FCC Catalyst Evaluation

1.0 Introduction
Catalyst management is a very important aspect of the FCC process. Selection and management of the catalyst, as well as how the unit is operated, are largely responsible for achieving the desired products. Proper choice of a catalyst will go along way toward achieving a successful cat cracker operation. Catalyst change-out is a relatively simple process and allows a refiner to select the catalyst that maximizes the profit margin. Although catalyst change-out is physically simple, it requires a lot of homework. As many catalyst formulations are available, catalyst evaluation should be an ongoing process; however, it is not an easy task to evaluate the performance of an FCC catalyst in a commercial unit because of continual changes in feedstocks and operating conditions in addition to inaccuracies in measurements. Because of these limitations, refiners sometimes switch catalysts without identifying the objectives and limitations of their cat crackers. To ensure that a proper catalyst is selected, each refiner should establish a methodology that allows identification of real objectives and constraints and ensures that the choice of the catalyst is based on well-thought-out technical and business merits. In todays market, there are over 120 different formulations of FCC catalysts. Refiners should evaluate catalysts mianly to maximize profit

opportunity and to minimize risk. The right catalyst for one refiner may not necessarily be right for another.

2.0 Catalyst Selection Methodology

One of the most important parameters that specify the competitiveness of a refinery FCC unit is the proper selection of catalyst, since the catalyst type determines both quantity and quality of the catalytic cracking products. Laboratory of Environmental Fuels and Hydrocarbons evaluates FCC catalysts, through MAT tests, specifying each catalyst activity and selectivity. For the above purpose a Short Contact Time Microactivity Test unit (SCT-MAT) was constructed in CPERI, at the beginning of 1999, in order to replace the conventional MAT unit, as an attempt to follow the worldwide inclination of short residence times during the FCC reaction. The unit's excellent performance along with the compatible results derived by comparing it with the FCC pilot plant soon lead to the construction of an identical unit (January, 2001). Catalysts are evaluated following a standard FCC evaluation protocol. Initially the catalysts are deactivated; either by metal deposition or by steaming sieved and finally tested in one of CPERI's MAT units. At least eight different tests are carried out for a specific catalyst and for each test detailed experimental and normalised mass balances are quoted. The individual product yields are plotted vs. conversion and catalysts evaluation is completed by comparing their product yields at a constant conversion level (65%wt). The microactivity test (MAT) unit was originally designed to determine the activity laboratory deactivated and selectivity fluid catalytic of either cracking equilibrium or catalysts. (FCC)

Currently, the MAT unit is accepted as a tool to perform general

laboratory scale FCC research and testing because of its simple operation and cost effectiveness. The unit only requires small quantities of catalyst and gas oil for each MAT test, compared with barrels of materials needed for a pilot-scale riser run. A comprehensive catalyst selection methodology will have the following elements: 1. Optimize unit operation with current catalyst and vendor. a. Conduct test run. b. Incorporate the test run results into an FCC kinetic model. c. Identify opportunities for operational improvements. d. Identify units constraints. e. Optimize incumbent catalyst with vendor. 2. Issue technical inquiry to catalyst vendors. a. Provide Test run results. b. Provide E-cat sample. c. Provide Processing objectives. d. Provide Unit Limitations. 3. Obtain vendor responses. a. Obtain catalyst recommendation. b. Obtain alternate recommendation. c. Obtain comparative yield projections. 4. 5. 6. Obtain current product price projections. a. For present and future four quarters. Perform economic evaluations for vendor yields. a. Select catalyst for MAT evaluations. Conduct MAT of selected list. a. Perform physical and chemical analyses. b. Determine steam deactivation conditions. c. Deactivate incumbent fresh catalysts to match incumbent E-cat d. Use same deactivation steps for each candidate catalyst. Perform economic analysis of alternatives. a. Estimate commercial yield from MAT evaluations. Request commercial proposals. a. Consult at least two vendors.

