ULSD 101100 Hp New Analysis for Flares

7/25/2019 ULSD 101100 Hp New Analysis for Flares

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ULSD PRODUCTION

Fayruzov D. Kh., Fayruzov R. Kh., Sitdikova A.V., Baulin O.A., Rahimov M.N.

Ufa State Petroleum Technological University

JSC Salavatnefteorgsintez

It is spoken about features US! pro"uction# $lso in article sho%n technicals an"

economics point some of main hy"rofining process "iesel fuel#

Keyword!"iesel fuel hy"rofining process& ultra'lo% sulfur "iesel& catalyst of hy"ro'fining& loa"ing metho" of hy"rofining catalyst& partial pressure& (&)'"imetyl"ibenzotiophen#

At lat time "uetion a#out develo$ment and a$$li%ation &%lean 'uel( i

worldwide $ro#lem. Sin%e )**+ -SD with ul'ur %ontent +* $$m i mandatory

$e%i'i%ation, net te$ to /* $$m will #e o%%ur at )**0 1+2.

Sin%e )*** mot o' re'inerie u%%e'ully %om$lete u$3radin3 $ro3ram 'or

$rodu%e new $e%i'i%ation -SD with +* $$m ul'ur %ontent. Fa%tor determine im$le4

mentation thi $ro3ram i uin3 new %atalyt, uin3 additional %atalyt volume, o$timi4

zation "uality o' 'eed, e$e%ially when 'eed i mi o' %ra%kin3 %om$onent.

5n Ruia and 65S $e%i'i%ation 'or ul'ur %ontent in dieel 'uel i +** $$m. 6on4

verion to ul'ur %ontent 7+* $$m $ro$oed in )**0, net redu%tion to +* $$m in )*/*.

Re'inerie in Ruia and 65S are threhold o' -SD era, and mot o' re'inerie

mut ada$t it hydro'inin3 unit to new %ondition.

-SD $rodu%tion determine a ul'ur %ontent with %y%li% tru%ture a aromati% 1+2.

5' $rodu%tion dieel 'uel with ul'ur %ontent *,/4*,) 8 wt. #ehavior hydro4

3enolii rea%tion o' mer%a$tan and ul'ide with ul'ur in alkyl #ran%h, $rodu%tion

dieel 'uel with 7+*4+** $$m ul'ur %ontent #y %onverion %y%li% %om$ound o' ul'ur

with rea%tion a#ility %han3e in line tia%y%lan 9 na'tenotio'en 9 alkyltio'en 9 na'teno4#enzin4tio'en 9 #enzenetio'en 9 di#enzentio'en.

-SD $rodu%tion with ul'ur $e%i'i%ation +* and /* $$m mandatory %ondition

i eliminated heteroatom ul'ur %om$ound like :,;4dimetyldi#enzenetio$hen. Rea%tion

a%tivity thi mole%ule )* time le %om$ared with mole%ule o' di#enzenetio$hen. A

o$$oed normal rea%tion deul$hurization, more $re'era#le i hydro3enation :,;4

dimetyldi#enzenetio$hen.


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Nitro3en removal 'ollow a very imilar rea%tion $athway, re"uirin3 a $re4

hydro3enation te$ #e'ore heteroatom removal. 5t there'ore %om$ete with the hindered

D@DB 'or a%tive ite on the %atalyt ur'a%e. Sin%e nitro3en $e%ie, $arti%ularly

#ai% nitro3en %om$ound, ador# more tron3ly to that %atalyt ur'a%e than ul'ur

$e%ie, near4%om$lete removal o' nitro3en i re"uired when tar3etin3 ul'ur level

/* $$m. Ce di%u the im$ortan%e o' %hooin3 a %atalyt havin3 thi dual DS?EDN

'un%tionality in u#e"uent e%tion 1+2.

Sul'ur %ontent de$end on the %rude nature and method o' re'inin3 and ha

"uite di''erent "uantity.

-6O o'ten add in dieel 'uel like %om$onent o' market 'uel. Be%aue -6O have

a low e''i%ien%y in tartin3 $eriod and %ontent a lot o' ul'ur, it i make im$oi#le to

ue -6O a %om$onent 'or -SD. $3radin3 the $e%i'i%ation o' %om$ound with

-6O i very di''i%ult, e$e%ially hi3h level %ontent o' aromati% and nature o' ul'ur

%om$ound. A lot o' mole%ule o' ul'ur i teri% hinder, and there'ore i eliminated

di''i%ult. hou3h re'inerie add -6O to 3aoil G/*47* 8 vol.H and hydrotreated mi 'or

o#tain -SD. Very im$ortant 'a%tor 'or -6O hydrotreated i end #oilin3 $oint. 5' end

#oilin3 $oint o' -6O in%reae at + I6 it i in%reae tem$erature o' rea%tion. A reult

%y%le run o' %atalyt de%reae and it i 'ater dea%tivation.

