chng 3807 nanotubes final

8/20/2019 CHNG 3807 Nanotubes Final

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CHNG3807 – Project 2 – LargeScale Carbon Nanotube

Synthesis

Plant design

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Contents(ecutie Su,,ary99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999"

:erall )ass ;alance9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999997

:erall Process 999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999#0

#9#9# Hoer9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999#0

#9#92 Pneu,atic coneying999999999999999999999999999999999999999999999999999999999999999999999999999#0

#9#93 -otary ?ale99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999#0

#92 /lternaties 4or design>999999999999999999999999999999999999999999999999999999999999999999999999999999#0

#93 )ass and (nergy ;alances>999999999999999999999999999999999999999999999999999999999999999999999999##

#9$ Process lo. =iagra,>9999999999999999999999999999999999999999999999999999999999999999999999999999999#3

#9* =esign Calculations>99999999999999999999999999999999999999999999999999999999999999999999999999999999999#$

#9*9# Hoer =esign>999999999999999999999999999999999999999999999999999999999999999999999999999999999999#$

#9*92 Pneu,atic Coneying =esign>9999999999999999999999999999999999999999999999999999999999999#7

#9*93 (thanol +an5>999999999999999999999999999999999999999999999999999999999999999999999999999999999999999#8

#9" Cost (sti,ate>99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999#%

#9"9# Hoers>9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999#%

#9"92 (thanol +an5>999999999999999999999999999999999999999999999999999999999999999999999999999999999999999#%

#9"93 -otary ?ale>999999999999999999999999999999999999999999999999999999999999999999999999999999999999999920

#9"9$ Pneu,atic Coneying Lines>999999999999999999999999999999999999999999999999999999999999999920

#97 Conclusion>999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999920

29 Catalyst Prearation99999999999999999999999999999999999999999999999999999999999999999999999999999999999992#

29# /lternaties 4or =esign99999999999999999999999999999999999999999999999999999999999999999999999999999992#

292 /ssu,tions9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999922

2929# )ass ;alance99999999999999999999999999999999999999999999999999999999999999999999999999999999999922

29292 +er,inal ?elocity999999999999999999999999999999999999999999999999999999999999999999999999999999922

29293 luidisation99999999999999999999999999999999999999999999999999999999999999999999999999999999999999922

2929$ Slurry99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999922

2929* Hydrocyclone99999999999999999999999999999999999999999999999999999999999999999999999999999999999922

2929" =rying9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999922

29297 Pu,ing9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999922

29298 ilter9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999923

2


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293 Preli,inary )ass ;alance99999999999999999999999999999999999999999999999999999999999999999999999999923

29$ Preli,inary (nergy ;alance99999999999999999999999999999999999999999999999999999999999999999999999923

29* Preli,inary Process lo. =iagra,999999999999999999999999999999999999999999999999999999999999992$

29" =esign Calculations9999999999999999999999999999999999999999999999999999999999999999999999999999999992"

29"9# luidisation and +er,inal ?elocity999999999999999999999999999999999999999999999999999992"

29"92 Slurry99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999928

29"93 Hydrocyclone9999999999999999999999999999999999999999999999999999999999999999999999999999999999928

29"9$ =rying999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999992%

297 Preli,inary Cost esti,ate9999999999999999999999999999999999999999999999999999999999999999999999999930

298 Conclusion9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999930

39 luidised ;ed -eactor9999999999999999999999999999999999999999999999999999999999999999999999999999999999993#

39# =escrition o4 the basic technology and its urose99999999999999999999999999999999993#392 /lternaties to design9999999999999999999999999999999999999999999999999999999999999999999999999999999932

393 General /ssu,tions used in the design99999999999999999999999999999999999999999999999999932

39$ )ass ;alances9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999933

39$9# Laboratory scale ;-99999999999999999999999999999999999999999999999999999999999999999999999999933

39$92 Co,,ercial Scale ;-99999999999999999999999999999999999999999999999999999999999999999999999933

39$929# Gas entering the ;-99999999999999999999999999999999999999999999999999999999999999999999999933

39$9292 Catalyst articles entering the ;-9999999999999999999999999999999999999999999999999933

39$9293 Particles leaing the ;- through the solid discharge99999999999999999993$

39$929$ Gas leaing the ;-99999999999999999999999999999999999999999999999999999999999999999999999993$

39* (nergy ;alance>99999999999999999999999999999999999999999999999999999999999999999999999999999999999999 3*

39*9# (nergy 4ro, Gas strea,s>9999999999999999999999999999999999999999999999999999999999999993*

39" Preli,inary P=99999999999999999999999999999999999999999999999999999999999999999999999999999999999999938

397 =esign Calculations9999999999999999999999999999999999999999999999999999999999999999999999999999999993%

398 Preli,inary costs esti,ates99999999999999999999999999999999999999999999999999999999999999999999$#

39% Conclusions999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999$2$9 Gas Cleaning Syste,9999999999999999999999999999999999999999999999999999999999999999999999999999999999999$2

$9# =escrition o4 ;asic +echnology and its Purose9999999999999999999999999999999999999$2

$92 /lternatie 4or design999999999999999999999999999999999999999999999999999999999999999999999999999999999$3

Searating Larger Particles999999999999999999999999999999999999999999999999999999999999999999999999999$3

Searating S,aller Particles99999999999999999999999999999999999999999999999999999999999999999999999999$3

$93 /ssu,tions99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999$$

-easonable Cyclone =ia,eter99999999999999999999999999999999999999999999999999999999999999999999999$$

Particle =ia,eters99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999$$

3


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$9$ )ass ;alance9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999$$

$9* Process lo. =iagra,999999999999999999999999999999999999999999999999999999999999999999999999999999999$7

$9" =esign Calculations999999999999999999999999999999999999999999999999999999999999999999999999999999999999 $8

$9"9@ Calculation )ethod9999999999999999999999999999999999999999999999999999999999999999999999999999999$8

$9"92 Cyclone =ia,eter and =i,ensions9999999999999999999999999999999999999999999999999999999$%

$9"93 Cyclone ?elocity99999999999999999999999999999999999999999999999999999999999999999999999999999999999*#

$9"9$ Pressure =ro999999999999999999999999999999999999999999999999999999999999999999999999999999999999999*#

$9"9* Su,,ary o4 -esults99999999999999999999999999999999999999999999999999999999999999999999999999999*2

$9"9" =esign Choice999999999999999999999999999999999999999999999999999999999999999999999999999999999999999*2

$9"97 Cyclone (Aciency99999999999999999999999999999999999999999999999999999999999999999999999999999999*3

$97 Cost (sti,ate999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999*3

$979# Cyclone Cost99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999*3$9792 urnace Cost99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999*$

Conclusion99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999 *$

*9 PuriBcation9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999*"

*9# =escrition o4 Process and +echnology999999999999999999999999999999999999999999999999999*"

*9#9# /cid PuriBcation99999999999999999999999999999999999999999999999999999999999999999999999999999999*"

*9#92 iltration99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999*7

*9#93 =rying99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999*7

*92 )ass(nergy ;alance999999999999999999999999999999999999999999999999999999999999999999999999999999*7

*93 Process lo. =igra,9999999999999999999999999999999999999999999999999999999999999999999999999999999*8

*9$ =esign Calculations999999999999999999999999999999999999999999999999999999999999999999999999999999999*%

*9" /lternatie =esigns999999999999999999999999999999999999999999999999999999999999999999999999999999999"3

*97 Cost (sti,ation999999999999999999999999999999999999999999999999999999999999999999999999999999999999999"3

*98 /ssu,tions99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999""

*9% Conclusion99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999"7

;ibliograhy999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999"8/endi ;> Calculations999999999999999999999999999999999999999999999999999999999999999999999999999999999970

No,enclature99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999970

)ass ;alance999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999970

)ass ;alance )atri9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999972

+er,inal ?elocity9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999973

+er,inal ?elocity )atri99999999999999999999999999999999999999999999999999999999999999999999999999999999999973

luidisation99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999997$

Slurry999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999977

$


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Slurry )atri99999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999 78

Hydrocyclones9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999978

Hydrocyclone )atri9999999999999999999999999999999999999999999999999999999999999999999999999999999999999999980

=rying999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999 8#

=rying )atri999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999999982

*


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Executive Summary

Dltra Nano is a co,any that roduces )ultiE.all Carbon Nanotubes !)FCN+s&using e2:3)g:9 +hese )FCN+s are used in the roduction o4 electroche,ical

double layer caacitors and


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Overall Mass Balance

7

,ass o4 N:2#2%#0320

0 5gs

,ass o4 Fater#%8$#0"$

88$ 5gs

,ass o4 HCL20$$3872

893 5gs

,ass o4 )gCl22278%88"

8# 5gs

,ass o4 eCl3%$#"83#8

92" 5gs,ass o4a,orhous carbon #$"8$%$ 5gs

,ass o4 )g: 09#3 5gs

)ass o4 iron nitrate 0902$ 5gs

,ass o4 /r39%70#

23 5gs

,ass o4 C2H209**$0

$$ 5gs

,ass o4 air going in #333700 5gs,ass o4 .ater goingin

*9##(K0% 5gs

CN+ roduction syste,


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Overall Process fow Diagram

8


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Overall Cost

Estimate

+he table belo. giesthe total Bed caital costs

4or the arious syste,s in the

lant9

+he total cost is 8'27%'27$ .hich .hen loo5ing at a lant roducing *0005g er

day o4 a high alue roduct' see,s li5e a s,all inest,ent9 Granted that this

reort does not include a running costs' it the alue aears rather s,all9

+he deiations in the cost 4or the arious syste,s .ithin the lant reuire 4urther

attention9 Fhilst arying alues are to be eected' the di1ering order o4

,agnitude bet.een the largest alue o4 $'%$*'0#0 and the s,allest o4

#*"'##$ could be attributed to seeral reasons9 +he ,ost robable reason

.ould be due to the a,ount o4 detail that each indiidual .ent to on their

resectie syste,9 +hose .ho 4ocused not only on the core eui,ent and

rocesses resent' but .ent 4urther and added additional etras such as

coneyor beds and ales etc9' .ould obiously hae a greater total Bed caital

cost9

+he alternatie reasoning behind the large alue deiation .ould be sources to

the use o4 P+F9 Fhilst the boo5 roides ecellent detail on ,ore co,,on

rocess instru,ents' those that are less co,,on and ,ore diAcult to establish

si6e to cost relationshis are oid 4ro, the boo59

Dn4ortunately this cost esti,ate is rather dry9 ?arious i,roe,ents could be

,ade in the 4or, o4 a running cost esti,ate and the eected roduct alues9

Ho.eer a reort such as this 4ocuses on good design and scale u

ri,arily' and econo,ic 4easibility secondly9

%

System Total Fixed

Capital !"Catalyst raw materials

storage

87#'$"0

Catalyst preparation "0"'"%0

Fluidised #ed reactor $'%$*'0#0

$as cleaning system #*"'##$

C%T puri&cation #'700'000

Total cost !'()*+()*,


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-. Storage /opper Design

-.- Description0

-.-.- /opper

+he shortEter, storage o4 articulate solids in rocess lants can resent

roble,s .hich are o4ten underesti,ated and can 4reuently cause


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Catalyst ra. ,aterials storage and deliery syste,

