acid works

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Noone could accuse reporters for the. Titusville Morning Herald newspaper in the. 1870s of having a dull writing style. "The straw that broke the camel's back" ...
ACID

WORKS:

0CY OF

YEARS, HE WORKED FOR A BIOTECHNOLOGY COMPANY IN

Above: The Boughton Acid Works, ca. 1883. Southwesterly view of the plant taken from the approximate location of the railroad station/company office. The Boughton plant recycled weakened sulfuric acid, used by oil refineries to clean kerosene, by distilling it back to full strength. Railroad tank cars for the shipment of acid sludge and finished acid are in the foreground. The wooden superstructure of the pan house can be seen (center), and the brick retort house is to the far left. (DW9621)

OAK RIDGE, TENNESSEE AND FOR THE U.S. BUREAU OF MINES IN PITTSBURGH,

PA. HE CURRENTLY CARRIES OUT

RESEARCH ON THE BIOREMEDIATION

OF CONTAMINATED

that

NATIONAL ENERGY TECHNOLOGY LABORATORY (NETI) IN PITTSBURGH.

"the

JAMES SAMS WAS BORN IN CHILLICOTHE, OH IN 1954. HE RECEIVED A B.A. IN CHEMISTRY AT WEST LIBERTY STATE

SpIll; casu

COLLEGE, B.S. AND MS.

IN EARTH AND ENVIRONMENTAL

SCIENCE FROM THE PENNSYLVANIA STATE UNIvERsITY. OF MINING AND RECLAMATION AND THE U.S. SOIL

By Harry M. Edenborn IV and James 1. Sams III ~

PA IN

1954. HE RECEIVED HIS B.S. AT NEW MExICO TECH AND PH.D. IN MICROBIOLOGY FROM RUTGERS UNIVERSITY. AFTER STUDYING THE BIOGEOCHEMISTRY

OF GULF OF ST.

LAWRENCE SEDIMENTS IN RIMOUSKI, QUEBEC FOR FOUR

187C

WATER AND SOIL AT THE U.S. DEPARTMENTOP ENERGY'S

AFTER WORKING WITH THE PENNSYLVANIA BUREAU

HARRY EDENBORN WAS BORN IN PHILADELPHIA,

1\

1871

slgm the s

CONSERVATION SERVICE, HE WORKED FOR 18 YEARS WITH THE U.S. GEOLOGIC SURVEY IN PITTSBURGH, RENTLY

CARRIES

OUT

RESEARCH

AT

NETI

ON

PA. HE CURSPATIAL

RELATIONSHIPS OF WATER QUANTITY AND QUALITY WITH SOIL AND GEOLOGIC PROPERTIES DETERMINED BY REMOTE SENSING TECHNOLOGIES.

locat

at a] call "

. . I

The place referred to was a site on the west side of Oil Creek at the Boughton switch, where a factory had recently been built to clean and concentrate sulfuric acid waste generated by oil refineries. These acid works had been constructed by the firm of nc. Hutchins & Co., which had carried out a similar business in Pittsburgh for the previous five years.'

N

oone could accuse reporters for the Titusville Morning Herald newspaper in the

1870s of having a dull writing style. "The straw that broke the camel's back" might become "the feather that dislocated the dromedary's spinal column" in the Herald. However, the

casualreader of the newspaperon May31, 1871, must have suspected that an odor of significant strength was emanating from the site of the new sulfuric acid works, [-

located just three miles south of Titusville,

E

call "Cologne:'

at a place that local wags were starting to

-

Late 19'h century map showing the location of Boughton on the west bank of Oil Creek, three miles south of Titusville.

ffaction was then

with sulfuric acid in a lead-lined

"agitator" or "treating tank." Approximately one

in tl

or two percent of concentrated sulfuric acid was

estel

added to the distillate, and this was agitated with

of a

iron paddles or forced air for 10 or 15 minutes.

