Document DDEJjaDMjYGJppLNeBQjB2Red

Hw 0> pH N40659 mSTUDIES! A. M. A u Solvent rec ster 1961 overy; - 1963 p-Toluidine tendling; process; P y E. I. W PONT DE MPMOURS & COMPANY Serial Ho. .FT-KK-63-S1 TECHNICAL SECTION - COLORS NEWPORT PLAHT PIGMENTS COLORS PROGRESS REPORT SUBJECT: ^UlRACRIDOHES - EHGIBESSJHS STUDIES Solvent Recovery Para-toluidine Handling TFA Process Pyrolysis ''Sitol" Solution Filtration Drying PERIOD COVERED: 1961 ~ 1963 DATE: MAY.20* 1965 r et ur n t o JACKSCN LABORATORY FILE ROOM SERIAL HO. P .T . KH-63-21 DUP050054987 P.T, KN-63-21 COPY NO, /l/ DISTRIBUTION: 1 - Research Numerical Pile 2 - Research Office Pile 3 - Library Pile 4 - M. Hunt/E. Goniek 5 - if, J. McClure/V. H. Chalupski 6 - W. S, Struve/A. A, Brizzolara 7 - P. J. Monahan (Vital Records) 8 - C. D, Atkinson/C, F,, Wood 9 - H. H,, Gyorgy/J. W. Minnich 10 - C. C. Ballard 11 - J. M,, Wesley 12 - P. H. Griswold 13 - J. C,, Chaney 14 - Research Pile Colors - Newport 15 - Extra 16 - Extra 17 - Extra TECHNICAL SECTION - COLORS NEWPORT PLANT PIGMENT COLORS PROGRESS REPORT SUBJECT? QUINACRIDOMES - ENGINEERING STUDIES Solvent Recovery Para~tolui dine Handling TPA Process Pyrolysis nSitol" Solution Filtration Drying PERIOD COVERED; 1961 ~ I963 SUBMITTED BY; A. M. AUSTER APPROVED BY: H. H, GYORG DATE SUBMITTED; 1963 DATE ISSUED; 5/20/65 ABSTRACT Status of QJk engineering studies, DUP050054988 TABLE OP CDHTSfPS Solvent Recovery I. Wet Methanol Recovery A. Capacity B,, Methanol Purity II. Pyrolysis Dowtherm Recovery III. 74 Still Operation A. DPU System Alcohols B. Pyrolysis Distillate Recovery C. "A" Tank Dowtherm Recovery D. Methanol Recovery Magenta I o Equipment A. Cooling System B. Para-toluidine Handling System C. Centrifuge Bag ' D. Wet Methanol Recovery E. TEA Process Aniline Condensation - Distillation I. Standard Process II. Continuous AnilineDistillation III. TFA Catalysis A. Corrosion B Distillation C. Catalyst Recovery and Re-use D. Laboratory TFA Process Development E. Semi-works Tests Pyrolysis I. Pressure Pyrolysis II. DAT Column Feed QA Filtration QA Drying Nutsche Filtration Solution "Sito.l" Facilities List of Contacts and Consultants Page 1 1 2 2 2 3 3 4 5 5 5 5 6 6 8 9 9 10 10 10 23 23 23 24 24 24 DUP050054989 -1- Solvent Recovery I. Wet Methanol Recovery A, Capacity The capacity,, in terns of QA production, has not been determined recently* So far, 75 still has not limited production and is not a bottleneck at 36m lb, QA/raonth. A feed rate of 2,400 lb./yr, (approx, 300 gph) was measured prior to steam revisions (NB-5089-9), She filtrate tanks, H and J, hold a combined total of about 8,200 gallons. Prom the above, a 27 hour cycle results. Since the current maximum feed rate is higher than 300 gph, the unit is able to keep up with production. Peed rate is limited by pressure drop and methanol bottoms concentration. Steam feed rate is not con trolled, reflux is controlled by top temperature and feed is set to maintain between 10 and 12" BgO P across the column as well as 102 C, minimum bottoms temperature, Normal feed valve setting is 1,4-1,5* Under these conditions, the still is operating at maximum capacity with incipient flooding. No more 3till capacity is possible without changing packings. If it is ever necessary, I suggest "Glitch Grid" Type E-25 in 304 S/S. Based on current sales fore* cast and a reduction of filtrate after the installa tion of the new filter, new capacity should not be required. B, Methanol Purity Current purity is in the neighborhood of 90+$ methanol product. Dimethyl DQA oxidation requires 98+$. To achieve this degree of purity, take the following approach: 1, Cut feed rate to 1.0-1.2 on valve 2, Raise automatic reflux controller sensitivity to "High" for on-off control 3, Set top temperature pointer to 65C 4, Check overhead purity and reset pointer as needed. This system will cause the still to cycle badly, but when feeding only 250 gph of 15$ methanol feed 37.5 gph pure MeOH - a variation of only one gph in Overhead takeoff will upset the purity. This sensitive control cannot be readily achieved in the steady state, so cyclic control is necessary. DUP050054990 II. XXI, -2~ Pyrolysis Bovrfeherm Recovery Some Dovffchem from the bottom of the pyrolysis column is collected in "F" tank for reuse in subsequent pyrolyaes . This type of recovery is "free" and should be exploited to its limit. Past attempts to increase recovery in this area showed suspicious affects on yield and were dropped. It a demister system is installed to reduce or eliminate non-volatile contaminants, and if the BPU removal system continues to operate properly, a further attempt to in crease recovery should be tried. This will both Increase available Bowtherm, reduce the Xoad on 74 