)g: O ##2279725g

e!N:3&39%H2: O $37$9#75g

(thanol O 7200897*5g

Figure 1: Mass Flow and Funnel Flow in Hoppers: (a) Funnel Flow; (b) Mass

Flow 26odes M. ( )77'"

/art 4ro, the di1erent


12/93

to the


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-., Process Flow Diagram0

#3


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8y

8c

-.9 Design Calculations0

-.9.- /opper Design0

No sheer cell test data could be 4ound 4or )agnesiu, :ide !)g:& or ron

Nitrate' thus another article that .as si,ilar in roerties .as used to calculate

the hoer9 SCE# !)cay' #%%$& .as used in lace o4 )g:9 )g: is 4ound in the

co,osition o4 SCE#' and there4ore they both hae si,ilar roerties9

Figure 3: Sheer ell !est Data

#$


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igure 3 is the sheer cell test used to calculate Q !angle o4 internal 4riction&' Rc!co,acting stress& and Ry !unconBned yield stress&9

+he angle o4 internal 4riction .as already calculated to be Q O $*9 Rc and Ry .eredeter,ined 4ro, the ends o4 the se,iEcircle as sho.n in igure 3

!able 1: o"pa#ting and $n#on%ned &ield Stresses

8c 237.705 kPa 482.3 kPa 654.55 kPa

8y 34.45 kPa 68.9 kPa 96.46 kPa

ine,atic angle o4 .all 4riction TFO2$92

Dsing igure $ !-hodes )9 ' 2008&and a sa4ety ,argin o4 #0' the hoer


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#9* ,290 ,#9* ,

Figure ': Hopper Flow Fa#tor alue or oni#al hannels* +,'-.

RyPo.derlo. unction

Polyno,ial!Po.derlo.

unctio

n&

Figure /: Deter"ination o #riti#al #onditions or 0ow

igure * clearly sho.s the critical alue 4or 4lo. is RcritO79* 5Pa9 /ll stresses aboe

this alue .ill cause

B= H (θ)σ crit

ρB g E:uation )

Fhere H!U& is a 4actor deter,ined by the sloe o4 the hoer .all9

H (θ )=2.0+ θ60 E:uation 1

ro, (rror> -e4erence source not 4ound and(rror> -e4erence source not 4ound ;O

$29$ c, 4or the )g: hoer9

Su,,ari6ing' to achiee ,ass


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MgO Iron Nitrate MgO/Fe2O3

Figure : Di"ensions o ea#h hopper

-.9.) Pneumatic Conveying Design0

Pneu,atic coneying reuires trial and error in selecting the correct ie

dia,eter9 irstly an initial ie dia,eter o4 *#,, is selected9 ro, here the gas

elocity i4 4ound using the saltation elocity9 !Note that air is used in this syste,

as the coneying gas as it is chea and readily assessable9&

U salt =(4 M P10α g β /

2

D(

β

2

)−2

π ρf )1/( β+1 )

E:uation ,

Fhere V O #$$0 K #9%" and W O ##00 K 29*

+here4ore suerBcial gas elocity' D O #9*Dsalt

D O #9* 89%"2

D O #39$$ ,s

+he net ste is to calculate the ressure losses through the hori6ontal andertical sections and the bends9

Horizontal Sections:

+he ressure loss in the hori6ontal sections o4 the transort line is gien by>

∆ p H = ρf ε H U fH

2

2+

ρ p (1−ε H ) U pH 2

2+2 f g ρ f U

2 L H

D +

2 f p ρ p (1−ε H ) U pH 2

L H

DE:uation

9

Hin5leMs correlation gies DH>

U pH =U (1−0.0638 x0.3

ρ p0.5) E:uation >

+here4ore DHO#0900 ,s

ro, continuity' G= ρ p(1−ε H )U pH E:uation*

+hus' ε H =1− G

ρ p U pH =0.998 ' and' U fH =

U

ε H =13.46 ,s

-e .as calculated using the transitional euation and there4ore C= O 298*3

#7

UUU

$29$ $39"#0#9$


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f p=3

8

ρf

ρ p

D

x C D( U f −U pU p )

2

=0.019

+here4ore using (rror> -e4erence source not 4ound' XH O #"2%792$ Pa' ta5ing f gO 0900*

Vertical Sections:

+he ressure loss in the ertical sections o4 the transort line is gien by>

∆ pv=2 f g ρf U

2 LV

D +0.057GLv √ g D+ ρ p (1−ε v) g Lv+ ρf ε v g Lv E:uation '

U pv=U

ε v−U E:uation +

Co,bining (rror> -e4erence source not 4ound(rror> -e4erence source not

4oundand ro, continuity' (uation 7' creates a uadratic in Y .hich only

has one ossible root9

ε v2

U −(U +U + G ρ p ) ε v+U =0 E:uation -7Soling the uadratic euation' Y O 09%%%' and thus X O #*"#9*$* Pa

Bends:

+he ressure loss across each %0 bend is ta5en to be euialent to that across79*, o4 ertical ie9 !-hodes )9 ' 2008&

Pressure loss er ,etre o4 ertical ie O #*"9#*$ Pa

+here4ore' loss across t.o %0 bends O 2 79* #*"9#*$ O 23$293 Pa9

/nd so'

+otal ressure loss O loss across ertical sections K loss across hori6ontalsections K loss across bends

#8


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O #*"#9*$* ? #"2%792$ K 23$293

O 2020# Pa

O 092 bar

+he allo.able syste, ressure loss is 092 bar there4ore the si6e selected 4or theie dia,eter is .ithin the range9

+hese calculations .ere reeated 4or the other coneying lines9 +able 3>Su,,ary o4 Pneu,atic Coneying Lines sho.s the su,,ary o4 results 4or all theneu,atic coneying lines9

!able 3: Su""ar o neu"ati# on4eing 5ines

PipeDiameter

mm"

@P/Pa"

@PvPa"

Bends

4llowa#lePressureloss #ar"

TotalPressureloss #ar"

MgO *# #"2%792$

#*"#9*$*

2 092 092


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%" c,

# ,

? O 097* ,3

stainless steel' .ith a olu,e o4 097* ,39 +he dia,eter is # , giing a height o4 %" c,9

Figure 6: Di"ensions o the 7thanol Storage !an8

-.> Cost Estimate0

-.>.- /oppers0!able ': ost esti"ate o hoppers

Mg9 ron itrate Mg9l 3-?1$30000 $20000 $!"000

!otal hsi#al lant

ost !=!9 et-3 >l 3-?1$#000 $"%000 $2000

C+/+:N Pet03 Zl 308# &'rc(ased cost calc'lated fro) !Peters' +i,,erhaus' [

Fest' 2003& *g!2+"2 ,g""- for stainless steel20


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!otal Fi@ed

apital !=!9 et-3 >l 3-?1$!!300 $-"%00 $"%-00

-.>.)Et6anol TanA0!able /: ost esti"ate o ethanol tan8

7thanol !an8

ur#hased ost 1 $"0000

!otal hsi#al lant ost 2 $!-0000

!otal Fi@ed apital 3 $2%"00

-.>.1 2otary 3alve0!able : ost esti"ate o rotar 4al4es

Aotar al4e (3 4al4es in total)

ur#hased ost !=!9 et-3 >l 3-?1 $!0000 ,er .al.e

!otal hsi#al lant ost 2 $"00

!otal Fi@ed apital 3 $!32300

-.>.,Pneumatic Conveying ines0!able 6: ost esti"ate o pneu"ati# #on4eing lines

neu"ati# on4eing 5ines (' lines in

total)

ur#hased

ost !=!9 et-3 >l 3-?1$!000 ,er line

!otal hsi#al lant ost 2

$!-%00

C+/+:N Pet03 Zl 308# otal ,(1sical ,lant cost calc'lated fro) !Sinnott'

200"&tale %! ,g 2"2 Incl'des installation ,i,ing instr')entation electrical

'ildings 'tilities storages site de.elo,)ent and ancillar1 'ildings

C+/+:N Pet03 Zl 308# otal *4ed ca,ital calc'lated fro) !Sinnott' 200"& tale

%! ,g 2"2 Incl'des design and engineering contractor5s fee and contingenc1

C+/+:N Pet03 Zl 308# Purchased cost calculated 4ro, !Peters' +i,,erhaus' [

Fest' 2003& Bg #2E"$' g *7*

C+/+:N Pet03 Zl 308# Purchased cost calculated 4ro, !Peters' +i,,erhaus' [

Fest' 2003& Bg #2E"3' g *7*2#


22/93

!otal Fi@ed apital 3 $2%%0

Total Cost o5 storage o5 raw materials !'*-(,>7 S Dollars"

-.*Conclusion0

:erall' 3 hoer storage deices !.ith rotary ales& .ill be used to store the

ra. ,aterials9 +hese are connected to a neu,atic coneying syste, that .ill

transort the articulates to the catalyst rearation9 +hese hoers use ,ass


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). Catalyst Preparation +he ter, catal1st ,re,aration deBnes itsel49 t is the rearation o4 a catalyst that

.ill be used 4urther on in another reaction9 / catalyst increases the rate o4 a

che,ical reaction .ithout be consu,ed in the reaction itsel49 Prearing one canbe as si,le as adding t.o che,icals together' or ,ore co,le such as the one

that this chater outlines

+he catalyst rearation ,ethod used .ith the reort Ma'ron et al utilises a

suorted ,etal oide as a catalyst to the reaction9 +he conentional

aroaches to rearing this ,aterial include euilibriu, adsortion' gra4ting'

coEreciitation and i,regnation9 +he 5ey 4unction in characterising suorted

,etal oides is the a,ount o4 the suorted ,etal oide relatie to the

underlying suort sur4ace area9 +hus it is i,ortant to use an underlying

suort substance .ith a high sur4ace area as the catalytic actiity correlates tothe sur4ace densityEdeendant structure o4 the suorted secies !-egalbuto'

200"&9

+he ,ethod utilised by Ma'ron et al inoles a ,agnesiu, oide !#00 ,2 gE#&

suorted iron oide o.der' roduced by i,regnation in an iron nitrate

ethanol solution9 ts urose is to aid in the deosition o4 carbon nanotubes 4ro,

acetylene by che,ical aour deosition

).- 4lternatives 5or DesignFithin the design o4 the syste, there are irtually a li,itless nu,ber o4 ,ethods

to reare the suorted ,etal oide !S):&9 / ariety o4 eui,ent can be used

to arying eAciencies9 =oes one use a cyclone or a Blter\ :ne large u, or

seeral s,aller u,s\ (ssentially the Bnal design only ends .hen the rocess

engineers are satisBed that the roduct' energy' and cost balances are

suAciently iable9 Fithin this catalyst rearation section' the di1ering ,ethods

4all into one o4 4our categories>

,regnation> +his chater is an ea,le o4 i,regnation' .here a orous

suort substance !)g:& is i,,ersed in a solution !ethanol& .here a reaction

occurs and the desired catalytic agent !e2:3& i,regnatesadsorbs to thesuort substance9

