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Feasibility study of production of

Hydrogen

Report submitted in partial fulfilment

Of the requirement for degree of

B.TECH

IN

CHEMICAL ENGINEERING

Under the supervision of

Dr. RAKESH ANGIRA

BY

MAANK

SCHOOL O CHEMICAL TECHNOLOGY

GURU GOBIN! SINGH IN!RA"RASTHA UNI#ERSITY

!$AR%A SEC&'(C

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Acknowledgeme

nt

I )ish to th*n+ !R. RA%ESH ANGIRA, - supervisor, for his /onst*nt support *nd 0uid*n/e

throu0hout the /ourse of the pro1e/t report.

I *2so )ish to th*n+ for the 0uide2ines, su00estions *nd en/our*0e-ent th*t /ontri3uted

i--ense2 to the ide*s of -*+in0 this report su//essfu22 /o-p2ete.

I )*nt to th*n+ *22 the f*/u2t -e-3ers *nd - fe22o) 3*t/h-*tes for sh*rin0 their ide*s *nd

+no)2ed0e )ith -e.

I -ust th*n+ universit s/hoo2 of /he-i/*2 te/hno2o0 for providin0 the opportunit to

investi0*te the produ/tion of hdro0en.

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INDE!

S.N" #"$I% $AGE N".

&' %HA$#ER & (((((((&a' IN#R"D)%#I"N ((((((((((&

b' HIS#"R ((((((((((*

c' $HSI%A+ $R"ER#IES (((((((*

d' #HERM"DNAMI%A+ $R"$ER#IES.....*

e' %HEMI%A+ $R"$ER#IES ((((...(..,f' %HEMI%A+ REA%#I"NS ((((((...-

g' )SES ((((((((((((((((

/' IND)S#RIA+ )SES (..(((((((..&0

i' MAN)FA%#)RING $R"%ESSES (.......&*

&' $AR#IA+ "!IDA#I"N "F HDR"%AR1"N (((((.&*

*' HDR"GEN FR"M %"A+ (((((((((((((..&*

2' HDR"GEN $R"D)%#I"N FR"M %"A+ ((((((.&2

3' S#EAM REF"RMING $+AN# (((((((((.&3

*' %HA$#ER * (..(((((.&a' MA#ERIA+ 1A+AN%E ((((((...&

b' ENERG 1A+AN%E((((((((.*4

Feasibility Study

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Production ofHydrogen

CHAPTER -1

INTR!"CTIN

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Hydrogen )*s first sep*r*ted *nd identified in the se/ond h*2f of the '4th /entur. ro- -*n

e*rs the industri*2s de-*nds for hdro0en )ere 2i-ited to the re2*tive2 s-*22 5u*ntities used in

oper*tin0 o6&hdro0en 2*-ps used for pro1e/tion purpose *nd for use in the o6hdro0en

32o)pipe for -e2tin0 refr*/tor -*teri*2s. But in '7889s )e st*rted usin0 it in produ/tion of

*--oni*, -eth*no2 *nd on * *2/oho2:s *nd for the refiner purpose other th*n this no) it is used

in /he-i/*2 refiner, -et*2 tre*tin0, f*ts *nd oi2 hdro0en*tion. Ho)ever, hdro0en&

-*nuf*/turin0 pro/ess deve2oped the 2*st ;

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hdro0en *s *n ener0 /*rrier, then the e*r2 Dni/he *pp2i/*tionsD in the tr*nsport *re* or fue2 /e22

*pp2i/*tions present the first *v*i2*32e -*r+ets. A 2o) /ost introdu/tion *nd testin0 ph*se /*n

t*+e p2*/e in the surroundin0s of /onvention*2 /he-i/*2 hdro0en produ/tion. $ithin the ne6t

five to ten e*rs, this shou2d 2e*d to *n e/ono-i/*2 -*r+et penetr*tion th*t /ou2d 3e sust*in*32

e6tended in the -ediu-&ter- )ith i-ported hdro0en *nd other hdro0en sour/es e.0. 3io-*ss

0*sifi/*tion.