No'

During this step, tar and other impurities settled to the bottom of the tank and were later removed.

knO'

Sulfuric acid had been used since the late 1700s

The kerosene was then washed several times

com

to refine whale and other animal oils, as well as

with water and treated with caustic soda to

pro(

vegetable and coal oil.3When freshly-distilled kerosene was burned in lamps, it produced

remove and neutralize any of the remaining acid. These latter steps were important to prevent the

only ofh

formation of sulfurous acid gas, a disagreeable

base

and strong irritant to the eyes and lungs that

asp!:

Treatment sulfuric

of kerosene

with

acid by refiners

a smoky flame and a strong odor. Therefore, refineries built to refine coal oil (see BeatQn" this

acid

issue) included the treatment or "deodorizing"

could be produced by the burning of residual acid

of lamp oil with sulfuric acid, and these facilities

in poorly-refined lamp oil. Following a resting

slud

were adapted to the refining of petroleum when the abundance and relative low cost of crude oil

period in bleaching tanks to further evaporate any potentially explosive components, the

prot acid

kerosene was fire-tested with a lit match. Finally,

mix1

it was drawn off for storage and shipment in white oak barrels.

for t

.

became apparent. Treatment of lamp~oil with sulfuric acid to improve its qualities was an integral part of both refining technologies. The typical method of refining crude oil in 1870, as carried out at the Economy Oil Works, Oil City, PA, involved several steps.' Crude oil

This

During the treatment of kerosene with

as ar

sulfuric acid, aromatic compounds that produce

man

the r

--~-",--

-"

~ ~ :II' j!

'IIi

asmoEYnant~?ate oxi,!~~da).1d~fo~ptoqUtts , ... '., ,,'

was'to dilute tbe acid siudgewith water, partly or

thafare insolul:!le in oil, Dut stay associated with

completely neutralize it, and discharge it into a local creek or river.

acid and organic component;in

the oil, resulting

in the production of mono- and dialkylsulfuric esters, the formation of alcohols, the sulfonation of aromatic compounds, and other re\lctions.6 No wonder the accumulated gunk was simply

Sulfuric acid manufacture

comes to Titusville

By 1867, editorial articles in the Titusville Morning Herald were pointing out the great volume of sulfuric acid used by the various refineries throughout the Oil Region, the

known as "acid sludge" or "sludge acid:' Sulfuric

relatively standardized process involved in its

acid treatment also removed foul-smelling sulfur

production, and the high costs incurred in

compounds and improved the color of the final

importing the acid from elsewhere.

--

product. Pennsylvania kerosene stock required only mild treatment with acid for the production of high -grade kerosene because of its paraffin base and general lack of impurities (sulfur and I

asphaltic compounds). The proper disposal of spent acid and acid

,'iJUiight; they preplaced

sludge after the kerosene cleaning process was a

~'with

problem. One option was to put the weakened

oth~r c~'mpetitors, I refiner,fl}s qave here, the oil is

acid to use, dissolving scraps of iron, roasting the

"

ut;;,in . , cities where these ~upplies '

mixture and forming copperas,or iron sulfate.? This material could then be sold as a raw material

red at 16'Wcost: pittsburgh,

New York

for the production of various iron pigments, or as an agricultural soil amendment. No doubt many or most of the earliest refineries followed the more common practice of the time, which

'I I Ii!' ,I , ~II

w

the acid orse.ftle out of solution; Many complex chemical reactions occur between the sulfuric

,' 'c , t.,,I ;i -I n, !,

"

---"'--"'"---"~

-...-..

.. ~----

~

I. lit

Having thrown down the gauntlet on this subject, nothing more was seen in the local

II

.

This article was followed soon after by the

plants

newspaper about sulfuric acid manufacture in

news that a sulfuric acid manufacturing plant would be soon constructed on ten acres of land

acquire 1928, t

Titusvilleuntil late 1870,when a very similar

in Oil Creek Township, just west of the Titusville

article appeared, reiterating the same issues.

city limits.