-SD hydro$ro%ein3 unit dei3n and o$timization mut take in to %onide4

ration the 'ollowin3 'a%tor!

J $rovide ade"uate %ontrol ytem and tanka3e to enure the %orre%t 'eed

"uality to the unit

J maimize rea%tor E)$artial $reure

J maimize rea%tor hydro3en4to4oil ratio

J $rovide a relia#le, ade"uate u$$ly o' hi3h4$urity make4u$ E)J $rovide ade"uate re%y%le 3a $urity and unit $reure %ontrol ytem

J minimize )S and NE7in the re%y%le 3a. e only the #et rea%tor internal

and %atalyt loadin3 method to enure 3ood %atalyt?oil %onta%tin3

J ele%t the ty$e o' %atalyt and $rovide u''i%ient %atalyt volume to meet all

$rodu%t "uality re"uirement and deired run len3th

J dei3n 'eed?e''luent and 'eed?$rodu%t e%han3er and unit tart4u$?hutdown

line to minimize the $otential 'or rea%tor #y$ain3

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Oil and >a Buine, )**0 htt$!??www.o3#u.ru?en3?

)


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J $rovide relia#le o$eration o' the $rodu%t 'ra%tion ator?)S tri$$er

J minimize $rodu%t %ontamination in o''4ite 'a%ilitie! rundown line, tanka3e et%.

More im$ortant $oint in -SD $rodu%tion i!

J %atalyti% ytem

J $artial $reure o' hydro3en

J modern internal devi%e in rea%tor

J dene loadin3 ytem.

Catalytic system#in3 a new hi3h4a%tivity Ni4Mo %atalyt havin3 very hi3h

hydro3enation a%tivity and i o$timal way 'or elimination ul'ur %om$ound. -eader in

hydro'inin3 %atalyt $rodu%tion i $reent in ta#le /.

a#le /

6atalyt 'or Dee$ Deul$hurization and Aromati% ydro3enation

6om$any 6o4Mo y$e Ni4Mo y$eLre%iou Metal

y$e

Akzo KF4+ KF4: KF4)**

6riterionD64/;*, D64/+,

D64)***DN4)**

o$oe K4+:K4+7, K4+)+,

K4+++K40*, K40*

OL N4:*, N4/*, N4)**

64, 64K, 64L, 64R, 64

AS4)+*

5FL R4:/; R4:: Llatinum ty$e

6656 6DS4-;

O66 OL4:; OL4:/:

Increasing the *y"rogen Partial Pressure# he hydro3en $artial $reure i

in%reaed #y in%reain3 the rea%tion $reure, the hydro3en?oil ratio, and the $urity o'the hydro3en. 5n the nited State the NL6 ha $u#li%ly releaed the re$one o' 'ive

%om$anie 4 OL, 5FL, Akzo, 6riterion, and o$oe 4 to "uetion re3ardin3 the

modi'i%ation o' eitin3 deul$hurization unit, $rodu%in3 dieel 'uel with a ul'ur

%ontent o' +** $$m, 'or redu%in3 the $rodu%t ul'ur %ontent. he modi'i%ation wa

etimated #aed on the ue o' 'eedto%k with a ul'ur %ontent o' *.0 wt. 8, a $e%i'i%

3ravity o' *.;/, and a 0*value o' 7)/ IP. he modi'i%ation re"uired to redu%e the

ul'ur %ontent to 7* $$m are ummarized in ta#le ) 1/2. A55 o' them re3ard an amine

=============================================================================


7


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%ru##er a indi$ena#le 'a%ility. OL and 5FL $ro$oe to minimize the %ut down o'

-SV #y in%reain3 the $urity o' %ir%ulatin3 hydro3en. On the other hand, the other

%om$anie $ro$oe to de%reae -SV to the 3reater etent without in%reain3 the

hydro3en $urity.

a#le )

