Document n9KwB29O7by26KdxRQaO23ayG

KN-68~1 COPY NO, DISTRIBUTIONS 1 Research Numerical Pile 2 Research Office Pile M* Hunt/E, Gonick W. s, Struve/A, A, Brizzolara J, H,, Cooper W, J, McClure/R Hageraan/HArnoul/Q,* C 4 Pile 7 P, J, Monahan (Vital Records) 8 E. L, Rodowskas/W. A. Jenkins 9 R, M. Salemi (3) 12 C, F, Wood/D, S. Watson 13 E B, Wetzel 14 B, H, Gyorgy RETURN TO 1 J, 'W, Minnich 16 J, F. Maurer JACKSON LABORATORY 17 R, A, Johnson 18 Research File - Colors Newport 19 Extra 20 Extra FILE ROOM 21 22 Extra 23 Extra 24 Extra 25 Extra NEWPORT PLANT PIGMENTS ffOOTOSgTOOH REPORT SUBJECT; 2* 9-DIMETHYL QUINACRIDONE - TFA CATALYSIS PERIOD COVERED,-! OCTOBER, 1966 to SEPTEMBER, 19&7 CHARGE: 4635-350-16 SUBMITTED BY: Rc A. JOHNSON $$DATE SUBMITTED: 12/6/67 APPROVED BY: H, H, GYORGY/^S^ DATE ISSUED: 3/7/68 ABSTRACT 2,9-dimethyl BQA was produced in the plant at 70$ of theory by a TFA catalyzed process at a 179$ batch size. The 2,9 MegDQA quality was borderline because of the instability of MegDAT at the 170C Dowtherm solution temperature. Oxidation variables were developed so that any quality of MeaDQA can be oxidized to good MeaQA, DUP050028218 INDEX lo Introduction and Objective II. Summary and Conclusions III, Patent Status XV* Suggestions for Future Work V* Discussion of Results A0 SSE B, FT Condensation and Distillation Co Pyrolysis D9 Me2DQA purification E0 MesDQA Crystal Phase Fc Oxidation 1,, General 2. Seeding 3 MeOH Concentration 4. Aqueous MSifcoX" 5. NaOH Concentration 6* Laboratory Oxidation 7. MeaDQA Purity Plant use of HT-MesQA Seed H* Determination of DQA in Me2QA by XR VI* References XOR-179 Closing Report XCR-lol Closing Report Page No, 1 1 1 2 2 2 I 6 8 11 12 13 15 17 17 18 18 DUP050028219 T o ZNTRCPUCTIOS AND OBJECTIVE Production found the FPSA process for MegDQA to be goorly operable. It was used for making batches 8000 through 017o The oxidation of many of these batches proceeded only with difficulty. Due to the poor quality of the MeaBQA and the high caustic concentration* the oxidation would stop at the laaMeaQA stage, When this occurss some of the MesDQA never oxidizes and remains as a diluent in the final product after hydrolysis.- In addition* the PfSA process leads itself to distillation system, pluggage problems because of the high (7/1) PT/SSS ratio. Also the neutralization and removal of PTSA after the FI condensation proved difficult due to the insolubility of the 2*9 MeaBAT. It was the object of this study to develop a workable TFA process which would eliminate the problems of the FISA process and would produce readily oxidiaable MegBQA., The TFA approach has the advantages of (1) a low (3/1) FT/SSE ratio and (2) easily removing the TFA catalyst by distillation. XX. SUMMARY AWD COHCLUSIOMS 1, The 70# MeaB|A goal yield by the 179$ TFA process was demonstrated in the May* X967 campaign This is an improvement over the PTSA process. 2. The Mea:DQA plant quality is borderline. The problem appears to be in Me^BAT stability in Dowthem at 170 C ., a problem common to both processes, 3,, MeaBQA oxidizability depends on purity. By varying conditions (seed and BaOH concentrations)* any quality MeaBQA can be oxidised. 4. HI? drowned MeaQA has been demonstrated to be the pre ferred seed for the oxidation of MegRQA. Dispersion mill powder (gamma or beta) can also be used, 5 The oxidizability of severely degraded MeaBQA can be Improved to a passable level by extracting with 5# MaOH/ MeOH. This treatment has no effect on borderline ma terial , 6.- Batch size cannot be increased by the existing process because of the low solubility of MegPAT. Ill, PATEH7 STATUS A patent proposal covering the use of seed to make the oxidation go to completion has been written. The details of this technique are covered in discussion section F~2,, The use of TFA is covered by 1572-K, allowed 10/18/6?, DUP050028220 SUGGESTIONS FOB FUTURE WORK The need for, additional work on the dimethyi-TFA process is discussed in the tody of this report. Several of these items are currently active. .1, low Temperature MeaDAT Solution Changing to a TEA catalyst for the FI` condensa tion eliminated many of the shortcomings of the FISA catalyzed process. The instability of MeoDAT at the 170 C * solution temperature in Sowfchena of the mixed methyl-ethyl ester results in low and erratic Me^BQA quality. To achieve lower operating temperaturess mixed esters of MesDAT were suggested by'W. S, Starve * The solution temperature of MeaBAT' (n~Bua]s {980C.) and MesDAT (Et/Bu) (90*Co} appear very promising. 2. MegSQA Quality To avoid the need of determining the quality (oxidizability) of MeaDQA by a series of laboratory oxidations* a direct analysis is required. 3* "Sitolt? Conesntration The amount of "Sitol" used in the present oxida tion is excessive. Additional work to establish the optimum amount vs. the variable MegBQ.A quality is re quired. 4, Other Desirable Analytical Procedures a. Improved MegQA standard for purity determination, b. A quantitative procedure for determining M@igD$A inMeaQA. 5. Verify Possible Polymorphic Nature of HegUQA DISCUSSION OF RESULTS Results will be discussed in the order in which they occur in the synthesis. A . SSE No work was done on SSE, This is a well established process developed in the unsubstituted quinacridone studies. DUP050028221 3 *" Ba PS Condensation and Distillation In this reaction* two moles of p-toluidine {PS} are condensed with one mole of the methyl/ethyl ester of suceirtyl succinic acid (SSE) in the presence of trifluoroaeetic acid (TFA). A third mole of PT is present during the condensation and is removed with the TFA by vacuum distillation at the completion of the 30-minute condensation. The laboratory condensation is normally run at 85-90*0. {plant 87-93*0.)0 Increasing the condensation temperature to 1100. had no adverse effects on yield or Quality* There is some indication that the higher temperature gives a higher yield - ?i# vs. 68#* The effect of varying the FT and TFA concentrations were also studied. The normal 1 mole excess of FT was varied from 0.4 moles to 1.3 moles (216# batch size) with out affecting 2*9 MegDQA yield or quality. Similarly* doubling the TFA catalyst was without effect, A study was made of the effect on stability of re fluxing MegEAT/iDowtherm in the presence of free FT and TFA at a pressure of 25 mm of Eg, Refluxing was main tained for periods up to 150 mlmites at pot temperatures ranging from 125*0. to 135*0, In no case was DRJ formed in subsequent laboratory (high boil-up) pyrolyses nor were any unusual difficulties encountered in oxidising this material. Increasing the FT excess from one mole to six moles and with either TFA or FTSA as catalyst gave similar results# The absence of DPR formation under these conditions was attributed to the temperature being too low for the secondary D?U reaction to occur. The experiment was repeated using