still, and further concentrate DF0 In 65-58 tank, A controlled program should be started to stagewise reduce offtake to 65-58, while main taining close watch on yield and quality. At least a 50$* reduction in offtake to 65-58 tank (150-200 gallons) should be possible, 74 Still Operation A, DHJ System Alcohols A real effort should be made to dispose of cascade alcohols without rediatillation in 74 still. Current Bowtherm concentration In this stream is about 10$ in a 60-100 gallon stream. If the concentration can be reduced below 5# by reducing cascade top temperature set point, the stream should be thrown away. When this is done, the forecut from 74 still to the sewer should he eliminated. In its place, substitute a long intermediate cut ~ l4o*C. at 240 mm to the inter mediate tank, B. Pyrolysis Distillate Recovery Inasmuch as this is the most difficult distilla tion, first efforts should be made to minimize ED by redcuing 65-58 product and by throwing away cascade alcohols. A normal charge will contain PT, intermediate tank material, and nAw tank Bowtherm. Our present procedure calls for starting up the still at 240 ram absolute, pressure, automatic top temperature control set at 90C. Product flows to the sewer until top temperature reaches 90C, where still goes on total reflux. Top temperature is reset to 140C. and alcohols and Bowtherm is stripped t the Intermediate tank. This saves Bowtherm and also keeps alcohols out of 65-58. The still is then set on manual reflux control at 160 mm and a Bowtherm Inter mediate cut is taken to 65-58 until it is aniline free. Good Bowtherm is then stripped under very little reflux to aGH tank. DUP050054991 -3 B. Pyrolysis Distillate Recovery (Continued) The above procedure is satisfactory for the present but it would be helpful to investigate intermediate cut (65-58) specifications and procedure* It would shorten the Intermediate cut considerably if the aniline speci fication could be raised. Something to keep in mind - traces of basic nitrogen compounds can be removed from Dowtherm more efficiently with acid resins than by distillation. Possibly the Intermediate cut could be purified this way, avoiding continued recycling. Also, since 65-58 tank PD is now 99+$ Dowtherm, check this first for reuse in pyrolyses after filtration only, and secondly after filtration and acid resin ex traction, The 1$ alcohols would be removed on heat-up of the pyrolysis vessel, C, lfA" Tank Dowtherm Recovery Occasionally, the still is charged with a full taiik of Dowtherm contaminated only with heavy residues. This type of distillation is very fast and requires only a minimum controlled reflux of about 300-500 pph, This serves only for de-entrainment purposes. Even with a manually set signal on the product control valve, It ` is hard to maintain low constant reflux. I suspect the valve trim should be changed to linear rather than equal percentage type for better control in the low range, D, Methanol Recovery This operation is the least trouble of all since mid-column feed was started. Feeding the column pro vides rapid cool down and minimizes reflux requirements. The plant wants this operation to be as completely automatic as possible, I have suggested, and the plant is going to install, the following control system: a. Reflux will be controlled by temperature in the mid upper section of the column. Top temperaturesis out since methanol purity cannot be controlled at its own boiling point. Set point should be only a fraction above the boiling point - 66C. b. Column feed will be automatically controlled by bottom column temperature. The optimum set point will have to be determined by trial and error with current temperatures used as a guide. c. Boil-up, as as present, will be controlled by column A P. DUP050054992 -4- D. Methanol Recovery (Continued) This system Is designed to control itself after start-up through its entire operation and finally shut itself down by going on total reflux. Occasionally, now, an operator is not present when feed runs out, allowing the MeOH storage tank to be contaminated with Dowtherm. The whole tank then has to be redistilled. --Er*--qr"u--*--ip-Tmrrr^er*n--t* A. Cooli: Paratoluidine distilled from 62 tank freezes at 45 C. when pure. This creates plugging problems in the over head condenser. Water, even heated, is not usable as a cooling medium.. Steam cannot be added to the recirculating cooling water without over-running the cooling tower and not enough purchased water is available. Cold Dowtherm, temperature-controlled by the Dowtherm cooler will be used. A set point will have to be determined but about 40*0. can be used to start. Due to lower A and lower film coefficient for Dowtherm, the capacity of the condenser