Lecture Outline - Sulfuric Acid

- History of Manufacture Development - Manufacture - Oleum Production - Heat Integration Issues / By-products - Markets - Usage in Caprolactam Manufacture

History of Manufacture of Sulfuric Acid

One of t!e oldest industrially applied processes" Discovered #y a Persian alc!emist in t!e tent! century" $altpeter and sulfur %ere mi&ed in a glass container and #urned in a moist atmosp!ere" 'cid %as collected from t!e condensed vapors" In (ngland) *+,-) t!e lead c!am#er reactor %as invented" .!is invention allo%ed for !ig!er production rates /0+123" In (ngland) *14*) a patent %as filed t!at descri#ed t!e o&idation of sulfur dio&ide over a platinum catalyst) t!e Contact Process" .!is ne% process increased yields of reaction from +5 to a#ove 672" In *6*4) B'$8 %as granted a patent for t!e use of vanadium pento&ide as a catalyst for t!e Contact Process By t!e *6459s) vanadium pento&ide %as #ecoming t!e dominate catalyst used #ecause of insensitivities to poisons and lo%er cost" In *6-5 a patent application %as filed #y Bayer using t!e so called dou#le-catalyst process /dou#le a#sorption3"

Manufacture

.!ree $tep Process *3 $ : O; ;3 $O; : */;O; 43 $O4 : H;O $O; $O4 H;$O,

Oxidation of Sulfur
*3 $ : O ; $O ;
$ulfur

$team *5-*;2 $O; <ater

'ir

642 H;$O,

Process? - 'ir drying to%er %it! acid

Primary =eneration of $O; -+62 Com#ustion of $ulfur -62 >ecovery from Metallurgic Processes - 72 >egeneration of $pent 'cids

- $ulfur is in@ected into #urner - >eaction .emperature ;555A8 - (&ot!ermic reaction must #e cooled - $team recovered

Oxidation of Sulfur Dioxide

Contact Process? -Banadium pento&ide catalyst - (&ot!ermic >eaction - Multiple $teps %it! cooling in #et%een - Dou#le a#sorption - Heat integration

$O; =as

=as Cooling

$O4 =as

Oxidation of Sulfur Dioxide

Because of t!e large effect temperature plays on t!e reaction) multiple catalyst layers are used) %it! cooling #et%een eac! step" 'dditionally) as t!e partial pressure of $O4 increases) furt!er reaction is limited" .!is is overcome #y removing t!e $O4 after t!e t!ird stage to drive t!e reaction to completion"
$O; =as $O; =as

=as Cooling

$O4 =as

$O4 =as

642 H;$O,

Oxidation of Sulfur Dioxide

Cinetic (ffects - O&idation of sulfur dio&ide is slo% and reversi#le - .!e reaction reDuires a catalyst and ,;-"+AC temperatures -.!e reaction is e&ot!ermic and sensitive to e&cessive !eat

(Duili#rium Constant /.!e degree at %!ic! t!e reaction proceeds is temp" dependent3 log Cp E ,"67- - ,"-+1 . . E a#solute temp" in kelvin Cp E eDuili#rium constant as a function of partial pressure of gases Cp E / P$O4 3 P$O; PO;
5"7

Oxidation of Sulfur Dioxide

.emperature Profile

$O; =as

$O; =as

=as Cooling

$O4 =as

5 0C 75 C 430 C 200 C
$O4 =as

25 C

642 H;$O,

Oxidation of Sulfur Dioxide

.emperature Profile

Oxidation of Sulfur Dioxide

.ypical Catalyst Distri#ution

Catalyst Bed * ; 4 , 2 Catalyst *6", ;7"5 ;-"+ ;1"6 Conversion 2 71+ 66"* 66"+

O!erall "roduction Sc#e$e

Oleu$ "roduction

$ulfuric acid %it! additional $O4 a#sor#ed ;52 Oleum contains ;52 $O4 #y %eig!t in t!e oleum Common strengt!s of oleum are ;5) 45) ,5) -7 percent" .o produce ;5 and 45 percent oleum) only reDuires an additional a#sorption to%er"

Oleum is used in reactions %!ere %ater is e&cluded

$O4 : H;$O,

H;$;O+

/disulfuric acid3

%eaction &y-'roducts ( Heat )nte*ration

By-products 7+ to -,2 of t!e energy input generates steam $team energy is used to drive t!e tur#ine t!at supplies po%er to t!e main air #lo%er 'dditional steam remaining is tolled internally for ot!er plant operations $O;/$O4 is vented in small amounts and is federally regulated"

Heat Integration $team is used to pre-!eat and vapor from t!e a#sorption to%ers used to cool MinimiFes t!e cost of manufacturing to ma&imiFe t!e profit"

"roduction Considerations

Metal corrosion is a #ig issue in t!e manufacture of sulfuric acid" $pecial alloy metals must #e used to guard against e&cessive corrosion" Gickel) c!romium) moly#denum) copper) an silicon are t!e most important elements t!at en!ance corrosion resistance of alloys"

Important varia#les for corrosion Concentration of t!e acid .emperature of service $peed of flo% in pipes and eDuipment 'lloy element make-up

+orld "roduction of Sulfuric Acid

Canada Me&ico Ot!ers Iapan Hatin 8-U$$> (urope 'frica U"$" 'sia 5"5 7"5 *5"5 *7"5 ;5"5 ;7"5 45"5
S#are ,'ercent-

+orld Su''ly ( De$and for Sulfuric Acid

,t#ousands of $etric tons. 00/ H2SO4-

;75)555 ;55)555 *75)555 *55)555 75)555 5 *617 *611 *66* *66, *66+ ;555

'nnual Capacity

Production

Mar0ets for Sulfuric Acid

.!e fertiliFer market is t!e largest U"$" single use for sulfuric acid and consumes 75--7 percent of all produced" $econd is t!e organic c!emical industry" Production of plastics and synt!etic fi#ers are e&amples" Production of .iO; consumes large Duantities of sulfuric acid" .iO; is a %!ite pigment used in paints and plastics" In t!e metal industry) sulfuric acid is used for pickling ferrous and nonferrous materials and in t!e recovery of copper) nickel) and Finc from lo%-grade ores" 8inally) t!e petroleum industry uses acid as a catalyst for various reactions"

Acid Stren*t#s
'ssociated (nd Uses
"ercent H2SO4 47"-+ -;"*1 Gormal superp!osp!ate and ot!er fertiliFers -6"-7 ++"-+ 15"55 64"*6 61-66 *5,"75 $urfactants) nitrations) !ydrofluoric acid *5-"+7 *56"55 ***";7 **4"75 **,"-4 >eagent manufacture) organic sulfonations) #lending %it! %eaker acids (&plosives Gormal superp!osp!ate and ot!er fertiliFers) isopropyl and sec-#utyl alco!ols Copper leac!ing P!osp!oric acid) tianium dio&ide) steel pickling) regenerating ion e&c!ange resins of utilities C!lorine drying) alkylation) #oric acid

1ses $torage #atteries) electric utilities

1sa*e in Ca'rolacta$ Manufacture

Production and consumption figures for caprolactam manufacture

Caprolactam Production >ate H;$O, Consumption /*552 'cid3 Oleum Consumption 'mmonium $ulfate Production *;5)555 ton/yr -4- kg per ton of CPH *455kg per ton of CPH 4*;)555 ton/yr

THANX