a 60 minute reflux* a 150*0. pot temperature and either TFA or FTSA as cat alyst, Only the FTSA catalysed material produced DPU in the pyrolysis. . Oxidation proceeded normally. At the completion of the condensation* the excess PS and.the TFA are removed by vacuum distillation. During this distillation* the pot temperature is allowed to rise to a maximum of 150*0' at a pressure of 25'mm of Eg. Under these conditions* part of the M32DAT is out of solution. This explains why yield samples taken at this stage of plant operation are generally low. Another result of having the MesDAT out of solution is that it can occlude FT. The presence of FT in the WesDAT during py rolysis could be responsible for the poor quality of plant Me2DQA. To check this out* a sample of MeaDAT/Dowtherm* DUP050028222 4 B o FT Condensation and. Distillation. (Continued) that had been distilled to the normal 0.05$ FT* ms dissolved,, cooled to. 150C,, and redistilled. The Dowtherm distillate contained 0,095$ FT indicating that it my be oeculuded in the MesDAT , By laboratory pyrolysis and oxidation* the re-distilled material was slightly purer than the'hs is"plant distilled MeaD^A based on oxidizability, An attempt to dupli cate this in the plant was unsuccessful. Considerable degradation took place during the extended processing and the oxidizability of the resulting Mea'DQA was very poor. in the May* 1967 plant campaign* it was necessary to replace most of the TFA in the recycled FT for each batch. Laboratory syntheses did not show -up this problem since the FT-TFA distillate was never recycled. To check out the loss in the laboratory* a distillation pot was charged with Dcvrtherm* TEA-PT salt* and FT, The water cooled condenser was maintained at 50~54Q <, to duplicate plant' conditions. Distillation was carried out at a maximum pot temperature of 150C ,, and a pres sure of 25 mm .of Hg At the completion of the distilla tion* 88$ of the TFA was in the distillate. lone was found in either the distillation pot or the cold trap, hence* it does not appear that the high condenser tem perature is responsible for the TEA loss in the plant. The problem is probably associated with the plant equip ment C. Pyrolysis In order to run a pyrolysis* it is necessary to have the MegDAT completely in solution. Otherwise* some of the MesDAT that was out of solution would plate out on the equipment causing pluggage, Solution of the MegDAT in Dowtherm is accomplished by heating to 170C.o and holding at that temperature until it enters the py rolysis tank. During this long hold at high temperatures* degradation of MegDAT occurs. This was demonstrated in the laboratory by holding the MegDAT in Dowtherm for 24 hrs, at various temperatures before running a normal 90 minute high boil-up laboratory pyrolysis . The dif ference in yield between these samples and one pyrolyzed without holding was taken as a measure of the degradation. Besults were as follows: 150*0, 160C, 170C, iSO^C. MegDAT -17 M -2.0.6% -11.2$ -19.4$ DAT 4,7$ - 53% ~ 5*9$ - 9.2$ DUP050028223 5 0 Pyrolysis (Continued) From these data, it appears that MeaDAT is less stable than unsubstituted DAT, In spite of the yield loss due to degradation, all samples oxidised readily, Shis is attributed to the large .boil-up in laboratory pyrolysis avoiding by-product formation0 The effect of boil-up rate ms demonstrated by reducing the boil-up rate to one-half of normal (see HH-67-ll for details.) and then oxidising the resultant MesDQA. The normal boil-up gave easily oxidised while the reduced boil-up produced ifgrane 3'uice" in the oxidation step* that Is,' it hung up as Sa^esQA, Sarly in the study of the MeaJK^-TFA process, an attempt ms made to determine the effect of small amounts of FT and TFA being carried over into pyrolysis ,, During the pyrolysis of the sample co.ntain3.ng PT.- a slight oily film formed on the side of the flask,. The sample containing the PT-TFA salt not only had the oily film, but also- appeared, dirty. The MsgBQA yields and the oxidation of these samples ware normal, This again Dints up the fact a high boil-up trill present a degrada tion of the Me.#BQA quality,, :os He^jpOA ^Purification The present pleat pyrolysis boil-up is -not suf ficient to overcome the effects of prior" .degradations on MeaBQA quality,, For this reason, a. means of puri fying 'MegDQA is sometimes needed* A pure product, as fudged bsr oxidizability, can be obtained by converting MeaDQA to the sodium salt in strong alcoholic caustic and then precipitating the with HaHO** This is similar to the method used to convert alpha D$iA to beta DQA except a higher EaOH concentration is needed. Unlike DQA, Me.aDQA does not undergo a phase change under these conditions. A procedure of this"type is not practical in the plant. The present means of cleaning up MesBQA after pyrolysis Is to wash it on a Mutsche with MeOH until essentially free of Bowtherm, The Dowthem contains the impurities. Since the in^urities are largely insoluble in HeOH, it serves no useful purpose to wash beyond this point. However, poor MeaBQA' is still far from being free of impurities" at this point. One or more of these impurities -acts to inhibit oxidation,, Additional impurities can be removed by washing on the DUP050028224 W 8 Do M6PQA Purification Nuteche with a 10-90 mixture of pC<0 JfeOH and MeOH, Wa&a this was done with fair quality MesD^/i from batch 8021* a dark filtrate was removed* Additional washings with MeOH were made until the filtrate ms colorless. This material oxidised a better than the .control* Apparently MeaBQA of at least fair quality cannot be helped by this technique* Since an'im provement Is obtained when the lie2DS)A is purified by precipitating from strongly alkaline MeOH'. some of the impurities must be occluded by the MesX^A .crystals. This experiment was repeated using poor quality Me^'DQA (batch 8025). The MeaDQA'was washed three time with 50$ HaOH/HeOH (10/90). ' Only the first wash gave a dark filtrate* The oxidation (no seed) of this material gave a mixture of Wa^eaQA and Me-sQA crystals * The un washed control formed "grape luioe" (U&sMssQA}* This improvement in the oxidizability of poor quality MesBQA was demonstrated in the 'September, 196? campaign on batches 8027 and 8028* Gleaning the crystal surfaces of these two batches of HegDQA mde it possible to oxidize with only 5$ ;HT iteaQA seed* Laboratory re sults .indicated that 8027 would have required 25$ seed without the alkaline wash. EU MeglSQA Crystal Phase .Some work has been done to determine if ieeBQA exists in more than'one phase* The normal crystal form has been designated beta phase since it is iso morphic with beta phase lle^QA,* The Newark group has an x-ray pattern of what is supposed to be a mixture of alpha and beta MegDQA. However* no one has been able to substantiate this by making a pure alpha phase-. An attempt to do this by the .method used for converting alpha 3QA to beta BQA was unsuccessful* Ifext* refluxing in solvents was tried. MH and Dowtherm both increased crystallinity and possibly mads a change in crystal habit. Phase .was not affected. This study is con tinuing as time permits. 