Document 0gY04nGYdzkZqkxvrNVNgmY6J

SUM MARY Operating limits for heat treated catalyst preparation have been defined and a Tentative Process Report is being written. All equipment for the pilot plant catalyst manufacturing unit is on order with start-up scheduled for August. Flammability limit studies have shown allowable oxygen concentrations for 100-4 safe operation of oxidative chlorination units to be so low that a different feed system will be necessary. Work on redesign, to give separate injection of oxygen and ethylene m the catalyst bed, has been started in the lab. The redesigned system is expected to give better economics m CSV as well as reduce operating hazards. EDC cracking to 997o conversion m the presence of cracking inhibitors I has been achieved using garnet as a catalyst. A detailed economic J evaluation is being made. The cause of high HC1 content in VCM tank cars at Springfield has been found to be stratified layers in the rundown tanks, spheres, and tank cars. Multi-level samples are being taken from tank cars for quality control and mixing studies'are in progress. Springfield reports that the cause of the paste resin coagulation problem is concentration of unknown impurities in a free water-phase which collected in their storage tanks during May. Study of the impurities present in the water at Springfield and the water at Texas City are in progress. CBY 1022526 RSV0032353 # 0 * ' V*1 to simulate a spectrum of impurities and determine if there is one present that might give problems in the cracking step. To date, no impurity has been found that inhibits reaction appreciably. This includes an extensive amount of chloroprene - one of the better inhibitors. Estimates would indicate that in our present chlorine catalyzed crackers, a maximum of 5-10% conversion would be achieved with the 2-1/2% chloroprene in the feed. Using the garnet catalyst, 100% conversion was realized. Attempts were made to make a very accurate material balance around the cracker and a 98fo closure was obtained. Work has been suspended on this cracking operation until a detailed economic evaluation is completed." Future work will depend on results of this evaluation. Flammability Studies Flammability data obtained at Texas City were reviewed with Fenwal m an attempt to determine why the major differences between Texas City and Fenwal data exists. The only obvious difference was in the ignitors used. Pictures of ignitor voltage drop taken from an oscilloscope indicated the Fenwal ignitor takes about ten times as long to discharge as does our ignitor, approximately 600 microseconds vs. 70 microseconds. Fenwal will do additional work to check their ignitor reproducibility. In any case, no reason for not accepting our data could be found, it is much more reproducible than Fenwal data and must be used. Additional work has been done to determine the effect of temperature and pressure on flammability limits for the systems ethylene-HCl-02 and ethylene-N2-02. An increase in either temperature or pressure decreases the allowable oxygen concentration. Results are shown in Graph IV and V. Extension of the study of these systems at 45 psia and 200C has shown a deflection in the allowable oxygen concentration between 10% and 19% ethylene when nitrogen is used as a diluent. These data are shown on Graph IX. Mixtures of HC1 and N2 as diluents have also been studied with results shown on Graph VI. Flammability studies have been extended to include three of the impurities normally found in oxidative chlorination feeds, methane, ethane, and CO. Data are shown m C-raphs VII, VIII and X. Graphs I, II, and III were in last months report. Two Surprising things were found: 1. Methane and ethane have very close to the same allowable oxygen concentrations. Both have much higher allowable oxygen concentrations than ethylene. CBY 1022528 RSV0032355 'J ), 1J =5 `tf*<*/(> C'/)}C RSV0032356 RSV0032357 (9 RSV0032358 RSV0032359 rmti i<i t ) j ) % Cs 0 >/) RSV0032360 9 2. The relative effects of KC1 and N2 are not the same for each material tested. HCl is the best diluent with ethane and CO, N2 the best with ethylene, and there is little difference wi:h methane. This suggests that reactions other than oxidation are taking place m the high temperature arc. Analytical data will be required to pin this down. Possible ways of modifying the oxidative feed system to allow operation with feeds which would be flammable are being considered. Engineering is designing a feed manifold for the EIF plant as one method. Data on pressure developed, with various feed compositions, when feeds are ignited are being obtained for use in design of this system. ! Means of separate injection of feeds are being tested in the lab and will be tested on a six-inch glass unit. This system is being considered for Dept. 26. > Project 1 043 - Oxidative Chlorination Catalyst Improvement Dab work to define operating ranges for preparation of heat-treated catalyst continues. Tests to define limits of time and temperature necessary to prepare active catalyst have shown a temperature of 450 C to 550 "C to be satisfactory with reaction time of 5-8 hours. Temperature as low as 400C is acceptable