a salute to the wwii pioneers in the petroleum refining & chemical industries

7/29/2019 A Salute to the WWII Pioneers in the Petroleum Refining & Chemical Industries

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A Salute to the WWII Pioneers in the Petroleum Refining & Chemical Industries

by G. T. Westbrook,

WWII came to an end over 60 years ago. There have been many appropriate

tributes to the veterans who gave so much to help this cause. Less notedindeed almostunnotedwere the incredible contributions made by the many communities in thepetroleum refining and chemical industries. In this report key efforts from theseindustries will be noted and a salute given to the pioneers in these areas who contributedso much to the successful completion of WWII. While it surely would be inappropriateto overstate the contributions from this sector, it may well be that this was the mostimportant supply effort of all industries and government programs. Without a successfulfulfillment of the missions assigned, WWII would have ended much differently.

Three interrelated programs will be reviewed briefly namely aviation gasoline(AGN), trinitrotoluene (TNT) and styrene butadiene rubber (SBR). Through acombination of factorsoutstanding research and engineering particularly considering

the conditions and the tools available; classic American ingenuity to beg borrow orsteal a component here or a blend-stock there; classic American creativity to find asolution when none seemed to exist; and finally mind numbing hours of effort in horribleconditionsthe pioneers of these industries got the job done. Not only did they solve thechallenges in the above three fields, but in doing so they literally gave birth to the processindustries that we know today.

Hitler's ambitions surfaced with the re-occupation of the Rhineland in March of1936, followed by moves into Austria, Czechoslovakia and Poland. The invasion ofPoland, in September of 1939, triggered UK and France to declare war. In January of1940, FDR initiated a major preparedness program. Then in May, 1940, Germanyinvaded the Lowlands and France. With the fall of France in June, FDR asked Congressto double his prior plan, including raising annual plane production from 5000 to 50,000.The Battle of Britain began in August, 1940. It was here that the critical role for AGNfirst emerged for "without 100 octane, we should not have won the Battle of Britain. It isa fact that this high performance fuel, spiked with aromatics such as cumene, gave BritishSpitfires and Hurricanes a distinct advantage over the much larger planes of theLuftwaffe." If this battle had been lost, it would have had major impact on the future ofWWII.

By December 1941, the Japanese military activity on the Asian mainland, hadbeen underway for years. But few, if any, predicted Japan's interests extended as far eastas Pearl Harbor. After that victory, Japan's forces rapidly movedinto the Philippines,the British East Indies, and the Netherlands East Indiesand seized control of the naturalrubber plantations. A critical need for synthetic rubber was at hand. Fortunately the U.S.had built a significant inventory of natural rubber. Equally fortunate was that a syntheticrubber, namely SBR, was in the pilot plant stage. This rubber, sometimes called BUNA-S(BU from butadiene, NA from the sodium catalyst used, and S for styrene), filled thelions share of WWII rubber requirements.

The Doolittle raid on Japan in April 1942, and the victory at Midway, in June1942, once again emphasized the need for AGN. This was further highlighted over themany island hopping campaigns that followed. "The addition of substituted aromatics to


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aviation gasoline would give a fuel which was desirable for high power takeoffs onshort runways and aircraft carriers." In November 1944, the first B-29 raid from Saipanoccurred. Unlike the strikes in Europe, these were long, roughly a 3000 mile round trip,and would require a major boost in AGN supply. Indeed these flights were so long theU.S. went after Iwo Jima, in part, for an emergency landing strip for the return flights.

The supply of materials of all types would thus play crucial roles in both theaters.One can imagine the confusion, even panic in London and Washington, as the supplyneeds became clearer. Staggering scale up efforts were going to be needed. These effortswould have to be achieved with marginal communication systems; terrible transportationfacilities; ugly lodging options; zero computers and zero linear programs the computersystems that plan and schedule refineries today. Shortages existed not only in fuels andchemicals, but for materials of all types: metals for tanks, guns, ships and planes, pluspumps, pipes, towers and so on; plastics, to save metals; rubber for tires, hoses and belts;paints for all types of hostile arenas; and sealants for ignition systems, and to seal radarunits.

Magnesium for war planes is an interesting, but not untypical example of the huge

scale-up efforts required. Government interest in magnesium was close to zero. Thischanged when it was discovered that German planes owed a great deal of their speed, andtheir capacity to carry fuel and bombs, to weight savings via liberal use of this metal.Initially mag use amounted to about 80 pounds per plane. By the end of the war this unitconsumption had become about 2000 pounds. With the annual output set to grow from5000 planes to FDR's goal of 50,000 (that actually hit 125,000), mag use exploded fromnear zero to 4 million pounds per year (MMPPY), then to 250 MMPPY.

