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TRAINING PROGRAM SECTION 5 50 - ALUMIKA "ALFOL" ALCOHOL UNIS xJVKE CHARLES. LOUISL isA 0000103Tb SAL 1 NJ'ROJ)]JCT ION Conoco recently decided to start producing CATAPAL-SB alumina at our Lake Charles Chemical Plant. CATAPAL-SB Is the trade name for the high purity, high surface area, powdered alumina which is currently being produced by Condea, a (Jorman company which is 50 percent owned by Conoco. This alumina is produced as a by-product of Conoco's primary alcohol ("ALFOL") process. In order to produce this alumina in the Lake Charles "ALFOL" Unit, the existing Section 500 which reaccs alkoxlde with sulphuric acid producing alum and alcohols will have to be replaced by a new Section 550. Section 550 will react the alkoxide with water forming alumina and alcohols. Start-up of section 550 is slated for November 1, 1976. Since this alumina is produced as a by-product, a basis of 240 MM Ib/yr of alcohol resulting in approximately 40 million pounds of CATAPAL-SB per year was selected. The plant's production should exceed 220 million pounds of "ALFOL" alcohols this year. The value of CATAPAL-SB alumina lies in its very high purity and its special physical properties (see Table I). Because of processing steps intrinsic to Conoco's primary alcohol process, much lower Iron, sodium, and silicon concentration specifications can be met than by conventional methods for producing alumina. The low sodium and iron concentrations arc particularly important for some catalyst applications. The unique physical properties of CATAPAL-SB are a result of the one particular difference between Conoco's process and other conventional processes for alumina catalyst-support production. This difference is that the alumina is produced as a fairly dilute wet slurry which is spray dried to produce the alumina product. This allows several degrees of freedom for varying the physical properties of the final product; for Instance, the amount of turbulence In the reactor and.the speed of the spray dryer atomizer wheel are two of the most important design criterions. The decision to produce alumina Is based on an expected threefold Increase in alumina catalyst-support demand between 1974 end 1985 (from 71.4 to 210 million pounds per year). This Increased demand is expected to arise from four areas: 1. Petroleum refining catalysts 2. Uesid desulfurization catalysts 3. Automobile emission reduction catalysts 4. Coal gasification catalysts The last two types of catalysts' markets are much more uncertain so Conoco management has decided to try to avoid them. Conoco is in the process of committing 70-75 percent of the expected alumina production by long-term contracts. These contracts are "take-or-pay" type covering 1977 through 1981. SAL CC001C377 I'ABLE I iWTAPAL-ji B SP EC1FLCATI UNS Chumlca1 ComposiLion (Weight Percent) Al 2O3 70% MLn. - 78% Max. C 0.5% Max. SiO? 0.01% Max. Fe23 Na20 0.01% Max. 0.01% Max. Physical Properties Particle Size Distribution Smaller Than 45 Microns, 55% Max. Greater Than 90 Microns, 15% Max. Bulk Density, Loose 730-810 Grams Per Liter (45-51 Lbs. per Cubic Foot) Pore Volume (0--800A)* 0.4 Milliliters Per Gram Min. Spec. Surface Area (BET)* 230 Square Meters Per Gram Min. (Approximately 25 Football Fields Per Pound) Crystallite Structure Boehmite Type *After calcination for 3 hours at 900F -2SAL 000010373 (iKNEKAI* _PR()CESS J> KSCK U'TION k'Llon 550 ot the l.akt* Uhurlcs M\l,Kl)l." Alcohol Unit provides for water