H. J . ROSE
AND
R. A. GLENN
Bituminous C o a l Research, Inc., 12 1 M e y r a n Ave., Pittsburgh, P a .
The authors of this article are making a comprehensive survey of a l l the uses of coal and coke i n the chemical, metallurgical, and other process industries. Coal resources and consumption studies are assuming s o much importance in long range national planning that IBEC's editors asked the authors to present information and data from this survey to bring the nonfuel coal use picture up to date and predict some of its futures. We believe this article will be informative for a large segment of our readers.
I
S T H E last I50 \.ears more than 27 billion tons of bituminous coal has been mined in the L-nited Statee. Production for 1955 is estimated between 415.000,000 and 425,000,000 tons (1, 2 ) , and more than 800,000,000 n-ill tie needed annuallg by 1975, according t o the 1952 estimate of the President's Material Policy Commission (Paley Report), About 100,000,000 tons is consumed nnnunllj- in the L-nited States for nonfuel purposes and for converting coal to other forms of fuel such as coke and fuel gases.
Coal to Chemicals-Seven
Processes
T h e chemical industry is the second largest industrial w e r of liituminous coal: t h e primary metal industries are the largest. T h e most important processes for the conversion of conl into chemicals, in approximate order of their current consumption of coal, are carbonization, gasification, h~-drogeiintion. hydrolysis, oxidation. combustion. and extraction. Individual chemical reactions taking place during conversion of coal into chemicals h ~ these processes are complex in nature, a natural consequence of the complex nature of the coal substance itself. Therefore only generalized equations are presented. Carbonization. By far the largest nonfuel use of coal is for carbonization-destructive d i d l l a t i o n with resulting production of coke, tar, gas, and other products (Figure 1I . This is the result of the extensive use of coke in the manufacture of pig iron and ferroalloys.
M a r c h 1956
Nonfuel uses of coal are those in which
. , .coal i s converted into other products b y processes such as carbonization, gasification, hydrogenation, oxidation, hydrolysis, and extraction
. ..coal or coke i s used to furnish carbon for reduction of ores to free metals, for reduction of nonmetals, and for conversion of oxides to carbides or to chlorides
. . .coal
i s used primarily for some particular physical property: manufacture of activated carbon, cation-exchange materials, artificial graphite, and molding materials
. .residual products from combustion of coal and the materials associated with coal i n the ground are used as a source of various chemicals; b y the building industry i n the manufacture of cement and concrete products and i n construction of bituminous roads; and for their physical properties
INDUSTRIAL AND ENGINEERING CHEMISTRY
351
-
ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT J.ields of t h e vnrious principal products from rnrlxxiization in slot-type o ~ e i i swith chemical rrcover>-var?- \\,ith thr. carI)oiiizing conditions and with t h e type of r o d charged. Yields of selected individual chemicnls, as givcn in Table I, wprewnt, :I conihined yield of only akJollt one third t h e total ) i r l d of t h v crritle tar and light oil. T h e complexity ol t h r l e matrrial;: is ~ I X J shown b y the fact t h a t with one exception, r:wh intlivit1ri:il
.Table II.
Plants in 1954 (39A)
(U.S. Bureau of Mines preliminary figures; production by tar distillers not included) Benzene, gal. 144,088,875 Toluene, gal. 33,403,286 Xylenes, gal. 9,936,250 Solvent naphtha, gal. 5,535,903 Phenol, lb. 8,650,000" Pyridine 2', gal. 580,669 Naphthalene, lb. 99,979,539 1,645,735,884 Ammonium sulfate, lb.
14.6
23.5%
RETAIL
'I
85,288,000
ELECTRIC UTILITIES
U. S. Production of Coke-Oven Chemicals at Coke
.\iitJ~ors' e s r l m a t e .
STEEL A N D R O L L I N G MILLS 1.3°/0= 4,944,000 2.2%: 8,153,000 AILROADS (CLASS I) 4.7%: 17,370,000
21.9%
w INDUSTRIAL 78,953,000
100%:362,559,000
Figure 1.
TONS
U. S. consumption of bituminous coal, excluding exports in 1954
Nonfuel uses included in "Carbonization" and "Other Industrial"; an undesignated portion of "Other Industrial" is used for fuel purposes
Seniicolx T a r (15.8 gal.] 1,ight oil 12.5 gal.: Gas (3720 cu. i t . 1 1,itluor ((i.6 gal. I
150 1 ti
250 110
Table I. Yields of Selected Chemicals from High Temperature Coal Carbonization ( 1 4A) Fromcoal tar and light oil Benzene Toluene Xylenes Naphthalene Phenanthrene Anthracene Pyridine Quinoline Phenol
Lb./Ton 11 .so 2.72 1.33 6.48 2.26 0.64 0.16
0.13 0.95
Lb. Ton I
From coal gas Carbon monoxide Hydrogen Methane Hydrogen sulfide Hydrogen cyanide Ethylene Propylene
43.2 30.4 132.0 6.7 1.7 19.6 3.4
From liquor Ammonium sulfate
20.0
Principal products from carbonization in slot-type" oven : Coke and breeze Tar Light oil Ammonium sulfate
Average YieldiTon, Lb. 1520 78 20 20
" Carbonization of 1 ton of roal in a beehive oven 1-ields only 13.32 Ih. of coke with no by-products.