Supply of chemicals had one of the major material interactions of the war,namely competition for the aromatics benzene and toluene. AGN, like all gasoline, ismade from many blend-stocks including aromatics, such as toluene, ethylbenzene (EB)and cumene. These were particularly useful blend-stocks. But the main role for toluenewas TNT. And the main role for benzene was ethylbenzene for styrene and hence SBR.Once the growing needs for SBR and TNT were met the excess would be used in AGN:toluene directly and benzene via either EB or cumene.

In 1939, benzene and toluene came from liquids recovered from coke ovens aspart of steel production. Output of benzene was about 125 million gallons per year(MMGPY), with an expected doubling needed. This scale-up could be handled by thecoke ovens. The situation for toluene was different. Current output was around 25MMGPY, but the expected increase was ten fold, and that could not be obtained fromthese ovens. A new source for toluene would be needed.

The AGN program had to produce a mix of rather complex fuels. AGN is a highoctane, controlled vapor pressure fuel for propeller based planes. In 1939, with motorgasoline at about 75 octane, AGN requirements would range from as low as 87 for thesimplest reconnaissance plane up-to and even above 100 octane, for high performancefighters and bombers.

In 1939 the U.S. AGN capacity was about 17 thousand barrels per day (MBPD).Early in 1941 forecasts were at 35 MBPD, but after Pearl Harbor, these jumped to 190MBPD. A year later they grew again to 300 MBPD. Finally, in 1945, AGN capacitypeaked out at over 600 MBPD.


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A strategy was developed to meet these changing requirements. Efforts were to bedivided between a major construction program and a "Quick 100" program. This lattereffort consisted of operational changes, small construction projects and blending policychanges. All of these could be accomplished relatively rapidly, but would involvechanges in over 300 relatively small refineries.

Operational changes would include such activities as: searching refineries for highoctane straight run blend stocks; coordinating inter-plant blend-stock moves; maximizingcracked gasoline output for AGN base and allocating more feed-stock to alkylation unitsfor more alkylate output. Part of alkylate would be 2,2,4-trimethyl pentane, a chemicalthat sets the upper, 100 octane, standard.

The small construction program included: de-bottlenecking refinery unitsextensively; converting 72 polymer gasoline units to co-dimer units, followedby hydrogenation at four major, central hydrogenation plants. (This would produce ablend-stock much like alkylate, called hydro-co-dimer); converting an additional 18polymer gasoline units to produce cumene; and finally adding distillation towers toextract high octane isopentane from refinery or gas plant streams.

The blending policy changes included: blending in toluene to the extent the TNTprogram could spare (by 1944, up-to 35% of the toluene was used in AGN); blending inEB to the extent the SBR program could spare; and finally using extra tetraethyl lead(TEL), up to 6 cubic centimeters per gallon, roughly twice the normal practice for motorgasoline at that time, and zero today.

The major construction program focused on construction of three types of units:alkylation, catalytic cracking (cat crackers) and catalytic reforming plants. Today, theseprocesses are the big ticket units in refining, producing about 6,000 MBPD of gasolineblend-stocks. In 1941 they barely existed. The new reforming processes would be theroute to toluene and seven units were installed. The new cat crackers were targeted to bethe bulk source of AGN blend-stocks. They would provide the base AGN blend-stockcalled (cat naphtha or cat gasoline), plus added olefins for use in other blend-stocks. Sixtyunits were built, with a total feed capacity of 760 MBPD. Sixty new alkylation plantswere also built, amounting to 178 MBPD of output.

The AGN program was an unquestioned success. Output, at the end of 1940, was25 MBPD, and up-to 40 MBPD by the attack on Pearl Harbor. By December 1942 it wasup-to 80 MBPD, and a year later, to 240 MBPD. At the end of June 1945, productionreached 650 MBPD, a 2500 % increase from 1940. Early in 1944 "an Army Generalstated: 'The job which has been done with 100 octane by the refinery experts is one of themost amazing things I have ever witnessed. It is almost unbelievable. They have almostsqueezed it out of a hat.'" Not only did the refining industry meet the challenges forAGN, but also for all the other refinery products required motor gasoline, diesel fuel,lube oils and greases for all sorts of hostile operating environments.

The story ofTNT over WWII is really the story of the development of a majornew source of purity toluene. In 1933, Standard Oil Development (S.O.D. or ESSO, aprecursor to Exxon) reported to the army Ordnance Department the detection of toluenein product streams from thermal reforming experiments on a petroleum based naphtha.While samples did not come up to nitration grade requirements, ESSO continued theresearch. By 1936 purity had improved, but not enough for the very demanding nitrationprocess to TNT. ESSO scientists, as a result, started to concentrate on catalytic


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reforming. This process gave much improved results over the thermal route, and a pilotplant was built in 1938. Ultimately a 99+% toluene stream was produced which could benitrated.

