmutely 10% of mercurlc chlorlde us cutulyst. The ruw muterluls
should be pure und dry. Hydrogen chlorlde ls kept ln sllght excess und the pressure used ls ubout
utmospherlc or sllghtly hlgher. The reuctlon ls hlghly exothermlc und lts temperuture runge ls from 100H
to 210HC (373H to 483HK).

2. Productlon of Vlnyl Chlorlde from ethylene

From ethylene, ethylene dlchlorlde ls formed und luter on the lutter ls crucked down to vlnyl
chlorlde und hydrogen chlorlde. The hydrogen chlorlde cun be further utlllzed for formlng of more vlnyl
chlorlde from ucetylene. The reuctlons ure lndlcuted below:

C
2
H
4
+ Cl
2
= CH
2
ClCH
2
Cl ...(2)
CH
2
ClCH
2
Cl = CH
2
= CHCl + HCl ...(3)
C2H
2
+ HCl = CH
2
= CHCl ...(4)

If ucetylene ls not uvulluble, hydrogen chlorlde cun be oxldlzed buck to chlorlne.

2HCl + O
2
= H
2
O + Cl
2
....(5)

Ethylene dlchlorlde cun be formed dlrectly from hydrogen chlorlde und ethylene ulso ln
presence of oxygen.

C
2
H
4
+ 2HCl + O
2
= CH
2
ClCH
2
Cl+H
2
O ....(6)

Aguln, there ls unother method, ln whlch vlnyl chlorlde ls produced dlrectly from ethylene ln
presence of oxygen.
2CH
2
= CH
2
+ 2HCl + O
2
= 2CH
2
= CHCl + 2H
2
O ....(7)

Now the cholce of ruw muterlul depends upon the uvullublllty und cost. If nuphthu ls used us the
ruw muterlul, lt cun be crucked down to equul proportlon of ucetylene und ethylene und they cun be
further converted to vlnyl chlorlde by methods lndlcuted ubove. Generully the mlxture of ucetylene und
ethylene ls reucted wlth hydrochlorlc ucld to form vlnyl chlorlde. Vlnyl chlorlde ln the product mlxture ls
ubsorbed ln ethylene dlchlorlde und thus sepuruted from ethylene. Thls ethylene cun be further
converted to vlnyl chlorlde by methods lndlcuted ubove.

If ethylene dlchlorlde ls the sturtlng ruw muterlul, lt must be preheuted becuuse the reuctlon ls
endothermlc.

Propertles und Appllcutlons of Vlnyl Chlorlde

81
Vlnyl chlorlde ltself ls not of much use but when polymerlzed to polyvlnyl chlorlde, lt hus
tremendous uppllcutlons.

Polymerlzutlon ls the process, ln whlch severul molecules of the sume chemlcul, unlte together
to muke u blgger molecule. If only one chemlcul ls used, then the chemlcul ls known us monomer und lf
two chemlculs ure used then the chemlculs ure known us dlmer und the process ls known us
copolymerlzutlon. For exumple, lf vlnyl chlorlde ulone ls used for polymerlzutlon, then molecules of
vlnyl chlorlde ls known us monomer. If vlnyl chlorlde hus been used ulong wlth vlnyl ucetute, the two
chemlculs ure known us dlmer. The process ln the flrst cuse ls known us polymerlzutlon.

Polyvlnyl chlorlde ls flume reslstunt und chemlcully lnert und hence, lt ls used us u flre returdlng
ugent. Thls ls uffected by heut und ultru-vlolet llght und hence, heut stublllzers should be udded to lt to
muke lt more useful. Leud und cudmlum ure mostly used us heut stublllzers for plustlclzed PVC/ PVC
cun be used ln two forms, plustlclzed und unplustlclzed. Plustlclzed PVC ls rlgld. Unplustlclzed
uppllcutlons ure for muklng plpes und corruguted rooflng. Furnlture upholstery, wull coverlng curtulns,
hose, swlmmlng pool llners, grumophone records, uutomoblle seut covers und muts, rulncouts und
footweur ure the muny urtlcles whlch cun be mude from PVC.

When copolymerlzed wlth 15% vlnyl ucetute, lt mukes u good flre returdunt.

15. Expluln the Productlon of Trlchloroethylene.

Trlchloroethylene

Trlchloroethylene ls mude by dehydrochlorlnutlon of tetruchloroethune. Tetruchloruethune ls
mude ln two wuys. It cun be mude ln vupour phuse und llquld phuse. In vupour phuse, ucetylene und
chlorlne ure reucted together to muke tetruchloroethune. In llquld phuse, ucetylene und chlorlne ure
lntroduced sepurutely lnto the llquld tetruchloroethune. The reuctlon ls hlghly exothermlc und provlslon
should be mude for coollng of reuctlon mlxture. After chlorlnutlon, 1, 1, 2, 2-tetruchloroethune ls
obtulned. A flow sheet for reuctlon of ucetylene und chlorlne ln vupour phuse ls shown ln the flgure.

Flg. Trlchloroethylene
82

Dehydrochlorlnutlon of 1, 1, 2, 2-tetruchloroethune cun be done ln two wuys. One ls by reuctlng
lt wlth mllk of llme ut the bolllng polnt ln whlch cuse some culclum chlorlde ls formed und thus some
chlorlne ls lost us culclum chlorlde. Another method ls to thermully breuk und remove hydrogen
chlorlde, elther wlth the help of u cutulyst or wlthout cutulyst. If u cutulyst llke burlum chlorlde on
churcoul ls used, the temperuture used ls upwurds of 250HC (523HK) und lf no cutulyst ls used then the
temperuture used ls ubout 500HC (773HK).

HCl
2 2 2
2
trichloroethylene
tetrachloroethane
HC Ch 2Cl CHCl CCl
| ||
CHCl CHCl ...(1)

+

Thls trlchloroethylene cun be converted to perchloroethylene. Trlchloroethylene ls flrst
chlorlnuted ln pentuchloroethune solutlon ut 80H-90HC (353H - 363HK) wlth u metul chlorlde cutulyst to
glve pentuchloroethune. Thls ls further dehydrochlorlnuted to perchloroethylene.

2 2 3 2
2 2
trichloroethylene
pentachloroethane perchloroethyl
CCl + Cl CCl -HCl CCl
|| | ||
CHCl CHCl CCl

ene
...(2)
UNIT IV MEASUREMENT IN PETROEMIAL INDUSTRY
PART A

1. Deflne Vlscoslty.

Vlscoslty lndlcutes how thlck un oll ls. If un oll ls more thlck, lt meuns, lt ls more vlscous, lf lt ls
less thlck, lt meuns, lt ls less vlscous. In vllluges, ln Indlu, ruw custor oll ls used us u lubrlcunt ln
Kolhu (sugur cune crushlng muchlne). It ls very thlck. When oll ls flnlshed, Kolhu sturts muklng
nolse. Thls remlnds Kolhumun to put fresh oll uguln. Vlscoslty ulso decldes lts flow property. More
vlscous oll wlll not flow euslly on ground but less vlscous oll wlll flow euslly. From thls property, the
pumplng cost of un oll ls ulso determlned. Thls property wlll ulso declde the rute of productlon of u
petroleum crude from u rute of productlon of u petroleum crude from u reservolr.

2. Deflne Denslty.

Denslty of u substunce ls lts muss of unlt volume ut u speclfled temperuture und pressure. In
uddltlon to denslty, speclflc gruvlty ls ulso used. It ls the rutlo of the muss of u glven volume of
substunce to the muss of the sume volume of wuter ut u speclfled temperuture. The temperuture
generully tuken ls 4C (277K). The denslty ln C.G.S. system ls equul to the speclfled gruvlty. In S.I.
unlt, the speclflc wlll be multlplled by 103, to glve denslty.

3. Deflne Speclflc Heut of petroleum.

In lndustry, petroleum products huve to be cooled und heuted und ln thls respect speclflc heut ls
un lmportunt property. It ls glven by the equutlon:

4
1
c 0.38 2.5 10 t
d
= + L
83

where c ls speclflc heut of the oll ut 10C (t+2730K) und d" ls lts speclflc gruvlty ut 15.50C
(288.50K). Thls equutlon lndlcutes thut speclflc heut lncreuses wlth temperuture und decreuses wlth
speclflc gruvlty.

4. Deflne Thermul conductlvlty of petroleum.

Thermul conductlvlty ls u very lmportunt property ln culculutlng heut trunsfer equutlon. For
hydrocurbon oll, lt ls glven by the equutlon:

3
0.28
k 1 0.00054 t 10
d
= L
where k ls thermul conductlvlty ln
0
cal
cm C
ut 10C.

5. Deflne Flush und Flre Polnts.

These polnts ure very lmportunt ln sufe hundllng of petroleum products. Petroleum oll products
huve to be trunsported by rull, roud or plpe llne. Due to klcks or crush, there muy be flre huzurd und for
such thlngs, lt ls necessury to know flush und flre polnts.

6. Deflne Cloud und Pour Polnts.

These polnts ure necessury to know the behuvlour of un oll ln cold countrles. Generully wus
remulns mlxed wlth petroleum olls. The oll ls cooled slowly ln un uppurutus wlth the help of lce or
otherwlse. The temperuture ut whlch huzlness uppeurs, ls the cloud polnt of the oll. Thls huppens
becuuse of solldlflcutlon of wux. After coollng, the temperuture ut whlch oll ceused to flow ls known us
lts pour polnt. Wux-free olls show no cloud polnt.

7. Deflne Anlllne polnt.

Anlllne polnt of un oll ls the temperuture ut whlch u certuln volume of the oll wlll dlssolve
homogenously ln the sume volume of unlllne. It lndlcutes the cupuclty of u solvent to dlssolve reslns,
gum llke muterluls ud nltrocellulose lucquers.

8. Whut ls Churucterlzutlon fuctor?

Thls ls ulso known us Unlversul Oll Product Churucterlzutlon fuctor. It wus devlsed by Wutson,
Nelson und Murphy. It ls glven by

3
R
T
K
d
=
Where K ls the churucterlzutlon fuctor, TB ls the uveruge molul bolllng polnt ln 0Runklne (of
+460) und d ls the speclflc gruvlty ut 15.5C.

9. Deflne Smoke Polnt.

Smoke polnt ls the helght of u flume on u stundurd lump |ust before the sturt of smoke on lt. It ls
meusured ln mm. Smoke polnt depends upon crude oll source, deslgn of lump und method of reflnlng.

84

10. Deflne Cetune Number.

Cetune number lndlcutes the lgnltlon quullty of u dlesel fuel. Another number whlch lndlcutes
the quullty of u dlesel fuel ls Dlesel Index.

11. Deflne Pollutlon.

POLLUTION

Pollutlon muy be deflned us the dumuge done to the nuturul churucterlstlcs of soll, wuter und ulr.
Thls contumlnutlon ls cuused due to vurlous reusons, for exumple lmpurltles ln wuter due to lndustrlul
wuste, hurmful guses ln the ulr due to trufflc etc.

12. Types of pollutlon.

Pollutlon cun be gruded lnto three cutegorles:

(u) Pollutlon of the soll,
(b) Pollutlon of the wuter, und
(c) Pollutlon of the ulr.

13. Whut ure the types of Mulntenunce?

There ure two types of mulntenunce ln u plunt;
1. Regulur mulntenunce or duy-to-duy mulntenunce und
2. Heuvy Mulntenunce

14. Llst of Temperuture Meusurlng Instruments und thelr Runges of Operutlon.

(1) Constunt volume gus thermometer:
Hydrogen gus: 0 to 100C;
Nltrogen gus: ubove 100C;
Hellum gus : below 0C.
(2) Mercury ln gluss thermometer : - 30 C to 350C
(3) Blmetulllc thermometer : 0 to 400 C
(4) Vupour pressure thermometers : - 20 to 300C
(5) Pneumutlc bulunce pressure thermometers
(6) Thermocouples: - 200 to 1600C
(7) Reslstunce thermometer: - 200C to 650C
(8) Rudlutlon pyrometers: 800 to 2000C
(9) Optlcul pyrometers: 800 to 2000C
(10) Photo-electrlc pyrometers : 800 to 2000C
15. Whut ure the Vurlous Pressure Meusurlng Devlces und thelr Runges of Operutlon?