hydrolysis of so Ivent - f i*ir aluminum alkoxlde (produced In Section 425) with the lormatlon ol alumina and straiglit-chain alcohols containing oven ifirDon numbers. High purity alumina, denatured ethanol, and solvent-grade butanol are recovered In tills section while C^+ alcohols .arc* sent to Section 600 for further processing. Three processing systems are contained in Section 550: A. Hydrolysis-Extraction System B. Fractionation System C. Alumina Recovery System In the hydrolysis-extraction system, stripped aluminum alkoxlde reacts with water according to the following equations: 2A1(0R)? + 3H20 - A1203 + 6R0H (Monoalumlnua Alkoxlde) (Alumina) (1) A12<0R)40 + 2H20 - A120-j + 4R0H (Dlaluminum Alkoxlde) (2) T1(0R)a (Titanium Alkoxide) b 2H20 - Ti02 + 4R0H (3) The above reactions are exothermic and carried out at 200F in the presence of excess water. The two products from the reaction are an aluraina-wacer slurry and crude alcohols. These are mutually insoluble and separate in the hydrolysis reactor. Any Cg+ alcohols contained In the alumina-water slurry from the hydrolysis reactor are removed In a two-stage countercurrent extraction with butanol. In the fractionation system, the wet crude alcohol from the hydrolysis reactor is sent to a dehydrator tower where the water Is removed. The condensed overheads from the dehydrator tower and the butanol stripper (In the alumina recovery system) are combined and sent to the dehydrator tower overhead accumulator. This combined stream, which consists of water, ethanol, and butanol, separates Into two phases in this accumula tor. The water phase is combined with makeup condensate and barometric condenser blowdown water and recycled to the hydrolysis reactor. The alcohol phase is fed to an ethanol tower where a 93 percent ethanol product is recovered. The bottoms from the ethanol tower consists of water and butanol which is used for extraction In the hydrolysisextraction system. The water-free crude alcohol from the dehydrator tower is sent to a butanol tower where a high purity butanol product is taken overhead. Host of the butanol product is recycled to the process while the net make butanol is sent to the hydrogenation section. The bottoms from the butanol tower is transferred to Section 600 for further fractionation. -3- SAL 00001C379 In tlu* .iluminn recovery system* the alumina-writer &>lurrv from the liyl 11> I y *; I-s-i'xi rar (. I on aystem Is sont to a butmiol utripper where lnij.inol Is snipped I rum the s Lurry with steam* The alcohol-frce slurry Is t I ion sont 1.0 a spray dryer lot recovery ol a high purity, high surface area powdered alumina* The spray dryer utilizes direct hc.itJng with air and flue gases which enter at 1400F and exit at 300350e'F. The alumina product (75 percent alumina/25 percent water) from the spray dryer is transferred to product storage where it is loaded into railcars and trucks for bulk shipment. DETAILED PROCESS DESCRIPTION A. Hydrolysis-Extraction System Stripped aluminum alkoxide is received from Section 425 at 160F. The alkoxide is pumped from intermediate storage tanks FB-506A or FB-508, heated to 200F with steam in EA-S51, and injected into the hydrolysis reactor, DC-551, through a small diameter nozzle which promotes turbulence. The alkoxide enters the reactor in the slurry phase between the two impellers of the reactor mixer. It reacts rapidly to form crude "ALFOL" alcohols and hydrated alumina. The hydrolysis water to the reactor consists of makeup condensate, barometric