SECTION 3 PROCESS DESCRIPTION

The feed. offgas

hydrogen

manufacturing supply Unit

unit

produces

hydrogen

by

the

conventional steam/methane reforming process using natural gas as a This hydrogen from is supplemented 7200. by the hydrogen-rich is predominantly Platformer The hydrogen

consumed by Hydrocrac er !eactor Unit "000 and secondarily by other refinery units. This hydrogen distribution system is discussed in more detail in subsection ".#". $everal process steps are employed to produce hydrogen from natural gas. They are described in the follo%ing se&uence' (#) (2) (") (-) (.) (1) (7) (3) *eed gas pretreatment *eed gas compression +esulfuri,ation $team reforming /0 conversion /02 removal 2ethanation /ondensate stripping

4n the follo%ing description the values used for flo% rates5 temperatures5 necessarily and pressures that %ill are be design to values be the and are not those found optimum during

operation of the unit. The Process *lo% $chemes (P*$s) can be found in $ection #".

OM/6000 Rev.1

3/1

September 1997

OM/6000 Rev.1

3/2

September 1997

3.1

FEED GAS PRETREATMENT *eed gas from Unit 6270 enters the Hydrogen 2anufacturing Unit

at a rate of #5#6-.# tpsd5 at a pressure that can vary bet%een 20.7 and .0 bar(g)5 and at a temperature that can vary bet%een #0 / and 70 /. 7 portion of this feed5 -07.2 tpsd5 supplies the the fuel

re&uired by the reformer furnace. The balance of 731.6 tpsd passes through Pressure /ontroller P!/-#5 %hich reduces incoming pressure to "2.0 bar(g) %henever it is above that level5 before the gas enters 8atural 9as :noc out +rum ;-10#" to remove any entrained li&uid. 7t later stage (in #66#)5 a plant change %as introduced %hich connects ;-#.02 %ith ;-10#" and provides deethani,er off gas as partial feed to H2U. (This ne% facility has not commissioned so far and the presence of unpredictable amounts of H 2$ %ill not permit the use of this line in future too.) The gas then flo%s to one of the 2olecular $ieve 7dsorbers ;-10#- 7/< for treatment to reduce the concentration of sulfur compounds to about #2 ppmv. This operation is cyclic and consists of adsorption5 depressuri,ation5 regeneration heating5 cooling5 and repressuri,ation. The complete cycle time is #1 hr. The adsorber effluent is filtered in $%eet 8atural 9as *ilter $-100"5 and then goes to the compression section. 8ormally5 the adsorption is one of the adsorbers cycle to had =ust ended The is in the absorption for an adsorber is cycle the to and Hot the

%hile the other is being regenerated. This description assumes that and operation has been s%itched to the other absorber. The regeneration procedure refinery P!/-65 about gas holds natural a 9as the commence. adsorber 9as the is then splits a depressured >-102drum. to heat fuel %hich via #".gas !egeneration bar(g) at 260 on / /ooler noc out used the

!egeneration 9as :noc out +rum ;-10#. through Pressure /ontroller

desulfurised regulated by

molecular sieve bed for regeneration. The temperature is manually three-%ay /ooler bed is valve5 >-102" cooled %hich and %ith flo% bypass. bet%een 7fter gas +esulfuri,ed regeneration5 hot-gas

desulfuri,ed

natural

leaving the cooler at .75 and then the adsorber is repressured. The regenerated bed is ready to s%ing into operation at the conclusion of the adsorption cycle of the other adsorber. 7utomatic valves
OM/6000 Rev.1 3/3 September 1997

provide for the s%itching of adsorbers and the proper se&uencing of the various steps during regeneration. +uring the depressuring and repressuring stages5 regeneration gas is still ta en from the outlet of +esulfuri,ation !eactor !1002< at the same rate5 to avoid disturbing the operation of the other 7s a part of the Hydrogen of the this feed 2anufacturing continuous gas Unit. flo% The of gas passes through >-102" and >-102- and discharges to conse&uence gas5 regeneration the refinery fuel gas. desulfuri,ed compression5

pretreatment5

preheating5 and final desulfuri,ation facilities have been designed for a 27? larger capacity than re&uired by the steam reformer. 3.2 FEED GAS COMPRESSION *eed gas from the molecular sieve system flo%s to 8atural 9as /ompressor $uction +rum ;-100#5 %here any li&uids are removed. 7t present 82 free gas line has been connected ;-100# %ith :-710". This booster compressor in U-7100 also provides partial feed for H2U. This facility %as successfully tested but continuous use of 8 2 free gas is said to be uneconomical %hen 82 content of 8atural 9as e@ceeds 2? vol. The gas is then compressed to about "2." bar(g). :100# is a single-stage centrifugal compressor driven by an electric motor. *rom the discharge5 a recycle line containing 8atural 9as compressor !ecycle /ooler >-100# is used for lo%-capacity operation to automatically recycle some gas to avoid compressor surge. +ischarge pressure is controlled by P!/7-#15 %hich controls the suction valve setting. startup. Bhen feed gas above "- bar(g) is available at the unit limit5 the compressor may be bypassed. The hydrodesulfurisation and the nitrogen controlled preheaters at "00 utili,e by T!/-#35 attemperated as the high-pressure medium. steam5 heat Three-vol? Aines are provided to route nitrogen through the compressor and through 8itrogen Preheater >-100" for

hydrogen5 under flo% control of *!/$7-15 is blended %ith the feed gas to promote desulfuri,ation.