but requires longer reaction time. Longer time at temperature is not detrimental, at leasrup to 21 hours tested. Commercial copper chloride has been tested (two sources) and found to be satisfactory. However, grinding to a finer particle size than commercial samples available was necessary. An attempt is now being made to obtain commercial material which passes through a 100-mesh screen (about 10% of present material is larger than 100 mesh). A Tentative Process Report for catalyst preparation is being written. Major equipment is on order and design work is almost complete. The reactor should be fabricated and installed during June for testing m July. Long delivery items are scheduled for July, which would allow August s up* j j > Project 1044 - VCM Quality, Cost, Capacity Improvement Quality Improvement Further HCl sampling and analysis technique studies have shown stratification m rundown tanks, storage tanks, and tank cars to be the cause for failure to consistently detect presence of HCl in the VCM. Samples of VCM m rundown tanks were taken by PTE from April 25 to May 2 m addition to the normal production samples. No CBY L02253* RSV0032361 4. sign:;;cant difference between Production and PTE samples were found (Table l). Samples were taken by PTE from three levels of VCM in tank cars between May 5 and May 14th. The HC1 concentration was found to vary significantly between top and bottom VCM levels in some tank cars. Table 2. Production reported that sampling frequently during a rundown tank transfer showed significant differences to exist in HC1 content of VCM throughout the tank. Piping modifications were made 5/15 to increase mixing in the rundown tanks by using the 300 C-PM transfer pump as well as the 70 GPM circulation pump. This change was an improvement but did not completely mix a tank m 13 hours as shown by production samples and tank car (3 level) samples. Studies of equipment needed for complete mixing in rundown tanks are in progress by PTE and Plant Engineering with a proposal expected by June 1. A recommendation was made that Material Handling sample each tank car at three levels for HC1 analysis (Done since 5/15). Springfield Research studies on the paste resin coagulation problem show the cause to be impurities concentrated in a free-water phase which appeared in their storage tanks. It was reported that a small amount of this water added to a ''coke-bottle1' test gave laboratory duplication of plant coagulations. Further test work is planned to identify compounds present in the water and to determine which ones cause the paste problem. The VCM processed just prior to the finding of the free-water was a test car (MCPX 21014) made during a period of water surge in the VCM product column while the VCM drier was being by-passed. Examination of an apparent polymer m one of the tank cars returned from Springfield turned out to be a frozen water emulsion. This was taken from the middle of a tank car, so we are evidently obtaining a material that is intermediate in density to water and VCM. Degassing of this ice through liquid EDC has resulted in the appearance of three or four unidentified peaks on the chromatograph that has been developed for light-ends analysis. If these compounds can be concentrated, then identification will be attempted by MS- GC. Plant Engineering is preparing a cost estimate for a second VCM drier which would elimmate'the once per week surge of water in product VCM. The control laboratory was requested to reactivate the equipment and to demonstrate ability for water analysis on product VCM samples. CBY 1022535 RSV0032362 I- -X > v- Tank No. 455 4 56 T4- 3 457 457 45S 458 459 460 TABLE I Bate, I965 4/28 4/28 4/28 4/28 4/28 4/29 4/29 4/29 ' 4/30 Time, Hrs. 1515 1600 1600 0625 0730 1430 1620 0600 1545 HC1, Dsm <. 1 <. 1 < 1 <. 1 <. 1 <. 1 <. 1 < 1 < 1 CBV 1022536 RSV0032363 PT5 Samples From Tank Cars Car No. MCPX 21002 MCPX 21000 MCPX 21005 MCPX 33002 MCPX 21007 MCPX 33004 MCPX 33016 MCPX 33024 MCPX 33015 MCPX 33005 MCPX 33025 MONX 14954 MONX 14961 Date, 1965 5/5 5/5 5/6 5/6 5/7 5/7 5/10 5/10 5/10 j 5/11 5/12 5/13 5/13 Gauge-Rod Positions (Normal) (Lowest) ppm HC1 tmai HC1 <. 1 <. 1 0. 3 <A 1.0 1. 0 < 1 0. 3 <. 1 <. 1 ` <. 1 <. 1 <. 1 1.0 <. 1 <. 1 <. 1 <. 1 <. 1 <. 1 <. 1 <. 1 <- 1 <. 1 <. 1 <. 1 Test Tube (Car Bottom) ppm HC1 <. 1 <. 1 * No Sample <. 1 2. 5 <. 1 < 1 <. 1 <. 1 0. 5 <. 1 * No Sample , * No Sample MCPX 33010 MCPX 33003 MCPX 33006 5/14 5/14 5/17 <. 1 <. 1 <. 1 <. 1 <. 1 <. 1 . <. 1 <. 1 <. 