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 almost unnotedwere the incredible contributions made by the many communities in the petroleum refining and chemical industries. In this report key efforts from these industries will be noted and a salute given to the pioneers in these areas who contributed so much to the successful completion of WWII. While it surely would be inappropriate to overstate the contributions from this sector, it may well be that this was the most important supply effort of all industries and government programs. Without a successful fulfillment 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 a combination of factorsoutstanding research and engineering particularly considering the conditions and the tools available; classic American ingenuity to beg borrow or steal a component here or a blend-stock there; classic American creativity to find a solution when none seemed to exist; and finally mind numbing hours of effort in horrible conditionsthe pioneers of these industries got the job done. Not only did they solve the challenges in the above three fields, but in doing so they literally gave birth to the process industries that we know today. Hitler's ambitions surfaced with the re-occupation of the Rhineland in March of 1936, followed by moves into Austria, Czechoslovakia and Poland. The invasion of Poland, in September of 1939, triggered UK and France to declare war. In January of 1940, FDR initiated a major preparedness program. Then in May, 1940, Germany invaded the Lowlands and France. With the fall of France in June, FDR asked Congress to 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 AGN first emerged for "without 100 octane, we should not have won the Battle of Britain. It is a fact that this high performance fuel, spiked with aromatics such as cumene, gave British Spitfires and Hurricanes a distinct advantage over the much larger planes of the Luftwaffe." If this battle had been lost, it would have had major impact on the future of WWII. By December 1941, the Japanese military activity on the Asian mainland, had been underway for years. But few, if any, predicted Japan's interests extended as far east as 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 natural rubber 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 synthetic rubber, 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 the lions share of WWII rubber requirements. The Doolittle raid on Japan in April 1942, and the victory at Midway, in June 1942, once again emphasized the need for AGN. This was further highlighted over the many island hopping campaigns that followed. "The addition of substituted aromatics to

aviation gasoline would give a fuel which was desirable for high power takeoffs on short runways and aircraft carriers." In November 1944, the first B-29 raid from Saipan occurred. 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 the U.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 supply needs became clearer. Staggering scale up efforts were going to be needed. These efforts would have to be achieved with marginal communication systems; terrible transportation facilities; ugly lodging options; zero computers and zero linear programs the computer systems that plan and schedule refineries today. Shortages existed not only in fuels and chemicals, but for materials of all types: metals for tanks, guns, ships and planes, plus pumps, 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 radar units. 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. This changed when it was discovered that German planes owed a great deal of their speed, and their 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 unit consumption had become about 2000 pounds. With the annual output set to grow from 5000 planes to FDR's goal of 50,000 (that actually hit 125,000), mag use exploded from near 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, is made from many blend-stocks including aromatics, such as toluene, ethylbenzene (EB) and cumene. These were particularly useful blend-stocks. But the main role for toluene was 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 as part 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 the coke ovens. The situation for toluene was different. Current output was around 25 MMGPY, but the expected increase was ten fold, and that could not be obtained from these ovens. A new source for toluene would be needed. The AGN program had to produce a mix of rather complex fuels. AGN is a high octane, controlled vapor pressure fuel for propeller based planes. In 1939, with motor gasoline at about 75 octane, AGN requirements would range from as low as 87 for the simplest reconnaissance plane up-to and even above 100 octane, for high performance fighters 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 190 MBPD. A year later they grew again to 300 MBPD. Finally, in 1945, AGN capacity peaked out at over 600 MBPD.

A strategy was developed to meet these changing requirements. Efforts were to be divided between a major construction program and a "Quick 100" program. This latter effort consisted of operational changes, small construction projects and blending policy changes. All of these could be accomplished relatively rapidly, but would involve changes in over 300 relatively small refineries. Operational changes would include such activities as: searching refineries for high octane straight run blend stocks; coordinating inter-plant blend-stock moves; maximizing cracked gasoline output for AGN base and allocating more feed-stock to alkylation units for more alkylate output. Part of alkylate would be 2,2,4-trimethyl pentane, a chemical that sets the upper, 100 octane, standard. The small construction program included: de-bottlenecking refinery units extensively; converting 72 polymer gasoline units to co-dimer units, followed by hydrogenation at four major, central hydrogenation plants. (This would produce a blend-stock much like alkylate, called hydro-co-dimer); converting an additional 18 polymer gasoline units to produce cumene; and finally adding distillation towers to extract high octane isopentane from refinery or gas plant streams. The blending policy changes included: blending in toluene to the extent the TNT program could spare (by 1944, up-to 35% of the toluene was used in AGN); blending in EB 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 motor gasoline 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, these processes are the big ticket units in refining, producing about 6,000 MBPD of gasoline blend-stocks. In 1941 they barely existed. The new reforming processes would be the route to toluene and seven units were installed. The new cat crackers were targeted to be the bulk source of AGN blend-stocks. They would provide the base AGN blend-stock called (cat naphtha or cat gasoline), plus added olefins for use in other blend-stocks. Sixty units were built, with a total feed capacity of 760 MBPD. Sixty new alkylation plants were also built, amounting to 178 MBPD of output. The AGN program was an unquestioned success. Output, at the end of 1940, was 25 MBPD, and up-to 40 MBPD by the attack on Pearl Harbor. By December 1942 it was up-to 80 MBPD, and a year later, to 240 MBPD. At the end of June 1945, production reached 650 MBPD, a 2500 % increase from 1940. Early in 1944 "an Army General stated: 'The job which has been done with 100 octane by the refinery experts is one of the most amazing things I have ever witnessed. It is almost unbelievable. They have almost squeezed it out of a hat.'" Not only did the refining industry meet the challenges for AGN, 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 of TNT over WWII is really the story of the development of a major new source of purity toluene. In 1933, Standard Oil Development (S.O.D. or ESSO, a precursor to Exxon) reported to the army Ordnance Department the detection of toluene in product streams from thermal reforming experiments on a petroleum based naphtha. While samples did not come up to nitration grade requirements, ESSO continued the research. By 1936 purity had improved, but not enough for the very demanding nitration process to TNT. ESSO scientists, as a result, started to concentrate on catalytic