3\ Oxidation 1. General When this study wae started, MesDQA had been made in the plant by the PTSA route. In the oxidation of the last five batches, made using FTSA., there was con siderable difficulty in hydrolyzing the .&#!e&QA to MoaQA, At the time, it was thought that a TEA process would yield a cleaner MegiDQA which would be' easier to oxidize. The oxidation process used at that time reduced to a laboratory scale is as follows; DUP050028225 -7- F, Oxidation (Continued) General (Continued) Gms. MX. Moles (1) Charge a 1 liter* 4-neak* r.b. flask equipped with agitation* reflux condenser* thermometer and dropping funnel with? 2,9-Ke*DQA 40.0 ... 0.12 MeOH 25I.O 322 7.86 (2) Add 50fo HaOH slowly keeping temperature below 60 C. 18O.O 1X8 2.25 (3) Stir 30 min. at 55-60*C (4) Add "S.itol" 40,0 - 0.18 (5) Heat to 75-80 in 30 min. (6) Add leOH in 5-10 min. main taining temperature at 75-80'3C, 218*3 280 6.82 (7) Stir 2 hrs, after slurry turns red at 75"80C. (8) Filter hot (9) Wash BY - with hot water (10)Dry at 80C, (11)Ooal yield 39.8 0.54 All of the previously discussed experiments under condensation and" pyrolysis were oxidized by this method. On heating to 75~80C. (step 4) all went into tfceM grapejuice" stage* This occurs when the IfasMesQA comes out of solution as blue plates rather than hydrolysing to MeaQA* The time required for the second methanol (step 5) to hydrolyze the EfegHesQA varied from 50 minutes to over 4 hours. Sto conclusions could be drawn from the oxidations since the hydrolyses times did not correlate with the vari ables studied. However* when the same sample of ISegDQA was oxidized* there was very little difference in hydrolysis time. Two samples required 100 minutes and the third* 115 minutes* Coal yields also had very little meaning as un~ reacted MegBQA will be recovered with the MeaQA. DUP050028226 Oxidation (Continued) 1, General (Continued) In plant operation* MeOH contains .about 3% water while laboratory MeOH is essentially anhydrous. To determine if this would be a problem* laboratory oxi dations were run with MeOH containing 3 and 5$ water. There were no differences noted between the oxidations with wet MeOH and the anhydrous control. The rate of HaOH addition (step 2) was thought to be critical in the conversion of IfeaDQA to its soda salt. A slow addition was supposedly needed for a complete con version. in this experiment,' no quality differences were noted between dumping the 50$ HaOK solution in as rapidly as possible and adding in 45 minutes. The only difference noted at the end of the addition was that of temperature-*63vs. 57 C. for caustic added in 30 minutes. A study was made to determine if that did not .get converted to the sodium salt could act as an inhibitor for the oxidation reaction. This was done by splitting the addition of Me^BQJu 2-2/2$ and 25$ portions were added after the "Sitol" (step 4), and 2-1/2$ was added after the second MeOH (step 6),, Where the second addi tion of leaQA was added after the "Sitoln* it apparently immediately converted to the sodium salt. Hydrolysis of HdsMeaQA took place in 45 minutes at both KegBQA levels. Where the MeaBQA was added after the HaaMea%A was al ready formed* hydrolysis took 175 minutes. Although considerably longer than the previous two* it was not considered an abnormal hydrolysis with this lot of Me^BQA. 2. Seeding Having to go through the "grape Juice" stage in an oxidation is highly undesirable since there is no guarantee that the HaaMasQA can be hydrolysed in a manner that will allow the reaction to go to completion. In the initial attempt at seeding, premilled, partly oxidised MegB^A was used as the seed* At 3.0$ and .25$ premilled MesDQA* the oxidation (the addition of. ,s.SitOl" to the hydrolysis of HajgMeg^A) required .240 minutes and 225 minutes respectively. Although premilled MeaBQA oxidizes rapidly by itself* it does not act as a seed for the normal particle size Me2B0Ac Beta and gamma dispersion milled QA laill powders were also investigated as seed at a 10$ toner leve3. (67$ mill powder) based on the weight of ilesBQA. These oxidations went directly to MeaQA without going through the ''grape Juice11 stage. Seeding with mill powder also affected*the crystal phase. The unseeded oxidation gave a mixture of alpha and beta MegQA. With seed, only beta MeaQA was formed. Another advantage of the rapid oxidation rate DUP050028227 9 F. Oxidation (Continued) 2, Seeding {Continued) was the possibility of eliminating the second -HeOH which was used to aid in the hydrolysis without stopping the oxidation, Working with a different lot of ' 1$ and 5$ (toner basis) seed levels were investigated. Only the 5% beta or gamma QA mill powder was effective. However* at this reduced seed level* .a mixture of alpha and beta MeaQA was obtained, '. At this point in the study* there was soiae question as to whether the small particle size QA was seeding the oxidation or the large quantity of Aia(S{V)s was producing local areas .of acid which hydrolyzed the Na.a$eaQA" to Me2QA, The following results were obtainedt Seed None Oxidation Rate 200 '* aE 0,624 Excellent Ale ( SO4-) a if QA mill powder1 155'* 70* 0,118 0,056 Good Clood { ) Went through "grape juice" stage {** ) Ratio of 7,40/5,6 2Q x-ray peaks These results indicate that AXa(S0<.)3 has some effect in depressing the formation of alpha phase Ma.sQA* How ever* its effect on the hydrolysis of BTaaMe,sQA was neg ligible , Hence* it is the small particle size QA that is seeding the reaction. Blspersioh mill powder contains about 14, $$ toner, The remainder is Als{S0s)e which is awkward to handle. One possible means of eliminating this problem would be to use extracted and washed dispersion milled QA press- cake. This was tried at both a 5 and ,a 10$ dispersion milled QA level without success. Both samples went through the "grape juice" stage. The failure was attributed to particle growth during the extraction, so that the QA particles were too large to act as seed. Since it was necessary to use mill powder to seed the reaction* the possible problem of high water soluble salts was investigated, A series of simulated oxidations were run in which"the "Sitol" and MeaDQA were omitted. This was done in order to see the effect of the aluminum salt and caustic at the reaction temperatures and concen trations . The control* as expected* formed a clear* DUP050028228 10 F,, Oxidation (Continued) 2. Seeding (Continued) colorless solution. When was added after the WaOH addition* an insoluble slurry ms formed and remained during the remainder of the reaction conditions. However* when the second MeOH was replaced