Effect of Vanadium and Nickel Oxides on Effect of Vanadium and - PowerPoint PPT Presentation

Effect of Vanadium and Nickel Oxides on Effect of Vanadium and Nickel Oxides on Petcoke Petcoke Ash/Slag Viscosity Under Gasification Petcoke Petcoke Ash/Slag Viscosity Under Gasification Ash/Slag Viscosity Under Gasification Ash/Slag Viscosity Under Gasification Conditions Conditions Sarma V. Pisupati Sarma V Pisupati* Aditi Khadilkar John and Willie Leone Family Department of Energy and Mineral Engineering f E d Mi l E i i Presented at EMS Energy Institute New Delhi, February 11-12, 2016

Presentation outline • Introduction • Introduction • Differences between Pet coke and coal • Inadequacies in predictive capabilities • Research objectives of this study • Experimental setup and samples used • Influence of Ni and V on the slag viscosity Influence of Ni and V on the slag viscosity • Interaction mechanisms • S • Some conclusions and future direction l i d f t di ti

Gasification: A Commercial Reality Nakoso, Japan Tianjin, China Polk, FL Wabash, IN Analysis of USDOE and other project reports indicated over 300 issues that needed to be solved for reliable operation. "Reliance Industries' Jamnagar, India Buggenum, Netherlands Puertollano, Spain Edwardsport, IN Jamnagar project...is one of the world's f th ld' largest gasification projects, processing 9.8 million t/a petroleum coke from t l k f the adjacent Reliance refineries.“ Power Magazine

Gasification of coal is growing in developing countries for chemicals countries for chemicals Source: Higman, C., State of Gasification Industry: Worldwide Gasification database 2014 Update, Gasification Technologies conference, Washington D.C., 2014

Gasifiers operational experience shows issues with availability issues with availability IGCC availability is GCC a a ab y s therefore, the most important technical issue governing the success or failure of these plants failure of these plants. Source: Barnes, Ian, Recent operating experience and improvement of commercial IGCC, IEA report 113/10, 2013

Petroleum coke as gasification feedstock is increasing is increasing • The amount of petroleum coke, a by- p , y product of the oil refining industry, has been increasing and is expected to continue to increase. • Due to low reactivity, high gasification temperature is required. Entrained-flow t t i i d E t i d fl gasification at high temperature and high pressure is more suitable for petroleum pressure is more suitable for petroleum coke gasification • Ash of petroleum coke is mainly Ash of petroleum coke is mainly composed of vanadium and nickel.

Petcoke availability Source: http://www.Roskill.com/petcoke accessed on Jan 24, 2016

Composition of slag from coal and petcoke from entrained flow gasifier (Texaco) are different g ( ) Coal Petcoke Eastern Western Type A Type B SiO2 52.1 42.0 4.4 40.6 Al2O3 15.4 25.0 1.5 9.6 Fe2O3 Fe2O3 7 3 7.3 20 9 20.9 23 0 23.0 6 3 6.3 CaO 17.4 9.5 7.5 1.4 MgO 3.7 -- -- 2.4 NiO NiO -- -- 20 9 20.9 14 0 14.0 V2O5 -- -- 40.3 16.6 Others 4.1 2.6 2.5 9.1 Carbon% 9,5 9.7 0.5 0.9 Ash Fusibility, °F Source : Najjar, M. S., Groen, J.C., Craig, J.R., ID ID 2120 2120 2140 2140 -- -- ACS Fuel Chemistry Div. Preprints, NY. August 1991 y p , g ST 2150 2210 -- -- FT 2250 2430 >2700 >2700

Rheological properties of petcoke slag need to be studied need to be studied High viscosity High viscosity – Difficult to remove Difficult to remove Low viscosity- Refractory corrosion Operating conditions need to be selected for optimum viscosity for optimum viscosity Models for prediction of viscosity of coal slag are well developed. However, methods g p to predict viscosity of petcoke slag need development. FactSage is also-not an adequate tool for this as Vanadium compounds not present in the solution database. It predicted more solid phase than actually present solid phase than actually present. Source: Marc A. Duchesne et al., Flow behaviour of slags from coal and petroleum coke blends

Slag Viscosity • Several methods of estimating or measuring the critical viscosity temperature of molten coal ash slags critical viscosity temperature of molten coal ash slags have been developed over time: • Empirical modeling based on ash cone fusion temperatures, Empirical modeling based on ash cone fusion temperatures, • Direct measurement of slag viscosity as a function of temperature, and • Thermophysical modeling based on coal ash composition P.Y. Hsieh et al. / Fuel Processing Technology 142 (2016) 13–26