OM/6000 Rev.1

3/4

September 1997

3.3

DESULFURISATION The 8atural 9as *eed and is preheated >-1002 / %ith %ith to the #-0 steam %ith in the in

Hydrodesulfurisation compressor on bypass

Preheater about #30

compressor

operation. The gas is heated further to about "70 / in /onvection /oils * and + of !eformer *-100#. The gas enters Hydrogenation !eactor !-100#. The reactor contains a catalyst bed of cobalt and molybdenum o@ide on an alumina carrier. $ulfur compounds are converted to hydrogen sulfide in the presence of this catalyst. The second stage of hydrosulfuri,ation is the absorption of the hydrogen sulfide on ,inc o@ide beds. The ,inc o@ide beds are contained in +esulfuri,ation !eactors !-1002 7/<. These reactors are manifolded so that either may be the first in series. Bhen a sulfur brea through is detected5 the flo% is s%itched to the other reactor %hile the spent ,inc o@ide in the first reactor is replaced. The reactor %ith the fresh load of ,inc o@ide is then placed onstream in the second position. This precaution is necessary to ensure complete removal of hydrogen sulfide5 because sulfur compounds are very detrimental to the catalyst in the process steps that follo%s. 7ssuming that the upstream molecular sieve adsorption system is operating properly5 the ,inc o@ide beds can operate continuously for appro@imately 2 years %hile producing specification product. 3.4 STEAM REFORMING The desulfuri,ed gas5 controlled at a rate of 736.- tpsd by *!/7-65 is mi@ed %ith superheated steam controlled at a rate of "7"3.2 tpsd by *!/-##5 and the mi@ture flo%s to the radiant section of !eformer *-100# in catalyst pac ed tubes. Heat is supplied in the reformer furnace by 270 do%nfiring burners in the roof5 %hich are designed to burn natural gas or a mi@ture of natural gas and

OM/6000 Rev.1

3/5

September 1997

hydrogen. *iring is controlled by Temperature-!ecording /ontroller T!/7-235 %hich senses effluent temperature in the radiant outlet manifold. The temperature controller there resets <urner *uel 9as Pressure /ontroller P!/7-12. The catalyst. hydrogen5 reformer The gas carbon has and 1"0 vertical react and tubes over pac ed the %ith a nic el form is

steam

catalyst This

to

mono@ide5

carbon

dio@ide.

process

called steam reforming. 7 steam-carbon ratio of ..-" to # is re&uired to limit the reformer effluent temperature and prevent the deposition of carbon the catalyst. The reformed gases from each tube5 at a design temperature of 3".5 are collected in a refractory header %ith an incoloy sleeve. *inal cooling of the effluent gas is achieved in Process 9as /ooler >-100by generating steam. The outlet temperature of >-100- is controlled at ""0-"70 by T!/7-".5 %hich

operates an internal bypass. $team is generated at a pressure of .. bar(g) by the natural circulation of boiler feed%ater from $team +rum ;-1002. Heat is recovered from the reformer flue gas by heat e@change %ith feed gas and combustion air. $team generation is also employed to recover heat. <oiler feed%ater preheating in >-1007 7/< is also used. These coils are included in the natural circulation from steam drum. 7dditional coils in the convection ban of the reformer are used to superheat the saturated steam from the steam drum. $team 7ttemperators C-100# and C-1002 are installed to maintain safe coil temperatures by using high-pressure boiler feed%ater to lo%er coil inlet temperatures5 as re&uired. $team 7ttemperator C-100" lo%ers the e@port steam temperature to -10 /5 and C-100- reduces steam superheat to the nitrogen and hydrodesulfuri,ation feed preheaters to "00 /. 3.5 CARBON MONOXIDE CONVERSION /arbon mono@ide conversion is a t%o-stage process. 4ts purpose

OM/6000 Rev.1

3/6

September 1997

is to remove carbon mono@ide to meet the final hydrogen purity specification of the product gas. $team and carbon mono@ide react over a catalyst and are converted to carbon dio@ide and hydrogen. 4n the first stage5 effluent gas from the process at about "70 / passes 100" and the bul dio@ide. through gas cooler

High-Temperature $hift /onverter !-

of the carbon mono@ide is converted to carbon

The reactor contains a bed of iron o@ide and chromium

catalyst. The reaction is e@othermic5 so there is temperature rise through the bed resulting in an outlet temperature of -#- o/. The increase in temperature can be used as an indication of the amount of conversion ta ing place. The gas is cooled to about 221 / by heat e@change %ith product hydrogen in High-Temperature $hift >ffluent/2ethanator *eed >@changer >-1001 and by preheating boiler feed%ater in >-1007 7/<. The cooled gas then passes through Ao%-Temperature $hift /onverter !-100-. catalyst This in reactor t%o beds. contains This a copper o@ide is and ,inc in o@ide lo%er catalyst active

temperaturesD ho%ever5 the %ater de%point should not be approached by less than "0 o/. The lo%er temperature favors carbon mono@ide conversion5 and a residual carbon mono@ide content of about 0." vol? in the effluent is attained. 3.6 CARBON DIOXIDE REMOVAL The process gas stream leaving the lo%-temperature shift

converter is cooled in $aturator /-100# to #30 / by direct contact %ith %ater to avoid degradation of the $ulfinol in >-10#0. Bater enters the saturator via / Process /ondensate Pump P-1002 under temperature control of the effluent gas by T!/7--#. The gas is further cooled to #"3 by serving as the heating medium for

!egenerator !eboilers >-10#0 7</+. 9as flo% through the reboilers is controlled by *!/-275 235 26 and "0 and reset by *!/-"# reflu@ flo% to the regenerator. 7 portion of the gas bypasses the reboilers through Pd4/--# and re=oins the main stream do%nstream of the reboilers. The cooled gas enters !eboiler >ffluent :noc out +rum ;-100-5
OM/6000 Rev.1 3/7 September 1997

%here the phases separate. The condensate from the bottom of the saturator also discharges to the noc out drum. The condensate is recirculated via the condensate pumps to the saturator. The ne@t condensate product is sent to /ondensate $tripper /-1001 via Aevel /ontroller A!/7-27. The operation of the /ondensate $tripper %ill be described later.

