IBP1219_12 DIESEL YIELD IMPROVEMENT AND FCC ENERGY RECOVERY Andrew W.

Sloley1,

Copyright 2012, Brazilian Petroleum, Gas and Biofuels Institute - IBP

This Technical Paper was prepared for presentation at the Rio Oi & Gas Expo and Conference 2012, held between September, 1720, 2012, in Rio de Janeiro. This Technical Paper was selected for presentation by the Technical Committee of the event according to the information contained in the final paper submitted by the author(s). The organizers are not supposed to translate or correct the submitted papers. The material as it is presented, does not necessarily represent Brazilian Petroleum, Gas and Biofuels Institute opinion, or that of its Members or Representatives. Authors consent to the publication of this Technical Paper in the Rio Oil & Gas Expo and Conference 2012 Proceedings..

Abstract
Heat recovery modifications affect FCC LCO yields both directly and indirectly. Direct changes improve LCO recovery by improved fractionation of LCO from both slurry and naphtha. Indirect changes increase LCO yields by increasing FCC reactor feed temperature. Improved diesel yields by direct changes (or higher recovery of the existing diesel) impose changes in internal liquid rates and column temperature profiles. Mechanical and reliability limits must be respected to maintain unit reliability. High diesel recovery from slurry oil increase the slurry oil temperatures. Reliable operation requires keeping the slurry oil operating temperature below roughly 382C (720F). Higher slurry temperatures create a high probability of coke formation in the main fractionators. Close attention to mechanical details is required for reliable operation at 382C (720F). High diesel recovery from naphtha product reduces tower top temperatures. This reduces the available driving force for heat integration. Reduced top temperatures also create the potential for chloride-related and water related corrosion problems. Proper design of equipment can circumvent both these problems. Improved diesel yields by indirect changes creates more shifts heat to feed preheat. This reduces the available heat to other services. The changing yield structure also modifies the required internal liquid rates inside the main fractionators. Again, careful attention to design for heat recovery at low temperature differences is required to maintain the duty to the FCC gas plant. A series of modifications to improve control, increase heat recovery at low temperatures, and circumvent some of the more serious maintenance problems is required.

1.0 Background
Fluid catalytic cracking (FCC) is a key refinery conversion operation. Traditional FCC operation uses catalysts and equipment optimized for naphtha and light olefins production. This achieves maximum gasoline production for the refinery. Over the last decade, the refining market growth has been much stronger for diesel fuels than for gasoline. FCC catalysts have been reformulated to increase light cycle oil (LCO) yields. LCO is the diesel boiling range material produced in the FCC unit. Less understood is the idea that diesel yields can be significantly improved with FCC main fractionator and gas plant modifications. The FCC main fractionator is the heat recovery and distillation tower that performs the initial separation of products downstream of the reactor section. The gas plant takes naphtha and lighter material from the main fractionator and separates these streams into light ends, recovered olefins streams, and stabilized naphtha streams. For a modern FCC unit, the main fractionator and gas plant are linked by heat integration systems. Heat removed from the FCC provides energy for the gas plant distillation tower reboilers. Heat recovery modifications affect FCC LCO yields both directly and indirectly. Direct changes improve LCO recovery by improved fractionation of LCO from both slurry and naphtha. Indirect changes increase LCO yields by increasing FCC reactor feed temperature. In concept, the FCC is a simple process. FCC units perform two basic functions. The first function is to break relatively high molecular weight hydrocarbon molecules into lower molecular weight molecules. The feed to the unit is a gas oil stream with an atmospheric equivalent boiling point range (AEBP) of roughly 350C to 600C (~660F to