History

In '488 first produ/tion of hdro0en *nd o60en 3 e2e/tro2sis *nd *fter th*t in '474

2i5uef*/tion of hdro0en usin0 2inde pro/ess )*s done. In '78 first /o--er/i*2 e2e/tro2sis

inst*22*tion )*s done. In '7

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properties differ /onsider*32. At 2o) te-per*ture "&H, O&! /*n 3e present in *

virtu*22 pure st*te.

Hdro0en 0*s is /o2or 2ess, non poisonous odor2ess *nd t*ste2ess. Contr*r to -ost other

0*ses, the inversion te-per*ture of hdro0en 2ies 3e2o) *-3ient te-per*ture. Li5uid

hdro0en is /o2or2ess, ver -o3i2e 2i5uid )ith 2o) vis/osit *nd surf*/e tension.

Solubility of /ydrogen in li5uids

Hdro0en is on2 s2i0ht2 so2u32e in 2i5uids. In /ontr*st to the hi0h2 so2u32e

0*ses ho)ever the so2u3i2it 0ener*22 in/re*ses )ith in/re*sin0 te-per*ture. The re2*tive

so2u3i2it differen/es in 3et)een hdro0en /o-pound is fe) per/ent *nd di-inish )ith

in/re*sin0 te-per*ture.

Solubility6s of /ydrogen in 7etals

Met*2s )ith not /o-p2ete2 o//upied inner e2e/tron 2eve2s h*ve * p*rti/u2*r2 hi0h

so2u3i2it potenti*2 for hdro0en. Hdro0en is disso2ved in -et*2s *nd not in the

-o2e/u2*r 3ut in the *to-i/ fro- )here 3 non&stoi/hio-etri/*2 or stoi/hio-etri/*2

/o-pound -* 3e for-ed.

The so2u3i2it of hdro0en in -et*2s *t s-*22 hdro0en /on/entr*tions is

proportion*2 to the root of the hdro0en p*rti*2 pressure. The hdro0en so2u3i2it

de/re*ses )ith in/re*sin0 te-per*ture. I-purities in the -et*2s *nd in the hdro0en /*n

2o)er the so2u3i2it or /*n/e2 it /o-p2ete2 disso2ved propert, -*0neti/ properties *nd

/*n /*use super /ondu/tivit.

T*32e '? "hsi/*2 *nd ther-odn*-i/ properties of Hdro0en

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%/e7ical properties

The /he-istr of hdro0en depends -*in2 on three pro/esses,

'. Loss of the v*2en/ e2e/tron to ie2d the hdro0en ion H

. G*in of *n e2e/tron to for- the hdride ion H&

>. or-*tion of *n e2e/tron p*ir 3ond.

$roperties

'. Hdro0en is not e6/eption*22 re*/tive, *2thou0h hdro0en *to-s )ith *22 other

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e2e-ents )ith the e6/eption of no32e 0*ses.

. The stren0th of the H J 3ond in /ov*2ent hdrides depends on the

e2e/trone0*tivit *nd siKe of the e2e-ent J.

>. The stren0th de/re*ses in * 0roup )ith in/re*sin0 *to-i/ nu-3er *nd 0ener*22

in/re*ses */ross *n period.

F. The -ost st*32e /ov*2ent 3ond *re those for-ed 3et)een t)o hdro0en *to-s,

or )ith hdro0en, o60en /*r3on *nd nitro0en

%HEMI%A+ REA%#I"N8S

Hydrogen producing reactions

'.On * 2*3or*tor s/*2e, hdro0en /*n 3e -*de fro- the */tion of *n *5ueous

*/id on * -et*2 or fro- the re*/tion of *n *2+*2i -et*2 in )*ter.

. Hdro0en 0*s /*n *2so 3e produ/ed on 2*3or*tor s/*2e 3 the e2e/tro2sis of

*n */idi/ so2ution.

>. Hdro0en /*n *2so produ/ed 3 ste*- refor-in0 usin0 hdro/*r3ons su/h *s

n*tur*2 0*s, petro2eu-, *nd /o*2

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F. Re*/tion )ith hdro0en *nd other e2e-ents

Hdro0en for-s /o-ponents )ith *2-ost ever other e2e-ent possi32e in

-*n /*ses.