7. 8.

b. c. 9.

Obtain references. Check references.

Test the selected catalyst in a pilot plant. a. Calibrate the pilot plant steaming conditions using incumbent E-cat. b. Deactivate the incumbent and other candidate catalysts. c. Collect at least two or three data points on each by varying catalyst-to-oil ratio.

10. Evaluate pilot plant results. a. Translate the pilot data. b. Use the kinetic model to heat-balance the data. c. Identify limitations and constraints. 11. Make the catalyst selection. a. Perform economic evaluation. b. Consider intangibles-research, quality control, price, steady supply, manufacturing location. c. Make the recommendations. 12. Post selection. a. Monitoring transitions-% changeover. b. Post transition test run. c. Confirm computer model. 13. Issue the final report. a. Analyze benefits. b. Evaluate selection methodology.

3.0 Reactors Used for FCC Studies

Catalytic cracking catalyst development requires the adequate evaluation of catalyst performance. Different kinds of laboratory reactors are available to evaluate catalyst performance. These reactors include fixed bed, fluidized bed, stirred batch, differential, recycle, and pulse reactors (Weekman, 1974: Sunderland, 1976). The testing of catalyst at the laboratory scale can serve many purposes. One possibility is the need of improving catalyst formulation or altogether to develop a new catalyst (Mooreheed et al., 1993). However, a common task for a bench scale unit is to compare the relative performance of two or more catalysts (Mooreheed et al., 1993). Regarding the specific approach used for FCC catalysts, very frequently catalyst evaluations are done on the basis of a microactivity test (MAT). MAT studies are hindered by mismatching of industrial operating conditions. Thus, MAT studies with long catalyst time-onstream, low hydrocarbon partial pressures, and cumulative coke content do not represent industrial operation. It is our view that to represent, in a laboratory scale unit, the reaction environment of a commercial riser, the operation of this unit has to be carefully controlled. The present dissertation considers in this respect, a novel CREC Riser Simulator invented by de Lasa (1992) at the University of Western Ontario.

3.1-Microactivity Test (MAT)

The Micro Activity Test (MAT) has been a main tool for basic FCC research, and this includes catalyst selection and feedstock evaluation (OConnor and Hartkamp, 1988; Campagna et al., 1986). This test

was developed due to its simplicity, reproducibility, and quickness of evaluation in comparison to tests in a continuous pilot plant. The MAT technique is an ASTM procedure (ASTM D-3907-88) which was developed on the basis of using a fixed bed of 4 grams of catalyst, operated with a continuous oil vapour feed for 75 seconds at a temperature range of 480-550 C and using an average catalyst/oil ratio of about 3. The standard MAT has had limited success predicting commercial unit performance and has provided limiting information about product selectivity (Mauleon and Courcelle, 1985; OConnor and Hartkamp, 1988; Mooreheed et al, 1993). There are important warnings in the technical literature about the value of the data obtained in the MAT for catalyst selection. Some authors claim, without fundamentally based arguments, that the MAT could provide some kind of relative comparison on catalyst activity and coke make selectivity (Humphries and Wilcox, 1990). Although the MAT unit can provide some data for catalyst screening, several important differences exist between MAT and the commercial FCC unit (Mooreheed et al, 1993) as follows; a-) The MAT reactor is based on a cylindrical (ASTM design) catalyst fixed bed with a flow of feedstock flowing through a bed of catalyst. A commercial riser uses instead an upflow of oil and catalyst circulating together (Mooreheed et al, 1993). b-) The MAT uses a cumulative catalyst time on stream of 75 second while a commercial riser uses a short contact time of 3-5 second. c-) The MAT employs a reactant partial pressure much lower than the one of the commercial riser: 0.05 atm for MAT and 1.5 atm for the commercial riser.