9as from the /ooler >-10## to .2 1002. The

o

noc out drum is cooled in 7bsorber *eed 9as /. 7fter condensate is removed in 7bsorber *eed condensate discharges to the condensate

9as :noc out +rum ;-100.5 the gas continues to $ulfinol 7bsorber /recovered stripper under level control of A!/7-26. 7 portion of the condensate is used as the cooling medium for !eclaimer Top /ondenser >-10#. before it goes to the condensate stripper. /ooled gas from the absorber feed gas noc out drum enters the

bottom section of $ulfinol 7bsorber /-10025 %here carbon dio@ide is removed by direct contact %ith lean $ulfinol solution. The treated gas leaves the top of the absorber and enters Treated 9as :noc out +rum ;-10075 %here entrained $ulfinol is recovered. Then the gas is %ashed in Bater Bash /olumn /-100" to remove any residual $ulfinol (vapor phase)5 so as to ma e the residual sulfinol level ($ulfolane) in the gas acceptably lo% for the methanator catalyst. The gas goes to the ne@t step in the process. Process in=ection %ater is sprayed into both the treated gas noc out drum and the %ater %ash column. The %ater is pumped from Process Bater 4n=ection Tan T-100" by Process Bater 4n=ection Pump noc out drum is returned to P-1007. The li&uid from the treated gas

the $ulfinol system via !egenerator 0verhead 7ccumulator ;-1001 and Aevel /ontroller A!/7-"-. 7ppro@imately one-third of the in=ection %ater from the %ater %ash column is also sent to ;-1001 via *!/--2 to maintain the %ater balance of the $ulfinol solution. The balance of the %ater is sent to /ondensate *lash +rum ;-1006 via Aevel

OM/6000 Rev.1

3/8

September 1997

/ontroller A!/7-"1. 0rganic vapors that drum. The %ater is sent to Unit 61.0

flash for

off in ;-1006 are via level

discharged to flare via P!/-305 %hich holds 2.. bar(g) on the flash treatment /ontroller A4/-1#. !egenerated solvent is introduced to $ulfinol 7bsorber /-1002 through *!/7-"6 at a rate of #2530- tpsd to the top tray and through *!/7--0 at a rate of #.5"1. tpsd to Tray 20. /arbon dio@ide is removed from the process gas entering the bottom of the column by direct counter-current contact %ith the solvent. The bul of the carbon dio@ide is removed in the lo%er section of the column. The upper section of the column performs a polishing action that reduces residual carbon dio@ide in the gas to the very lo% level of 0.#0 mol ?. !ich $ulfinol at 3".1 / from the bottom of the absorber e@changes heat %ith the lean $ulfinol in Aean/!ich Heat >@changers >-10#" 7/<///+/>/*. The solvent at #01 / then goes to $ulfinol !egenerator /-100-5 %here the absorbed carbon dio@ide is released by reducing the pressure and stripping %ith steam that is reboiled from the solvent. The reboilers discussed earlier furnish the necessary heat. 0verhead vapor from the regenerator is a mi@ture of carbon dio@ide and steam %ith a trace of $ulfinol vapor. The vapor is cooled from 73 / to .2o/5 and most of the steam is condensed in !egenerator 0verhead /ondenser >-10#2. The condensate drops out in !egenerator 0verhead 7ccumulator ;-10015 and the carbon dio@ide is vented unrestrictedly to the atmosphere. The condensate is returned to the top of the regenerator via !egenerator !eflu@ Pump P-100" through *!/-"# %hich is reset by 7ccumulator Aevel /ontroller A!/2". The lean solvent from the bottom of the regenerator is cooled by heat e@change %ith rich solvent and then is pumped by $olvent /irculation Pump P-100# through Aean $olvent /ooler >-10#- to return to the absorber. 7ppro@imately #0? (25700 tpsd) of the circulation pump discharge to is diverted the through $olvent of *ilter $-100# in and the returned to the pump section. This is part of a continuous cleaning operation prevent accumulation contaminants circulating solvent. 4n addition5 a small slipstream of regenerated
OM/6000 Rev.1 3/9 September 1997

solvent

at

rate

of

#-.-

tpsd

is

%ithdra%n

and

sent

to

the

reclaimer. The reclaimed solvent is returned to the system from the solvent storage and ma eup facilities5 along %ith any additional solvent re&uired to ma e up system losses. (8ote' !eclaiming operation is not continuous one5 but only5 %hen is re&uired to maintain degradation products in solvent.) The reclaiming unit removes degradation products from the

$ulfinol solvent. 7t concentrations above #0? %t5 these compounds decrease the capacity of the $ulfinol process as they only function as a physical component5 even though it is less effective than $ulfolane. transfer The and increase mass in solvent rates in viscosity an can affect %ay. heat The transfer unfavorable

degradation products are separated from the 7+4P5 $ulfolane5 and %ater by vacuum-steam distillation in a pac ed column operating at a pressure of about 0.#" bar(a) (bottom conditions). The li&uid at bottoms are continuously heated by an internal steam is medium-pressure steam coil5 a temperature controller maintaining the temperature #30-200 o/. +e-superheated lo%-pressure introduced directly into the bottom of the column as the stripping medium for t%o reasons' first5 to reduce the partial pressure of the recoverable components (7+4P and $ulfolane)5 and second5 the stripping steam carries enough o@a,olidone to deliver the re&uired heat to the $ulfinol solution for amongst other vapori,ation of 7+4P and $ulfolane by condensation of o@a,olidone in the pac ed-bed section of the reclaimer. 7 partial condenser at the top of the column condenses the 7+4P and $ulfolane vapors5 %hile the %ater vapor is condensed do%nstream in the overhead condenser. 7n e=ector set is used to provide the vacuum. 7 slipstream of hot lean $ulfinol from the bottom line of /100- enters the reclaimer column bet%een the t%o pac ed beds. The o@a,olidone li&uid in the bottom of the column is vapori,ed and rises to the top of the column5 %here the 7+4P and $ulfolane condense in the partial condenser5 some of the li&uid being returned to the column above the top-pac ed section as reflu@.