* Hdro0en /o-3ines dire/t2 )ith in/re*sin0 re2*tive2 iodine, 3ro-ine,

/h2orine, *nd f2uorine. The re*/tion )ith f2uorine o//urs spont*neous2 *nd

e6p2osive2 even in d*r+ *t 2o) te-p *nd 0ener*22 used in ro/+et prope22*nt

sste-.

Hdro0en re*/ts )ith o60en

Hdro0en /o-3ines dire/t2 )ith o60en, either ther-*22 or )ith *n *id of /*t*2st

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Ato7ic Hydrogen

Ato-i/ hdro0en is -u/h -ore re*/tive th*n the -o2e/u2*r for-. The disso/i*tion

re*/tion is hi0h2 endother-i/.

Ato-i/ hdro0en /*n 3e produ/ed 3 supp2in0 suffi/ient ener0. The hdro0en *to-

h*s * short 2ife *nd re*/ts even *t roo- te-per*ture )ith non&-et*22i/ e2e-ent su/h *s

h*2o0en, o60en et/. At roo- te-per*ture it redu/es -*n o6ides to e2e-ents.

Hydrogen ion

The ioniK*tion potenti*2 of *3ove re*/tion is '>.

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hdro0en in -et*22ur0 is 3*sed in p*rti/u2*r on its redu/in0 properties. At present, pure

hdro0en is not used dire/t2 to redu/e ener0.

!ifferent pro/ess in )hi/h Hdro0en is used *re? &

'. A--oni* snthesis

. Hdro0en in refiner pro/esses

>. Hdro0en in /o*2 refine-ent

F. Hdro pro2sis.

. Hdro0en in -et*2 pro/essin0.

F. Se-i/ondu/tor te/hno2o0.

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*/id, redu/in0 -et*22i/ ores, *nd fi22in0 3*22oons.

The 2iftin0 po)er of ' /u3i/ foot of hdro0en 0*s is *3out 8.8; 23 *t 8C, ;(8 -- pressure.

The Hdro0en ue2 /e22 is * deve2opin0 te/hno2o0 th*t )i22 *22o) 0re*t *-ounts of

e2e/tri/*2 po)er to 3e o3t*ined usin0 * sour/e of hdro0en 0*s. "u32i/ *//ept*n/e, hi0h

/*pit*2 invest-ent, *nd the hi0h /ost of hdro0en )ith respe/t to tod*:s fue2s *re 3ut * fe)

of the pro32e-s f*/in0 su/h *n e/ono-. Lo/*ted in re-ote re0ions, po)er p2*nts )ou2d

e2e/tro2Ke se*)*ter the hdro0en produ/ed )ou2d tr*ve2 to dist*nt /ities 3 pipe2ines.

"o22ution&free hdro0en /ou2d rep2*/e n*tur*2 0*s, 0*so2ine, et/., *nd /ou2d serve *s *

redu/in0 *0ent in -et*22ur0, /he-i/*2 pro/essin0, refinin0, et/. It /ou2d *2so 3e used to

/onvert tr*sh into -eth*ne *nd eth*ne.

Industrial uses of Hydrogen

Hdro0en finds use in diverse *pp2i/*tions /overin0 -*n industries, in/2udin0?

ood to hdro0en*te 2i5uid oi2s su/h *s so3e*n, fish, /ottonseed *nd /orn,

/onvertin0 the- to se-iso2id -*teri*2s su/h *s shortenin0s, -*r0*rine *nd pe*nut

3utter.

Che-i/*2 pro/essin0 pri-*ri2 to -*nuf*/ture *--oni* *nd -eth*no2, 3ut *2so to

hdro0en*te non&edi32e oi2s for so*ps, insu2*tion, p2*sti/s, oint-ents *nd other

spe/i*2t /he-i/*2s.

Met*2 produ/tion *nd f*3ri/*tion to serve *s * prote/tive *t-osphere in hi0h

te-per*ture

oper*tions su/h *s st*in2ess stee2 -*nuf*/turin0 /o--on2 -i6ed )ith *r0on for )e2din0

*usteniti/ st*in2ess. A2so used to support p2*s-* )e2din0 *nd /uttin0 oper*tions.