______________________________ 1 Chemical Engineer, Principal Engineer CH2M HILL

Rio Oil & Gas Expo and Conference 2012 1120F). Products range from fuel gases to an aromatic rich heavy slurry oil. Overall, the liquid product yield from the FCC shifts to liquids with a higher hydrogen-to-carbon ratio. The second function is to reject carbon from the process. The carbon rejection is a key step in meeting the overall objective of making products with a higher hydrogen-to-carbon ratio. The rejected carbon deposits as coke on the catalyst. The coke is burned and the carbon leaves the process as carbon dioxide. When the oil enters the process it is heated to improve injection into the catalyst and to control reactor heat balance. The entering oil is injected into a hot catalyst. The catalyst is a granular particulate. The oil vaporizes when mixed with the catalyst. Vaporized oil, injected steam, and catalyst create a solid-gas fluidized system. The low density fluidized bed creates a pressure differential between parts of the unit. The low density fluidized mixture rises. The oil and catalyst mixture reacts in a riser before entering a separation vessel for catalyst-oil separation in cyclones. Reaction products include hydrocarbons across a large range of molecular weights plus coke. The coke sticks to the catalyst. After separation, the catalyst coke is burned by blowing air through it. The burning heats the catalyst and drives the entire process thermodynamics. The vaporized hydrocarbon products and other gases from the FCC cyclones go to the FCC main fractionator. The main fractionator condenses liquid products and performs and initial separation of liquid streams. The lighter naphtha product stream plus condensable liquids are sent to an FCC gas plant for further separation. A typical FCC gas plant produces a fuel gas product (ethane and lighter), propene-propane (propylene-propane) liquids, mixed C4 products, and a stabilized naphtha stream. A traditional FCC yield balance has been roughly two volumes of material for gasoline production versus one volume of material for diesel production. This is the underlying logic for the oft-quoted 3-2-1 refinery economics cracking margin estimates. Over the last decade, diesel demand growth has dramatically exceeded gasoline demand growth. Europe has been the leader in this field. However, most refinery markets have seen similar situations. FCC catalyst suppliers have made great strides in developing catalyst formulations that shift the FCC yields to more LCO and less naphtha and olefins. The new catalysts make more LCO from the reactor. However, that does not mean all the additional LCO is effectively recovered. What really counts is not just the reactor yields. What really counts is the total yield from the unit. Significant yield can be lost due to energy recovery constraints imposed by the main fractionator and gas plant.

2.0 Case Study

A comparison basis for a 4,550 tpd (50,000 bpd) feed rate FCC unit illustrates recovery and yield; heat integration; control; and capacity shifts for different options to recover more diesel. For the base configuration, the following possibilities are examined: Increased fractionation for improved LCO recovery from heavier products (HCO and/or slurry oil). The improved fractionation may be from either increased reflux or increased fractionation stages. Increased heat recovery into feed by shifting gas plant absorber deethanizer duty to lower level heat. Reliability problems associated with LCO recovery from bottoms product (high bottoms temperature operation). Control of internal liquid rates in the main fractionator. Increased fractionation for improved LCO recovery from lighter products (heavy naphtha) via side-stripping. For each of these factors fundamental heat and material balance issues are examined. Equipment configurations that can reliably reach the required operation are shown. Reasons behind the choices made are explained. The analysis of how to get more diesel from the FCC starts with an examination of the reactor conditions that get maximum LCO yield. In general, higher oil feed temperatures to the unit increase LCO yield. Most FCC units include feed preheat as one service attached to the FCC main fractionator. Some units include a fired heater for control of the feed temperature. Others lack the fired heater. Yield benefit economics normally vastly outweigh direct energy economics. Both together can be very attractive. Increasing heat recovery from the FCC main fractionator to the feed can increase the unit LCO yield. However, increasing heat recovery to feed decreases available heat to the gas plant. To meet the gas plant requirements, the gas plant towers must be shifted to lower level heat sources. This requires changes to recover heat at lower temperature driving forces. The starting point for the analysis is the FCC product temperature enthalpy curve. This curve shows the maximum heat recovery possible with no product fractionation. Product separation requires reflux in the fractionation column. Generating reflux shifts duty from a high-temperature recovery level to a low temperature recovery level. Generating reflux also increases vapor traffic in the main fractionator. The most critical separation section of the main fractionator is the LCO-HCO or LCO-slurry section.

Rio Oil & Gas Expo and Conference 2012 Increased reflux to recover more diesel in the LCO reduces the duty available for feed preheat. Colder feed temperatures reduce diesel yield. Optimum operation must have equipment that can reach the optimum heat balance for the entire range of feed qualities, catalysts, and operating conditions required. Equipment includes control systems. Reflux changes imply heat balance changes. The heat is shifted from one part of the main fractionator to another by varying internal liquid rates. For a modern unit, the liquid rate shifts in the critical LCO-HCO or LCO-slurry section. Liquid rates in this section are very close to the operating limits of fractionation equipment. Additionally, liquid rates are so low that precise control is required. The best control method is to run the column at a total liquid draw control reflux to the fractionation section by direct metering and flow control. This maximizes diesel yields. Improved yields and fractionation increase the main fractionator bottoms temperature. Removing LCO from the bottoms makes the bottoms heavier. Heavier bottoms composition results in higher operating temperatures. Higher temperatures have both benefits and costs. The benefit is higher temperatures for feed preheat. The cost is increased risk of coking in the main fractionator. Coking results from a combination of time and temperature. Long residence times plus high temperatures generate coking problems. Steps to minimize coking by reducing temperatures are required. This is a direct trade-off against heat recovery to feed. Optimum FCC economics requires balancing equipment, operations, and process requirements to get maximum capacity and yield with high reliability. Major points are illustrated by examination of a model FCC unit. Significant improvements in diesel recovery can be made with a careful approach based on a fundamental understanding of both equipment and process constraints.