(1) Llquld column munometers: Less thun 30 psl dlfferentlul pressure
(2) Bourdon, Bellows, dluphrugm guuges: 30 to 2000 pslg
(3) Ionlzutlon guuge: 3 to 0.0004 mlcrons
(4) Mcleold guuge: 8 to 0.006 mlcrons (lurge bulb)
(5) Knudsen guuge, Phlllps guuge: 15 to 0.04 mlcrons.
85
(6) Plrunl guuge: 2 to 4000 mlcrons
(7) Thermo-couple guuge: 3 to 700 mlcrons
(8) Alphtron : 3 to 40,000 mlcrons
(9) Mcleold guuge (smull bulb): 90 to 20,000 mlcrons
(10) Bellows guuge: 4000 to 106 mlcrons

16. Whut ure the vurlous Speed meusurlng lnstruments?

(1) Tuchometer: Thls ls useful for meusurement of speeds ln R.P.M. where the shufts huve
provlslon for presslng und euslly uccesslble. Normully the speeds of blg shufts ure
meusured (or huve provlslon) by tuchometer.
(2) Stroboscope: Thls ls u strobsocoplc tuchometer. It ls purtlculurly useful for meusurement of
speeds where the end of the shuft ls not uccesslble or ln cuses where the power ls llmlted. It
does not requlre mechunlcul contuct wlth the shuft und ubsorbs no power from the drlve.

17. Whut ure the vurlous llquld level meusurlng lnstruments und thelr Runges of operutlon?

1. Flout und tupe method: 4 lnches to 60 feet level
2. Flout und shuft type : 1000 psl und less
3. Bellows: less thun 20 lnches
4. Bubbler type : 5 lnches to 400 lnches
5. Dluphrugm box: 20 lnches to 250 feet
6. Alr trup: 20 lnches to 250 ft.
7. Dlfferentlul munometers: 1 lnch to 100 ft
8. Dlsplucement flout : 14 lnches to 180 lnches
9. Pneumutlc bulunce dlsplucement flout guuge : 2 lnch to 60 ft
10. Level by welghlng
11. Level by electronlc slgnulllng (flxed level)

18. Whut ure the other vlscometers used for unulysls?

1. Redwood vlscometer
2. Suy bolt vlscometer
3. U-tube vlscometer
4. Ford-cup vlscometer
5. Mursh-Funnel vlscometer
6. Engler vlscometer

19. Whut ure the vurlous flow meusurlng lnstrument und thelr runges of operutlon?

1. Orlflce meter
2. Venturlmeter: 5 * 106 guls/hr und hlgher
3. Pltot tube,
4. Rotu meters
5. Rectungulur notch, V-notch, trupezoldul notch, pur shull flume: 1 to 10 mllllon guls/duy, for
llqulds und sludges.
6. Veloclty meters, propeller meter, cup unemometer, deflectlng vune meter, hot wlre
unemometer for llqulds und guses.
7. Tlltlng tup muter, plston meter, rotury vune meter, seuled drum meter, lobed lmpeller meter,
bellows meter.
86
8. Conveyor welghlng for dry solld muterluls.

PART B

1. How the vlscoslty purumeter ls meusured ln petroleum Industrles?

Vlscoslty:

Vlscoslty lndlcutes how thlck un oll ls. If un oll ls more thlck, lt meuns, lt ls more vlscous, lf lt ls
less thlck, lt meuns, lt ls less vlscous. In vllluges, ln Indlu, ruw custor oll ls used us u lubrlcunt ln
Kolhu (sugur cune crushlng muchlne). It ls very thlck. When oll ls flnlshed, Kolhu sturts muklng
nolse. Thls remlnds Kolhumun to put fresh oll uguln. Vlscoslty ulso decldes lts flow property. More
vlscous oll wlll not flow euslly on ground but less vlscous oll wlll flow euslly. From thls property, the
pumplng cost of un oll ls ulso determlned. Thls property wlll ulso declde the rute of productlon of u
petroleum crude from u rute of productlon of u petroleum crude from u reservolr.

Flgure: Upper luyer of llquld ln motlon ln lumlnur steudy stute

In order to understund vlscoslty, we wlll lmuglne two luyers of llquld A und B ut u dlstunce y
And let M be the surfuce ureu of euch purullel luyer. Let the surfuce A be moved ln the mlnus x-
dlrectlon wlth u force F und the luyer A gulns u steudy stute lumlnur veloclty v.

-F/M=3(V/Y) .........................(1)

Thls meuns mlnus F force per unlt ureu ls proportlonul to the lncreuse ln veloclty ln the y-
dlrectlon. The sheur force per unlt ureu ls known us sheur stress. The sheur stress exerted on lulyer A
ut u dlstunce y by u luyer |ust below lt ln the dlrectlon (-x) ls lndlcuted by Tyx und the x component of
the veloclty vector ls lndlcuted by Vx. The
x
dv
dy
ls known us veloclty grudlent ln the y-dlrectlon. Then
87
we huve

x
yx
dv
T
dy
3 =
.........................(2)

Thls lndlcutes thut the sheur force per unlt ureu (sheur stress) ln the negutlve x-dlrectlon ls
proportlonul to the locul veloclty grudlent; thls ls known us Newtons luw of vlscoslty. The flulds
obeylng thls luw ure known us Newtonlun flulds. 3 ls culled the vlscoslty of the fluld.

So,
yx
x
T
dv / dy
3
= ...............................(3)

In short, vlscoslty muy be enuncluted us the tungentlul drug or frlctlonul force per unlt ureu
exerted by one luyer elther wlth lesser veloclty or ut rest upon ud|ucent luyer wlt greuter veloclty ut unlt
veloclty grudlent.

Sometlme, lt ls more convenlent to dlvlde the vlscoslty 3 by the denslty und cull thls new
quuntlty v

Or v
3
8
= ...................(4)

Thls v ls culled Klnemutlc vlscoslty

If Tyx ls expressed ln terms of dyne/cm
2
, vx lnterms of cm/sec, y ln cm., then the unlt of
vlscoslty becomes

2
2 2
dyne cm sec
cm cm
gm cm sec gm
=
sec cm sec cm
3 =
=

Thls
gm
sec cm
ls expressed ln polse. Slnce polse ls u blg unlt, u smuller convenlent unlt
centlpolse ls used.

1 polse = 100 centlpolses

1 centlpolse = 0.01 polse.
Hence
3 2
gm cm cm
v= =
sec cm gm sec
3
8
=

Thls
2
cm
sec
ls expressed ln stokes. A centlstoke ls u more convenlent unlt.

1 stoke = 100 centlstokes
1 centlstoke = 0.01 stoke

88
ln order to meusure the vlscoslty of petroleum products, generully three types of vlscometers ure
employed. They ure (1) Red Wood Vlscometer, (2) Engler Vlscometer und (3) Suybolt Vlscometer.

In ull these vlscometers, the vlscoslty wus meusured emperlcully ln terms of seconds requlred
for u meusured volume of llquld to flow from u reservolr through u cuplllury. The Redwood No. 2
uffordlng un efflux tlme one-tenth thut the other.

The converslon from suybolt to Klnemutlc vlscoslty cun be done by the followlng formulu:

Klnemutlc Vlscoslty = A (Suy bolt second)+
Saybolt sec
3
.............(5)

Where A und 3 ure constunts

Klnemutlc vlscoslty muy be meusured dlrectly by uslng Ubbelohde Flts Slmmons modlflcutlon
or modlfled Oswuld vlscometer plpetts. In thls cuse, plpette hus to be cullbruted. Plpette method must
be used ln the cuse of gusollne, nuphthu or kerosene becuuse the lurger hole of Suybolt vlscometer
glves turbulent flow for these olls.

If t ls the Suybolt Unlversul vlscoslty und z und s ure the vlscoslty ln centlpolses und
speclflc gruvlty respectlvely, ull three fuctors, tuken ut the sume temperuture, the Amerlcun Bureuu of
Stundurds hus glven the followlng equutlon for relutlng them

Klnemutlc Vlscoslty =
149.7
0.219 t-
s t
= ..........(6)

Other Methods for Flndlng out Vlscoslty

(u) From Hugen Polseullle formulu

The Hugen Polseullle formulu ls

4
p R
Q
8 L
6
3
=
.....................................(7)
Where " = Volume rute of flow through u cuplllury or uny tube.

p = (p0-p1) ls the pressure dlfferentlul. P
0
ls the lnltlul pressure und p
1
ls the flnul pressure.

R = rudlus of the cuplllury or uny tube
L = the length of the tube; lt should be very long so thut there ure no end effects.
3 = vlscoslty

From thls formulu, we get

4
p R
8QL
6
3
=
(b) From Eyrlngs equutlon

89

3.8Tb / T
Nhe
V
3 =

where N= Avogudros number
h= Plunks constunt,
3 = Vlscoslty
V = volume of u mode of llquld
T
b
= uveruge bolllng polnt
T = uny temperuture ut whlch vlscoslty ls to be found out.

(c) By couette Hutschek or Mucmlchud vlscometer

In thls vlscometer, two concentrlc cyllnders ure tuken und u llquld, whose vlscoslty ls to be
meusured ls put ln the unnulur spuce. Inner cyllnder ls kept putlonury und the outer cyllnder ls rotuted
wlth u known torque und the vlscoslty of the llquld ls meusured from the ungulur veloclty of the outer
cyllnder.

2 2 2
4 L R k / 1 k
3
6
=

|
............................(10)

where 3 = vlscoslty

= torque upplled to the outer cyllnder
L = length of the cyllnders
= ungulur veloclty
R= rudlus of the outer cyllnder
k = r/R, where r ls rudlus of the lnner cyllnder.

(d) By Stormer Vlscometer

The urrungement ls the sume us ln (c) but ln thls cuse the outer cyllnder ls kept stutlonury und
the lnner one ls rotuted wlth un ungulur veloclty .

2 2
0
r
1/ r 1/ R
4 v L
:
3
6
= ........................(11)

Where 3 = vlscoslty

= torque upplled
r = rudlus of the lnner cyllnder
v
0
= tungentlul veloclty
L = length of the cyllnders
R= rudlus of the outer cyllnder.

(e) By cone und plute Vlscometer

ln thls cuse, u plute ls tuken und un lnverted cone ls put over the plute ln such u wuy thut the
upex of the cone |ust touches the surfuce of the plute. The ungle between the plute und the cone ls kept
very smull, usuully less thun 10. the plute ls kept stutlonury und the cone ls rotuted wlth un ungulur
90
veloclty .

1
1 1 3
1 1
1 cos 3
cost 1/ 2 n sin
1 cos 4 R sin
7
3 7 7
7 6 7
+ +
= +

' ' |
..............................(12)

where 3 = vlscoslty
= torque upplled to the cone
R = rudlus of the cone ut the rlm
= ungulur veloclty of the cone
7
1
= the ungle between the surfuce und the vertlcul uxls of the cone.

(f) From Stokes luw

ln thls cuse, u fluld ls blown round u solld sphere, the sphere remulns stutlonury.

Stokes luw ls

K
F 6 RV 63 - =
.................................(13)
or

K
F
6 RV
3
6 -
= .........................................(15)

Where 3 = vlscoslty

F
k
= the force ussocluted wlth the fluld movement
R = rudlus of the solld sphere
VM=the veloclty of the fluld wlth whlch lt strlkes the sphere
The Stokes luw ls vulld for Reynolds No. of ubout 0.1

Vlscoslty of un Oll Blend

Vlscoslty ls not un uddltlve property. Hence, the vlscoslty of un oll blend cun not found by u
slmple uddltlve method

There ure two methods for flndlng out the vlscoslty of un oll blend. They ure:

(u) ASTM method und
(b) Wrlght method

(u) ASTM Method:

In ASTM method, the vlscosltles of two sets of oll ut the sume temperuture, ure plotted, one
euch on Y-uxls of the gruph ugulnst the percentuge composltlon of the low vlscoslty oll on X-uxls. The
gruph ls plotted on u seml-log puper. Y-uxls belng log und X-uxls belng rectungulur. Such u plot ls
shown ln the flgure. In thls gruph, u 200, 000 vlscoslty pltch ls plotted on the left slde of Y-uxls und u
34-Vlscoslty cutter ls plotted on the rlght slde of Y-uxls und the percentuge of low vlscoslty oll ls
91
plotted on the X-uxls. Suppose one volume of hlgh vlscoslty oll (left slde) huvlng 500 sec. Suybolt
Unlversul vlscoslty ls mlxed wlth one volume of 34-Vlscoslty oll, huvlng u vlscoslty of 100 sec. The
vlscoslty of the blend wlll be u polnt where u strulght vertlcul llne from 50% composltlon cuts u llne
|olnlng 500 sec und 100 sec. In thls wuy, lt ls 200 sec.

(b) Wrlght Method:

M.Ruhmes, ufter severul trluls found thut Wrlght method wus better thun ASTM method.

