Brassylic Acid: Chemical Intermediate from High-Erucic Oils

3989

Purchased by the U.S. Department of Agriculture for official use.

Kenneth D. Carlson- and Virgil E. Sohns

Northern Regional Research Center. Agricultural Research Service. U.S. Department of Agriculture. Peoria. Illinois 61604

R. Beltron Perkins. Jr., and Everett L. Huffman

Southern Research Institute. Birmingham. Alabama 35205

Techniques and information derived from laboratory studies of a two-stage cleavage of erucic acid with ozone and oxygen have been translated to a small pilot-scale operation to produce brassylic acid (72-82% yield) of high purity (99 %) with pelargonic acid as a coproduct. The initial ozonolysis phase is yield-limiting while the sec ond stage oxidation of ozonolysis intermediates appears to be quantitative. A preliminary cost estimate has been prepared for production of polYJTler-grade brassylic acid from Crambe abyssinica seed oil. The effects of bye product credit and crambe oil cost on the net cost-to-make brassylic acid are illustrated.

Introduction In general, the properties of nylon 1313 are similar to those Aliphatic dibasic acids are versatile chemical intermediates. commercial engineering polyamides. nylon 11, 12.610. and 612 Bifunctionality, from which their importance arises. permits (Chern. Eng.. 1969; Chern. Week. 1971; Mod. Plast., 1970), the acids or their derivatives to undergo various reactions for Probably the most straightforward method of producing the preparation or modification of certain polymers. Only a brassylic acid involves oxidative ozonolysis of erucic acid few long-chain a,w-alkanedioic acids have gained commercial (cis-13-docosenoic) (Blackmore and Szatkowski, 1959; Greene importance (Pryde and Cowan. 1972). most notably adipic et aI., 1967; Greiner. 1970; Grynberg et aI., 1970; Holde and Zadek, 1923; Mirchandani and Simonsen, 1927; Nieschlag et (Co), azelaic (Cg), sebacic (C w), and dodecanedioic (C1:!l. Both adipic and dodecanedioic are derived from petroleum feed aI., 1967b; Verkade et al.. 1926). Erucic acid has been avail- stocks, whereas azelaic and sebacic are made from vegetable oils. Dibasic acids and their derivatives supply important CH:l(CH.l)7CH=CH(CH~)11CO~H 0" [ .] "d --- IntermedIates markets as plasticizers, lubricants, and hydraulic fluids; in ErUClC aCI alkyd resins, polyurethanes, and polyamides; as monomers for certain copolymers. ~ CH:I(CH2hC02H + H02C(CH2h IC02H First prepared and characterized in the last half of the Pelargonic acid Brassylic acid nineteenth century (Pryde and Cowan, 1972), brassylic acid able from imported rapeseed oil and occurs to the extent of (1,13-tridecanedioic) is the 13-carbon relative of these com 55-60% in the seed oil of Crarnbe abyssinica. a domestic in mercially important acids. Selected esters of brassylic acid are dustrial crop being promoted by the U.S. Department of Ag excellent low-temperature plasticizers for poly(vinyl chloride) riculture (Nieschlag and Wolff, 1971: Tallent, 1972), The (Nieschlag et al.• 1964; 1967a; 1967c; 1969). Reportedly. esters ultimate yield of brassylic acid from erucic acid depends upon of brassylic acid are suitable as lubricants over a wide tem conversion efficiencies attwo distinctstages ofthe reaction perature range (Critchley, 1962), and the macrocyclic ester. ozonolysis and oxidation. Evaluation of the two stages indi ethylene brassylate. has been prepared as a synthetic musk cates that ozonolysis is more important than oxidation in (Chern. Week. 1965; Emery Industries, 1965; Vonasek and determining the final product yield. We also found excellent Trepkova. 1963). Brassylic acid also serves as the dicarboxvlic correlation between bench-scale and small pilot-scale syn acid monomer for preparing such polyamides as nylon 1:313 theses of brassylic acid. and nylon 61.3 (Chern. Eng. News, 1972; Greene et al., 1967; Kestler, 1968; Perkins et al., 1969). The inherent low-moisture absorption of these nylons makes them suitable for uses re Bench-Scale Studies quiring retention of strength, toughness, abrasion resistance, Ozonolysis. First, consider laboratory ozonolysis experi and electrical properties under varying conditions of humidity. ments. Because esters are more easily analyzed by GLC than