will be reduced and distillation rate will have to be reduced accordingly. This should be determined in practice. It would be helpful to raise the pressure in the column overhead vapors to 40 mm, increasing temperature, Tjja, and condenser capacity. Laboratory studies at 40 nan distillation pressure showed little effect - N..B, 5090. Another method of raising vapor temperature and lowering freezing point is to operate initially at no reflux, re ducing poluidine purity. Lower distillation rates also have the effect of raising top column pressure and tem perature by lowering column pressure drop. If TPA catalyses is used at 50$ toluidine excess (versus current 300$), overhead purity will be too low to create a problem. Mater can be used for cooling. Optimum distillation conditions will have to be de termined. Use minimum distillation time as a criterion since time effects yield In the presence of TPA. Hint use minimum reflux rate, maximum boil-up and about 350 gallons of distillate at end. DUP050054993  5,, B. Parafcoluldine Handling System The ''Tote" tanks used for handling p-toluidine are novel in that they are the first steam heated liquid tanks Tote has built. They are also the first to in corporate a flush bottom ball valve. Only one heating plate coil was used for ease of construction and main tenance. It should be sufficient to melt the contents in about eight hours. I am relying on the insulating effect of the solid on the walls to prevent heat escape. Temporary insulation may be required - asbestos blankets. The plate-coil is the heaviest available and will take our 150 psig steam. This should be tested prior to filling tanks. The tanks should also be tested full of water. The flush type ball valve design will minimize freeze-up tendencies, but in practice, it may have to be heated to start flow. A1.1 fill lines are steam jacketed. The tanks will be unloaded into second floor storage tanks 62-9 and 12 by vacuum. Transportation to and from Orchem will be by company truck - contact H. Jedlieka and . Sutton for arrangements. Also contact W. Huxtable, Orchem, Dyes and Chemicals Office, Telephone 8-172-388. G. Centrifuge Bag "Teflon" bags tear in this service and no other common fiber is usable. No explanation for "Teflon" failure is apparent. J, Flood and J. C. Chaney are looking at replacements. As a last resort, a solid bowl could be used but this presents a cleanout problem. Check manufacturers of fiberglass cloth, graphite or spun silicate fabrics. So far it appears that the TFA process requires no filtration. D. Wet Methanol ^Recovery The Magenta (2,9 dimethyl DQA) oxidation requires 99$ methanol. Before producing this, 75 still should be adjusted to see if we can produce this purity. Especially determine capacity under these purity con ditions , E. TFA Process Obviously, we should expedite development of the TFA process since it bypasses the disadvantages of the PTSA process and eliminates the capacity penalty. Laboratory development has yet to be taken through the quality evaluation stage. So far, the process looks good. DUP050054994 -6- Aniline Condensation - Distillation I. Standard Process Little has been accomplished recently by modifying the existing process aside from installation of the DAT hold tank. A small distillation cycle reduction accrued from raising the maximum heating jacket Dowtherm from 50C. to ?0C. Lowering the aniline;SSE mole ratio from 7:1 to 5sl helped significantly (X0R-105) but was dis continued because it may have been causing lower yield. This XOR can be reopened if necessary* Reflux control via top temperature was tried but showed no cycle advantage over hand control. I do not recommend any further work in this area. Some help may be obtained by using the reboiler in stalled for continuous aniline distillation to boil up column bottoms. This increases boil-up to the limit of column capacity at 25 mm* aiding separation. The problem here is controlling boil-up to maintain 25 mm. It is easy to overrun this point with the reboiler since only hand control is available. Operation of this system is obvious by inspection. Start-up and shut down procedures should be designed to keep the reboiler full of liquid to minimize operating effort. II. Continuous Aniline Distillation The purpose and test results of this system are des cribed in attached X0R-77 and its Closing Report. Original calculations are contained in TS Notebook 2078, Test data is still in its original form in A-10 engineers* office file. Detail drawings NPD-10188, 10191* and 10190 describe the system. Copies are in the aniline distillation file. Since 62 tank capacity is no longer needed* it will be some time before the system is again operated, especially if TFA shortens