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IBP1283_12 IMPACT OF FCC REGENERATOR DESIGN IN THE NOx EMISSIONS Hugo B. Pereira1, Emanuel F. Sandes1, William R.

Gilbert1, Rodolfo E. Roncolatto1, Rodrigo Gobbo1, Luiz C. Casavechia1, William V. C. Cândido2, Patrícia E. Bridi3
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
Fluid Catalytic Cracking (FCC) is the main point source of NOx in the refinery and it is responsible for at least 20% of the total NOx emissions from the refineries. The thermal NOx formation in the FCC regenerator is negligible. However, half of the feed nitrogen is converted to coke, and is burned in the regenerator. The majority of coke nitrogen is reduced to N2 and less than 10% is converted to NOx. This number may vary significantly with the oxygen excess in the flue gas and other operational conditions. With the purpose of evaluating the impact of different regenerator designs in NOx formation, several tests were carried out in the Petrobras FCC prototype unit. The test unit is equipped with adiabatic insulation and a CO boiler, allowing it to reproduce the heat balance of a commercial FCC and to operate either in full combustion or partial combustion. Two different designs of FCC regenerators were evaluated: single stage regenerator (the existing configuration) and two stage regenerator, with the catalyst bed divided into two sections by a structured packing baffle. It was observed in the tests that the combustion regime had a very strong effect on NOx formation. In full combustion, the effect of the FCC operating variables: excess oxygen, combustion promoter content in catalyst and regenerator design could be identified. The two stage configuration was capable of decreasing NOx emissions by 30%. In partial combustion, the effect of the CO-boiler variables on NOx emissions was overwhelming, but the use of the structured packing baffle was able to improve the catalyst regeneration.

1. Introduction
Fluid Catalytic Cracking (FCC) Units are the refinery biggest atmospheric emission point source, responsible for at least 20% of refinery’s total NOx emissions. With a better control of other sources, the relative contribution of the FCC to the refinery total NOx emissions is expected to increase. Moreover, more restrictive legislation for this pollutant is being implemented in ozone saturated regions near large cities, often in areas where the refineries are located. There are three mechanisms that describe NOx formation from fuel combustion. The first, called thermal NOx, occurs when the nitrogen in the air reacts with oxygen at high temperatures. The second is attributed to fast reactions between nitrogen in the air and free radicals produced in the fuel combustion and it is called prompt NOx. The last, and the most important for FCC, is the combustion of the nitrogen containing species present in the fuel and, for this reason, it is called fuel NOx. In the FCC regenerators, the majority of NOx is produced from the coke combustion. The Thermal and Prompt NOx are negligible in the FCC regenerator conditions. Studies conducted in pilot plant and in industrial units revealed that nitrogen feed nitrogen has a typical distribution in the effluent streams (Zhao et al., 1995; Rosser et a., 2004; Sexton, 2010). The nitrogen balance results show that 10% or less of the feed nitrogen is encountered in gas stream as ammonia, 35% to 50% goes to the liquids products and 35 to 50% goes to coke. The ammonia in the refinery fractionation section is absorbed by the condensing sour water. The majority of coke nitrogen is converted to N2 and only 6 to 25% to NOx. Thus, the authors conclude that only 3 to 13% of feed nitrogen is transformed into NOx.

______________________________ 1 Chemical Engineering - PETROBRAS 2 Maintenance Technician – PETROBRAS 3 Chemical Engineering – POSSEBON ENGENHARIA

Rio Oil & Gas Expo and Conference 2012 There are a few strategies for controlling NOx emissions from FCC units. The most common are feed hydrotreatment and flue gas post-treatment, but these options are more capital intensive than “in situ” methods. In other words, the use of additives, small changes in hardware design and optimization of operating conditions are easier to implement and are cheaper. The purpose of this work is to present the results of tests carried out in a pilot plant, in which two different regenerator configurations were tested: single stage and two stage regenerator, with the catalyst bed divided into two sections by a baffle located 1/3 of the way up the bed. The tests were done with typical Brazilian FCC feeds, with high nitrogen content.