OM/6000 Rev.1

3/10

September 1997

The overhead vapor from the column5 consisting mainly of %ater and some inerts5 passes to the overhead condenser5 %here the %ater vapor is condensed. The e=ector set is located do%nstream of the overhead condenser and maintains the column operating pressure at #00 mbar vacuum. The top product of the reclaimer5 consisting of 7+4P and $ulfolane5 =oins the %ater from the overhead condenser and the combined stream flo%s by gravity to the solvent ma eup tan . The bottom product (mainly o@a,olidone) is dra%n off continuously or intermittently and is pumped to the disposal system. 7 recirculation line is provided from the discharge of the bottoms pump to the feed inlet line for circulation of the feed during startup. 7nother recirculation line enters the column above the medium-pressure steam coil and is used under normal operation to circulate the bottom product to prevent any bloc age in the system. /ontinuous operation of reclaimer could not be established from the very 3.7 beginning5 METHANATION The product hydrogen from the carbon dio@ide removal section at .2 / and #1.. bar(g) contains about 0."7 vol? carbon mono@ide and 0.# vol? carbon dio@ide on a dry basis. 2ethanation reduces carbon o@ide concentration to a very lo% level so that its effect on do%nstream processes %ill be less pronounced. 2ethanation is the reverse of reforming. /arbon o@ides react %ith part of the product hydrogen to form methane are and %ater vapor. These The are catalytic rise reactions and they highly e@othermic. temperature therefore it is operated batch-%ise %henever re&uired.

through the reactor may be used as an indication of the amount of conversion ta ing place. Hydrogen effluent hydrogen in is from the %ater %ash column in the carbon dio@ide *eed/>ffluent by heat >@changer e@change >-1003. %ith Preheated the high-

removal section is preheated by heat e@change %ith the methanator 2ethanator heated further

temperature shift converter effluent in the High-Temperature $hift >ffluent/ 2ethanator *eed >@changer >-1001. /ontrolling the gas inlet

OM/6000 Rev.1

3/11

September 1997

temperature to 2ethanator !-100. at "20 / is achieved by bypassing some of e@changers the methanator feed gas around both sets of heat through T!/--3.

The methanator contains a catalyst bed of nic el o@ide in its active form on a carrier. The temperature rises through the bed as the carbon o@ides react5 provides some of the heat re&uired to preheat the feed gas in >-1003 as the effluent is cooled. *inal cooling of the methanator effluent to .7 / is achieved in Hydrogen Product /ooler >-1006. Bater is separated in Hydrogen Product :noc out +rum ;-100". The product hydrogen5 at the design rate of 272.2 tpsd ("16.7 tpsd total gas)5 is sent to *resh 9as /ompressor :-"00# in Hydrocrac er Unit "000. The %ater is sent to the condensate stripper through A4/--05 %here dissolved hydrogen can flash off. *or product pressure control5 refer to subsection ".#".

3.8

CONDENSATE STRIPPING 4n the condensate stripper5 mainly /0 2 and some methanol are

removed from the process condensate streams in ;-100- and ;-100.. $tripping for methanol is the design determining case. Process condensate from !eformer >ffluent :noc out +rum ;-100- is fed under level control of A!/7-27 to /ondensate $tripper /-10015 above Tray 2#. Process condensate from 7bsorber *eed 9as :noc out +rum ;-100. is routed through !eclaimer 0verhead /ondenser >-10#. under temperature control. The balance5 under level control of A!/7-265 combines %ith the heated effluent from >-10#. and =oins %ith the process condensate from Hydrogen Product :noc out +rum ;-100" / in

released through A4/--0. The combined stream is heated to #02 the stripper above Tray 2..

/ondensate $tripper *eed/>ffluent >@changer >-102# before entering

OM/6000 Rev.1

3/12

September 1997

Ao%-pressure steam at a rate of "0#.# tpsd is used as the stripping medium. 0verhead steam and stripped gas at ##3 / are routed through /ondensate $tripper 0verhead /ondenser >-1022 to /ondensate $tripper 0verhead 7ccumulator ;-10#25 %here the stripped gases are vented to atmosphere under pressure control of P!/-735 %hich holds 0... bar(g) on the accumulator. Under level control of A!/-.15 condensate from ;-10#2 is

pumped as reflu@ to the condensate stripper above Tray 2.. $tripped condensate from the base of /ondensate $tripper /1001 is pumped by Pumps P-10037/< through /ondensate $tripper *eed/>ffluent >@changer >-102# and is sent to Unit 60.0 at #03 / under level control of A!/-.- at a rate of 257"0.3 tpsd. 3.9 PROCESS VARIABLES REFORMING