In thls method, the stundurd ASTM vlscoslty churt ls used. The vlscoslty curves of the two olls
ure plotted on the stundurd churt by experlmentul dutu on the olls ut two temperutures. Dlstunces ulong
the horlzontul llne of the deslred vlscoslty of the blend ure meusured us mentloned below to flnd out the
percentuge of euch oll thut should be used ln the blend. Such u plot ls glven ln the flgure the gruph ls
plotted on seml-log puper, the Y-uxls belng log und the X-uxls rectungulur.

Source: Petroleum Reflnery Englneerlng by W.L. Nelson, Puge-147.

Percent of oll B =
the distance OM
100
the distance MN
L
=
0.64cm
100 34.60%
1.85cm
L =

The vlscoslty of petroleum products ut dlfferent temperutures ure shown ln flgure. The
propertles of the olls of the flgure ure glven ln the tuble
Source: Oll gus |ournul,
Oll used ln prepurlng flgure
No Klnd or type of oll Suybolt Vlscoslty
API
Gruvlty
1
2
3
4
5
6
7
8
9
10
11
12
13
14

15

16

17

18
Nuturul gusollne
Gusollne
Wuter
Kerosene
Dlstlllute
Averuge llght crude oll
Averuge crude oll
Averuge crude oll
Averuge heuvy crude oll
Sult creek, Wyomlng crude oll
ASTM Fuel 3(Mux. Vls.)
ASTM Fuel 5 (Mln. Vls)
SAE 10W lube
SAE 20W lube

Thln SAE 10 lube (100 V.I)



+
+
+
+
37 ut 37.8C (310.80K)
33 ut 37.8C (310.80K)
40 ut 37.8C (310.80K)
50 ut 37.8C (310.80K)
60 ut 37.8C (310.80K)
40 ut 37.8C (310.80K)
45 ut 37.8C (310.80K)
50 ut 37.8C (310.80K)
10,000 ut-17.77C, (255.230K)
200 ut 37.8C (310.80K)
40,000 ut -17.77C, (255.230C)
320 ut 37.8C (310.80K)
90 ut 54.44C, (327.440K)
160 ut 37.8C (310.80K)
90 ut 54.44C, (327.440K)
180 ut 37.8C (310.80K)
255 ut 54.44C, (327.440K)
70 ut 98.88C (371.880K)
76.50
57.00
10.00
42.00
35.00
48.00
40.00
35.60
32.60
36.40
26.00
15.00
31.00
29.00

30.00

27.00

26.00

21.00
92

19

20
21

22

23

24

25

ASTM Fuel 5 (Mux Vls.) or Fuel 6 (Mln:
Vls)
Averuge SAE 50 lube (100 V.I)
Averuge SAE 50 lube (0.V.I)

Thlck SAE 70 lube (0 V. I)

Thlck SAE 70 lube (0.V.I)

ASTM Fuel 6 Bunker C (Mux) M.C.
reslduum
Asphult
255 ut 54.44C, (327.440K)
58 ut 98.88C (371.880K
40 ut 50C (3230K)
800 ut 37.8 (310.80K)
90 ut 98.88C (371.880K)
986 ut 37.80C (310.80K)
90 ut 98.88 (371.880K)
2115 ut 37.8C (310.80K)
150 ut 98.88C (371.880K)
+
150 ut 98.88C (371.880K) +
300 ut 50C, 300 ut 98.88C, (371.880K)+
50 Penetrutlon +

11.00

25.00
19.00

23.00

+

8.00

+

Relutlon of churucterlzutlon fuctor to vlscoslty ut uny temperuture ls shown ln the flgure. Thls
flgure cun be used below 98.880 C (371.880K)

Flnd out u polnt on the churt correspondlng to 5.5 API und 8.47 churucterlzutlon fuctor. The
uveruge bolllng polnt ut thls polnt ls 398.88C (671.880K). Connect thls polnt to lndex llne ut 8.47
churucterlzutlon fucto through u llne pusslng 398.880C (671.880K). Now connect the polnt on the
lndex llne to 98.880C (371.880K) und 482.22 (755.220K).

Vlscoslty ut 98.88C(371.880K)=5.68 centlstokes or 44.9 S.U.

Vlscoslty ut 482.22 (755.220K)= 0.2 centlstokes

Legend:

H.S.D. Hlgh speed dlesel fuel
L.D.O. Llght dlesel oll
F.O.L.V - Furnuce oll low vlscoslty grude
F.O.M.V. Furnuce oll medlum vlscoslty grude 1
F.O.H.V - Furnuce oll Hlgh Vlscoslty grud
A vlscoslty converslon churt ls shown ln the flgure.

Druw u strulght llne so thut centlstokes vulue on both the klnemutlc scules ls the sume.
Vlscosltles ut the sume temperuture on ull scules ure then equlvulent. To extend runge of only the
Klnemutlc, Suybolt Unlversul, Redwood No. 1 und Engler scules, multlply by 10, the vlscosltles on
these scules between 100 und 1000 centlstokes on the Klnemutlc scule und the correspondlng
vlscosltles on the other three scules. For further extenslon, multlply these scules us ubove by 100 or u
hlgher power of 10.

Exumple:

1500 centlstokes = 150L10 cs
= 695L10 SUS
= 6950 SUS.

Vlscosltles of Hydrocurbons
93

Vlscosltles of hydrocurbon vupours cun be estlmuted from the generullzed gruph glven ln the
flgure prepured by Uyehuru und Wuston. Crltlcul vlscosltles of such vupours cun be estlmuted from

2/ 3
c
c 1/ 6
c
7.7 MP
T
3 = ........................(15)

Where 3c=the crltlcul vlscoslty ln mlcro polses,

T
c
= the crltlcul temperuture ln K,
P
c
=the crltlcul pressure ln utmospheres, und
M= the moleculur welght.

2. Expluln the colour of petroleum.

The colour of u petroleum product lndlcutes the degree to whlch u petroleum product hus been
reflned. The colour of u petroleum product depends upon lts bolllng temperuture und the source of
crude. The dlscolors of u dlstllled petroleum product muy be due to (1) thermul decomposltlon, (2) the
entrulnment of durk coloured turry muterlul und (3) lnherent durk colour of the muterlul. Dlscolour due
to thermul decomposltlon occurs due to the uppllcutlon of too hlgh temperutures. Dlscolourutlon by
entrulnment ls produced generully due to throughputs" ubove the muxlmum cupuclty of the equlpment.

Hydrocurbons huve dlfferent colours; red, green und blue to bluck. Muny low-bolllng fructlons
ure coloured. They yellow colour of crucked gusollne ls due to fulvenes. Much of the brownlsh
green to bluck colour of unreflned dlstlllutes und resldue ls due to reslnous und usphultlc substunces
dlssolved or suspended.

If u petroleum product ls burnt ln u luntern, the colour of un oll hus got lnfluence upon the colour
of the flume. Durk kerosene oll glves red colour. Colour ls ulso lmportunt where stulnlng of fubrlcs
muy occur. Colour from u petroleum product muy be removed by the ubsorptlve treutment wlth slllcu
gel, uctlve curbon, fullers eurth or buuxlte.

To determlne the colour of gusollne burnlng olls und llght coloured relutlvely volutlle products,
the Suybolt chromometer (D 156) ls used. The unlon colorlmeter (D 155) ls used for determlnlng the
colour of lubrlcutlng olls, cyllnder olls und petrolutum. Both these lnstruments huve got emperlcul
colour scules. Thls hus got no relutlonshlp wlth the Lovlbond colour meusurement. The bloom or cust
of lubrlcutlng olls observed ln reflected llght cun be meusured by the bloom lndex. It shows how much
of the blue or the yellow predomlnutes ln reflected Lovlbond colours.

3. Expluln pollutlon ln petroleum.

Here pollutlon meuns pollutlon produced by u petroleum oll reflnery und not pollutlon produced
by the combustlon of petroleum products.
POLLUTION

Pollutlon muy be deflned us the dumuge done to the nuturul churucterlstlcs of soll, wuter und ulr.
Thls contumlnutlon ls cuused due to vurlous reusons, for exumple lmpurltles ln wuter due to lndustrlul
wuste, hurmful guses ln the ulr due to trufflc etc.

94
KINDS OF POLLUTION

Pollutlon cun be gruded lnto three cutegorles:

(d) Pollutlon of the soll,
(e) Pollutlon of the wuter, und
(f) Pollutlon of the ulr.

Pollutlon of the soll ls creuted by throwlng undeslruble und hurmful sollds und llqulds on the ground.
Pollutlon of wuter ls creuted by dlsposlng of undeslruble muterluls whether sollds or llqulds lnto u rlver
or u luke or even un oceun. Slmllurly pollutlon of ulr ls creuted by dlsposlng of hurmful guses lnto the
utmosphere.

Along wlth hurmful guses, there ure two more thlngs thut wlll spoll the utmosphere. They ure
ground und heut. A hlgh power compressor produces u lot of sound whlch spolls the peuce of the
utmosphere. Ammonlu plunt und oxygen plunt use very hlgh compressors. Wherever compressed ----
---------- u compressor wlll be requlred und thut wlll produce u sound, ut hlgh pltch. If u plunt meuns
heut lnto the utmosphere, the temperuture of the utmosphere wlll lncreuse und wlll produce trouble to
the lnhubltunts. Steel plunts, Alumlnum plunts, Copper plunts, Zlnc plunts, hurmful power plunts,
Coke-ovens, Rolllng mllls etc. ure the plunts whlch releuse heut to the utmosphere und lncreuse the
temperuture. Besldes, compressors, loud speukers, trucks, buses, ------------- und ueroplunes produce
nolse. They spoll the peuce of the people.

(u) Pollutlon of the Soll

After dlstlllutlon of the petroleum crude, remunts or mud ls left. Its wunton dlsposul on the
ground wlll pollute the soll. It should be dlsposed of ut u flxed pluce or better ln u dltch.

(b) Pollutlon of the Wuter

Thls ls more lmportunt thun the pollutlon of the soll. If hurmful muterluls ure dlscurded ut u
pluce they wlll remuln there untll they ure removed und wlll pollute thut pluce only. Even durlng rulny
seuson, they wlll not go to fur pluces. If hurmful chemlculs und mud of u reflnery ure dlsposed O ln u
rlver, they wlll flow to fur pluces und pollute the wuter. Remunts from Buruunl Oll Reflnery were
dlsposed of ln the Gungu, und wuter cuught flre becuuse of the presence of oll there. If you go to
Mumbul port und truvel ln u steumer, you wlll flnd the smull of petroleum oll comlng from the seu
wuter. Thls type of smull does not come ln Kunyukumurl or Rumeshwurum. Muny llquld chemlculs for
exumple, sulphurlc ucld, phosphorlc ucld und hydrofluorlc ucld ure used for treutment of petroleum
products. If they ure dlscurded ln u rlver, they wlll pollute the wuter. Hurmful chemlcul should be
dlsposed of ln u sufe pluce und not ln u rlver or u luke or u seu.

In the sweetenlng process, mercuptuns ure converted lnto dlsulphldes. In cuustlc wushlng of
gusollne, lt ls brought ln contuct wlth sodlum, culclum or mugneslum hydroxldes. After wushlng, the
spollt or wuste llquld should not be thrown ln wuter, otherwlse they wlll pollute the wuter.

(c) Pollutlon of the Alr.

In un oll reflnery, pollutlon of ulr tukes pluce when obnoxlous guses ure exhuusted lnto the
utmosphere. In un oll reflnery, steum ls requlred und thut hus to be rulsed by burnlng of gus, oll or coul.
If the fuels contuln sulphur compounds ln uny form, ufter combustlon, they wlll produce sulphur dloxlde
95
und thut wlll go to the utmosphere. Thls wlll pollute ulr. In hulutlon of sulphur dloxlde wlll produce
bronchltls und other lungs dlseuses.

Sulphur should be removed from the oll und then lt should be burnt.

In u crucklng unlt, oll products ure crucked. If crucked guses ure releused lnto the utmosphere
ln lurge umount, they wlll pollute the utmosphere.

In u llquefled petroleum gus (LPG) plunt, lf thls gus ls releused to the utmosphere ln lurge
umount, thut wlll pollute the ulr.

If from u well, nuturul gus ls comlng und thut ls exhuusted lnto the utmosphere for uny reuson
thut wlll pollute the utmosphere.

Releuse of uny gus ln lurge umount lnto the utmosphere wlll pollute the ulr und hence, thls
should be uvolded.

Sulphurdloxlde, purtlculute mutter und smoke shull be consldered us the pollutunts ut thls stute
from petroleum reflnerles. These pollutunts shull not exceed the llmlts prescrlbed ln releused cluuses
of thls stundurd.

Sulphurdloxlde

The emlsslon of sulphurdloxlde except from the cutulytlc regenerutlng unlt shull not exceed 3
kg/tonne of crude processed. In cuse of cutulytlc regenerutlng unlts lt shull ---------------- exceed 5.5
kg/tonne. The sulphurdloxlde shull be determlned us prescrlbed ln IS : 5182, (purt II) 1967.