d-) Coke profiles develop in the 150 mm long catalyst bed of the MAT and the catalyst deactivates at different rates. On the other hand, in the riser all catalyst particles experience the same feed exposure having at the riser outlet uniform coke concentration. e-) The operation of the MAT provides average results over a 75 second period. These results are by nature different than those taken after 3-5 seconds contact time in the riser. For instance, this difference explains the low olefinicity of the MAT products (Mooreheed et al, 1993). f-) The MAT cannot provide information about catalyst attrition since it is a fixed bed unit. As a result of the above described inadequacies, some

modifications have been suggested to the MAT to provide a more reliable method for catalyst testing (OConnor and Hartkamp, 1988; McElhiney, 1988, Mott, 1987; Tasi et al., 1989). However, and despite the proposed modifications the MAT still allows coke profiles and temperature differences. Consequently, the kinetic modeling of catalytic cracking reactions using the standard MAT test is rather unreliable, and a number of strong approximations are needed (Froissier and Bernard, 1989). Corma et al., (1994) highlighted the limitations and the inadequacies of MAT unit to compare different FCC catalysts made from different materials. These authors pointed out that when two different FCC catalysts, one made from ultrastable Y-zeolite and the other was made of SAPO-37, which had a faujasite structure with different framework composition, were used in the MAT, the tests performed were not reliable. It was recommended, by these authors, to use different tools with short contact times and based on minifluidized beds.

3.2- Pilot plant unit.

A successful scale up procedure is essential for further

advancement of any chemical technology. Usually, if the tested catalyst passes the bench scale reactor test (like the MAT), the following level of demonstration is the pilot plant unit. In this respect, it is extremely important to bridge the differences between the labscale and commercial FCC units. According to Carter and McElhiney (1989), circulating riser pilot plants can provide the best small-scale simulation of commercial FCC yields. Several pilot plants are available for the FCC process, with the favored ones being those with a riser reactor and continuous catalyst regeneration (Yang and Weatherbee, 1989). Davison Circulating Riser (DCR) unit is one of the most effective FCC pilot plants. It includes an adiabatic riser reactor where the reactor temperature is maintained by controlling the circulating rate of the hot regenerated catalyst. This process is identical to the commercial unit. This unit can work in the isothermal mode for certain kinetic studies. It is reported that this unit can be used to process heavy oils and it can be also used for catalyst studies. The DCR unit is 12 feet in height and it has a catalyst and vapor residence time of about 6 and 3 sec respectively (Yang and Weatherbee, 1989). While, these pilot plant units provide, in principle, good simulation for commercial FCC units, they are expensive, difficult and costly to operate, and they are not suited to test large number of catalyst samples. Furthermore, there is an intrinsic difficulty to operate these pilot plants isothermally, showing some limitations in catalyst/oil ratios and contact times (Corella et al., 1986).

3.3- CREC Riser Simulator

As stated, one of the most important challenges for FCC catalyst development has been the one of simulating catalyst performance under commercial conditions and in this respect, a laboratory scale unit is needed (Book and Zhao, 1997). The Riser Simulator is a novel unit invented by de Lasa (1987) to overcome the technical difficulties of MAT units. This unit can be used for several purposes: a) to test industrial catalysts at commercial conditions (Kraemer, 1990), b) to carry out kinetic and modeling studies for certain reactions, c) to develop adsorption studies (Pruski, 1996). d) to use the data of this unit for assessing the enthalpy of cracking reactions. The different characteristics and advantages of the CREC Riser Simulator can be summarized as follows: a-) Temperature, reaction time, cat/oil can be varied in a wide range, b-) Different feedstocks (VGO, gas oil, and model compounds) can be tested, c-) Different chemical reactions such as alkylation, hydrogen transfer, transalkylation, and coke formation can be investigated, d-) Catalyst regeneration is simple and can be conducted at typical regeneration conditions, e-) For testing a catalyst, only a small catalyst sample (0.8 g) can be used throughout many runs at different temperatures, contact times, and cat/oil ratios, f-) For testing a feedstock, only a small amount of feed (0.16 g) is needed,