condenser blowdown water, recycle water 1rom the distill.iion system, and ammonium hydroxide solution from the ammonia absorber. Condensate is used as process water to prevent contami nation of product alumina with foreign minerals. The hydrolysis water is pumped from the hydrolysis water tank, FB-551, to the hydrolysis reactor, DC-551, via the steam ring heater, PA-551. In this heater, the water temperature is raised to about 170F by direct steam injection. An ammonia concentration of about 0.15 weight percent is maintained in the hydrolysis water. The ammonia prevents formation of emul sions In downstream equipment. This concentration is maintained by injection of ammonium hydroxide into this stream Intermittently. A wet butanol stream from the extraction system also enters the slurry phase of the reactor to enhance removal of heavier alcohols. A crude alcohol phase and an alumina-water slurry phase are pro duced in the hydrojysis reaction. A nitrogen pressure of 80 psig is maintained in the hydrolysis reactor to permit transfer of slurry by pressurization rather than pumping. In normal operation, most of the crude alcohol is pressured directly from the reactor to the dehydrator tower to conserve energy. The remaining alcohol is cooled in EA-553 to 175*F and sent to the alcohol surge tank, FB-553. Five recycle alcohol streams also flow into this tank: 1. Remelted barometric condenser cooling tower sump scrapings -4- SAL 0000103P0 > Remelted railcar scrapings ). *6' tower overheads from Section 600 off-spec, alcohol* from Section 600 5. Skimmed alcohols from hydrolysis water tank, FB-551 These alcohols are pumped from FB-553 to the dehydrator tower continuously during normal operation. The alumina-water slurry phase from the hydrolysis reactor con tains dissolved and entrained alcohols. The alcohols must be removed and recovered to avoid an unacceptable carbon content In the alumina product and avert an alcohol product loss. A two-stage countercurrent extraction with butanol is used to remove the C^+ alcohols from the slurry. The alumina slurry is pressured from the hydrolysis reactor, DC-551, to the first stage mixing drum, FA-553. Here, contact is made with the butanol phase from the second stage phase separator drum, FA-55A. The effluent from Che first stage mixer is phase split In the first stage phase separator drum, FA-552. The alcohol phase from FA-552 is pumped to the hydrolysis reactor. The alumina slurry from the first stage phase separator is pres sured to the second stage mixing drum, FA-551. Here it contacts fresh recycle butanol from the recycle butanol tank, FB-552. In order to maintain the alumina slurry at 185F, the recycle butanol is preheated to 169K In EA-552. The alcohol/slurry mixture from the second stage mixer is transferred to the second stage phase separator, FA-554. The alcohol phase from this separator Is pumped to the first stage mixing drum. The slurry is pressured to the butanol stripper, DA-554. Parameters effecting the operation of the reaction-extraction system are reaction and extraction temperatures, hydrolysis water and recycle butanol flow rates, and ammonia and ethanol concentra tion. The most economical operation is at the following conditions: 1. Minimum Hydrolysis Water Flow (or Maximum Slurry Concentration)-- since the water in the slurry is evaporated during spray drying, less water results in less condensate makeup and fuel requirements. 