Ind. Eng. Chern.. Prod. Res. Dev.• Vol. 16. No.1. 1977 9S 9A Hnnannl Istd.j 13A[ -91 :~/'/f l J8=8 8

"u :f""/~~ln·,, ." "- "'- 40

\ \ $'/ft/ '", ~ '. u m A 1 ll...... 11 __a_a_""_:l ._~ o" 60 100 140 30 60 90 120 150 190 220 ~20L n.e, Ilia '" "'- ~[ Figure 1. Product assay as a function of time for the two stages of "" bench-scale oxidative ozonolvsis of methvl erucate (ME) in acetic acid (aliquots hydrogenated bef~re GLC an~ysis).

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91, B 131'£ ~~ I \t __LJ l,,- - ~ 10 20 30 R.I••tin na. ~~ Figure 3. GLC of products of ozonolysis of methyl erucate in acetic I...A...A 22E acid. (A) Aldehyde products from hydrogenation of ozonolysis in termediates. 12E = methyllaurate, 20E =methyl eicosanoate. (B) ------Products from thermal cleavage (glc without hydrogenation) of ozo ~ ~l - nolysis intermediates. SHC =octane. 10 20 30 40 50 Rltll1l0D Tuu Figure 2. GLC of products of oxidative ozonolysis of methyl erucate genated (Pd/C). and analyzed in turn by GLC for methyl in acetic acid. (A) Aldehyde products at end of ozonolysis (after hy erucate, aldehydes, and acids. The maximum yield of al drogenation). (B) Acid products at end of oxidation. dehydes in this run (80-85%) was assumed to occur at 140 min when ozone appeared in the effluent gases and the disap pearance of methyl erucate (ME) ceased. In a separate ex are the corresponding acids, methyl erucate rather than erucic periment (K. D. Carlson. unpublished), aldehyde yields de acid was ozonized, thereby providing bifunctional interme creased on continued exposure to ozone after similar indica diates with one ester group. Also, the ozonolysis intermediates tions that the reaction was complete. Over-ozonization is to were hydrogenated over Pd/C, and yields of the major alde be avoided if maximum yields are expected. In Figure 1 re hyde products-nonanal (9A) (see Nomenclature) and methyl sidual "ME" at 140 min is actually methyl behenate (the 12-formyldodecanoate (13AE)-were then determined by saturated analog of methyl erucate) that was present in the GLC (3% OV-101 on Gaschrom Q). This procedure enabled substrate and not resolved from the methyl erucate under our us to isolate the ozonolysis step to evaluate its influence on the GLC conditions. The aldehyde product distribution (ozono ultimate yield of brassylic acid. Ozonolysis was controlled by lysis stage of Figure 1) is shown in Figure 2A. monitoring effluent gases from the reactor with an ozone Oxidation, For the run illustrated in Figure I, the oxidation meter, and flow rates of ozone-in-oxygen (2-3%, 40-50 mg/l.) stage was carried out at two temperatures. 65 ± 5 °C for the were adjusted so that ozone absorpion was complete in the first 90 min and 96-100 °C for the remaining time. We found reaction medium until all double bonds were cleaved. The no exotherm at either temperature in these bench-scale oxi substrate solutions were 0.67 M in methyl erucate. dations (20 g substrate). Yields of pelargonic (9Ac) and 12 Preliminary experiments (K. D. Carlson. unpublished) carbomethoxydodecanoic (13AcE) acids reach a maximum evaluated effects of different solvents, temperatures. and at 2.5 h (83-86%) and then remain constant. Since additional ozone exposure times frem which a process evolved that could oxidation beyond 225 min does not lower the yields. we con be used efficiently in the pilot plant. Reductive ozonolytic clude that the acids (Figure 2B) are stable to these oxidation cleavage of methyl erucate in glacial acetic acid at 20-24 °C conditions. Direct conversion ofthe aldehydes to acids is ap proceeded cleanly. Yields of9A (88-91%) and 13AE (81-85%) parent from the relative product yields at the end of each stage were reproducible and significantly higher than in inert or (Figure ll. and therefore acid yields depend upon aldehyde mixed solvents (K. D. Carlson, unpublished), and it was ap and aldehyde precursor yields in the unreduced ozonolysis parent that acetic acid was a good solvent for scale-up studies. products. The ozonolysis step is most difficult and product We next defined the ozonolysis end point in this solvent both losses are more likely to occur during this step than during for maximum conversion of erucic acid and for product yield. subsequent oxidation. Probably one factor responsible for this Similar information was needed for the oxidation stage, i.e., fact is the thermal lability of intermediates during ozonolysis conversion of ozonolysis intermediates to brassylic acid. (Pryde and Cowan. 1971). This lability is illustrated in Figure Figure 1 shows the productdistribution as a function oftime 3. Hydrogenation of the ozonolysis products before GLC for ozonolysis and subsequent oxidation in glacial acetic acid. analysis gives the usual distribution of aldehydes (Figure 3A, Aliquots were removed during the reaction sequence, hydro- 89% yield of9A, 81% yield of 13AE). but direct GLC analysis