(uilibriu, adsortion> Si,ilar to the i,regnation ,ethod' the solid suort is

i,,ersed in an ecess solution o4 dissoled sur4ace oide recursor 4or long

eriods o4 ti,e9 +he do,inant driing 4orces .ithin this reaction are the

concentration gradient and electrostatic interactions9 t is generally thought to

yield better disersion o4 sur4ace ,etal oide oerlayers than i,regnation

!-egalbuto' 200"&9

Gra4ting> =eosition inoling the 4or,ation o4 a strong bond' usually coalent'

bet.een the suort substance and the actie ele,ent9 t is achieed through ache,ical reaction bet.een a 4unctional grou !e9g9 hydroal grous& on the

23


24/93

sur4ace o4 the suort and an aroriately selected inorganic' or organo,etallic

co,ound o4 the actie ele,ent !Louis [ Che' #%%*&9

CoEreciitation> noles reciitating the solid 4ro, a solution containing

soluble recursors o4 both the suort and sur4ace oides9 t is ri,arily 4ocused

around the recursor condensation that 4or,s oides or hydroides .hen the Ho4 the solution changes !-egalbuto' 200"&9

2$


25/93

).) 4ssumptions=ue to the nature o4 the roble, and arious undeBned ele,ents .ithin the

recie' seeral assu,tions hae been ,ade throughout the calculations so as

to gie the best ,odel o4 data9

).).- Mass Balance

• +he ,ajor i,urities .ithin the Bnal roduct consist o4 e2:3' )g:' and

a,orhous carbon9• /,orhous carbon accounts 4or #I o4 the Bnal i,urities9

• /ll carbon in the roduct are CN+s9

• CN+ yield is 28I o4 unuriBed ,ass !)auron et al9' 2003&9

).).) Terminal 3elocity

• +he e2:3)g: density is a co,bination o4 %*.tI )g:' and *.tI e2:39

• +he article dia,eter is #00J,9

• Particle dia,eters are o4 ho,ogenous si6e .hen entering the 3 4or radius to height 4or the colu,n9

• +he N:2 released in the


26/93

Catalyst Prearation)g: O ##2279725g

e!N:3&39%H2: O $37$9#75g(thanol O 7200897*5g

N:2 O #$%$92*5g

(thanol O 7200897*5gFater O #7**9"%5g

e2:3)g: O #20%29#$5g

).).* Pumping

• +he only dros in ressure in the syste, are attributed to the arious

ieces o4 eui,ent9• +he centri4ugal u,s used are only "0I eAcient9

).).' Filter• =ue to a lac5 o4 suorting calculations' the Blter .as not included in the

,ass' energy' and cost balances9 Fhilst it .ould be aluable to hae this

data' the Blter .as included to sho. ho. al,ost all o4 the S): could be

retrieed 4or later use9

).1 Preliminary Mass Balance/ si,liBed ,ass balance oer the catalyst rearation syste, is dislayed

igure #' .hile a ,ore detailed balance oer the syste, can be 4ound in

/endi ;9 t is designed to cater to a roduction rate o4 *0005g o4 roduct erday and thus all the corresonding alues in the ,ass balance are oer a eriod

o4 one day9

Figure '0 Catalyst preparation mass #alance

=ue to the undeBned nature o4 the recie in ter,s o4 the roducts Bnal

co,osition and uality' it is assu,ed the three ,ajor i,urities accounting 4or

*I o4 the Bnal roduct are a,orhous carbon !assu,ed to be #I o4 the total

.aste&' e2:3' and )g:9 +he yield .as deter,ined to be 28I !)auron et al9'

2003& at the syste, seciBcations' thus denoting that the a,ount o4 e 2:3)g:'

the suorted ,etal oide !S):&' reuired .as aroi,ately #20%25g er day9

Fith an iron to ,agnesiu, oide ratio o4 *I this corresonded to $37$5g o4

e!N:3&39%H2:' and ##2285g o4 )g:9

/ substantial a,ount o4 N:2' #$%$5ger day' is 4or,ed 4ro, the degradation o4

e!N:3&39%H2: to e2:39 +his roduct is not reuired on site and could otentially

be sold eternally9 Potential uses 4or N:2 include use as an anesthetic and use

.ithin the auto,otie industry to roided etra o.er to engines9 Fater is also

roduced 4ro, o4 e!N:3&39%H2: and as can be seen in the P=' .ill be used

.ithin the heat echanger CPEH]0# as an etra source o4 energy' thus saing

,oney9

2"


27/93

Fhile a large a,ount o4 ethanol' 7200%5g er day'

P!"#r=$%∆P&'pi(g

p&'p #ffici#(cy

+able 8 gies an esti,ation o4 the total

o.er reuired by drying syste, .hile

+able % gies an esti,ation o4 the total

o.er reuired by the u,ing syste,

!heat echanger ressure dros hae

been esti,ated !Che Plus&&9 urther

energy calculations can be 4ound in

/endi ;9

Ta#le '0 Power re:uirements 5or drying Ta#le +0Power re:uirements5or pumping

27

%ame

CPCP7-

CPCP7)

s-" #9#8# 09*0"

@P CP

/G7)

E 300000

@P CP/G7)

E 300000

@P CP

C7-

#$0*97

7

E

Total 297"75

F

#8925F

%ame PowerCPD7- 3$39#"5

F

CP

DC7-

*%*93*5

F

CP

/G7-

E$*9835F

CP

/G7)

E

78#9875F

Total ##098#5

F


28/93

+he total energy use is #3#985F9 +his is a realistic a,ount o4 energy 4or a

rocess o4 this scale and .hilst 4urther energy saings can be ,ade by

increasing the eAciency o4 the co,onents' a large saings in energy could only

co,e 4ro, the alteration o4 the design9

).9 Preliminary Process Flow Diagram +he reli,inary rocess


29/93

Figure C atallst preparation FD

2%


30/93

).> Design Calculations

).>.- Fluidisation and Terminal 3elocity

+he batch deBned by )auron et al9' 2003' inoles dissoling )g: and

e!N:3&39%H2: in ethanol be4ore ,iing together and sonicating to roduce aho,ogenous roduct9 +his rocess ta5es aroi,ately 20 ,inutes9 ollo.ing

this the S): roduct is dried' and then grinded into a Bne o.der9 or a scaled

u rocess o4 *00o5g er day this is not 4easible and thus alternatie ,ethods

,ust be e,loyed9

Co,bing single article hysics .ith ;- technology' this roble, can be

oerco,e and roide continuous roduction o4 the S): catalyst9

;e4ore designing the ;-' the ter,inal elocities o4 the S): and )g: .ere

deter,ined9 +hese t.o alues are i,ortant .ithin the ;- as a di1erent

ter,inal settling elocity .ould allo. the 4aster one to sin5 .hile the other tostay susended in the solution9

Ta#le -70Hey 5actors 5or designing a FB2

Density Ag m

1"

Shae

Fe)O1 *2$0 trigonal

)g: 3*80 cubic

Fe%O1"1.+/)O #"80 ,onoclinic

(thanol 78% E

Fe)O1=MgO 3""3 trigonal

Fhilst there is no seciBc density o4 the S): catalyst' it suggested that there is

#E" .t9I uta5e rate !Stobbe et al9' #%%#& o4 the e in the e2:3)g:

co,bination' .hich corresonds to the *I ratio used .ithin the recie9 /ssu,ing

the e2:3 is deosited on the inside o4 the )g:' a density can be esti,ated using

the alues in +able #0by>

Catalyst )#(sity=0.05%5240+0.95%3580=3663 *g '−3

=eter,ining the drag coeAcient using euation #9# 4or both the )g: and the

S): and then substituting the, into euation #92 gies ter,inal elocities o4

090*32,sE# and 090*#7,sE# 4or the S): and )g: resectiely9 +he ter,inal

elocity o4 the e!N:3&39%H2: is not reuired because it is less dense than the

)g: and is assu,ed to hae a ,uch lo.er ter,inal elocity and hence .ill not

be a roble,9

C D= 4 g ) p

3

ρ ( ρ p− ρ )3 +

2 1.1

30


31/93

V t =ℜ p + ρ ) p

1.2

+he signiBcance o4 these alues cannot be stressed enough9 +hey i,ly that

roided the 3 4or

the radius to height .as ai,ed 4or9

H = ∆ P

(1−ε )% ( ρ p− ρf ) % g1.5

+he Bnal and ,ost i,ortant calculation .as the deter,ination o4 the ,ini,u,


32/93

ter,inal elocity o4 the )g: because i4 it is not then the graity settling is no

longer be a iable otion as the )g: articles .ould also settle out and 4urther

rocessing .ould be reuired9

U 'f =

( ρ p− ρ ) % g % ) p2

1650% + 1.6

+he ,ini,u, reactor olu,e o4 7%9%$L .as si,ly deter,ined 4ro, the crossE

sectional area ,ultilied by the height o4 the reactor9 Ho.eer i4 one .as to

assu,e that the reaction reuires 4resh ethanol then the olu,e .ould be closer

to #37#L' in .hich case the di,ensions .ould be di1erent to those currently

stated9 n this case the olu,e o4 7%9%$L .ill be used so as to reduce the cost o4

the lant9

Proided the ;- is oerated at aroi,ately 2#9#C or aboe !easy as this is

al,ost roo, te,erature&' the N:2 in the solution .ill boil and can be collected

4or sale9

).>.) Slurry

/4ter the ;- the S): .ill co,e out as a slurry in a .aterethanol solution .ith a

ratio o4 #98%I to %89##I resectiely9 +he iscosity o4 a slurry can be ,easured

i4 the articles settle slo.ly9 or dilute susensions o4 Bne articles' slurries ,ay

ehibit Ne.tonian behaiour9 n this case' the iscosity o4 a ery dilute

susension !solids olu,e 4raction less than 2I& o4 uni4or,' sherical articles

can be described by the theoretical euation deried by (instein !(instein'

#%0"&9

+s= + f % (1+2.5C v )1.7

Soling this euation gies a resulting solution iscosity o4 0900#3Pa9s' a ,inor

change 4ro, the reious iscosity o4 0900#2Pa9s9 +his increase' though ,inor'

.ill increase the a,ount o4 4riction in the ie and hence the a,ount o4 o.er

reuired to u, the


33/93

this case .ill result in lo.er o.er reuire,ent and hence cost less to run

!-hodes )9 ' #%%8&9

).>.1 /ydrocyclone

/ hydrocyclone oerates ery si,ilarly to a cyclone' .ith the only di1erence

being that instead o4 a gas as the


34/93

Cyclonetype

/ ; C ( L N

Stairmand( /.E.

$ 29* 09* 0937*

09* 092 09* 09*

Final 09$0

2

092*

#

090*

0

0903

8

090*

0

0902

0

090*

0

090*

0).>., Drying

+he drying stage is the ,ost energy intensie stage .ith the catalyst rearation

syste,9 t is here that the ,ajority o4 the running costs .ill be incurred9 t

consists o4 t.o di1erent drying aaratuses' a traditional dryer and a distillation

colu,n9 +he di,ensions o4 these t.o syste,s hae not been resented' ho.eer

the ,ost i,ortant asect o4 energy consu,tion has9

+he ,ethod o4 drying inoles the %0I S): strea, and its resectie

.aterethanol solution being dried in a traditional drier9 +he S): is then carried

on to.ards the net syste,' .hile the .aterethanol gas


35/93

capital !"