Modi'i%ation 'or redu%in3 the ul'ur %ontent to 7* $$m 'rom +** $$m

6urrent OL 5FL Akzo 6riterion o$oe

-SV ) /.+ /.:+ /.* *.+ /

Amine %ru##erintalled

no ye ye ye ye ye

Lurity o'%ir%ulatin3hydro3enGmol 8H

+ 0* 0/.7 + + +

Ratio o'%ir%ulatin3hydro3en

/ /.0 7.;:0 / /.; /./;

6atalyt $a%kin3method

So%k Dene So%k So%k So%k So%k

hey re"uire the i3ni'i%ant a%ri'i%e o' -SV. 5n addition, 5FL ay that a ul'ur

%ontent level o' /* $$m %an not #e a%hieved at eitin3 unit $reure and that new unit

mut #e %ontru%ted. 6riterion alo ay that althou3h the data i tentatively hown, new

unit i tron3ly re%ommended.

a#le 7

Modi'i%ation 'or redu%in3 the ul'ur %ontent to /* $$m 'rom 7* $$m

OL 5FL Akzo 6riterion o$oe

-SV/.+Q

*.0

/.:+Q/

/.*Q

*.:+

*.+Q

*.:

/Q

*.

Ratio o'%ir%ulatin3hydro3en

/.0Q)

7.;0:Q

//.;Q

/.+/./;

Lartial $reure,k3?%m)

:; + :; :; :;

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:


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!istribution tray#o enure e''i%ient utilization o' all the %atalyt $a%ked into

the rea%tor it i eential to attain a uni'orm ditri#ution o' the 'eedto%k and hydro3en

throu3hout the entire %atalyt layer. he miditri#ution may alo %aue $ro#lem, u%h

a o%%urren%e o' a#normally hi3h tem$erature area Ghot $otH due to uneven rea%tion

tem$erature ditri#ution or a rie in $reure di''erential a%ro the rea%tor, that 'or%e

ometime di%ontinuan%e o' o$eration. 5' the rea%tion 'luid on%e #e3in to #e%ome

de'le%ted within the %atalyt layer the normal tate i hardly retored.


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Catalyst oa"ing Systems#5' the %atalyt i loaded in u%h a way that the to$

ur'a%e o' layer i at an in%line on the way o' the loadin3, the %atalyt $arti%le #e%ome

lanted alon3 the in%lination. 5t i known that the oil tend to 'low alon3 the in%lination

and may #e de'le%ted #y the lanted $ortion, even i' the to$ ur'a%e o' the %atalyt i

$a%ked 'lat.

5n the $at, to kee$ the ur'a%e 'lat durin3 the %atalyt loadin3, the work wa

halted $eriodi%ally and the ur'a%e wa leveled #y man$ower. owever, there were

limit to the e''e%tivene o' u%h te%hni"ue, and the 're"uent interru$tion o' the

loadin3 work lowered the e''i%ien%y. 5n order to 3et around thee $ro#lem a %atalyt

loadin3 ytem ha re%ently #een develo$ed that in%or$orated monitor whi%h allow

real4time meaurement o' the 'latne o' the %atalyt ur'a%e without interru$tin3 the

work and a %atalyt loadin3 ma%hine whi%h i a#le to %ontantly %ontrol the in%line o'

the ur'a%e.

5n%reain3 re"uirement to "uality 'or dieel 'uel #e%ome develo$ment

hydro'inin3 te%hnolo3y -SD $rodu%tion Gta#le +H.

a#le +

i3h4"uality dieel 'uel $rodu%tion te%hnolo3y

Process Licensers

SynSat 6riterion, ABB -ummu, Shell

ltra Dee$ DS o$oe

MAK Finin3 Mo#il, Akzo, Kello33, Fina

MUD nion'inin3 OL

Dee$ DS, DAr 5FL

SynSat Process#he SynSat $ro%e ue either one rea%tor or two rea%tor in

erie and divide the rea%tion zone into two ta3e. 5n the 'irt ta3e #oth 'eed oil and

hydro3en 'low downward, while in the e%ond ta3e dire%tion o' hydro3en 'low %an #e

et u$wardly or downwardly de$endin3 on %ondition. he SynSat $ro%e i #ein3 ued

%ommer%ially in Sweden, >ermany, and the nited State Gta#le ;H.

=============================================================================


;


7/12

a#le ;

6ommer%ial a$$li%ation o' SynSat Lro%e

6om$any

Lro4

%ein3volume

Feedto%k %hara%teriti% Lrodu%t %hara%teriti%

Rea%tionty$e

Sul'ur%ontent

0+ Den4ityAroma%ontent

Sul'ur%ontent

Den4ity

Aroma%ontent

BLSD 8 wt. IP 3?%m7 8 vol. $$m 3?%m7 8 vol.