the distillation cycle. However* since this type of distillation provides minimum DAT retention at distilling conditions, it is reasonable to expect in creased yield. This is especially true if integrated into a continuous condensation, distillation, pyrolysis sytem. I recommend that TFA development precede any further distillation study since it provides more immediate benefits and it increases probability pf success of continuous aniline stripping by lowering aniline concentration. Further dis cussion is contained in the TFA section. DUP050054995 -7" II, Continuous Aniline Distillation (Continued) If continuous distillation follows TFA development, the only problem to be considered is separation of TPA from Dowtherm, Batch distillation shows that TPA dis tills after aniline In both standard and dimethyl DAT synthesis. TPA distills early from a DiCl DAT mass. Since no prediction methods are available, the extent of this problem can only be determined by laboratory or plant test. Prom observation, I expect that lower Initial aniline concentration will more than compensate for TPA tails. If continuous distillation is tried with catalyst neutral!zation, problems of DAT solution and carbonate filtration present themselves. DAT is difficult to solubulize after cooling, but this can be done by heating to 115-120C, and holding about one-half hour. Overheating may cause yield loss. Carbonate., filtration will require installation of the vertical tank, vertical leaf, sluicing filter stored in A~208. The complicated nature and operation of this filter is dictated by the hard filtering nature of the cake and by safety con siderations in handling amiline-Dowtherm solution. Operation is straightforward up to the point of un loading carbonates from the aniline - Dowtherm - DAT solution in the filter at the end of a distillation. At this point, there is DAT and aniline in the filter and DAT in 62 column which must be purged to the pyrolysis tank. This should be done first by blowing the filter down as far as possible with Ns, flushing with a 50-galln flush, and repeating the cycle. The DAT - aniline - Dowtherm will be pushed into the column, stripping out the aniline. DAT will be purged from the bottom of the column by a stream of hot Dowtherm from 65 column bottoms. The 65 column bottoms stream will also be tied Into the filter feed line where it can serve as an Intermittent flush stream. When aniline is purged from the filter, carbonates are unloaded to the centrifuge by flushing with Dowtherm through the sluicing''nozzle! The centrifuge will send any remaining EAT and Dowtherm to the pyrolysis and retain solids to be unloaded manually as at present. The filter Is somewhat oversize and should hold two batches before unloading, halving during purging, sluicing, unloading operations Is complicated and critical, A detailed operation procedure will have to be worked out. DUP050054996 -8- II. Continuous Aniline Distillation (Continued) The 65 column bottoms purge stream is necessary to both the distillation as discussed in XOB-77 and monthly reports and to flushing as above. This means that a system will have to be worked out to split this stream between "F" tank and 65-1 at atmospheric pressure and 62 column under vacuum. This can be handled with a pressure regulation valve going to 62 column and check valves to "F" and 65-1 for protection. The bottoms reboiler circulation pump is not now hooked up. Even when reinstalled, the pump circulation rate is suction head limited due to low vacuum operation, however, it can be satisfactorily operated by throttling the reboiler dischage line valve. Before reinstalling, it is worthwhile to consider ways of increasing NPSH, 111* TFA Catalysis Development of the TFA catalysis route is covered in monthly reports and in TS Notebook 5990. The attached tables list all experiments from inception to date and are taken from the monthly reports. Original laboratory sheets and further information can be found in the "DAT Gatalyst Neutralization" file, TFA catalysis has the following benefits: 1. Eliminates catalyst neutralization and watersremoval saving at least three hours cycle time. 2. Cuts distillation time from 6-8 hours to 2-3 hours by reducing excess aniline. 3. Eliminates tank cleanout after transfer saving 1/2 - 1 hour, 4. Eliminates centrifuge solids saving cleanout labor. 5. Increases DQA yield about 1% saving $8-10M/year ingredients. 