Seeral assu,tions .ere ,ade .hen calculating the costs 4or the eui,ent9Stainless steel .as selected as the ,aterial o4 choice due to is roerties9 t issecure choice as it has high corrosie resistance' tension strengths' andlongeity' desite its slightly higher rice9 +he total hysical lant cost iscalculated 4ro, !Sinnott' 200"& table "9#' g 2*29 t includes the installation'iing' instru,entation' electrical' buildings' utilities' storages' site deelo,entand ancillary buildings9 +he total Bed caital is calculated 4ro, !Sinnott' 200"&table "9#' g 2*29 +his also includes design and engineering' contractorMs 4ee andcontingency9

Fhen co,bining the costs o4 the indiidual co,onents' a total alue "0"'"%0reached9 or a lant o4 this scale the total cost aears so,e.hat lo.' ho.eerthe si,le elanation eists that this is a reli,inary reort and ariousco,onents .ere le4t out so as to roide greater detail on the ,ajor eui,ent

ieces .ithin the lant9

).' Conclusion +he scaling u o4 a literature recie to a *0005g er day lant is diAcult9 )ajor

challenges included selecting the correct eui,ent so as to ,ini,ise initial

costs and running costs9 +he eui,ent chose .ithin this reort costs a total o4

"0"'"%0 to urchase and install .hile the o.er reuired 4or the lant is

#3#985F9 / ,ore detailed cost analysis is reuired so as to deter,ine the costs

o4 ,aterials as .ell as the selling rices o4 the otential roduct9 Labour'

,aintenance' and other utilities also need to be calculated to get close to a

realistic esti,ate o4 econo,ic 4easibility9 +his chater 4ocused on the design and

calculations rocess oer the econo,ic 4easibility o4 the lant' thus i4 a ,ore

detailed analysis o4 the Bnancial situation o4 the lant is desired' then 4urther

inestigation is reuired9

1. Fluidised Bed 2eactor

1.- Description o5 t6e #asic tec6nology and its purposen this design )ulti.all Carbon Nanotubes !)FCN+& are roduced usingChe,ical ?aour =eosition !C?=&9 C?= is a ,ethod in .hich a gaseous

hydrocarbon is crac5ed into carbon and hydrogen by ther,al degradation using

a transitional ,etal catalyst9 Fhen using a


36/93

Figure --0 diagram o5 t6e FB2

+he Bgure aboe is a basic i,age o4 the ;- being used9 !-e4er to section 39" 4or

P=& +he ;- runs in 30,in batches ensuring that those reactants are in contact

.ith each other 4or the 20 ,in residual ti,e9 +he gas ! argon and acetylene&

enter the ;- through the strea,s called argon inM and acetylene inM9 ;e4ore

entering the ;- the gases are stored in tan5s at double the at,osheric

ressure9 +he catalyst !e2:3 and )g:& enters the ;- 4ro, a buc5et coneyer

belt 4ro, the solid 4eed strea, aboe9 +here is an auto,atic ale at the

entrance o4 the solid 4eed strea, to the ;- .hich is only oened 4or the Brst 30

sec o4 each batch to ensure that all the catalyst reuired reacts and contacts thegas 4or the reuired a,ount o4 ti,e9 +here is another ale at the eit o4 the ;-

into the solid discharge strea, !through .hich the CN+ and catalysts and

a,orhous carbon are released&9 +he ale is only oened 4or the last #0,ins o4

each batch and the solid discharge 4alls directly to a tan5 .here the s,aller

a,orhous carbon !ujita' shida' chihashi' :chiai' aito' [ )atsui' 2003& is

Bltered out and is collected into a tan5 4or disosal9 +here is a ale in the

Bltering tan5 .hich is oened a4ter #0 ,ins to allo. the CN+s K catalyst to 4all

into another tan5 to be uriBed !see section *&9 +he gas out strea, contains

hydrogen gas' argon' and a ,inute a,ount o4 CN+ and catalysts9 +his strea, is

connected to the cyclone !see section $&9

1.) 4lternatives to design )ethods to roduce CN+s beside C?= include lastic yrolysis'


37/93

other electrode9 !Chea +ubes nc' 2008&9 /rc =ischarge and laser ablation are

si,ilar in that they both use ther,al energy to roduce CN+s9 Laser ablation uses

a laser source to cause high te,eratures on a carbon electrode so that carbon

is aorised9 +his carbon is then cooled using a carrier gas strea,9 +his results in

the 4or,ation o4 CN+s and other carbon byEroducts9

1.1 $eneral 4ssumptions used in t6e design• n the laboratory design !)auron' (,,enegger' Sudan' Fenger' -entsch'

[ ûttel' luidisedEbed C?= synthesis o4 carbon nanotubes on e2:3)g:'

2003&' 0900#g o4 CN+s .ere roduced er batch9• +he *0005gday roduct being roduced is %*I ure9 !)auron'

(,,enegger' Sudan' Fenger' -entsch' [ ûttel' luidisedEbed C?=

synthesis o4 carbon nanotubes on e2:3)g:' 2003&• +he density o4 the catalysts and the CN+ are all the sa,e in the ;-9

• +he dia,eter o4 the catalysts and the CN+ are all #00J,9• /ll the articles in the ;- are shere shaed9

• =ia,eter o4 the ;- is #9* ,

• /ll the argon that enters the ;- leaes the ;- through the gas outlet9

• /ll the carbon that enters the ;- in the acetylene is in the CN+s

roduced9• /ll the re,aining hydrogen 4ro, the acetylene 4or,s hydrogen gas9

• +he ;- is er4or,ing at "*0:C and no heat is being lost9

• #I o4 the CN+s and catalyst articles are lost 4ro, the ;- through the

gas strea,9•

+he ;- has a cera,ic lining .ith a ,ildEsteel essel9• +he ;- is being run in 30 ,in batched 4or 2$ hrs a day' 3"* days an year9

1., Mass Balances

1.,.- a#oratory scale FB2or the laboratory scale assu,e>

• the gases are entering the ;- at at,osheric te,erature and ressure

• 0900#g o4 CN+ is being roduced

• (ach batch is 30 ,in

+he olu,e o4 argon !/r& going into the ;- is $2c,3 er batch9 !)auron'

(,,enegger' Sudan' Fenger' -entsch' [ ûttel' luidisedEbed C?= synthesis o4

carbon nanotubes on e2:3)g:' 2003& Dsing P?On-+ !assu,ing an ideal gas&'

there is 0900#72 ,oles o4 /r going into the ;- er batch9 !as P O #0#32* Pa' -

O 893#$ ,3Pa!,ol&' + O 2%8 &

+he olu,e o4 /cetylene !C2H2& going into the ;- is 3"8 c,3 er batch9

!)auron' (,,enegger' Sudan' Fenger' -entsch' [ ûttel' luidisedEbed C?=37


38/93

synthesis o4 carbon nanotubes on e2:3)g:' 2003& Dsing P?On-+ !assu,ing

an ideal gas' there is 090#*# ,oles i4 C2H2 going into the ;- er batch9 !as P O

#0#32* Pa' - O 893#$ ,3Pa!,ol&' + O 2%8 &

1.,.) Commercial Scale FB2

+otal roduction o4 roduct er day O *000 5gday

/ssu,ing the urity o4 the roduct is %*I' a,ount o4 CN+ roduced O $7*0

5gday O #0$9#7 5g30,in !assu,ing one batch is 30 ,in and that the rocess is

being run 4or 2$ hrs' 3"* days a year&

1.,.).- $as entering t6e FB2

/ssu,e that the gas is stored in tan5s at double the at,osheric ressure and at

roo, te,erature9

'!l#!f -rc!'i(g∈¿

'!l#s !f -r 1#i(g&s#)∈t,#la1ar!tary %a'!&(t !f pr!)&ct

¿¿1# p r!)&c#) p#r 1atc, 1y Ultra 2a(! ¿a'!&(t pr!)&c#) p#r 1atc,∈t,# la1ar!tary

+hus' ,ole o4 /r reuired er batch O #78%239% ,oles

Dsing P?On-+ olu,e o4 /r going into the ;- .as 4ound to be 2#879" ,330

,in !using P O 202"$0 Pa' + O 2%8 ' - O 893#$ ,3Pa!,ol&&

Si,ilarly the ,oles o4 C2H2 .ere deter,ined to be 3833393 ,olebatch and the

olu,e er batch .as 4ound to be $"89"8 ,39

1.,.).) Catalyst particles entering t6e FB2

ro, Section $ it can be seen that 8"$9$ 5gday o4 e2:3 and ##227972 5gday o4

)g: .ill be reuired9 +his indicates that there is ##2977 ,ole30,in batch o4

e2:3 and "2*#9## ,ole30,in batch o4 )g: entering the ;- !as the ,olar

,ass o4 e2:3 O #*%97 g,ole and the ,olar ,ass o4 )g: O $093 g,ole&9 +hus

er batch there is #890# 5g o4 e2:3 entering the ;- and 2339%2 5g o4 )g:

entering the ;-9

1.,.).1 Particles leaving t6e FB2 t6roug6 t6e solid disc6arge

ro, the beginning o4 Section 39$2 it can be seen that the a,ount o4 CN+ beingroduced er batch is #0$9#7 5g9 t can be assu,ed that the catalysts !2*#9%25g

er batch& are attached to the CN+ articles9 +hus the ,ass o4 the solids in the

;- O 3*"90% 5g er batch9 t is assu,ed that %%I o4 these solids eit the ;-

through the solids discharge strea,9 +here4ore the ,ass o4 the CN+ K catalyst in

the solid discharge strea, O 3*29*3 5g30,in batch9 +he total ,ass o4 the

carbon entering the ;- .as 4ound to be %20 5g er batch9 +he carbon that is

not conerted to CN+ !that is 8#*983 5g er batch& can be assu,ed to be

a,orhous carbon9 +his carbon is s,aller than the CN+ K catalyst articles

!ujita' shida' chihashi' :chiai' aito' [ )atsui' 2003& so it can be Bltered out

be4ore sending the CN+ K catalyst articles to the uriBcation rocess9

38


39/93

1.,.)., $as leaving t6e FB2

/ssu,ing that all the /r entering the ;- leaes the ;- at the gas outlet' ,oles

o4 /r leaing the ;- er batch O #78%239% ,oles9 +he ;- is oerating at "*0:C

!)auron' (,,enegger' Sudan' Fenger' -entsch' [ ^uttel' luidisedEbed C?=

synthesis o4 carbon nanotubes on e2:3)g:' 2003&9 /ssu,ing the /r is an ideal

gas and is leaing the ;- at at,osheric ressure' using P?On-+ the olu,e o4 /r leaing the ;- is #3**#9$2 er batch9