96 Ind. Eng. Chern., Prod. Res. Dev.. Vol. 16, No.1, 1977 116 \ \ B A\ ;-0 115 o a6~. 3)c/ ...... \ ...... - ;;.. ~ \ 114 '\ 111' ,,, ...e fp 11320C :00 9;! 9; ;!! ~ . ~\ -: __ ~~~":t~,._"_. __._ 113 \. . 1120~--J.--1Ol...O--'---20l."O-...L-.....,.30~O-...L--4J..OO-..J,..../ Time. Sec Figure 4. (A) Cooling curve for purified brassylic acid. (B) Freezing point of brassylic acid as a function of purity; 0, calibration data: X, pilot-scale data.

OlDIE OITSEJI Figure 6. Pilot-scale reactor for ozonolysis-{)xidation.

CKiltOll Brassylic acid of >98% purity was recrystallized from toluene to a constant freezing point (113.8 °C, five recrystallizations). After known amounts of pelargonic acid were added to two CIUGE !IISSTllC samples of this presumably pure brassylic acid. freezing points ICIO for the mixtures were determined: 0.86% pelargonic. fp 113.2 azoxlm OXIDIZER CEXTRIFUGE CRYSTAlliZER CEXTRIfUGE °C; 1.80% pelargonic. fp 112.5 °C. In this range. freezing point Figure 5. Process scheme for pilot-scale preparation of brassylic vs. purity of brassylic acid is nearly linear (Figure 4B), and acid. brassylic acid from the pilot-scale process was judged ofsat isfactory purity if a freezing point of 112.5-113.8 °C was ob tained. of the ozonolysis products without hydrogenation leads to much lower 9A (74%) and 13AE (48%) yields (Figure 3B). Pilot-Scale Preparation Thermal degradation of the ozonolysis intermediaj:es in the Basically. the process involved treating erucic acid in glacial GLC inlet port forms significant amounts of methyllaurate acetic acid with ozone at room temperature until ozonolysis (12E, 13%, identified by GLC-mass spectrometry) from the was complete and then oxidizing the intermediates at about 13-carbon portion and probably octane (8HC, 8%) from the 100 °C. The reaction mixture was then cooled to 20-25 °C. 9-carbon fragment. These chain-shortened products account The brassylic acid was separated by centrifugation and for about one-half the decrease in aldehyde yields. Thermal washed first with water to remove acetic acid and then with degradation at 25°C is slow as evidenced by the small amount toluene to remove pelargonic acid and other impurities. The of methyl laurate (-1%) present in the reduced products crude brassylic acid was purified by one recrystallization from (Figure 3A). Since the temperature used for oxidation is toluene. The complete process is illustrated schematically in generally about 100°C, some yield-lowering thermal degra Figure 5. dation of intermediates may occur before oxidation can take Process Equipment. Two ozonolysis-oxidation reactors place. like the one shown in Figure 6 were used. Glass resin kettles, Although addition of a small amount of water «10%) to the having a nominal capacity of 5 gal and measuring 14.5 in. in ozonolysis intermediates before oxidation had negligible effect diameter and 14.5 in. in depth. served as reactors. Each reactor on oxidation, its presence facilitated the isolation of crude was supported inside a stainless steel tank and was closed with brassylic acid. a stainless steel cover. Attached to the cover was a coil of 0.25 Purification. Procedures have been published (Greene et in. X 18 ft stainless steel tubing for cooling or heating, a stirrer al., 1967) for purifying brassylic acid by crystallization from bearing, a gas inlet tube, a condenser. and a thermometer. The benzene and then from ethanol, but the chronic toxicity of 4-in. diameter Teflon stirrer was centered about 1 in. above benzene and Government regulations concerning ethanol are the bottom of the kettle and was driven with an air motor (ca. drawbacks to their use. Freezing points of brassylic acid 400 rpm). The gas inlet tube was a 0.5-in. open-end tube with fractions showed that toluene and benzene were equally ef the opening located even with and about 0.5 in. from the fective recrystallization solvents for brassylic acid, whereas stirrer. recrystallization from methanol, ethanol. and 2-propanol did The ozone generator. a ModeI400-18-0DR Corona gener not improve the quality of the acid that had been recrystal ator and air preparation unit. was supplied by Purification lized from toluene. Furthermore, essentially quantitative Sciences, Geneva. N.Y. Oxygen was fed to the generator from recoveries of the acid from toluene should be possible since a liquid oxygen tank equipped with an evaporator. This gen the solubility of brassylic acid in toluene at 25°C is only 0.04%. erator was operated at a gas flow rate of 6.28 SCFM and at an Yet a 28% solution is obtainable at 80-90 °C. Bench-scale ozone generation rate of 0.64-0.65 lb/h (ca. 85% of rated ca recoveries were 93%. Treating the toluene solution of brassylic pacity). acid with activated charcoal (2% Norit EX) improved the color Filtrations were performed in a Model AF basket centrifuge of the recovered acid. supplied by Tolhurst Centrifugals Division. American Ma Recrystallization of brassylic acid from toluene was chosen chine and Metals. Inc., East Moline. Ill. The basket was 20 in. for the pilot-scale operation. and the quality of the recovered in diameter and 9.5 in. deep. Spinning speed was 1750 rpm. acid was determined from freezing points obtained from The liner of the basket was 20 X 250 mesh stainless steel cooling curves plotted for 18-20 g samples (Figure 4A). screen.

