Project Report of Production of Butadiene from Butane part 1.docx

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    2.3 Market :

    According to CMAI (2007), global butadiene demand is expected to grow at just under

    3 !"#$ear t%roug% 20&2, slig%tl$ abo'e t%e a'erage o 3 2"#$ear growt% o t%e past i'e

    $ears emand in India will be t%e largest, growing nearl$ &!"#$ear or t%e next i'e$ears emand in Asia is expected to exceed !"#$ear, alt%oug% demand in some

    countries, primaril$ C%ina, will be at more t%an &0", anal$sts sa$ emand in *ort%

    America and +estern urope is expected to rise at less t%an &"

    Most o t%e capacit$ will be added in Asia, particularl$ C%ina, w%ic% will account or

    nearl$ 7!" o new capacit$, added be ore 20&2 -perating rates in Asia are expected to

    be strong at .!"/ 0", w%ile operating rates in urope will be %ig%est, at about 0",

    anal$sts sa$ -perating rates in *ort% America are expected to %o'er in t%e 70" range,

    t%e$ sa$ 1able 2 3 s%ows t%e butadiene producer and production rate in Asia *otice

    t%at in Mala$sia, t%ere is onl$ &00,000 mt #$ear production totall$

    Country ProducersProduction Rate

    (in thousands of MT./year)

    C%ina

    ang i 4etroc%emical &.!C*--C 5%ell 4etroc%emicals6 &!!Maoming 4etroc%emical &!0

    ilin C%emical &608ilu 4etroc%emical &309an %ou 4etroc%emical &205%ang%ai 4etroc%emical &20

    ans%an 4etroc%emical &&3-t%ers 3 !1otal &!0.

    India:eliance Industries &!0-t%ers &721otal 322

    apan

    apan 5$nt%etic :ubber 2;.C%iba a$ama

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    9? C%emical &6!9otte aesan 4etroc%emical &05amsung 4etroc%emicals9? aesan 4etroc%emical .5@ Corp 725@ nerg$ 721otal &0&.

    Mala$sia 1itan 4etc%em &001otal &00

    5ingapore ;01otal ;0

    1aiwanormosa 4etroc%emical 373

    C%inese 4etroleum &731otal !6;

    1%ailand

    o> 5$nt%etics &60

    I:4C! ;!1otal 20!Average: !"."#$%&

    2.! 'utadiene Manufacturing Process nfor ation :

    ing o 4ara inic $drocarbonsB In t%is process, butadiene is a co/ product

    in t%e manu acture o et%$lene (t%e et%$lene co/product process)

    2) Catal$tic e%$drogenation o n/ing process is reported to be t%e predominant met%od o t%e t%ree

    processes o production, accounting or greater t%an &" o t%e worldEs butadiene

    suppl$ igure depicts a low c%art or a t$pical ole ins plant +%ile t%is does not

    represent an$ particular plant, and t%ere are certainl$ man$ 'ariations among ole ins

    plants, t%is representation will pro'ide t%e reader wit% a general understanding o t%e

    process

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    1%e indicated eedstoc>s (et%ane, propane, butane, nap%t%a and gas oil) are ed to a

    p$rol$sis (steam crac>ing) urnace w%ere t%e$ are combined wit% steam and %eated to

    temperatures between approximatel$ &6!0/&!2! F (7 0/.30 FC) +it%in t%is

    temperature range, t%e eedstoc> molecules Gcrac>G to produce %$drogen, et%$lene,

    prop$lene, butadiene, ben ene, toluene and ot%er important ole ins plant co/products

    A ter t%e p$rol$sis reaction is Huenc%ed, t%e rest o t%e plant separates t%e desired

    products into streams t%at meet t%e 'arious product speci ications 4rocess steps include

    distillation, compression, process gas dr$ing, %$drogenation (o acet$lenes), and %eat

    trans er 1%e ocus o t%is re'iew is &,3/butadiene %owe'er, since butadiene is created in

    t%e ole ins plant p$rol$sis urnace, and is present in t%e crude butadiene product stream

    at concentrations up to approximatel$ 7! wt", t%e ole ins plant process and t%e crude

    butadiene stream are addressed in t%is publication to a limited degree

    1%e low pat% o t%e C6 components (including butadiene) are indicated b$ bold JredK

