I N D U S T R I A L AND E N G I N E E R I N G C H E M I S T R Y 483

Mineral and Fuel Resources RICHARD J. LUND AND DAVID D. MOORE

BILTTELL~ m o m msrmm, COLUMBUS. orno

From the standpoint of mineral and fuel resources for the chemicd industries, the five East North G n t d staten Wring the Q-t I&w o h r eMund futurn supplien of Nch h d c materids M coal, limeatone. dolomite, d t , brinw, fluonpar. silica, iron, copper, and zinc. By- products of such industrim as iron nnd &eel manufacture. paml.um dining, and zinc melting in the M(L d l continue to supply large gUMtitir of chemical raw ma- t*.

HE five East North Central states bordering the Great 'T Lakes are richly endowed with mineral and fuel resources that ensure adequate raw material supplies to support long-con- tinued growth of chemical industries in this area of high indus- trial and population concentration, Miuerals are generally of the common work-horse variety rather than 0ashy specialties, but these are the ones needed in large tonnages by chemical plants. The area is charact+zed by huge reserves of coal, limestone, dolomite, salt, brines, 0uompar, silica, and iron, and lesaer amounts of copper, zinc, oil, and gas. In 1950, these five states accounted for mineral and fuel output valued at ahout $1.2 billion or 10% of the value of the total U. 5. output. Large additional supplies of valuable raw inaterials or intermediates for chemical indwtries are available at the large steel-producing, petroleum-relining, and einc-smelting centem in the m a .

Michigan, Ohio, and Illinois ranked among the firat four states in production of crushed limestone for miseellaneons use8 (in- cluding chemicals) in 1950. Michigan and Ohio ranked fist and tbird in output of salt; Illinois was fust in 0uompar produc- tion: and Ohio waa first in lime manufacture.

Southwest. Large reserves of excellent coal in Ohio, Illinois. and Indiana assure plentiful local supplies for chemical industries that will depend more and more in the future on thia material not only for relatively cheap power and process steam, but also for a cheap baeic raw material from which to produce increasing amounts of chemicals.

LIMESTONE AND DOLOMITE

Figure 1 shows the general distribution of high calcium lime- stone and dolomite in the five-&ate m a under review. With the exception of Wisconsin, high calcium limestone is abundantly distributed throughout the area. Probably the largest limestone quarry in the world is found in theuorthern part of the Lower Pen- insula of Michigan, near Rogers City. Huge tonnages of Dun- dee limestone are quarried there by most modern methods and shipped by self-unloading lske carriers for u88 as 0ux stone by the steel industry; for lime manufacture, and to alkali, carbide, and other chemical works. Reserves are huge, especially if the overlying Traverse formation is included. Limestones and dolo- mites of northern Ohio, in the general Toledo-Sandusky area, supply the most productive lime-manufaturing diatrict in the country. Areas of high calcium limeatone in central and west central Ohio are importaut sources of 0ux stone for the steel industry of the Ohio-Kentucky-West Viginia m a . While the really Luge operations are opencut quarries, there are &able underground dope and shaft limestone mines in the area, per- haps the hest known of which is the 2300-foat mine of the Colum- bia Chemical Division of the Pittsburgh Plate Glaas CO. at Barherton, Ohio.

SALT AND B R I m i fue l s , all the states except Wisconsin have important prcduc- tion and reserves of coal, petroleum, and natural gaa. Oil and gas are largely from old settled production, but substantial quan- tities d l be produced for some time to augment supplies coming into the m a via pipelme from the large producing areas of the

Michigan and Ohio have long heen among the principal salt producing states in the country. Figure 2 shows the general area in the five-state region underlain by the well-known Salina

484 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 46, No. 3

salt beds, with smaller areas delineated where natural brines have been produced. Location of evaporated salt and brine works is also shown. I n Ohio, the depth of the salt beds increases south- easterly from around 1500 feet near Cleveland to over 6000 feet along the Ohio River in the southeastern part of the state. Salt is obtained (1) by underground mining of the thick salt bed, as in the large mine (1100 feet deep) of International Salt Co. a t Detroit, (2) from natural saline waters. either flowing or pumped, and (3) by pumping water into salt formations and recovering the resulting artificial brine. The flourishing chemical industries of central Michigan and northern Ohio owe their location to these extensive deposits of salt and brine. e% WISCONSIN

CCiL-;" HIGH CALCIUM LIMESTONE

DOLOMITE

Occurrences of High Calcium Figure 1. Limestone and Dolomite

Salt reserves in Ohio and Xichigan have been estimated by the U. S. Bureau of Mines and by the U. S. Geological Survey as somewhere between 100 billion and 1000 billion tons in each state.