Ind. Eng. Chern.• Prod. Res. Dev.• Vol. 16, No.1. 1977 97 ,Jl, OXlcatlon r~ ! II i ~ :i '," nl'i )l 11 II r: LJ 60 "~,,! " d i ~ I fill" Ii II II I':: ~=

.. 40 !,',lllJ'I'I , I,tI U I :!~ C'1stalllzer Tank Sle,;m·Jackued Autocl.ne Figure i. Schematic of brassylic acid recrystallization unit. 4.0 4.5 1.0 2.0 3.0 Time. Hr The equipment used in recrystallizing brassylic acid con Figure 8. Product assay as a function of time for the two stages of sisted of a 50-gal stainless steel autoclave, a small percolating pilot-scale ozonolysis of erucic acid (EA) in acetic acid (aJiquots hy. tower filled with Norit 4 X 14 granular activated charcoal drogenated and treated with acidic methanol before glcL 13AcAc = (American Norit Co., Inc., Jacksonville, Fla.), a cartridge fIlter, brassylic acid. and a 55-gal stainless-steel drum. A schematic of this equip ment is shown in Figure 7. The autoclave, jacketed for heating Table I. Material Balance and Solvent Loss during with steam, was equipped with a propeller stirrer. The per Oxidative Ozonolysis of Erucic Acid colation tower (3 X 36 in.) was steam traced as were the lines from the autoclave to the tower. The filter was a Micro-Klean Reactor 1 Reactor 2 Filter manufactured by Cuno Engineering Corp. and fitted with a cartridge having a 1- to 3-~ rating. The filter and con Reaction time, h necting lines were heated with electrical heating tape. Ozonolvsis 3.5 6.0 0 Process Conditions. Temperature during ozonolysis was Oxidation 3.0 2.8 easily controlled by circulating water through the cooling coil Total 6.5 8.8 Charge. lb inside the reactor. The cooling coil in the water-filled jacket Erucic acid 11.90 11.90 surrounding the reactor normally was not used but served as Acetic acid 18.75 18.75 a safety feature. The ozonolysis temperature generally ranged Total 30.65 30.65 between 18 and 24 DC. Oxidation of ozonolysis intermediates Final wt.lb on the pilot scale proved to be mildly exothermic. The reaction Product, theory 13.68 13.68 can be quenched by stopping oxygen flow, and heat can be Prod. + solvent. theory 32.43 32.43 removed rapidly by flowing water through the cooling coil in Prod. + solvent, recovered 25.97 26.68 the reactor. The water in the surrounding jacket also serves Total wt loss 6.46 (19.9%) 5.75 (17.7%) as a heat sink in the early exothermic stage of the reaction. Wt loss, %/h 3.06 2.02 With these provisions for temperature control, oxidation of o Includes 3.5 h of effluent flow from reactor 1 during ozonolysis the ozonolysis intermediates proved to be simple and trou in reactor 1. ble-free. Reaction times for ozonolysis were established in prelimi sylic acid (l3AcAc) and 88% 9Ac in Figure 8 agree well with nary experiments by monitoring ozone consumption, ob corresponding values (83% 13AcE and 86% 9Ac, respectively) serving the viscosity of the reaction mixture in the reactor (as noted for the related products in laboratory experiments reflected by the power required to maintain constant stirring (Figure 1). rate), and determining isolated yields ofcrude brassylic acid Solvent Loss. Better process control and economic evalu· from subsequent oxidation. As ozonolysis progressed, viscosity ation of the process required that data be gathered on material of the reaction mixture increased and appeared to stabilize balance, particularly solvent loss, during the reaction. An ef after 3.5 h. At this time, ozone consumption was about 110% ficient condenser is needed to reduce the vapor temperature of theory, and ozone content of gas exiting the reactor was of reactor exit gases to 20 DC or less if comparable solvent about 90% that of the gas entering the reactor. Isolated bras losses are to be expected during ozonolysis (20 DC) and during sylic acid yields were essentially the same after 3, 3.5, and 4 oxidation (l00 DC). Data in Table I were collected from a h of ozonolysis. The time required for oxidation of the ozon routine pilot run (described below) with the two reactors op olysis intermediates \,ras determined to be 2.5 h, when a neg erating in tandem. A 19% increase in weight, relative to sub ative test was obtained on a sample with potassium iodide strate charge, is anticipated if pelargonic and brassylic acids starch indicator. are formed in quantitative yields (l3.68Ib products) and, with These findings were confirmed by making a pilot-scale run no solvent loss, the reactor contents should then weigh 32.43 in which samples were removed during both the ozonolysis lb at the end of reaction. Actual recoveries. however. show and oxidation stages of reaction. Aliquots of these samples total weight losses to be 18-20%. or 2-3%/h (Table n. If the were hydrogenated (Pd/C), treated with acidic methanol (to acetic acid loss rate is essentially constant over the entire re generate esters and acetalsl, and then analyzed by GLC. Data action period, as appears likely, then calculation of an average were corrected for concentration increases during reaction due loss rate is valid. A calculation based on the vapor pressure of to solvent losses (see below). The product assay as a function acetic acid at 20 DC reveals that under the conditions used of time is shown in Figure 8. The yield of ozonolysis products acetic acid loss should be 2.7%/h, in good agreement with the reaches a maximum at about the same time that the viscosity estimated total loss of 2-3%/h (Table n. In four laboratory of the reaction mixture was observed to stabilize (3.5 h). Also. experiments reactor gas effluent passing through a water the oxidation to acids is essentially complete when the cooled (20 DC) condenser was trapped downstream (-78 DC) starch-iodide test is negative (2.5 h). Comparison"of Figures and an average weight loss of 2.3%/h occurred. complementing 1 and 8 shows that pilot-scale results virtually duplicate the pilot-scale data. Evidently, weight loss is caused pre bench-scale results. Indicated maximum yields of 82% bras- dominantly by escaping acetic acid during the reaction.