S%anra'' :***

*,+:7)7

*,:/ )),/ /** *,7+ //,7

6o?6nt

*,7:);

*,) )/,+ / *,/) :,:

Lreem 7***

*,/:77

*,;; 4 /** *,+ 4

6o?6nt

*,/)

*,) )/, ) *,/+ 7

-yondell46it3o +**** /,7 7; *,0*) +,) + *,;/ 7:, 6o?6o

Topsoe Ultra !eep *!S process# o$oe ltra Dee$ DS GDDSH $ro%e

i a two4ta3e $ro%e 'or $rodu%in3 low4ul'ur and low4aromati% dieel 'uel. 5n the 'irt

ta3e rea%tor Ni4Mo %atalyt are ued. he e%ond ta3e rea%tor em$loy a $re%iou

metal %atalyt, T40*. he San oa"uin re'inery in the nited State $rovide an

eam$le o' the %ommer%ial a$$li%ation o' thi $ro%e Gta#le H.

a#le

6ommer%ial a$$li%ation o' o$oe ltra Dee$ DS

Denity,3?ml

Sul'ur,$$m

Nitro3en,$$m

Aromati%,8 vol.

Rea%tiontem$erature,

IP

Feedto%k *,0/ ;,+/+ + 77 4

Firt ta3e

out$ut*, 0 7 ): 7;

Se%ondta3e out$ut

*, / * 7,+ )

+$, -ining process# @AT Finin3 i a hydrore'inin3 $ro%e li%ened #y

a Buine, )**0 htt$!??www.o3#u.ru?en3?


8/12

)H EDEDP! Mild hydro%ra%kin3 o' heavy ditillate GNi4Mo %atalytH

7H DAr! ydro3enation o' $oly%y%li% aromati% %om$ound G$re%iou metal

%atalytH

:H M5DC! Dewain3 #y hydroiomerization o' Lara''in

+H 6F5! 6old4'low im$rovement #y ele%tive hydro%ra%kin3 o' n4$ara''in.

OMV >ermany GBur3hauen re'ineryH ue a ytem %om#inin3 DDS and

M5DC. Althou3h the detail o' the 'eedto%k $ro$ertie are not %lear, dieel 'uel with a

ul'ur %ontent o' /* $$m or le and a %loud $oint o' 4// IP or le Gim$rovement o'

/ IPH wa re$ortedly #ein3 $rodu%ed.

Lro$ertie o' 'eedto%k and $rodu%t $ro%eed at a $ilot $lant o' the %om#i4

nation o' DS and EDEDP uin3 a zeolite %ontainin3 %atalyt are hown in ta#le .

a#le

@AT Finin3 $ro%e

0+,IP

Sul'ur,$$m

otalaromati%,

8 wt.

Loly%y%li%aromati%,

8 wt.

6etanenum#er

Feedto%k 7+; /;,; 70 /+ +/

6ae / 7+7 )+ )) /,) +

6ae ) 7:0 7 /0 *, +

./! Unionfining Process# OL MUD nion'inin3 em$loy either in3le4

ta3e or two4ta3e rea%tor ytem. 5t $rodu%e hi3h4"uality, low4ul'ur dieel 'uel #y

%om#inin3 hydro3enation $ro%e with other $ro%ee u%h a hydro%ra%kin3, %atalyti%

dewain3, aromati% hydro3enation and hydroiomerization.

I-P 0rime'!12 Process#5FL WXime4D7* i a $ro%e 'or $rodu%in3 dieel 'uel

with ultra4low ul'ur %ontent, redu%ed $oly%y%li% aromati% %om$ound, and a #ooted

%etane ratin3. wo4ta3e hydro3enation i re"uired to a%%om$lih aromati%

hydro3enation aimed at in%reain3 the %etane inde. 5n the 'irt ta3e an Ni4Mo %atalyt

and %om$aratively hi3h $reure G; to MLaH i ued to redu%e the ul'ur %ontent o'

%ra%ked dieel 'uel to +* $$m wt. or le. A'ter 'ra%tional ditillation o' the rea%tion

$rodu%t, the dieel 'uel 'ra%tion %ontainin3 virtually no ul'ur and hydro3en ul'ide i

