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Selective Oligomerization of Ethylene by Homogenous Catalysts Reliance Technology Group, Reliance Industries Limited PETROTECH, 2010 New Delhi Vadodara.

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Presentation on theme: "Selective Oligomerization of Ethylene by Homogenous Catalysts Reliance Technology Group, Reliance Industries Limited PETROTECH, 2010 New Delhi Vadodara."— Presentation transcript:

1 Selective Oligomerization of Ethylene by Homogenous Catalysts Reliance Technology Group, Reliance Industries Limited PETROTECH, 2010 New Delhi Vadodara Manufacturing Division Vadodara- 391346

2 Linear Alpha Olefins

3 Applications of Alpha Olefins * Data Ref.2005

4 Major producers of C 4 -C 18 range LAO Shell Oligomerization / Metathesis, SHOP BP-Phillips Cr /TEAL/donor catalyst IFP α-Select, Ziegler chain growth SABIC- Linde α-SABLIN UOP/Union Carbide Linear-1 Sasol produces α-olefins from coal-based synthesis gas using F-T process 1 –C 4 30-40 Wt % 1 –C 6 25-30 Wt % 1 –C 8 15-20 Wt % 1 –C 10 8-10 Wt % C 12 + Desired C 4 -C 10  K = C n+2 / C n (~ 0.5-0.6 )

5 Typical  -Olefin Distribution Desired Maxima ( ) Albemarle (  ) Chevron ( _ _ _ ) Idemitsu and Shell ( )

6 Product distribution of full range LAO producers - mass (%)

7 1 –C 4 30-40 % 1–C 6 25-30 % 1–C 8 15-20 % 1 –C 10 + 8-10 % Poly < 1 % 1–C 4 0.5 - 2 % 1–C 6 25-30 % 1–C 8 68-70 % 1 –C 10 + 4-5 % Poly < 0.5 % 1–C 4 < 2 % 1–C 6 90-95 % 1–C 8 2-3 % 1–C 10 + < 2 % Poly 0.5 - 2 % LAO Trimerization Tetramerization Proven Technology Commercialized Not yet commercialized Early 2005 The process is commercially viable when the overall C 6 + C 8 yields = 90 % Processes for Alpha Olefins

8 Process  Gulf/Chevron AmocoShellSablin RIL * α-OlefinHeavyLightTypicalMediumLight  C4C4 13.922.9122440.230 C6C6 14.620.61327.128.133.5 C8C8 13.716.21213.21418.5 C 10 1212.31211.28.49.1 C 12 108.9108.358.6 C 14 8.26.285.82.3 C 16 6.24.374.81.4 C 18 5.22.96 0.5 C 20 14.95.3202.80.1 Comparison of Product Distribution (Wt%) Co-monomers for PE Heavy AO * Lab Process (Zr-Cat.) US 6930218 (2005)

9 Typical LAO process & reactor LAO Reactor

10 Examples of Oligomerization Catalyst Systems PPh 3 SHOP, Shell - LAO Phillips - Hexene-1 + BP - Hexene-1 + Sasol - Hexene-1 Sasol - Hexene-1 + Octene-1

11 M = Fe, Co L = N,N,N tridentate VERSIPOL ® (DuPont) Alpha Olefins HDPE TiCl 4 + Mitsui - Hexene-1 Zr(OR) 4 / ZrCl 4 Alpha Olefins Idemitsu, Sabic-Linde Examples of Oligomerization Catalysts

12 Phillips Trimerization catalyst & process (CPC) + DEAC, 115 0 C, 100 bar C 2, toluene + decenes Knudsen et.al US 5856257, (1999)

13  1-C4 = 0.2; C10 + = ~ 13.1  Internal Hexenes ~ 30.0 %  By products : Methyl / Methyelene cyclopentane Sel. 70.3 98.8 SASOL Tetramerization Catalyst & Process [Cr] activator productivity PE 1- C6 1-C8 MAO (g/g Cr) (%) (%) (%) _______________________________________________________ 0.033 300 eq. 272400 1.05 16.9 68.3

14 Metallacyclic Mechanism for ethylene oligomerization Butene-1 DimerizationTrimerization

15 M-H + C 2 H 4 M-C 2 H 5 M-H + 1-C 8 H 16 M-C 8 H 17 M-H + 1-C 10 H 20 M-C 10 H 21 M-H + 1-C 6 H 12 M-C 6 H 13 M-H + 1-C 4 H 8 M-C 4 H 9 C2H4C2H4C2H4C2H4 C2H4C2H4C2H4C2H4 C2H4C2H4C2H4C2H4 C2H4C2H4C2H4C2H4 Metal Hydride Mechanism of Oligomerization Cossee-Arlman

16  Synthesis of Novel Ligands  Complexation with Cr(III) salts (in-situ)  Evaluation of catalysts for selective ethylene oligomerization Present Work

17 Synthesis of Schiff Base Ligands

18 Tridentate [OSN], [PNO] ligands L1 L2 L3 L4 L5 L6

19 High Pressure Ethylene Oligomerization System 4 x 100 mL High Pressure Parallel Parr reactors (4593) with gas pipette dosing arrangement connected to 4871 process controllers.

20 Ethylene Oligomerization with Schiff Base ligands RunLigand Oligomer % PE % Productivity (g/moleCr) Distribution of α-olefins, wt% 1-C 4 1-C 6 1-C 8 1-C 10 C 12 + 1L19377140 21.048.020.66.54.0 2L270304620 24.838.418.19.29.5 3L387133360 13.829.919.512.324.4 4L442581680 -19.215.3-65.5 5L548521974 12.123.818.813.331.8 6L680202016 0.487.134.456.91.1 8*8* L19198960 12.823.319.113.331.6 Reaction conditions : Cr(acac) 3 -Lig-MAO (Cr/Al=500); 70 0 C, P C 2 H 4 =300 psi, toluene, 1hr, 600 RPM

21 Synthesis of Imidazolyl Ligands Characterization : Micro analysis, IR, NMR, Mass

22 Multidentate Imidazolyl Ligands L7 L9L10 L8

23 Ethylene Oligomerization with Cr-Imidazolyl Ligand RunLigand% C 2 H 4 conversion Productivi ty, gm/g.Cr Distribution of α-olefins, wt% 1-C 4 1-C 6 1-C 8 1-C 10 C 12 + PE % 1L792.6798711.227.42214.624.711.5 2L893.1809718.530.721.512.616.712.3 3L978.1763621.429.719.411.418.118.5 4L1078.6709914.828.624.813.917.822 Reaction conditions : Cr(acac) 3 -Lig-MAO (Cr/Al = 250 ) ; 45 0 C, P C 2 H 4 =400 psi, toluene, 1hr, 600 RPM

24 SUMMARY  New Ligands based on S, N,O, P synthesized and characterized  Complexation with Cr-salt leads to active catalyst system for ethylene oligomerization  Optimization of process can offer a unique catalyst for tailoring the desired range of  -olefin for end use


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