98 Ind. Eng. Chem.. Prod. Res. Dev.. Vol. 16. No.1. 1977 Economic and environmental considerations make it im perative that volatilized acetic acid be recovered and its loss 9E minimized by installing efficient refrigerated condensers in the effluent gas lines. Alternatively, pelargonic acid. a co j I3EE product of the process, has been used successfully as an ozo I i nolysis medium (Goebel et aI., 1957; Greiner, 1970; Grynberg I et a1.. 1970; Nieschlag et al., 1967b) and could effectively and economically replace acetic acid to alleviate solvent loss in our ~i process. Adequate temperature control during the oxidation ~I stage and recovery of the pelargonic acid by distillation are ~I prerequisites of this attractive process variation that elimi 1 nates the need for a primary distillation unit for recovery of 12l:E :i '! acetic acid. Nevertheless, cost estimates discussed below in tl!Li'.! ! clude a charge for 5% loss of acetic acid. I Ii i llEE. ITI'~Illml5[iyEEI: PilotQScale Runs. Ozonolysis and oxidation were carried j. I \ J. ; out sequentially in the same reactor and two reactors were ~\.l I 1j 'I "U I utilized to achieve higher hourly output. Each reactor was charged with a premixed solution containing 11.9Ib (5.41 kg) IB "-.,)uI"\..-.\...J~ of erucic acid (95.6% pure) and 18.75 lb (8.51 kg) of glacial i acetic acid. During ozonolysis, a stream of ozone-in-oxygen Retention Time- (27 mg/L, 0.64-0.65Ib/h) was passed into the reactor at 6.28 Figure 9, GLC of (A) crude brassylic acid (92%) and (B) purified brassylic acid (98.9%) recovered from pilot-scale oxidative ozonolysis SCFM (179 l./min). The effluent gas from the first reactor of erucic acid in acetic acid. 9E = methyl pelargonate, llEE = di passed into the second reactor so that any excess ozone was methyl undecanedioate. l2EE = dimethyl dodecanedioate, 13EE = trapped effectively. The ozonolysis temperature was main dimethyl brassylate. l-lEE =dimethyl tetradecanedioate. l5EE = tained near 20°C. When ozonolysis was completed in the first dimethyl pentadecanedioate. reactor (3-3.5 h), the ozone-

Ind. Eng. Chern.• Prod. Res. Dev.. Vol. 16. No.1. 1977 99 Table II. Estimated Cost to Make Polymer-Grade 110 Brassylic Acid (99% Purity) from Crambe Oil a I I