The amounts of chemirals recovered t)). cwke-oven oprrator;: c-rudc t:ir produced :ire given in Table I1 1&.4 1 , The production o f these chemicals by tar distillcrs from the processing of almost half the tar (46'%) is not inclluded in the tal)le hiit m:i?. be found in reports of t h e U. S . Tariff Commission (4824). In l%:i, tar distillers produced 162,862,000 pounds of rriide iiapht haleiie and 68,140,000 porintis of refined flake naphthalene (from ;Inirrican crudes I ill r producwl :iddition to the 112..et. 1'rdi:ct.i. gas is 5oinetinies i i d ill the niniiii€xture of ainmonin a s n source of nitrogen a s well a' hydrogen, h u t the. qiiaiitity of producer gns i i s d for this piirposc is not repo1,tcd. The siircwsfiil coinniercinl operntiori of the \ \ - o r l d ' ~first pulverizeti coal gnsifirntion p h i i t iii Finlnnd (35.1 1' h:r-. stimu1:itetl iiirthcr research in the id the coristructiori of similar p h i i t s in Fr:mcc and ,Japan. The e o n ~ t r i i i ~ t i o n01' a 1:ir;e ecnlrs, atmospheric premire. pulverized coal ii!iit h:is I i t w i reported i i i ;he Viiited S t n t w (6-4) f:ti, o1il.v pilot p l m t stiidie.< COURTESY C A R B I D E A N D C A R B O N CHEMICALS GO. hnvc lieen 1 c>poitetl on piocesscView of coal hydrogenation plant shows recycle still and solids separation equipoperating c i / l o \ e ,itiiio~phciicpieqsiiie ment; control building and chemicals separation unit in background 11 1, %+*I, 40.1 1 Hydrogenation. The high p r e s x m hydrogenation of coal in tlie liquid phnae a t clevntetl temperntu:e.+ is another outstanding e z a n i ~ ) l i ~ ion of coal into products useful i l ~c ~ h c i n i r a l ~ Table IV. Yields of Principal Products from Ccal in and internietlintcs. The chrmii~:dreactions occurring diiring tlic Hydrogenation Processes Producing Motor Fuels of coal are as coiiiples as the reaction. o ~ u r Primarily Typical Yields", ring during carbonization. Consequcii:ly the>- arc t l r , v r i l d Gallons per Ton of Coal Illinois No. 6 Bituminous coal bituminous coal of 12,000B.t.u. of 11,000B.t.u. Products (15~) (13A) Gaso!ine 74.3 (motor'' 2 5 . 6 (motor and aviation) ... 30.3 Aromatics Phenol, cresols, and xglenols 4.2 5.0" 20.2L.P.G. 24.4 __ ~. the outpiit ui' ~ r ~ , p o ; c dfull sc:ile commerci:d p1:iiits. Total 102.9 8!,1 C':dcul;itc.tl \-i(,lds of the principnl p?odiict:' are given in T:ililr Ditiercnce in yit,lfls apparInciurlec coal required f u i p o v e r a n d heat 11 aitc3i :illowing credit f u r thc various hy-product cheme n t l y resulta from f a c t r h t c r u d e product.? from tlie Illinoi- K O ,C coal are icals. sucli :is pheiio!, cresol., q-lcriols, Iienzcne, toluene, s ~ - ! e n e ~ . proccssed f u r t h e r t o prodlice greater a n i o i i n t i uf Ion. boiling :ironlatics a n d phenols. 3 Includes resorcinol. nap1ith:ilene. :mil liquefied petroleum gases (L.P.G.), the economics of ih(x process have not led to commercinlizaiion of t h e proccas io tliia r i i i t c d Statc?. pilot plant prowesing 300 to 500 tons por ~ 1 3 ~ of. roal. I t is T h e production of chemicals rather than motor fuels hJ- liquidclttimcd t h a t reducing the contact timc from n fcn- l i o u r ~t o :I few phase h\-drogenntion of coal is currently being investigated in :L minutes, incremw yicI(1s of vdiiaI)le c h r i n i c : ~ !(?.i, ~ I ZA, 2i.t) (1:igiire 2 ) . L i q u i d - p h i r s e coal hydroTable Ill. Coal and Coke Requirements for Gasification Processes genat,ion is n-idely recognized Coal and Coke Consumed for its potential RS a process Raw Materials/1000 Raw for the volume production of Process Cu. Ft. Year Tons material Product a r o m a t i c c h e ni i a1s . T h e realization of this potent,ial deLump Coal or Coke pends, hos-ever, on the adCoke Methanol Blue water gas 32 lb. coke; 55 lb. steam 1953 300,000 (290B.t.u./cu. f t . ) 545,000 Coke Ammonia vances made in the technology 1954 1,030,569 Coke All purposes of t,he process and of the recovery and utilization of t h e Producer gas, hot raw 16.7 lb. bituminous coal ; 1948 ,ooo coal resultant products. (167B.t.u./cu. ft.) 6.7 lb. steam 1953" 421,272 Coke Producer gas, cold 13.5 lb. coke; Oxidation. The conversion Coke 1 1954" 352,152 clean 7.2 lb. steam of coal into chemicals by oxidation processes has been studied a Coal consumption not available. extensively for years. hIany I:
~3
I
March 1956
Bituminous
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
353
ENGINEERING, DESIGN, A N D PROCESS DEVELOPMENT
NAPHTHALENE PHENOL
-- -
-- -- - - -
5X
- 8X
6 0 X - 8OX
UNCONVERTED X = Y I E L D BY C A R B O N I Z A T I O N
Figure 2.