g-) The Riser Simulator can be operated in a broad range of total pressures, h-) The Riser Simulator can be used in the fluidized bed mode with active mixing of catalyst particles. In this respect, perfect mixing with the absence of coke profiles and gas channeling can be obtained with all catalyst particles being exposed to the same reaction environment. In conclusion, and in order to obtain reliable cracking results, the appropriate tools have to be used in conducting reaction runs. For example, it is well known that to measure catalyst activity and selectivity of FCC catalysts a number of conditions have to be met: a) a short contact time, b) fluidized bed conditions, c) appropriate temperatures, d) adequate hydrocarbon partial pressure, e) representative cat/oil ratio. The CREC Riser Simulator, experimental tool employed in the present study, allows to study FCC catalyst performance under relavant conditions used in commercial units and this secure the value. 1. STEAMING The deactivation evaluation step that of fresh catalysts the normally activity includes test. a

precedes

actual

This

deactivation typically involves the steaming of a catalyst sample at temperatures ranging from 550 to 930 oC for 2 to 24 hr. The primary objective is to deactivate a fresh catalyst such that its performance in the activity test is representative of what is observed when testing a commercially deactivated sample of the same catalyst. In this way, prediction of commercial performance for new catalysts can be made. In addition, the steaming was used in this study to vary the unit cell size.

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Y-Zeolite

Matrix SiO2Al2O3

520-710 m
Figure 3.1. Particles of FCC catalyst.

11

Laboratory steaming of fresh FCC catalysts is generally done in the presence of 100 percent steam in fluidizing nitrogen while temperature is increased to the desired target. Steam, obtained by vaporization of injected water, was introduced and the nitrogen flow was stopped. After a specified period of time (6 hr), the water injection was stopped, the nitrogen was introduced again and the temperature was set back to an ambient level. Then the catalyst was unloaded and screened to remove fines, if necessary. The steaming temperature

was varied in order to change the unit cell size and hence, a large range of unit cell sizes was obtained. For all runs, the catalyst was steamed at constant temperature for 6 hr. For example, a part of fresh catalyst B was steamed at 810 oC for 6 hr, while other parts of fresh catalyst B were steamed for 6 hr at 760 and 710 oC, respectively.

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4.0 CATALYST EVALUATION

The catalytic experiments were carried out in a microactivity test (MAT) unit which is basically a fixed bed reactor, which has been designed according to ASTM D-3907 method. The following section

describes the experimental setup, and the experimental procedures. 4.1 Experimental Apparatus

A schematic diagram of the MAT unit used in this study is shown in Fig. 4.1. The main parts of the unit are: Syringe (used for feed addition) Syringe heater Syringe pump Furnace Glass reactor Liquid product collection system Gas product collection system Analytical balance and weights Chromatographic equipment Carbon analyzer The syringe was 2.5 ml and used for VGO addition. The syringe should be equipped with a multiport, high-pressure valve to allow nitrogen and VGO entry to the reactor through a common feed line. The syringe heater was used to heat the syringe to 405 oC using a heat lamp. The syringe pump has to be able to deliver uniform flow of 10.03 g of VGO in 30 sec.

13

Figure 4.1: Schematic for the MAT unit.

14

A three-zone furnace was used middle zone of 150 mm length and top and bottom zones of 75 mm length each. The temperature controllers of the three zones were calibrated to achieve a constant temperature 5201 oC over the whole length of the catalyst bed (actual bed temperature). A glass reactor of 15.6 mm internal diameter was used. Dimensions and details of the reactor are given in Figure 4.2. Quartz wool is usually put beneath and above the catalyst bed. product was collected in a glass receiver (Fig. 4.3). The liquid

15

Figure 4.2 MAT reactor

16

Figure 4.3: Liquid receiver.