2. Experimental
The tests were performed in the FCC pilot plant located in São Mateus do Sul - Paraná, Brazil. The pilot plant capacity is about 5 m³/d for vacuum heavy gasoil (VGO) and 3 m³/d for atmospheric tower bottoms (ATB). The test unit is equipped with adiabatic insulation and a CO boiler, allowing it to reproduce the heat balance of a commercial FCC and to operate either in full combustion or partial combustion. Two different regenerators designs were evaluated in the tests. The single stage (SS) is a bubbling bed model and was the existing configuration of the unit. A structured packing baffle (BA) was installed in the original vessel, dividing the catalyst bed into two counter-current sections, according to the design proposed by Miller et al. (1999). Figure 1 illustrates the two configurations. The feeds used in the tests were typical of Brazilians refineries streams and their characterization is presented in Table 1. Both the VGO and the ATB have a high content of total nitrogen and of basic nitrogen. A summary of the test’s experimental conditions indicating the regenerator configuration and feed used is presented in Table 2. The SS and BA configurations were tested in total and in partial combustion regime. The operational conditions used in each test are shown in the Table 3.

3. Full Burn Tests
The tests using the regenerator in total combustion were conducted with SS and BA configurations. The catalyst and operation conditions used for processing ATB were different than the ones used for VGO. The catalyst used in ATB tests contained combustion promoter. As expected, NOx emissions were lower for the catalyst without combustion promoter. The VGO catalyst didn’t have any combustion promoter and when it was dosed to achieve 1 ppm of platinum, NOx emissions increased by 40%, as presented in table 4. Table 5 shows the mass balances of the unit for each test. The ATB feed as expected produced substantially more coke than the VGO. However, the differences in yield structure between the SS and the BA configurations were minor in the full combustion operation. The nitrogen product distribution calculated from the pilot unit results was in good agreement with the literature (Table 6). The ammonia produced in the cracking reactions was absorbed and measured in the sour water and represented approximately 10% of the feed nitrogen. The nitrogen remaining in the cracked oil product varied between 20 and 30% and the nitrogen estimated in the coke (N2 in the flue gas calculated by difference) varied between 60 and 70%. The percentage of the feed nitrogen released as NOx was only 1 to 4%. Consistent with expectations, high conversions of basic nitrogen were observed. NOx emissions for the VGO feed combustion promoter free catalyst were the same for the two regenerator configurations, SS and BA (figure 2). On the other hand with the ATB feed and combustion promoter blended catalyst there was a significant reduction in NOx for the BA configuration (figure 3).

4. Partial Combustion Tests
Tests in partial combustion regime were also performed with the two regenerator configurations: SS and BA. The regenerator bed temperature profile was changed in BA configuration. As expected, the upper bed section temperature was reduced, demonstrating that the baffle indeed reduces the backmixing between the upper and lower sections of the fluidized bed (Table 7).

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Rio Oil & Gas Expo and Conference 2012 The BA configuration was very effective for catalyst regeneration, resulting in lower carbon on regenerated catalyst than the SS configuration for the same CO2/CO ratio (Table 8). Carbon on regenerated catalyst in its turn was a determining factor of conversion (Table 9). The nitrogen product distribution obtained from the mass balance (Table 10) shows a decrease of nitrogen content in the liquid products with conversion. The percentage of feed nitrogen transformed into NOx is about 2 and 6% and is larger than that observed in full combustion tests. Contrary to initial expectations, there was no correlation between NOx emissions and the FCC regenerator main variables in the partial burn operation. Partial burn NOx was entirely dominated by the CO boiler variables such as the excess oxygen in the CO boiler flue gas.

5. Conclusion
The combustion regime defines the mechanisms of NOx formation. In full combustion, the main parameters affecting NOx are the FCC regenerator variables: oxygen excess, combustion promoter content in catalyst, operational conditions and regenerator configuration. The use of a baffle to create a staged combustion bed in units processing atmospheric tower bottoms in full combustion can decreased NOx emissions by at least 30%. In partial combustion, the CO-boiler’s variables dominated NOx emissions. The two stage baffle configuration could improve the regenerator performance, reducing carbon on regenerated catalyst and increasing cracking conversion.

6. Figures

Figure 1. Regenerator design of (a) single stage – SS and (b) baffled two stage (BA)

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VGO feed nitrogen converted to NOx, % wt.

1,0 0,8 0,6 0,4 0,2 0,0 0,0 1,0 2,0 3,0 4,0 5,0 6,0

Flue gas excess oxygen, % molar SS BA

Figure 2. Percentage of feed nitrogen converted to NOx as a function of flue gas excess oxygen and regenerator configuration (SS or BA) for the VGO feed in full combustion.

ATB feed nitrogen converted to NOx, % wt.

5,0 4,0 3,0 2,0 1,0 0,0 0,0 1,0 2,0 3,0 4,0 5,0 6,0

Flue gas excess oxygen, % molar SS BA

Figure 3. Percentage of feed nitrogen converted to NOx as a function of flue gas excess oxygen and regenerator configuration (SS or BA) for the ATB feed in full combustion.