6. Makes consistently good fluorescence DQA and should be less "accident-prone" than the present process. In addition to the above, the standard reaction rate is fast enough with TFA (about 15 minutes to completion at 85C,) to consider a small, continuous reactor in place of 62 tank. DUP050054997 -9- A. Corrosion Under certain conditions, TPA will attack steel, forming a black residue which will spontaneously ignite in air at about 130C. This effect accounted for failure of the plant TPA * continuous aniline dis tillation test. Simple refluxing of a TPA - aniline Dowtherm mixture through steel packing did not show this effect, but a complete distillation cycle showed a fast reaction forming black residue near the end of distillation. Corrosion of steel in aniline - TPA Dowtherm at 100C, is 7 mpv average with localized pitting (Notebook 5090-115). These phenomena may be explained by the chemical bonding of TPA by aniline as a neutral salt except when the salt is decomposed during distillation, leaving it free to attack the packing. 316 stainless steel, the tower lining material, hardly affected by either dry distillate vapors (vapor line conditions - see Notebook 5090-63) or refluxing conditions in aniline or substituted anilines service (Notebook 5090-116), 316 stainless steel then is an acceptable packing material. Hastelloy C and Inconel, materials in the reaction vessel and condenser tubes respectively, are also satisfactory in their services (Notebook 5090-115). A storage test of aniline - Dowtherm - TPA was not done in the laboratory. However, weak aniline dis tillation from semi-works tests containing aniline, Dowtherm, TPA and o-cl aniline, Dowtherm, TPA have been stored on the dump since May, 1963. They should be emptied and inspected shortly. B, Distillation TPA - aluminum salts probably successively decompose and recombine during distillation depending on temperature and aniline concentration. Observations are that TPA begins to distill from aniline at about 120C. and from o-cl aniline and p-toluidine about 100C, In all cases, some TPA strings along behind after aniline has apparently distilled. This will slightly lengthen distillation cycles. In any case, since long hold times, especially in the presence of TPA, reduces yield, the shortest possible plant distillation cycle must be developed. A plant test uing TPA, 3 si ratio anilinesSSE and neutralizing catalyst would help (see reference letter AMA to AAB attached). DUP050054998 10 - C, Catalyst Recovery and Re-use This has been established in the laboratory for DAT, DiCl DAT and DiMe DAT syntheses. An acceptable procedure for analyzing and sampling plant distillates still has to be developed. The TFA salt will probably be crystalline in storage depending on distillate aniline con centration. Tank agitation with nitrogen may yield a representative sample, A laboratory pro cedure is available for analyzing TFA in aniline Dowtherm but the accuracy of this test must be checked. D, Laboratory TFA Process Development This is geared first to meeting or surpassing standard PTSA process yields and secondly, taking advantage of increased TFA catalytic activity by reducing aniline excesses and/or hold times and/or catalyst amount. Also, the effect of fractional distillation times are checked. In all cases of longer than standard fractional distillation, yields are lowered but similar losses are true for the standard PTSA process. In Scarlet synthesis, a 6;1 mol ratio of o-cl aniline:SSE is apparently required versus 3:1 aniline:SSE in standard and Magenta syntheses. If this proves to be a true picture, it means only that the o-cl aniline con densation cycle will be longer than the others by added hold and distillation times. The process is still satisfactory. Experiments have not yet progressed into the distillation study (Notebook 5090-108 to 5090-114), E, Semi-works Tests These were run at 216$ batch size DAT and DiCl DAT with TFA versus 216$ DAT and 108$ DiCl DAT with PTSA. Yield data is not available due to improper charging of the reaction vessels (SSE not dissolved). Operability was demonstrated (Colors Monthly Report Semi-works DQAs were laboratory oxidized to crudes showing little quality differences. Laboratory DQAs were also included in this evaluation. Laboratory millings of the above crudes showed very similar tints by rubout but TFA QAs showed light masstones, indicating undermining (data sheets are attached). Obviously, these conclusions are preliminary and more oxidations with longer milling and rubouts against extended standards are required. DUP050054999 COPY 11 E. I. DU POUT DE NEMOURS & COMPANY PIGMENTS DEPARTMENT CC: A. A. Brizzolara H. H. Gyorgy, Newport A. M. Auster, 11 NEWARK, NEW JERSEY JULY 24, 1963 J. C. CHANEY PIGMENTS NEWPORT TFA VERSUS PTSA QUALITY Samples of laboratory oxidized 3-QA and 4,11-dichlor-QA (from lab and semi-works TFA and PTSA catalyzed condensations) for dispersion milling in you 1-2/3 gallon mills were mailed to you last week. The oxidations of DQA to P-QA were all made on the