17

The balance was used to weigh the catalyst sample, liquid receiver before and after the reaction, and the syringe before and after the reaction. Analytical weights were of precision grade or calibrated against a set of certified standard weights. An accurate balance was very significant for mass balance. Liquid product was analyzed by GC to determine the boiling range distribution by simulated distillation. The gasoline boiling range was from 0 to 221 oC, light cycle oil (LCO) from 221 to 343 oC, and heavy cycle oil (HCO) from 343 to 650 oC. The GC was equipped with flame ionization detector (FID). The column for simulated distillation is 1/8 x 20 inches stainless steel, 10% UC-W982 on 80/100 mesh Chromosorb PAW. This column was attached to the FID with a 0.030 inch jet. Gaseous product was analyzed by another GC to determine its composition as hydrogen, and C1 to C5 hydrocarbon. A thermal

conductivity detector (TCD) was used. The analytical columns were: Reference column: 20 inch, 2% OV-101 Chromosorb W-HP. on on 100/120 80/100 mesh, mesh,

Analytical columns: 1A. 5 ft, 35% DC-200 Chromosorb P-AW

1B. 24 ft, 20% bis(2-methoxyethyl) adibate on 80/100 mesh, Chromosorb P-AW 2. 3. 6 ft. Porapak Q, 80/100 mesh 10 ft, molecular sieve 13X, 45/60 mesh

All columns were 1/8-inch OD stainless steel. The carbon analyzer used was CS244 (LeCo Corp.). Oxygen was supplied to the unit directly.

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Demands on the MAT lab involve more than the simple rating of catalyst activities. At the very least, there is sufficient interest in characterizing the coke and hydrogen producing properties of a catalyst to require collection and analysis of the gas and to determine the carbon on the discharged catalyst. Calculation of a weight balance is another reason for obtaining samples for gas and coke analyses. Most MAT

laboratories are capable of obtaining mass balance of around 95% in studies using VGO feedstocks. A major interest for the MAT is in obtaining product selectivity data because it is recognized that this inexpensive laboratory test can provide good replication of plant yields if suitable chromatographic technology is used with both the liquid and gaseous products .

MAT operating conditions are shown in Table 4.1. The commercial vacuum gas oil (VGO) was obtained from Neghishi Refinery and its properties are shown in Table 4.2.

Before testing the prepared catalysts the MAT unit was examined by running a commercial catalyst. The same catalyst, conditions and almost the same catalyst amount was tested twice to investigate the reproducibility of the unit. The MAT data for both runs is shown in

Table 4.3. Hence, it can be said that the unit was ready to examine the prepared catalysts.

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Table 4.1: Mat operating conditions Temperature Feed rate Amount of catalyst Feed type 520 oC 1 g/30 sec 0.53.0 g VGO

Table 4.2: MAT feed oil properties

Specific gravity (15/4 _C) Sulfur (wt %) Conradson carbon (wt %) Refractive index (15 _C) Bromine number Ni (ppm) V (ppm) Distillation data (vol. %) 10 50 90

0.8821 0.18 0.09 1.4719 3.2 <1 <1 ASTMD-1160 Temp. (_oC) 376 oC 437 oC 518 oC

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Table 4.3: The yield reproducibility of MAT unit Test cat/oil ratio Conv. (wt%) Component H2 C1 C2 C2 C3 C3 iC4 nC4 t2C4 1C4 iC4 c2C4 Total C4 C5 + Gasoline LCO HCO Coke Total 1 2.78 68.3 Yield (wt%) 0.70 0.26 0.20 0.36 0.54 4.86 4.00 0.60 2.08 1.58 1.98 1.58 7.23 48.41 19.12 12.61 1.66 99.93 0.60 0.28 0.21 0.39 0.55 4.82 3.87 0.59 1.97 1.52 1.91 1.50 6.91 47.97 18.37 14.17 1.74 99.93 2 2.82 67.5

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4.2

Procedure

In the MAT test, 3 g of catalyst was packed in the glass reactor (Fig 4.2). The reactor was installed in a vertical tube furnace and purged with nitrogen until it attained the required temperature (520
o

C).