reforming. This process gave much improved results over the thermal route, and a pilot plant was built in 1938. Ultimately a 99+% toluene stream was produced which could be nitrated. With war pending, the Army's interest in toluene became grave and they ordered a first 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 streamcontaining aromatics, aliphatics and naphthenes of the same boiling rangewas returned to Texas, in 22 tank cars, for aromatics recovery. Next the aromaticsbenzene, toluene, xylenes and EBwere shipped to Louisiana for recovery and purification of toluene. Finally the toluene was shipped to Maryland for nitration. Needless to say ESSO did not make any money on this 1940 contract, but business did improve dramatically after that and Humble Oil built the Baytown Ordnance Works, a plant that ultimately produced more than half of the total supply of wartime toluene 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 been imported." The challenge in the SBR program may best be seen by reviewing the status of commercial polymer know-how in 1939. This was terribly austere. Polymer production amounted to only 200 million pounds per year (MMPPY) versus 80,000 MMPPY in 1990. Polystyrene was barely out the door, and polyethylene was not commercially available. Any elastomer production was strictly pilot plant. In order to produce the large quantities of SBR that would be required, three major olefins had to be available, namely ethylene, styrene and butadiene. To help solve this problem the Rubber Reserve Program set up a Technical Committee comprised of government and 36 companies. In 1939 styrene production amounted to less than 1 MMPPY. Styrene required a benzene source, and an ethylene source. Ethylene supply itself, was in its infancy with some coming from refinery off-gases, some from ethanol dehydration (one plant in the UK had the option to start with molasses, as its basic feedstock, to get to ethanol and then to ethylene) and some from the precursors to the technology of choice today steam cracking of hydrocarbon feed-stocks. Ethylene output amounted to about 200 MMPPY versus about 45,000 MMPPY today. Over WWII ethylene supply would have to be quadrupled. The Technical Committee, of the Rubber Program, ultimately put Dow Chemical in charge of the Styrene Program. At this time Dow had the only commercial styrene plant, 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 of Houston) on the Gulf Coast. Construction started in March of 1940 on what became known as Plant A of the Dow Chemical Texas Division. Chemicals included caustic, chlorine, ethylene, ethylene dichloride, vinylidene chloride (for Saran), bromine, ethylene dibromide (for use in TEL fluids), magnesium and finally ethylene glycol (for antifreeze). Plant B followed shortly thereafter for ethhylbenzene, styrene and magnesium. At the peak of construction 10,000 workers were involved at what was at one time a rather sleepy little fishing village. Housing problems were monumental with workers staying in

tents, trailers and farm houses as far away as 50 miles. And air-conditioning was nonexistent. In total, six styrene plants were built. Dow built three of these and assisted on the others. Approximately 90% of the styrene production came from plants based on the Dow process. For butadiene, there were three options: extraction from steam cracker byproduct streams; de-hydrogenation of n-butylenes; and dehydration of ethanol. Esso committed to install 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 became aware of the possibilities of using grain based alcohol to make a critical war material, it mobilized its friends in the Senate and the House." Although it was somewhat more expensive than the butylene based material, it received strong consideration and at one time appeared that all on-purpose butadiene would come from alcohol. (The conflict on oxygenates today, between ethers and renewable ethanol, is very much analogous to the conflict 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 based options. This was cut in half to 39% by 1945. Production jumped from 360 in 1943, to nearly 1200 MMPPY in 1945. The overall Rubber Program built 51 plants for feed-stocks, monomers, and synthetic rubber. The SBR production grew from 7 MMPPY in 1942 to 1580 MMPPY in 1945. In 1944 the Chemical Engineering Award was given to 67 companies for "crowding into 24 months, chemical engineering planning and construction that normally would have required many years." The cost of these programs was high, estimated at 42 billion$ (B$), in 1990$.The AGN program was estimated at 15 B$; other refinery programs at 20 B$; (toluene is included in these numbers); and the SBR program at 7 B$. Yet one can only stand in awe at the incredible accomplishments of this effort. Not only did the pioneers solve the AGN, 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 gave birth to the petrochemical, rubber, plastics and refining industries that we know today. So give a salute and a cheer to the pioneers of these industries, who, in their own way, gave so much to the successful completion of the war effort.