Products from hydrogenation of coal to produce chemicals
MOhOAND SOLID AROMATIC ACIDS IO00 L B
71 3
DI-
TRI- T E T R A -
FEN~ACARBOXYLIC
M E T H Y L P H T H A L I C ACID AND OTHERS
LIC AC;D OXALIC ACETIC TIC ACID
3 0 0 0 LE.
4.0% 170 LE. I 0% 4 4 O0 L B .~ ~ .
/ IOC%~4210LB
Figure 3.
(EXCL ASH AND RESIDUE)
Products from pressure oxidation of one ton of coal with alkali and oxygen
Y I T R O G E N BASES, 0 7 %
[
21 % DIOXIDE C z i k N CAREON DIOXIDE
Figure 4.
1,
PH E N C L S F AlI 5T% TY
5
y
FATTY ACIDS
Products from alkaline hydrolysis of Wyoming subbituminous coal
different kind? OI oxidation reagents hayc h e n used--liitri(, acid, potassium permanganate, ozone, and osygen are examples. The oxidation of alkaline slurries of coal with oxygen under prwsure at elevated temperatures has been studied on both laboratory and pilot plant wale. -4bout half the carbon in the coal may be recovered in tlie form of carboxylic acids follon-ing a 2-hour oxidation a t 270" C. and a n oxygen pressure of 900 pounds per square inch. Figure 3 shov-s t h e amounts of these acids and other materials prodnced per ton of coal oxidized ( f 8 A i ) . Some 35 individual componcnts have been identified in the reaction mixt,iire; t,hey include t h e m n n n - , di- , tri- tetraand pentabenzenc-carbosylic acids (23-4, 31 111 , T h e acids ohtained by this process are of potenti:il value as drilling mud additives and as intermediates for the manufacture of plasticizers, Pynthetie fibers, glyptxl t?-pc' resins. and similar materials. T h e future of t h e process will tlcpend on the progreas ~
3.54
made in the development of economical methods for the proceseing of the comples mixture of acids produced and on the availahility of cheap oxygen. Hydrolysis. Lon- rank coals may be converted in good yield to soluble products of hydrolysis. T h e a1k:iline hydrolysis of a Kyoming subbituminous coal has been investigated on a laboratory scale a t temperatures up to 429' C. The composition of the products from hydrolysis at 330" C. with 5.\- alkali for 24 hours has been studied in detail aiid the complex reactioua believed to occur have been discussed (204). Altogether some three fourths of the coal is converted into soluhle or gaseous products (Figure 4). T h e phenols positively identified in the products include phenol, 3,5-diniethylpheriol, o-ethylphenol, arid m-ethylphenol; the carboxylic acids include acetic, propionic, n-butyric, and succinic acids. The relative high yields of l o ~ rboiling phenols, 3.7 wt. yo, and of fatty acids, 1 5 . i wt. yo, indicate that, hydrolysis is potentially significant as R process for t h e conversion of low rank coal into chemicals. Extraction. The extraction of coal with solvents ha:: been studied perhaps more extensively in the laboratory than any other process for the resolution and conversion of coal into simpler materiale. XI1 types of solvents have been tried on all types of coal a t various temperatures. T h e processes tried may readily be grouped into t\vo clnsees according to the ternprr:itures employed-naniely, procesee; above and below 390" C . T h e extrnction of coal at temprraturcs above 350' C. was conducted on a commercial scale during Korld IY-ar I1 in Germany t o o1)tain a very loiv-ash coal Lvhicti was valuable as a raiv m a tcria! €or the mnnufacture of electrode carbon (27-4). About 5 . 3 tons of coal m r e procesred per hour n i t h a j-ield of 3.7 tons of ncarly ash-free extract. This extract was processed further by carhonization in regular cokc ovens. .Uthough there is a large market for elcctrode carbon in t h e Vnited States today, the high temperature extraction of coal to separate it from the ash has not heen attempted on a commercial scsle. Low temperature extraction of certain low rank c o d s h:ie been vommercially successful on a liniited ~ c a ! r . Sonic Utah coals contain 5 to ;70 resin and n-:ise.; n.hich arc I)cirig extracted commercially and proccssed into diclcctric en:imi.ls arid similar material (%A). -At least one 25-ton-pcr-day i h n t is extracting California lignite n-ith solvents to recover 280 pounds of crude & A ) . The lignite is extracted montan ~ v a xper ton of lignitc (8-4, further to recover :I quantity of humate material, and finally the spent lignite is used ns fertilizer filler. ;iriothor plant is extracting S o r t h Dakota leoriarditt,, n naturally oxiclizctl lignite, to rccover alkali-soluble materials va1u:ible for tiic.ir woodstaining propcrties. Leonardite, however. is used mainly as a drilling mud additive (3r1, 4lrl ~ 1 , Combustion. O r d i n a d > - com1)ustion is not considerctl a9 a process for the conversion of coal into chemicals. IIowcvcr, it i3 used as a means of convertirig coal and coke into c:irhn dioxide hoth ne the main product and as a by-product. Both dr!, ice and liquid carbon dioxide are produced comnirrc.ially from c.oa1-the combustion of con1 producing hoth the carbon dioxide to he rerovered anti the heat and p o ~ e needed r in the prows.. Coal combustion products are also processed along with the gases from the dcconiposition of cnrhonate in mnn!- pro' where carbon dioside is required in quantity. T h r 30d:i :ish and the basic magnesi:t induptries are examplw. The qiiulitic~. of coal so used :ire not, availnhle.