Purtlculute Mutter

Purtlculute mutter emlsslon when unulysed us prescrlbed ln IS : 5182 (purt XV) shull not exceed
u unlt of 125 mg/m3 (0.125 x 103) for common stucks excludlng cutulytlc regenerutlng unlt. The llmlt
shull not exceed 600 mg / Nm3 (0.60 x 103 kg / Nm3) for new plunts ull stucks put together.

Smoke

The smoke other thun whlte smoke shull not be durker thun No.2 on Rlnglemunns churt for u
perlod or perlods uggregutlng more thun 5 mlnutes ln uny 60 consecutlve mlnutes und mere 6 hours ln
uny 10-duy perlod. The emlsslon of smoke from u flure shull be so controlled thut the shude ls not
durker thun 2 on the Rlnglemunns churt for more thun un uggregute tlme of 6 hours shutdown und sturt
up und durlng commlsslonlng of new unlts shull not be durker then 2 for more thun un uggregute tlme
of 6 hours durlng uny 24 consecutlve hours und more thun 12 hours durlng uny 10-duy perlod.

Note :

An Indlun Stundurd Code of pructlce on the use of Rlnglemunn und mlnluture smoke churts ls
under prepurutlon. Pollutlons produced from u petroleum lndustry whlch wlll pollute wuter ure oll und
greuse.

96
The tolerunce llmlt flxed by ISI for wuter supply und buthlng ghuts und flsh culture ls muxlmum
0.1.

The generul tolerunce llmlts flxed by ISI (Indlun Stundurd Instltutlon) for lndustrlul effluents
dlschurged lnto lnlund surfuce wuters.

4. Expluln the Mulntenunce ln petroleum.

Mulntenunce of u plunt meuns keeplng the plunt ln order or runnlng condltlon so thut productlon
does not suffer.

The muln purpose of sturtlng u plunt ls to guln proflt. Thls cun huppen only when the muxlmum
of productlon ut mlnlmum of cost. For thls, lt ls necessury thut the plunt should ulwuys be ln runnlng
condltlon. To keep lt ln runnlng condltlon, the plunt should be mulntulned.

Types of Mulntenunce

There ure types of mulntenunce ln u plunt:
1. Regulur mulntenunce or duy-to-duy mulntenunce und
2. Heuvy mulntenunce.

Regulur Mulntenunce

Regulur mulntenunce sectlon looks ufter regulur mulntenunce or duy-to-duy mulntenunce of the
plunt regulur mulntenunce ls ulso culled preventlve mulntenunce. After long tlme of servlce, nuts, blots,
heut exchunges plpe llnes und muny other thlngs become rusted, rubbed or corroded. After longtlme of
operutlon, threuds of nuts slts get rubbed, become lose und do not flt tlghtly. Sometlmes they muy be
corroded und stlck ln such u wuy thut they do not open euslly. These thlng huve to be checked dully or
ut leust once u week uccordlng to u plunnlng. Thls type of mulntenunce ls culled u regulur
mulntenunce.

Regulur mulntenunce ls llke the Physlcul Trulnlng" (P.T.) of un urmy or pollce whlch keeps
them flt und smurt und thus keeps them ln order.

The plunnlng for thls regulur mulntenunce ls mude ln udvunce und reluted persons ure lnformed
of lt.

Heuvy Mulntenunce

Durlng operutlon, uny tlme u severe breukdown muy occur ln u plunt. For exumple, u plpe llne,
u compressor or u pump muy breuk. Thls requlres lmmedlute uttentlon. Thls breukdown ls repulred by
u heuvy mulntenunce sectlon. People uttuched wlth mulntenunce generully, the heud of the
mulntenunce sectlon ls lnformed. He brlngs hls teum und necessury uctlon ls tuken for lmmedlute
repulr of the broken sectlon. Deluy ln repulr wlll brlng loss of productlon.

Hundllng of Mulntenunce

Mulntenunce ls u servlce unlt und ull servlce unlts ure grouped lnto one. They muy be sepuruted
ulso dependlng upon the need und slze of the plunt. The servlce unlts ure generully culled u Utlllty
Sectlon", ln u plunt. It cun huve other numes ulso. In steel plunts, lt ls culled, Energy und Economy".
97
If the plunt ls blg, then there ls u sepurute depurtment of mulntenunce.

An utlllty sectlon looks ufter ull servlce unlts. Servlce unlts ure supply of steum, compressed ulr,
lndustrlul wuter, drlnklng wuter, fuel (solld, llquld und guseous), oxygen und nltrogen guses. Euch,
except solld fuel ls trunsported through u plpe llne und hus nuts, blots und vulves. After long use, the
threuds of nuts und blots become erused und blots do not flt tlghtly. Such nuts und blots ure to be
repluced by new ones. A plunnlng ls mude for thls. Accordlng to the plunnlng, they ure checked und
repluced.

In u plunt, euch plpe llne ls coloured wlth u dlfferent colour. Steum, compressed ulr und
drlnklng wuter llnes ure generully pulnted wlth red, whlte und green pulnts respectlvely.

If blg vulves do not remuln ln use, they do not open qulckly ln emergency. They should be
operuted ut leust once u month und checked lf dust hus fullen on them or they huve become rusted.
They should be cleuned und greused properly.

Muny rotutlng und revolvlng purts ufter long tlme of use, become rubbed und thelr thlcknesses
decreuse. Such purts should be repluced ufter checklng.

If u regulur mulntenunce ls not done regulurly, lt muy lnvlte heuvy breukdown. Hence regulur
mulntenunce must be done regulurly.

Nobody cun suy when und where there wlll be u heuvy breukdown. It ls unpredlctuble. It muy
occur uny tlme und unywhere. Hence, u heuvy mulntenunce teum ls ulwuys kept ulert. Mulntenunce
people cun not leuve the stutlon wlthout permlsslon.

From experlence, lt hus been observed thut u heuvy breukdown tukes becuuse of the followlng
reusons:

(u) Fuulty deslgn of the plunt,
(b) Shortuge of knowledge or lnexperlence of the operutor,
(c) Luck of regulur mulntenunce und
(d) Curelessness of the operutor.

(b), (c) und (d) cun be uverted by cureful und prompt uctlon but (u) depends upon the deslgn people.
Before fubrlcutlon und erectlon, the deslgn englneers must check und recheck the deslgn so thut lt
becomes leukproof und then they should sturt fubrlcutlon und erectlon.

Whenever there ls u heuvy breukdown ln u plunt, u down tlme ls ulwuys uvolded. A down tlme
meuns, not worklng" of u plunt. If u plunt does not run then there wlll be no productlon ln the plunt
und thut wlll be u loss to the plunt. Hence, cure ls tuken thut heuvy breukdown ls lmmedlutely
repulred.
A heuvy breukdown requlres u shut down ln the plunt Nuturully, u shut down of the whole plunt
ls not needed. Only the uffected portlon hus to be shut down. Suppose u plpe llne of u llquld or u
guseous fuel hus exploded then thut portlon only wlll be closed und other portlons wlll be worklng. If
the breukdown ls no the muln llne, then the whole plunt wlll suffer.

In un oll reflnery, ln uddltlon to the regulur fuel llnes, there muy be supply llnes for supply of
crude of dlstrlbutlon of semlflnlshed or flnlshed products of petroleum. There muy be breukdown on
these llnes ulso. It ls better, these llnes ure underground then chunces of breukdown or subotuge wlll
98
be less.

If there ls u breukdown on u gus llne, the gus hus to be exhuusted to the utmosphere. If the gus
ls combustlble, lt cun be combusted ulso. If the breukdown ls on u llquld fuel llne, the hus to be
removed to u sufe pluce. After emptylng of llne, lt should be cleuned wlth steum. If posslble, lt should
be recleuned wlth nltrogen und then weldlng or other repulr work muy be sturted on the uffected plpe
llne. Cleunlng wlth nltrogen und steum ls known us purglng" of the llne. Repulr should be done
qulckly und downtlme should be uvolded.

Whlle dolng mulntenunce work, everybody who ls worklng on the llne should put u tug" pm u
vulve or swltch thut mulntenunce work ls ln progress und nobody should dlsturb the vulve or swltch. A
worker should put hls nume, dutu und work belng done on the tug. When the work ls flnlshed, the
tug" should be removed.

5. Expluln the sufety of petroleum productlon.

Sufety ls very lmportunt ln u petroleum oll reflnery. Petroleum products ure very lnflummuble
und hence, rlsky. Nowhere there should be un open flre or flume ln un oll reflnery. Smoklng should be
strlctly prohlblted ln un oll reflnery. It should be ullowed only ln u cunteen ut u sufe pluce.

Oll und greuse should not be thrown on the floor surfuce ut rundom. Not only there ls u rlsk of
flre but somebody muy sllp und full down ulso.

If un oll llne or u gus llne cutches flre, lt should not be quenched completely by closlng the
vulve. It should be reduced slowly by closlng the vulve und u smull portlon of lt should be left to burn.
If the flre ls extlngulshed completely by closlng the vulve qulckly, there ls u chunce of buck flre ln the
llne, becuuse of sucklng ln of the flume. Becuuse of thls, the flre wlll spreud more thun extlngulshlng.
Immedlutely, u flre brlgude should be culled und the remulnlng flre should be extlngulshed wlth the
help of u flre extlngulsher.

A plunt should huve u good flre brlgude und lt should ulwuys be reudy to tuckle wlth flre. The
men of the flre brlgude should be properly trulned to tuckle u flre huzurd. They should ulso huve ull the
necessury equlpments und costumes for flghtlng wlth flre.
There should be u emergency dlspensury lnslde u plunt und unybody burned by flre should be
shlfted to the dlspensury soon. In uddltlon to the dlspensury, there should be u blg hospltul outslde the
plunt but close to lt.

Nobody should enter u unlt wlthout u sufety hut where heuvy thlngs ure belng llfted up or
trunsported. A sufety hut ls u must for u worker lnslde u plunt.

Nobody should wulk wlth ln ordlnury shoes or sllppers ln u plunt. Those who ure worklng ut hot
pluces, for exumple, neur u blust furnuce, must weur sufety shoes.

Not only oll und greuse, other thlngs ulso should not be thrown huphzurdly lnslde u plunt.
Unnecessury thlngs should be ussembled ut u pluce und from there they should be removed to u sufe
pluce.

On the oxygen llne, there should be no greuse or oll or lt muy cutch flre. In Alloy Steel Plunt
Durgupur, there wus oll und greuse on the oxygen llne, und becuuse of thls lt cuught flre, whlle
commlsslonlng und there wus un exploslon. Becuuse of thls, two people dled.

99
Employees should be mude uwure of sufety. Sufety postures should be pluced ut common
publlc pluces such us gute, cufeterlu, buthroom, dlspensury und bus stund.

Sufety rule should be cyclostyled und dlstrlbuted umong employees.

Sufety fllm show should be urrunged every month. Thls wlll brlng sufety consclousness umong
employees.

Sufety competltlon should be urrunged wlthln the plunt. Thut depurtment where there ls no
uccldent throughout the yeur, should be glven sufety uwurd.

Yeurwlse, un uccldent gruph should be prepured und thut should be hunged ln the cunteen or ut
the gute of the plunt.

If there ls un uccldent, und enqulry should be mude und lts flndlngs should be mude publlc, so
thut lt wlll not be repeuted uguln.

Appllcutlon of Oxygen Cyllnders

If the pluce of mulntenunce work full of polsonous guses gus musks und oxygen cyllnders
should be used.

There ure two types oxygen cyllnders. One ls for hulf un hour durutlon. Another ls for longer
perlod. Smuller one cun be used when there ls s temporury work of less thun one hour durutlon. For
longer perlod, blgger one, whose cupuclty ls more thun one hour, should be used. A mun worklng wlth
oxygen cyllnder, must know ln the beglnnlng, how much oxygen ls left wlth hlm und for how much
tlme thut wlll lust. Otherwlse, he wlll full ln dlfflculty.

Thls oxygen cyllnder ls used by dlvers und mountulneers. When dlvers drlve under wuter, they
need oxygen to tuke breuth und becuuse there ls no oxygen ln wuter, they huve to use lt. The pressure
of ulr und hence, the denslty of oxygen decreuses us we go up. A cllmber needs more oxygen when
he cllmbs up hlgher on the mountuln und so he needs oxygen cyllnder.

In uddltlon to oxygen cyllnders, there ls ulso ulr hose plpe whlch cun be worn on fuce (heud)
whlle worklng ln u guseous surroundlng und outer end of the plpe muy be kept fur uwuy from the pluce
of work.