Slag formation and ash fusion temperatures • The AFT results only indicated the initial • The AFT results only indicated the initial deformation temperature (IDT) at 1300 °C, whereas slag formation already , g y started to take place from 1000 °C. • An AFT analyses only supplies y y pp information on the temperature where a mass of material, enough to deform the structure of the cone, starts to slag. t t f th t t t l J.C. van Dyk et al. Fuel , 88 (2009) 67–74 • The AFT also gives no information on the properties of the slag below that point. ti f th l b l th t i t

Recent study of synthetic slags did not show a good a good correlation between ST and Tcv g g NETL (USDOE) Correlation between ST and HT with Tcv was found to be poor, with R 2 values between 0.04 and • 0.06.We observed a positive linear correlation between FT and Tcv, with a R 2 value of 0.77. p • They also found that it was possible to fit a plane to the Tcv data, using the silica-to-alumina ratio (S/A) and the iron(III) oxide equivalent (F) as independent variables (R 2 = 0.96) P.Y. Hsieh et al. , Fuel Processing Technology, 142 (2016) 13–26

Kalmanovitch or Modified Urbain Equation Modified Urbain Equation Calculation Procedure Kalmanovitch DP, Frank M. An effective model of viscosity for ash deposition phenomena . University of North Dakota Energy and Mineral Research Center North Dakota, Energy and Mineral Research Center, Energy Foundation Conferences, Grand Forks; 1988. p. 89–10

Plastic Viscosity (Einstein-Roscoe equation) • S.-H. Seok, S.-M. Jung, Y.-S. Lee, D.-J. Min, Viscosity of highly basic slags, ISIJ Int. 47 2007) 1090–1096 • Mukherjee, A., Pisupati, S.V. “Inter-particle interactions in highly concentrated coal-water slurries and their effect on slurry viscosity", Energy and Fuels , 2015, 29 (6), pp 3675–3683. • Mukherjee, A., Rozelle P. L., Pisupati, S.V. “Effect of Hydrophobicity on Viscosity of Carbonaceous Solids-Water Slurry", Fuel Processing Technology , 2015, Vol. 137, pp 124-130.

Research Objectives • To understand the effect of vanadium and nickel oxides on • To understand the effect of vanadium and nickel oxides on Petcoke slag viscosity • To modify existing empirical correlations such as the Modified Urbain equation for prediction of viscosity of Petcoke slag. Urbain equation for prediction of viscosity of Petcoke slag.

Systematic variation of V and Ni based oxides using synthetic ash performed oxides using synthetic ash performed Effect of V oxides Effect of Ni oxides Effect of interaction between V and Ni between V and Ni oxides 3 runs with 3 runs with increasing Effect of V 2 O 3 increasing V 2 O 5 5 NiO content, without NiO content without 3 runs with content, without V 2 O 5 increasing V 2 O 3 NiO conversion. Containing both Containing both V 2 O 5 and NiO A baseline without any V or Ni oxides, containing other oxides in the same ratio was also used

Composition of slag samples used in the study the study SiO 2 Al 2 O 3 Fe 2 O 3 CaO TiO 2 K 2 O MgO Na 2 O SrO BaO MnO Baseline 48 07 19 73 14 60 4 867 1 867 5 867 1 467 3 733 1 467 0 267 0 067 48.07 19.73 14.60 4.867 1.867 5.867 1.467 3.733 1.467 0.267 0.067 Ratios studied V 2 O 5 NiO V 2 O 3 0 0 0 0 35 35 E Example comparing measured l i d 0 viscosities of synthetic and real ash 35 0 0 0 25 20000 0 0 25 25 0 0 0 ity (Pa.s) 15000 0 15 0 15 0 10000 0 0 8 75 8.75 26 2 26.2 Viscos 0 5000 17.5 17.5 0 26.2 8.75 0 24 9 24.9 8 75 8.75 1 30 1.30 1350 1400 1450 21 8.75 5.25 BR_ASTM BR_syn ash 13.1 8.75 13.1 Sample Temperature (°C)

Several parameters that affect slag viscosity were considered viscosity were considered Chemical composition iti (Ni, V content) Gaseous Temperature atmosphere atmosphere Slag Viscosity Number of Number of Size of Si f crystals crystals Oxidation Oxidation state of phases 18

Methodology used for measurement of slag viscosity slag viscosity S Synthetic ash th ti h C Compact slag t l Viscosity Vi it Grinding of slag Preparation preparation Measurement Theta HT - Rotating 4000 Example of p Viscometer Specifications Viscometer Specifications cosity (Pa.s) measurement 3000 • Maximum furnace data temperature = 1600 ˚C 2000 • Viscosity range possible = Viscosity range possible Visc 100 - 4 x 10 7 cP 1000 • Any gaseous atmosphere 0 or under vacuum 1300 1350 1400 1450 1500 Temperature (˚C) 19