"h*r-*/euti/*2s ... to produ/e sor3ito2 used in /os-eti/s, *dhesives, surf*/t*nts, *nd

vit*-ins A *nd C.

Aerosp*/e ... to fue2 sp*/e/r*ft, 3ut *2so to po)er 2ife&support sste-s *nd /o-puters,

ie2din0 drin+*32e )*ter *s * 3&produ/t.

E2e/troni/s ... to /re*te spe/i*22 /ontro22ed *t-ospheres in the produ/tion of

se-i/ondu/tor /ir/uits.

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"etro2eu- Re/over *nd Refiner ... to enh*n/e perfor-*n/e of petro2eu- produ/ts

3 re-ovin0 or0*ni/ su2fur fro- /rude oi2, *s )e22 *s to /onvert he*v /rude to

2i0hter, e*sier to refine, *nd -ore -*r+et*32e produ/ts. Hdro0en:s use in

refor-u2*ted 0*s produ/ts he2ps refiners -eet C2e*n Air A/t re5uire-ents.

"o)er Gener*tion ... to serve *s * he*t tr*nsfer -ediu- for /oo2in0 hi0h speed tur3ine

0ener*tors. A2so used to re*/t )ith o60en in the /oo2in0 )*ter sste- of 3oi2in0

)*ter nu/2e*r re*/tors to suppress inter0r*nu2*r stress /orrosion /r*/+in0 in the

/oo2in0 sste-.

Manufacturing process

partial o

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'. He*tin0 *nd /r*/+in0 ph*se

. Re*/tion ph*se

>. So*+in0 ph*se

Hydrogen fro7 coal

The Te6*/o /o*2 0*sifi/*tion sste- of those used for r*) 0*s 0ener*tion. Under hi0her

te-per*ture /onditions, -eth*ne for-*tion is -ini-iKed *nd no t*rs *nd oi2s *re produ/ed.

Hi0h&pressure 0*sifi/*tion resu2ts in si0nifi/*nt po)er s*vin0s fro- e2i-in*tion of r*)&0*s

/o-pression. A 2o) te-per*ture 0*sifi/*tion pro/ess su/h *s the 2ur0i 0*sifier or BGC

Lur0i s2u00in0 0*sifier re5uires * -ore /o-p2e6 pro/essin0 se5uen/e.

A22 /o*2 0*sifi/*tion pro/esses /*n 3e used to -*nuf*/ture hdro0en. The hi0hest

ie2d in the pri-*r 0*sifi/*tion step ho)ever is */hieved if pu2veriKed /o*2 is 0*sified

)ith o60en *t hi0h te-per*tures.

%oal gasification on an industrial scale produces?

'. Sntheti/ 0*ses, ri/h in CO *nd hdro0en

E.0. 0*s for fisher&Trops/h snthesis of 0*so2ine

. Sntheti/ 0*s for the produ/tion of */eti/ *n Hdride

>. A--oni* Snthesis 0*s

F. Su3stitute n*tur*2 0*s

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"ure )*ter is not suit*32e *s *n e2e/tro2te 3e/*use of its ver 2o) /ondu/tivit.

Therefore *5. So2ution of pot*ssiu- or sodiu- hdro6ides et/ *re used.

Tpes of e2e/tro2sis "2*nts9

'. Nor-*2 pressure e2e/tro2sis units.

. "ressure e2e/tro2sis.

>. Adv*n/ed /onvention*2 e2e/tro2sis.

F. $*ter v*por e2e/tro2sis.

E2e/tro2sis p2*nt?

A p*rt fro- the e2e/tro2sis unit e2e/tro2sis p2*nt /onsists of nu-3er of different

Inst*22*tions. Su/h *s e2e/tri/it supp2 )*ter tre*t-ent, e2e/tro2te fro- produ/t 0*ses.

G*s purifi/*tion *nd the instru-ent *nd the /ontro2 sste- dedi/*ted ther-*2 e2e/tri/

p2*nts for the produ/tion of hdro0en -* 3ui2d in the future.