Processes Requiring Coke or Coal to Supply Carbon for Reduction
~
I3y far the largept chemical iihc' of cokc or c o d carbon t o t h e n1et:illurgical indiistrice for u'e in tliv ore?. For esamplc, tlie reduction of iron oxidcs fiirnacr alone corisuiiietl some 887, of all tlie cuke 1954.
INDUSTRIAL AND ENGINEERING CHEMISTRY
i i t o supply riductiori of in the blast prodricctl in
Vol. 48, No. 3
ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT Reduction of Oxides with Production of Free Metals. The production of free metals from ores by reduction with carlion a t high temperatures is based on the conversion of the ore, if necessary, to the oxide form usually b y roasting and then heating the oxide n i t h carbon in the form of coke or coal in a fiuitahle furnace. T h e heat r e q u i r d in the process mal- he supplied by the combustion of an added amount of coal or coke or it may be supplied separately from electric pon-er or hy the combustion of either solid or gaseons fuels. Pig Iron. T h e reduction of iron ore in the blast furnace to produce pig iron i h 17)- far the greatest use of coke for any purpose. I n 1953, for enrh t o n of pig iron produced, there was used 1813 pounds of lilast furnace coke; this is t h e equivalent of 2G2i pounds of hitiiniinous coal. T h e total consumption of coke fnrriacea in operation in 1!153 amounted to almost G1).000.000 toils ( I R ): in 1954 only :ihout 52,000,000 tons v a s consumed (.TlB), T h e estimated consumption of coke for pig iron renrhes 90,000,000 tons per year hy l 0 i 5 (.T.?B). Sponge Iron. T h e direct redurtion of iron ore a t temperatures Iielow the melting point of iron is econoniiral for a t least one use. At present. one conipnny is operating a 45-ton-per-dny Uruckiier furnace t o produce pponge iron suitable for use in the recovery of copper from solution. For each ton of sponge iron produced. 800 pounds of slack coal are required ( I ? B ) , Ferroalloys. Currently, ferroalloys are produced in blast furnai'es and in electric furnares. T h e average consumption of rolce for tlie production of d l kinds of ferroalloys in the blast furnace is almut 1.7 tons of coke per ton of ferronlloy (1Ri. T h e production of frrromnnganr,se requires considerably more2.25 toris of coke per ton of ferrom:mg:inese I"?). I n 1953, the I)lnst furnace producation of 055,000 t o m of ferronlloys required 1,G80,000 tons of coke ( I B ) . T h e :tmount of coke for tlie 1.303~000tons of ferronlloys mnde in electric f i x naces [ I B >.$8B: l i : ~not hecn reported. I t has h e n predicted o ~ ~ lie , ~ produced in t h e (Llrctric furthat 1))- 1975 :ill f ~ ~ r r o : i I l will nace (.?@!. Electric Furnace Steel. T h e production of steel in electrii, i u r n a w ~roquiri>s 12 pounds of elrctrode c:irl)on and 470 t o 525 I;\v..-Iir. of elrc.tiii* power per ton, depending on whethcr the charge t o tlii' !iii.t::iw i$ hot or cold (.5B). T h u s . the production 01 '7,280.1!ll toils or' (-lectric fiirnncr itecl in 1953 ( I B ! required : i l l estinintctl -4:1,700 toric of clcctrotlt. clir1)on and 3.8 Iiillion l ~ \ ~ - . - I i r , of electric I ) I J \ W I . Entire Steel Industry. III 1?- the I-ellas t o supply heat for the proces3. T h e generalized equation for this type of process may he written
XO -
c + c1*
--t
JfCl!
+ co
where .I/ rcprc8eiits LL hivalent niet:il. Aluminum Chloride. One ton of :iluniinuiii chluride produced from bauxitr requires 275 pounds of coke niid 80 pour id^ of asphalt binder in addition to the fuel needed for the c.alcination of the ore and for the baking of the briquets of bauxite and coke (13B). In 1953, eight or more p h i i t s produced 4 8 3 4 toils of aluminum chloride of all grades ( J 9 B ) ; this is the eqiiivdent of GGOO toris of coke. Titanium Tetrachloride. For the prudurtioii of 1 tori of titnnium tetrachloride in a shaft furnace, 0.86 ton of coal arid O.-K toii of titariiuni dioxide are required ( 2 6 B ) . ZIininiuni czt'im:tt,es show t h a t iii 10.53. 11,000 tons of titaiiiwii tetracfli!oridc wcrc produced iisiiig 9500 tons of coal. Tlic production of titnriiuni tetrachlori(1c i3 espcwted t o increase r a p i d > - arcorcling t o the increasing demand for titanium metal. Magnesium Chloride. One ton of magnesium vhloride produced from niagnesite requires 0.5 ton of coal :is reducing agent and 0.4 ton of coal :IS fuel for calcination in addition t o elcc.tric3 po\ver (%B, 37B:. This method of protiiic4iig ni:igicsiuni chloiide Iiiis not bccn economic:tl in pc.:ic'c,tiiiicl.
-
Processes for Reduction of Nonmetals
+ 3 3 0 % + 5C
-+
3CaSiOa
+ 2P +
4FeS04
+c
--f
2Fez07
i
-4SOz
+
('O?