2. Minimum Butanol Recycle Flow--since less butanol decreases the load on the fractionation system. Hydrolysis water flow rate should be set to give a butanol stripper slurry feed concentration of 9-12 weight percent solids; higher solids concentrations can cause slurry transfer problems. Recycle -5- SAL oooci 361 butanol Mow rate should he set at the minimum value which con sistently gives acceptable extraction. The design hydrolysis reaction temperature is 200F. Higher temperatures will decrease alumina product surface area and increase butanol solubility In the slurry. The reaction temperature is regulated by adjusting hydrolysis water and alkoxide feed temperatures. Temperature of the second stage extraction is set based on butanol solubility in the slurry and slurry flow characteristics. Emulsions can occur in the reaction-extraction system due to ammonia deficiencies or excess ethanol concentrations. The ethanol tower removes the net make ethanol and is designed to give minimum ethanol recycle. B. Fractionation System Crude alcohol containing approximately 11 weight percent water is fed to the dehydrator tower, DA-551, directly from the reactor, DC-551, and from the alcohol surge tank, FB-553. Before entering the tower, the feed is filtered in FD-551 to remove any entrained alumina particles and then heated to Its bubble point of 208F In EA-555. The dehydrator removes the water, as a butanol/water azeotrope, along with the ethanol and ammonia. High purity butanol from the butanol tower Is "refluxed" to the top tray of the tower to minimize Cg+ alcohol carryover. The water-free crude alcohol bottoms from the dehydrator tower is fed to the butanol tower, DA-553. A 99+ percent butanol product Is distilled overhead in the butanol tower. The butanol tower overhead product provides reflux to the dehydrator tower and supplements the recycle butanol requirements (to the hydrolysisextraction system). The net make butanol is sent to the hydro genation section. The butanol-free tower bottoms is transferred to intermediate storage located In Section 600. The dehydrator tower overhead is condensed, subcooled to 160F, and combined with the butanol stripper overhead (also at 160F). The combined stream enters the dehydrator tower overhead accumu lator, FA-555, and separates into an alcohol phase and an aqueous phase. The aqueous phase is pumped to the steam ring heater, PA551, for recycle to the hydrolysis reactor. The alcohol phase from the dehydrator tower overhead accumulator is fed to the ethanol tower, DA-552. The ethanol tower removes the net make ethanol and minimizes ethanol recycle to the hydrolysisextraction system. Low ethanol recycle rates reduce emulsion formation in the hydrolysis reactor. The ethanol product is removed as an ethanol/water azeotrope (about 93 weight percent ethanol) from a sidedraw on tray 11 of the ethanol column. The ethanol sidedraw product gravity flows to product storage FB-506C. The top ten trays of the ethanol tower remove ammonia from the ethanol product. The overhead vapor consisting of most of the ethanol and water and essentially all of the ammonia is partially -6- SAL 000010382 feed filter, FD-5S2, to the spray dryer, EC-551, using another positive displacement pump with a variable--speed drive. The slurry enters the spray dryer through a centrifugal wheel atomizer. The resulting slurry droplets contact the hot air and flue gases from the spray dryer air heater, BA-551. Combined stripper over head from Section 425 (liquid fuel) is pumped in from FB-555 to fire the heater. The inlet hot air temperature is