Costs, centsllb of f::t· iWI Cost item brassylic acid ~ aot MFA 'I 12 cenlS~:::;: .. i Raw materials ~I Crarnbe oil at 30 centsllb 100.7 i 70 MFA ,t t6 centS/lr>!/ I Other (acetic acid, ozone, toluene, etc,) 8,5 .- '!;' , ' I ::E_~ 60~ /;' ,/ 'I Total material costs 109,2 I ;' / ,'-..- MFA II 20 centsllb Other direct and indirect costs Utilities 2,9 :~ 5°l //:// :' MfA al H ce:nts/lb Labor and supervision 6,3 ~.O /::»,'~ Maintenance and supplies 2,3 Fixed charges (depreciation, taxes, 4,5 .::: 3D ,',',' I insurance) ", 20 I_...J'_...J'"--_'L...--l-'// " _J...I_,"--....J Packaging materials 0.4 10 15 20 25 3D 35 .0 .5 Charge on working capital 1.1 Cram!>. Oil Cast. centsllb General plant overhead 4,2 Figure 10. Effect of prices for crarnbe oil and mixed fatty acids CMFA) Total direct/indirect costs 21.7 on cost to make brassylic acid (99% purity). By-product credit fixed Estimated gross cost to make brassylic 130,9 for glycerin at 12.8 cents and for pelargonic acid at 29.2 cents per acid pound of brassylic acid. Cost estimate of Table II shown by @. Byproduct credit Glycerin at 40 centsllb 12,8 Mixed fatty acids at 20 centsllb 25,0 been in the range of 20 to 40 cents per lb. At these price ex Pelargonic acid at 40 centsllb 29.2 tremes the net cost to make brassylic acid is projected to be Total byproduct credit 67.0 31 and 97 cents per lb. respectively (MFA credit of 20 cents Net cost to make brassvlic acid 63.9 per lb). Estimated fixed capitai investment: $3,7 million If instead of polymer-grade brassylic acid the unrefined a Plant capacity: 10 million lb annually, operating 300 days/ brassylic acid (95% purity) is recovered as the primary prod year, 24 h/day. uct, then the net cost to make this product is about 54 cents per lb when crambe oil is available at 30 cents per lb. Here the of crambe oil, a fatty acid distillation system to recover erucic net cost-to-make includes a by-product credit of 63 cents per acid, and facilities for converting erucic acid to brassylic acid Ib of crude brassylic acid. Yield of the acid is about 321b per by the procedures depicted in Figure 5. Methods for preparing 100 Ib of crambe oil. the estimate follow generally accepted cost estimating pro Conclusions cedures described in detail elsewhere (Sohns, 1971). Calcu lations are based on costs in mid-1975. A 300-fold scale-up of brassylic acid production by ozono The hypothetical plant, considered to be an adjunct to an lysis of erucic acid has been achie\ied in conjunction with existing vegetable oil processing plant, has an annual rated bench-scale studies. Although process control at several stages capacity of 10 million lb (dry basis) of polymer-grade brassylic is necessary for maximum yield of products, no difficulties in acid when operated 24 h per day, 300 days per year. Fatty acids controlling the reactions were encountered. The results lead from the oil contain 59% erucic acid. The predicted quantities us to expect success in further scale-up of this batch-type