GYPSUM

Although of more importance presently as a raw material to the building materials industry than to the chemical industry, gyp- sum may some day assume more importance in the chemical field. Michigan has for many years led all states in gypsum out- put. Gypsum beds of Mississippian age outcrop near Grand Rapids and a t Alabaster on the north shore of Saginaiv Bay, and another occurrence is reported near llackinac Straits. Re- serves that can be quarried or mined from shafts of moderate depth are large. TTO quarries in northern Ohio, near Snndusky, produce substantial amounts of gypsum from beds of Silurian age-the same formation that accounts for the large output of western Yew York.

FLUORSPAR

Raw material for the rapidly growing field of fluorine chemicals is amply supplied in the area by the huge reserves of the southern Illinois district near Rosiclare. Illinois has long occupied the top position as a fluorspar producer, with the area acrosq the Ohio River in Kentucky running a rather poor second. Together they accounted for almost S O Y , of the U. S. fluorspar output in 1951. Kith Illinois alone supplying about 60%. Reserves for

the Illinois-Kentucky area have been estimated by the U. S. Department of the Interior a t over 11,000,000 tons of material averaging 50% calcium fluoride, with about 5,000.000 additional tons of low grade material averaging 15% CaF2.

SILICA

I n reviewing silica, discussion is confined to quart)eose material of high purity-of the order of glass-sand grade of minimum 95 to 99.5% SiOa. Quartz of this purity is also usable in making high grade silica refractorics and for premium metallurgical uses.

The extensive pure glass sands near Ottawa, Ill.! have for many years kept Illinois in first place as a producer of high purity silica sands. The material is obtained either by quarrying or under- ground mining operations.

Ohio has limited amounts of quartzose mat,erials of high enough purity to be used in their natural condition for highest quality glass sand, but many deposits in eastern Ohio can be washed and treated to obtain the necessary purity. Principal formations presently exploited or that offer promise of future development for uses requiring high purity are the Berea, Black Hand, and Massi- lon Jandstones and the Sharon conglomerate. Outcrops of these formations form a broad belt (with interruptions) from Scioto County in the south to Geauga County in t>he northeast.

i WISCONSIN

I OHIO I N D I A N A

w BEDDED SALT DEPOSITS

~ NATURAL BRINES, LAKES, MARSHES,OR SPRINGS

0 EVAPORATED SALT WORKS * BRINE WORKS

Areas Underlain by Salt Beds and Figure 2. Natural Brines

Recent investigations in Indiana have shown numerous de- posits of high silica sand mainly in formations of Mississippian and Pennsylvanian age in the western part of the state.

Figure 3 s h o w general locations of silica deposits in the five- state area.

CLAYS

Various types of clays are of interest to the chemical industries either directly for processing-as absorbent, filtering, and clari- fying uses-or for ultimate use as refractories or protective-lining material for production equipment. Illinois has produced full- er's earth in the past, and all five states are producers of a variety

Mamh 1954 I N D U S T R I A L A N D E A G

of claw for vnriow purposes, with Ohio, Illinois, and Michigan standing high in the national picture.

IRON, FPPER, ZINC Michigan and Wisconsin have been important suppliers of

iron ore for many decades, with mbahtial production from the Marquette, Menominee, Crystsl Falls, and Qogebic districts. Most of thia is from relatively deep underground mines, in con- trast with the open-pit operations of the Meeabi range of Minne- sota. Reserves of directdhipping ore are Still large, and quanti- ties of low grade iron formation or taconite amenable to conoen- tration by preasntly known economic methods are almost limit- less.

Michigan has been an importsnt copper producer nationally for about a century. Present development of the long-known low grade rema from the white Pine district by the Copper FLmge CO. suggests that this region cannot be counted out of the copper picture for soma time to come. Mines farther up on the Kewee- nawa Peninsula are very deep and require relatively higb copper prima for profitable operation.

Exploration in the upper Miasiasippi zinc-lead district of south- western Wisconsin and northwestern Illinois in the past decade baa brought &able new lie to this old mining district. During the period 1946 to 1950, output of zinc from Wisconsin was cut in half, while that from Illinois mines was tripled. But a new operation in Wieoonain only came into production in 1950, and this should ensure continued activity there for many yeara. Illinois' output of recoversble zinc in ores in 1950 was about 27,- 000 tom compared with WMO tons for Wisconsin. Almost SAYo of the Illinois output is from the northern part of the State, the remainder coming as a by-product of fluorspar operations in southern Illinois. Together these two ststes account for only about 5% of total mine production of zinc.