T t i ~rcdiictioii of 1 tori of dr:. ferrous w l f a t t ~o i i the, sintcii.irig niachiiie requires 0.1 toii of coal in addition 10ignitiori fuc.!. A 50-tou-pc.r-da:P semi-commercial plaut \v:i* wiiorte(i to he ope~:itin,gljy the sinter process in 1950 (2Bi. Sodium Sulfite from Salt Cake. In the ni:inuf:ti~tiir~01 gl 10 pounds of coal per ton of glass sand is added in tlic' iicc' the salt cake to sodium siilfite accorili!ii: to thc. R )>
Co:d :in11 coke :ire also nsed in quantit). i,etiriciiig ngeiits i'or istiiig :is salts of metal;: or i i i ttie frc9e state. The p l i o s p l i s t ~sulfates, ~~~ and aiilfur w e t~x:tmples. s. 111 tile electric furnace procesa for ma! of c~)l;c. or carhon is required as the reducing agent for each ton of phosphorus produced in addition t o 13,000 to 13.200 kw,-hr. of electric power and 34 poiinds of electrode carbon ( I I B , 16R, ,57B). T h e eqiiation for the over-all cheniicul reaction ma>-be w i t t r i i
Ca3(I'OI)2
In addition to the coal needed for fuel, 0.5 tori of coal per ton of salt cake is used in the charge as a reducing agent (21B, S J B ) . For the production of 40,000 tons of sodium sulfide in 1953 (47s)45,000 tons of coal was required as reducing agent. Barium Sulfide from Baryte. T h e process for the production of IJaritini sulfide from baryte i3 similar to t h a t for production of black ash from salt cake. About 0.33 ton of coal is required per ton of baryte ore for reducing agent in addition t o 0.35 ton of coal for f u r l (.32H, 4-2B). I n 1931, twelve plants produced 152,792 tons of black :ish (2713;)and coiisunietl approximately 104,000 tolie O f C'oiii. Sulfuric Acid from Waste Pickle Liquor. The sulfuric acid preeerit in the free and cornbiiied state? in t h e n m t e pickle liquor of the steel industry arid in the ivaste liquor from the titanium dioxide indu.qtr5-may he recovered by roasting the recovered salts x i t h con1 ill B rot:trg kiln ($OB, JOB) or on a Dwight Lloyd siiitrring Inachiric and recovering the resultant sillfur dioxide for sub;.equeiit conversion to sulfuric acid. Tlici i~c~;~c~tions which occur may h~ written
SapSO4
+c
--+
SianSO3
1 .
C.'O
Tlie l!l54 consumption of eo:\! for this p u r p o s ~ ~i;:' cr$tiniated a:! 26,000 tons a n d the requircnirrit for 1975 as -10.000 tons.
5CO
One ton of 8593 phosphoric acid produced by the elcrtric f i i r i ~ : ~ ~ process requires only 0.38 ton of coke brcaeze in additiuii to 3 160 km-,-hr, o l electric Don-er ( 3 9 B ) . In the blast furiince, :3,5 tons of coke per ton of phosphoric acid is required 1)utIi rcdiicing agent arid fuel ( 1 5 E ) . In 1953, 380,000 tons of coke and 3.:320.000.000 k~\-.-lir.of electric poivcr \\ere used hy the phosphuriis iii(iiisti)- to produce 8ome 254,000 tons of elpmc~iital phosphorus (4713 ) . Iii 1!EXjJ approximately 410.000 tons of colic w:~;: i i s c d l o r t!w p i othictioii of 275,000 tous of c1enient:il phosphorus Carbon Disulfide. Tlie tlieoretical ani for tlie production (Jf 1 ton of carhon d i w ing t o t h r i equntion
c+
28
--+
CS?
T h e aniouiit of ac1ditiori:il fuel iecjriilcd iii t rc-tort pro( not been reported. 111 thc rlcctro?hertii:il process. thci ca:c.c~tric power rcquircd amouiits to 800 to 1000 Ii\v.-hr. prr toii of i ~ r o d uct (7H, lOB, I @ , 25Bj. In 195:1, 250,600 tons of c:irlion tlisulfide \\-:E prodiictd (:iGB) u5ing approximately 40.000 toris of carbon: about 300/, \vas niade I)?. the electrot1ierni:i.l proec~ss( ; J B ! . Black Ash from Salt Cake. Sodium d f i d e i3 produced primarily by the reduction of sodium sulfatv with po\i-dered coal in a reverberatory furnace according to the equations li(3
+ 4C + 4C0
SazSOa Na&O,
356
--f
Sals NanS
+ 4CO + 4C02
INDUSTRIAL AND ENGINEERING CHEMISTRY
Vol. 48, No. 3
ENGINEERING, DESIGN, A N D PROCESS DEVELOPMENT p o n ~ i(2 {B,29I1, 38B) T h e over-Lill reaction betneeri carbon and sitrid is represc~ntctlby SiOl
+ 3C
+
Sic
+ 2CO
III 1952, the Criited States and Canada produced 91,531 tons silicon cwliide (6R)which required 128,000 tons of coke and 823,779,000 kw.-hr. of electric povier.