The various process variables affecting the hydrogen reforming operation are ' level !eforming temperature $team-to-carbon ratio *eed gas charge rate *eed gas composition Hydrogen of hydrogen in the product of shift purity carbon reactors is and additionally to the carbon affected dio@ide by the and conversion mono@ide carbon dio@ide

removal

efficiency in the $ulfinol contactor. 3.1! EFFECTS OF PROCESS VARIABLES ON REFORMER The most important variables used in maintaining the desired hydrogen purity and long catalyst life in the reforming reactor are the reforming temperature and the steam-to-carbon ratio. The charge rate of feed gas %ill not normally be ad=usted5 e@cept as necessary to meet the hydrogen re&uirements of the hydrocrac ing unit5 and therefore is not5 strictly spea ing5 a process variable5 although the effects of changes in the feed rate %ill be covered. *eed composition %ill not be directly accessible to the hydrogen plant
OM/6000 Rev.1 3/13 September 1997

operator as a process variable5 but a summary of the effects of feed gas composition changes is also presented to assist in coping %ith variations in feed gas &uality. ".#0.# !>*0!2489 T>2P>!7TU!> The primary factor affecting hydrogen purity is the methane content at the outlet of the reformer.
o

7d=usting

the

outlet

temperature5 up to the design ma@imum of 3". /5 is the main variable used to control the methane content. 4n other %ords5 raising the reformer outlet temperature %ill increase hydrogen purity (assuming that all other variables %ill are ept result constant). in an 8ote that in lo%er reformer pressures also increase hydrogen

purity (less methane)5 but pressure variations are not normally used as an operating variable. ".#0.2 $T>72-T0-/7!<08 !7T40 7n ade&uate ratio of steam to carbon in the feed gas is important in protecting the catalyst from carbon formation5 %hich can plug the catalyst pores causing catalyst deactivation5 local tube overheating5 and increased pressure drop through the reformer tubes. The design steam-to-carbon ratio on a mole basis is ..-" to #. 4n normal operation5 the %eight e&uivalent to this ratio is ept constant at a pre-selected value by automatic ad=ustment of the steam flo% by Beight !atio /ontroller HE--05 %hich receives its input from *eed 9as *lo% Transmitter *T-6 signal5 as modified by *eed 9as +ensity 7naly,er F!--5 so that $team *lo% /ontroller *!/-## is responsive to the actual %eight of feed gas. 4n other %ords5 %ith the same feed gas flo% at higher density (reflecting an increase in percentage of heavier hydrocarbons)5 the steam rate %ill automatically increase. 4ncreasing the steam-to-carbon ratio on the ratio controller %ill increase hydrogen purity (all other variables being constant)5 but the increase that is feasible may be limited5 %hen at design
OM/6000 Rev.1 3/14 September 1997

charge rate5 by pressure drop considerations and steam ma e. 8ote that e@cessively lo% operating temperature5 belo% 700 / at the outlet5 or insufficient steam5 promotes increased carbon formation on the catalyst. ".#0." *>>+ 97$ /H7!9> !7T> The feed gas rate %ill normally be ad=usted to meet the hydrogen re&uirements of the hydrocrac ing unit5 and is designed to be capable of turning do%n to -0? of design rate. Bhen changing feed rate5 "#$ %"$&' (&"$ ')%" &*+&,% -$ ./0($&%$1 -$23($ "#$ 2$$1 4&% &/1 1$0($&%$1 &2"$( "#$ 2$$1 4&% . Bith the automatic ratio control system provided5 changing the steam rate is best accomplished by ta ing $team *lo% /ontroller *!/-## off ratio control and using it as a straight flo% controller during the feed gas rate changes. 7n alternate method is to increase the steam ratio above the design rate for the duration of the rate changes. 4n either case5 the system should be returned to automatic control at the desired ratio setting after completing the rate change. The rate of change should be limited to .?/#. min.

7t lo%er than design feed rates5 the steam-to-carbon ratio should be increased to protect the catalyst against carbon formation. purity 2ethane or 4t is usually feasible to also lo%er the reforming causing increased F!-7 is carbon formation to on the catalyst. the

temperature some%hat %ith lo%er feed rates %ithout reducing hydrogen 7naly,er provided continuously monitor

methane content of the reformer effluent gas. ".#0.*>>+ 97$ /02P0$4T408 7lthough the feed gas composition is determined by operating conditions outside the unit limits of the hydrogen unit5 a no%ledge of the effects of composition changes %ill enable the operator to
OM/6000 Rev.1 3/15 September 1997

minimi,e

the

adverse

effects

%hile

the

upstreams

units

are

correcting the problem. The variation in feed &uality is anticipated to be as sho%n in $ection 25 %ith the normal feed gas having about 60? methane and .0 ppm total sulfur. +uring upsets5 the methane can drop to 70? (%ith a corresponding increase in heavier components5 primarily ethane)5 %hile total sulfur can rise to "-. ppm. The unit is designed to be able to reduce this higher total sulfur the ("-. ppm) in the feed to #2 ppm at the outlet of the molecular sieve adsorbers and to less than 0.. ppm at the outlet of desulfuri,er. 7naly,er F!7-# continuously monitors the total sulfur at inlet of ;-10#" or outlet of the molecular sieve adsorbers and sounds an alarm if the level reaches 20 ppm. ($%itch over of sample ta e-off options are there as either at ;-10#" inlet or at $100"7/< out-let). The increased percentage of heavier hydrocarbons in the feed gas during upsets %ill5 to a large e@tent5 be compensated for by +ensity density5 7naly,er !ecorded the F!--5 %hich5 to upon sensing E-#..5 the higher then increases signal 2ultiplier %hich

increases the signal to $team *lo% /ontroller *!/-## (through !atio /ontroller HE--0)5 thereby increasing the steam-to-carbon ratio. 4n the first order5 the same purity H 2 %ill be produced as a result of this. The normal steam/carbon ratio is high enough to safeguard against possible carbon deposit due to the higher amount of heavier hydrocarbons. 4t is5 therefore5 important to eep this control system on full automatic and functioning properly.