$73 mj TI ,

However, this time, the article strongly hinted that a sulfuric acid works in Titusville might be just around the corner:

The TitusvilleChemical Works :

dawn (

voluml

In 1871, a f~ctory for the manufacture of sulfuric

and su

acid was constructed by Rennie, Roberts & Dunn

fertilize

on the western edge of town, between Garden

southe

Street and Oil Creek (see page 24). The company

shippir

had previously supplied acid to Titusville refiners

needs (

from their acid works in Lodi, New Jersey.10The following year, the operation of the plant was put into a joint stock company and was named

the pet northe used e,

the Titusville Chemical Works. On January 25,

A stead

1873, the Titusville Morning Herald announced the further sale of the works to the Cleveland

acid oc

Chemical Company, although the name Titusville Chemical Works remained. The Cleveland group

King oj industr

manufacture, the article went on to try and anticipate the potential concerns of local citizens

consisted of names very familiar to the petroleum industry at the time: D.M. Marsh, president; c.A.

was the

about living near such a factory. Although the

Grasselli, treasurer; and LH. Mansfield, secretary.

years 0: 1914, f(

In describing the method of sulfuric acid

logic is somewhat twisted, we suppose that some

50 year

in peak

The Grasselli family descended from a long

may have found comfort in the thought that all

line of Italian chemists and had immigrated to

greater

mosquitoes might be eliminated by the plant.

the United States from Strasbourg, France in 18~6.11Eugene R. Grasselli operated a coal-oil

explosi'

At the ] manuf2

works in Kentucky in the 1850s, but soon diverted his energies to the production of sulfuric acid in Cincinnati for the petroleum refining industry.

acid, ar

produc acid frc

In 1866, reacting to the increased demand for sulfuric acid from refineries in Cleveland, he

the dev

established a chemical plant near the Standard

effectivi

Works refinery of John D. and William

also CO

Rockefeller. Apparently refusing an offer to merge business interests with Rockefeller, he became

steadily WJ

and remained the major supplier of acid to Standard Oil. The Grasselli family papers indicate

Works 1

that the price pf acid sold to Standard Oil was discounted relative to that supplied to Standard's

manufa

sulfuric the lead

competitors," which may have been due to the

m

sheer volume of business generated by Standard Oil. However, it seems likely that the Grasselli

:'

Sulfur i

(brimst

nitrate 1

move into the Titusville Oil Region in 1873 was

in a fur

.closely tied to Rockefeller's goal of monopolizing the Titusville refining industry. After Eugene

sulfur d

Grasselli's death in 1882, the company was run by his son, Caesar A. Grasselli, and later by his

vapors.

grandson, Thomas S. Grasselli. By 1900, the

large an

Grasselli Chemical Corporation operated five

to prod

along w

I

~i~ 1 ,.iiI,

il 1

plants in four states; and by the time they were

chambers. The floors of these chambers were

acquired by E.!. DuPont de Nemours & Co. in 1928, the company operated 23 plants valued at $73 million.'3 The end of the Civil War marked the

covered with three to four inches of water, which gradually became impregnated with acid. The Titusville plant consisted of two main buildings; the burner and chamber house, connected to

dawn of two new industries that required "large volumes of sulfuric acid: Petroleum refining

the still house by means of a condenser pipe. In the still house, the weaker "chamber acid"

and superphosphate fertilizer manufacture. The southern states, where plants were built to avoid

(62% sulfuric .acid)17was further purified and concentrated to 93% sulfuric acid by distillation in a platinum retort, a vessel used to heat and

shipping costs and to supply the agricultural needs of cotton and tobacco farmers. Most of

distill liquids. In the same way that the barrel was the standard unit of measure in the oil industry,

the petroleum refining was concentrated in the northern states, and this expanding industry

the carboy, equaling about 12 gallons, or 175 lbs., was the unit of measure at the sulfuric acid

fertilizer industry was centered mainly in the

used ever increasing quantities of sulfuric acid.

plant, whether the acid was placed in individual

A steady expansion in the production of sulfuric acid occurred in the United States over the next

glass carboys or shipped by tank car. In 1880, the Titusville Chemical Works produced 28,037

50 years, ultimately earning it the name "The

carboys of sulfuric acid, or a total weight of

i Iq lli IiI ! i " ,I

I"

King of Chemicals;' with an ever escalating list of industrial uses." One new use for sulfuric acid was the manufacture of explosives, resulting in peak outputs of the material during the years of World War 1. Between 1909 and 1914, fertilizer manufacture accounted for .

greater than 50% of all sulfuricacid use and explosives accounted for less than 5%.15 At the peak of the war in 1918, explosives manufacture used 36% of all sulfuric acid, and fertilizers less than 30%. The production of by-product sulfuric acid from smelter stack fumes, and the development of new and more effective ways of making sulfuric acid also contributed to this ability to steadily increase production. When the Titusville Chemical Works was constructed in 1871, sulfuric acid was typically manufactured by a method called

,t

'J

the lead chamber process." Sulfur imported from Sicily (brimstone) and sodium nitrate were burned together in a furnace, and the resulting sulfur dioxide was oxidized to produce sulfuric acid vapors. These were passed along with steam into large and partitioned lead

II I. I' Ii,/

J r I

.