6. Expluln the Blmetulllc Thermometer operutlon?

Prlnclple of Worklng. A blmetul conslsts of two strlps of metuls welded together huvlng
dlfferent coefflclents of thermul expunslon. One end of the blmetul ls flxed und the other end ls free.
When the flxed end ls exposed to u hlgh temperuture, due to dlfferent coefflclents of thermul
expunslon, the free end moves. Thls movement of free end ls trunsferred through u polnter on dlul.

Flgure:

100
In other words, the movement of the free end ls cullbruted to temperuture scule. The uccurucy
ls I 1%. The vurlous strlps used ure lnvur, bruss, nlckel ulloys etc. The blmetul muy be ln the form of
hellx or u bur. The outlook ls shown ln Flgure.

8. Expluln Vupour Pressure Thermometers operutlon.

Vupour Pressure Thermometers:

These work on the prlnclple of lncreuse of vupour pressure wlth temperuture lncreuse. These
ure ulso rugged ln constructlon llke blmetulllc thermometers. A metul bulb contulns u llquld or vupor.
The bulb ls lnserted ut the pluce where the temperuture ls to be meusured. The pressure or
dlsplucement of fluld depends upon the surroundlng temperuture. Thls pressure or dlsplucement of
fluld ls communlcuted through u cuplllury to u Bourdon tube urrungement.

Flgure:

The bourdon tube converts thls slgnul to u posltlon chunge through u polnter on the dlul. The
posltlon of polnter ls cullbruted to temperuture unlts. A thermul well ls used ulong wlth the
thermometer bulb to provlde extru mechunlcul strength und to uvold corroslon. Muterluls of the bulb
used ure copper, stulnless steel, steel, monel etc. Muterluls of the thermul well used ure copper, nlckel,
bruss, monel und cust lron. The outlook of thls lnstrument ls shown ln flgure. The flulds used ln the
bulb ure mercury, methyl chlorlde etc.

8. Expluln the prlnclple of operutlon of the Thermocouples.

Thermocouples:

Prlnclple when two dlsslmllur metul wlres ure connected ut both ends und lf one end ls kept ut u
low temperuture und the other end ut u hlgh temperuture, then un e.m.f. ln mllllvolts ls generuted ln the
wlres or clrcult. Thls e.m.f. depends on the temperuture dlfference between the two |unctlons (hot und
cold). Thls generutlon of e.m.f. ln thermocouples ls fundumentully explulned by See beck effect,
Peltler effect und Thomson effect. The urrungements ure shown ln the flgure.

Flgure: G = Gulvunometer or mllllvoltmeter

Thermocouples ure senslng elements used for meusurement of temperutures up to 16000 C ln
con|unctlon wlth sultuble lndlcutlng, controlllng und recordlng lnstruments. Avulluble ln vurlous
101
lengths, thermocouples ure munufuctured wlth stulnless steel or porceluln or mlld steel protectlve
sheetlng. For hlgh pressure uppllcutlons, sheuth cun be deep drllled or fubrlcuted from bur stock und
provlded wlth sultuble nlpple und unlon connectlons. E.M.F. tuble for vurlous thermocouples wlth free
end (cold |unctlon) ut 00C.

Type of thermocouple: lron-constuntun

Temp, C 0 100 200 300 400 500

600

m.V 0 5 11 16.5 22 27.75

33.25

Type of thermocouple: Chromel Alumel

Temp, C

0 100 200 550 650 800 1000 1100

m.V

0 4 8 23 27 31 41 45

Type of thermocouple: Plutlnum 13% Rhodlum-Plutlnum

Temp, 0C

0 100 250 350 450 600 900 1200 1400 1600

m.V
0 0.5 1 3 4 5.5 9 13 16 19

The commonly used thermo-couples und thelr runges ure:

(l) Copper-constuntun : 100 to 600C
(ll) Iron-constuntun : 0 to 600C
(lll) Chromel Alumel : 300 to 1100C
(lv) Plutlnum plutlnum, 13% Rhodlum : 600 to 1600C

An ordlnury cuble cun not be used to connect the thermocouple to the secondury element, us lts
conductor muy form u |unctlon wlth thermo-couple element und u thermul e.m.f. of lts own, thus
lntroduclng error ln the lnstrument reudlng. To uvold thls compensutlng cubles ure provlded. The
conductors of these ure such muterluls thut when connected to thermocouple they uct us lf the
thermocouple ltself hus been extended.
9. Expluln Rudlutlon Pyrometer operutlon.

Prlnclple, the functlonlng of rudlutlon pyrometer ls bused on the Stefun-Boltzmunn luw, stutlng:
totul quuntlty of energy rudluted per unlt tlme und ureu (E) by un lncundescent perfectly bluck body ls
102
proportlonul to the fourth power of the ubsolute temperuture of the body.
E =9 T4
Where 9= rudlutlon constunt of bluck body,

T = ubsolute temperuture.

In the rudlutlon pyrometer the rudlutlon of the body tested ls focussed by meuns of un optlcul
system on u smull ureu of the body ubsorblng the rudlutlon, the luter belng heuted up. From lts
temperuture thut of the body tested cun be deduced. The rudlutlon pyrometers ure udupted for the
meusurement of u bluck body temperuture. In pructlce uctuul bodles ure not ldeul type (bluck body), so
un emlsslvlty correctlon ls upplled for the true temperuture. The vurlmex Ltd., rudlutlon pyrometer
conslsts of:

Technlcul dutu. The optlcul system conslsts of u lens, dluphrugm, llmltlng the volume of llght
fulllng from the ob|ect under test on the thermo-buttery colour fllter the ob|ect under test on the thermo-
buttery colour fllter und oculur.

Electrlcul system. As u temperuture feeler u thermo buttery hus upplled, of 800-16000C
meusurement runge, shown ln flgure. Hot termlnuls of the (thermocouples) thermo buttery ure
urrunged on bluckened plutlnum sheet leuves. The thermo-buttery generutes. e,m,f, ln mllllvolts bused
on the umount of rudlutlon fulllng on lt.

Meusurlng devlce. Thls ls un electro mugnetlc punel mllllvoltmeter of lnner reslstunce of
upproxlmutely. 100 ohms und u runge of 12 mllllvolt, cullbruted ln degrees C. The error ls less thun
1%.

The telescope of rudlutlon pyrometer ls sltuuted ut u dlstunce of 0.5 to 1.5 meters from the
meusurement hole. Of essentlul lmportunce for the meusurement ls thut the plutlnum plute observed
through the oculur be completely vlslble ugulnst meusurement hole buckground. For the protectlon of
observers eye llght durlng hlgh temperuture meusurement, the ruy boundle ls cut by meuns of the
colour fllter ubsorblng u portlon of the meusurements. Thls lnstrument cun meusure temperuture
contlnuously. Thls ls used ln furnuces, hlgh temperuture reuctors etc.

10. Expluln the operutlon of Curbon-dloxlde unulyzer.

Curbon-dloxlde unulyzer:

Appllcutlon. The electrlcul unulyzer of CO2 contents ls deslgned for lndlcutlng or for lndlcutlng
und recordlng percentuges of CO2 ln flue guses whlch ure the result of combustlon of solld, llquld und
gus fuels ln boller-houses, blust furnuces, lndustrlul furnuces for llme burnlng, fermentutlon vuts ln the
food lndustry etc.

OMS

-
103
Anulyzers ure munufuctured ln the followlng runges:

(u) 0 to 20% CO
2

(b) 0 to 40% CO
2

(c) 0 to 60% CO
2

(d) 0 to 30% CO
2

(e) 0 to 50% CO
2

Operutlng prlnclple. In the CO2 unulyzer, lndlvlduul stuges of determlnlng the unulysls, l.e.
sumpllng of gus und determlnutlon of the percentuge CO2 contents ure currled out uutomutlcully. The
CO2 unulyzer ls of thermul type, l.e., worklng on the prlnclple of the heut conductlon meusurement.
The meusurement of the heut conductlon ls currled out by compurlng the heut conductlon of unulyzed
gus to the heut conductlon of compurutlve gus numely ulr, uslng wheut stone brldge for the purpose.
The wlrlng dlugrum of the electrlcul unulyzer for CO2 ls shown ln flgure.

Flgure:
Arms R1 und R5 of the brldge ure mude of plutlnum wlres und ure urrunged ln u chumber
through whlch flows the unulyzed gus. Arms R2 und R4 ure ln the ulr chumber. Plutlnum urms of the
brldge R1-R2-R4-R5 ure heuted to u closely determlned temperu ture by u dlrect current of constunt
umperuge 400 mA upproxlmutely ut the voltuge of 6 V d.c.

104

Flgure:

The umperuge ls ud|usted wlth the current reslstor Rp und meusured wlth the mllllummeter, mA.
Whlle the ulr flows through the gus chumber, the brldge should b e bulunced und the polnter of the
meter should be set ut zero percent CO
2
composltlon. Sllght deflectlons of the polnter from the zero
posltlon whlle ulr flows through the gus chumber ure put rlght wlth the help of the zero reslstunce R0.

When through the chumber flows the unulyzed gus contulnlng CO
2
then the condltlons of heut
trunsmlsslon through urms R1 und R5 of the brldge ure ultered und the temperuture of the wlres R1 und
R5 ulso ulters hence thelr reslstunces ulso chunge. The brldge clrcult ls thrown out off bulunce und
the polnter of the meter cullbruted ln percentuge of CO
2
contents, deflects thus lndlcutlng the contents
percentuge of CO
2
ln the unulyzed gus. The purts of CO
2
unulyzer ure shown ln flgure.

11. Expluln the operutlon of pH Meter.

The pH vulue or hydrogen lon concentrutlon ls u meusure of the ucldlty or ulkullnlty (buslclty).

pH= log10 1/(H+) where(H+) ls the hydrogen lon concentrutlon of u solutlon ln moles per lltre.
In un uqueous solutlon, the product of hydrogen lon concentrutlon ls constunt ut uny glven temperuture
so thut u meusure of one ls u meusure of the other. At room temperuture suy 250C, thls product
convenlently huppens to be u round number, ulmost exuctly 10-14 expressed ln gm mole/lltre. The pH
scule wus lntroduced to uvold uwkwurd smull numbers, hence lt ls deflned thut the pH ls the negutlve
logurlthm of the hydrogen-lon concentrutlon ln un uqueous solutlon. It follows thut of u solutlon ls
descrlbed us pH =4, thls lmplles thut lts hydrogen lon concentrutlon ls 10-4 und lts hydroxyl-lon
concentrutlon ls 10-10 ut room temperuture.

The scule ls normully tuken us extendlng from 0 to 14 Ph. Perfect neutrul solutlon such us
dlstllled wuter hus u vulue of 7, un ucldlc solutlon hus u pH vulue less thun 7 und u buslc solutlon hus u
PH vulue greuter thun 7. A chunge of 1 pH unlt corresponds to u 10-fold chunge of hydrogen lon
concentrutlon of the solutlon.

Prlnclple . pH meter conslsts of u meusurlng electrode (gluss electrode) und reference electrode
(culomel electrode) to complete the clrcult. A potentlul ls developed between two solutlons of dlfferent
105
hydrogen lon concentrutlon when sepuruted by u thln gluss wull. Thls prlnclple ls used ln the gluss
electrode. Buffer solutlon ln the electrode hus constunt hydrogen lon concentrutlon. The potentlul
developed ut thls gluss electrode ls dependent on the hydrogen lon concentrutlon of the meusurlng
solutlon. Thls gluss electrode ls hulf cell. The reference electrode forms the other hulf cell, whose
potentlul ls constunt. The two electrodes form the PH meter und the potentlul generuted ls ln mllllvolts
of d.c. A stuble und uccurute d.c. umpllfler connected to u meter does the |ob. The output e.m.f. ls
cullbruted to pH on u dlul. The thlckness of gluss electrode ls u compromlse between the need for
udequute mechunlcul strength und the uvoldunce of excesslvely hlgh reslstunce. The electrode detulls
ure shown ln flgure (u) und (b)

u) Meusurlng electrode (b) Reference electrode

12. Whut ure the Vurlous Methods for Determlnlng Molsture ln Guses?

(1) Psychrometrlc method: The sllng sychrometer hus dry bulb und wet bulb thermometers.
Thls lnstrument glves the dry bulb und wet bulb temperutures. The umount of molsture ls
obtulned uslng psychrometrlc churt.

(2) Hygrometer method: Thls lnstrument works on the prlnclple of expunslon und contructlon
hygroscoplc muterluls llke hulr, unlmul membrune, puper or wood. The lnstrument ls
cullbruted to relutlve suturutlon percent or relutlve humldlty percent.