    lines

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    +%ile some ole ins plant designs will accommodate an$ o t%e listed eedstoc>s, man$

    ole ins plants process onl$ *atural ?as 9iHuids (*?9s) suc% as et%ane, propane and

    sometimes butane 1%e mix o eedstoc>s, t%e conditions at w%ic% t%e eedstoc>s are

    crac>ed, and t%e p%$sical plant design, ultimatel$ determine t%e amount o eac% product

    produced, and or some o t%e streams, t%e c%emical composition o t%e stream

    2.!.2 'utadiene Production via Cata ytic ehydrogenationof n0'utane and n0

    'utene (the ,oudry 1rocess)

    1%e catal$tic de%$drogenation o n/butane is a two/step process initiall$ going rom n/

    butane to n/butenes and t%en to butadiene

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    in t%e reactor is approximatel$ !/&! minutes As t%e endot%ermic reaction proceeds, t%e

    temperature o t%e catal$st bed decreases and a small amount o co>e is deposited In

    t%e regeneration c$cle, t%is co>e is burned wit% pre%eated air, w%ic% can suppl$

    essentiall$ all o t%e %eat reHuired to bring t%e reactor up to t%e desired reaction

    temperature

    1%e reactor e luent goes directl$ to a Huenc% tower, w%ere it is cooled 1%is stream is

    compressed be ore eeding an absorber#stripper s$stem, w%ere a C6 concentrate is

    produced to be ed to a butadiene extraction s$stem or t%e reco'er$ o %ig% purit$

    butadiene

    2.!.3 'utadiene Production via idative ehydrogenation

    of n0'utenes (the o0 or 040 1rocess)

    -xidati'e de%$drogenation o n/butenes %as replaced man$ older processes or

    commercial (on/purpose) production o butadiene 5e'eral processes and man$ catal$st

    s$stems %a'e been de'eloped or t%e ox$de%$drogenation o eit%er n/butane or o n/

    butene eedstoc>s in t%is process ma$ not be

    practical

    In general, in an ox$de%$drogenation process, a mixture o n/butenes, air and steam is

    passed o'er a catal$st bed generall$ at low pressure and approximatel$ 30/&&&0 F

    (!00/;00 FC) 1%e %eat rom t%e exot%ermic reaction can be remo'ed b$ circulatingmolten %eat trans er salt, or b$ using t%e stream externall$ or steam generation An

    alternate met%od is to add steam to t%e eed to act as a %eat sin> 1%e %eat can t%en be

    reco'ered rom t%e reactor e luent :eaction $ields and selecti'es can range rom 70/

    0", ma>ing it unnecessar$ to reco'er and rec$cle eedstoc>

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    'utadiene Production via idative ehydrogenation

    In t%e -xo/ process s%own in igure, a mixture o air, steam, and n/butenes is passed

    o'er t%e de%$drogenation catal$st in a continuous process 1%e air eed rate is suc% t%at

    an ox$gen#butene molar ratio o approximatel$ 0 !! is maintained, and t%e ox$gen is

    totall$ consumed A steam to butene ratio o &0B& %as been reported as necessar$ to

    absorb t%e %eat o reaction and to limit t%e temperature rise

    1%e reactor e luent is cooled and t%e C6 components are reco'ered in an

    absorber#degasser# stripper column combination 1%e lean oil lows rom t%e bottom o

    t%e stripper bac> to t%e absorber, wit% a small amount passing t%roug% a sol'ent

    puri ication area Crude butadiene is stripped rom t%e oil, reco'ered in t%e o'er%ead o

    t%e stripper, t%en it is sent to a puri ication s$stem to reco'er t%e butadiene product

    2.!.! Conc usion of Product +e ection :

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    Comparisons or all our products %a'e been tabulated in 1able 2 6 et demand especiall$ in Asia region emand in Asia will grow at a

    more rapid rate, at !" #$ear, alt%oug% demand in some countries, particularl$ C%ina,

    will be at more t%an &0"#$ear (CMAI, 2007)