7. Tables
Table 1. Feed characterization

T10%, ºC T30%, ºC

VGO 370 435

ATB 380 459
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T50%, ºC T70%, ºC T90%, ºC Asphaltenes, %wt. RCR, %wt. ºAPI Total nitrogen, ppm Basic nitrogen, ppm Sulfur, ppm Fe, ppm Ni, ppm Na, ppm V, ppm

486 545 638 <0.5 2.0 19 3,600 1,300 6,700 4.3 2.4 0.5 2.2
Table 2. Test Summary

523 595 685 1.5 7.0 17 3,900 1,430 4,500 6.8 10.6 2.7 16.5

Regenerator Configuration SS SS SS SS BA BA BA BA

Feed

Combustion regime Full Full Partial Partial Full Full Partial Partial
Table 3. Operational Conditions

Catalyst

CO promoter

VGO ATB VGO ATB VGO ATB VGO ATB

A B A B A A A A

No Yes No Yes No No No No

Variable Reactor Temperature, ºC Feed rate, m³/d Feed Temperature, ºC Reactor Pressure, kgf/cm² Riser water, feed %

VGO in full combustion 550 5.1 320 2.10 -

VGO in partial combustion 550 5.4 350 2.10 -

ATB in full combustion 545 2.5 260 1.65 7.0

ATB in partial combustion 545 2.5 210 1.65 -

Table 4. Effect of combustion promoter in VGO full combustion test

Variable Flue gas oxygen content, % NOx emission, ppm

Catalyst without combustion promoter 5.0 56

Catalyst with combustion promoter 5.0 78

Table 5. Mass balance in full combustion tests (%wt.). 5

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Conversion GC+H2S LPG Gasoline LCO DO Coke

VGO / SS 68 4 15 42 18 14 7

VGO / BA 70 5 18 40 17 13 7

ATB / SS 74 3 14 45 15 11 12

ATB / BA 73 3 15 43 15 12 12

Table 6. Nitrogen balance in full combustion tests (%wt.).

Water sour Liquid products N2 NOx Basic Nitrogen to coke

VGO / SS 8 30 61 1 83

VGO / BA 11 30 58 1 85

ATB / SS 12 18 66 4 91

ATB / BA 9 20 69 2 91

Table 7. Average temperature gradient in Partial Combustion Tests

SS – Base Case Lower bed Upper bed Diluted phase 0 0 0

VGO / BA, T (ºC) 0 -20 -30

ATB / BA, T (ºC) 0 -12 -17

Table 8. Average regenerated catalyst carbon content in the partial combustion tests processing VGO

CO2/CO ratio 1.5 2.5 3.0

SS 0.910 0.176 0.070

BA 0.330 0.067 0.025

Table 9. Mass balance in partial combustion tests (%wt).

CO2/CO ratio Conversion GC+H2S LPG Gasoline LCO DO Coke C on Rg Catalyst

VGO / SS 1.5 57 7 15 30 18 25 5 0.91

VGO / BA 1.5 67 5 18 38 18 15 6 0.33

ATB / SS 2.0 67 4 14 40 17 16 9 0.44

ATB / BA 2.0 71 4 19 39 16 13 9 0.23
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Table 10. Nitrogen balance in partial combustion tests (%wt).

Sour Water Liquid products N2 NOx Basic Nitrogen to coke

VGO / SS 10 46 40 4 83

VGO / BA 20 36 40 4 85

ATB / SS 29 30 38 3 84

ATB / BA 26 28 41 5 87

8. References
MILLER, R. B., YANG, Y-L, JOHNSON, T. E., MCCARTHY, S. J., SCHARTZ, K. W. REGENMAX TM Technology: Sataged Combustion in a single regenerator – AM-99-14. In: NPRA Annual Meeting, Santo Antonio, USA: mar., 1999. ROSSER, F. S., SCHNAITH, W., WLKER, P. D. Integrated view to understanding the FCC NOx puzzle. In: AIChE Annual Meeting, Austin, USA: nov., 2004. SEXTON, J. A. Advances in Fluid Catalytic Cracking, p. 257-351, 2010. ZHAO, X., PETERS, A. W., WEATHERBEE, G. D. The Origin of NOx in the FCCU Regenerator – AM-95-59. In: NPRA Annual Meeting, San Francisco, USA: mar., 1995.

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