by water* practically all of the aluminum salt was in solution--probably as the aluminate ion. By using water in place of the second MeOH* it should be possible to wash the fleaQA to a low water solu ble salt level. A series was run in which the dispersion milled, gamma QA mill powder was'varied from 2$ to. 5$ on a toner basis. Unexpectedly* all of the samples went through the "grape juice" stage. Since the 5$ level was previously shown to be satisfactorywith another lot of MeaDQ7* this experi ment pointed up the importance of determining the proper seed level for each lot of MbaBQA. in the March* 1967 di methyl campaign* this technique was used with each lot of MeaDQA, The following tabulates the use of seed in this eampalgm September* 1966 Campaign hot Laboratory Test Level Used in Plant 3R $ MesQA* 8018 7$ seed 10$ Good 94,4$ 8019 10$ seed 10$ Good 87.6$ 8020 7$ seed 7 4- 3$ Good 96.1$ {*) 5120-22A used as standard. Batch 8018 used 10$ seed in the pisint rather than the 7$ found needed in the laboratory because the latter appeared borderline. It was decided to go with 7$ seed in the plant with batch 8020* since 5$ seed gave "grape juice" in the laboratory. However* the plant batch gave 11 grape juice". It was saved by adding an additional 3$ seed, The reason for the difference between the laboratory end plant run was never determined, it was suspected that 8020 may have contained more Fs.OH than it should have. Another pos sibility is that the laboratory washing of the test sample was more effective than the normal plant washing. To eliminate the large amount of Als{.804)3 diluent associated with the beta and gamma QA mill powders* the work started by W* A. West on Hi' drowned MegQA as a seed for the oxidation was reactivated. The quantity of B.T-MesQA needed to seed the reaction varied with the quality of the DUP050028229 - 11 - F Oxidation {Continued) 2. Seeding {Continued) MeaXJQA, Many of the batches of Me.sDQA tested could be oxidized with as little as 2-1/2$ seed. The seed was added as a dry powder. It was effective because of its very small particle size. X-ray evidence indicates that HT-MeaQA is an effective means of suppressing the alpha phase. As a result of the work on seeding, the oxidation process was modified to the followings Pros, Ml. {!) Charge, a 1 liter, 4-neek, r.b. flask equipped with citation, reflux condenser, thermometer and dropping funnel with?9 10 11 Moles 2,9--MeaBO-A MeOH {2} Add 50$ MaOH slowly keeping temperature below oOG. ' (3) Stir 30 min. at 55~6oC, vO.C 251.0 180.C 0.12 322 7.86 118 2.25 {4$ Add HT--MeaQA seed' (2-1/2$) l.C O.OO3 (5) Add ' Sitol" (dry) . 40.0 O.I8 (6) Heat to 75aC. in 30 min. (7) Stir 1 hr. at 75-30C. (8) Add water 280.0 280 15.56 (9) Stir 30 min. at 75"8oe, (10)Filtex' hot (11)Mash BY - with hot water {12}Dry at 8oC, (13)Goal Yield 39-8 - 0.12 3. HeOH Concentration in some cases, regardless-of the seed concentration, a few crystals of EfagMeaOA would not hydrolyze until water was added in step 8, Prior to the addition of the water, the oxidation was so thick that there was very little if any agitation. Increasing the MaOH concentration by as little as 5$ appeared to have eliminated the MaaMesQA DUP050028230 - 12 - F 4 Oxidation (Continued) 3 * MeOH Concentration (Continued} problem. The oxidation slurry was still very heavy* but generally stirrabls. increasing the .MeOH concentra tion in excess of 50$ resulted in the hydrolysis of -some .ftagMeaDQA * This could he detected in the find product by IE as fesiP^A, To prevent the undeslred hydrolysis from occurring and yet still have an oxidation that goes to completion before adding water in step 6* the MeOH in step 3. was increased 10$ to 354 ml * (276.1 gjas.). 4, Aqueous ^Sitol*1 The addition of dry lsSitol:' (sodium salt of m-nitro-befizene sulfonic acid) is a hazard because of a possible dust or MeOH explosion in the chute. 'Hence., it was highly desirable to convert the oxidation process to aqueous "SitolM, There was some question as to whether this could be done* since the presence of water was thought to hydrolyze HagMeaBQA back to tfejgSQA, The re sulting MegKkA will not oxidize. This was the reason that the original oxidation process used 97$ MeOH and dry "-Sito1*1 To determine the tolerance of the oxidation for water* a ladder series was run. The water was added right after the "Sitol" in step 5. Expressed as a ifSitol" solution concentration* the following results were obtained: "Sitol" Solution .MegQA Purity by IB 100$ (no water) Excellent 67# Excellent 50$ G-oocl 4- m Good 36% Good 33$ Good ~ 31* Fair 29$ Poor Based on these results* it should a 36$ "Sitol" solution without the final product containing an excessive amount of MeaPQA. The plant uses a 43% '"5tol,! solution which is well within the process limits. DUP050028231 - 13 7. Oxidation (Continued) Aqueous l!Sitplli (Continued) For laboratory studies, it is not practical to use aquous 'Sitol". At room temperature, s 43$ aqueous "Sifcol" is more like a press cake than a solution, For this reason, it is handled hot in the plant, The same effect is obtained in the laboratory by adding dry "Sitol" and an equivalent amount of water. Hence, in step 5, 40,0 gms. of "Sitol" are washed into the oxidation flask with 60 ml. of water. This modification was cheeked out using batches 80l8, $019 and 8020 of MesTO. All gave good quality MeaQA by IB* The amount of "Sitol" used is far in excess of that required on a molar basis to oxidise MeDQA. A ladder series was run in which aqueous ''Sit!1' was varied from , a 33$ excess to a ?8$ excess. The normal excess :is 52$., The 3.5$ excess of "Sitol" when run with .2-1/2 BT Mb s QA seed gave excellent Me^OA by IB, Increasing the excess to 28 to 52$ gave good MeaQA while a 78$ excess gave only fair MeaQA* Hence, it would be desirable to re duce the "Sitol" concentration for improvements in both quality and economy. Similar results were obtained in the absence of seed. An attempt to confirm this reaction with a 3$ aqueous "Sitol" excess was unsuccessful. Additional work will be needed,.to establish a safe "Sitol" level. Because a lower "Sitol" level also means less water in the oxidation, it will be necessary to reduce the amount of $0$ HaOH added to maintain the same caustic concentration. Due to a lack of time, this phase of the dimethyl work is cur rently inactive. 5* KaOE Concentration A study was undertaken on the effect of WaOH concen tration, since it plays a most important part in the oxi dation of MeaDQA. In the absence of WaOBQ a "Sitol" oxi dation does not take place. With insufficient UaOE, part of the MeaDQA is not oxidized. This was demonstrated by a ladder series in which the WaOH concentration was re duced, 2-1/2$ HT MegQA was used as seed and dry "Sitol" was the oxidant. HaOH MesQA Quality ClH) 19.6$ 17.8$ 15.9$ 14. 