OM/6000 Rev.1

3/16

September 1997

3.11

OTHER PROCESS VARIABLES Process variables that apply to the feed gas and product

hydrogen cleanup portions of the unit are of lesser importance than those discussed aboveD in normal operation5 little variation in hydrogen purity should be caused by changes in the carbon mono@ide and carbon dio@ide content of the product gas due to changes in feed composition or minor s%ings in process operation. ".##.# *>>+ 97$ P!>P7!7T408 4n preparing the feed gas for the reforming process5 it is necessary to reduce the sulfur content to a minimum and5 %hen necessary5 compress the gas to the re&uired pressure. The first stage of sulfur removal5 in the molecular sieve adsorbers5 normally re&uires no ad=ustment of any process variable. 7s long as the adsorbers are properly regenerated5 %hich occurs automatically through a programmer that performs all the valve operations at the right time and in the proper se&uence5 the sulfur removal efficiency should remain effective indefinitely. The gas compression step5 re&uired %hen feed gas supply pressure is belo% "- bar(g)5 also has no normal operating variable once the system is set up for the proper conditions. 7n important consideration is getting the antisurge system properly ad=usted to prevent compressor surging at lo% rates %ithout %asting horsepo%er by recycling more gas than re&uired. The final sulfur removal occurs in the hydrogenation reactor and the t%o desulfuri,er reactors. 4n normal operation there are no operating variables to change as long as the inlet temperature to the hydrogenation reactor is maintained at the desired "70 / and sufficient hydrogen is being introduced5 via *!/$7-1 from Hydrocrac er Unit "0005 to react %ith the sulfur compounds in the feed gas to convert them to hydrogen sulfide (H 2$). This H2$ is then removed in the desulfuri,er reactors5 as long as the ,inc o@ide catalyst is not spent5 %ithout having to be concerned %ith any operating variables. Bhen routine testing of the first desulfuri,er

OM/6000 Rev.1

3/17

September 1997

reactor ".##.2

effluent

sho%s

brea through

of

H2$5

the

,inc

o@ide

catalyst must be replaced5 as it is not economical to regenerate it. PU!4*4/7T408 0* HG+!09>8 P!0+U/T The reformer effluent contains significant &uantities of /0 and /02 (on the order of #0 to #2? of each)5 %hich are removed to increase hydrogen purity to the desired level of about 67?. *irst5 most of the /0 is converted to /0 2 in the t%o shift converters5 and the /02 is then reduced to a lo% level by being absorbed by a lean $ulfinol solution in the $ulfinol absorber. The absorber overhead gas contains small &uantities of /0 (0."7?) and /0 2 (0.#0?)5 %hich are then reacted %ith hydrogen in the methanator and converted to methane and %ater. The only operating variables available in the operation of the t%o shift converters are Temperature /ontrollers T!/7-". on the high-temperature shift converter gas feed and T!/7-"3 on the gas feed to the lo%-temperature based shift on converter. evaluation The of optimum catalyst inlet bed temperature to each shift converter has to be determined by trialand-error ad=ustments temperatures and analysis of each effluent gas stream. $ince the activity of the shift catalyst gradually decreases during operation5 this has to be offset by increasing the inlet temperature as re&uired to maintain optimum carbon mono@ide conversion. !emoval of the /02 from the hydrogen product stream ta es place in the $ulfinol absorber. The design solvent circulation has been based on the design feed gas flo%5 composition5 and other operating conditions5 such as pressure and temperature. /onsiderable deviation from one of these criteria %ill

strongly influence the re&uired circulation rate. (#) /hanges in the of the feed gas flo% re&uire rate pro ratio

ad=ustment

solvent

circulation

(assuming

all other conditions on the design values). Ho%ever5 proper attention should be paid to the design turndo%n
OM/6000 Rev.1 3/18 September 1997

ratio of the plant (typically "'-).

(2) The hydrocarbon de%point of the feed gas determines the minimum lean solvent temperature to prevent condensation of hydrocarbons. The higher the feed gas temperature5 the higher also the temperature effect of on the the lean acid solvent5 gas %hich has a negative e&uilibriaD more

solvent circulation is re&uired for sufficient driving force for absorption in the bottom of the absorber and5 moreover5 a leaner solvent is necessary to meet the specifications in the treated gas. 0n the other hand5 a too-lo% 7 temperature minimum has a bad

influence on the viscosity of the solvent5 leading to mass-transfer constraints. lean solution temperature to be applied e&uals to 20o/. (") 7 higher acid gas content in the feed gas %ill re&uire a higher solvent circulation rate to remove all the acid gas5 although this is some%hat compensated for by the higher acid gas partial pressures in the feed gas. (-) 7 deviation from the correct solvent circulation rate at constant heat input in the reboiler %ill sho% one of the follo%ing effects' 7 decrease in the circulation rate %ill result in a gradual increase in the acid gas content of the treated gas due to insufficient driving force for absorption and occur mass once transfer the constraints. absorption *inally5 capacity a of sharp the increase in acid gas content of the treated gas %ill ma@imum $ulfinol solvent is e@ceeded. 7n increase in the solvent circulation rate (recall at

OM/6000 Rev.1

3/19

September 1997

same

heat

input

into

the

reboiler)

