SIMULATION OF OIL SHALE RETORTING USING THE ICON STEADY STATE MODEL Shahrul Azman Zainal Abidin PETRONAS Group Technology Solution Ahmad Junaidi Jalaludin PETRONAS Group Technology Solution Dr. Omar Bekri CHAPEM Consultants, Morocco 2006 PETROLIAM NASIONAL BERHAD (PETRONAS) All rights reserved. No part of this document may be reproduced, stored in a retrieval system or transmitted in any form or by any means (electronic, mechanical, photocopying, recording or otherwise) without the permission of the copyright owner.
PRESENTATION OUTLINE Introduction to Malaysia PETRONAS An Overview Shale Oil Modeling Questions
INTRODUCING MALAYSIA A NATION AT THE HEART OF SOUTH EAST ASIA NEIGHBOURING THAILAND, SINGAPORE AND INDONESIA POPULATION OF ABOUT 25 MILLION
INTRODUCING MALAYSIA A MODERNIZING NATION BLENDED WITH A MULTICULTURAL SOCIETY RICH IN THE ARTS, TRADITION AND NATURAL BEAUTY
INTRODUCING MALAYSIA FULL OF NATURAL WONDERS
INTRODUCING MALAYSIA HISTORY & HERITAGE
INTRODUCING MALAYSIA MODERN INFRASTRUCTURE
PETRONAS and Formula 1
PRESENTATION OUTLINE Introduction to Malaysia PETRONAS An Overview Shale Oil Modeling Questions
PETRONAS Corporate Profile PETRONAS is the national oil corporation of Malaysia. PETRONAS was incorporated on 17 th August 1974, vested with the entire ownership and control of the petroleum resources in Malaysia. PETRONAS also competes with other multinational oil companies operating in the downstream sector of the petroleum industry. Over the last 32 years, PETRONAS has evolved into a fully integrated oil and gas multinational corporation with global presence in 31 countries. PSC Manager PSC & Project Manager/Operator - Integrated Oil Company Global Player 1970s 1980s 1990s 2000s
Vision: To be a leading oil and gas multinational of choice MISSION We are a business entity Petroleum is our core business Our primary responsibility is to develop and add value to this national resource Our objective is to contribute to the well being of the people and the nation
PETRONAS An Integrated Petroleum Company Corporate Shipping Exploration LNG Production Gas Refining Oil Petchem Marketing
Status as at 31.3.2006 PETRONAS Group Comprises 127 Direct Subsidiaries and 54 Associated Companies Wholly Owned Subsidiaries 105 Overseas Domestic 64 41 Partly Owned Subsidiaries 22 Overseas Domestic 4 18 Associated Companies 54 Overseas Domestic 33 21
PETRONAS An Integrated Petroleum Company CRUDE OIL OIL MARKETING FACILITIES REFINING PETROLEUM PRODUCTS AROMATICS PETROCHEMICAL EXPLORATION & PRODUCTION GAS CONDENSATES PROCESSING LPG SALES GAS FERTILISERS LIQUEFACTION LNG LNG
PETRONAS has interests in 30 countries worldwide UPSTREAM (14 countries) Algeria Angola Benin Equatorial Guinea Ethiopia Iran Mauritania Morocco Myanmar Mozambique Niger Pakistan Turkmenistan Yemen UPSTREAM & DOWNSTREAM (8 countries) Chad Cameroon Egypt Indonesia Philippines Sudan Vietnam Malaysia DOWNSTREAM (8 countries) Australia Argentina Cambodia China India South Africa Thailand United Kingdom
Organisational Structure of PETRONAS BOARD OF DIRECTORS BOARD AUDIT COMMITTEE PRESIDENT AND CHIEF EXECUTIVE MANAGEMENT COMMITTEE CORPORATE HSE PRESIDENT S OFFICE INTERNAL AUDIT LEGAL AND CORPORATE AFFAIRS CORPORATE SECURITY REGIONAL OFFICES E & P BUSINESS OIL BUSINESS GAS BUSINESS PETROCHEMICAL BUSINESS CORPORATE PLANNING & DEVELOPMENT DIVISION EDUCATION DIVISION FINANCE DIVISION HUMAN RESOURCE DIVISION RESEARCH & TECHNOLOGY DIVISION
Organisational Structure of PETRONAS BOARD OF DIRECTORS BOARD AUDIT COMMITTEE PRESIDENT AND CHIEF EXECUTIVE MANAGEMENT COMMITTEE CORPORATE HSE PRESIDENT S OFFICE INTERNAL AUDIT LEGAL AND CORPORATE AFFAIRS CORPORATE SECURITY REGIONAL OFFICES E & P BUSINESS OIL BUSINESS GAS BUSINESS PETROCHEMICAL BUSINESS CORPORATE PLANNING & DEVELOPMENT DIVISION EDUCATION DIVISION FINANCE DIVISION HUMAN RESOURCE DIVISION RESEARCH & TECHNOLOGY DIVISION
