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Reliance Industries Limited BUTADIENE EXTRACTION Sanjay Rinke Dr.G.Padmavati,Vimal Shah,Nitin Pal 1.

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Presentation on theme: "Reliance Industries Limited BUTADIENE EXTRACTION Sanjay Rinke Dr.G.Padmavati,Vimal Shah,Nitin Pal 1."— Presentation transcript:

1 Reliance Industries Limited BUTADIENE EXTRACTION Sanjay Rinke Dr.G.Padmavati,Vimal Shah,Nitin Pal 1

2 BASF NMP Process – VMDBASF NMP Process – VMD JSR Acetonitrile Process – HMDJSR Acetonitrile Process – HMD Simulation of HMD Process - RTGSimulation of HMD Process - RTG Agenda 2

3 BASF NMP PROCESS RELIANCE INDUSTRIES LIMITED VADODARA MANUFACTURING UNIT 3

4 PASTPRESENT PRODUCT1,3-BUTADIENE CAPACITY20,000 MTA50,000 MTA LICENSORUOP; USABASF; GERMANY BASIC ENGINEERINGUOP; USAABB LUMMUS; USA DETAILED ENGINEERINGEIL;NEW DELHIIDEA; CHENNAI YEAR OF COMMISSIONING19791996 RIL VMD BD UNIT-OVERVIEW 4

5 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 PROCESS 5

6 Non corrosive, Non Toxic solvent Safe plant operation–No acetylene accumulation Low Energy Consumption High turndown ratio ADVANTAGES OF BASF NMP PROCESS contd. 6

7 FLOW DIAGRAM 7

8 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. 8

9 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) 9

10 PRODUCT QUALITY Sr. No.ProductPurity 1 1:3 Butadiene 99.7% 2 Butadiene Dimers 200 wt ppm (Maximum) 3Total Acetylenes 200 wt ppm (Maximum) 4 Other C4s (Cis-2- Butenes) 10

11 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 11

12 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. 12

13 JSR ACETONITRILE PROCESS RELIANCE INDUSTRIES LIMITED HAZIRA MANUFACTURING DIVISION 13

14 RIL HMD BD UNIT-OVERVIEW 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 14

15  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 Design Considerations 15

16 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. Critical to Safety Operation 16

17 Butadiene Product Solvent Wate r Butanes + Butenes Solvent + water 1,2BD + C5+ & 1,3BD (traces) Wate r Water + HCs Lean Solvent Water B & B Diluent s C4s Acetylenes + B & B Water + Solvent EDC No.1U EDC No.1L Solvent Stripper BB Washer EDC No.2 Side Cut Column Washer Column Tailing Column BD Washer Topping Column C4 Feed Solvent Process Flow Diagram 17

18 C4 FEED EDC1 TOP SCC TOP TAIL BTM TOPP TOP TOPP BTM BBW TOP SRC TOP Butane+ Butene ___ 100%___ Trans- Butene ___ 100%___ CIS- Butene ___ 0.2%99.8%___ 1-3BDSMALL 98%___ 1-2BD___10%90%___ MA___ 100%___ EA+VA___100%___ C5+___ 100%___ DIMER___ 100%___ C4 Hydrocarbon Balance 18

19 C - 5101 Butane & Butene 1,3 BD & Heavies Vapor from no.1 EDC lower ( Raffinate) Liquid reflux Solvent C4 feed vapor 95 84 TO No.1 EDC COLUMN (LOWER) 4.4Kg/cm2 BB Washer 1 19 30 SRC V – 5101 E – 5103 Diluents SRC C-5111 TO SRC Raffinate to OSBL Solvent bleed 40Deg C 12.4 MT/hr ANALYE R – 51002 FOR 1-3 BD & OTHERS ANALYZER 510001 FOR 1-3 BD, EA, VA, & MA NO:1 EDC COLUMN (UPPER) 19

20 C – 5102 Solvent & EA,VA Vapor from C-5104 Vapor to No.1 EDC Upper Liquid from C-5101 7 Vapor to C-5103 ( EA,VA,MA,1-3 BD ) Liquid from C-5103 ( EA,VA & Solvent ) 90 1-3BD & Butane Butene To Solvent stripper 6 5 ANALYZER – 51005 FOR MA & 1-2 BD NO:1 EDC COLUMN (LOWER) 20

