SOx-FGD-limestone.PPT

8/18/2019 SOx-FGD-limestone.PPT

1/30

1SOx Control processes

AE/CE 524B

J. (Hans) van Leeuwen


2/30

SO Control processes Legislation

2

In March 2005, the U.. E!A "#na$#%e& the Clean Air Interstate

Rule (CAIR). CAI' cas e#ss#*ns *" su$"ur *+#&e (2) an&

n#tr*-en *+#&es (+) #n the eastern Un#te& tates.1 he ru$e

#nc$u&es three searate ca an& tra&e r*-ras, #nc$un- annua$

2 an& + re&uct#*n r*-ras t* $##t "#ne art#cu$ate atter

"*rat#*n (!M2.5), an& a seas*na$ + re&uct#*n r*-ra t*

&ecrease *%*ne "*rat#*n.21


3/30

3

Sources of SOx

3 he a*r#t *" su$"ur*+#&es c*e "r*

*wer -enerat#*n

s*urces6

7 c*a$7 *#$

S + O2 SO2

ther s*urces #nc$u&e6

7 *ther #n&ustr such as aer #$$s

7 *8#$e s*urces

7 natura$ s*urces (e.-. v*$can*es)


4/30

4

Specific Pollutants Involved

9h#$e 2 #s the a#n su$"ur7c*nta#n#n-

*$$utant, there are var#*us *thers6

3 : (the *ther “*+#&e”) 2 ; ½ 2

:

3 H2 (r*tten e-- se$$)

3


5/30

5

ffects

3 !u"an !ealt# (as $ell as ani"als)

3 Plants

3 Corrosion

3 Acid Rain


6/30

6

Huan Hea$th E""ects

3 Lun- an& thr*at #rr#tat#*n3 9*rse st*s "*r th*se w#th 8r*nch#t#s3 9ea=en#n- *" the #une sste

3 u$"ur *+#&es #n c*8#nat#*n w#th *ther a#r

*$$utants see a""ect hea$th even *re6

€ + w#th ac#& aer*s*$s can r*&uct chr*n#c c*u-h

an& ""#cu$t 8reath#n- € + w#th !M has r*&uce& s*e *" the w*rst a#r *$$ut#*n

sasters (Meuse :0, ?*n*ra >4@, L*n&*n >52)


7/307

E""ects *n !$ants

3 ecr*s#s – *rh*$*-#ca$

chan-es &ue t* ce$$ &eath(r*&uces 8r*wn *r 8$ac= s*ts)

3 Ch$*r*s#s – “8$each#n-” *"

$eaves, r*&uc#n- a e$$*w *rwh#te sc*$*rat#*n

ecr*s#s (a8*ve)

Ch$*r*s#s (8e$*w)

u$"ur *+#&e can enter $ea"st*ata, caus#n-6

hese e""ects can haen w#th *ther a#r *$$utants as we$$


8/308

C*rr*s#*n

3 Aart "r* ac#& ra#n, su$"ur7c*nta#n#n--ases can rect$ c*rr*&e eta$s

3 H2 #s *st n*t*r#*us "*r c*rr*s#*n, 8ut

su$"ur *+#&es an& ercatans can a$s*c*rr*&e. Man t#es, c*rr*s#*n #s actua$$

&ue t* #cr*8#a$ act#v#t act#n- *n the su$"ur

as #e$#ne

ta#n$ess tee$


9/309

Ac#& 'a#n

u$"ur *+#&es are n*t the *n$c*ntr#8ut*r t* ac#& ra#n, 8ut the are a

r#ar cause. he che#str #s6

2 ; hν → 2

2 ;2 → : ;

: ; H2 → H24


10/3010

Ac#& 'a#n –

he r*cess


11/3011

!r*8$es w#th Ac#& 'a#n

3 Increase& ac#t #n 8*es *" water

3 ?estruct#*n *" ve-etat#*n #n "*rests

3 C*rr*s#*n *" a#nts

3 ?eter#*rat#*n *" 8u#$n- ater#a$s

3 ?eter#*rat#*n &ec*rat#ve ater#a$s

(e.-. st*ne *n statues)

3 ?ecrease& v#s#8#$#t

3 ?eter#*rat#*n *" huan hea$th


12/3012

Control %easures for Sulfur Air Pollutants

Main Option Suboption Exampl! o" #$o%!!!