4,880,949 pounds.18The plant also produced minor amounts of hydrochloric acid and ammonium hydroxide as by-products of sulfuric acid manufacture. The Titusville Chemical Works

The isolated location of the Boughton Acid Works was ideal for its purpose. Because much of the acid concentration done there was carried out by evaporating the excess water in

plant was dismantled in June of 1909.19

lead pans open to the atmosphere, more noxious

Its demise was certainly a function of the

fumes were released to the atmosphere than

declining amount of oil refined in Titusville,

from the Titusville plant. The fumes emitted by the works killed the surrounding vegetation, so

as well as new improvements in sulfuric acid manufacturing methods that made the almost

that the nearby hillsides were eroded down to

40-year old plant inefficient, expensive, and technologically obsolete.

the bare rock.25The immediate area was sparsely

The Boughton Acid Works The acid works at Boughton were built in 1871

populated, except for the company houses of the workers, whose tolerance of the fumes seemed to be a condition of employment. The location of the plant along the railroad line between

by D.C. Hutchins & Co., fast on the heels of the construction of the Rennie, Roberts and Dunn

Titusville and Oil City meant that the company

acid plant," and largely converted from the remains of old sawmill buildings on the site}1

generated by refineries in both areas.26

From the start, the purpose of this acid works

Refining Acid Sludge at Boughton

had ready access to the supply of acid sludge

was decidedly different from the Titusville plant.

The processing of acid sludge at the Boughton

lead

Its main purpose was to recover the sulfuric

plant began with the delivery of acid sludge in tank cars from a refinery." The company

and'

acid from acid sludge generated by the regional refineries, and to sell the recovered acid back to

maintained 11 railroad tank cars for shipping

pan; thrOl

them for reuse. Additional by-products expected

the sludge to the plant and five clean cars for

sO-C(

to be produced by the factory included lamp

returning the refined acid. The sludge was a dark,

evap

black for the manufacture of printers' ink and

viscous, tar-like liquid. The full-time job of one

or bottle house

black varnish, and some copperas." In 1878, the

employee in Titusville was to obtain the acid

prob Wor]

of the Boughton Acid Works, unknown date. Each retort held

plant was sold to the Titusville Chemical Works Co., so that both sulfuric acid plants in the

sludge from the refineries and have it delivered

Inside the retort

600 pounds of sulfuric acid, which was dis-

Titusville area were now effectively controlled by the Grasselli organization. In 1888, the

perfe

to the plant. Once there, the contents of the tank car were pumped into one of the separator tanks

pani was,

(16 x 16 x 6 feet deep) on the hillside. The tank contained between 36 and 42 inches of water,

blad

tilled to its final

Boughton works was completelY,destroyed by fire and was rebuilt by the American Chemical

according to the volume of acid sludge that was

full strength

and Manufacturing Co., still under Grasselli

to go inside it. Excess tar and acid also apparently

tern]: then

using natural gas

nott

(Ridgway, H., TItusville Herald,

contro1.'3 Plagued by a variety of technological

made their way to the small walled-in creek

and

and economic troubles, the Boughton Acid Works

July 5,1953).

finally closed in 1918.24

that ran through the property (affectionately referred to as "the old tar ditch"); acid burns

doul:

were sometimes reported by bathers in Oil Creek downstream of the plant.28 When the water and acid sludge were mixed, oil and tar rose to the top. This was drawn off into a tar tank and was used for fuel to boil the acid in the lead pans. When the acid sludge first arrived it was about 59% sulfuric acid, but dilution with the water reduced it to about 30%

1

glass pour seate 1500 were retor final that]

in strength. The acid was drawn off into the free acid tanks and stored there until it was used in

retor

the pans.

stren

The acid was then gravity-fed from the free acid tanks to the pan house, where twelve solid-

TheJ itwa

and weighing over a ton apiece. The acid entered

using compressed air. It was now ready to be sent to refineries in tank cars and used to refine

pan #1 at ambient temperature and meandered

oil. Large amounts of coal were also burned at

through one heated pan after another via a so-called "cascade pan method:' The constant

the plant, fueling boilers that, in turn, powered

lead pans were located, each 8 x 12 feet in size

evaporation of water from the heated acid

compressed air and water pumps. A number of factors were involved in the

probably cloaked the plant in a constant fog.

ultimate downfall of the Boughton Acid Works.