    • ig% mar>et pricing o L5 0 ;6#lb w%ic% will gi'e %ig%er pro it

    • -nl$ one competitor in Mala$sia, w%ic% is 1itan 4etc%em (M) 5dn

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    agriculture

    c%emical

    and oil

    additi'es

    construction

    mar>et

    1%e process w%ic% is %ere described in t%e project among t%ese t%ree processes is t%e

    production o t%e n/

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    . Production rates:

    4lant t%at %as a capacit$ t%at is greater t%an &0 x &0; Ib#$r is usuall$ continuous In

    contrast, i t%e plantNs capacit$ is less t%an & x &0; Ib#$r, t%en batc% process will be

    c%osen ind o process instead o continuous

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    i' I a eed impurit$ is present in large amounts, remo'e it

    ' I a eed impurit$ is present as an a eotrope wit% a reactant, o ten it is better to

    process t%e impurit$

    'i I a eed impurit$ is inert but is easier to separate rom t%e product t%an t%e eed, it

    is better to process t%e impurit$

    'ii I a eed impurit$ is a catal$st poison, remo'e it

    1able s%ows t%e composition o t%e component in eed 1%e main component t%at is to

    be used in butadiene production is n/butane owe'er, t%e amount o isobutane in t%e

    stream is large (3 3 mole ") I isobutane is not separated rom t%e eed and is

    processed, additional b$ product mig%t be produced and t%us complicated t%e separation process downstream 1%is will imposed additional cost (capital and operating) to t%e

    plant ence, wit% re erence to guideline i and i', t%e team decided to puri $ t%e stream

    irst be ore entering to t%e reactor

    Ta- e : Composition of the Components in the Feed

    Co 1onent ;or u a Mo e <

    4ropane

    i/

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    ;igure : 4uri ication o t%e eed

    igure s%ows t%e sc%ematic diagram o t%e eed puri ication section istillation column

    is used to separate t%e impurities rom t%e eed As s%own in t%e diagram, n/butane will

    be wit%drew as side draw product, w%ile isobutane and propane will be wit%drew rom

    t%e distillation column as t%e top product and C!O as bottom product

    1o con'ert n/butane to butadiene, two stages o de%$drogenation reaction are in'ol'ed(non/oxidati'e and oxidati'e de%$drogenation) 1%e b$ product o t%e processes are

    %$drogen ( 2), carbon monoxide (C-), carbon dioxide (C- 2), s%ort c%ain %$drocarbon

    (C&/C3) and steam ( 2-) igure 6 3 s%ows t%e sc%ematic diagram o two stages o

    de%$drogenation process -nl$ approximatel$ 33" o n/butane will be con'erted to

    butadiene ence t%e unreacted n/butane will be rec$cled

    ;igure : 1wo 5tages e%$drogenation o n/butane

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    5ince onl$ approximatel$ 33" o n/butane will be con'erted to butadiene, t%e unreacted

    n/butane will be rec$cled a ter separated o t%e product stream It is impossible to

    ac%ie'e s%arp separation in t%e separation process ence, t%e rec$cle stream will

    consist o low raction o impurities ence, part o t%e rec$cle stream will be purged to

    a'oid accumulation o t%e impurities in t%e process stream

    2.# n1ut ut1ut +tructure B

    2.% R6C C86 / R6ACT R + 5T,6+ +

    ?ood reactor per ormance is o paramount importance in determining t%e economic

    'iabilit$ o t%e o'erall design and undamentall$ important to t%e en'ironmental impact

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    o t%e process (5mit%, 200!) 1%ere ore, issues to be addressed or a good reactor design

    s%ould include

    & :eactor t$pe

    2 Catal$st

    3 5i e

    6 -perating Conditions (1emperature and 4ressure)

    ! 4%ase

    ; eed Conditions (Concentration and temperature)

    At earl$ stages in design, a >inetic model normall$ is not a'ailable 1%us, material

    balance calculations s%ould be based on a correlation o t%e product distribution

    ( ouglas, & .) 1%is t$pe o >inetic anal$sis is 'er$ crude but in most cases t%e reactor

    cost is not nearl$ as important as t%e product distribution costs

    2.%. Reactor +e ection

    1%e selection o reactor is cruciall$ important in order to ma>e sure t%at t%e eed

    operates at its maximum or single reaction, t%e %ig%est rate o reaction is maintained

    b$ t%e %ig%est concentration o eed (5mit%, 200!)