Stea7 refor7ing $lant

In this pro/ess, hdro/*r3on feeds *re /onverted to snthesis 0*ses is usu*22 oper*ted *t

(

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. Ste*- refor-in0.

>. Co /onversion.

F. G*s purifi/*tion.

&. !esu2puriK*tion9 Be/*use hdro0en feed for ste*- refor-in0 shou2d 3e free

of su2fur, feed !esu2puriK*tion is re5uired. This is done 3 usin0 Co Mo

/*t*2st in the presen/e of H

*. Ste*- refor-in09 In this desu2phuriKed 0*s is introdu/ed in the pri-*r

refor-er. This refor-er is * dire/t&fired /h*-3er /ont*inin0 -u2tip2e hi0h

ni/+e2 *22o tu3es. The 0*s 2e*vin0 the pri-*r refor-er is *3out ;( H '

/o. '8 Co *nd '> CHF.

2. Co&/onversion? $*ter 0*s shifts or /o&/onversion of e6it 0*ses fro- the

se/ond*r refor-er is /*rried out in this se/tion.


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$artial o

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feed *nd the /*p*3i2it of uti2iKin0 *n hdro/*r3on *s feed re*/tion /onverts CO to CO

in t)o st*0es.

'. Hi0h te-per*ture shift.

. Lo) te-per*ture shift.

%arbon Dios9 R*n0e fro- n*tur*2 0*s to he*v *sph*2t.

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>. %o77ercial Installations9 &30 /o--er/i*2 inst*22*tion '7;7. $ith * tot*2

/*p*/it of > 3i22ion SC! of H CO *re in oper*tion throu0hout the )or2d.

The prin/ip*2 *dv*nt*0e of the p*rti*2 o6id*tion pro/ess over Ste- refor-in0 is th*t the

/*n oper*te on *n hdro/*r3on feedsto/+ th*t /*n 3e /o-pressed or pu-ped, fro-

n*tur*2 0*s to oi2, residu*2 oi2s or *sph*2t .No desu2furiK*tion is re5uired prior to the

p*rti*2 o6id*tion step. Their prin/ip*2 dis*dv*nt*0e is the ne/essit for providin0 * supp2

of 7

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p*rti*2 o6id*tion o//urs *t '78 'F888C, )ith 2ess th*n sto/hio-etri/ o60en for

/o-p2ete /o-3ustion. The over*22 re*/tion is represented 3

The over*22 pro/ess /*n 3e divided into three ph*ses.

&. He*tin0 /r*/+in0 ph*se9The *to-iKed

hdro0en is he*ted *nd v*poriKed 3 3*/+ r*di*tion fro- the f2*-e front *nd the

re*/tor )*22s so-e /r*/+in0 to /*r3on, -eth*ne *nd hdro/*r3ons r*di/*2s o//urs

durin0 this 3rief ph*se.

*. Re*/tion ph*se? Hdro/*r3ons re*/t )ith o60en *//ordin0 to hi0h2 e6other-i//o-3ustion re*/tion p*rti*22 *22 of the *v*i2*32e o60en is /onsu-ed in this

ph*se.

The -*in endother-i/ re*/tion is the

refor-in0 of hdro0en 3 )*ter viper

The /o-p2e6 re*/tor9s resu2ts in ther-*2 e5ui2i3riu- *t '>88 'F88C

2. So*+ed ph*se? The fin*2 ph*se t*+es p2*/e in the rest of the re*/tor )here the 0*s

is *t hi0her te-per*ture. A portion of the /*r3on dis*ppe*rs 3 re*/tion )ith CO

*nd ste*-. So-e /*r3on is present in the produ/t 0*s

O7


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E5uip7ent?p*rti*2 o6id*tion e5uip-ent /onsists essenti*22 of

'. G*sifi/*tion re*/tor.

. $*ste he*t e6/h*n0er.

>. E/ono-iKer he*t e6/h*n0er.