21 C – 5103 Solvent & EA-VA Vapor from C-5102 (1-3 BD, EA-VA,MA & Heavies ) Vapor to C-5107 ( 1-3 BD, MA & Heavies) Reflux (1-3 BD & Heavies) Solvent 90 110 1-3BD,MA & Heavies To C - 5102 ANALYZER – 51004 FOR MA,VA & EA NO:2 EDC COLUMN 21

22 C – 5104 Solvent Vapor to C-5102 ( 1-3 BD, MA & Heavies) From C-5102 (Solvent,EA,VA,1-3BD & 1-2 BD ) Vapor to C-5105 ( Solvent,EA,VA,1-3BD & 1-2 BD ) From C-5105 (Solvent &1-3BD) 26 55 1-3 BD, MA & Heavies To solvent loop SOLVENT STRIPPER 22

23 C – 5105 Solvent & 1-3 BD Vapor-Liquid from C-5104 (1-3 BD, EA-VA & Solvent ) Vapor (Solvent,EA-VA &1-3BD ) Reflux (Solvent & 1-3BD) 1 15 TO C-5104 (1-3 BD & Solvent) 25 TO SRC C4 Acetylene TO C4 Hydro. Unit Water C – 5106 V – 5102 E – 5110E – 5111E – 5112 Brine 1 ANALYZER – 51003 FOR EA & VA DILUENT FROM V – 5101 SIDE CUT COLUMN SIDE CUT WASHER SIDE CUT COLUMN SIDE CUT WASHER 23

24 C – 5110 V – 5106 E – 5123 E – 5122 E – 5124 21 25 01 V – 5110 CWS OWS BB-W SCC-W LP-FLARE BB-W V-5105 V-5104 V-5101 LP-Steam SOL. V-5117 V-5109 From SCC-W E – 5121 E – 5126 94 Deg C 114 Deg C ACN 62.52%, H2O 28.84%,ETOH 8.64% TO C-5104 BOTTOM V – 5107 TO E - 5112 2.84 MT/hr CAUSTIC PH Analyze r 24

25 V-5105 Boot V-5104 Boot BB-W C - 5109 SSC-W C - 5106 3025 11 19 SRC C - 5110 V - 5106 V - 5110 E - 5121 A/B TO V – 5118 CWS CWR E – 5126 25 1 SCN BD-W C - 5111 8 MT/hr 4 MT/hr 1 21 25 25 MT/hr V-5101 Boot FROM V-5101 LP - FLARE TO E – 5112 13 MT/hr FROM E-5112 FROM V-5104 WATER CIRCULATION LOOP 25

26 C - 5104 TO C - 5103 TO C - 5101 E – 5114E – 5115 E – 5102 A/B E – 5117 E – 5105E – 5106E – 5107 A/B E – 5123 E – 5127 FROM C - 5110 138 Deg C 126 Deg C 110 Deg C 97.3 Deg C 88.6 Deg C 78 Deg C 73 Deg C 70 Deg C 58.7Deg C 50 Deg C 2 MT/hr TO C-5109 SDN TBC C – 5102 Bottom E - 5108 C – 5102 Tray 2 C – 5102 Tray 1 C – 5102 Tray 4 C – 5102 Tray 3 C – 5110 Boot C 4 Feed E – 5101 A/B C – 5107 Boot C – 5108 Boot C – 5107 Tray 25 C – 5107 Tray 26 CWS CWR DENSITY ANALYZER SOLVENT LOOP 26

27 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. 27

28 SIMULATION OF ACETONITRILE PROCESS RELIANCE INDUSTRIES LIMITED CEPD GROUP-RTG VMD 28

29 Simulation of BD Process 29

30 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 30

31 Comparison of Design and Simulation Temperatures Top temp.,CBottom temp.,C DesignPred.DesignPred. ED1U (C-5101)44417172 ED1L (C-5102)717296103 ED2 (C-5103)45 5759 Solvent stripper (C-5104)110 138135.5 Tailing column (C-5107)40 6053 Topping column (C-5108)42 52 Topping column (feed tray)50.6 Solvent purification column (C- 5110) 92.492.5113.7114 RadFrac (rigorous distilaltion for two & three pahse fractionation) Aspen Plus module used for simulation 31