%ill

cause

an

increase in the acid gas content of the lean solvent as a result of less efficient strippingD conse&uently5 the acid gas content of the treated gas %ill rise. !$H and other organic sulfur compounds do not react %ith the amine5 but their removal is based upon the physical solubility in the $ulfinol solution. 7 ey parameter in this respect is the solvent-to-gas etc. to be is The used more physical %hen the solubility re&uired is also of the

ratioD the higher the ratio5 the better the removal of mercaptans5 the tools increased at lo%er absorption temperatures. These are removal %ith organic sulfur stringent compared

design basis. The final hydrogen product purification step is achieved by converting the residual /0 and /0 2 in the $ulfinol absorber effluent gas to methane in the methanator. The only operating variable is Temperature /ontroller T!/--35 %hich maintains the desired ("20 / design) inlet gas temperature. Ho%ever5 the actual inlet temperature is not nearly so critical as the amount of residual /0 and /0 2 in the inlet gas5 since the conversion reaction is highly e@othermic and a sudden increase in /0 and/or /0 2 can cause dangerously high temperatures in the methanator that cannot be ade&uately compensated for by reducing the inlet temperature on T!/--3. Therefore5 continuous monitoring of /0 7naly,er F!7-#"5 at the lo%-temperature shift converter outlet5 and /0 2 7naly,er F!-#15 on the gas outlet of the %ater %ash column5 is necessary. 7n increase on. either analy,er should be immediately investigated and corrected to prevent temperature runa%ay of !-100.. 3.12 5UALIT6 CONTROL /ontinuous stations are analy,er %here recorders regular
3/20

are

provided are

%here

a to

continuous analysis is needed for positive process control. $ampling provided analyses sufficient

OM/6000 Rev.1

September 1997

ensure ade&uate process control. plant laboratory. 7naly,ers listed in Table and a procedures conditions. are "-2. listed !efer in to

These samples are analy,ed in the

Table the the

"-#. 9eneral

$ample $afety

stations 2anual of

are for

description

of

various

types

sample

OM/6000 Rev.1

3/21

September 1997

T&-*$ 3 1 Tag 8umber 0-F!-# 10-F!-10-F!-. 10-F!-1 10-F!-7 10-F!7-6 10-F!7-#0 10-F!7-#2 10-F!7-#" 10-F!-#1 10-F!-#3 10-F!7-#6 10-F!-2# 10-F!-22 Aocation ;-10#" inlet/ $-100" 7/< outlet !-1002 < outlet !-1002 < outlet *lue 9as $tac >-100- 0utlet ;-1002 <+ ;-1002 <+

A/&*,7$(% $ervice /H"$H content 9as density 9as density

4nlet

02/flue gas /H/onductivity pH /0 content /0 content /02 $pecific 9ravity /02 content 9as density /0 content

>-1007 0utlet(process side) !-100- 0utlet /-100" 0utlet ;-100" 0utlet ;-100" 0utlet *uel gas from ;-1003 ;-100" outlet

OM/6000 Rev.1

3/22

September 1997

T&-*$ 3 2

S&'8*$ S"&".3/% *re&uency H $tartup 8orm

8umber ties 10#.7/<

Type

Aocation

7naly,ed proper

>

;-10#-7/< 4nlet 8atural 9as

$ $ $

+ + + !

/omposition /02 H2$/!$H//0$ /omposition /omposition /02

10#.27/< > 10#."7/< >

;-10#-7/< >@haust ;-10#- 0utlet 8atural 9as $ $ $

! + +

H2$/!$H//0$ 10#.+ ;-10#. 0utlet *uel 9as ! ! /omposition /02 H2$/!$H//0$ 102.# > !-100# 0utlet 8atural 9as 102." > !-10027/< 0utlet 8atural 9as 10".#/ 2/" + *-100# *lue 9as + /omposition ! $ $ /omposition H2$/!$H//0$ H 2$

H + I +aily ! I 0n re&uest $ I Per shift

OM/6000 Rev.1

3/23

September 1997

T&-*$ 3 2

903/":

8umber ties 10".-

Type

Aocation

*re&uency H $tartup 8orm 7naly,ed proper

<

;-1002 0utlet $team

$ $ $ +

pH /onductivity Hardness $i02 /omposition /0//0 2 /omposition /0//0 2 /omposition

10-.#

!-100- 4nlet Process 9as

$ $

$ $ ! !

10-.2

!-100Process 9as

10-."

!-100- 0utlet Process 9as !

/0//0 2 /omposition

10-./0//0 2 101.#

!-100. 0utlet Process 9as

/-1002 4nlet Process 9as

$ $

+ + $ $ $ $

/omposition /0//0 2 /oncentration /02 content /oncentration /02 content /omposition 2B /0//0 2

101.2

<

/-1002 4nlet Aean $ulfinol

101."

<

/-1002 0utlet !ich $ulfinol

101.-

/-1002 0utlet Hydrogen

OM/6000 Rev.1

3/24

September 1997

T&-*$ 3 2

903/":

8umber ties 101..

Type

Aocation

*re&uency H $tartup 8orm

7naly,ed proper

;-1007 0utlet Hydrogen

/omposition 2B $ $ + pH /onductivity Hardness $ulfinol content

101.1

;-1006 0utlet /ondensate

107.#

P-100- +ischarge 7+4P 0@a,ol

107.2

T-100#

! !

$ulfinol content /02 content pH /onductivity Hardness

103.#

<

>-102# 0utlet $trip. /ond.

$ $ +

OM/6000 Rev.1

3/25

September 1997

3.13 H6DROGEN DISTRIBUTION S6STEM (!efer to +ra%ing 8o. T-#.-36.-".5 4ntegration $cheme of the Hydrogen $cheme5 in $ection #"). Hydrogen is produced in Hydrogen 2anufacturing Unit 1000 and Platformer Unit 7200. The hydrogen is consumed predominantly by Hydrocrac er !eactor Unit "0005 and secondly Units by Hydrodeal ylation and Unit 7.005 Hydrodesulfuri,ation #200/#"00/#-005 Platformer