Minor mounta of lead are recovered along with the zinc in northern Illinois and southwestern Wisconsin-a total of 2800 tone having been produced in Illinois in 1950 and 500 tons in Wiscon-

< WISCONSIN //f [ '

( ILLINOIS I INDIANA 1 J

I N E E R I N G C H E M I S T R Y

pcesources COAL F w e 4 shows the widespread

distribution of coal reserves in -4x -

485

.'-. EAST the East North Central States.

Recoverable reserves, estimated by the U. S. Geological Survey and aasuming a 50% recovery, amount to more than 150 billion tone. Economically recoverable reserves are estimated by the Bureau of Mines to be 25

tons in Indiana, and 0 billion tons in Ohio, plus about 60,000,000 tons in Michiaan. This minimum indicated reserve

4$ billion tons in Illinois, 7 billion w

is more than 80 times the present total annual U. 8. demand. If and wheqthe manufacture of synthetic liquid fuels from coal hecomes an economic reality, Illinois and Ohio would stand high as promising areas for initial U. S. development. Pend- ing such time, coal remains the basic fuel for chemical, elec- trical, and most other industrial demands in the region under dia- cussion.

Figurn 4. G O M ~ hlu Underlain by Bituminolv coal.

Illinois ranked fourth in coal output for 1952, producing 43,500,- 000 tone, followed by Ohio in 6fth place with 37,000,000 tons, and Indiana in seventh place with 17,000,000 tom. Michi- gan, in spite of the widespread area in which coal deposits LUB located, has little economically minable coal; ita production in 1952 was only 7000 tone.

The presence of low cost coal along the Ohio River has led to vast expansione in electric-power generation, which in turn en- nure8 continuing growth of vnrioun chemical industries dependent primsrily on low coet electric power. Aa natural gas prices con- tinue to riee and new, auitable hydroelectric mtes become more sc-, this area should develop the lowest cost electria power in the United States.

P E r R o m Figure 5 shows the dmtribution of the oil and gas reserves in

thia region. Aa mentioned earlier, this area is no longer a major

486 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y Vol. 46, No. 3

oil province. The days when Ohio was the center of the oil in- dustry have long since passed. Even a t the height of production, Ohio, Indiana, and Michigan had relatively small crude oil out- puts, and in 1952 their combined production vias slightly under 30,000,000 barrels-less than a 5-day supply for the United Statc- or between 25 and 30 days’ supply for the five East S o r t h Cen- tral States.

111 O I L

(4-J

Figure 5. Occurrences of Oil and Gas

The present crude oil production in Illinois is about double this amount, so the area as a whole produces between 20 and 2670 of its needs. Proved Illinois reserves are 640,000,000 barrels, compared with 57,000,000 barrels in Michigan, 56,000,000 hai- rels in Indiana, and 29,000,000 in Ohio.

Present crude oil production and pioved ieseiveb in Illnlois vould be materially greater if conservation had been practiced following the large scale oil discoveiieb of the 1030’s. Present and future developments in secondary recovery techniqueo even- tually may recover a substantial portion of this lost oil but onl) at a considerable increase in recovery costs.

Far more important than the present oil ~ C S ~ I ~ I C C P in this region ia the fact that the crude oil production led to oil refining in the area, which in turn provided the necessary raw materials for numcrous chemical industries thal have been drvclol)etl.

NATURAL GAS

Proved reserves of natural g : ~ in this legion itre also snia11 compared with total U. 5. reserves of more than 190 trillion cubic feet. Ohio has the largest regional reserve i-,ith i30 billion cubic Ieet, followed by Michigan with 254 billion cubic fect, Illinois with 212 billion cubic feet, and Indiana with 37 billion cubic fwt. On the other hand, this area has used natural gas for various chem- ical, heating, and other industrial purposes for almost 100 yeais. When area supplies n-ere no longer able to meet the demands, ready markets in the East S o r t h Central States brought low cost Southwest gas into the area, thereby retaining many chemical and other industrial concerns dependent on gas for a raw material or for close temperature control.

Production of natural gas in 1952 anlouiitrd t o 32.5 billion cubic feet in Ohio. 32 billion cubic feet in Illinois, 11 billion cubic feet in Michigan, and 7 billion cubic feet in Indiana. This pro- duction amounts to only dightly more than 10% of the total

consumption in the area, Ohio alone consuming 325 billion cubic feet in 1950.