high water formula. The "Higgins Oxidation" was used for making the 4,11-dichlo-QA. Below are listed the identification and rubouts of all samples: Exp. No. TSC-94-4A1 TSC-94-4A2 TSC-94-4B1 TSC-94-4B2 TSC-94~7Ai TSC-94-7A2 TSC-94-7B3 TSC-94-7B4 TSC-94-IOA1 TSC-94-10A2 TSC-94-IOBI TSC-94-IOB2 DQA Source TFA i'Lab) TFA ([Lab) PTSA (Lab ) PTSA (Lab) PTSA (SW-00557} PTSA (SW-00557) TFA \fSW-00558) TFA |[SW-OO558) PTSA (SW-00559) PTSA (SW-00559; TFA |[4,ll-Dichlor) SW-00560) TFA |[4,ll-Dichlor) [SW-00560) Yield (from 40g DQA) 3g.9s 38.8g 39 ag 39. Og 38.9s 3g.9s 38.7s 38 . og 39.2 39.4 39.4 39.3 Composite Settle for Milling TSC-94-4A TSC-94-4A TSC-94-4B TSC-94-4B TSC-94-7A TSC-94-7A TSC-94-7B TSC-94-7B TSC-94-10A TSC-94-10A TSC-94-10B TSC-94-IOB DUP050055000 ~ 12 - (Rubouts TSC-94 4Ax v s 4A2 4Bi v s 4b 2 4Bi vs 4A2 4A2 v s 4B2 4Bi v s 4Ax 4Ax v s 4B2 TAx vs TA2 7B3 vs 7B4 7Al vs 7B3 7Ai vs 7B4 Ax vs A2 Bl vs B2 A2 v s Bx A2 v s B2 B2 vs Ax Ax vs Bl -2- by W. W. West) Tint 99t 96, 105, n97. 98, 108, 112, no. 99} 99} 104, 103, 98, 102, WAW:mae/tmj s/ W. 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Pi 1 3" 3 43 P OVrS O M p v bD Qj a? .$ 3 IS- 03 i & -9 P ft 03 Pi H * O CD <1 H =H < P ft =f o h Q i 1X3 03 -si- <D H ri o <0-1 X3 Pi P Eh Jtf- o w tQ 03 =d" ro LO 03 rH & s O _ P^<5.P H ; O at H C$ rH P rH H P 3 0 ft * s Pi s S3 H t P pi CD p H N i t> 0 > 0 0) OHri S3 AH 0 CD 5 O ft s <8 *<S1 P CiJ *p 3 *v CQ OO S3 GOO 0 ft >f O cS ft O r-l *H (S | CQ ty. .9 =!- Pi #**> *r-** S3 03 O0O Pi Pi O -rl Ofo T3 X1 O on w ft rH H! w p M p 0 P ft ft 4 >ft 44 q > > s> O H po pra 0 on CO ft O CQ ?-i ft -s8f sj" 0 ft 0 C1-j FI- 0 0 IS8 - O H 9 H 0 S 1 > 03 03 S2i 03 a H rH cS o Pi rH J < < < is- ft s- <1 O rH fOt rH 0 1 St 18 -=J* 9 1 1 03 03 03 c- 03 03 03 03 gl a co H A rH a is CD ) CU CD H CS i! ri CD rH PS3 3N H n 'd H CO la r&-rlilfv> pP.OJI o tIoI h> Qi ** tsH 8& p* .o POi *troi HP 43 43P *\ n Pi *3 . t* 3 f. ri r=3 St gS3 g j-i 3 <oH-i Sui -H CCS H t3 O 53 g _<h 4O3 H 03 * DUP050055003 X08 2 hx4.- B atch d i s t i l l e d T F M 03 -P d o p & o s ft II i i i S* *- _ $4 43 SB CM CM f 1 ns? rC a 0* HO .m*>*-4 a 'Cl 133 P S&ti` ^ *.6.*.P s*ss P* 13 0g3 'fSt 'SI-rff!i s ,* Jl is CM ll 04 3 ii n r-4 B s* r & M M is 04 ass CO && r*8 **J r-9 69.0 TABLE Aim ~ XX Development o f TFM C a ta ly s t in A n ilin e Condensation s CO CO IT\ \o i <rt 5m fc $ KS S o 0 o S3 Wcu -a 3 4 in in 4* ** # Ie> P (II (V! 1 s te sn &> 60 ffl ^5- S O O $ o > CM CM O O in 8 Q O .04 tn in -5* * <2 oo 33s s3 6Q 60 o CM CM (B .KS- CO + *r HI tN> t- O CO $ ^VO 0 3 0] ocvt SC in ? in a in *4- + + 1.fti 3o 3 gII &3 in 68 ISO oo Hone p ES 3 a33 C 1 B ft ft ft ft 60 60 60 60 60 * vi m8 8 8 CO 0 <& CM ro on on 3 $1 ft ft ft &o 60 60 ft ft ft H r*i H mO ...y. CM mV 0v3' {& &S a mcAn- O s{,*H*: 50 cq s?3 2h i -f-r 3 3 ft ft to 60 ft xfr m HH TCMt *m.r% a.9S%4 < %% g ft ft tf 68 60 tn o *e o oo c"5 4* P ft iinn v-ion ite fMc3 Uthi <h k DUP050055004 i,,0S g WhA  o< SSI w OJ oo o f 8 4 g 31 is! . 13 *4 r~t s**$ CO 9 &s - 3.6 - TftBLE A M - X I (C o n tin u e d ) c *3 ffi i-4 f" rt 03 5 *CJ *r4 t, SA ,j 8 SI S 5 5 t! 1 4* $ 60 88 H 00 0\ n *x* s .'!! DUP050055005 30 tain. 63 82.0 104 Batch d is t ille d p'S &f < I ol !"4 Pu o4go* (SO R? <& O -P-H O 'O x! i3H ^ ySj '-wP 0$ Pac<3* "4d3 p <(30 a! sk SoSc0-vp4 IT 'S3 SSf p*6 p *r4 4o3 3 fe e* sr-j P a* a^3 VQ p* 5c?143 P S3 oO PPaS3 fSffS3lVH&P' o-ts P 5: <4 * rt 0S<4aH 43 <Oj 4S 43 4H3 40 '.<3 483* * SeS3 g Jeoo aOclof\ (`4 g Is s co & 2; o jS rt vps r$ d 43 -P 1 l*~* 0 o\ rrtt i0rrii\ *HO*{ =$* 00 8 t r<-n t- II m * c: 0-a os 10 00'5VoD\ COK cn 10 mw VCOT\ Ch 0> O9 U00 Cb0~ 0VO0 0Js> iA m co<i et-- VqO> Osi" <rrtt in- co oo rt rt i~i vo0 O0 in*> cvj C0O cO f*4 CO rt 00 TABLE A M - I I Development o f TFA C a ta ly s t I n A n ilin e Condensation A n ilin e DQA BQA Hold Excess Y ie ld F lu o r,, 0CCJO s ~ s X " ~ St -- 52 <* .J 0 r. 3 a XI rii Cl .si C0M S3 r tn PSS3* O<-{ a in & 43 rt S3 $3 0O4 d t U01"\ S3 (OO 0 & <3 oiyCtVJ r-i s U"\ 4" - oO OJ 8 iO I4 o OJ S3 c? Q w S fcO in -Si' 6 o oG 25 < pi fri &: ?">] I-il . w el| t-- pj <s| 0! d U JS U c S2 bC in 0 3 64 to O ol sj pHe]l iinnU CO vc<:5$> 150 54 fc v.ro%t CO fc4 V jDy ii CO 54 vtooi 54 t0nsIV 0rm*4l 4* W CSOfii os (Si CO 54 cn 0i0t th b4 .=8! Om0O% ss tOn oCO irn-* 0 it U & t S3 t S3 t 43 ~S t0o CoO CoO o tn 5090-60 0 ,3 g TFA None o o g |69 m iSinjh J2S 5* f#mo ?* ?5 +&o3k* *C3O5 <s 64 4 to = *0 tin ; 0O 2 iantt i0n4 5 cn ine isni" s 0Ol mO 0cn O CSV 0in i0n 0in 0in DUP050055006 - 18 - g*p.# Catalyst PTSA Control 5090.38 1.4g TFA 5090-39 5090-40 5090-41 X.4g TFA l,4g TFA 10 4g TFA DiCl DiCl DQA. DQA Yield Fluor 83. Og 8l. 6g - S3.5g 80 83.2g 80 84 .Og 77 Reaction Time Comments 2 hr. 110C. PTSA control 2 hr. 110C. Some catalyst lost 2 hr . 