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Reliance Industries Limited. BUTADIENE EXTRACTION. Sanjay Rinke Dr.G.Padmavati,Vimal Shah,Nitin Pal. Agenda. BASF NMP Process – VMD JSR Acetonitrile Process – HMD Simulation of HMD Process - RTG. BASF NMP PROCESS RELIANCE INDUSTRIES LIMITED VADODARA MANUFACTURING UNIT.
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Reliance Industries Limited BUTADIENE EXTRACTION Sanjay Rinke Dr.G.Padmavati,Vimal Shah,Nitin Pal
Agenda • BASF NMP Process – VMD • JSR Acetonitrile Process – HMD • Simulation of HMD Process - RTG
BASF NMP PROCESS RELIANCE INDUSTRIES LIMITED VADODARA MANUFACTURING UNIT
ADVANTAGES OF BASF NMP PROCESS • BASF Process commercialized since 1968 • Total BASF capacity more than 2000 KMT • High Yields • Higher Butadiene Purity • Ability to process wide variety of feed
ADVANTAGES OF BASF NMP PROCESScontd. • Non corrosive, Non Toxic solvent • Safe plant operation–No acetylene accumulation • Low Energy Consumption • High turndown ratio
BASF NMP PROCESS PERFORMS SEPARATION • Extractive Distillation Butenes, Butanes & C4 Acetylenes have B.P. close to 1,3 Butadiene. Separation is not possible by conventional distillation. However solubility of these components in NMP is very different from 1,3 Butadiene. Therefore separation by extraction distillation. • Conventional Distillation 1,2 Butadiene, Propyne & some C5 HC have high boiling point compared to 1,3 BD. Therefore separation by conventional distillation.
SEPARATION STEPS • Extractive distillation-1 (Separation of C4 Raffinate) • Extractive distillation-2 (Purification of Crude butadiene for separation of Ethyl Acetylene/ Vinyl Acetylene) • Degassing (Solvent Recovery & Removal of VA Stream) • Product Purification (For removal of traces of lighter & Heavier impurities)
RELIABILITY ISSUES • Popcorn formation & fouling in final column overhead condensers • Fouling in degasser column • Final Column PSV line rupture • Prime reason is oxygen initiated polymerization • Higher losses of solvent in acetylene washer wash water stream
MEASURES IMPLEMENTED • Nitriting of system with hot nitrite circulation and monitoring of NO3 conversions. • Oxygen level measurement from the vents of the receiver twice a week • Continuous venting from the condenser dome cover end. • Installation of one spare condenser and changing over at regular frequency of 80-90 days in Final Column • Installation of in line oxygen measurement from the vents (commissioned by Nov 07) • TBC dosing across the shell (at 5 locations) and in the vapor line to the condenser for oxygen scavenging.
JSR ACETONITRILE PROCESS RELIANCE INDUSTRIES LIMITED HAZIRA MANUFACTURING DIVISION
RIL HMD BD UNIT-OVERVIEW PRODUCT : 1,3-BUTADIENE (99.5% pure) CAPACITY : 140 KTA LICENSOR : JSR, Japan BASIC ENGINEERING : JSR, Japan DETAILED ENGINEERING : Toyo Engineering India YEAR OF COMMISSIONING : 2005 PLANT INSTALLATION TIME : 16 MONTHS Winner of International Project Management Award
Design Considerations • Designed to process the Mix C4 from In house Cracker Plant & Imported Mix-C4 • Case 1 : High severity operation - 1,3BD (54%) • Case 2 : Low severity operation - 1,3BD (44%) • BD recovery : Case1- 98% / Case2- 98.9% • Solvent used : Acetonitrile • Selectivity :VA>EA>1,2BD>MA>C5+> 1,3BD>cis-Butene>n- Butene> t- Butene>C3
Critical to Safety Operation • Build up of MA > 50 wt% explosive decomposition, alarm, TALO trip to purge the stream to flare • Build up EA + VA > 45 wt% explosive decomposition, alarm, low diluents flow trip • Build up of 1,2 BD > 50 wt% decomposition takes place.Temp cascade control with bottoms with drawl and hard wired alarm provided.