RAW MATERIALS FROM BY-PRODUCTS

.Uthough not’ raw materials in the strictest sense, some inention should be made of the by-product gases and liquids from iron and steel manufacturing, pet,roleum refining, and zinc smelting operations.

Iron and Steel Processing. The area has long been a major coking area, having present capacities and production rates amounting to more than one third of the U. 5. totals. Rlajor coking centers are located at steel-producing districts in the Chicago, Detroit, Cleveland, Youngstown-Canton, and southern Ohio areas.

Coking operations, both in the iron and steel industry and in merchant plants, are still one of t’he primary sources of raw ma- terials for the chemical industries,

Ammonia, methanol, nitric acid, toluene, benzene, phenol, and many other c o l e and coal t,ar cheniicals \yere produccd for years before petrochemicals became important sources of chemical raw mat’erial. Even today many by-products of coking opera- tions can be produccd and sold a t lorrer prices than competitive chemicals made from petroleum or natural gas. R e r e it not for the development of chemical uses from coal tar by-products many of the present-day markets for petrochemicals would not exist. As it is, recent developments in hydrogenation and low- temperative carbonization of coal may lead to a renewed expan- sion in chemicals based on coal as a raw material within the next several years.

Petroleum Refining. A41most one sixth of the total U. S. re- fining capacity is located in the area, mostly centered around Chicago and St. Louis. Large chemical plants have been de- veloped using the C,, cal and Ca paraffins and olefins produced at several of these refineries. Also, in recent years many re- fineries have converted the hydrogen sulfide present in the gases to sulfur and sulfuric acid. To mention some other by-products: hlercaptans have been separated from various pctroleum fractions; cresylic :wid has been recovered from spent treating solutions; and graphite a d carbon electrodes have hccn made from petroleum coke.

Zinc smelters in the region are located a t East St. Louis, LaSalle, and Depue, 111. These provide sulfur dioxide as a major by-product for conversion t o sulfuric acid.

Zinc Smelting.

REFERENCES (1) Am. Bur. Metal Statistics, New York, Yearbook, June 1953. ( 2 ) -\m. Gas Assoc. and Am. Petroleum Inst., New York, “Proved

Reserves of Crude Oil, Natural Gas Liquids, and Natural Gas, December 31, 1952,” Vol. 7 .

(3) Am. Petroleum Inst., “Petroleum Facts and Figures,” 10th ed., New York, 1962.

(4) 13altimore and Ohio Railroad Co., Baltimore, >Id,, IIigh-Cal- cium Limestones in thc Area Served by The Baltimore and Ohio Railroad (1950-51).

( 5 ) Bodes, Oliver, “Stone Indust.ries,” Ken, York, hIcGraw-Hill Book Co., h e . , 1939.

( 6 ) Bull. Am. Aesoc. Pet.roZeicm Geol., 37, No. 6, 1280-4, 1301-29 (1953).

(7) Corps of Eiigineors, Dept. of Army, Rept. for Bureau of Mines, Dept. of Interior on Synthetic Liquid Fuel Potentials of Various States, by Ford, Bacon, and Davis, Inc. , Engineers.

(Y) Illinois State Geol. Survey, ‘Winois Mineral Industry in 1951,” Rept. Inoest. 158, 1952.

(9) Lilley, Ernest, “Economic Geology of Mineral Deposits,” Sew York, Henry Holt and Co., 1936.

(10) Nurray, H. H., arid Patton, J. B., “Preliminary Report on High-Silica Sand in Indiana,” Indiana, Dept. Conservation, Geol. Survey, Rept. Piogr., 5 , 1953.

(11) Ohio Chamber of Commerce, Industrial Development Depart- ment, Information about Ohio and Her Natural Resources:

Muoh 1954 I N D U S T R I A L A N D E N G I N E E R I N G C H E M I S T R Y

* .

No. 1 caal, 1949 No. 2 Cement. 1949 No. 6 Molding @and (Naturally Bonded) 1949 No. 6 Molding @and (8ynth. Fdry. Sands) 1960 No. 6 hlstursl cfi4 1949 No. 7 Petmlsum. 1949

No. 10 Sulphur, 1861 No. 12 Lime Industry. 1961 No. 13 Gmurn. 1962

, No. 9 Chemical Limeatone, 1961

No. 16 lndustriSl8snds and Sendstones. 1953 (12) Ohio De*. Ioduatrial Rela t io~ . Columbus, Ohio. Annual Cos1

Remrt md Nonmstsllia Mineral Remrt with Direotories of

(15) U. 8. Bur. Mi&, “Minerela Yearbook 19M1.”