Workers skimmed off floating waste using large

The pan system of acid renewal was costly

perforated spoon-like tools. When the acid left

to begin with, suffering from relatively poor

pan #12, it had reached a temperature of 360°F, was about 81% sulfuric acid, and was still a

percent acid recovery, and high labor, fuel, and maintenance costS.'9New technologies were

black color. Higher concentrations of acid could not be reached at this stage because, at greater

cheaper, quicker, more effective, and produced less noxious fumes. Combined with the decline

temperatures, the lead pans would melt. The acid then went to a large cooling tank (32 x 8 x 6 feet)

in petroleum refinery orders and the general economic inflation associated with World War I,

and was ready to be placed in the retorts. The retort or bottle house contained a long

the plant became obsolete after 50 years of almost continuous operation, and finally closed in 1918.

double row of 72 retorts, 36 to a row. These large glass bottles were four feet high and held 600

Life at Boughton Acid Works, 1911-1918

pounds of acid apiece. Each retort was carefully

Leon White Stufflebeam began work at the

seated in a compartment called a "boot:' About

Boughton Acid Works on March 20, 1911, just

1500 cubic feet of natural gas and 21 hours were needed to boil and finish the acid in each

a few weeks short of his 39th birthday. He had

retort. Filling the retorts and drawing off the final acid product was a complicated operation that required expertise, and the breakage of glass retorts was a relatively constant business expense. The final refined and clarified acid was 93% in strength. After the acid had cooled for 24 hours, it was forced into storage tanks from a "blowcase"

spent the previous four years peeling bark and cutting logs in various lumber camps in Forest County, PA, most recently at Golinza, on Big Coon Creek, near the town of Nebraska. His decision to leave the lumber camps for Boughton had not been one of mere whimsy. The sobering reality was that, by his own detailed accounting,

he had spent $200 more than he had earned

Group of workers at the Boughton Acid Works, 1883. Workers in the foreground are holding parts of the glass retorts used in the final step of acid concentration. Employees wore wool clothing year-round; these were somewhat resistant to destruction by the acid. (DW580)

during the past four years of lumbering. Given

recorded over 4,000 hours of labor per year at the

the nomadic life of a professional lumberman,

acid plant, earning between $2.20 and $3.60 per

pou ofti

and a family of four to support, it is not

12-hour day during a six-day work week. For $4

in E

surprising that the relative stability of work at the

a month, he rented a company house supplied

acid plant appealed to him. Stufflebeam was a meticulous man who kept

with water and gas, and a one-half acre garden,

a journal for much of his life.3DIt is fortunate that

acid fumes. When he arrived at Boughton in

this journal was preserved and eventually donated to Oil Creek State Park by one of his descendent$, as it provides a fascinating account of life at the acid works. Stufflebeam worked at Boughton

east of the acid plant. Two annual events broke

for the final seven declining years of the plant's

the monotony of routine life in Boughton for the

operation, and he helped to close the works in

Stufflebeam family; an annual International Order

1918, when the plant was dismantled, salvaged,

of Odd Fellows picnic (Grand Valley Lodge 1072),

and abandoned. Sadly, his journal accounts end

held every August near Star Siding in Warren

with the closing of the Boughton Acid Works, and

County, and the Titusville Fair, a September event that could draw 20,000 or more attendees from the surrounding area. Leon Stufflebeam raised poultry in Boughton

Bou

Boughton was quiet, and that most of his time

as a source of additional income, selling eggs and

wit} feed

was spent working in the plant. He typically

day-old chicks. The level of detail found in his

the

Stufflebeam's journal suggests that life in

!1m

1911, six families, including Stufflebeam, lived in the company houses, all of which were located between Oil Creek and the railroad tracks, to the

nothing is currently known about the final years of his life.