0$ 12.6$ Excellent Hood -f Hood Fair Boor DUP050028232 Oxidation (Continued) 5. HaOE Concentration (Continued) Increasing the HaOH concentration beyond an optimum level will result in "grape juice" (Ha.aMesOA). When this occurs., the final product will be loaded with unoxidized. MegDiJA, How this can occur can be better under stood by examining the reversible reactions involved in the oxidation. WezTjQA jssssS EaaMea:PQA (Soln,) -- Ha^Mes!/ (Solid) i (o) la^CeaQA (Soln.) HajsMSsQA (Solid) It MeaQA (Soln.) ~5; MeaQA (Solid) A large HaOH excess is needed to shift the equilibrium to form HagMesHQA as completely as possible. Too large an excess results in large blue crystals of Ha.aMegQA coming out of solution. When this occurs, the oxidation does not go to completion. In the presence of seed, Heg&A comes out of solution and the reaction goes essentially to completion at the higher HaOH concentration. The amount of seed necessary for this to occur increases directly nifch the HaOH concentration* The HaOH concentration needed for a good oxidation depends upon the purity of the MesEQA. This will be discussed under HaaDQA purity. In a series using aqueous nSlto3.'! and 2-1/2# seed, the optimum HaOH concentration is seen to be a range for fair quality Me2BQA, HaOH Me,aQA Qua' 17.3# 17,9# 18.4# 18.9# 19.4# 19.6# 20.4# 21.3# Fair (food- GoodGood Good Good C4ood Poor At the 21.3# concentration, the oxidation hung up as a mixture of MeeQA and Na^e&QA. Hydrolysis to MeaQA was completed after adding water (step o). The optimum HaOH concentration with 2-1/2# seed lies between 18.9# and 20.4#, DUP050028233 13 F, Oxidation (Continued) 5. laOH Concentration (Continued) By reducing the H&OH concentration, it is possible to oxidize MesD&A without seed. This is demonstrated in the following series: NaO><H! 16,0$ 3.6,7$ 17.3$ 17.9$ 18.5$ 19.1$ 19.7$ 20,2$ 20,6$ 21.2$ MeaQA Quality Poor Fair Good" Good Good Good* Excellent Poor "Grape"juice" "Grape-juice" The optimum laOH concentration for the oxidation run without seed is 17.3$ to 3-9.7$. The spread remains essentially unchanged. Only the concentration is changed by using seed. -All of the preceding data were obtained using MeaDQA from batch 801o, 6. laboratory Oxidation Based on the results of all the oxidation studies* the following is the currently used oxidation formula: 6ms. Ml0 Moles (1) Charge a 1 liter* 4~neck*r.b. flash equipped with agitation* reflux condenser* thermometer and dropping funnel with: 2* 9-Me2DQA 40.0 MeOH 280 e 4 ,.W 0.3.2 354 8.76 Add 50$ laOH slowly keeping temperature below 60C, Formal caustic Low caustic Low* low caustic 216.O 200,0 184.0 142 2.70 131 2.50 121 2.30 (3) Stir 30 min, at 55-60C, (*) Add BT~Me2QA seed 0$ 2-1/2$ 5$ 0.0 0.00 1.0 - 0.003 2.0 * 0.005 3. 0,009 4,0 - 0,012 DUP050028234 ** 16 P0 Oxidation (Continued) 6, Laboratory Oxidation (Continued) Gms. Ml. Moles (5) M& s,SitolM (dry) 36,0 - 2.67 (6) Add water 48.0 48 2.67 7) Heat-to 75*C. in 30 min. (8) Stir 1 hr. at 75~80C . (9) Add water 280.0 280 15.56 (10) Stir 30 min. at 75-8o*C. (XI) Filter hot - recycle bleed, (12) Wash BT ** with hot water (13) Wry at 8oC . (14) Goal yield; 0% seed 2-1/2$ seed 5$ seed 7-3/2# seed 10% seed 8 So .8 41.8 42.8 43.8 0.12 0,12 0,3.2 0,13 0,13 The reaction in a good oxidation is usually complete by the time the reaction reaches 75C* (step 7). This is easily determined under the microscope (oil" immersion lens) by the -absence of blue crystals of HasMeaQA, . A starting series for testing the quality of plant MeaDQA consists of the following; HT-MeaQA Seed 0fo 2-1/2$ 5$ 5$ 50? NaOH low normal normal low If all of these end up looking like grape-attics in step 8 higher quantities of seed and/or lower quantities of FfaOH must be tried* Depending on the quality of the MeaDQA^ it will generally take between one and three sets of four oxidations to determine plant oxidation conditions. DUP050028235 - 1? - F. Oxidation (Continued) 7. MegDQA Purity The ease of oxidation of MaslQ-A depends upon its purity. As purity decreases, the IfevOH concentration must be decreased and the seed concentration increased in order to have the oxidation go to completion. This is why each batch of MeaBQA made in the plant ms checked in the laboratory to determine fi'aOH concentration and seed level before the plant oxidation ms run. Where possible, the ffaOH level was reduced so that not more than 5$ BT MsaOA seed was needed. The effect of the iCeaBQA impurity as demonstrated in the laboratory by carrying out a normal oxidation ex cept for omitting the "Bitol . This amounts to rep re*, cipitating the MeaBQA. The filtrate was extracted" with xylene to recover the impurity. This material repre sented 0,^$ of the starting material. When it was dis solved and charged into an oxidation (step 1), the reaction did not go beyond the "grape-^uica*1 stage. This same lot of Ke*33QA without the extra added impurity readily oxi dises without seed, Similarily, a very poor lot of MeaBQf was made easily oxtdizable without seed, As was done before, the oxidation was run in the absence of "Sitols1. The purified Me.aDQA was then isolated and dried. The original MseBQA required 10$ IT MeaQA to oxidize while the purified material oxidized readily without seed, G. Plant Use of HI MesQJ\ seed Hay, 1967 Campaign Lot 8021 8022 8023 8024 8025 8026 ET Mes Seed tab Plant NaOS Gone. 2.5$ 2.5$ 19.8$ 2.5$ 2,5$ + 2.5$ 19,8$ 2,5"50$ 5$ 19,8$ 2.5-5.0# 5$ 19,8$ 5*o$ 5$ 18,9$ 9,0$ 1$ -?* 8$ 18.9$ m SMd Excellent $ MeaQA* 10002$ Poor 92,6$ Good X037$ Good. 102.0$ Good 99.8$ Poor 90.0$ {*) Standard DUP050028236 18 G. Plant Use of HP MegQA Seed (Continued) Where the laboratory tests indicated borderline quality, the higher amount of seed was used in the plant . Batch 8022 plant quality was apparently somewhat worse than the laboratory tests had indicated. The second addition of seed did not appear to' have helped the situation. Batch 8026 MeaDQA was of very poor quality. By mistake, only 1# seed was initially added. It was partially recovered by adding the other 8$ seed. The other four oxidations behaved as expected based on laboratoey oxidations, K. Determination of MegDQA in MeaQA by XH All attempts to quantitatively measure the Me;sDQA in HsQA by XR have been unsuccessful. However, by the following pro cedure, an .approximate measure of the Me*QA quality can be de termined, A small sample of the MeaQA to be tested is ground into .JSu^ol with a spatula* For good grinding, the mix should be' viscous. The sample is then fluidised by the dropwis addi tion of more Sujol while mixing with the spatula. This is con tinued until the diversion has the approximate viscosity of NuJol itself. The instrument, a Ferkin-Blmer double beam XR, is turned on and warmed up in the normal manner. Settings are as follows Resolution $27 Response 1 Gain $ Speed 4 Suppression 6 Nujol is placed between two NaCI plates (part #027-1182) in the reference beam. Set the instrument to 6.197^ Place the Me^QA/NuJol dispersion between two other Bad plates in the sample beam. Adjust the sample thickness so that absorbence (optical density) at 6,197^lies between 0.6 and 0,8. Then set the instrument at 5,8^ and scan to 7,0^ , The relative quality of the MegQA is obtained by comparing the spectrum with the spectra that follow, MegBEA absorbs at 6.58/^. IT. REFERENCES Additional data may be found in the following references 1 1, FT Condensation and Distillation 512.0-2 - Vary PT concentration from 8c$ to 110^-216$ batch size. DUP050028237 DUP050028238 i I DUP050028239 j! ' I -2i i DUP050028240 if t I DUP050028241 i DUP050028243 " 25 " i DUP050028244 ~ 26 - 1. FT Condensation and Distillation {Continued} 5X20-3 - 85-90G . vs. 105-110*0. condensation temperature and doubling TFA catalyst. 