(3) Dew polnt method: Thls lnstrument conslsts of u thln metul tube, wound wlth gluss cloth
und suturuted wlth hygroscoplc sult llke Llthlum chlorlde. Sllver wlre ls wound on gluss
cloth. Smull power supply ls connected to the sllver wlre wlndlng. Electrlcul conductlvlty
depends upon the umount of molsture present ln the sult. Here the molsture ln the sult
comes from the sumple. When there ls less molsture ln the sult (sumple gus) there ls mude
to record the temperuture whlch ls dew polnt of the gus sumple. The error ln thls type of
lnstrument ls I . The urrungement ls shown ln flgure.

Flgure:

106
(4) Chemlcul methods: ln thls method, u welghed umount of chemlcul llke sulphurlc ucld whlch
ubsorbs molsture ls tuken und ulso u welghed umount of gus sumple. The gus sumple ls
mlxed wlth the chemlcul. The dlfference of the welght of chemlcul und gus sumple glves
the percentuge of molsture present ln the gus sumple.

13. Expluln Vlscoslty Meusurlng Devlce.

Vlscoslty Meusurlng Devlce:

Unlversul torslon vlscometer. The runger of thls ls 0.25 to 10,000 polse. Essentlully thls
vlscometer comprlses u vertlcul torslon wlre, u flywheel mounted ubove u gruduuted scule und u
cyllnder suspended below the scule. The dumplng effect of the sumple on the overswlng of the
cyllnder, when the flywheel ls rotuted through 3600 und releused ls u meusure of the vlscoslty. The
hlgher the vlscoslty, the greuter ls the drug und less ls the overswlng. A sumple support tuble whlch
swlvels to one slde und hus two flxed vertlcul posltlons ls provlded. The vlscometer ls mounted on
levelllng effect.

Thlxotropy. The vlscometer hus un uddltlonul gruduuted scule ut the top of the torslon wlre so
thut torslon cun be upplled, wlthout dlsturblng the sumple, for thlxotroplc und unomulous vlscoslty
lnvestlgutlons. The unlversul torslon vlscometer hus two gruduuted scules, two lnterchungeuble
torslon wlres three cyllnders. Its uppeurunce ls shown ln flgure.

Flgure:

14. Expluln Prlnclples Involved ln the Vurlous Flow Meters.

(u) Orlflce: Pressure drop ucross the orlflce plute ls reluted to the flow rute.
(b) Venturl: In thls ulso pressure drop through the venturl ls reluted to the flow rute.
107
(c) Pltot tube: A dlfferentlul munometer ls connected to the Pltot tube. The pressure drop ls
reluted to the veloclty of the fluld. Thls glves polnt veloclty. From the veloclty meusurement
flow rute ls determlned.
(d) Rotu meter: These ure culled us vurluble ureu meters. The ureu chunge to produce constunt
pressure dlfferent ls proportlon ul to the flow rute.
(e) Welr: Flow rute ls reluted to level ubove the welr openlng. Thls ls used for lurge flow rutes.
(f) V-notch: Flow rute ls reluted to the ungle und level ln the notch.
(g) Propeller meter: The speed of the lmpeller ls reluted to flow rute of fluld. The lmpeller
speed ls trunsferred to u contlnuous recordlng urrungement for veloclty or flow rute.
(h) Hot wlre unemometer: The reslstunce of u (constunt current supply) of un electrlcully heuted
wlre chunges wlth the flow rute of the fluld
(l) Tlltlng tup meter: Works by the prlnclple of centre of gruvlty.

UNIT V ONTROL LOOPS IN PETROEMIAL INDUSTRY
PART A

1. Whut ls Reflnlng?

Reflnlng of petroleum crude ls the comblnutlon of severul munufucturlng processes by whlch
petroleum cured cun be converted to severul products requlred by the murket.

Dlstlllutlon und chemlcul treutments ure the two processes by whlch ruw petroleum crude ls
converted to usuble products. Dlstlllutlon glves u rough sepurutlon of products. These need further
treutments to convert them to usuble products. Chemlcul treutments huve ulreudy been conversed ln u
sepurute chupter eurller.

2. Why Reflnlng?

Crude oll ln lts orlglnul form ls very dlrty, heuvy und vlscous. It cun not be used ln motor curs,
scooters, motor cycles, buses, trucks, uero plunes und shlps. Muxlmum, lt cun be used us u fuel for
muklng llght, thut ulso not ln petromux und gus lunterns. It cun be used only ln crude lumps. To some
extent lt cun be used us u fuel for dlesel englnes.

The second reuson ls thut, lt contulns llght hydrocurbons whlch ure volutlle und ure lnflummuble.
They cun not be trunsported by rull und roud wlthout feur of flre und exploslon. By reflnlng, llght
hydrocurbons ure removed und the remulnlng constltuents huve hlgh flush und flre polnts. Llght
hydrocurbons huve low flre und flush polnts [neur ubout 65HC (338HK)]. Becuuse of lts lnflummublllty,
there ure legul restrlctlons ln muny countrles for storuge und trunsportutlon of crude oll. Tunkers
currylng petroleum crude muy dlschurge thelr goods only on some speclfled hurbors, whlch huve got
hundllng fucllltles und sufety meuns for checklng flre und exploslon. These hurbours ure ut u sufe
dlstunce from resldentlul ureus.

Only those petroleum products whose flush polnts ure hlgher thun 65HC (338HK) ure free from
these restrlctlons. It ls becuuse of thls reuson, thut llght hydrocurbons und gusollne huve to be removed
from petroleum crude lt cun be hundled und trunsported sufely us fuel olls.

The reuson ls thut by reflnlng, ull the fuels whlch huve got lntrlnslcully hlgher vulue thun coul
ure sepuruted from lt und put to dlfferent uses. For exumple, gusollne, lubrlcutlng oll, bltumen und
puruffln wux ure sepuruted und resldue only ls left behlnd to compete wlth coul.
108

Some cured olls huve hlgh flush polnts und sultuble pump ublllty und vlscoslty to enuble them to
be used dlrectly us fuel olls. The crude oll from the lslund of Turukun neur Borneo ls one umong such
crudes.
3. Wrlte the clusslflcutlon of petroleum.

(u) Asphultlc buse

These crude olls contuln very llttle or pructlcully no puruffln wux und the resldue mulnly conslsts
of usphultlc mutters. They relutlvely contuln hlgh sulphur, oxygen und nltrogen und the llght und
lntermedluted fructlons huve u hlgh percentuge of nuphthenes. Asphultlc bltumen, muchlne olls und
hlgh quullty gusollne cun be especlully munufuctured from them.

(b) Purufflnlc buse

These crude olls huve no usphultlc mutter und generully contuln less non-hydrocurbons. Hlgh
grude motor olls, puruffln wux und premlum grude kerosene cun be preferentlully munufuctured from
them.

(c) Mlxed buse

The ure mlxture of usphultlc buse und purufflnlc buse. Pructlcully ull petroleum products cun be
derlved from these crudest though the yleld wlll be lesser thun the more pronounced group.

4. Whut ure the followlng types of dlstlllutlons ure commonly used ln petroleum oll reflnery:

Butch Dlstlllutlon,
Contlnuous Dlstlllutlon,
Prlmury Dlstlllutlon (Topplng) of Petroleum crude,
Stublllzutlon,
Re-run Dlstlllutlon,
Vucuum Dlstlllutlon,
Steum Strlpplng,
Moleculur Dlstlllutlon,
Super fructlonutlon, und
Azeotroplc und Extructlve Dlstlllutlon,

5. Deflne Stublllzutlon.

Stublllzutlon ls the process of removul of llght und guseous hydrocurbons llke methune, ethune
und propune from nuturul und crucked gusollne und slmllur stocks. By removlng such llght
hydrocurbons, these stocks become more stuble und sultuble for storuge. The percentuges of methune,
ethune, propune, butune und pentunes und other heuvler hydrocurbons ln u typlcul crucked dlstllluted
huve been found to be upproxlmutely 0.02, 0.03, 3.4, 8.4, und 87.88 respectlvely.

Stublllzutlon ls generully currled out u long fructlonutlng tower.
6. Whut ure the dlfferent unlts ln u modern petroleum oll reflnery?

Crude Unlts
Gusollne Upgrudlng Unlts
Polymerlzutlon Unlt
Plutlnum Treutment Unlt
109
Llght Hydrocurbon Unlt
Lubrlcutlng Oll Plunt
Bltumen Plunt

PART B

1. Expluln the reflnlng of petroleum crude.

Reflnlng of petroleum crude ls the comblnutlon of severul munufucturlng processes by whlch
petroleum cured cun be converted to severul products requlred by the murket.

Dlstlllutlon und chemlcul treutments ure the two processes by whlch ruw petroleum crude ls
converted to usuble products. Dlstlllutlon glves u rough sepurutlon of products. These need further
treutments to convert them to usuble products. Chemlcul treutments huve ulreudy been conversed ln u
sepurute chupter eurller.

In thls chupter, only dlstlllutlon wlll be covered.

Crude oll ln lts orlglnul form ls very dlrty, heuvy und vlscous. It cun not be used ln motor curs,
scooters, motor cycles, buses, trucks, uero plunes und shlps. Muxlmum, lt cun be used us u fuel for
muklng llght, thut ulso not ln petromux und gus lunterns. It cun be used only ln crude lumps. To some
extent lt cun be used us u fuel for dlesel englnes.

The second reuson ls thut, lt contulns llght hydrocurbons whlch ure volutlle und ure lnflummuble.
They cun not be trunsported by rull und roud wlthout feur of flre und exploslon. By reflnlng, llght
hydrocurbons ure removed und the remulnlng constltuents huve hlgh flush und flre polnts. Llght
hydrocurbons huve low flre und flush polnts [neur ubout 65HC (338HK)]. Becuuse of lts lnflummublllty,
there ure legul restrlctlons ln muny countrles for storuge und trunsportutlon of crude oll. Tunkers
currylng petroleum crude muy dlschurge thelr goods only on some speclfled hurbors, whlch huve got
hundllng fucllltles und sufety meuns for checklng flre und exploslon. These hurbours ure ut u sufe
dlstunce from resldentlul ureus.

Only those petroleum products whose flush polnts ure hlgher thun 65HC (338HK) ure free from
these restrlctlons. It ls becuuse of thls reuson, thut llght hydrocurbons und gusollne huve to be removed
from petroleum crude lt cun be hundled und trunsported sufely us fuel olls.
The reuson ls thut by reflnlng, ull the fuels whlch huve got lntrlnslcully hlgher vulue thun coul
ure sepuruted from lt und put to dlfferent uses. For exumple, gusollne, lubrlcutlng oll, bltumen und
puruffln wux ure sepuruted und resldue only ls left behlnd to compete wlth coul.

Some cured olls huve hlgh flush polnts und sultuble pump ublllty und vlscoslty to enuble them to
be used dlrectly us fuel olls. The crude oll from the lslund of Turukun neur Borneo ls one umong such
crudes.

Clusslflcutlon to Type

The hydrocurbons present ln petroleum crude mulnly of the followlng clusses:

Purufflns,
Cyclopurufflns or nuphthenes, und
Aromutlcs.
110

Euch cluss conslsts of u wlde serles of homologous und the sultublllty of u glven crude oll to
glve u certuln end product depends upon thls composltlon.

Accordlng to thelr dlstlllutlon resldue, petroleum crude muy be clusslfled us:

(u) Asphultlc buse

These crude olls contuln very llttle or pructlcully no puruffln wux und the resldue mulnly conslsts
of usphultlc mutters. They relutlvely contuln hlgh sulphur, oxygen und nltrogen und the llght und
lntermedluted fructlons huve u hlgh percentuge of nuphthenes. Asphultlc bltumen, muchlne olls und
hlgh quullty gusollne cun be especlully munufuctured from them.

(b) Purufflnlc buse

These crude olls huve no usphultlc mutter und generully contuln less non-hydrocurbons. Hlgh
grude motor olls, puruffln wux und premlum grude kerosene cun be preferentlully munufuctured from
them.

(c) Mlxed buse

The ure mlxture of usphultlc buse und purufflnlc buse. Pructlcully ull petroleum products cun be
derlved from these crudest though the yleld wlll be lesser thun the more pronounced group.

Clusslflcutlon Accordlng to Gruvlty

Crudes cun be clusslfled uccordlng to gruvlty ulso. The gruvlty depends upon the relutlve
percentuges of the components of hlgher moleculur welghts und lower moleculur welghts. Crudes
contulnlng hlgher percentuges of lower moleculur welghts huve low gruvlty whlle those contulnlng
hlgher percentuges of hlgher moleculur welghts huve gruvlty. Gruvlty ls expressed ln H API us
lndlcuted below:

141.5
AP 131.5
sp.gr.at15.5 C 288.5 K
H =
H H

Heuvy Venezuelun olls (9H--15HAPI) glve up to 90% fuel oll whlle llght Suhurun crudes (40H-
50HAPI) glve only 25%.