Processes Using Coal Primarily for Its Physical Properties In addition to the uses of coal and coke which are based on the chemical reaction between carbon from coal or coke with some other element, therc are a number of uses which are based on the ph?-sic:il properties of either processed or unprocessed coal. Activated Carbon. Bituininous coal from Pennsylvania is used as the rau- material for the manufacture of granular activated carbon iri one plant and Texas lignite is used in the manufacture of a powdered activated carbon in another (I&'). Four to 5 toris of bituminous coal is required for heat and power and as the raw mntc,rial for the manufacture of 1 ton of granular activated carbon. The unit processes involved include low temperature carlmiizatioii followed by high temperature steam activation. The 01 her carbonaceous materials vliich may be used include co:d refuse and anthracite (3C, 6C, 8 C ) . Cation Exchange Materials. Coal mal- be sulfonated to pro\\-hi& has sufficient cation exchange capacity to nl value. A ton of this cation exchange material requires 1.-l tons of coal refuse besides t h a t needed for heat and poner ( I C ' > 2C, IjC'). Only oiie manufacturer i3 k n o v n t o be m:iking such ni:iterials from coal. Foundry Mold Facing Materials. Littlr $tatistical inforination ie nvai1:iijl~on the manufacture of fountlrJ- mold faring materials froni 1)itiiininoiis coal, but this is an cst:iblislieti use. For esanii)lc~,o i i t ' plant lias a 140-ton-per-d:xy capacity (4C, I l C ) . Atioiit 1 .0 ton of coal is required per ton of product hesides t h a t ncwled for 11c.at mid po\\-c'r Electric Furnace Graphite. hrtificial electric furnace graphite x a s l ) r o t l u ~ ~ in ~ c lfour plant. in 1'362 b!- the graphitization of i ton of carljoii:iccwua mntcii:i:s :it high temperatures (W). ; synthetic, grnpliite requires 1.15 ton of m t h r a c i t r , petroleum coltc. or w t o i ~ t(,(>kc' p l u ~ti000 t o 10,000 h . - l i r . of electric pon-er (6C, I O C ' ] l Z ' , 1,3C'1. Graphite EIectrodes. Thc protluc~tionof 1 ton of high calcined i,tyuircF 0.4 ton of coal tar pitch and 1.25 ton 11 addition to 0.3 to 1.0 ton of coal for producer gas for Ixiking tho picen electrodes and 11,600 t o 1i:000 kx~-,-hr.of electric ~ ~ C I T T foI - ~ ~ calcination. I~ Tlic 1953 production of graphite electroilrs h:ts I w ~ iieportcd 2s: 170,000 tons: production for 1963 is e ~ t i n i ; i t ~:is t i 230,000 tone ( 7 C ' ) . Amorphous Electrode Carbon. Certain electric f u r n w e processes c.niplo>-:I. lo\\- calcine electroi!c ciirbon. The clectroilc; are prep:ir~(Ion the, sit13 anti conscqiirntly 110 d a t a are availahle on the total protlucwl. Tlic c.lec,trol!-tic production of aluminum is a good eznniple of ,mc.li :I prows?. Uses for Residual Products from Combustion of Coal
COURTEEY B I T U M I N O U S C O A L INSTITUTE
Anisic aldehyde, perfume component with odor of hawthorne, being distilled from coal tar, Du Pont's New Brunswick, N. J., plant p u r ~ ~ o1nay ~ l ' ~he replacY.tl I1y fix costs :inti iinprovemtmt in quulit larly t r u e of tiL(.coi,crcte used ii F!?. :IP!I is :~I;;cJ 1 1 4 in n a p h u l t liigh\\-:Ly w : " t ri;vtion, iri t lic nianiif:ic.trir.e of lightn-c+ht :iggrcg:itr; for co11(*1 m:inui:ictiii c. of I~:iildingston .llthoiigli f i i i e dust is the commcrci:il s o i u w hg1:irid. 110 eonimercid proccssing of' f l y :is11 iii t h e i . l i i t c d Kt:itrs has Iiccii i ~ c ~ p o r t c d= \ h u t 9 ~ i o r i n t l01 ~ g e i ~ ~ i i ~ i ~ iis i u rohtniricd n fi.oni 1 ton 01 ywrial fiiic dust ( d D , 8D;. Coal Ash and Cinders. The nianufacturr of i iiidcr blocks ior the 1)uiiding intlustr>. coiiquniPs large q u a i i t i t i c ~of~ r o d rintlers yearly. C o d ash i q :I potcJiiti:t: s o u r ~ eof s e ~ 11 oi' tlie iincomiiion rni:Lniuni, m d c.\-en elemmts such a+ vanadium, litliiuni, urariiuni rdD, !ID Lignitic iir;iniiim ows 01' corninc,rei:il inip o r t a n c ~1i:ivc hecn tlixovered in Xorth D:iltot:t ( > I ] ,IODi. Coal ash h:is :ilw Iieeri used during wartimi, :IS a source of a1uniiri:r: 1 ton alumin:i is o1it:iinetl from i 0 to 12 twis of ash im,5Dl. Carbon Dioxide. T h e coriiixMioii of i ~ i diositle in large quiritities since coal it>.clf is ; T h e t h y ice and liquid c:irhon di 1.
