Indigenous development of Novel Magnesium Precursor and High Performance Ziegler-Natta Catalysts for Polypropylene & Polyethylene

Transcription

1 Indigenous development of Novel Magnesium Precursor and High Performance Ziegler-Natta Catalysts for Polypropylene & Polyethylene Gurmeet Singh Research & Development Centre Indian Oil Corporation Limited INDIA Global Refining & Petrochemicals Congress May 217

2 Polyolefin Catalysts PP catalyst market to reach $1.33 bn by 22 (CAGR of 5-6%) ZN catalysts - ~8 percent PP Catalyst market share by value in Indian Oil Corporation Ltd (IOCL) Second largest producer of PP & PE in India 3 KTA HDPE Production Hostalen 6 KTA PP Production - Spheripol Technology Another 7KTA Capacity Under commissioning Internal Donor ~5 mol% Titanium chloride fragments ~6 mol% (14) Catalyst Producers Catalyst Precursor MgCl 2 Matrix ~89 mol% Lyondell-Basell MgCl 2.xROH Grace (DOW) Mg 3 Ti(OEt) 8 Cl 2 Mitsui / BASF MgCl 2.xROH IOCL Targeting Novel Precursor No Dependence on Exotic Raw Materials Ineos Mg(OR) 2.xCO 2 Borealis BOMAG

3 IOCL Execution Strategy Turning Challenges into Opportunities Limited TiCl 4 Usage Easily Available Raw Materials Catalyst Precursor PP Catalyst Constraints Reasons Effect IOCL Strategy Benefits IP IOCL being late entrant Limited scope of operations White space analysis Designing of unique process Patentable process FTO Limited availability of MgCl 2 Limited vendors Vendors are ZN catalyst manufacturers High cost Availability constraints Reduced competitiveness Designing of novel process Synthesis of catalyst using basic and of the shelf available raw materials Cost competitive catalyst Supply chain management Handling of TiCl 4 Corrosive nature of TiCl 4 Equipment life Disposal issues CAPEX & REVEX costs Reducing alcohol content in carrier Synthesis of catalyst using basic and of the shelf available raw materials Energy efficient process Environmentally sustainable CAPEX & REVEX management Team Work Brainstorming Efficient Project Execution Knowledge Creation

4 Design of Precursor-1 Mg RX RMgX* MgX 2 + R 2 Mg* R OH R OH R OH Mg(OR )X MgCl 2.xR OH Mg(OR ) 2 {Mg(OR )X}.x{MgX 2 }.y{mg(or ) 2 }.z{r OH} Precursor-1 Mg:Alcohol as low as 1:1 Attributes Precursor Processing Single-pot Synthesis Re-crystallize Precursor Precipitated Precursor Dissolved Precursor Precursor Yield 1% Conversions Precursor Composition Tunable Composition Reproducible Composition Temperature: Schlenk Equilibrium Control Halide: To control MgCl 2 Formation (Butyl chloride, Benzyl chloride) Alcohol: EHA, Isobutanol, Benzyl alcohol, Catechol, 3- Methoxy 1-butanol 4

5 Design of Precursor-2 Mg RX R OH R OH MgX 2.nR OH R OH Mg(OR ) 2 + RMgX* MgX 2 + R 2 Mg* R OH Mg(OR )2 Mg(OR )X {Mg(OR )X}.a{MgX 2 }.b{mg(or ) 2 }.c{r OH} Precursor-2 Mg:Alcohol :: 1:1 to 1:1.5 Temperature: Schlenk Equilibrium Control Halide: MgCl 2 Formation (Butyl chloride, Benzyl chloride) Alcohol: EHA, Isobutanol, Benzyl alcohol, Catechol, 3-Methoxy 1-butanol Attributes Stability of Precursor No precipitation for last 18 months Precursor Processing Single-pot Synthesis Single-step synthesis Precursor Yield 1% Conversions Precursor Composition Tunable Composition Reproducible Composition 5