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    temperature control because %eat loads 'ar$ t%roug% t%e bed 1emperature in t%e catal$st

    mig%t become locall$ excessi'e, w%ic% ma$ lead to undesired product and catal$st

    deacti'ation 1%e catal$st is usuall$ troublesome to replace too ed

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    isad'antages

    • i icult to control t%e

    temperature because %eat loads 'ar$

    t%roug% t%e bed

    1emperature in t%e catal$st becomes locall$ excessi'e, w%ic% ma$

    lead to undesired product and catal$st

    deacti'ation

    • 1%e catal$st is usuall$

    troublesome to replace

    • C%anneling o t%e gas low

    occurs, resulting in ine ecti'e use o parts o t%e reactor bed

    • ig% cost o t%e reactor

    and catal$st regeneration

    eHuipment

    Attrition o catal$stcan cause generation o catal$st

    ines w%ic% could be carried o'er

    and lost in t%e s$stem, and ma$

    cause ouling in pipelines and

    eHuipment downstream

    • 4re erable or gas/solid

    non/catal$tic reactions

    A ter comparing bot% t$pes o reactor, tubular ixed/bed catal$tic reactor is c%osen or

    all t%ree reactors in'ol'e in t%e process 1%is is due to t%eB

    a lower capital and operating cost

    • 1%e reactions in'ol'ed in t%e butadiene production are reHuired to be operated in

    %ig% pressure condition

    • 1%e reHuired 'olume or tubular ixed bed catal$tic reactor is smaller compared

    to luidi ed bed reactor or %ig% pressure operation, and t%us lower capital cost

    • 1%e operating cost or luidi ed bed reactor is 'er$ %ig% because it is more

    di icult to maintain t%e gas p%ase reactant and catal$st to be in t%e well mixed

    condition i it is operated in %ig% pressure

    b less losses in catal$st

    • 1%ere will be losses in catal$st i luidi ed bed reactor is selected

    • 1%e losses in catal$st are resulted romB

    • catal$st will settle at t%e bottom o t%e reactor i it is not well mixed wit% t%e gas

    p%ase reactant

    catal$st ine mig%t be generated during t%e operation o t%e reactor w%en t%ecatal$st %it on t%e wall o t%e reactor or t%roug% attrition 1%e catal$st ine will

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    be broug%t to t%e downstream o t%e process w%en toget%er wit% t%e product

    stream

    c lower maintenance cost

    • I luidi ed bed reactor is selected, t%e catal$st t%at settle at t%e bottom o t%e

    reactor will oul and plug t%e reactor w%ile t%e generated catal$st ine will cause

    ouling in t%e pipeline and eHuipment downstream

    • 4lant mig%t need to be s%ut down o ten or maintenance

    2.$ +6PARAT 5 +TR7CT7R6

    1%e core reaction in butadiene production is t%e de%$drogenation using n/butane as t%e

    reactant owe'er, t%e eed stream contains signi icant amount o i/butane w%ic% is up

    to 3 3" 1%us, in order to increase $ield, we need to con'ert i/butane into n/butane

    1%e con'ersion is done in t%e Isomeri ation :eactor

    1%e deisobutani er column in pretreatment section emplo$s side draws to $ield puri ied

    n/butane 1%e n/butane stream is drawn as a 'apor side product a ew tra$s abo'e t%e

    bottom, lea'ing a small %ea'$ end stream w%ic% is onl$ about &" o t%e eed stream to

    be t%e bottom product 1%us, t%e s$stem consists o two prominent products and we can

    assume t%at t%e small stream does not exist

    1%e initial assumption or distillation columns is to %a'e 0 02 mole percent o lig%t >e$

    component in bottom and 0 0& mole percent o %ea'$ >e$ component in t%e o'er%ead

    product Also, we assume t%at all t%e component lig%ter t%an t%e lig%t >e$ lea'e wit%o'er%ead and t%at all components %ea'ier t%an t%e %ea'$ >e$ are ta>en at t%e bottoms

    2.$. esign of 6 tractive isti ation Co u n :