Butanes + Butenes Solvent Water Topping Column EDC No.1U C4 Feed BB Washer BD Washer Solvent + water Butadiene Product Water EDC No.1L Tailing Column Solvent Water + HCs EDC No.2 1,2BD + C5+ & 1,3BD (traces) C4s Acetylenes + B & B Solvent Stripper Water Washer Column Side Cut Column B & B Diluents Water + Solvent Lean Solvent Process Flow Diagram
NO:1 EDC COLUMN (UPPER) ANALYER – 51002 FOR 1-3 BD & OTHERS E –5103 ANALYZER 510001 FOR 1-3 BD, EA, VA, & MA V –5101 Butane & Butene BB Washer C -5101
NO:1 EDC COLUMN (LOWER) ANALYZER – 51005 FOR MA & 1-2 BD C –5102
NO:2 EDC COLUMN ANALYZER – 51004 FOR MA,VA & EA C –5103
SOLVENT STRIPPER C –5104
SIDE CUT COLUMNSIDE CUT WASHER E –5110 E –5111 E –5112 V –5102 ANALYZER – 51003 FOR EA & VA C –5105 C –5106
V –5106 LP-FLARE OWS PH Analyzer ACN 62.52%, H2O 28.84%,ETOH 8.64% BB-W 94 Deg C TO E - 5112 E –5122 SCC-W CWS V –5110 E –5126 E –5121 V –5107 BB-W V-5105 TO C-5104 BOTTOM V-5104 V-5101 E –5124 E –5123 114 Deg C SOL. From SCC-W LP-Steam CAUSTIC V-5117 V-5109 C –5110
WATER CIRCULATION LOOP CWR TO V – 5118 LP - FLARE 8 MT/hr E – 5126 4 MT/hr CWS 30 25 TO E – 5112 V - 5110 13 MT/hr SCN 25 19 BB-W C - 5109 SSC-W C - 5106 V - 5106 BD-W C - 5111 25 E - 5121 A/B 21 1 1 FROM E-5112 FROM V-5101 1 FROM V-5104 SRC C - 5110 V-5101 Boot V-5104 Boot 1 V-5105 Boot 25 MT/hr
SOLVENT LOOP C - 5104 SDN TBC 88.6 Deg C E –5105 E –5106 E –5107 A/B E –5123 110 Deg C 97.3 Deg C 126 Deg C 138 Deg C FROM C - 5110 E –5115 E –5117 E –5114 50 Deg C E –5102 A/B E –5127 73 Deg C 70 Deg C 78 Deg C 58.7Deg C DENSITY ANALYZER TO C-5109 TO C - 5103 TO C - 5101
Process & Quality Control • Butadiene Process Controls and Quality Control systems are well established. • Strong on-line and off-line Quality control system is followed to ensure that customer gets the right material. • Logistics systems are designed to ensure on-time and reliable supplies. Proper tracking methodologies are set. • Fully equipped QC & QA set-up available. • All the parameters are checked for conformance to specification and certification is done through COA. Labs are accredited to ISO:17025:2005 • Well defined customer feedback/ complaint management procedures exists for improving QA systems.
SIMULATION OF ACETONITRILE PROCESS RELIANCE INDUSTRIES LIMITED CEPD GROUP-RTG VMD
Butanes + Butenes MA & other C4s Solvent Water Topping Column EDC No.1U C4 Feed BB Washer BD Washer Tear1 Butadiene Product Tear4 Water EDC No.1L Tailing Column Tear2 Solvent Water + HCs Solvent Tear3 EDC No.2 1,2BD + C5+ & 1,3BD (traces) C4s Acetylenes + B & B Solvent Stripper Water Solvent recovery column Washer Column Side Cut Column B & B Diluents Water + Solvent Lean Solvent Waste water Simulation of BD Process
Thermodynamics • Selection of VLE model is crucial for BD ED simulation • UNIFAC Activity coefficient model used for all columns • UNIFAC-LBY Activity coefficient model used for Topping column simulation • ASPEN Plus 10.2 version used for simulations • To use latest ASPEN plus v7.0 pure component properties are to be updated by user • NRTL, WILSON, UNIQUAC Activity coefficients are not supporting well
Comparison of Design and Simulation Temperatures RadFrac (rigorous distilaltion for two & three pahse fractionation) Aspen Plus module used for simulation
EDC-1 Upper Column Simulation Results U/B L/D Reflux ratio is provided as input for simulation
EDC-1 Upper Column Simulation Results Solvent D/V C4 Feed D/L Columns converged without any errors
EDC-1 Lower Column Simulation Results SC/V B/L 1-3 BD flow in bottom six trays is found to be very sensitive to temperature 2C difference in temperature results in major difference in BD flow.
Solvent Stripper Simulation Results To C-5106 SC/V R/L 1,2-Buatdiene stripping observed to be difficult
EDC2 Column Simulation Results D/V B/L C5 heavier is considered as n-pentane in simulations
Tailing Column Simulation Results D/L SC/L B/L
Topping Column Simulation Results D Excellent matching between simulation & design values Thermodynamics: UNIFAC-LBY From BD washer top
Solvent Recovery Column Simulation Results D Simulation results and design results matched very well Opportunity for reflux ratio optimization observed B
Observations • ASPEN Plus RadFrac module is used for simulation of all the columns • Used default value for efficiency • Considered four tear streams from EDCU, EDCL, EDC2 & solvent stripper • EDC1U, tailing, topping & solvent recovery columns design reflux is provided as input • In solvent recovery column opportunity for reflux ratio optimization noticed • EDC1L Bottom 6 trays flow is found to be very sensitive to change in temperatures. 2ºC difference in temperature resulted in major difference in 1,3 BD flow
Conclusion • UNIFAC Thermodynamic activity coefficient model seems to simulate the process reasonably well • The simulations are to be done for the actual plant conditions to conclude the effectiveness of the UNIFAC model for the system & optimization
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