from the, eoniliiistiori T l i ~utilization of the rcmidunl products from the comhwtion thc g : w s from t h e coni1 of co:tl is lieconiirig oi' gre:itPr :ind greatcr importance, p:rrticuif linicsiont~ alii1 doloinitc~:iw ~ :iir pollution and n-nstc ilisposd ~ . ~ g i i l i % t i o n ~ . larly i i i : i i ~ ' : i 11:iviiig cnrlboii dio\idc, the!. coiltriii. Fly Ash and Flue Dust. In pon-er plants burning pulverized Sulfur Dioxide. The major portiun of the wlfur in co:d i? coal, iiliiiut XI$; of tlie ash p r e x n t in the c o d is emitted to the converted to sulfur dioxide during comliustioii :ind is emitted atmoyjliere a s fly a311 unless step5 are tnlien to collect i t . The to thc :ttnio~phcrr along n-ith the other + t a c k amount of fij- ash potcntially av:dable iii tiic 14 -Appalachian moval and 'or rerover?- of thc sulfur dioxide from stack gaies is states has Iieeii estimatid a t 5,000,000 tons per year. F h - e n becoming of con,4dcrahle economic importanr,e as :iresult of air utility companies non- sell fl>- ash. Two companies sell approxipollution control. mately 100,000 tons a ?-ear each ( I D ) . Several procwses have been propostd and a t least one is under T h e largest use of fl>- ash is in the building industry ( 6 D ) . About 20 t o 30y0 of the portland cement in concrcte for many investigation for t h r recover>-of the d f u r as ammonium sulfate
March 1956
INDUSTRIAL AND ENGINEERING CHEMISTRY
357
ENGINEERING, DESIGN, AND PROCESS DEVELOPMENT (2.4) l b k L s pp. 196-206. (3-4) Budge, C. E., "IIineral Itesources of S o r t h Dakota," pp, 28-30 North Dakota Research Foundation. Bismarck. S . D., (Bull. 8) 1954. (4.1) J b i d . . pp. 3 2 . 39. (5.1) Chaffee, C . C . . Ilirst, I>.L., ISD. Enn. C H L ~ I45, . 822-38 (1953). (6.i) Chem. B r i g . 61, S o . 3. 114-16
C D U R T L S Y P l i i S s U R O H COSE h C H E M I C A L
co
"Pusher" side of coke ovens; overhead DiDes convey oases and vapors to recovery' and chernicai refining plants I
"
for d e :LS a fertilizer. R c c o v e r ~ -or removal of riiliiir dioxide froiii power-plant stack gases on a conimercial s c d r h attempted in this country although it' is being done in
Uses of M a t e r i a l s Associated w i t h C o a l
This nnterials associated with c o d in the proiuid vary consid(brab1:- iii composition from one region to ailother. Iii ccirt:iiri :ireas these materials are of economic import:~iice arid mny lw use!l in conPicier:tble quantity fo 115 ]lnrposes. Til(' ~ l l ~ i i l l ~ l l coiisumption of' these niateri:ils i 111 rPporteti, fioivewr. 1,ightn-eight aggregate for con made from certain shuiw. Building 1)rick are iiinde from the fire cl:i~.fouiitl in certain arcxi. T h e Lum-out shales f r o m gob piles which are commonly c:iilid "red dog" are used as a roac-ll)uilding material in man)' a r Sandstone, limestone, ailti Finiilnr s t o w s c.ricoiintcred i i i strippitig operatioria :irc snlalile in some localities. Pyrite or iron sulfide occurs iii eonsideralh quniitities in sonic coal seams arid has heen rccoverrtl commercially :it various times. A p1:11it \vas opcratcd in Teq, vol. 2, I?. g;111, Ileiiihcld, S e w York, 1952. I r o n Age 174, S o . 21. 96-97 (1954). I h i d . , 175, S o . 1. 341 (1955). Kobe. K . -1,. "Inorganic Process Induatrie.i," pp. 88-9, lIacmillan. S e w York. 1948. Lipkowitz. Irving. E n g . Mining J . 156, S o . 2 , 82-4 (1955). Lippert, T. IT., I h i d . , 156, S o . 2. p. 79 (1955). llantell, C . L., "Industrial Electrochemistry." 3rd ed.. p . 634-40. llrGraw-13iIl. S e w York. 1950. Ihid.. p. 650-1. 3IcBerty. F. €5.. U. 3. Office Publication Board, Rept. PB-22,626, 1946 (PI.17 Final Rept. 774). l l c G a n n , P. IT., U. S. Bur. 3Iines. "IIinerals Tearhook,
1951." p. 190, 1954. Sational Serurity Resources Board (prepared by C.5. Bureau of AIines with cooperation of U. S. Geological Survey). "llaterials Survey. I\Ianganese-l953," chap. TI. p. 10. October 1952. Olive, T . li., Shreve, R . M.,"Chem. and N e t ' s Cheniical Engineering Flow Sheets," diagram S o . 60. Cheniical a n d MetaUzirgical Engineering, S e w York, 1944. I b i d . . diagram L-0. 69. I b i d . , diagram ?;o. 87. Ibid.. diagram S o . 100. Reichek, 11. -4.. Eng. M i n i n g J . 156, S o . 2 . 148-50 (1955). Ricgel, E. 11.. "Industrial Chemistry," 5th ed.. pp. 80-3, Reinhold. S e w York. 1949. I b i d . , p. 352 -5. Scholes. 3. I%., "Modern Glass Practice." rev. ed.. p. 65--96, Industrial Publications, Chicago. 1952. Shreve. R. S . , "Chemical Process Induatries," p. :309-10 lIcGraw-Hill, S e n - York, 1945. I h i d . , p. 321-3. Ibid.,p. 342. I b i d . , p. 357. I b i d . . p. 391. I b i d . , p. 403+i.