&o not %$at SO2 &!ul"u$i' t( "ul Oil )!ul"u$i'ation* +oal

%lanin,

-o./!ul"u$ "ul

&i!p$!ion uil) tall !ta%1!

SO2 !%$ubbin,

($o.a.a4 t !%$ubbin, -im* -im!ton* &ual al1ali*

Mit!ubi!(i* i!%(o""* 6o$%)

oxi)ation 7.8 ,4p!um)i!po!al9

&$4 !%$ubbin, -im !p$a4 )$4in,* -im

in:%tion* $ona* ;a(%olit

b!o$ption .it( .at$

7!mlt$!9* llman/-o$)*

M,O* +it$at* >?uou!

%a$bonat* S@-6/x*

+O;OSOx* 6o$%) oxi)ation

7.8 ,4mp!um !al!9

&$4 p$o%!!! >%ti=at) %a$bon a)!o$ption*

+opp$ oxi) a)!o$ption


13/3013

&uel 'esulfuriation

Oil & natural gas

RS H H S R + → +− 2$a%tion%atalti%

2

Claus process

S O H SOS H

SOO H OS H

322

23

2

$a%tion %atalti%

22

2222

+ → +

+→+

Coal

Mineral sulfate wash away

Organic sulfur + O2 SO2 SO2 removal


14/3014

SO2 Re"oval!ig# concentration (e.g. s"elting)

>b!o$bin, SO2 to ma A2SO4

Lo$ concentration ( 2*** pp")

lu ,a! )!ul"u$i'ation


15/3015

Li"estone Scruing

O H g COCaSOCa HSO sCaCO

g CO HSOCaSOO H sCaCO

2232

33

23

2

223

972297

972297

++→++

++→++

+−

−+

Li"e Scruing

( )

O H CaSOOO H CaSOO H CaSOOH CaSO H

SO H O H SO OH CaO H CaO

24223

23232

3222

22

25B02

297

⋅→+⋅

⋅→+

⇔+

→+

'ual Al,ali

NaOH yCaSO xCaSO

O H Na ySO xSOCaCOCaO

O H ySO xSO NaSO NaOH SO Na

++→

++++

+++→+

+−−

−−+

34

2

2

3

2

43

2

2

3

2

4232

5B0

5B0

$%%l)


16/30

Scruing $it# a asic solid or solution

16

2 #s an ac#& -as s*r8ent s$urr#es use& t* re*ve

2 "r* "$ue -ases a$=a$#ne.

-et scruing us#n- a CaC:

($#est*ne) s$urr r*&uces Ca:

(ca$c#u su$"#te)6

CaCO (solid) + SO

2 (gas) / CaSO

(solid) + CO

2 (gas)

Ca(H)2 ($#e) s$urr, the react#*n a$s* r*&uces Ca

: (ca$c#u su$"#te)6

Ca(O!)2 (solid) + SO

2 (gas) / CaSO

(solid) + !

2O (li0uid)

M-(H)2 (a-nes#u h&r*+#&e) s$urr r*&uces M-

: (a-nes#u su$"#te)6

%g(O!)2 (solid) + SO2 (gas) / %gSO (solid) + !2O (li0uid)

* art#a$$ *""set the c*st *" the D?, #n s*e &es#-ns, the Ca: (ca$c#u su$"#te)

#s *+#%e& t* r*&uce ar=eta8$e Ca42H

2 (-su) 8 forced oxidation6

CaSO (solid) + !

2O (li0uid) + 1O

2 (gas) / CaSO

(solid) + !

2O

A natura$ a$=a$#ne usa8$e t* a8s*r8 2 #s seawater. he 2 #s a8s*r8e& #n thewater, an& *+-en #s a&&e& t* react t* "*r su$"ate #*ns

47 an& "ree H;.

he sur$us *" H; #s *""set 8 the car8*nates #n seawater ush#n- the car8*nate

eFu#$#8r#u t* re$ease C2 -as6

SO2 (gas) + !