100C. ] Higher yields probably effect 2 hr. <100C. of lower temp. 2 hr. 90C, DUP050055007 - 19 * r-i 0 I- & .8 Oi a O .fa 0N 04 rr** CO vd ie><~~ o cd mm \o fiW} t"S *l M O Ol O U) ft! 04 o <s t o a cs ^ co VO b*- t"~ fx * O VO % B 0*0 & tft Ifk tf S) VO VO VO VD Ift VO & o ea ion l^s {s j h s ej vo M> vo VO VO * <^4 .54" S? 'tX*"l. Hi "4 ?*4 r* I si J: is? &? SB cu * 4* ft 0 H & 5 60 in sS** H & <A *n *. 6 on w O K < *s s > *0 <* * *> m as m <M> as m tb- i.4n*>* -i4n0" m to. in 00 o H P"f Hr*} ft VHO $ S m VO VO vo 6On O!.A d $ u\ QOaN m om6a, OaON UN n OON m S g? IIi 60 60 as 0 m&0 .=fn' ao o Vts) ,v o OoN in aaiOnN o oo n . DUP050055008 - 20 ~ DUP050055009  4* S g H 0 o ' oj fPti S3 o TO B A* 21 - ft ft S8 } ka . .ft 62 ft 03 fti 5* !*> <3 a 'O H M 0 0 f&t 00 *4 )1 ft ft 0 o_ * 3 H ft * 3 ft C) 0 ft HI ft XJ !> *r4 O a ft X3 3 3 4*^ Pa . "rt 5 XI 0 ft S3 !n> B 0 4 1S3? S3 vH 03 O -H S3 4 a 0 < r1# H 0 *d H PH ^frtt ft f~l f0t T3 9 & ft g 05 CH 00 HftI 0 -S}o t cn 3 H 4 & *0 o 39 O 0 0 XI o , ft N > ft 0 4* a -J <Tj .0 H ft & A B >."1 o -H O *3 r4 ux XH H ft 0 4 ft 0 > "0 xs Pj 5 *0 ^0 ft 0 XJ H 0H $2 <t 4 ft 0H U 4*43 3 <53 O 5 S3 0 3 Pt 3 55 .2 O Ml h? -l H ft. ft 0O A 3 01-4 *CO ss2 B 03 ft ft 0 j-s H 0 g ft oo !-l ft 0 ft ft f&t fOt s P CD & MQ ft ft ft ft 01 Pi <& Rj 3 ftCQ 5s R* j 3" CO m * CO or> CO H :a A A H =i- a A s***' sn Oo O IA cn VO O VO IA A 5A Ra>S. 3 : CO *3 % CO* AV CM VO& tA9 IA VO*! A ft- c-i 9 Oft Aft ri Jf cu 2^ H f* 6 t- VO .6"" cn MO H t- cn VO O tH O |V_ CM f-~ CM CJsM*- o IS* NO* < fi &ort 4Oft Ss<6* S0C Bft O o HH rH-i HSO'*? ocn con iH cn ocn con ocn O 0% S XS HSH SHOi Q OPM--PHi HH .90 *> fc* 6-- H *e r-1 0l Hi W* H o H<* t- Snw is* HHI !* frO irt HI H * <j # Hl*I tTH SO <n cn ro 00 f3t ra g of Qr4 HB wtl!j tH r-i in 9 eH V a <3 m in v HI *rf * HH * tf *) -=3` 0 ' ri g a SO3 Rri ESdt 04 CM CM CM OJ cu CM CM OJ CM CM CM CM <5 oat O oocu J1 Sf3t .S3 .60 ft. AA ml So0S3 SS05* 63 H > .. ,IBSo3? A0Smt< sAn ,TMi SM3 SfS3t3 sS9o3; soS3; S(f33t fSt3 .2SE5 fEtt! 05 g <=3 fBe fBet sj RBi 4B^ <fe g < sS P CS$ E-5 SEf3et B aj fei oH-nffptt ftft a CM WJ A o SSJ A=#O fcO -A=* fcO JAS3j") at) 01 OJ &0 H<i> CM so A HtI* 68 A=S` tH J 60 60 C16M>0- On OCO$ Ooo 63 <On3 O 5o5 . 0t Wj CoOO3 . coAn S>*j CAcoOsn CCnO5ft AOv OVODJ odAv Acan. cAo6n Vcf'O;n). 0o1 A tcO$--n soi>rs 0oH33n A6v c<oG"nn: Aoo\ Oo ooOA3n o oAsn of- oAn AO rooA>in DUP050055010 TABLE " AM& { C ontinued)I - 22 mon cvi * crs vo *00aaH>sj BaSa)oo wo *1o 3ri HS *P8> aw 1 < 4SB3 0 > ggJ Is 0 O -rt Wfr* a m & oo sb cvs .<p 8>3> 3 P 38'2 S S) 05 09 \irov m o o b- & rt n cn >St' as H -6p9, B o<s MOHOID ff3f .Sin' & o in DUP050055011 REV. I0-5V ENGINEERING COMPUTATION SHEET Sh e e t No Tit l e o f Pr o j o r St u d y Su b j e c t <iDL3. PyJrel y. 5 iP... . Co mp u t e r . Pr o j o r s t u d y No . . Wo r k s .Da t e . o -1 *** v p * *ruc DUP050055012 Pyrolysis 23 - I. Pressure Pyrolysis As would be expected, temperature affects the rate of pyrolysis reaction. The extent of this effect was reported in the 3-V63 Monthly Report. Apparent re action time was reduced from 45 minutes at 250C0 to 5-10 minutes at 278C. These rates permit considera tion of a continuous reaction system using Dowtherm under pressure or a higher boiling solvent. The rate data contained in KB-3127 may be enough to determine rate constants for the two step pyrolysis reaction as well as an Arrenius relationship. With this data, a satisfactory mathematical model of a continuous reactor can be established for computer evaluation, A feed to pyrolysis vapors heat exchanger should be included in the system for heat economy and a BQA - Dowtherm vacuum flasher after the reaction should be included to both recover Dowtherm and cool the stream. Attached is a sketch of a possible system, II. DAT Column Feed Aside from its use in a continuous system, the concept of using latent heat in vapors to preheat feed can be useful in the present equipment, laboratory experiments (KB-5090-20-24) showed that this approach increased pyrolysis yield. This was tried in XOR-95 but showed no advantage. I suspect this was due to too much hold-up in the bottom of 65 column, allowing DAT to partially pyrolyze under unfavorable conditions (see Monthly Report 3-4/63, page 36). This equip ment should be tried again as soon as the vapor line demister is installed. QA Filtration The filter system design can be completed only if the projected drying route is known, since the presscake handling system affects both. The dryer - handling system study then, must be considered top priority. Keep in mind that the handling system must also be adaptable to the present drying system for the short term. Some alternatives are a simple press pan