maintained at 1,400*F by using excess air supplied by GB-551, the combustion air blower. The exhaust gases and alumina leave the spray dryer at 300-500F and enter a baghouse, FD-555, which recovers the alumina product. The alumina-free exhaust gas is vented to the atmosphere from the spray dryer exhaust fan discharge, GB--552. -700010363 SAL 0 ondt'UKCtl In EA-560 And enters the overhead accumulator, FA-558. The liquid in FA-55B ia returned as reflux to the ethanol tower. The uncondensed vapor from FA-558 is partially condensed In the ethanol tower vent condenser, EA-562, and returned by gravity flow to FA-558. The purpose of EA-562 is to minimize ethanol recycled to the hydrolysis-extraction system. The uncondensed vapor from FA-562 which is mostly ammonia with some ethanol and water, is absorbed with service water in the ammonia absorber, DA-555. The ammonium hydroxide solution gravity flows from DA-555 to the hydrolysis water tank, FB-551. This enables almost all the ammonium hydroxide introduced into Che process to be recycled, minimizing fresh ammonium hydroxide makeup and pollution problems. The ethanol tower bottoms is cooled to 150F In EA-558 and trans ferred to the recycle butanol tank, FB-352. Alumina Recovery System The alumina slurry from the second stage separator drum, FA-554, is pressured directly to the butanol stripper, DA-554. The slurry Is fed to the top tray. Live steam, desuperheated in PA-552 to process conditions, is used to strip all butanol (as a butanol/ water azeotrope) and lighter components from the slurry. A cyclone, FA-560, is provided In the butanol stripper overhead vapor stream to remove any entrained alumina particles. The overhead is condensed and subcooled to 160F In EA-565 and com bined with the dehydrator tower overhead stream (see above). The alcohol-free slurry is pumped from the butanol stripper using a positive displacement pump with a variable-speed drive. This slurry first enters EA-566 where it is cooled to 195*F and then it flows to the alumina slurry surge tank, FB-554. The alumina slurry is pumped from FB-554 through the spray dryer feed filter, FD-552, to the spray dryer, EC-551, using another positive displacement pump with a variable-speed drive. The slurry enters the spray dryer through a centrifugal wheel atomizer. The resulting slurry droplets contact the hot air and flue gases from the spray dryer air heater, BA-551. Combined stripper over head from Section 425 (liquid fuel) is pumped in from FB-555 to fire the heater. The inlet hot air temperature is maintained at 1,400F by using excess air supplied by GB-551, the combustion air blower. The exhaust gases and alumina leave the spray dryer at 300-500F and enter a baghouse, FD-555, which recovers the alumina product. The alumina-free exhaust gas is vented to the atmosphere from the spray dryer exhaust fan discharge, GB-552. -7000010383 SAL The alumina product from Che baghouse is transferred to one of the alumina check bins, FB-556A, B, and C (one for each shift). After product testing, the alumina is transferred to one of the product silos, FB-557A, B, C, and 0. The product is loaded into trucks and railcars. Inventories are measured by load cells on the silos. An off-specification product silo, FB-558, is also available when needed. 