/ssu,ing that all the hydrogen in the C2H2 that enters the ;- beco,es

hydrogen gas that leaes the ;- through the gas outlet' ,oles o4 H 2 leaing the

;- er batch O 38333933 ,oles9 /ssu,ing that the H2 is leaing the ;- at the

sa,e conditions as the /r' olu,e o4 H2 leaing the ;- er batch O 2%0393# ,39

t can also be assu,ed that #I o4 the CN+ K catalysts are lost through the gas

outlet in the ;-9 +hus the a,ount o4 CN+ K catalyst in the gas outlet o4 the ;-

er 30 ,in batch O 39*" 5g !#I o4 3*"90%5g – see section 39$23&9

1.9 Energy Balance0

1.9.- Energy 5rom $as streams0

3%

Figure -)0 mole #alance overt6e FB2 over a 17 min #atc6

$as disc6arge)g: O "29*# ,olee2:3O#9#3 ,oleC !in CN+& O#0$9#7_090#_#03#2,oleO8"980,ole/rO#78%239% ,olesH2 O 3833393 ,ole !that is ,oles o4 HO7""""9" ,ole&

4r gas#78%239% ,oles

Solid disc6arge)g: O "#889"0 ,olee2:3O###9"$ ,oleC !in a,orhous Carbon& O8#*983_#03#2,ole O "7%8*98 ,oleC !in CN+& O#0$9#7_09%%_#03#2,oleO8*%$90,ole

Solid 5eed

)g: O "2*#9## ,olee2:3O##2977 ,ole

C)/) gas O3833393 ,oleC O 7""""9" ,oleH O 7""""9" ,ole

Figure -10 energy #alance over FB2 re5er to

Ta#le -1 5or calculations

/eating re:uired #y t6e FB2 Oenergy in – energy out !assu,ing noheat loss&O !*#298$K%223"#8"9#&E!2#$#9$*K0K$8289%$&FO%222%7289**

$as disc6arge*#298$F

Solid 5eed

2#$#9$* F Solid disc6arge%223"#8"9# F

C)/) gas $8289%$F4r gas

0 F


40/93

Ta#le -10 calculation o5 energy per stream

Strea, H4 ̀ C ∫C P ) + ^ H +otalenergy

4ro,

strea,

a b c d

C2H2 strea, going in 22"97*

,ole

N/ N/ N/ N/ N/ 2*:C 22"97*

,ole

$8289%$F

/r strea, going in 0

,ole

N/ N/ N/ N/ N/ 2*:C 0 ,ole 0 F

Catalysts

going in

)g: "0#98

,ole

N/ N/ N/ N/ N/ 2*:C "0#98

,ole

208%9%*F

e2:3 82292

)ole

N/ N/ N/ N/ N/ 2*:C 82292

)ole

*#9*0 F

+otal 2#$#9$*

F

Gas

discharge

strea,

/r 0 ,ole

#93$3%_#

0E*

E

#9%8%$_#

0E3

##90$3 0 298_#0% "*0:C 27%70"%92

# ,ol

27803$7*8

9* F

)g: "0#98

,ol

#098" 0900##%7 0 208700 77#89$* "*0:C 832092"

,ol

2889%* F

e2:3 82292

,ol

2$972 090#"0$ 0 $23$00 22*3293* "*0:C 233*$9**

,ol

#$9"3F

H2 0 ,ol 392$%

09000$22 0 8300 22#09*0$ "*0:C 22#09*0

,ol

$707*9**

F

CN+!i9e9 C& 0 ,ol #977# 0900077# 0 E8"700 #20$90* "*0:C #20$90* *#298$F

$0


41/93

,ol

+otal 278082"*0

9*

Solid

discharge

)g: "0#98

,ol

#098" 0900##%7 0 208700 77#89$* "*0:C 832092"

,ol

28"0*9%*

F

e2:3 82292

,ol

2$972 090#"0$ 0 $23$00 22*3293* "*0:C 233*$9**

,ol

#$$89$%

F

C!including

CN+ and

a,orhou

s&

0 ,ol #977#

0900077# 0 E8"700 #20$90* "*0:

C #20$90*,ol

%220"#3#9"$ F

+otal %223"#8"9

#

!Coulson' -ichardson' ;ac5hurst' [ Har5er' #%*$& !Perry [ Green& !Finni5' #%%7&`re4erence te,eratureO2*:C

$#


42/93

1.> Preliminary PFD

Figure -,0 PFD o5 t6e FB2 design re5er to section 1.- 5or description"

$2


43/93

1.* Design CalculationsDsing the conditions deter,ined in section 39$2 the density !09$382 5g,3& and

iscosity !090000*03 Pa& o4 the gas in the ;- .as deter,ined using Hysys9

ro, section 39$22 the calculated ,asses o4 e2:3 and )g: entering the ;-can be obsered9 +he density o4 e2:3 !*2$0 5g,3 !(niron,ent' Health [

Sa4ety E DS' 2007&& and )g: !3700 5g,3 !Science S+u1 inc& enables the

esti,ation o4 the olu,es o4 the catalysts entering the ;-9 !0900$8"7232 ,3 o4

e2:3 and 090$$"3%$82 ,3 o4 )g: er each 30 ,in batch&9 +he density o4 CN+ is

#300 5g,3 !Physical roerties o4 carbon nanotubes&9 Dsing this the olu,e o4

the CN+ .as 4ound to be 0907832#,3 er batch9 Dsing the total olu,e and

total ,ass o4 the CN+ and the catalysts the aerage density o4 articles in the

;- .as deter,ined to be 278*9"85g,39

D,4 !090032%0 ,s& .as calculated using these densities and iscosities9 Since

the


44/93

U

2(¿¿ 2)

g)BV =¿

U B=∅ -(g ) BV )0.5

",#r#∅ -=2.5as D>1'

Dsing ε B=U −U 'f

U B Y; .as 4ound to be 09$3289 +he Y,4 .as assu,ed to be 09$

!-hodes )9 ' 2008&9 +hus using !#EY&O!#EY;&!#EY,4 & the oidage in the ;- can be

deter,ined9 +his allo.s 4or the deter,ination o4 the bed density %$890%5g,3 !as

bed density O !#EY&_article density&9 /s the ,ass o4 the articles in the bed is

5no.n !3*"90%5g30 ,in& the olu,e o4 the bed can be deter,ined !0937*" ,3&9

Dsing this and the crossEsectional area o4 the bed the height o4 the bed can be

deter,ined as 092#3,9

/ssu,ing D,4 OD,b !-hodes )9 ' 2008& DED,b O 098309 Dsing this and the #9*,

;- dia,eter the +ransort disengage,ent height !+=H& is deter,ined to be 39*, !Bgure #7E8 !Perry [ Green&&9 /ssu,ing the slash 6one is #0I o4 the +=H'

and the dilute transort height is *0I o4 the +=H' the slash 6one height O

0902#, and the dilute transort height O #97*,9 +his results in a total 4reeboard

height o4 *927#,9 +he height o4 the lenu, cha,ber is assu,ed to be 097 , to

allo. roo, 4or ,aintenance .hen reuired9 +he uart6 layer lace in bet.een

the siee and the bed can be assu,ed to be 09003, !)auron' (,,enegger'

Sudan' Fenger' -entsch' [ ^uttel' luidisedEbed C?= synthesis o4 carbon

nanotubes on e2:3)g:' 2003&9 +his results in a total height o4 "9#87,9

$$


45/93

Figure -90 /eig6ts o5 t6e FB2 26odes M. ( )77'"

+he ressure dro oer the ;- is then calculated to be #%7"9$$ Pa using

∆ P= H (1−ε ) ( ρ p− ρf ) g 9 Gien the ressure dro oer the cyclone is #0$%9#$#Pa !see section $& and that that gas leaes the ;- at the to at at,osheric

ressure' the assu,tion that the inlet gas is ressurised to 2 at, is a suAcient

assu,tion9 +his is because the addition o4 the ressure dro oer both the ;-

and cyclone to the at,osheric ressure !#0$3$*9*8 Pa& is less than 2 at,

!202"$0 Pa&9 +his conBr,s the ie. that this ressure .ill be enough to cause a

driing 4orce that 4orces the gas to ,oe into the ;- .hen the ale at the gas

inlet to the ;- is oened9

+he solid 4eed strea, is a buc5et coneyer that ,ust carry 2*#9%25g to the ale

at the ;- by the ti,e each ne. batch begins9 +his it can be assu,ed that the

coneyer ta5es 20 ,ins to carry all the ,ass to the ale9 +here .ill be #0 ,ins

in bet.een each batch 4or the coneyer9 +hus the coneyer belt needs to be

able to carry 092# 5g,in o4 the catalyst to the ale at the ;-9 +his ale .ill

oen 4or 30 secs ensuring that all the catalyst 4alls into the ;-9

+he ressurised tan5s 4ro, .hich the /r and the C2H2 enters the ;- ,ust be

large enough to hae enough gas to last a .ee59 +hus the /r tan5 ,ust be large

enough to hae 73*03"93,3 !2#879"07%*_2_2$_7& .hile the C2H2 tan5 ,ust belarge enough to carry #*7$7"9% ,3 !$"89"8#_2_2$_7&9

$*

+otal heighto4 ;- O

097,

39*,

*927#,

#97*,

0902#,

092#3,


46/93

+he solid discharge 4ro, the ;- dros by graity to a tan5 .hich contains a

Blter that has siees .ith a dia,eter o4 8n,9 +his is so the a,orhous carbon

!.ith a dia,eter o4 *n, !ujita' shida' chihashi' :chiai' aito' [ )atsui' 2003&&

4or,ed in the ;- can be searated 4ro, the CN+ and catalyst articles9 +he

discharge straight 4ro, the ;- .ill stay in the 2 ,3 Blter tan5 4or * ,ins9 +he

a,orhous carbon .ill be collected and disosed o4 /4ter the *,ins a ale .illoen .hich .ill allo. the CN+ K catalyst articles !3*29*2*$5g30 ,in batch& to

,oe into another 2 ,3 tan5' 4ro, .here they .ill be uriBed !see section *&9

n designing the 4urnace used 4or this heat echanger' it can be assu,ed that

coal .ill be used as the 4uel9 +hus the seciBc heat caacity o4 carbon can be

used9 /n assu,tion can be ,ade that the coal .ill be heated 4ro, 2*:C to

"*0:C9 +he ,ass o4 carbon reuired .ill be %#%92 5gs

!%222%7289**_#2#20$90_#0005gs&9

1.' Preliminary costs estimatesTa#le -,0 Purc6sed costs( Total p6ysical costs and total &xed costs o5 t6ee:uipment

4r Feed

tan

A C


47/93

l

cost

s C


48/93

Ta#le -9 Particle SiKe and Separation Tec6ni:ue 26odes( )77'"