RESEARCH & TECHNOLOGY DIVISION Legal Entities OGPTSSB PRSSSB PTSSB AERSB Research and Technology Division VP Office Group Research & Technology Mgt Policy, strategy & direction Technology Condition Diagnostics Consolidation of business technology requirements Technology fore-sighting Venture capital management Group Technical Capability Mgt Policy, strategy, guidelines & system Technical staff development plan, career progression and movement Technical knowledge sharing Group Technical Capability Mgmt Group Research Group Research Applied research Fundamental research Group Technology Solution Group Technology Solution Plant Performance Management Plant Project Studies Engineering Expertise Knowledge Management Note : * Plant include E&P facilities, pipelines, and downstream plants
PETRONAS GROUP TECHNOLOGY SOLUTION Group Technology Solution Group *Plant Performance Mgt Engineering *Plant Project Studies Knowledge Mgt (KM) Performance Improvement Mgt Process Engineering Technical Studies KM Strategy, Planning & Dev t. Process & Hydrocarbon Value Chain Mgt Asset Reliability & Integrity Mgt Plant Engineering Process Automation & Optimisation Technical Assurance Technology Development KM Asset Mgt Plant modelling Advanced Process Control Real Time Optimization
PRESENTATION OUTLINE Introduction to Malaysia PETRONAS An Overview Shale Oil Modeling Questions
SHALE OIL MODELLING: INTRODUCTION Why model shale oil? To pursue knowledge and expertise in shale oil To provide fundamental understanding in shale oil reactions and processing capabilities The necessity to understand the basic reaction mechanism/ discarding other side reactions to ensure proper development in shale oil program Use of icon, PETRONAS s own steady state process simulation software PETRONAS direction in acquiring alternative sources of fuel Potential of shale oil Opportunities in developing new technology
INTRODUCTION TO ICON PRSS GUI Proprietary & customized PRSS simulation kernel - Membrane - LNG Exchanger - Shortcut distillation - Vessel sizing - Vacuum pump -. etc Non-proprietary & literature based Steady state process simulator Open source simulation kernel VMGThermo Microsoft productivity tools
METHODOLOGY Modeling Approach Experimental Methodology Mathematical Modeling
EXPERIMENTAL METHODOLOGY Thermo Gravimetric Analyzers (TGA) are used to obtain processed data for model (require sample of <50mg and crushed to <300μm) Isothermal and non-isothermal operation possible Non-isothermal TGA used Fast Simple Easier to manage information Disadvantage is no detailed compositional analysis Modeled Area Oil Vapor + N 2 Oil Shale N 2 T~260-550ºC
MATHEMATICAL MODELLING The modeling is based on the equation: Where k 1 and k 2 are reaction rate constants Arrhenius equations k 1 =k 10 e -E1/RT f 1 represents the conversion of kerogen to oil & gas f 2 represents the conversion of bitumen to oil &gas Follows a 6-step process including an iteration procedure Step 1 k oil & gas k oil & gas 1 2 Kerogen bitumen residual carbon dp E1 ln V = + ln dt RT dp dt 2 k10. RT E RT 1. 1/ 1 10 e. E1 V ( Mo. f. k ) Plot ln V versus 1/V will provide T = cons tan t k10 2 E1/ RT A1( T) = RT. e E1 E1 B ( T ) = + ln( Mo. f 1. k RT 1 10 )
KEROGEN DECOMPOSITION Step 2: Find E1 and k 10 Plot B1(T) vs. 1/T and obtain A2 = -E1/R so E1 = -A2.R B2 = ln (Mo.f 1 k 10 ) Calculate k 10 = (E1.A1 (T)/RT 2 ) e E1/RT from Step 1 Step 3: Calculate f 1 E1/ RT dp e P = 1 V Mof dt k 10 1 Step 4: Refine values 2 dp E1 k. RT E RT 1 V ( Mo f k ). 1/ 10 ln ln.. = e. Plot to obtain the slope & intercept k10 A3( T ) = RT E1 E1 B3( T ) = RT dt 2. e E1/ RT 1 10 RT E1 V Step 5: Use new k 10 and E1 to calculate new f 1 Step 6: Repeat Step 4 until achieve convergence