8- - SAL 0C0010334 i@ FB-508 A LKOXIDE FEED TANK FB-S06A ALKOXIDE FEED TANK FB-SOS AMMONIUM HYDROXIDE STORAGE TASK FB--551 HYDROLYSIS WATER TASK PC-516 ALX0X1DE feed nmr GA-501 AUCOXIDE FEED POMP GA-560 AMMONIUM HYDROXIDE POMP GA--SSI HYDROLYSIS WATER FEED GD-551 HYDROLYSIS REACTOR MIXER DC-551 HYDROLYSIS REACTOR FB-5S3 ALCOHOL SURGE TANK EA-SS3 WET CRUDE ALCOHOL COOLER GD-S52 2ND STAGE EXTRACTION MIXER FA-552 1ST STAGE PHASE SEPARATOR DRUM GA-553 1ST STAGE EXTRACTION MIXER FA-551 2ND STAGE MIXING DRUM GA--553 1ST STAGE SEPARATOR OVERHEADS PUMP EA--552 RECYCLE GA-S52 RECYCLE BUTANOL PUMP FA-552 RECYCLE BUTANOL TANK FA-553 1ST STAGE MIXING DRUM GA--554 2ND STAGE SEPARATOR OVERHEADS PUMP FA-5' 2ND SI PHASE SEPARATOR DRUM i BUTAN' IPPER 0VERBS'- -YCLONE EA-565 BUTANOL STRIPPER OVERHEAD CONDENSER DA-554 BUTANOL STRIPPER GA--569 BUTANOL STRIPPER BOTTOMS PUMP PA-5 52 STEAM DESUPERHEATER EA--566 BUTANOL STRIPPER 30TTCMS COOLER FB--554 ALUMINA SLURRY SURGE TANK GD-5 54 ALUMINA SLURRY SURGE TANK MIXER GA--567 . SPRAY DRYER FEED PUMP FD-552 SPRAT DRYER FEED FILTER RA-5S1 SPRAY DRYER AIR HEATER FD-5S4 COMBUSTION AIR FILTER EC-551 ALUMINA SPRAY DRYER GB--551 COMBUSTION AIR BLOWER GA--566 AIR HEATER FUEL PUMP FB--555 AIR HEATER FUEL TANK FO-555 SPRAY DRYER DUST COLLECTOR SB-552 SPRAY DRYER EXHAUST FAN FB-556A,8.C ALUMINA CHECK BINS PA-5 54 SOLIDS IANDLING SYSTEM FB-SS7A,8,C,D PRODUCT ALUMINA STORAGE SILOS FB-55S OFP-SPEC ALUMINA STORAGE SILO EA--555 DRHYDRATOR TCMfBR FEED PREHEATER FD-551 DEHYDRATOR TOMER FEED FILTER OA-557 DEHYDRATOR TOWER OVERHEAD MATER PHASE PUMP DA-551 EA-5S7 EA-558 DEHYDRATOR DEHYDRATOR TCTfKR ETHANOL TOMER TOMER OVERHEAD CONDEMSER BOTTOMS COOLER SA-556 DEHYDRATOR TOWER REBOILER FA-555 FA-559 DEHYDRATOR TOWER CONDENSATE OVERHEAD ACCUMULATOR DRIB* GA--558 DEHYDRATOR TOWER QVHD ALCOHOL PHASE PUMP OA-556 DEHYDRATOR TOMER BOTTOMS PUMP EA-S52 ETHANOL TOMER FA-558 ETHANOL TOMER OVHD ACCUMULATOR EA-560 ETHANOL TO. OVHD CONDENSER EA-559 ETHANOL TOMER REBOILER QA-559 ETHANOL TOMER BOTTOMS PUMP QA--561 ETHANOL TOMER REFLUX PUMP EA-5 ETHANOL 4R VENT CONDENSER DA-555 AMMONIA ABSORBER FB-506C ETHANOL PRODUCT TANK EA-563 ETHANOL TOMER REBOILER GA-565 BUTANOL TOMER REFLUX PUMP DA-553 BUTANOL TOMER EA-564 BUTANOL TOMER OVHD CONDENSER FA-557 GA-564 BUTANOL TOMER BUTANOL TCMER TOR BOTTOMS PUMP EA"5<&4- o PRESS., R5IG I T TEMP.,F NOTE: HEAVY LIMES ARE MAlkJ PEED PRODUCT STREAMS EUCAWOL TO BUTAVJOC HYOROSeU^nOKJ FEED PUMP CRUDE ALCOHOL TO " eecnow goo 'AmMOUIUM HYDROXIDE TO HYDROLYSIS WATER .TAUK, FFS-5SI_________________ *DEWVBRATC TOSVER OVHD. WATER PHASE TO STEAM .P1MG HEATER, PA-SSl SA-3S7 (SA*5a S/VS5& 6A-SS9 SA-561 <s> m Il2l Il6l I l2I0jl il2l4ll I12l01{ 13 2| 1361 140 24 22 20 18 16 14 12 10 SCALES FOX MICROFILMED DXAWINOS i V I<5)(gi...............i 10 12 Mil III 4-282 S _____ ______________________________ 1 PROGRAM S Vf OAR iSU date! DESCRIPTION BY CKD APO CONTINENTAL OIL CO MP AN't ENGINEERING CEN TER PONCA CITY, OKLAHOMA GA-SGS (3A-S&4- PROCESS FLOW DIAGRAM sECTIOkl 330. ALUMlfcJA. ALFOL' ALCOHOL UKJ IT O LAKE CHARLES. LA, 12 SHEET 'l OP 9 USE tOXDEX SCALE: I I 1 1 I I I l t il f l l 1 I l 1 l t < i 11 I I t I t 11 1 1 I I M tJ-L appd: jr* DATE: IZ/M/tV- .. NO.SD2I26-A2-2S-C SAL 00CC10356 )*}**??dV'on <i i i . i N. SO f 5 2 5 - > couoeusett i HOT WATER ! & COLLOID CHARGE VCW CKAA3C O O o o o i OJ CO o 4-2*1 S CHgM.ngAwms 4CHXmaw OOOUKK WATER SUPPLY CMEM, n Pin 6ouom>j RETURM PVC. SUJRRY ELSVJO TAWK CEWTRlPLKSB TD WASTE WATER 9EWCER CXERSfZE TO STORASG cmed pvc to mooucr LO*0ie j * i-m HUMRORAM A** | rsu OJCtK Omm oco IBB CONTINENTAL OIL COMPANY IKOINUKINO Cl NT t ft PONCA CITY, OKLAHOMA 4IMPLIP1ED PROCESS PLOW CTA6PAM UAPeg REACTOR PVC Pl/QT ABCRCEEM, MtSS- Am: date: No.SO 1525-^2 3 8