Exceed Your Hydrocracker Potential Using The Latest Generation Flexible Naphtha/Middle Distillate Catalysts

Transcription

1 Exceed Your Hydrocracker Potential Using The Latest Generation Flexible Naphtha/Middle Distillate Catalysts Criterion Catalysts & Technologies/Zeolyst International Prepared by: Ward Koester on March 2001 for NPRA Hydrocracking Technical Services Manager Updated by: Juan Carlos Estrada for LARTC 2014 Hydrocracking Technical Services Engineer

2 Outline Diesel to Gasoline Differential Volatility Criterion/Zeolyst Proprietary Zeolite Manufacturing Technology Expanded Hydrocracking Catalyst Portfolio bridges naphtha to diesel selectivity gap Optimized Flexible catalyst solutions for your application AM LARTC 3rd Annual Meeting Page 2

3 Message Zeolite Innovations. Giving you the Flexibility to Thrive! AM LARTC 3rd Annual Meeting Page 3

4 Dieselization of U.S. Hasn t Yet Fully Materialized Large scale Refinery closures in North America and Europe Inventory building as economy recovers Uncertainty in E-15 implementation Growth in demand for light products in Far East Diesel/Gasoline Differential Volatility Reduction in sulfur content of road transport fuels outside U.S. Electrification of vehicle fleet through subsidies New fuel economy standards Complex Biofuels legislation Tightening of marine ECAs in U.S and Europe New proposed CO 2 limits in road transport fleet AM LARTC 3rd Annual Meeting Page 4

5 Price Differential, Cents per Gallons U.S. Monthly Diesel to Gasoline Price Differential (Source: EIA) AM LARTC 3rd Annual Meeting Page 5

6 Outline Diesel to Gasoline Differential Volatility Criterion/Zeolyst Proprietary Zeolite Manufacturing Technology Expanded Hydrocracking Catalyst Portfolio bridges naphtha to diesel selectivity gap Optimized Flexible catalyst solutions for your application AM LARTC 3rd Annual Meeting Page 6

7 Absorbance F Proprietary Zeolite Manufacturing Technology for Hydrocracking High Target Low Previous generation Generation SAR from SEM/EDX SAR from SEM/EDX SAR from SEM/EDX Current Generation generation AM LARTC 3rd Annual Meeting Page 7

8 Catalysts Based on Proprietary Zeolite Manufacturing Technology NiMoS x Carrier Zeolite Previous NiMoS x Carrier Proprietary Zeolite State-of-The-Art Proprietary Zeolite Higher purity Improved product selectivity More activity Extra room for hydrogenation (or other functions) Better HDS, HDN, and HDA AM LARTC 3rd Annual Meeting Page 8

9 Outline Diesel to Gasoline Differential Volatility Criterion/Zeolyst Proprietary Zeolite Manufacturing Technology Expanded Hydrocracking Catalyst Portfolio bridges naphtha to diesel selectivity gap Optimized Flexible catalyst solutions for your application AM LARTC 3rd Annual Meeting Page 9

10 Criterion/Zeolyst Hydrocracking Catalysts AM LARTC 3rd Annual Meeting Page 10

11 The Quest for Higher Mid Distillate Selectivity Introduces Z-2723 in 2008 AM LARTC 3rd Annual Meeting Page 11

12 New Z-FX10 Catalyst Introduced in 2011 Z-FX20 New modified Y zeolite Z-3xxx HDA HDS + other large pore zeolite Z-2723 MD Cold flow H 2 in UCO Further modification Z-FX10 MD Cetane Z-FX20 Z-3733 Activity Z-3723 Selectivity AM LARTC 3rd Annual Meeting Page 12

13 Z-FX10 Performance Feed Middle Distillate selectivity (%) Diesel Cetane Z-3723 Z-FX10 Canadian Synthetic VGO HVGO (Ring Rich) Base Base +4 Base +3 Base Base +1 Base AM LARTC 3rd Annual Meeting Page 13