Stanford Research Institute, Stanford. Calif., "C'llenlirxl? Economics Handhook," vol. 2, Data Sheet 240.60, 1'155. Surzay of Ciirrent Brisiriess 35, S o . 2 . S-33 (1955).
March 1956
(45B) Talbot, F.. ISD.EXG.C H E M46, 1115-22 (1954). (4GB) U. 9. Bur. Census, "Censu. of ~lanufaciures-1947,'' pp. 12-13 ~ u p p l . ,1949-50, (47B) I h i d . , "Facts for Industry: Inorganic Chemicals and Ga>c3-1953," Oct. 20, 1954. (48B) U.S. Bur. Mines, Mineral 3Iarket Rept. M M S 2308, .tug. 30, 1954. (49B) I b i d . , M M S 2322, August 1954. (5OB) I h i d . , M M S 2353, Jan. 4, 1955. (5lB) I b i d . , Monthly Coke Rept. 323, ippl., p. 7 , Feb. 4, 1955. (52B) U. S. President's lIaterials Polic Commission, "Hesoiirces for Freedom," vol. 11, p. 76, 1952. (53B) Ibid., p. 118. (54B) I h i d . , p. 165, (55B) Ibid.. rol. IV, pp. 162, 191. (56B) U. S. Tariff Comm., "Synthetic Organic Cheniicals---U. S. Production and Sales, 1953." Reut. 194. 2nd scr.. .. DD. 54. 142, 1954. (5iB) Waggaman, K.H., "Phosphoric Acid, Phosphates, and Pliosphatic Fertilizers," p. 151, Reinhold, h-em York. 1952. (58B) Wartman. F. S., Walker, J. P.. Fuller, 15. C., Cook, 11. A , Anderson, E. L..U. 8.Bur. Alines. Rept. Invest. 4519, 1949.
Processes Using Coal Primarily for Its Physical Properties
S. J., Bogard. D . . ISD. F ~ G CHEM. . 33, 1'701-8 (1941). (2C) Broderick. S.J., Bogard. D., U. S, Bur. IIiiich, Iiei)t. Invest. 3559, 1951. (3C) Broderick. S.J.. Hertzog, E . S., Itlid.. 3548, 1941. (4C) Chem. Eug. .\-ezcs 32, 2524 (1954). ( 5 C ) Encyclopedia of Cliemir,al Technology, (It. E. Kirk alld L). F. Othmer, editors). v d . 3 , p . 1-16, Interscience. Sen- York, 1949. (GC) Fieldner, A. C.. IIall. ti. E.. Gallon.ay. -1. E . . U. S . Bur. l 1 i n ~ s . Tech. Paper 479, I Y 3 1 . (7C)Hnder. 11. S . ,Ganr.mn, B. IT-., Bailey, €3. L.. 11-D. 1 : ~ C~I I~I .: ~ . 46, 3-11 (1954). (8C) Heating and Ventilating 49, S o . 7 , 98 (1952). (9C) Lamb, F. D., Blankenbaker, E . I-.,"Grar)liitc." L-, ,S. I3ur. lIines, llineral learbook, 1952, 1954. (IOC) 31antel1, C. L.,"Indu4trial ~lectroclielni-;try," 3 r d t.(l., p . 644-8, IIcGrsn--Hill, S e w T o r k , 1950. ( I l C ) X i n i n g E n g . 6 , 777 (1954). (12C) Olive. T. R,,Shreve, R. T.. "Chem. and l l e t ' s Clieniical Engineering Flow Sheets," diagram S o . 144, Chemical and Metallurgical Engineering, L-em York. 1944. (1 3C) Shreve. R . S.."Chemical Process Indu.;trier." p. 158. IId;1,awHill, S e n . York, 1945. (14C) C.S. Bur. Jlines, Inform. C'irc, 7692, part 11, g p . 110 11, 11C) Broderick,
19.54. ~~.~
Cl5C) Weast, R. C., Busrrell, .i. AI,, C'hem. .lief. Eng. 49, So. 11,
169-70 (1942).
Uses for Residual Products from Combustion of Coal
(1D) Bittiminous Coal Research 14, S o . 3. 3-6, 16 (1955). (2D) Chem. A g e ( L o n d o n ) 54, 573-6 (1946). (3D) Daridson. C . F., Ponsford, D . R. A , , Mining Mag. (Lo,!do?z) 91,265-73 (1954). 14D) Johnstone, 9 . J.. "2Iinerals for the Chemical and lllied Indu?tries," p. 191-6, Wiley. T e w York. 1954. (5D) Lea, E'. 11..C'hem. X e t . Eng. 53, S o . 6, 210 (1940). (GD) Littlejohn. C . E . , Clemson -1.and 11.College, Clemson. S.C., Eng. Expi. Station Bull. 6, 1955. (7D) Mining. Conor. J . 41, KO.2 , 159 (1955). . (8D) .lfirling Erig. 5 , 782 (1953). (9D) Simon-;. IIownrd, Science .\-elcs Letter 67, Xo, 0 , 90-1 11955). (10D) Waylett, TT, J.. .lfinillg Corigr. J . 41, S o . 2 . pp. 131-9 (195.51.
Uses of Materials Associated with Coal (117) Bttzcminozie Coal Research 14, S o 3. 3-6, 16 (1955). 12Ej \-enter, J . Stassen, P.,U. S Bur. IIines, Inform. Cirr.
7670, 1957 RECEIVED for re\-iew July
2 0 , 19.53.
INDUSTRIAL AND ENGINEERING CHEMISTRY
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