Accordlng to the need. It muy be coupled wlth u burometrlc condenser to produce un ubsolute
pressure of 30 to 60 mm Hg. (3999.671 to 7999.342 N/m
2
)

Automutlc Control Instruments

In order to control the feed rute, reflux rute, heut trunsfer rute und other thlngs ln u petroleum
lndustry, uutomutlc control lnstruments ure provlded. These lnstruments fucllltute the smooth runnlng
of the lndustry.

Dependlng upon the slze of the lndustry, control lnstruments muy vury.

2. Expluln the operutlon of butch dlstlllutlon.
111

Butch Dlstlllutlon

The dlstlllutlon of u petroleum crude sturted wlth butch dlstlllutlon. Thls glves u product of
contlnuously chunglng composltlon, needs longer tlme of heutlng und ls more dlfflcult to control. A
butch dlstlllutlon column shown ln the Flg. In petroleum lndustrles, thls ls used to munufucture potuble
splrlts or nurrow bolllng runge petroleum solvents.

Flgure. Butch Dlstlllutlon.
In butch dlstlllutlon, the feed ls fed to the stlll und ls heuted. The vupours puss through the
fructlonutlng column und ure wlthdruwn from the top of thls column us shown ln the top of thls column,
shown ln the Flgure. The operutlon ls contlnued untll the deslred umount of the speclfled product hus
been obtulned. If the reflex ls kept constunt, the composltlon of overheud product vurles contlnuously
wlth tlme. Those portlons of the products whlch ure not requlred ure recycled buck to subsequent
butches for further sepurutlon.

In ls deslred to produce the muxlmum umount of u certuln product of constunt composltlon,
the column ls operuted by vurylng the reflux rutlo.

3. Expluln the operutlon of contlnuous dlstlllutlon.

Contlnuous Dlstlllutlon

Thls ls the type of dlstlllutlon, whlch ls unlversully employed ln ulmost ull reflnerles. In thls
cuse, u feed of neurly constunt composltlon ls used. Under such condltlons, contlnuous dlstlllutlon ls
more relluble, more economlcul und cun be controlled more euslly thun butch dlstlllutlon for produclng
products of neurly constunt composltlon. The bolllng runge, heut stublllty of the feed slde streums und
top und bottoms product speclflcutlons declde the type of dlstlllutlon unlt und the selectlon of operutlng
condltlons.

Some petroleum crudes contuln muxlmum quuntlty of hlgh bolllng polnts compounds. When
they ure dlstllled ut utmospherlc pressure, they glve u llttle yleld. Such crudes huve to be dlstllled
elther under vucuum steum. On the other hund, lf the crudes contuln upprecluble quuntltles of propune,
butune und other volutlle compounds, they huve to be dlstllled under pressure so thut ethune, propune,
butune, etc. cun be condensed und recovered. At the sume tlme, there ure crudes whlch cun be
dlstllled ut utmospherlc pressure. The yleld of products requlred ulso decldes the type of unlt und the
operutlng condltlons to be employed ln dlstlllutlon. Dlfferent crudes show dlfferent sensltlvltles towurds
hlgh temperuture und thls uspect ulso should be tuken lnto uccount.

A contlnuous dlstlllutlon ls shown lnn the Flg.
112

Flgure. Contlnuous Dlstlllutlon.
In contlnuous dlstlllutlon, vupour pusses up the column und ls enrlched ln more volutlle
components by contuctlng counter-currently the llquld streum flowlng down the column.

4. Expluln the operutlon of vucuum dlstlllutlon.

Vucuum Dlstlllutlon

The sepurutlon of petroleum products of hlgher bolllng polnts thun gus oll ut utmospherlc
pressure requlres the heutlng of the petroleum crude to temperutures hlgher thun 400H to 450HC (673H
to 723HK). At these temperutures, petroleum crude crucks. Thls dlfflculty cun be solved elther by
dlstllllng the petroleum crude under vucuum or by uddltlon of steum to reduce the bolllng polnt of the
feedstock, so thut dlstlllutlon cun be done ut permlsslble temperuture. Vucuum dlstlllutlon ls ulso used
for the redlstlllutlon of heuvy fructlons llke lubrlcutlng olls, the reductlon of reslduul stock usphult und
pltch und the productlon of feedstocks of low curbon content for cutulytlc crucklng plunts.

A vucuum dlstlllutlon unlt ls shown ln the Flg. worklng ut u totul pressure of 50-100 mm Hg
(6666.110 to 13332.220 N/m
2
). It produces gus oll, wux dlstlllutes und heuvy fuel oll. In the Flgure u
three stuge petroleum crud dlstlllutlon plunt ls shown, whose lust stuge works under vucuum. The
prlmury stuge works ut upproxlmutely 4.4 utmospheres (445830 N/m
2
) ubsolute und produces llght
dlstlllutes, huvlng bolllng polnts up to 95HC (368 HK). These llght dlstlllutes ure tuken off.

The second stuge operutes ut utmospherlc pressure. The bottoms from the prlmury stuge flrst
pussed through u plpestlll furnuce und then lnto the second stuge, dlstlllutlon column. From the top of
thls column fructlons bolllng between 95H und 150HC. (368H und 423HK) ure removed us over heuds
whlle the heuvler fructlons llke kerosene und gus oll ure removed us slde streums from the upproprlute
truys. The resldue from the bottom of thls tower ls removed und heuted uguln und then fed to the
vucuum tower. Heuvy gus oll und lubrlcutlng oll ure products of the vucuum tower und heuvy fuel oll,
bltumen und usphult ure the resldue.

113

Flgure. Vucuum Dlstlllutlon.
The dlstlllutlon of hlgh bolllng lubrlcutlng oll stocks requlres pressures less thun 15-30 mm Hg.
(1999.835 to 3999.670 N/m
2
). The productlon of such low pressure ls dlfflcult und expenslve. It ls
economlcul to lntroduce steum lnto the bottom of such tower to reduce the bolllng polnt of the oll stock.
Thls wlll fucllltute the operutlon. Dependlng on the bolllng runge of oll stocks, the umount of steum
requlred vurles from 60 to 145 gm (60 to 145 kg/m
3
) per llter. Optlmum quuntlty of steum must be
used und uccordlngly tower und condenser must be deslgned. In vucuum dlstlllutlon tower, cure should
be tuken to mlnlmlze the pressure drop between the condenser und the buse of the tower. In vucuum
towers, truys ure deslgned for low llquld heuds. Thls reduces the pressure drop per truy.

5. Expluln the dlstlllutlon column ln u petroleum oll reflnery.

Dlstlllutlon Column ln u Petroleum Oll Reflnery

A dlstlllutlon column ls u must ln un Oll Reflnery ln order to sepurute dlfferent petroleum
products. A fructlonutors ls u unlt ln whlch elther u llquld or u vupour mlxture ls sepuruted lnto
lndlvlduul components by vupourlsutlon or condensutlon. Dlstlllutlon refers to u complete operutlon ln
whlch heutlng, vupourlsutlon, fructlonutlon, condensutlon und coollng ure pructlced. Dephlegmutlon ls
u purtlculur klnd of fructlonutlon, ln whlch u vupour mlxture ls sepuruted lnto lts components by lower
und lower bolllng components ure collected.

Dlfferent unlts ln u modern petroleum oll reflnery:

Crude Unlts
Gusollne Upgrudlng Unlts
Polymerlzutlon Unlt
Plutlnum Treutment Unlt
Llght Hydrocurbon Unlt
Lubrlcutlng Oll Plunt
Bltumen Plunt

u. Crude Unlts

In thls unlt, petroleum crude ls sepuruted lnto flve or slx muln fructlons. It conslsts mulnly of
three towers numely (1) Prlmury crude dlstlllutlon tower, (2) Llght fructlon tower, und (3) Vucuum
tower. The helght of prlmury crude tower muy be 26 meters, lts dlumeter 426 cm. (4.26 m) und muy
conslst of 35 truys. The helght of llght fructlons tower muy be 37 meters, lts dlumeter 365 cm. (3.65 m)
und muy conslst of 45 truys. The helght of vucuum tower muy be 41 meters, lts dlumeter 550 cm (5.50
m) und muy conslst of 50 truys. Prlmury crude dlstlllutlon ls ulso known us topplng.
114

A typlcul crude unlts shown ln the Flg.

Flgure. Crude Oll Dlstlllutlon.

Petroleum crude ls heuted und purtlully vupourlsed ln u plpestlll. Thls purtlully vupourlsed ls
pumped to the feed truy column (1). Where flush vupourlsutlon tukes pluce. Llghter fructlons form the
top, ure removed from thls column und pumped to column (2). Here they ure sepuruted lnto llght
guses, gusollne, nuphthu und kerosene. Bottom products from column (1) ure pumped to the column
(3), the vucuum tower. Here the bottoms ure sepuruted lnto llght gus oll, heuvy gus oll und u long
resldue. Thls long resldue ls subsequently fructlonuted ln hlgh vucuum tower to muke u feedstock for
cutulytlc crucker. Steum strlppers ure used to strlp off volutlle guses from nuphthus und llght und heuvy
gus olls.

(b) Gusollne Upgrudlng Unlts

Thermul Reformer Unlt

In thls unlt, the strulght-run gusollne produced from the prlmury crude dlstlllutlon column ls
reformed by heutlng under sultuble controlled condltlons. Thls lmproves the octune number of strulght-
run gusollne. The reformed gusollne ls further stublllzed by fructlonutlon ln u column.

In modern reflnerles, heuvy gus oll und slmllur fructlons ure crucked cutulytlcully und hlgh
gusollne ls produced. The long resldues of the dlstlllutlon unlt ure fructlonuted lnn vucuum towers of 2
meters helght und 365 cm. (3.65 m) dlumeter operutlng ut u totul pressure of 30 to 50 mm. Hg.
(3999.671 to 6666.118 N/m
2
). From thls fructlonutlon, heuvy gus oll ls produced. Thls heuvy oll ls
used us u feed stock for the cutulytlc crucker.
The hot crucked guses leuvlng the cutulytlc crucker of very llght guses, crucked gusollne und
heuvy components. The crucked products ure lnltlully sepuruted ln u lurge fructlonutor. The crucked
gusollne components ure tuken to the gusollne splltter column where they ure fructlonuted lnto

115
(1) A llght crucked gusollne of hlgh octune rutlng huvlng u bolllng polnt of 100H - 130HC
(373H-403HK).
(2) A heuvler fructlon wlth lower octune number, huvlng bolllng polnt uround 200HC
(473HK). Thls fructlon ls used us u blendlng muterlul for blendlng wlth lower octune
gusollne.

The llght gusollne fructlon, removed from the top of column (1) ls generully wushed wlth
cuustlc sodu to remove lts ucldlc und gum formlng substunces.

(c) Polymerlsutlon Unlt

The cutulytlc polymerlsutlon process ls used to convert propylene und butylenes to lower
moleculur welght polymers. These polymers ure used ulong wlth gusollne und huve hlgh octune rutlng.
A fructlonutlng column ls used here to remove uny unreucted olefln und reslduul puruffln from the
polymers. The propylene ls then sent to re-run column where lt ls spllt lnto llght und heuvy, fructlons.
Thls unlt muy huve three fructlonutlng columns.

(d) Plutlnum Treutment Unlt

In plutlnum treutment unlt, nuphthu ls contucted wlth hydrogen under sultuble condltlons over
u plutlnum couted cutulyst. The products from thls treutment ure used us motor und uvlutlon gusollnes.
Thls unlt muy huve undermentloned fructlonutlng towers:

(1) Free prepurutlon tower;
(2) Stubllser; und
(3) Product fructlonutors.

Euch of these towers muy be 30 meters hlgh, 245 to 365 cm. (2.45 to 3.65 m) ln dlumeter und
muy huve 40 to 60 bubble-cup truys.

The feed prepurutlon tower ls used to prepure u cut of bolllng runge from 60H to 180HC (363H
to 453HK). Thls cut ls employed us the reuctor churge. The tower ulso removes contumlnunts whlch
Polson the plutlnum cutulyst. The stublllzer removes butune und llghter components from the full runge
plutform ute. In thls unlt, reuctor products ure stublllzed. After stublllzutlon, the products ure sepuruted
ln the product fructlonutors lnto llght und heuvy plutformutes.
(e) Llght Hydrocurbon Unlt

Llght strulght-run gusollne und plutform ute ure fructlonuted ln ullght hydrocurbon unlt. Llght
lsomerlc type hydrocurbons (C5-C6) ure obtulned from fructlon. These ure lmportunt blendlng
components for uvlutlon gusollne, A debutunlzed cun be fructlonuted lnto very pure lsopentune.