6 Precursor-1: 25 Mg NMR IOCL Mg_1; CPMG with 2us tau delay in CDCl3 IOCL Mg_1; CPMG with 2us tau delay Different Mg Environments in CDCl3 MgCl 2 NAME IOCL Mg Sample EXPNO 1 PROCNO 1 Date_ NAME IOCL Time EXPNO INSTRUM spect PROCNO PROBHD 5 mm PABBO BB- Date_ PULPROG cpmg1d Time TD INSTRUM SOLVENT CDCl3 PROBHD 5 mm NS 1 PULPROG DS TD 8 SWH 5. SOLVENT Hz FIDRES NS Hz AQ DS sec RG 128 SWH DW 1. FIDRES usec DE 6. AQ usec TE 299. RG K D1 1. DW sec D11.3 DE sec D2.2 TE sec L4 D1 1 TD D11 1 D2 ======== CHANNEL f1 ======== L4 NUC1 25Mg TD P1 18. usec p2 36. ======== usec CHAN PL1 1. NUC1 db SFO P1 MHz SI p2 SF PL1 MHz WDW SFO1 EM SSB SI LB 25. SF Hz GB WDW PC 1.4 SSB LB GB PC ppm ppm

7 Precursor-2: 13 C{ 1 H} NMR {Mg(OR )X}.a{MgX 2 }.b{mg(or ) 2 }.c{r OH} Lock: DMSO-d6: ppm A 1 x x Liquid Precursor Mg(OEHA) 2 2 x x MgCl 2.EHA EHA in Toluene 7

8 ZN Catalyst Synthesis Precursor Internal Donor X Titanations Ti (wt%) Mg (wt%) Composition ID (wt%) Hx Washings Method Development PP Catalyst

9 STP (cc/g) Catalyst Characterization XRD & BET Surface Area Crystallite width calculated from the diffraction peak at 5.3 2θ (11) planes of α-mgcl 2 and β-mgcl 2 and (18) plane of α - MgCl 2 PANalytical Empyrean Crystallite Size in the Range of 4-6Å Quantachrome Autosorb Relative Pressure, P/Po Surface Area = 35-4 m²/g

10 Unit 2.16kg PP Catalyst Performance Productivity Hydrogen Response Prod TS MFI ZN# H 2 (ml) Prod Productivity (Kg PP/g Cat) TS Total Soluble (wt%) MFI (g/1min) Desired Performance

11 % Retention Morphology, PSD & Isotacticity Regular Morphology > 1um > 71um > 5um > 25um > 15um > 75um Pan Particle Size (um) PP#1/Precursor-1 PP#2/Precursor-2 Nil resin in the Pan Narrow Particle Size Distribution NMR Isotacticity mmmm Content in the range of 85-87%

12 Productivity (KgPP/gCat) 17L Reactor Bulk 3 rd Party Evaluation 2 IOCL Catalysts evaluated against reference commercial catalyst XS(Wt%) MFI@2.16Kg Ref/C-donor IOCL#C/C-donor IOCL#B/C-donor Desired Performance Achieved with IOCL Catalysts

13 Elemental Composition wt% PE Catalyst Catalyst Evaluation 2 PE catalyst Elemental Composition Ti Wt% Mg wt% Experiment No Stable Elemental Composition Achieved

14 5 Kg/ Kg 21.6 Kg PE Catalyst Product Evaluation 3 25 In-house MFI@5 Kg Cat-1 Cat-2 MFI@2.16 Kg Cat Experiment No bar In-house > Cat-1 > Cat-2> Cat Kg/5Kg; 1 bar In-house > Cat-1 > Cat-2> Cat In-house Cat Cat-2 Cat Experiment No

15 FRR Density PE Catalyst Product Evaluation Flow Rate Ratio In-house Cat-1 Cat-2 Cat-3 Flow Rate Ratio: In-house Cat-1 Cat-3 > Cat Experiment No Density of PE samples In-house Cat-1 Cat Cat Experiment No

16 Productivity/ Hexane Solubles PE Catalyst Performance Evaluation 5Kg In-house Vs Cat-1 Vs Cat-2 Vs 1 bar H2 KgPE/gCat Hex Sol wt% MFI@5 Kg In-house Cat-1 Cat-2 Cat Experiment No In-house catalysts are superior with respect to productivity and hydrogen response

17 Korea China 2649/MUM/ /MUM/212 EP WO/214/ US 15/ RU US US JP JP JP JP SA4895 SA514 EU Korea China 2765/MUM/212 EP Patents WO/214/4 526 US 15/ RU /MUM/ /MUM/ /MUM/ /MUM/ /MUM/215 9 Patent Families Covering Synthesis of Novel Magnesium Precursors & Subsequent Ziegler-Natta Class of Catalysts filed to Protect IOCL Innovation

18 Conclusions Robust precursors developed using extensive parallel and automated process Precursors established for synthesis of high productivity Ziegler-Natta catalysts for producing PP & PE The catalysts showed excellent performance and desired PP & PE product characteristics Extensive IPR protection 1 Foreign Patents Granted, 51 Patents filed Thank You All