1 All samples were clear and colorless wirh no suspended matter except MCPX 33025 (5/12) which showed a small amount of suspended matter similar to cigarette ash in the sample taken at the normal gauge-rod position. * Unable to take samples due to leaking fittings. CBY 1022537 RSV0032364 *---% ' s Product VCM Column Stabihtv \ 5 profile and pres,sure drop across the lower part of the column. Occasional partial or complete flooding at the 40th tray or below has been detected. Temperature records show a cycle of about 20 minute duration occurs most of the time but at varying amplitudes with the flooding incidents being more frequent when the cycle amplitude is large. The pressure drop record does not show the 20 minute duration cycle at all but often shows a more rapid cycle of about 3 minute duration prior to onset of flooding incidents. No connection between flooding incidents and control of KC1 m product has been found. Collection and observation of the data will continue but little progress in analyzing it is expected until after completion of work on HC1 control. Optimization of Acetylene Purification The review of the safety of handling acetylene at high temperatures indicated that it would be safe to drop the required water concentration in. the acetylene to 30% instead of the 42% previously specified. This relieves the reactor from highly corrosive conditions and will allow more leeway m keeping out of the corrosive range. The acetylene purification system was brought on stream on May 9th. However, onJMay 14th a tripour occurred with indications of a tube failure. Operating data for this five day period is being reviewed for other possible inter-related causes for the tripout. - Dent, 23 Caustic Automation The system continues to operate satisfactorily. Report to be completed m June. Project was closed out. Cracking VCM Column Control (2ZD7) A PAFE covering the installation of the 22D7 feed forward control system is circulating for approval. Improve Raw Material Accounting and Weight Recovery A brief discussion with the Yield Department revealed that the C3H2 m the acetylene purification recycle gas is not being included in the acetylene distribution balance due to lack of data, A CBY 1022538 RSV0032365 -S. calculations :r. mic-May. Calculations will be complete by end of montn. iwo more material balances will be made in June to determine reproducibility and stream compositions at current "standard" operating conditions. Work will begin m June or. a computer program to make material balance calculations in Dept. 26, Target date for completion of program is July 1 5. In view of the flammability report of last month, a recommendation has been made that the operating department reduce the allowable oxygen concentration to 9%, which is about 1% below the allowable limit as defined m last month's report. Operation has been smooth at this lower oxygen concentration. Oxidative Chlorination Optimization Collection of operating data has begun. Data correlation will begin m June and completed by July 31. ______ Minor Approved Capital Projects An extensive'study ox the automatic Ci2 control system costs is complete. A letter is being prepared describing the history of the project from its initial concept to the present, showing the effect of changes of the control system design on the project costs. It has been reported that approval of the PAFS supplement is imminent. Work will resume as soon as official approval is received with installation complete by August 31 and the project complete by September 30. Tar make, although slightly higher in April, is being held in 5 lbs tar/100 lbs of cracked VCM range by manual Cl2 control. See Figure I for the tar make history m VCM plant. Job Xo. iS58 - Pilot Plant Catalyst Manufacturing Unit Fequipment is on order with electric heater and off-gas scrubber scheduled for delivery m early July. The reactor will be shop fabricated. Dismantling has beer, completed. Start-up is scheduled for August. \ Na::t Job on Arsnda Vinyl cnlonce irom etn. ane p.i.lot plant cesign. ! CBY 102253 RSV0032366  J. n V*V' --s.'.to 225 25, L 26 -:9o-:~'i9op CBY 1022540 RSV0032367 pEC. V 1 xzous T. P. Li preserved a paper at the Xcr.sar.to Catalyst Conference or. May 24. J. C. Parks, T. B. Shirley and 17. 3. : Area Conference cn Industrial Relations ;n attended the Southwest -louston on. May 13 and 14. V/. R. Johnson and O. A. Koskela visited Fenwat, Inc. on May 6th to discuss differences m flammability data. Our work on oxidative chlorination of hydrocarbons was discussed with two visitors from Societa Scison (Cavallo and Renaldi). This is part ot our contract for exchange of information. A trip to discuss their work on oxidative chlorination of methane is tentatively scheduled .o. 2 e .em**e_. 'ersor.net Technical S. 3. Walker T. P. Li O. A. Koskel/a J. C. Holland C. J. Lament a H. S. Leach C-. Mayorga Group 13 Lab Technicians G. L. Biggs R. J. Armstrong Grout I 5 p_ ij'uX S R. D. Me Grew C. G. Standard Attached Wi CBY 1022541 RSV0032368 | SUMMARY OF MAJOR PROJECTS APPROVED - )96 VINYL CHLORIDE Request No. TiUe .Authorized Appropriation Estimated Target Date Expenditures of Plant Start-up Predicted Plant Start up Comment s 2.6 Reactivated Oxidative $ 230, 000 $ 234, 1 53 January, '63 In operation Catalyst level indicator \w s Chlorination Pacilitics ordered in May. Tins v.ill complete installation of . TOTAL - VINYL CHLORIDE 230, 000 234, 153 facilities for tins project. An overrun of no more- than 5'/,, i*. expected. SUMMARY OP PAPF.'S Al^PROVET) __May_3)_, 1_965_ PAl-'K No. YJN Y L_C) ILORIUL 12805 22J-I1 Chk ' ine Contiols 42, 000 42, 104 Sept. 1964 3rd qlr. '65 Supplement for S> 13, 900 circulating now. 14858 Pilot Plant Catalyst Manufacturing Unit 30, 000 4,000 Aug. 1965 Aug. 1965 Equipment ordered Major items scheduled for early July delivery. CBY 1022542 'V or RSV0032369