With war pending, the Army's interest in toluene became grave and they ordered afirst batch amounting to 20,000 gallons. A logistics nightmare existed at that time as seen

in the steps taken to fill this contract. The naphtha feed-stocks were refined in Texas.They were then shipped to New Jersey for reforming. This reformate streamcontainingaromatics, aliphatics and naphthenes of the same boiling rangewas returned to Texas,in 22 tank cars, for aromatics recovery. Next the aromaticsbenzene, toluene, xylenesand EBwere shipped to Louisiana for recovery and purification of toluene. Finally thetoluene was shipped to Maryland for nitration.

Needless to say ESSO did not make any money on this 1940 contract, butbusiness did improve dramatically after that and Humble Oil built the Baytown OrdnanceWorks, a plant that ultimately produced more than half of the total supply of wartimetoluene from petroleum.

The SBR program. One WWII executive stated in 1944 --- "Without a doubt, the

most critical war material shortage was that of rubber, practically all of which had beenimported." The challenge in the SBR program may best be seen by reviewing the statusof commercial polymer know-how in 1939. This was terribly austere. Polymerproduction amounted to only 200 million pounds per year (MMPPY) versus 80,000MMPPY in 1990. Polystyrene was barely out the door, and polyethylene was notcommercially available. Any elastomer production was strictly pilot plant. In order toproduce the large quantities of SBR that would be required, three major olefins had to beavailable, namely ethylene, styrene and butadiene. To help solve this problem theRubber Reserve Program set up a Technical Committee comprised of government and 36companies.

In 1939 styrene production amounted to less than 1 MMPPY. Styrene required abenzene source, and an ethylene source. Ethylene supply itself, was in its infancy withsome coming from refinery off-gases, some from ethanol dehydration (one plant in theUK had the option to start with molasses, as its basic feedstock, to get to ethanol and thento ethylene) and some from the precursors to the technology of choice today steamcracking of hydrocarbon feed-stocks. Ethylene output amounted to about 200 MMPPYversus about 45,000 MMPPY today. Over WWII ethylene supply would have to bequadrupled.

The Technical Committee, of the Rubber Program, ultimately put Dow Chemicalin charge of the Styrene Program. At this time Dow had the only commercial styreneplant, in Michigan, and was independently looking for a new plant site. Late in 1938,Dow had obtained major land holdings around Freeport, Texas (60 miles south ofHouston) on the Gulf Coast. Construction started in March of 1940 on what becameknown as Plant A of the Dow Chemical Texas Division. Chemicals included caustic,chlorine, ethylene, ethylene dichloride, vinylidene chloride (for Saran), bromine, ethylenedibromide (for use in TEL fluids), magnesium and finally ethylene glycol (for antifreeze).Plant B followed shortly thereafter for ethhylbenzene, styrene and magnesium. At thepeak of construction 10,000 workers were involved at what was at one time a rathersleepy little fishing village. Housing problems were monumental with workers staying in


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tents, trailers and farm houses as far away as 50 miles. And air-conditioning was non-existent.

In total, six styrene plants were built. Dow built three of these and assisted on theothers. Approximately 90% of the styrene production came from plants based on the Dowprocess.

For butadiene, there were three options: extraction from steam cracker byproductstreams; de-hydrogenation of n-butylenes; and dehydration of ethanol. Esso committed toinstall three steam crackers and to extract the butadiene as a major by-product. However,there was insufficient butadiene in these streams to meet the massive scale-up required.On-purpose production would be required. "As soon as the agriculture lobby becameaware of the possibilities of using grain based alcohol to make a critical war material, itmobilized its friends in the Senate and the House." Although it was somewhat moreexpensive than the butylene based material, it received strong consideration and at onetime appeared that all on-purpose butadiene would come from alcohol. (The conflict onoxygenates today, between ethers and renewable ethanol, is very much analogous to theconflict in 1941-42.) Finally, the decision was made to use both processes. However, the

ag route dominated early on capturing a 78% share in 1943, versus petroleum basedoptions. This was cut in half to 39% by 1945. Production jumped from 360 in 1943, tonearly 1200 MMPPY in 1945.

The overall Rubber Program built 51 plants for feed-stocks, monomers, andsynthetic rubber. The SBR production grew from 7 MMPPY in 1942 to 1580 MMPPY in1945. In 1944 the Chemical Engineering Award was given to 67 companies for"crowding into 24 months, chemical engineering planning and construction that normallywould have required many years."

The cost of these programs was high, estimated at 42 billion$ (B$), in 1990$.TheAGN program was estimated at 15 B$; other refinery programs at 20 B$; (toluene isincluded in these numbers); and the SBR program at 7 B$. Yet one can only stand in aweat the incredible accomplishments of this effort. Not only did the pioneers solve theAGN, TNT and SBR challenges, but met the needs of the war effort on a broad front,including other fuels, plastics, metals and chemicals. And in so doing they literally gavebirth to the petrochemical, rubber, plastics and refining industries that we know today. Sogive a salute and a cheer to the pioneers of these industries, who, in their own way, gaveso much to the successful completion of the war effort.

a salute to the wwii pioneers in the petroleum refining & chemical industries

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