6 - 0-150 * reflux after -condensation (3/1 FT/SSE); 60* reflux (7/1 'PT/SSE)s FTSA catalyst^ 6of reflux. 7 - 60*'reflux (7/1 PT/SSE) - TFA vs. PTSA 44 - Attempted oxidation of precipitated MaaBQA 79 - Redistillation of plant Meg.I>AW 96 - Plant TFA loss is 5120-83 - Contaminate pyrolysis feed -with FT and TFA. MeaBAT stability. 85 - Eeduced laboratory pyrolysis boil-up. 3. Me-aPQA Purification 5120-98 - Wash fair KeaB(JA with 5% WaQH/MeOH 99 - Wash poor Me*DQA with 5% WaOH/WeOH 4. MegDQA Crystal Phase 5120-39 - Recrystallize IfegBQtA from MaGH/MeOH,, 51 - Reflux MegSQA in EMF and Dowtherm. 5. Oxidation, of MegDQfi a. General 5120-8 -Oxidation of experiments 1-7 9 -Reproducibility of laboratory oxidation 10 -3-5$ water in MeOH 11 -50$ NaOH addition rate 12 -Contamination of oxidation with MeaDQA after "Sitol" addition. 13 - Water in oxidation 14 - Oxidizability of MeaDQA batch 8OO6 15 - Water in oxidation DUP050028245 ~ 27 5* Oxidation of MesDQA (Continued) b, Seeding 5120-17 - Beta QA mill powder with prenilled HeaBQA 18 - Gamma QA raillpowder with prenilled Me^DO/i 19 ~ Seeding with beta Q& millpowder, gasrt QA millpowderj, and premilled' 20 - Go-oxidise MeaBOjA and alpha DQA ,, 21 - '!& 4- 5$ beta and gamma 'Qfl millpowcler levels 22 - Co-oxidize IfesBQA and beta BQA* 23 - Water soluble salts from Ala{04)3 24 - Ala{S04)s as seed 25 - Extracted Dispersion Milled beta and gamma Q,A presseake as seed* 26 - Millpowder concentration* 2? * Gamma Q.A millpowder level, 30 Gamma QA millpowder required to oxidize MesDQA batch 8018 31 * Gamma <&A miXXpowder required to oxidize MeaW batch 8019 32 - Gamma -QA millpowder required to oxidise Me2DQA batch 8020 35 - If? MesQA level 36 - " w 40 2-1/2% HP MeaQA at increased MeOH. 49 Laboratory H? drowning of M.e20/ 52 Evaluation of 5120-49 68 ,s " plant If? MeaQA 70 71 Oxidation conditions for MegDQA batch 8021 72 tt 8022 DUP050028246 ** 28 ~ 5. Oxidation of Meg?DO/- (Continued) b, Seeding {Continued) 5120-73 - Oxidation conditions for MegDQ.A batch 6023 74 - " " " 11 " 8024 75 - " " "" n 8025 76 - " " n" " 8026 c MeOH Concentration 5120-37 - Increased MeOH 38 - d* Aqueous . "Sitol" 5120-41 - G*67$ water 45 - 67-111$ water 46 - Oxidize MeaBQA batches 8018., 8013 and 8020 with aqueous "Sitol" . 55 - Aqueous "Sitol" addition temperature 63 - Aqueous"Sitol" concentration (68-13.6$) 66 - " " (68-116$) 97 - 68$ aqueous "Sitol4 -20$ KeaDQA ee ivTaOH Concentration 5120-47 - Concentration reduced from 100$ to 56$ 48 - Add aqueous "Sitol" at reflux (NaOH 100-120$) 53 - Aqueous "Sitol" (HaOH 100-140$) 54 - Dry "Sitol", no seed (NaOH 56-100$) 57 - Aqueous "Sitol" {NaOH 100-12:0$) 58 - " " , no seed (He.OH 89-111$) 59 - GoodqualityMeeDGA{NaOH 89-111$) 60 - Aqueous"Sitol", no seed (NaOH 100-122$) 62 - " " " " (NaOH 122-144$) 64 - Aqueous "Sitol", 11$ NaOH - 20$ MeaD0A DUP050028247 29 5 * Oxidation of MeaBQA (Continued) f, MeaDQA Purity 5120-86 - Oxidation of re-precipitaied Me3DQA 6, XOR-179 Closing Report - Attached 7. XOE-181 Closing Report - Attached DUP050028248 Ds; pa#' aa s c o u r s .& c o mpan y . cc? if, s,, struve/ , A. Au Brizzolara - Newark Iiy R0 tipton/R.FoWhite ~ n H.ArnouiA.S.Wilson Gedd - 11It w. A. Jenkins 6; F Wood (5) E, M. :Saleml (5) Newport - * L. S. MiHelot R. H. Wetzel H,. H, Gyorgy J. N... Minnich *hr Maurer . ... tt .If ** : It - It Bile ... :.Newport, .-Delaware- :". / August 16, I967 y~7 QRGANiC CONORS - mflptiftT - XCR~I79 CLOSiJSq REBW- TlTild: Plant Synthesis + S,.9 Dimethyl <1A . BACKGROUND 1 Research has shown .in . the. laboratory that, the use of TPA- rather , than PTSA* as a condensation ..catalyst allows a reduction in the T-D/SSB. mole ratio from 7/1 to 3/1.' A reduction.In the amount of -73 used will ' speed the recovery of 9ED and may ease some of the plugging: problems encountered: earlier. Use of 'PFA. , also eliinlmteo, the P7.SA neutralisation step pro-' viously paztially responsible for poor yield, Quality.' and operability* Research has also shown that the problems associated with the oxidation cap be over come by using dispersion milled gamma tyA mill powder as seed. ; onJBCTlVB: Synthesise 2,h-dimethyl' DQA using 101?A. as the con densation catalyst and omidice it tp 2,9-diraetby.l QA using dispersion milled gamma QA mill powder as seed. OGNCRUSIOKS': 1. Yielir were: low fox* several reasons: a,, Two of the three lots had low $SB yields* i>, ila^or loss due to an'inoperable Shriver.This necessitated using the loaf filters. One of the leaf filters was subsequently found to bo bleeding badly to the sewer* ,, The dimethyl DQA TF& process is operable-. 3. - . Satisfactory oxidations were.'obtained by using 10$ dispersion 'milled- gamma QA.rail 1 powder as' seed laboratory tests demonscrated that the oxidations would not have gone -without the seed. /. . XOjR-179 CLOSING REPORT (Contd,) C0HCLU3I01V-&; (Continued) 4, i'ho driver became inoperable probably because it was already partially plugged (QAQ from beta oxi dations) when the dimethyl campaign began,. Because of this', pressing was so slow that the dimethyl Q& slurry cooled and set up,, 5- tv'orr.u'j. dispersion milling* with QA gave products yell.vi'/ vs. standard(i fnis neccasltafced using in- creased 'quantities of dimethyl- QA to get standard color.: iho problem appears to be incomplete solid solution-, . Rt-bUHiil; Tuc following in process yields wore obtained! CCL/Lt Step After filtration . M"' othe1WI' <**v---* XR 80.18 8019 680 :630 8020 730 Vi.v.y]m/^C/W A ft or e en&eftsa tion 'Distillation 540 470 620 and. pyrolysis Kognftj:/;*?; After dietillation Pyrolysis Start of ttransfer Pyrolysis 59% Cl) (1) 50% 460 630 k : -Mim'./Uf lb }/>&(-/ 'i: Bnd of transfer End of pyrolysis Pyrolysis 65 tank 600 (1) (D 25% 580 . 710 )AC; 68 ca fe Chapmen 63^ . 