14 Good stability of Z-FX20 HC with synthetic customer feed AM LARTC 3rd Annual Meeting Page 14

15 Z-FX10 Hydrogenation Activity Mono-aromatics saturation Hydrogen consumption Z-FX10 Z-FX10 Z-3723 Z-2723 Z-2723 AM LARTC 3rd Annual Meeting Page 15

16 Advanced Trilobe extra (ATX) Shape TL Trilobe Shape TL Trilobe Shape All HC catalysts after 1994 Gradient High content ATX Trilobe Shape ATX Trilobe Shape Advanced Trilobe extra Advanced Trilobe extra Improves diffusion Now for majority of HC catalyst Now for majority of HC catalyst Increases particulates uptake Improves diffusion Delays onset SOR to rapid P 0.75% P increase x TL SOR P 0.75% x TL Delays onset to rapid P increase Strength 0.8 x TL Low content AM LARTC 3rd Annual Meeting Page 16

17 Outline Diesel to Gasoline Differential Volatility Criterion/Zeolyst Proprietary Zeolite Manufacturing Technology Expanded Hydrocracking Catalyst Portfolio bridges naphtha to diesel selectivity gap Optimized Flexible Catalyst Solutions for Your Application AM LARTC 3rd Annual Meeting Page 17

18 Example 1: Z-853 Naphtha vs Z-2723 Flexible Catalyst FF BLEND: HVGO / LVGO / DAO API 26 Sulfur, wt% 0.60 Nitrogen, ppm 1000 FF BLEND: HVGO / LVGO / DAO D-2887, ºF 10% % 821 FBP 1372 AM LARTC 3rd Annual Meeting Page 18

19 Example 1: Yields and Product Properties Z-853 vs Z-2723 Z-853 Z-2723 Z-853 Z-2723 Conv to 650-ºF, vol% ff Product Yields, vol% ff Multiplier LPG Base Total Naphtha Jet Diesel C5+ Yield Chemical H2 Cons, scfbff Delta to Base HC Catalyst WABT, ºF ULSD Cloud Pt., ºF ULSD Sulfur, ppm AM LARTC 3rd Annual Meeting Page 19

20 Example 1 Summary Catalyst Considerations LPG constraints Product Sulfur or Cetane constraints Cold Flow constraints Value and Definition of Volume Swell C3+ or C5+ yield Value of Unconverted Oil Reactor Temperature impact on Cycle Life AM LARTC 3rd Annual Meeting Page 20

21 Example 2: Naphtha Selective vs Stacked Naphtha/Flexible Catalyst HC FEED BLEND: LCO / LVGO D-2887, ºF 10% % 586 FBP 829 AM LARTC 3rd Annual Meeting Page 21

22 Example 2: Naphtha Selective vs Stacked Naphtha/Flexible Catalyst HC Z-863 Z-763 Z-753 Z-753 HC Z-863 Z-853 Z-3733 Classic State-of-the-Art AM LARTC 3rd Annual Meeting Page 22

23 Example 2: Yields and Product Properties Naphtha vs Stacked Naph/Flexible Catalyst 70 wt% Net Conversion to 495- F Z-863/Z-763/Z-753 Temperature Base + 5 F H2 Consumption scf/bbl Gas + LPG Yield - 1 wt% Naphtha Yield + 1 wt% Distillate Yield + 2 wt% Naphtha Octane Aromatics Distillate Density Aromatics Cetane Sulfur Smoke Pt. Z-863/Z-853/Z-3733 AM LARTC 3rd Annual Meeting Page 23

24 CASE 1: HC WITH PRE-TREATED HEAVY FLASHED DISTILLATE FEED PROPERTIES AND TEST CONDITIONS Elements (w%) Sulfur : Nitrogen : ) Carbon : Hydrogen : Density (g/ml) 70/4 : D-2887 Distillation (wof% at o F) IBP : : : : : : : 1006 FBP : 1081 UV aromatics (rings only, w%) Mono : 4.67 Di : 0.69 Tri : 0.53 Tetra+ : 0.26 Test conditions WABT ( o F) : W(L)HSV (kg/l.h) : 1.5 H 2 /feed (nl/kg) : 1500 H 2 PP in (bar) : 134 H 2 S PP in (bar) : 5.6 1) Feed doped with 12.3 g/kg decylamine to provide an ammonia partial pressure equivalent to 1100 ppmw organic feed nitrogen Copyright of Shell Global Solutions Downstream - Catalyst Technology AM LARTC CONFIDENTIAL 3rd Annual Meeting Page For Criterion Phillips 66 use only