F. C*r3on re-ov*2 sste-.

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%HA$#ER ? *

Material balance

A-ount of Hdro0en re5uired to 3e produ/ed '6'8( ->d*

F'(((.(; ->hr

B*sis ? ' hr of oper*tion

A-ount of 0*s *t NT" is 0iven 3

"#nRT

n"#RT F'(((.(; 6 '8.84

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In this /*se it is *ssu-ed th*t *22 other /o-ponent *re ne02i0i32e *s /o-p*red to Meth*ne

so *22 other *re ne02e/ted.i.e on2 Meth*ne *nd Nitro0en *re present in eed.

No) snthesis 0*s /o-position for s/ell type process is 0iven 3 &&&&&&&&&&&ref'

G*s /o-position vo2

CO F.>

CO F(.>

CO F(.

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G*s /o-position vo2

CO F.>(

CO F(.7>

H F;.

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Then )e h*ve

CO *fter H.T.S

;.7'88 F(.

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$e h*ve

G*s /o-position vo2 +-o2

CO >>.4( F4.7 8.

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N 8.>7 8..;>'886Y ';8>.7; +-o2hr *-ount of hdro0en to 3e produ/ed is ';8>.7;

+-o2 hrof -i6ture(FF

No) +-o2es of other /o-ponents in 0*s -i6ture *re

At inlet of absorption coloumn we have


CO >>.(4 47.(FCO '.(8 F.F8

H (>.78 '(7>.>

No) J -o2es of CO is re-oved, *2so *-ount of hdro0en is /onst*nt is /onst*nt

Therefore

7.7;Q';8>.7; 78(&J F.(4 ''.> '8.F8

J 4(;.(F+-o2

PROJECT WORK Page 2

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CO '.F' F.774 F.F8

H 7

N 8..78 '(7>.>

At inlet of LTS we have

/o-position vo2 +-o2

CO 7.;( ;F

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CO F.>( (F.'7

CO F(.7> 4(.;F

H F;..4

N 8.

N 8.

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Mo2es of /*r3on in snthesis 0*s (F.'7'FF 4(.;'4 ''.>''(

>77784.'; +-o2hr

ENERG 1A+AN%E


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Ener0 3*2*n/e for "re he*ter

In this feed is he*ted fro- initi*2 *v*i2*32e te-per*ture of 8.F>8 %+-o2%

C"-i6 8.77( 6 F'.4 8.88F>8.F>

C"-i6 F'.;< %%-o28C

A2so he*t tr*nsferred 3 ste*- )i22 3e used 3 eed 0*s for he*tin0.

He*t re/eived 3 0*s n 6 Cp 6 T

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>;4('.( %h

He*t supp2ied 3 ste*-

Let ste*- f2o) r*te 3e M %0h

A2so

M 6 >;4('.( %h

M 8.FF +0se/

He*t 3*2*n/e for )*ste he*t 3oi2er is 0iven 3

In $.H.B 0*s fro- re*/tor *re /oo2ed fro- /o2d )*ter )hi/h is /onverted to

ste*- )ith the he*t tr*nsferred 3 0*s /oo2in0.

!*t* ?

In2et te-per*ture of 0*s '>88C

Ou2t2et te-per*ture of 0*s '.;(4


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CHF 8.(8 '88.F4

N 8.(.>F>

HS 8.4' ne02e/ted

C" of -i6ture > ++-o2C

He*t tr*nsferred 3 0*s '4>.F4 6 > 6 '8.'

H 7''.>7 H >(4

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LHS 7(;.4'; &(F'( .8< & dT

74

& '4;>F(;.'

RHS '7>.F&(F'( '4>.'< &7F8 '8 7

T> dT

T

Ener$% balance aroun& LTS

CHF ;.;> CHF ;.;>

CO '7>..'< CO 'F(< F;> 74

'(.>7 '8 >&74>&

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#4$))).ie*.or0pu32i/*tionhdro0en

#5$))).*2tener0.or0rene)*32eshdro0en
http://www.iea.org/publication/hydrogenhttp://www.altenergy.org/renewables/hydrogenhttp://www.altenergy.org/renewables/hydrogenhttp://www.iea.org/publication/hydrogen

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