Particle SiKe Separation Tec6ni:ueL-77m Graity settling techniues

N-7m iltration' Fet Scrubbing or

(lectrostatic Preciitation

L-7m and as large as -mm Gas cyclones

t can be seen 4ro, +able #* aboe' a gas cyclone .ould be the ,ost suitable

technology to use' as it can easily re,oe the catalyst articles and the catalyst

articles .ith the CN+s still attached' and this solids strea, can then be ta5en to

the net stage 4or uriBcation9 +he cleaned gas' contained carbon nanotubes can

be disosed o4' by burning the, in a 4urnace9

+he reerse


49/93

,.) 4lternative 5or design

Separating arger Particles

Searation techniues' such as Graity Settling or ilters can be used be4ore the

unclean gas enters the cyclone' to re,oe the larger articles' such catalyst

articles and catalyst .ith CN+ articles attached' .hich otentially haedia,eters greater than #00J,9

Separating Smaller Particles

/dditional searation deices' such as electrostatic reciitators' .et scrubbers

or 4abric Blters could also be e,loyed do.nstrea, to hel re,oe ,ore o4 the

Bner CN+ articles still le4t in susension9 +his use o4 this alternatie deice

should be considered' as gas cyclones are not al.ays suitable 4or searation .ith

a large uantity o4 articles less than #0J,9 Since CN+ articles are ery Bne'

they can easily brea5 a.ay 4ro, the catalyst' and there4ore' on occasions' the

gas


50/93

,., Mass Balance

Figure -* Standard Per5ormance Curve 5or Stairmand /ig6 Flow 2ate Cyclone

at a given particle diameter Sinnott( )779" pg ,9-"

ro, igure #7' it can be deter,ined that the eAciency o4 Stair,and H9- cyclone

is around 70I9 +his ,eans that 70I o4 the ,ass o4 articles in .ill be catured

and .ill eit the cyclones ia the solids outlet' and the re,aining 30I o4 the

articles stay susended in the gas9

)ass !articles in& O #9878gs

)ass !articles out ia solids& O 70I #9878gs

O#938*gs

)ass !articles out .ith gas& O 30I #9878gs

O09*%gs

ro, this' it can be reco,,ended that 09*%gs o4 clean gasM can be added to the


51/93

Figure -' Mass Balance over t6e two cyclones

)ass o4 articles accu,ulated oer the reaction ti,e o4 30 ,inutes>

• +otal )ass o4 solids in O 39*"#5g30,ins

• Solids !to 4urnace& O #90"25g30,ins

• Particulates !in clean gas& O29$%35g30,ins

*#


52/93

,.9 Process Flow Diagram

Figure -+ $as Cleaning Process Flow Diagram

*2


53/93

Dnclean gas e,issions 4ro, the ;- enter t.o cyclones in arallel so that the

gas can be cleaned by re,oing the articles in susension 671clone ! and

71clone 28 +he solid articles collected at the botto, o4 the cyclone contain

catalysts and catalyst .ith CN+ articles still attached9 +hese solid articles are

ta5en to the uriBcation section' so that CN+s collected 4ro, the cyclones can be

.ashed and cleaned9 +his strea, ,ini,ises catalyst and CN+ loss through thegas strea,' and also increases the oerall roduct o4 CN+s9

t is reco,,ended that the clean gases 4ro, the to o4 the cyclones are sent to

a 4urnace 4or burning9 ;urning the CN+s articles allo.s C:2 to be released into

the at,oshere' .ith little eniron,ental e1ects9 CN+s are thought to be

carcinogenic' and hae the sa,e e1ects are that o4 /sbestosis9 t is there4ore

i,ortant that the articles are burnt be4ore they are released to the

at,oshere9

?ales' are laced at the gas entrance 6Val.e ! and Val.e 28 and gas eit 6Val.e

3 and Val.e "8 o4 both cyclones' as .ell as the solids eit o4 the cyclones 6Val.e

and Val.e %8 to allo. one cyclone to 5ee running i4 the other is haing

,echanical roble,s' and also' allo. one or both cyclones to shut 4or cleaning'

or scheduled lant shutdo.n eriods9 Chec5 ?ales !7(ec9 Val.e ! and 7(ec9

Val.e 28 are laced in the gas eit strea, to reent bac5 Design Calculations

,.>. Calculation Met6od +he total unclean gas


54/93

/ 4ull .or5ed ,ethod' 4or t.o cyclones in arallel .ith cut dia,eter o4 #0J, oer

both the Stair,and H9( and Stair,and H9- are sho.n belo.9

,.>.) Cyclone Diameter and Dimensions

ro, this assu,tion o4 the article cut dia,eter' Cyclone =ia,eter' =' can be

calculated' using the euation belo.' by ,aniulation o4 both the cut dia,etereuation and the characteristic elocity euation and soling si,ultaneously9

$

2:

;<

π =

and

I

,

St <

:

ρ

µ #8d2

c =

I

,

St :

<2

cd

#8

ρ

µ =

I

, St

:

:

;2c

2 d

#8$

ρ

µ

π =∴

3

2

#8

$

µ π

ρ

I

c ,

St

d;:=

/ .ell designed cyclone is assu,ed to hae a dia,eter o4 around 093,E#93,9

!-hodes' 2008&

Ta#le -> Diameter Calculation over Stairmand /.E and Stairmand /.2 Cyclones

Stairmand /.E Cyclone Diameter Stairmand /.2 Cyclone Diameter

3

2

#8

$

µ π

ρ

I

c ,

St

d;:=

3

2$#00339*#0$9##8

00000903*79$0232

#$9%$

−−×××××

×××

=π

:

D ).-7m

3

2

#8

$

µ π

ρ

I

c ,

St

d;:=

3

23#00339*#0"#8

00000903*79$0232

#$9%$

−−×××××

×××

=π

:

= O 097*,

:nce' the cyclone dia,eter is deter,ined' the di,ensions listed belo. can be

deter,ined relatie to the dia,eter length9

Dimension etter 2e5erence

in Figure )7 #elow"Diameter o5

Cyclone

=


55/93

Outlet lengt6

Outlet diameter N

Cylinder 6eig6t C

Overall 6eig6t /

Dust outlet

diameter

(

Conical /eig6t ;

Figure )7 Cyclone Dimensions

+able #7 belo. sho.s the di,ensions 4or both Stair,and H9( and Stair,and H9-

cyclones 4or the calculated cyclone dia,eters o4 29#0, and 097*, resectiely9

Ta#le -* Dimensions o5 Stairmand /.E and Stairmand /.2 Cyclones

Dimensions

Dimensions2elative to

Diameter /.ECyclone"

Stairmand/.E

Cyclonem"

Dimensions2elative to

Diameter /.2Cyclone"

Stairmand/.2

Cyclonem"

4 $90 = 893%0332 $90 = 390207*B 29* = *92$3%*7 29* = #9887%"8C #9* = 39#$"37$ #9* = #9#3278#E 0937* = 0978"*%$ 09*7* = 09$3$233 Q 09* = #90$87%# 0987* = 09""078% 092 = 09$#%*#7 0937* = 09283#%*

H 09* = #90$87%# 097* = 09*""3%#% 09* = #90$87%# 097* = 09*""3%#

**


56/93

,.>.1 Cyclone 3elocity

:nce the dia,eter o4 the cyclone is 4ound' the characteristic elocity is then

calculated using either the characteristic elocity euation sho.n belo.9

$

2:

;<

π =

+yical elocity 4or .ell designed cyclones is around #0E20,s !Sinnott' 200*&

Ta#le -' 3elocity Calculation over Stairmand /.E and Stairmand /.2 Cyclones

Stairmand /.E Cyclone 3elocity Stairmand /.2 Cyclone 3elocity

$

2:

;<

π =

#0922

#$9%$

2×

×

=π

<

7.>>m=s

$

2:

;<

π =

7*902

#$9%$

2×

×

=π

<

D O #0920,s

,.>., Pressure Drop

/ ressure dro is then calculated by the ,aniulation o4 the (ulerMs nu,ber

euation' sho.n belo.9

2

2

<

&='

g ρ

∆=

2

2> Pa

2

2


57/93

,.>.9 Summary o5 2esults

+able 20 belo. sho.s a co,arison o4 the calculated results 4or both Stair,and

H9( and Stair,and H9- cyclones .ith a total


58/93

Figure )- Dimensions o5 Designed Cyclone

Cyclone =ia,eter O 097*,

nlet O 09*7, 0928,

:utlet O 09*7,

Cylindrical Height O #9#3,

Conical Height O #98%,

,.>.* Cyclone ERciency

Cyclone (Aciency .as deter,ined using the cure sho.n in igure #7 in the

,ass balance section9 +he cure sho.s that at a article si6e cut dia,eter' the

eAciency o4 the cyclone is around 70I9

,.* Cost Estimate

,.*.- Cyclone Cost

+able 2# belo. sho.s the costs 4or 2 Carbon Steel Cyclones' each .ith

olu,etric gas rate o4 $9*7,3s .as deter,ined using igure #*E$8 !Peters'

+i,,erhaus' [ Fest' 2003& g 8"89 t includes the ruchase cost' +otal Physical

Plant Cost and +otal ied Catial Cost9

Ta#le )- Costing Cyclones

Cost For Two Cyclones

Purc6ased Cost ##'800

*8


59/93

!*'%00 each&

Total P6ysical Plant Cost ###'*#0 C+/+:N Pet03 Zl 308#

Total Fixed Capital Cost #*"'##$ C+/+:N Pet03 Zl 308#

ull .or5ed alues can be 4ound in /endi /39

+otal Cost o4 Gas Cleaning Syste, O #*"'##$ !DS&

,.*.) Furnace Cost

Purchase Costs o4 urnaces range bet.een *$0 to *"09 !Sinnott -9 ' 200"&

Conersion o4 this alue into /ustralia dollars .ith ary each day' deending on

echange rates9

Conclusiont can be seen 4ro, the design calculations that haing t.o Stair,and H9-

cyclones in arallel .ith a cut dia,eter o4 #0J, is a .ell suited design to the

needs o4 our rocess9 +his is due to the 4act that the dia,eter and di,ensions o4

the cyclones' the elocity and the ressure all lie .ithin the tyical alues range9

+he cyclone also oerates .ith a high eAciency o4 70I9 (lectrostatic

reciitators are not necessary in this rocess' as they are ery energy intensie

and eensie' just the eui,ent costing #009700!DS& !4or carbon steel& 4ro,

igure#*E$8 g 8"8 !Peters' +i,,erhaus' [ Fest' 2003&9 +he t.o cyclones are a

,uch cheaer otion costing only *'%00 and a total Bed caital cost o4

#*"'##$9 ;y ,ass balance calculations' it can be seen that i4 the eAciency o4

the electrostatic reciitator .as oerating at its ,ai,u,' it .ould only recoer

#90"25g er 30 ,inutes !reaction ti,e&' and is there4ore not .orth the cost9

t is reco,,ended that the articles that are not catured by the cyclones are

sent to a 4urnace and burnt9 ;urning carbon .ith oygen 4or,s C:2 and can be

released to the at,oshere in s,all a,ounts9

Sa4ety is also an i,ortant 4actor .hen using cyclones to clean carbonnanotubes articulates 4ro, /rgon and Hydrogen gas9 +he Bne CN+ articles arethought to be carcinogenic' and are thought to hae the sa,e a1ects asasbestosis9 t is there4ore i,ortant that great care is ta5en .hen burning thesearticles' and that they are not released into the at,oshere9 +he gas cyclonesyste, ,ust be chec5ed regularly 4or lea5s9 +his is because hydrogen gas is astable' but ery