500 540 itjAA'r-l'ri'-' Bnd of oxidation Chapman 510 490 740 (j ) fnmple. not taken. /: :} luslm nu 130#.'1A seed, ,. ' `I.'tune data indicate that part of the yield loss occurred in t, filf rc-cibsntatioa of batches 80l0 and 30X9. The volume of 8019 point tW: aDproximecely 800 of the other two, I?o conclusions .1 -.id lni ci-wu C* ora'iho in-procosn camples that were, laboratory finished, 'V :.vr this is rot clearly 'understood, but. appears to relate to ' y of the PAX ample and to o. Ic-sser extent, tank level's, Ei.cmeot Ion*: os for the run esn be -disbursed as follows::'. DUP050028250 XQB~179 (CLOSING REPORT) (Contd,) RESULT;;: -3- ' synthesis 549# Samples 30# Spill (8019) 30# Filter amt Prying I05<5# Rework Lot .400# total losses 2065# QA Paused out 3300# Expected -QA Production 5365# (based on 71*7# yield) Tbeorotical QA Production 7486# In oi.,: j&tion subsequent to the run hue brought out that, one leaf jh-(vj <U' one blooding -badly, and it way not 'have always been backed.up by <hc other leaf filter,, Tills' could help explain the disastrous loss botwuor oiltalien and puckont* Unfortunately, no.samples were taken of the loaf wash water to the sewer* . so that no concrete sewer .losses cap lie ascertained, . : ,, Ho taa.jc-c operating problems were encountered during the Campaign. Vie only problem was a *erfciaily plugged condenser during, the ..distillation of;' Hateli 0019,, This occurred when the cooling Bowthem get below the norma? 48-9 3 (J. The process itself gave no problems, . In the laboratory, it wap found that 10$ dispersion milled gamma QA ml 1.1 powder Man needed- for batches 8018 and 8019 oxidations to go to eviction,. 'Butch 0020 required only 7# dispersion milled gamma Oft., mill powder to go to completion*' However* in'the plant* .a sample of batch 8rib t-nlco, then 68-1 reached reflux*was in the "grape juice" stage./ TM.n hutch /as recovered by the. addition of 3$ mill powder* , The percent fer those batches was: 80l8 ~ $$ 4#5 029 - 8f .6#$ 8020 - 96*1$ (v-f. r:/22 A otd.) * ' .c u k .?c - of the large amount of tlaOH and "Sitol" used in the oxidation, /. a-'::'itont of the" filial slurry is very high. Hence, when the temper- >; <:br;:r: Y.,u:h ferClOi, (iOC., \1 \ >./ - : :' 2!:iriver slow) ' i * " / -r u; : "a-ool down m.'.cugi At that point, the press was 1' ' . .x . i- fi.T M.' wa:.: e ;:ou'A .. Ct : a : eatery pressure filter. Hence, the P*- ;I'/liV, n > 'one iv..>t r:- to the dimethyl OA particle ' sixe - J/'cae'u . .... : tL^bi: cr/ attached. DUP050028251 XPB * 179 C1031KG REPORT (CotrU.) -4~ RESULTS; (Continued) The first 7 mill charges'used 05-5# dimethyl QA (100$ basis) vs,, a normal charge of 80*p## This was. done because the product v/sis running on the yellow side in previous campaigns. As the product was still yellow* the dimethyl QA charge wap increased to 90.0# (100$ basic) ., A satisfactory product was obtained after this change* The follows rv. tabulates Newport quality I'csults on each mill charge? Lot From To W Mr J.,99 ,/ it a L'*'1 :V>-j d?-9 3320 1[V) ibl iff BS0 ^ 3M III " ) 93 b X5 b15 195 p29 gl5 P^-'1 B20 157 1.99 b99 vv iGo v29 b29 161 1)29 529 16 y '7*3 lf)9 b99 166 d99 b S9 167 ` 170 169 I>99 B9S 172 If-9 b 29 rn,x7'b 176 i>25 b 25 177 ir: '.i .:uU. is1^ i20 l7 Y10 stv 83 96 96 92 95 . 91 100 92 97 92 90 97 87 90 93 90 99 Y5 j5 I2? jU F5 l11 y29 -j-15 y29 jl5 B20 L15 B2'5 d 13* d25 p20 y5 d8 jjll q !8 3:*5 d 25 B1? 1)15 B-5 pl5 B15 jp20 BH p? Y^o 17 B15 DU Mill Hrs. 8-1/2 IT If = 8 11 n it 7 . it , r? 8-1/2 5-1/2 U *r 100$. MtsQA . 85.5// 11 !t It U 90.0# It V T< It 11 tv It n IV *? n '`u.;,- T.a;:on for* the yellowness is believed to be due to incomplete -(.Iff noei:ion formation :lx the acid extraction. It should be possible to c-vu-cei. file situation by changing the acid concentration and/or coniaut The .following. tabulates Newport rubouts of mill charge to bo extracted and Newark alkyo. plant tests of the extractions vs. ifb/VfU-D sbd. DUP050028252 X0R-I79 CLOSING {Contd,,) - 5~ ' RESULTS . (Continued) . Lot w 11 Charge Rubout Alkyd Ml' Str, 3 40? 147, 148., 194, 155 158, 159/ 'j 60, :io2s I63, 3.67, l68. 172, 17* d20 9% b6 B* X2 100 B8 * 410 3/1 . 150, 191, 152, 164, 165, p29 93 YX . B* }C/j\ 1/0. 175/ 176, 177 100 B4 41' i *3*r'*. 5 */>.- 157, 3.61, 163* 166, \P9 92 Bio Bio I10 102 Bl8 -U .ii. l>)v 174., 170 A).' th ;-io Jots were OK to ship.. 2,9 DiMe QJ\ Plant Cycle Times The C,ellowiag is a summary of the cycle times experienced during cbri recent 2,9 Dimethyl QA plant run. Lost time xs not shown. c:/.-a.e uni 1 Aytuol Jilmo __ 3.hooretteal Time Plant Std* Comments OOio 8019 f'.r<po :'ID C-0 inij.fj 5 o:i 9. >.\V9 ) pvi" 4 O'! 5 36 . 12 13 24 hr. lag between DES and SSE 19 12 13 Lost 5 hrs, dissolving solids. . 17 12 13 Good run a "inti-w/Distil'X&tion {SSE transfer to final level adjustment) 10 7 6 Lost 2 hrs,, fixing rotameters and finding DT line 3 *i7 6 Erratic distillation (line (. pluggage ?) 7 6 Good run {Start of tra; infer to final cool- down) tX- 11 11 10~hr,, transfer 16 11 11 10-hr, transfer - lost 2 hrs. 11 11 8-hr. transfer DUP050028253 Cycle Actual and .Parch . Ump Kutscbc Pi:i.t ration 801B 1.6 OU.i.') 10 8020 10 OxlcV'ticm BOX! 5 15 80x9 1C-1/2 Bop!) 16 tpytA ; ! ^'1* OoxO >Vvi', (T 13 9 XOB-179 CLOSING REPORT (Contd.) -e- Theoretical Time Plant Std,,. Comments 10 ... 11 10 11 (Kufcshee used as hold tank ibecause of long press 10 11 (cycles 10 12(a) Lost time getting sample results 10 ' 12 10 12 Insufficient seed - lost 6 hrSo. '3 3 .. 3 3 (Blinded Shriver - all batches (dumped to leaf filters at 3 (end of times shown 3 tuoKiw*- bj ?p c it mremt mr.: A HI 7\ //Johnson \y APPh OV-I) BY: Research Supervisor A/> l::eft*f. /I ;.`,j DUP050028254 c\s PORT BE NEMOURS & COMPANY OC: V, S, Struve/ A, A. Brizzolara - Newark H. R, Binton/R.F,White - II, Arnoul/T,E,Wilson - 11 R, Gedd . " W, A, Jenkins - Newport R. M Salerai - '* J. J, Adams C, F. Wood (5) P, le Odell - . J. C. Chaney !> B, H/MaeAlltster -" X.. S, Millolot -" R, H,Wetzel -" H, Hc Gyorgy - ,l J, W, Minnieh ~ 11 J, F, Maurer - ' File . ~" Newport, 'Delaware Octooer 3* 19^7 547 ORGANIC COLORS - HBWPORT XOR-lGl * CLOSING REPORT TITUS; Plant Synthesis - 2*9 Dimethyl QA BAC^GkROCFRD-} TFA, rather than PTSA/ was shown to he a suitable catalyst for the p-ioluidine (PT)-SSE condensation in the laboratory and the plant (XOR-179} The more soluble and active TFA permits a reduction in . TD/SSB ratio from 7/1 to 3/1., reducing pluggage problems and the catalyst neutralization step which previously resulted in reduced yield .and quality . Further, laboratory study on the oxidation has shown that the voluminous 7-10/ gamma (as raillpowder) seed , can he replaced by 2.5$ 1ST drowned dimethyl Q,A<. Dimethyl DQA, tested in the laboratory* showed instantaneous hydrolysis from NaalihaQA to Me^QA with this seed. It was further found that a small reduction in NaCH concentration eliminates the need of seed in this oxidation using normal MOaDQA* Modifications of the ratio of ingredients nov? per mits, use of "Sito!" solution; with the elimination of seed* ho dry colids need be added to the tank. This eliminates extensive equipment requirements which would be required for safe solids addition. OBJECT!'