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9/12

ent to the e%ond ta3e, where aromati% hydro3enation take $la%e. he $re%iou metal

%atalyt ued in the e%ond ta3e i a hi3hly a%tive hydro3enation %atalyt. 5t i %a$a#le

o' $ro%ein3 even 'eedto%k %ontainin3 i3ni'i%ant amount o' ul'ur. Chen -6O with

a ul'ur %ontent o' /.+ wt. 8 i u#Ye%ted to the two4ta3e $ro%e, the ul'ur %ontent i

lowered to 7 $$m in the 'irt ta3e, and then the aromati% %ontent i redu%ed to /.: 8 in

the e%ond ta3e, a%%ordin3 to re$ort Gta#le 0H.

a#le 0

5FL WXime4D7* Lro%e rea%tion

0+,

IP

Sul'ur,

$$m

Nitro3en,

$$m

Aromati%,

8 wt.

6etane

num#erFeedto%k 7/0 /+, /,/ ;;,: ),+

Firt ta3eout$ut

) 7 / 7:,) :+

Se%ond ta3eout$ut

)7 *,+ *,+ /,: +7,:

-SD $rodu%tion need a lot o' invetment 'or re%ontru%t eitin3 unit

Gta#le /*H. 5t i reaon why $e%ial te%hni%al re3ulation atta%hment at 7/./).)**0 in

Ruia.

a#le /*

6ot o' u$3radin3 %onventional e"ui$ment 'or ltra4Dee$ Deul$hurization

Upgrade ItemSulfur,

ppm

Amount of Investment,

million

Standard +** 4

6atalyt %han3e

G+*8 in%reae in a%tivityH )+ 4

>a re%y%le?%ru##er /* /,

5n%reain3 $urity o' makeu$hydro3en

/:* ),:

5n%reaed a Buine, )**0 htt$!??www.o3#u.ru?en3?

0


10/12

he %ot o' #uildin3 a new ultra4dee$ deul$hurization unit, $reented #y the

li%ener, are hown in ta#le //. hey vary widely, runnin3 anywhere #etween [/,/**

and [7,*** $er BLSD, de$endin3 on the 'eedto%k $ro$ertie and the re'inery

environment. hi invetment i e"uivalent to #etween [;* and [/+* million 'or a $lant

with a %a$a%ity o' 7*,*** to :*,*** BLSD.

a#le //

6ot o' intallin3 Dieel 'uel ultra4dee$ deul$hurization e"ui$ment

ProcessProcessing

volume !"PSD#$ualit% target

&'uipment cost

!("PSD#

SynSatGtwo4ta3eH

7****S! /* $$m,Ar! + 8 vol

777*

5FLGtwo4ta3eH

7****S! + $$m,

6etane ratin3)**

MAK Finin3 7+*** S /* $$m //**4)***

MUD nion'inin3 :+***S! /* $$m,Ar! ) 8 vol.

77/*

5FL \6 :****S! /* $$m,Ar! 8 vol.

)+**47***

-SD $rodu%tion have 'eature. hi 'eature a%tivate #y hi3h "ualityre"uirement and $ro#lem in re%ontru%t eitin3 ytem.

he re'iner 3oal i to $rodu%e -SD that not only meet the re3ulatory

re"uirement o' /* w$$m ul$hur, #ut alo the additional %ommer%ial re"uirement o' a

hi3h "uality $rodu%t.

i3h everity hydrotreatin3 i known to $rodu%e %olor4unta#le $rodu%t. A

variety o' reaon are 3iven 'or the o%%urren%e o' $oor $rodu%t %olor ta#ility, #ut one

%ommon 'a%tor i the rea%tor outlet tem$erature! at rea%tor outlet tem$erature a low a

7;* I6, dieel #e3in to #e%ome %olor enitive. Althou3h %olor i not a re3ulatory

$e%i'i%ation, it i a ]workmanhi$] iue and $oor %olor ta#ility will adverely a''e%t

%utomer ati'a%tion.

Very im$ortant $oint in -SD $rodu%tion i lu#ri%ity. -u#ri%ity ha #een

de'ined a ]a li"uid intrini% a#ility to $revent wear on %onta%tin3 olid ur'a%e in the

a#en%e o' any hydrodynami% lu#ri%atin3 'ilm]. hi $ro$erty ha #een a %on%ern due

to $ro#lem e$erien%ed with a%%elerated Yet en3ine 'ailure 'or low ul$hur Yet 'uel.

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/*


11/12

he $ro#lem wa linked to everely hydrotreated Yet 'uel havin3 #oth low ul$hur and

low aromati% %ontent.


12/12

Documents

ULSD 101100 Hp New Analysis for Flares