2O + 1O

2 (gas)/ SO

23 (solid) + 2!+

!CO3

+ !

+

/ !2O + CO2 (gas)


17/3017

Li"e3spra4 dr4ing

ae as $#e scru88#n- e+cet the water eva*rates8e"*re the &r*$ets reach the 8*tt* *" the t*wer

'r4 scruing?#rect #nect#*n *" u$ver#%e& $#e *r $#est*ne, a$s*

tr*na (natura$ a2C:) *r nahc*$#te (natura$ aHC:)

Ca2+

SO2

Ca2+

CaSO

CaO

CaSO

CaO


18/3018

-ell"an3Lord (-3L) process() D$ue -as retreatent6 (ventur# rescru88er) t* re*ve

art#cu$ates, : an& HC$(2) 2 a8s*rt#*n 8 a2: s*$ut#*n

3422332

42232

32232

22

5B02

NaHSOSO NaO H SOSO Na

SO NaOSO Na

NaHSOO H SOSO Na

+→++

→+

→++

(:) !ur-e treatent6 centr#"u-e the s$urr t* re*ve s*$#&s

(4) a2: re-enerat#*n

232232

223232COSO NaSOCO Na O H SOSO Na NaHSO

heat

+→+

++ →

%gO process##$ar t* $#e/$#est*ne scru88#n-

a=$a,* 1 mol ;a2SO3 "o$ 42 mol! o" SO2


19/3019

Citrate scruing process

−+−

−−+−

−+

⇔+

⇔+

+⇔

⇔+

Ci H H HCi

Ci HCi H Ci

HSO H SO H SO H O H g SO

2

2

323332

3222

ion%it$at

5S 6ureau of %ines process

2 #s re&uce& w#th H2 t* #n a $#Fu#& hase react#*n

&la,t36oliden process

Use stea t* str# 2 *"" the $#Fu#&.

he 2 can then 8e r*cesse& "urther t* v#a a

C$aus r&n *r t* H24 8 *+#&at#*n an& a8s*rt#*n


20/3020

-estvaco process

O H S S H SO H

SO H OO H SO

2

%a$bona%ti=at)

242

42

%a$bona%ti=at)

222

443

5B0

+ → +

→ ++

CuO process

422 5B0 CuSOOSOCuO →++


21/30

IR POLLUTION CONTROL WITH LIME SLUDGE

SO

2

+ CaCO

3

CaSO

3

+ CO

2


22/30

Water Softeningater Softening

The removal of divalent metal ions

Precipitation/settling or IX resins

Ca(HCO32

+ Ca(OH2 2CaCO

3+ 2H

2O

MgCO3 + Ca(OH2 Mg(OH2 + CaCO3

Note that the CaCO3precipitated

is chemically identical to limestone


23/30

T!"i#a$ %ater treat&ent

"ro#e'' %it( $i&e 'oftening

Li&e '$)*ge

Ca(OH2Li&e


24/30

SETTLINGSETTLING


25/30

LAGOON DEWATERING


26/30


27/30

STOCPILING


28/30

ISU Po%er P$ant

Re)'e A""$i#ation' in Po%er P$ant'


29/30

CONTROLCONTROL O, POWERO, POWER

PLANT ANDPLANT AND EMISSIONSEMISSIONS

RESULTS-ENCOURAGING


30/30

&lue 7as Scruing $it# &l4 As# and

Oxidant $it# Production of a 8e$

-aste$ater 9reat"ent C#e"ical

NaClO3 + 3H2O + 3SO2 3SO42- + 6H+ + Na+ + Cl-

Fe2O3 + 6H+

+ 6e

3H2O + 2Fe3+

Al2O3 + 6H+ + 6e 3H2O + 2Al3+

2Fe3+ + (3-n/2)(SO42-) + n (OH-) Fe2(OH)n(SO4)3-n/2

2Al3+ + (3-n/2)(SO42-) + m (OH-) Al2(OH)m(SO4)3-m/2

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SOx-FGD-limestone.PPT