32 EDC-1 Upper Column Simulation Results EDC-1 Upper Column Simulation Results C-5101DesignPred.DesignPred. StreamED1L/DED1U/B MA/PD011/34024/65 1-Butene0927009278 Iso-butene0286102860 Trans-2-Butene195005204207005234 Cis-2-Butene2600281032323016 1,3-Butadiene27479243764376940693 1,2-Butadiene10024269155 Ethylacetylene5035135112 Vinylacetylene150146202659 C5 heavier100145270159 Acetonitrile110164265175862169212 Ethanol15415051748116483 Water25510193198232881 Reflux ratio is provided as input for simulation 32 L/D U/B

33 EDC-1 Upper Column Simulation Results EDC-1 Upper Column Simulation Results C-51010DesignPred.DesignPred. StreamED1U/D V ED1U/DL MA/PD0/10/00/100/0 Iso-butane4.90.471.470.2 n-Butane26.425.0385386.7 1-Butene227.822933293289 Iso-Butene452.6466.466146589 Trans-2-butene73.562.210731075 Cis-2-butene52.843.5771807 1,3-Butadiene1.70250 C5 heavier01.86084 Acetonitrile02.9070 Water03.9083 Solvent C4 Feed Columns converged without any errors 33 D/V D/L

34 EDC-1 Lower Column Simulation Results C-5102DesignPred.DesignPred. StreamSC/VB/L MA/PD0/8810.9/57.30/5512/77 1-Butene07.600 Trans-2-butene04500 Cis-2-butene43836066012 1,3-Butadiene42092425255093028871 1,2-Butadiene395241210192 Ethyl acetylene8854275336 Vinyl acetylene3951551430972 C5 heavier306624402.5 Acetonitrile43104170186289195457 Ethanol3755371814119763 Water61510873640938834 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. 34 SC/V B/L

35 Solvent Stripper Simulation Results Solvent Stripper Simulation Results C-5104DesignPred.DesignPred. StreamD/VB/L MA/PD0/07/650/0 Cis-2-butene5421200 1,3-Butadiene520222889400 1,2-Butadiene488550122 Ethyl acetylene 16321700 Vinyl acetylene 596430019 C5 heavier3792.500 Acetonitrile502313440183596181992 Ethanol46821291770717603 Water116436913534535146 D/V B/L 35

36 Solvent Stripper Simulation Results C-5104DesignPred.DesignPred. StreamSC/VReturn/L 1,3- Butadien e 2693861 1,2- Butadien e 1356041 Ethyl acetylene 9213416 Vinyl acetylene 615624103 Acetonitrile14981129251491712900 Ethanol2229245621802425 Water1966389719663900 To C-5106 SC/V R/L 1,2-Buatdiene stripping observed to be difficult 36

37 EDC2 Column Simulation Results C-5103DesignPred.DesignPred. StreamD/VB/L MA/PD0/1116/420/05/28 Trans-2- butene 0320635 Cis-2-butene4441056273163 1,3-Butadiene54409561622610726263 1,2-Butadiene27739.613727 Ethyl acetylene 0010954 Vinyl acetylene 00545155 C5 heavier2776810941 Acetonitrile002105221211 Ethanol1020252188 Water29936539154087 D/V B/L C5 heavier is considered as n- pentane in simulations 37

38 Tailing Column Simulation Results C-5107DesignPred.DesignPred.DesignPred. StreamSC/LD/LB/L MA/PD0/781.5/12.60/30.55/29.50/0 1-Butene0301.700 Trans-2-butene02503.900 Cis-2-butene3128893225.52102.55 1,3-Butadiene3882039898159691607545141 1,2-Butadiene1952800118188 Ethyl acetylene0000010.8 C5 heavier27740.50011627.66 38 SC/L D/L B/L

39 Topping Column Simulation Results Topping Column Simulation Results C-5108 DesignPred.DesignPred.DesignPred. Boot WaterDistillate1,3 BD MA0030.530.3300.172 cis-2- Butene000032 1,3-BD0045.845.61596815922 Water1312.6100.3800 Total, kg/hr1312.6176.3 1600015954.6 From BD washer top Excellent matching between simulation & design values Thermodynamics: UNIFAC-LBY 39 D

40 Solvent Recovery Column Simulation Results C-5110DesignPred.DesignPred. Distillate Bottom Acetonitrile1772 00 Ethanol245 00 Water815817.82501325012 Total, kg/hr28322834.92501325012 Simulation results and design results matched very well Opportunity for reflux ratio optimization observed 40 B D

41 Observations 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 41

42 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 42

43 GROWTH IS LIFE 43


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