/E: Synthesize 2,9 C%Methyl QA at the 179$ hatch size using TFA as the condensation catalyst; 2,5/ IB? drowned 2,9~ dimed yl QA as seed, and* if possible 9 no seed in the or-vi.dction. DUP050028255 - 2~ CONCLUSIONS; 1. The laboratory 70$ goal yield for MeaDQA was demonstrated in the plant. 2. The oxidation yield is essentially quantitiative 3. Dry 2,9 dimethyl QA yield is dependent on re covery efficiency which in this six batch campaign was 90$ versus 86$ for B~QA* 4. Me2DQA quality was poor. This appears to relate to Mg 2DAT degradation during pro cessing . 5* Because of quality deficiencies# it was not possible to oxidize MeaD/-> without seed* 6 - Some operating problems were encountered in this run. a,, Disappearance of TFA and TB. b. A need to modify the TFA/TD distillation . to . better remove D* c. Filtration losses. d. Maintain batch, identity to establish batchwise yields.. 7. The first two batches of' 3~QA coming out of . the MesA campaign were poor in yield and fluorescence,' Due to other operating .changes on these batches# the degree to which this degradation was due to the 2,9 Ke20A run cannot be established.,. KKSO ITS: YleX a $ 63 - SSJi The following yield. data were obtained! 8021 70 8022 66 8023 76 8024 f5 8025 77 . 8026 77 C>2 - xmy sii 62 59 66 60 59 53 Pyr. 53 58 03 55 77 Pyr* - 73 - ~ 65 57 69 - TDA 08 JX!A JA <y\ 72 71 7-4 72 997 68 61 82 66 91? cl 7. 62 6.5 . 71 77 68 74 .45 - 58 56 58 70 DUP050028256 RESULTS: (Continued) The low 62 DAT yields vs, 77 pyrolysis yields indicate . non-uniformity of the 62 tank sample. The nohfuniformity results from part of the Me&D&f- feeing out of solution at the 120-50*0. tank temperature. It is believed that the Me0HAT pomes out on the side of the tank rather than as a slurry} hence, a weak sample is obtained,, " An excellent material balance was obtained on this run,' Matorial Balance Lbs. 0021 8022 8023 8024 $02? 8026 Me^>33QA 65 Tk. 68 Tk, Seed Total Me^Q/y 1472 1451 87 1488 1472 1249 37 . 1286 (?) 1666 3. 1749 1394 1349 . 68 141? 1566. 1395 78 1473 1182 1140 109 1249 68 Tk . . Leaf filter Spray Drier Total Loss Cumulative Tar ~ 74 Still 1533 : . -' 0 1100 . 1100 -388 -388 (?) .0 1200 1200 + 14 -374 1737 b: ; 1400 1400 -349.-': -723 1486 600 900 1500 + 33 -64o 1572 1280 0 ' 222 1000 1300 1000 ' 1522 - 473 -1113 +242 -871 Calculated, Cumulative Found ; l>3 , I63 ** 163 206 13(?) 489 241 730 1080 69 453 799 1252 - 1430 The overall MeaBQA yield was 67$. Batch 8026 was considerably lower in BQA yield probably due to;degradation of the MegDAT during re~ dlstillation- of the TO, Excluding this, the first five batches average TO#.. This compares favorably with a laboratory yield of 70*2$, The yields check out v?ol3, with the tars found in 7^. still./ The oxidation yield for KeapQA to McaQA in 68 tank was 103# for the five batches for which data aye available.. This, corresponds to '* 99-3% laboratory yield and is'within expected sampling/analytical accuracy,. DUP050028257 KKSUbTS: (Continued) A 90% yield was obtained across the filters and drier. Pigment was found in the filtrate storage tanks* Ho quantitative measure is possible'; since' these tables are fed continuously to methanol recovery and the solids are sewered* Based on storage tank measurements, the yield from BBS to dry MCfc-ciA was 6l$. This excludes the added seed* The only presently available measure of MeaBQA quality is its erase of oxidation* Good quality oxidizes readily at high Had! levels and without seed* Poor quality MegBQA re quires seed and/or reduced HaOH levels to be oxidized* Yield is not aerected* The MesDQA quality in., this campaign was poorer than tie previous one in March (iOR-179)* The oxidation conditions re-' quirod were as follows: 8021 8022 8023 8024 8025 WnOU level (lbs,/gal.) 0 *16S" # Id' KcaQfi seed 2.5 0*166 2.5 0.166 0.156 5*0 ' 5.0 0*156 5.0 The product quality was as fellowss : QA - XR Good Poor Good Good Good # QA (std. 5119-71B) 100 93 104 102 100 .Hased on these data, four of the six QA batches were of excellent quality. The other two could be consumed by blending. The poor quality of #022 probably relates to 1$# of the MoaBQA remaining on the Hutschc. This resulted in a 15#'.HaOE. excess, JBy an error .in eal emotion, only 10# of the seed required for 8026 was added initially. Particle grpwth'-.of the SaaQA made the subsequent addi tion of the remainder of the seed result in borderline quality - Meoj5QA in-the produet* One problem encountered in this campaign was the disappearance of TFA It was necessary to make an addition of virgin TF.A for each 62 tank condensation -- TFA 8021 8022 8023 3024 8025 8.026 10# 3# 10# . oj 3# Initial charge initial charge I- 8026 1.56 9.0 Poor 90 DUP05002825S On batch 8026, virgin TD and TFA were used in an attempt to improve qualityv There was no evidence that any of the lost TFA was hung up in the 62 system as the TD salt. Further studies will be needed to solve this problem ' . Another problem involves the removal of TD by. vacuum . dir ti nation'`after' the condensation, K'ojitjal procedure, is to distill until there is 0,05# or less TD in the column bottoms* Since MG;'DAT will cctoe out of solution at the 130*0i 6g ik. tempera ture., ;tt is possible that soraeTD is trapped* This trapped TD could then be available to cause' trouble in the subsequent pyrolysis* An attempt was made on 8.026 to overcome this problem by heating 62 tank to 170*0. at the end of the distillation to put everything into solu tion* cooling back to 150*0.# and redistilling* Additional TD was removed by this techniquea However* the extra heating was apparently more barm Pul than allowing some of the TD to remain. The Me2DQA (8028) was the poorest made as measured by ease, of oxidation. It was necessary to use 9# seed to make the oxidation reaction go to completion, There x*ere no filtration problems in this campaign.. The problem of the Shriver being plugged in the March campaign 'Y wan overcome by preheating the Shriver to 60C* and maintaining the MonQA siurry at 62-8C These steps were necessary to keep the salts in the Me.-jQA slurry in solution. It was the precipitation of these salts combined with a partially QAQ blinded cloth that blinded the Shriver in the first campaign* , The post McsQA performance was as follows-5 9578 ' 9^-72 9580 9581 63-SSE 62-DAT 65-jXlA Fluorescence 37 {?) 58 51 3*8? 72 7k 60 55P 72 76 72 1180 74 80 92< ?) 124G 9582 76 7^ 118g The first two batches subsequent to this campaign xtere poor in yield and in quality while the next three were excellent. The first batch had previously drummed out SSB added which apparently had degraded. The second batch showed ah unexplained degradation in pyrolysis. There was no firm relationship of either to the MeaQA campaign. J | f CLOMbG REPORT WRITTEN Mi .. . ssearch Division APPROVE]} py> /WZ/jf-^^rrsyxVxAsu--------,--- 11,. ir.lGyor^ Research Supervisor /lw;i DUP050028259