of products obtained per 100 lb ofcrambe oil are: brassylic acid operation. Furthermore, we are optimistic that modification (99% purity) 29.8lb, crude glycerin 9.6 lb, mixed fatty acids of the process for continuous or semicontinuous operation is (MFA) 37.21b, pelargonic acid (95% purity) 21.7 lb. Estimated feasible. For example, with a nonvolatile solvent such as pel fixed capital investment for a battery limits installation in argonic acid both the ozonolysis and subsequent oxidation cluding land and buildings is $3.7 million. Much of the phases are well suited for continuous operation when properly equipment in the plant is fabricated of stainless steel. controlled and monitored. The crude brassylic acid serves as The estimated net cost to make polymer-grade brassylic excellent feedstock for pilot-scale preparation of 1,13-diam acid is about 64 cents per Ib (includes byproduct credits of67 inotridecane, one monomer for nylon 1313 (Nieschlag et al., cents per lb of product). Crambe oil is assumed to be available 1977). The quality of the purified brassylic acid assures its at the plant for 30 cents per lb and is the largest cost item in suitability as a high-grade monomer for polyamides and other the process at $1.00 per lb of product. Ozone at 12 cents per polymers, as well as a starting material for other specialty lb represents about 4 cents per lb of product. Credits for products such as lubricants and plasticizers. glycerin and pelargonic acid are relatively easy to assign within the context of our calculations-in our example 13 cents and Nomenclature 29 cents, respectively, per Ib of brassylic acid. Credit for the A number/letter shorthand is used to identify compounds MFA is more difficult to estimate. We have chosen a value of by chain length/class. For example. for monofunctional 20 cents per lb, the mid-1975 price of inedible tallow fatty compounds. A = aldehyde, Ac = acid, E = methyl ester; for acids, which represents a credit of about 25 cents per lb of a,w-difunctional compounds, AcAc =diacid, AE = aldehvde brassylic acid. Figure 10 illustrates the relationship between ester, EE = diester, etc. Thus. 9A = nonanal; 13AE = methvl the value of the raw material, crambe oil, and the net cost to 12-formyldodecanoate. 13AcE = 12-carbomethoxydodecanoic make brassylic acid as a function of byproduct credit for the acid, 13EE = methyl12-carbomethoxydodecanoate (dimethyl MFA (glycerin and pelargonic acid credits held constant at brassylate), etc. 42 cents per lb of brassylic acidl. Thus if MFA credit drops to 16 cents per Ib, or alternatively increases to 24 cents per lb, Acknowledgments then the corresponding net cost to make brassylic'acid is 69 J. English, S. Henry, W. Mayfield, A. Hopson. and J. Long or 59 cents per lb, respectively. Illustrating further, actual for technical assistance; W. H. Tallent, J. A. Rothfus, H. J. price experience for crambe oil in the period 1972-1975 has Nieschlag, 1. A. Wolff, and A. C. Tanquary for contributions