BOUGHTON R'NtW'NG

presumably somewhere upwind of the noxious

WORKS.

. !5iJrffif flU

.

poultry records for 1914 may be one indication of the level of general "excitement" to be found in Boughton:

Life at the acid plant itself was clearly busy as long as acid sludge continued to be delivered from the local refineries. The reduced staff at the plant in these declining years included a foreman; an

Average number of hens: Eggs laid:

65 8,211

employee who stayed in Titusville and loaded acid sludge into tank cars; a general repairman/lead

Eggs set:

431

burner (or lead welder); a bookkeeper; two men

Chicks hatched:

309

on the boilers and pans; and two more on the

Chicks raised:

159

retorts. Stufflebeam rarely coil1mented on paper

Net profit per hen:

$1.20

about the working conditions in the plant, but the incidence of acid burns and employee turnover makes it clear that work in the plant was anything

March hens laid

1,522 eggs

April hens laid

1,606 eggs

May hens laid

1,118 eggs

but pleasant.

Stufflebeam continued to raise poultry at Boughton until 1917, when inflation associated with the onset of World War I drove the cost of feed up faster than the price of eggs, and he quit the business in disgust.

Right: GPS survey of foundation

reference points

at the Boughton site (photograph by J. Sams) Below: Remains of a stone foundation

at the acid works

(photograph by J Sams)

_I

1913

1915

Th

In October,LutherDavenport quitthe Co.and movedaway.

October4th.Duringa severewindandrain stormonehalfof the panhouseroofwasblown off.

It i

It wasmyturnto taketheextrawork onthe boilersandpans,butI did notwantit, soArthur Meyerstriedit for aboutsixweeks,thengaveit up.Saidhecouldnotstandthework. December 1st. I begandoingtheextraworkon the boilersandpans.

1914 September 30th.Theboilersandpansbecame minefor a steadyjob,Mr.IsraelMotterhaving quit.

1916 In May,Mr.Almanwasquiteseriouslyburned withacid,andin October,Mr.Berlinwasburned. Eachonewasunableto workfor sometime. AfterBerlingot burned,hequitthe retortsand wentto workin theyard,andMr. Deyeworked on theretorts.

1917 January3rd.Almanwasagainburnedwithacid. AlmanandBerlinhadnotifiedParkstheywere goingto quit,andMarch5th,RalphDeye becamemy partneronthe boilers. July16th.Deyequitafterhavingafight with Dickie. July17th.ArthurMeyersbecamemy partner,but wasnotableto standthework. August28to November 1. Dickiewasmy partner. November1to December 28.Moreheadwasmy partner. December 28.Dickieagainbecamemy partner. The weather also dramatically affected life at the acid plant, freezing water lines to both the acid works and the company houses during the winter. Strong storms periodically blew down parts of the old and acid-weakened plant.

1912 January13th.Thewaterline(3 inch),which suppliestheworkswithwater,frozeup anda largepartof the linehadto dugup andthawed out anda largepartofthe linehadto be replaced with newpipe.It wasMarch1st beforethe line wasrepaired.Thelineis nearlya milelong. Theweathercontinuedcoldall of this time-the thermometerregisteringaslowas40 degrees belowzero.31 Thewaterto supplytheworkswaspumpedfrom a run nearby. June15th.At oneo'clockP.M.the northhalfof the panhousefell down.Noonewashurt.

Winter 1917-1918 WinterbeganearlyandDec.8 thethermometer registered10degreesbelowzeroandcontinued coldallthe month,registeringaslowas 22 degreesbelowzerobeforethe endof the month. January2ndwasthe lastdaywe hadwaterin the houses.Thatdaythe lineswerefrozenup, andneverthawedout. Theweathercontinuedextremelycoldand January4ththe mainlinethatsuppliestheworks withwaterwasfrozensolid.Wehadto pumpthe waterout of a smallrunneartheworkto supply the boilersandto beusedinthe separators. January24th.Thelinewasthawedoutasfar as the run,butneveranyfarther. Therun wasdammedup andthewaterfrom the linerunintothe pond.Fromthe pondwe pumpedthewaterintothestoragetanksto be usedwhenneeded.

act to

ev(

an