    According to 5eader (& .), extracti'e distillation is a partial 'apori ation process in

    t%e presence o a miscible, %ig%/boiling, non/'olatile mass separation agent, normall$

    called t%e solvent, w%ic% is added to an a eotropic or non/a eotropic eed mixture to

    alter t%e 'olatilities o t%e >e$ components wit%out t%e ormation o an$ additional

    a eotropes

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    2.$.2 +o vent se ection:

    5ince t%e sol'ent is t%e %eart o extracti'e distillation, more attention s%ould be paid on

    t%e selection o potential sol'ents 1%e a init$ o %$drocarbon to polar sol'ent depends

    directl$ on t%eir degree o un/saturation A %ig%l$ unsaturated %$drocarbon is moresoluble in a polar sol'ent, and t%e sol'ent decreases t%e 'olatilit$ o t%e %$drocarbon

    , se'eral eatures are essentialB

    & 1%e sol'ent must be c%osen to a ect t%e liHuid/p%ase be%a'ior o t%e >e$

    components di erentl$ ot%erwise no en%ancement in separabilit$ will occur

    2 1%e sol'ent must be %ig%er boiling t%an t%e >e$ components o t%e separation and

    must be relati'el$ non'olatile in t%e extracti'e column, in order to remain largel$ int%e liHuid p%ase

    3 1%e sol'ent s%ould not orm additional a eotropes wit% t%e components in t%e

    mixture to be separated

    6 1%e extracti'e column must be a double/ eed column, wit% t%e sol'ent eed abo'e

    t%e primar$ eed t%e column must %a'e an extracti'e section

    rom LllmanNs %andboo> (& .!), t%ere are i'e sol'ents t%at are commonl$ used in

    industr$Ba n/met%$l/2/p$rrolidone (*M4),

    b dimet%$l ormamide ( M )

    c imet%$lacetamide ( MAC)

    d Acetonitrile (AC*)

    e ur ural

    - all possible sol'ents t%at can be used or t%e separation o butadiene/butane mixture

    we %a'e c%osen dimet%$l ormamide ( M ) M is recommended as a potential

    entrainer because it gi'es great alteration in relati'e 'olatilit$ 1%is in turn will ma>e t%e

    separation easier and c%eaper, as t%e utilities and tra$s reHuired are lesser 'en t%oug%

    *M4 gi'es greater 'alue, it costs almost twice t%e M

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    C,APT6R 3: PR C6++ 6+CR PT 5

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    Process escri1tion

    In t%is project, butadiene is produced in continuous process ere t%e &,3/butadiene is

    produced b$ oxidati'e de%$drogenation reaction

    3. Pre1rocess Purification > eiso-utani=er :

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    3

    4

    6

    C-101

    E-101

    E-102

    ;igure : 4reprocess 4uri ication 5ection

    1%e main objecti'e o t%is pre/treatment unit is to extract n/butane rom t%e eed 1%e

    extracted n/butane will be used as t%e reactant or t%e de%$drogenation process in order

    to produce butadiene

    1%e eed omposition is as ollows B

    Ta- e : eed Composition

    Co 1onent ;or u a Mo e

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    4ropane

    i/

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    1%e process gas rom 5ection &, t%e preprocess unit enters t%e urnace ( 30&) at

    62 2oC 1%e urnace will %eat up t%e process gas up to ;00 oC 1%e %eated process gas

    will enter t%e e%$drogenation :eactor (:30&) w%ere t%e n/butane will be con'erted in

    to butenes $drogen and ot%er b$product suc% as C & P C3 will also orm 1%e

    e%$drogenation :eactor (:30&) is a ixed bed tubular reactor operating at temperature

    o !00oC and pressure o 3 bar 1%e reaction is an exot%ermic reaction and t%e

    temperature is maintained using molten salt at t%e s%ell side o t%e reactor 1%e catal$st

    used in t%e reactor is t%e Pt ?.3 +n ?.# Cs ?.&@ ?.& 8a 3.? w%ic% gi'es t%e con'ersion o 32 "

    and selecti'it$ o ;"

    1%e butenes rom :30& will be cooled down rom ;00 oC to 620 oC b$ e%$drogenationInter/cooler ( 30&) be ore urt%er supplied to -xidati'e e%$drogenation :eactor(:302) 1%e :302 is also a ixed bed tubular reactor and is operating at temperature o330 oC and pressure o 3 bar