Hydrotreater Unit 7#00. !eference should be made to the manuals for the individual units for further details. The hydrogen from Hydrogen 2anufacturing Unit 1000 is sent to *resh 9as /ompressors :-"00#7/<// of Hydrocrac er !eactor Unit "000. T%o of these compressors are normally in operation. The gas is compressed to #-6.2 bar(g) and fed into the discharge of !ecycle 9as /ompressor :-"002. 7 side dra%-off is ta en from third-stage $uction ;essel ;"0## at about 12.. bar(g)5 of %hich a part is recycled to Hydrogen 2anufacturing Unit 1000 under flo% control. The remainder is fed to the refinery hydrogen header under pressure control. The tie-in to the refinery hydrogen header is located at the unit limit offta e from the refinery header of 9as 0il Hydrodesulfuri,er Unit #-005 as the latterJs operation is enhanced by feed hydrogen of higher purity. The header pressure is set at "3 bar(g) and controlled by a pressure controller in the main header. The <ooster hydrogen /ompressor ma eup from Platformer and Unit 7200 is fed to

:-72027/<

compressed

into

the

refinery

hydrogen header. The remaining consumers are supplied %ith hydrogen from that

OM/6000 Rev.1

3/26

September 1997

header. ".#".# /08T!0A 0* TH> HG+!09>8 $G$T>2 >ach of the fresh gas compressors (:-"00#7/<//) is designed for .0? production of Hydrogen 2anufacturing Unit 1000. The normal hydrogen consumption of Hydrocrac er !eactor Unit "0005 Hydrogen 2anufacturing Unit 10005 Hydrodesulfuri,er Units #200/#"00/#-00/7#005 and Hydrodeal ylation Unit 7.00 is lo%er than the production of Hydrogen 2anufacturing Unit 1000 and Platformer Unit 7200. >@cess control. product hydrogen from Hydrogen 2anufacturing Unit

1000 is discharged to the refinery fuel gas system under pressure The letdo%n control valve allo%s a ma@imum flo% of -- tpsd of contained hydrogen. This is the &uantity of e@cess hydrogen %hen Hydrocrac er !eactor Unit "000 is do%n and Unit 1000 is operating at about .0? capacity heat load of radiant cell %ith a ma@imum recycle of hydrogen to reformer fuel. This -- tpsd can be handled in the refinery fuel gas system %ithout disturbing burner operation. *urther e@cess is sent to flare. +uring The resulting normal operation5 bet%een fresh design hydrogen gas inta e to and

:-"00#7/<// is e&uivalent to the total normal hydrogen consumption. difference compressor capacity actual consumption is recirculated through the first t%o stages of *resh 9as /ompressors :-"00#7/<//. The hydrogen recycle from the suction of the third stage of /ompressors :-"00#7/<// to Hydrogen 2anufacturing Unit 1000 is under flo% control located at Unit 1000. The supply of hydrogen from the suction of the third stage to the refinery hydrogen header is under pressure protection flare. The main hydrogen flo% to Hydrocrac er !eactor Unit "000 is control to the located refinery at the header %ith and an overpressure to fuel gas system subse&uently

OM/6000 Rev.1

3/27

September 1997

controlled

by

pressure

controller

in

the

suction

of

!ecycle

/ompressor :-"0025 %hich regulates the recycle flo% from the thirdstage suction to the first-stage suction. This control %or s along %ith a hand-operated valve unloading system on /ompressor :-"00#7/<//. Bhen the pressure in the suction of !ecycle 9as /ompressor :-"002 decreases5 it closes the control valve in the recycle line from third-stage suction to first-stage pressure suction. drops and 7s the a result5 pressure /ompressor :-"00#7/<// suction

controller in Hydrogen 2anufacturing Unit 1000 closes the control valve(s) to the refinery fuel gas system (or flare). 4f the control valve in the third- to first-stage suction recycle is fully closed and the suction pressure of !ecycle /ompressor :-"002 is still too lo%5 the pressure controller in this suction line closes the control valve in the hydrogen supply to the hydrogen header by means of a lo%-signal selector. This feature ensures the priority of the hydrogen supply to Hydrocrac er !eactor Unit "000 over the consumers fed by the hydrogen header. 7 third signal to the control valve is available from a flo% controller in the hydrogen supply line to the hydrogen header5 %hich enables the operator to restrict the amount of hydrogen going to the hydrogen header. The hydrogen to the various consumers from the hydrogen header is either under flo% or pressure control %ithin the respective unit limits. +uring Hydrocrac er !eactor Unit "000 catalyst regeneration5 /ompressor :-"00#7/<// discharge pressure is controlled by s%itching over to /ontroller "0-P!/-"0 via $elector $%itch "0-H-"3. ".#".2 0P>!7T489 <7A78/>$ T%o limiting cases are sho%n in the material balance on +ra%ing 8o. T-#.-63.-".'

OM/6000 Rev.1

3/28

September 1997

/7$> 7

7ll units operating at their design capacity %ith their respective hydrogen productions and consumption.

/7$> <

Platformer

Unit

7200

is

do%n

and

Hydrodeal ylation Unit 7.00 is in operation on feed from tan age.

".#"."

$G$T>2 /08+4T408$ Parameters for system conditions are sho%n in Table "-"' T&-*$ 3 3 *lo% in tpsd of pure hydrogen H S,%"$' C3/1.".3/% Pressure bar (g) Temperature

Unit (o/) <loc 4

Unit #200 Unit #"00 Unit #-00 <loc 44

3.00 ..#"

"3 "3 "3

10 10 10

- 21.30

Unit 1000 Unit "000 Unit 1000 (recycle to) <loc 444

K272.20 -2-0.00 2..0

#. #-6.2 10 ("3)

.7 66 .7

Unit 7000 Unit 7200 Unit 7100 >@cess to fuel LLLLLLLLLLLLLLLLL

#.-#

"3 "3 "3 #.

10 10 10 .7

K .-.30 - 27.#0 - #1.#0

OM/6000 Rev.1

3/29

September 1997

HK I production - I consumption

OM/6000 Rev.1

3/30

September 1997