60/93

that causes raid breathing' 4atigue' i,aired ,uscular coordination andso,eti,es death i4 it is released in a conBned sace !;:C Gases' #%%"&9 +hee1ects o4 these gases lea5ing is etre,ely har,4ul to all e,loyees9

"0


61/93

9.Puri&cation

+he uriBcation rocess is one o4 the ,ost i,ortant arts o4 the CN+

,anu4acturing rocess' trans4or,ing the i,ure ra. CN+s into the

roduct to be sold to the consu,er9 / urity o4 %*I is reuired 4or the

alication o4 the CN+s in consu,er electronics' and so a robust

uriBcation rocess is essential9 +he uriBcation rocess is inherently

si,le due to the solubility o4 the ,agnesiu, oide substrate used9 +he

uriBcation rocess .ill 4ocus solely on the re,oal o4 the catalyst and its

substrate' assu,ing that a,orhous carbon is resent in such s,all

a,ounts as to be negligible9 +he rocess is run as a continuous rocessas this is a ,ore co,,ercial iable ,ode o4 oeration' reducing both the

caital eenditure co,ared to a batch rocess' and also roiding the

ossibility o4 scale u9

9.- Description o5 Process and Tec6nology +he rocess can be bro5en do.n into 3 ,ain stes' each .ith seeral unit

oerations

• >cid &'ri*cation ? +his stage inoles ,iing the unEuriBed CN+

roduct .ith concentrated HCl to dissole the catalyst and itMssubstrate' under ,icro.ae assisted digestion9

• Filtration ? +he net ste re,oes the CN+ articles 4ro, the slurry by

hysical searation9 =uring this searation ,ost o4 the .ater resent

and all o4 the acid and dissoled substrate are re,oed9• r1ing ? +he last stage dries roduct through ther,al eaoration to

roduce the ready to shi roduct9

9.-.- 4cid Puri&cation

Since the CN+ synthesis rocess is a batch oeration' +he Brst ste in designingthe continuous rocess is to insert a ra. CN+ holding tan5 holding' so the ra.

CN+Ms can be deliered to the uriBcation rocess in a continuous strea,9 +he

CN+Ms are 4ed by graity into a stirred tan5 .here they are ,ied .ith the

concentrated HCl !$0 .t I& and u,ed into a Plug lo. -eactor .here they are

rocessed 4or 30 ,inutes9 +he P- is Btted .ith ,icro.ae e,itters to roide

the energy to ,aintain the reaction te,erature at #"0C9 +his increases the

reaction 5inetics and allo.s such a short residence ti,e .ithin the digester9 +he

resulting slurry is then .ashed .ith distilled .ater oer a cellulose nitrate Blter

beds to re,oe the re,aining HCl and the dissoled catalyst and itMs substrate9

Fhile the ores in a cellulose nitrate ,e,brane Blter are larger than the #

"#


62/93

,icron si6e o4 the nanotube agglo,erations' an initial layer o4 nanotube articles

.ill Bll the ores not allo.ing any o4 the articles to escae

9.-.) Filtration +he Bltration rocess uses a screen bo.l decanter centri4uge to 4orce the

nanotubes to sedi,ent out o4 solution9 / decanter centri4uge' .ill oerate by

4eeding the slurry into the centre o4 the hori6ontal centri4uge' .here the solids

settle at the edges and are re,oed by a helical scre.' rotating a di1erent seed

4ro, the centri4uge9 +he tye o4 decanter centri4uge used is a secialised tye o4

centri4uge called a screen bo.l centri4uge9 n this tye o4 centri4uge an etra

screen is added at teh solids collection outlet allo.ing etra .ashing o4 the solid

.ith ure .ater9 t is in this ste that the ,ajority o4 the .ater' the re,aining HCl

and the dissoled ions are re,oed9 C+/+:N Pet03 Zl 308# +he liuid is discharged to

.aste .ater treat,ent and recycling .hile the sedi,ent ,oes on to the Bnal

drying rocess9

9.-.1Drying

+he ca5e 4ro, the centri4uge is then 4ed into the rotary dryer' .here any

re,aining ,oisture is re,oed by the assage o4 dried air9 +he Bnal granular

roduct is the ,oed by coneyor belt to roduct storage 4ro, .here it can be

shied9

9.) Mass=Energy Balance +he ,ass balance .as calculated based on a roducing *000 5gday o4 %*I ure

carbon nanotube roduct9 +he ,ass balance .as conducted using the si,li4ying

assu,tions #E7' 4ro, section *989 +he su,,ary o4 the ,ass balance is listed in

section *92 .hile calculations and ecel sreadsheetMs are detailed in aendi 9

/ si,le energy balance .as calculated to deter,ine the te,erature o4 each

strea,9 /ssu,tions ##E#2 4ro, section *98 .ere used to calculate the energy


63/93

9.1 Process Flow Digram

"3


64/93

9., Design Calculations

/'1 Storage !an8s

/s the synthesis o4 CN+s is a batch rocess' a reseroir o4 the unEuriBed CN+

roduct ,ust be stored to roide a continuous 4eed to the uriBcation rocess9

our batches or t.o hours o4 roduct are to be stored' i9e9>

? ¿

2,r %7.06 *g

,r

2785.68 *g

'3

O09*#,39 Dsing a sa4ety 4actor o4 2*I to account 4or any

rocess disrutions ?O09"8,39 or a #9* , high tan5 this corresonds to a

dia,eter o4 097",

+he HCl storage tan5 is constructed o4 ibreglass -ein4orced Plastic !-P& in order

to .ithstand the corrosie e1ects o4 concentrated acid9 +he HCl tan5 .ill hold 2

days storage lus the sa4ety ,argin9

"$


65/93

? ¿2)ay %58550.8

*g

)ay

1035 *g

'3

O##3,3 O #*098,3 .ith sa4ety 4actor9 or a tan5 o4 this

si6e #2 , high the dia,eter ,ust be $, to gie the reuired olu,e9

Hl Storage !an8

Material o5

Construction

-P

/eig6t #2,

Diameter $,

/'2 Mi@er

Dsing assu,tion #"' .ith a residence ti,e o4 092* hour and


66/93


67/93

#owl lengt6 093$ ,

#owl diameter 09## ,

#owl speeds %00E2000r,

Flow rate %2 5g,in

n order to characterise the er4or,ance o4 the centri4uge' the caacity alue

.as calculated 4ro, euation %9#% !C[- 2& C+/+:N )au03 Zl 308# 9

!3&

+he ter,inal sedi,entation elocity u0 .as calculated 4ro, euation $

!$&:nce u0 .as 4ound euation 3 could be reEarranged to Bnd the sig,a alue o4 89*2

/'/ Aotar Drer

n order to calculate the di,ensions o4 the rotary drier the 4ollo.ing data .as

used>

nlet air te,erature !assu,ed& "*0

nlet roduct te,erature !4ro,

,ass balance&

28"9%

Solid te,erature rise !assu,ed& #"3

+he energy reuired eaorate the ,oisture in the Blter ca5e .as calculated to

be

pr!)&ct ∈¿ )#" pt − ¿

¿$"at#r='li3 C p li3&i) ¿

Fhile the energy reuired to heat u the solid granules .as calculated as>

pr!)&ct ∈¿ pr!)&ct !&t − ¿

$s!li)='C p s!li)¿

"7


68/93

+his led to the oerall heat duty o4 the dryer

$t!t al=$"at#r+$ s!li)

$t!tal=2931.1 *4

ro, here a seciBc gas


69/93

/' u"ps

1-2

Material o5

Construction

Carbon steel

Flow rate 0900#,3,in

Pressure drop

ERciency

Power

9.> 4lternative Designs +here are ,any di1erent design alternaties 4or the uriBcation rocess9 Starting

.ith the acid digestion' it has been sho.n that the tye o4 acid used has little

e1ect on the rate and etent o4 uriBcation C+/+:N )au03 Zl 308# ' and so a ariety o4

di1erent ,ineral acids !H2S:$' HCl' HN:3& can be used in the digestion rocess9

HCl .as used as it .idely aailable .ith .ell docu,ented roerties9 t is also a

ery strong acid' 4ully deErotonating in .ater9

:nce the tye o4 acid .as chosen the ,ethod o4 acid digestion also has to be

deter,ined9 +here are ,any otions 4or the acid digestion' including large

CS+-Ms and acid re

"%

1-1

Material o5

Construction

-P lined steel

Flow rate 090$ ,3

,in

Pressure drop

ERciency

Power


70/93

/61 !an8s and Mi@ers

Ta#le ), Summary o5 Costs 5or tanAs and mixers

Aaw rodu#t

Storage

Hl

Storag

e !=!9 et-3 >l 3-?1

Mi@er (with

agitator

) !=!9 et-3 >l 3-?1

Purc6ased

Cost C


71/93

/63S#reen Bowl De#anting entriuge

Ta#le )> Costs o5 Sceen Bowl Decanting Centri5uge

/6'Aotar Drer

Ta#le )* Cost o5 2otary Dryer

/6/u"ps

Ta#le )' Costs 5or P-7- and P-7)

1-1 1-2

Purc6ased

Cost C


72/93

$9 ro, )auron et al C+/+:N un08 Zl 308# the yield o4 CN+ to i,urities is

28I9*9 /,orhous carbon ,a5es u #I o4 the unEuriBed

,ass9 C+/+:N )au03 Zl 308#

"9 +he i,urities in the CN+Ms consist solely o4 a,orhous carbon and

catalyst K substrate979 HCl is used at #9## stochio,etry as a sa4ety 4actor to ensure

co,lete consu,tion o4 substrate989 +he a,ount o4 .ater needed to co,letely re,oe all HCl and

dissoled catalyst K substrate is eual the a,ount o4 HCl used9%9 /ll residual HCl and ions in solution are re,oed during .ashing

rocess9#09 /ssu,e Centri4uge re,oes %0I by .eight o4 .ater 4ro,

solution9##9 /ssu,e centri4uge ca5e contains #*I .ater by .eight o4

ca5e9#29 inetic and otential energy changes o4 the strea,s are

negligible9#39 +here are no heat losses oer any o4 the eui,ent9#$9 +he density o4 slurries can be aroi,ated by co,bining the

densities o4 the constituent solids and liuids' ta5ing into account

their ercentage contribution by ,ass9#*9 / stirred tan5 .ill aroi,ate a ,ier9#"9 i4teen ,inutes residence ti,e in the ,ier .ill ho,ogenously

,i the slurry9#79 +he seciBcations 4or a ,ier in a s,all dia,eter tan5 ta5en

4ro, PerryMs C+/+:N )au03 Zl 308# .ill roide ho,ogenous ,iing o4 the

slurry9#89 +he designed centri4uge .ill cature all articles o4 #00

,icron si6e at the olu,etric throughut9#%9 ;y the ti,e the slurry asses to the centri4uge' the ,ajority o4

the acid has reacted' relieing the need 4or -P corrosion rotection9209 +here are no heat losses 4ro, the dryer2#9 +he cost relatie to carbon steel 4or -P is 097* 4or ure -P

and #92* 4or -P lined carbon steel tan59 Calculated 4ro, !Peters' +i,,erhaus' [ Fest' 2003& Bg#2E*3' g**8 4or)aterial adjust,ents based on carbon steel