BITUMEN DECOMPOSITION Need to find f 2 in bitumen decomposition V dp E2 ln. = + ln( k 20 ) P Po dt RT Plotting the LHS of equation as a function of 1/T gives a slope of A4 = -E2/R B4 = ln (k20) A value for f 2 can be calculated 1 Po = Mof 1 + Mo(1 f ) f 1 2 or f 2 1 Po Mo. f = Mo.(1 f ) 1 1
RESULTS
RESULTS
RESULTS
RESULTS
RESULTS Sample Layer M1 Layer Y TEST Fischer Assay TGA Fluidized Bed Fischer Assay Sample Size 100 g 20mg 1.3 kg/hr 100g Particle Size 3.3mm <150 µm 300-400 µm 3.3mm Oil 7.2 16.5 11.3 Gas 1.7 13.3 6.0 3.7 Water 2.4 2.8 2.8 Carbon Residue 3.9 1.9 2.6 6.2 Spent Shale (Mineral) 84.3 84.8 72.1 76.0 Spent Shale (Total) 88.7 86.7 74.7 82.2 -Layer M1 Timahdit shale has an organic matter content of 15.28% -Fluidized bed on Timahdit sample utilizing 3kg/hr Hamburg continuous bench-scale facility -Layer Y Timahdit shale has an organic matter content of 24%
Results Summary Weight% 100.0 90.0 80.0 70.0 60.0 50.0 40.0 30.0 20.0 10.0 0.0 88.7 86.7 11.3 13.3 Fischer Assay M 25.3 74.7 17.8 82.2 TGA Model Fluidized Bed Fischer Assay Y Test Method Oil+Gas+Water Spent Shale(Total)
CONCLUSION The model was based on the simplified kerogen and bitumen decomposition reactions ignoring residual carbon in kerogen decomposition and carbonate decomposition reactions. The main parameters from this model are the conversion of kerogen and bitumen into oil and gas which were represented by the values of f1 and f2. The hydro-cracking and hydro-coking products from shale oil pyrolysis were discarded in the model. The raw data obtained from TGA of Timahdit shale oil samples were used to validate the model that had been developed using Microsoft Visual Basic. It was proven that the model is true for any type of heating.
CONCLUSION The major limitation of the non-isothermal TGA analysis as the basis for this model was the inability to characterize the oil and gas composition due to the small sample mass used in the TGA. Increase number of test data using different experiments to further validate the model and to ensure robustness of the shale oil model. Model embedded in icon, PETRONAS steady state process simulation software. The model can be used as a tool to predict oil and gas production capacity for given shale sample.
WAY FORWARD Extend study of the kerogen and bitumen decomposition reactions To Include carbonate decomposition. Varying the samples from different shale deposits to further validate the model. Validating model with existing shale mathematical models. Consider results of isothermal operations or use of other retorting methods. Include a more detailed reaction set as part of the model. Most importantly hydro-coking and hydro-cracking reactions Developing a new experimental methodology using other gas medium More detailed mathematical derivation Physical and chemical characterization with kinetics and reaction mechanisms would also assist in the development of a more comprehensive model.
WAY FORWARD Consider an extensive study on the effects of particle size, mass and heat transfer and reactor design on shale decomposition. Consider the various aspects of shale oil upgrading such as oily fines and loss of oil along the line. Improvements in the model to increase robustness and user friendliness. The model would be tested using icon where further trials would be conducted and downstream processing of the shale oil (upgrading) would be possible.
Thank You
PRESENTATION OUTLINE Introduction to Malaysia PETRONAS An Overview Shale Oil Modeling Questions