100 Ind. Eng. Chern., Prod. Res. Dev., Vol. 16, No.1, 1977 to the planning and direction of the work; R. Kleiman for Mirchandani. T. J.• Simonsen. J. L.. J. Chern. Soc.. 3':'1 (1927). Mod. Plas/.. 47 (10). 107 (1970). GLC-mass spectrometry data. The pilot-scale work was car Nieschlag. H. J.. Hagemann. J. W.. Wolff. I. A.• Palm. W. E.. Witnauer. L. P.• Ind. ried out at the Southern Research Institute, Birmingham. Ala.• Eng. Chern.. PrOd. Res. Dev.. 3. 146 (1964). under Contract 12-14-100-10298(71) with the U.S. Depart Nieschlag. H. J.. Tallent. W. H., Wolff. I. A.. Palm, W. E.. Witnauer. L. P.. Polym. Eng. Sci.. 7.51 (1967a). ment of Agriculture and authorized by the Research and Nieschlag. H. J.. Wolff. I. A.. Manley. T. C.. Holland. R. J.. Ind. Eng. Chern.. PrOd. Marketing Act of 1946. The contract was supervised by the Res. Dev.:6. 120 (1967b). Nieschlag, H. J.. Tallent. W. H.. Wolff. I. A.. Palm, W. E.. Witnauer. L. P.• Ind. Eng. Northern Regional Research Center of the Agricultural Re Chern.. PrOd. Res. Dev.. 6,201 (1967c). search Service. Peoria. Ill. From a presentation before the Nieschlag. H. J.. Tallent. W. H.. Wolff. I. A.. Ind. Eng. Chern.. PrOd. Res. Dev.. symposium on "Novel Uses of Agricultural Oils" at the Spring 8.216 (1969). Nieschlag. H. J.. Wolff, I. A.. J. Am. Oil Chern. Soc.• 48.723 (1971). meeting of the American Oil Chemists' Society. Apr 29-May Nieschlag. H. J.. Rothfus. J. A.. Sohns. V. E.. Perkins. R. B.. Jr.. Ind. Eng. Chern.. 2. 1973. New Orleans. La. PrOd. Res. Dev.. 16.000 (1977). Perkins. R. B.. Jr.. Roden. J. J.. III. Tanquary, A. C.. Wolff, I. A., MOd. Plas!.. 46 (5), 136 (1969). Literature Cited Pryde. E. H.. Cowan. J. C.. in "Topics in Lipid Chemistry." F. D. Gunstone. Ed .. Blackmore. R. L.. Szatkowski. W. (A. Boake Rober1S and Co. Ltd.l. British Patent Vol. 2. Chapter 1. Logos Press, London. 1971. 810571 (Mar 18. 1959). Pryde, E. H.. Cowan. J. C.. in "Condensation Monomers." J. K. Stille. Ed.. Chapter Chern. Eng.. 76 (20).82 (1969). 1. Wiley. New York. N.Y.. 1972 Chern. Eng. News. 50 (39).6 (1972). Sohns. V. E.. J. Am. Oil Chern. Soc.. 48. 362A (1971). Chern. Week. 97 (15).69 (1965). Tallent. W. H.. J. Am. Oil Chern. Soc.. 49. 15 (1972). Chern. Week. 109 (2).27 (1971). Verkade. P. E.. Har1man. H.• Coops. J.. Ree. Trav. Chim. Pays-Bas. 45. 380 Critchley. S. W. (Geigy Co.. Ltd.), British Patent 896436 (May 16, 1962). Emery (1926). Industries. Inc.. Chern. Eng. News. 43 (41). 101 (1965). Vonasek. F., Trepkova. E.. CZech. Patent 108762 (Oct 15. 1963); Chern. Abstr.. Goebel. C. G.. Brown. A. C., Oehlschla8ger. H. F., Rolfes, R. P. (Emergy Indus 60. 9156d (1964). tries. Inc.). U.S. Patent 2 813 113 (Nov 12. 1957). Greene. J. L.• Jr.• Huffman. E. L.. Burks. R. E., Jr.. Sheehan. W. C.. Wolff. I. A .. Received for review October 26. 1976 J. Polym. Sci.. Part A-I. 5.391 (1967). 1, Greiner. A.• Zesz. Probl. Postepow Nauk Roln.. 351 (1970); Chem. Abstr.• 73. Accepted December 1976 76617j (1970). Grynberg, H.• Beldowicz. M.. Cyganska. J.. Zesz. Probl. Postepow Nauk Roln.. The mention of firm names or trade products does not imply that they 359 (1970); Chern. Abstr.. 73. 76618k (1970). Holde. D.. ladek. F.. Chem.8er.. 56.2052 (1923). are endorsed or recommended by the Department of Agriculture over Kestler. J.. MOd. Plast.. 45 (12), 86 (1968). other firms or similar products not mentioned.