(18) U. 8. Bur. Mines snd U. 8. Geol. Survey. “Mineral Position of the United States,” Appendix to In- vestigation of National Resouroas, Hearing# before a subcommittee of the Committee on Publio h d s , u. 8. 8enste. 80th Congress. 1st 8ecdion. May 16.16. and 20. 1947.

(17) Wright, A. J., “Economio Geography of Ohio.” Divi- sion of Geologioal S m e y . Ob. Bull. 50.186a.

R W ~ V E D f ~ r ~ugvat ai . 1968.

Water Resources A. M. BUSWELL

UNNBRSITI or u u i o m l u l ~ m o m STAR WATER E-, -A, ILL.

W. J. ROBERTS ILUNOIS STAR W A R SUBVII. uRBIu(h U L

~ A S T

ENTRAL . . . . i

Tha Eut North C.ntrJ. Statu haw upuioncod indus- M.l e whioh hu m r l t d in oartrdng d d o p u l -t.r ~ p p h in mm. UU.. Than statu haw a com- hind ht-d of 2S billion ON pa &y of nuku w a t r or OM dghth tlu rtknrtd ~t i~d withdrawal UI. Th.y pump 0.0 1.23 billion gallons of ground

hthdmd YY in th. unitd statu. Tha ODcUmTLc. of &urd ground r a t . r i s a h o m by map.. and spmci6c daelopnunt. tluoughout th. area am dirurd . Tlu prmult stat. of inwntmy of -tu msourcu is outlird. th. inrd.guacy of pnvnt vakr - information im indiutd, md th. u v u whuu impronmont is nudd in collection of hdc water -uhu data a m ~(l(lrt.d.

1% water resources are the basis of existence, for without 0 them there would be no lXe-plant, animal, or industrial. The history of water development in an ancient an the history of man, and the availability of water has been a prime factor in the riae of civilizations and the loration of large centera of pop& tiOL

Industry. which in the paet has taken whatever water it re- quired, now is forced to inventory ita m u r e e and use it care fully. The time has come, eepecidy in the field of industrial chemistry, when quality and quantity requiremenin for water place a hi# priority on that m i m e . Elice the growth of the chemical industry has been especially rapid in the East North Centrd S t a h , let un look at the water mmurcen of that part of the country.

M d w k (‘7) suggeete that the water mmu1ce8 of an area may best be determined by answering the following questions:

Let 2 repwent any given geographical d a c e or area for which this dormation is sought. Firsf what in the total annual avarap precipitation falling

upon m a 27 b n d l y , of the total average a ~ u a l precipitation what pro-

po.hion ta into dream channels where it can be measured and uwiaei $y man?

.R* pa &y. Nu19 O M M t p 6 f t h th. m t d

Thirdly, of the total precipitation what proportion is returned

Fourthly, of this precipitatioq what roportion gets into to the atmosphere aa vapor?

underground channels and mrvom and wtat becomes of it?

0- PIWSIOORllpm OF EAST NORTH CENTRAL S T A W

The five states comprising this seotion cover a total area of nearly 250,OOO square miles or a little over 8% of the area of con- tinental United States.

The northernmost state, Michigan, consiata of two peninsub separated by a strait. The Upper Peninsula in bounded by Lakes Superior, Huron, and Michigan and by White Fish Bay and St. Mary‘s River which separate the peninsula from Ontario. Thin northern part is relatively rugged and mountainous with tittle wear by emsion In contrast the southern peninsuls is a portion of the younger marine sediments whose layers contain oil and coal an well as salt and gypsum. Thin area, only slightly elevated above the lakes, has a gently undulating d a c e , with low d- lands common to many parta of it. A large plateau of conaider- able dimension is situated in the northern part of the Lower Penineula, but the northwestem part of the Upper Peninsula is rugged with hilla and mountains. The state in drained by many amdl streams of clear water. In the w e s b part of the Lower Peninsula are the following rivers: Muakegon, Grand, St. Joseph, Manietee, and Ralamssw. Several glacial lakes dot the d a c e of the lower peninsula. . The climate of the Upper Peninsula varies from extremely cold

in winter to warm or mild summers. Prevailing winda in this area am from the northwest. The Lower Peninsula is intluenced greatly by Lake Michigan, and the isotherms have a W e r a l aouthwesbnortheast slant along the enatem half of the Lower Peninsula. July is the hottent month and February the coldest month. Precipitation averages 31 inches annually and is evenly distributed throughout the area. About one half of this falls be tween May and October. Wisconsin, the next northernmost state in this group, is bounded

by Lake Superior and the Upper Peninsula of Michigan; on