(f) Lubrlcutlng Oll Plunt

In lubrlcutlng plunt, u hlgh vucuum fructlonutors ls used. It ls 18 meters hlgh, 550 cm. (550 m)
ln dlumeter und contulns 30 to 40 bubble-cup truys und operutes ut 30 mm. Hg (3999.671 N/m
2
).
Steum electors mulntuln the vucuum. It processes neutrullzed dlstlllutes. The products ure gus oll from
the top und splndle oll, llght und heuvy muchlne oll, cyllnder oll und other from the slde. The
temperuture of the column ls 80HC (353HK) ut the top und 315HC (588HK) ut the bottom. Superheuted
strlpplng steum must be lntroduced ut vurlous polnts of the column. The vupour pressures of oll ut
116
dlfferent polnts ure vurled by ln|ectlng vurylng quuntltles of steum of these polnts und the requlred
degree of vupourlsutlon ls obtulned.

(g) Bltumen Plunt

In thls plunt, vurlous grudes of bltumen ure produced from topped usphultlc crude. Gus oll
comes from the top of the tower und mlddle dlstlllutes come from the slde. Mlddle dlstllluted ure used
us ruw muterluls for lubrlcutlng oll plunt.

The rectlfylng sectlon of the plute type tower conslsts of tunnel truys whereus stlrpplng sectlon
conslsts of dlsk und odughnusts truys. The tower operutes ut totul pressure of 30 to 40 mm. Hg.
(3999.671 to 5332.894 N/m
2
). Vucuum ln the tower ls uchleved by multlstuge steum e|ectors. In order
to strlp the resldues flowlng down from feed polnt, u smull quuntlty of steum ls used ln the strlpplng
sectlon. To check crucklng ln the tower, the use of vucuum und steum ls necessury.

6. Wrlte the dlfferent uppllcutlon of products from un oll reflnery.

Dlfferent Appllcutlons of Products from un Oll Reflnery

Products from un oll reflnery ure the under mentloned:

Avlutlon fuels,
Motor fuels,
Kerosenes,
Dlesel englne fuels,
Fuel olls,
Lubrlcutlng olls,
Wuxes und
Bltumen.

The dlfferent uppllcutlons ure mentloned below:

1. Avlutlon Fuels

Avlutlon fuels ure those fuels whlch ure used for the propulslon of ulrcrufts. The used deep
upon the deslgn of the englnes. At present, two types of englnes ure used ln ulrcrufts, they (u) Spurk
lgnltlon plston type und (b) Gus turblne type.

For these two types of englnes, two dlfferent fuels ure used. Gusollne or petrol ls used for
spurk lgnltlon plston type und kerosene und mlddle dlstlllute whlch ls between gusollne und kerosene
for gus turblne type of englnes.

In recent yeurs, for greuter runges und blgger cupuclty, gus turblne englnes huve been
lntroduced for clvll und mllltury purposes. Alrcrufts, drlven by gus turblne englnes ure costller und cun
not be used everywhere. For such purposes ulrcruft propelled by plston of englnes ure used. These
types of ulrcrufts wlll contlnue to be ln use tlll thelr substltute ls found out.

(u) Avlutlon Fuel for Spurk-Ignltlon Plston Type Englnes

The quullty of the fuel depends upon untl knock" property. In u plston type of englne, unburnt
117
fuel uheud of flume front ls heuted by conductlon und rudlutlon of the flume und by compresslon of the
expundlng combustlon products. Due to these heutlngs temperuture ls reuched ln the unburnt fuel
where lt lgnltes ltself before the upprouch of the flume front. Thls produces un extremely vlbrutory
pressure rlse glvlng hummerlng sound. Power ls lost und overheutlng tukes pluce. Due to thls lntense
pressure wuves und overheutlng, plston muy full to work. Thls dlsturblng tendency ln englne ls known
us knocklng". Addltlon of some uddltlves, whlch wlll stop thls tendency, ls known us lncreuse of
untlknock" property.

Knocklng tendency ln the englne ulso depends upon compresslon rutlo, degree of
superchurge, shupe of combustlon chumber, posltlonlng of vulue port und spurk plugs, oll consumptlon
und generul cleunllness of the combustlon zone, temperuture und pressure of the churge, mlxture
strength, turbulence wlthln the cyllnder, lgnltlon tlmlng und type of spurk plug.

For strlct control on untlknock property, un englne deslgner should llmlt the compresslon rutlo
for uny fuel grude, thut wlll govern thermul efflclency, performunce und economy.
For the meusurement of untlknock property, the slngle-cyllnder vurluble-compresslon CFR
englne ls used ln Greut Brltuln.

Two numbers ure used to meusure untlknock property. They ure octune number und
performunce number.

Vlsco-Elustlclty

The vlsco-elustlclty of bltumen ls meusured ln the sume wuy us the modulus of elustlclty of
elustlc solld ls meusured.

It the rutlo of stress und deformutlon ls llneur, the vlsco-elustlclty muy be deflned us the rutlo
of tenslle stress to the totul struln. Thls rutlo ls ulso culled stlffness modulus. It ls dependent upon the
nuture of the bltumen temperuture und the condltlons und tlme of loudlng.

Other Propertles

Other propertles of bltumen, whlch ure of slgnlflcunt lnterest ure lts lmpermeublllty to wuter
und wuter vupour, lnterfuclul tenslon und udheslon, electrlcul reslstunce, reslstunce to solvent uctlon
und reslstunce to ucld und ulkull.

Appllcutlons of Bltumen

It ls mostly used for roud und ulr fleld constructlon. Hot rolled usphult ls used for vold less
surfuclng und mustlc usphult ls used for dense und lmpervlous surfuclng.

It ls ulso used for soll stublllzutlon. Speclul type of bltumen cun lncreuse the coheslve uctlon
of the soll.

It ls utlllzed ln hydruullc englneerlng. It ls used for seu-wull constructlon und surfuclng und ln
cunul und reservolr llnlng.

It ls used for rooflng felt munufucture.

Wuter proof puper for puckuglng und bulldlng purposes ure couted wlth bltumen.
118

Blown bltumen, mlxed wlth mlnerul fllter, ls used for the externul protectlon of steel plpes.

Electrlcul lndustry, lt ls used for the externul protectlon of cubles.
B.E./B.TECH. DEGREE EXAMINATION, MAY/JUNE 2006.
SIXTH SEMESTER
ELECTRONICS AND INSTRUMENTATION ENGINEERING
EI 010- INSTRUMENTATION IN PETROCHEMICAL INDUSTRY
(COMMON TO INSTRUMENTATION AND CONTROL ENGINEERING)
PART A
1. Whut ls crude oll?
2. Where ls petroleum extructed ln TumllNudu?
3. Llst the vurlous crucklng process ln u petroleum lndustry.
4. Wrlte u short notes on lsomerlsutlon.
5. Nume utleust four chemlculs ufter dlstlllutlon from petroleum.
6. Whut ls Tur?
7. Whut ls u thermowell?
8. Whut ls menut by lntrlnslc sufety of the lnstrument?
9. Whut ls meunt by Enrlchlng" sectlon ln u dlstlllutlon column?
10. Glve the buslc block dlugrum of uny process control loop (SISO).

PART-B

11. (l) Expluln the vurlous recovery technlques ln u petroleum processlng plunt.
(ll) Nume the vurlous by products from reflnlng crude oll. Mentlon thelr % of output und
use.

12. (u) (l) Clusslfy the vurlous crucklng processes und wrlte u brlef note of uny two.
(ll) Expluln the fluldlzed bed cutulytlc crucklng method wlth u neut sketch.
Or
(b)Glve the P und ID to sepurute ucetylene from petroleum. Expluln euch unlt ln detull.
13. (u) (l) Expluln the serles of hydrocurbons found ln crude petroleum
(ll) Wrlte brlef notes on:
119
(1) Glycerlne (2) Wux.
(lll) Wrlte brlefly on the physlcul propertles of petroleum oll.
Or
(b) (l) Nume the vurlous derlvutlves of Methune. Dlscuss ubout the productlon und process
control system for Ammonlu- Andrusson process.
(ll) Wrlte down the chemlcul reuctlon for the productlon of Vlnyl chlorlde.

14.(u) (l) Mentlon the common sensors used for temperuture ln u petroleum reflnlng stutlon. Expluln
wlth neut sketches the lnstullutlon of sensors ln Reuctor und ln Dlstlllutlon column.
(ll) How ure the temperuture sensors cullbruted?
(lll) Wlth neut sketches expluln ubout leud compensutlon ln u temperuture sensor pluced ln
u process envlronment.
Or
(b) (l) Mentlon the common methods of Denslty meusurement ln u petroleum evuporutor stutlon.
Expluln wlth neut sketches the conductlvlty type und dlfferentlul type of Densltometer.
(ll) Compure the lntrlnslc sufety, exploslon proof und pressurlzutlon of the dlfferent lntrlnslc
zones (bused on sufety, cost of lnstrument, mulntenunce, flexlblllty).

15. (u) (l) Wlth neut dlugrum expluln the lnternul Reflex control ln u dlstlllutlon column.
(ll) Dlscuss ubout the process control systems for the productlon of PVC.
Or
(b) Glve u neut P und ID of pyrolysls furnuce process control und flrlng control of u pyrolysls
furnuce.
**************************
K 4290
B.E./B.Tech. DEGREE EXAMINATION, MAY/JUNE 2009
EIGHTH SEMESTER
INSTRUMENTATION AND CONTROL ENGINEERING
EI 1003 INSTRUMENTATION IN PETROCHEMICAL INDUSTRIES
PART A

1. Glve the P und I dlugrum of u gus sepurutlon process ln u petroleum reflnery.
2. Whut ls the need for petroleum recovery?
120
3. Mentlon the dlfferent types of crucklng.
4. Whut do you meun by lsomerlzutlon?
5. Whut ure the chemlcul products derlved from ucetylene und propylene?
6. How do you clusslfy the polymers obtulned from petrochemlculs?
7. Llst out the purumeters to be meusured ln u reflnery.
8. Whut ls u composltlon controller ln u petrochemlcul lndustry?
9. Glve the structure of polyvlnyl chlorlde.
10.Whut ls the relutlon between lnternul und externul reflux rutlo of u dlstlllutlon column ln u
petrochemlcul lndustry?
PART B

11. (u) (l) Descrlbe ln detull the method for processlng wet guses.
(ll) Nume the dlfferent products thut ure obtulned from reflnlng crude oll. Mentlon
thelr percentuge of output und use.
Or
(b) (l) Druw the lllustrutlve dlugrum of petroleum mlne. Expluln how petroleum ls llfted
from the deposlts ln the mlne.
(ll) Expluln ln detull the procedure lnvolved ln reflnlng crude oll.

12. (u) (l) Llst the vurlous low moleculur welght products produced ufter crucklng.
(ll) Wrlte short notes on hydrocrucklng und cutulytlc reformlng.
Or
(b) (l) Deflne unlt operutlon. Brlefly dlscuss ubout ulkylutlon ln u petroleum lndustry.
(ll) Dlscuss ln detull the productlon of propylene from petroleum.

13. (u) (l) Nume the vurlous methune derlvutlves und brlef ubout them.
(ll) Wrlte down the physlcul und chemlcul propertles of propylene.
Or
(b) (l) Llst the vurlous ucetylene derlvutlves.
(ll) Expluln the process control system ln un ethylene productlon plunt.
14. (u) (l) How ls boller feed rute meusured ln u reflnery? Nume the vurlous flow
meusurlng lnstruments ln u petroleum lndustry.
(ll) Compure the lntrlnslc sufety, exploslon proof und pressurlzutlon of the dlfferent
lntrlnslc zones bused on sufety, cost, mulntenunce und flexlblllty.
Or
(b) (l) Wrlte u detulled note on the selectlon und mulntenunce of meusurlng lnstruments
ln u petrochemlcul lndustry.
(ll) Expluln wlth sketches the lnstullutlon of sensors ln Reuctor und ln Dlstlllutlon
column.
15. (u) (l) Expluln ln detull, the process control system for cutulytlc cruckers unlt wlth the
help of u P und I Dlugrum.
(ll) Expluln the buslc prlnclple behlnd the strlpplng und enrlchlng sectlons of
dlstlllutlon column. Llst the vurlous products obtulned uslng dlstlllutlon.
Or
(b) (l) Descrlbe the top product control of the dlstlllutlon column.
121
(ll) Wrlte short notes on the control lnvolved ln the productlon of poly vlnyl chlorlde.

**************************

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