229+hat the cost o4 the screen bo.l centri4uge 4ro, !Peters' +i,,erhaus' [

Fest' 2003& *g!"+- ,g#%# .ith a solid roduct caacity o4 #5gs .ill

aroi,ate the cost o4 the designed centri4uge9239+hat the cost o4 a Stirred reactor 4ro, !Peters' +i,,erhaus' [ Fest'

2003& .ill aroi,ate the cost o4 the designed P-

9.+ Conclusion/ uriBcation rocess 4or roducing *000 5g day' o4 %*I urity CN+s has been

deeloed9 +he rocess consists o4 storage tan5s 4eeding into a ,ier and a,icro.ae assisted acid digester to re,oe all the catalyst and substrate9 +he

72


73/93

.ater and dissoled solids are then re,oed in a screen bo.l decanting

centri4uge9 +he resulting ca5e is dried in a rotary dryer to roduce the granular

Bnal roduct9 +he design seciBcations 4or these unit oerations hae been

listed9 +he uriBcation section o4 the lant is eected to cost DS#97 ,illion9

73


74/93

Bi#liograp6y;randt9 / ?arco Coreration9 !200$&9 !#"0 ecanting 7entrif'ge -etrieed #0

20' 2008' 4ro, Product seciBcations9

Che Plus9 !n9d9&9 esign considerations for s(ell and t'e (eat e4c(angers9

-etrieed #0 23' 2008' 4ro, Che Plus>

htt>...9cheresources9co,designe669sht,l

Chea +ubes nc9 !2008&9 7aron Nanot'es &rod'ction Met(ods for 7aron

Nanot'es Incl'ding >rc isc(arge @aser 7(e)ical Va,or e,sition and Ball

Milling 1 7(ea, 'es Inc9 -etrieed :ctober 20' 2008' 4ro,

htt>...9a6onano9co,=etails9as\/rticle=O#*"#

Coulson' 9' -ichardson' 9' ;ac5hurst' 9' [ Har5er' 9 !#%*$&9 7o'lson and

Aic(ardsons 7(e)ical =ngineering: Fl'id FloC Heat ransfer and Mass ransfer6Vol')e !8 :4ord> Perga,on Press9

(instein' /9 !#%0"&9 =ine ne'e Besti))'ng der Mole9'ldi)ension /nn9 Physi59

(niron,ent' Health [ Sa4ety E DS9 !2007&9 Ferric O4ide9 -etrieed :ctober 20'

2008' 4ro, htt>...9jtba5er9co,,sdsenglishht,l4#30"9ht,

ujita' 9' shida' )9' chihashi' +9' :chiai' f9' aito' +9' [ )atsui' S9 !2003&9

Dra,(itized Ca.1 traces of iron ,articles oser.ed in a)or,(o's caron nano+

,illars

Gillies' -9 G9' Schaan' 9' Su,,er' -9 9' )cibben' )9 9' [ Shoo5' C9 /9 !2000&9

e,osition .elocities for NeCtonian sl'rries in t'r'lent EoC Can9 9 Che,9 (ng9

Harris' /9 !n9d9&9 380*EProduct or,ulation and design9 @ect're @!0+

F@'idisation 9 Dnieristy o4 Sydney9

un' L9' [ Harris' /9 +9 !2008&9 )icro.ae assisted acid digestion o4 alu,ina

suorted carbon nanotubes9 Se,eration and &'ri*cation ec(nolog1 ' "02E"089

Louis' C9' [ Che' )9 !#%%*&9 &re,aration of solid catal1sts FileyE?CH9

)auron' P9' (,,enegger' C9' Sudan' P9' Fegner' P9' -entsch' S9' [ ^uttel' /9!2003&9 luidised ;ed C?= synthesis o4 carbon nanotubes on e2:3)g:9

ian)ond and Aelated Materials ' 780E78*9

)auron' P9' (,,enegger' C9' Sudan' P9' Fenger' P9' -entsch' S9' [ ^ttel' /9

!2003&9 Fl'idised+ed 7V s1nt(ese of caron canot'es on Fe2O3/MgO

ribourg> =ia,ond and -elated )aterials9

)auron' P9' (,,enegger' C9' Sudan' P9' Fenger' P9' -entsch' S9' [ ^uttel' /9

!2003&9 luidisedEbed C?= synthesis o4 carbon nanotubes on e2:3)g:9

ia)ond and Aelated Materials ' 780E78*9

7$


75/93

)cay' =9 !#%%$&9 GS7+!: > N= @A SOI@ SIMN 9 -etrieed :ctober 20'

2008' 4ro, htt>...9li9usra9edulunarstrategiesjsclunarsi,ulant9d4

:erca,' +9 9' [ )anth' S9 ?9 !#%%8&9 > si),le )et(od for esti)ating c1clone

ecienc1 /nderson> (niron,ental Progress9

Perry' -9 H9' [ Green' =9 F9 !(ds9&9 &err15s c(e)ical engineers (andoo9 !7 ed9&9

Perry' -9 !#%%7&9 &err1s 7(e)ical =ngineers Handoo9 Dnited States> )cGra.

Hill9

Peters' )9' +i,,erhaus' 9' [ Fest' -9 !2003&9 &lant esign and =cono)ics for

7(e)ical =ngineers Ne. for5> )cGra. Hill9

&(1sical ,ro,erties of caron nanot'es9 !n9d9&9 -etrieed :ctober 22' 2008' 4ro,

htt>...9a9,su9educ,cscntroertieseuilibriu,structure9ht,l

-egalbuto' 9 !200"&9 7atal1st &re,aration: Science and =ngineering C-C9

-hodes' )9 !#%%8&9 Introd'ction to &article ec(nolog1 Susse> ohn Filey [ Sons

Ltd9

-hodes' )9 !2008&9 Introd'ction to &article ec(nolog1 Fest Susse> ohn Filey9

Science S+u1 inc9 !n9d9&9 MSS:: Magnesi') O4ide9 -etrieed :ctober 20' 2008'

4ro, htt>...9sciencestu19co,,sdsC202"9ht,l

See' H9 !2008&9 7HND3#0": &rod'ct for)'lation and design Sydney> +he

Dniersity o4 Sydney9

Sinnott' -9 !200"&9 7(e)ical =ngineering esign :4ord> (lseier9

Stobbe' =9 (9' an ;uren' 9 -9' StobbeEree,ers' /9 F9' an =illen' /9 9' [ Geus'

9 F9 !#%%#&9 Iron o4ide de(1drogenation catal1sts s',,orted on )agnesi')

o4ide 9 Che,9 Soc9

Finni5' 9 !#%%7&9 7(e)ical =ngineering (er)od1na)ics ohn Filey and Sons

nc9

7*


76/93

4ppendix B0 Calculations

%omenclature%omenclat

ure

De&nition %omenclat

ure

De&nition

Fe)O1=MgO Suorted ,etal oide

catalyst

C Heat caacity

)g: )agnesiu, oide Particle density

Fe)O1 ron oide 4 luid density

Fe%O1"1.+

/)O

ron nitrate J ?iscosity

C)/9O/ (thanol -e -eynolds Nu,ber

!s& Solid ?t +er,inal elocity

!l& Liuid C= =rag coeAcient

!g& Gas Y ?oidage

G Graity Pi

dp Particle dia,eter XP Change in ressure

m5 )ini,u,


77/93

+he ratio o4 the )g: to e in the recursor is gien as *.tI !)auron et al9'

2003&

/,ount o4 total catalyst>

catalyst (s )=16964−4740−122=12092.14 *g

Co,osition>

5 .#=12092.14 %0.005=604.61*g

.#2

53(s)=(604.61 /55.85) %0.5% (3%16+2%55.85)=864.42*g

∴ Mg5 (s)=12092.14−864.42=11227.72*g

Nu,ber o4 ,oles>

2%55.85

(¿+3%16)=5.41*g'!l .#

25

3(s)=864.42 /¿

2 53 ¿3 .9 H 25(s)=2%5.41=10.83*g'!l .#¿

/,ount o4 iron nitrate>

2 53¿3 .9 H 25(s)=10.83% M 64 6=10.83%404.06=4374.17 *g .# ¿

+otal eed>

11227.72+4374.17=15601.89 *g

/,ount o4 ethanol>

+he recie used by )auron et al9' 2003' seciBes an a,ount o4 200,l o4 ethanol

er batch9

25+9.19(¿¿ )%15601.89=91265.84 L=72008.75 *g

200/¿#t,a(!l (l 7 g)=¿

/,ount o4 byEroducts>

"at#r(g)= (9%10.83) % (2%1.01+16.00)=1755.69*g

252(g)=(3%10.83 )% (14.01+2%16.01 )=1494.25 *g

77


78/93

Mass Balance Matrix

Catalyst PrepBalance Hnown 3alues

,urities consist o4 a,orhous carbon'e2:3' and )g: )ass roduct *000 5g

/,orhous Carbon #I )ass CN+ $7*0 5g

/,orhous Carbon #229#$ g/ssu,e all carbonis CN+>

e!*I& or)g:!%*I& field 28I

Catalyst#20%29

#$ 5g DnuriBed )ass#"%"$9

2% 5g

e2:3 8"$9$2 5g M..

)g:##2279

72 5g e **98*

C #290#

ron :ide *9$# 5g ,ol : #"900

ron Nitrate #0983 5g ,ol )g 2$93#

)ol Ft ron Nitrate $0$90" g ,olE# N #$90#

)ass ron Nitrate$37$9#

7 5g H #90#

(thanol $"907

eed to Cat9 Pre#*"0#9

% 5g

ethanol

%#2"*9

8$ L

Catalyst Prep

Balance

ethanol720089

7* 5g e "0$9"# *I

=ensity o4 ethanol 0978% 5g LE# e2:3 8"$9$2

Mass Balance


79/93

72 %

e!N:3&39%H2: #0983$37$9#

7 N:2 329$8#$%$92

*

ethanol#*"39#

3720089

7* ethanol#*"39#

3720089

7*

Catalyst>#20%29

#$

Total excludeet6anol"

-9>7-.+7

-9>7-.+7

7%


80/93

Terminal 3elocity/ssu,tions>

• +he e2:3)g: density is a co,bination o4 %*.tI )g:' and *.tI e2:39

•

+he article dia,eter is #00J,9• /ssu,e article is sherical9

• Particle dia,eters are o4 ho,ogenous si6e .hen entering the

Catalyst )#(sity=0.05%5240+0.95%3580=3663 *g '−3

e2:3)g: drag coeAcient>

C D= 4 g ) p

3

ρ ( ρ p− ρ )3 +

2

¿ 4 %9.81%0.0001

3%789 (3663−789 )

3%0.00122

=20.59at ℜ=1

Dsing Bgure 293 o

chng 3807 nanotubes final

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