with manual presscake handling, a ribbon mixer with repulping and subsequent pump discharge, a steam heated mixer for partial drying, granulating and dry discharge, or direct drop into the dryer (that is, heated flight or rotary vacuum). The initial installation calls for use of the present leaf filters as scavengers, one each for beta and gamma. Maroon has little tendency to bleed and will not need scavenging. Either initially or as they wear out, the type FPF-19W woven "Nylon" cloths on the leaf filters should be replaced with eggshell "Nylon" felt type 6INYI8B. This type provides more positive retention of fines. TheKPF-19N to oe DUP050055013 -- 24 -- used on the recessed-plate filter will be pre-shrunk to prevent dislodging cloth. The heat treatment and porosity should be specified and standardized. See J. Flood, Louviers, for recommendations. If the dryer type calls for high feed solids, steam blowing - 90 psig through the wash port should be used. This will displace imbound water. Excess filter cycle time can possibly be used for hot air blowing to further i increase solids. This is riot in the project. Installation design details, such as pan arrangment and isolation of filter from unloading, remain to be com pleted. A filtrate measuring device and steam pressure regulator must be specified. QA Drying The choice of a dryer is mostly dependent on economics and handling difficulty. Assuming that spray drying is too expensive, and heat screw drying is not much better econom ically, I suggest we reconsider rotary conical vacuum dryers. It offers no more difficulties than either of the above choices and is decidedly less expensive - $25M equipment if one dryer is sufficient for the short term. The tests conducted at Patterson Foundry in April, 1962 indicated a probable cycle of 15-20 hours with 1500 lbs. (dry) loading - 35$ solids. Current status of drying studies is covered in attached letter Uutsche Filtration The Mutsche automation system is covered in the letter on the subject - AMA to FJS - 8/63 and in Monthly Report 7-8/63. Orientation and specification of new nozzles should be directed toward sealing of cake cracks as well as mixing to prevent solvent bypassing. For future exoansion, I suggest the recessed nlate filer be considered", To ainimlsi cake eemprassibllity effects, the filter may be used in conjunction with tne Hutsche which would filter off Dowtherm and reslurry in methanol for transfer to the recessed plate. Solution "Sitol" Facilities The installation and operation of this system is straighforward. Aside from its project stated advantage, this system can be used to increase Maroon oxidation eapacity by titrating the "Sitol" itself with'acid to remove carbonates prior to oxidation. This will prevent foaming on acidification of Maroon. j i I j ; j \ ] j J f I i I j j |j j f 1 \ DUP050055014 List of Contacts Vendors P W. Glitsch Co. - Valve trays and Glitsch Grid Mr. Butterworth New York, N.Y, YW-6-6357 Jordan Pressure Regulators Fred Weldsford Philadelphia, Penna. MQhawk 4-8026 Sparkler Mfg. Company - Horizontal plate filters J. C. Sharbaugh 11 Park Road Havertown, Penna. Briggs Filtration Company - Cartridge filters and coalescer J. L. Beatty 919 B. Darby Rd. Havertown, Penna. JA-8-56I3 or Hilltop 7-1180 Bowser, Inc. - Leaf and cartridge filters (DPU and carbonates) James A, Parente 3639 No Broad St. Philadelphia 40, Penna. Baldwin 8-2582 Fairbanks, Morse and Co, - C.M. Pumps D. P. Caldwell 1005 Baylor Drive Newark, Delaware 368-8862 Warner-Lewis Co. - Coalescers Roger Sanborn 545 Fifth Ave. New York 17, N.Y, Oxford 7-2769 and Oxford 7-6175 Pittsburg Brass Mfg. Co. - Ball valves Richard H. Bill 2409 Chatham Drive Wilmington, Belax\'are P0-2-3065 Tote System, Inc. - Tote Tanks Vincent B. Janson l8l Warrior Rd, Drexel Hill, Penna. 215 Hilltop 6-2134 DUP050055015 List of Vendors Patterson Foundry Co. - Conical vacuum dryers P. L. Dolon R. B. Mack or Juliane 298 Levering Mill Rd East Liverpool, Ohio Bala-Cynwyd, Pa. 385-2400 Mohawk 4-5522 Western Precipitation - Screw dryer E. F, Ewing, Inc. Board St. Trust Bldg. Glenside, Pa. Hancock 4-2074 Bobbins and Meyers, Inc. - Moyno Pump D. P. McCulloch 84l8 West Chester Pk. Upper Darby, Pa. Sunset 9"2523 Bietz Mfg, Co. - Thermoscrevr Robson B. Dunwoody P.0. Box 690 West Chester, Pa. Owen 6-6313 Bowen Engineering C.b,, - Spray Dryers R. W. Bayless T. E. Grimac R, DeHoff P.Q. Box 7 Worth Branch, W.J. Cherry Hill, H,J. Randolph 5-3232 (609) Hormandy 3-4900 Consultants R. B. Akell - Distillation F. T. Wyman - Corrosion F. J. SercelJ - Instrumentation J. E. Flood and J. Chalmers - Filtration R. Leedom - Agitation L, DeFrate - Powtherm Power System H. Jacobs - Waste Disposal J. Folsom - Dowtherm Heater DUP050055016