25 CASE 1: HC WITH PRE-TREATED HEAVY FLASHED DISTILLATE Selectivity towards different boiling fractions at 65 wof% 698+ o F conversion Values Z-3733 Z-FX20 Z-3723 Shape TL TX TL Catalyst CBD WABT/ F Base Base +2 Base +14 C 1 -C 4 /%w Base Base -0.6 Base -1.0 C 5-82 C/%w Base Base -0.2 Base C/%w Base Base -1.3 Base C/%w Base Base +2.1 Base +0.8 Copyright of Shell Global Solutions Downstream - Catalyst Technology AM LARTC CONFIDENTIAL 3rd Annual Meeting Page For Criterion Phillips 66 use only

26 CASE 2: HC WITH A SYNTHETIC CUSTOMER FEED FEED PROPERTIES AND TEST CONDITIONS Elements (w%) Sulphur : 2.57 Nitrogen : Carbon : 85.7 Hydrogen : 11.6 Density (g/ml) 70/4 : D-2887 Distillation (wof% at F) IBP : : : : : : : 984 FBP : 1067 Copyright of Shell Global Solutions Downstream - Catalyst Technology UV aromatics (rings only, w%) Mono : 6.52 Di : 3.77 Tri : 4.28 Tetra+ : 2.87 Test conditions PT volume (ml) : 20.6 HC volume (ml) : 10.3 W(L)HSV (kg/l.h) : H 2 /feed (nl/kg) : 1360 H 2 PP in (bar) : 125 PT effluent contains 10 ppmw nitrogen AM LARTC CONFIDENTIAL 3rd Annual Meeting Page For Criterion Phillips 66 use only

27 CASE 2: YIELD PROFILE OF Z-FX20 HC WITH SYNTHETIC CUSTOMER FEED Yields towards different boiling fractions at 89 wof% 667+ F net conv. Values Z-3723 Z-FX20 Shape TL TX Catalyst CBD WABT/ F Base Base -11 C 1 -C 4 /%w Base Base +0.3 C 5-75 C/%w Base Base C/%w Base Base C/%w Base Base C/%w Base Base -1.4 >352 C/%w Base Base Copyright of Shell Global Solutions Downstream - Catalyst Technology AM LARTC CONFIDENTIAL 3rd Annual Meeting Page For Criterion Phillips 66 use only

28 Example 2 Summary Significant catalyst changes are not needed to produce desired selectivity changes Application of Stacked bed of Flexible Z-3733 produced significant product quality improvement Changing from the classical portfolio s Z-763/Z- 753 to the state-of-the-art Z-853 contributed to the improved selectivity in the stacked system AM LARTC 3rd Annual Meeting Page 28

29 Conclusion Diesel to Gasoline Differential Volatility Criterion/Zeolyst Proprietary Zeolite Manufacturing Technology Expanded Hydrocracking Catalyst Portfolio bridges naphtha to diesel selectivity gap Optimized Flexible Catalyst Solutions for Your Operation AM LARTC 3rd Annual Meeting Page 29

30 Criterion/Zeolyst Zeolite Innovations. Giving you the Flexibility to Thrive! AM LARTC 3rd Annual Meeting Page 30

31 CRITERION/ZEOLYST DISCLAIMERS Copyright 2014 Criterion Catalysts & Technologies, LP, and Zeolyst International, LP. All copyright and other (intellectual property) rights in all text, images and other information contained in this publication are the property of Criterion Catalysts & Technologies, LP, and Zeolyst International, LP. Permission should be sought from copyright owners before any part of this publication is reproduced, stored or transmitted by any means, electronic or mechanical including by photocopy, recording or information storage and retrieval system. AM LARTC 3rd Annual Meeting Page 31