Vacuum gas oil (VGO) was pumped using the syringe pump at a controlled rate to deliver 1 g over 30 sec. The feed passed through a pre-heater before it contacted the catalyst bed. In the MAT setup, as shown in Fig. 4.1, the reactor outlet was connected to the liquid product receiver immersed in an ice bath. The outlet of the receiver was connected to a gas holder from which water was displaced. Following the injection of the VGO, the MAT reactor was swept with an inert gas (usually nitrogen) for a period of time sufficient to sweep all vapors from the reactor and to transfer all noncondensed material into the gas holder. This stage was called stripping and it usually lasted around 25 min. At this point the products of the reaction were collected in three locations: the coke and a small amount of liquid residue are in the reactor; most of the liquid are in the receiver; and the gaseous products are in the gas holder. After the stripping stage, the liquid receiver was removed from the ice bath and warmed to 25 oC in order to remove the liquid product easily from the receiver. Nitrogen should flow to the gas collector to remove the volatile materials that would otherwise be lost during handling. Following the gas sweep, the liquid receiver was disconnected, sealed and weighed. The volume of gas product and flush nitrogen was equal to the volume of liquid displaced from the gas holder. Then the furnace was switched off and the reactor removed and cooled by air. Catalyst was removed from the cooled reactor after the run. The quartz wool which was placed above the catalyst bed was removed so that the

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spend catalyst could be analyzed for carbon individually. Liquid holdup in the bottom of the reactor was typically measured by using filter paper and weighing it after wiping. Collecting this liquid was important for accurate mass balance. 4.3 A. Product Analysis Coke Coke deposition on spent catalysts was determined by a common combustion method. In this method, a carbon analyzer Cs 244 (LeCo Corp.) was used. Oxygen was supplied to the unit directly. A small amount of spent catalyst (0.25 g) was used for the desired analysis. The sample was burned completely, which converted all carbon to carbon dioxide. Carbon dioxide was removed by Kolt adsorption, so that by re-measuring the volume of gaseous products, carbon dioxide, and thus carbon, could be determined. B. Liquid Product Yields Simulated distillation by ASTM method D-2887 was used to determine the boiling range distribution of the liquid receiver contents. This method was used to give three different boiling ranges as follows: 36221 oC 221343 oC 343650 oC C. gasoline wt% light cycle oil (LCO) wt% heavy cycle oil (HCO) wt%

Gaseous Products A sample of gaseous product was analyzed by a GC to determine its

composition such as, nitrogen, hydrogen, and C1C5 hydrocarbons.

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The amount of C5 found in the gas must be added to the C 5 (gasoline

+

range) in the liquid. 4.4 CHARACTERIZATION OF CATALYSTS

The catalyst properties, such as zeolite content, the unit cell size of the zeolite, and the surface area determine the activity and selectivity of the catalyst. Instrumental methods were used to characterize the FCC catalyst particle both fresh and steamed. Instrumental methods were used to characterize the changes that occur in the catalyst during the FCC process. These changes were related to desirable or undesirable changes in the selectivity and activity of the catalyst. In most advanced technology catalysts, the zeolite is designed to hydrothermally dealuminate in a controlled and stable way to the intended unit cell size and surface area. Catalyst characterization is essential in order to define key features and to understand variabilities in catalyst performance. For FCC catalysts, the important

characteristics are surface area, acidity, and unit cell size.

4.5

Catalyst Evaluation The catalytic reaction experiments are carried out, in the present

study, using a novel Riser Simulator unit. The Riser Simulator is basically a mini fluidized bed reactor operating in the batch mode with intense gas recirculation. The following section describes the experimental setup, and the experimental procedure adopted during this study.

4.5.1

Experimental Apparatus 24

Experimental catalytic cracking runs were carried out in a Riser Simulator reactor in operation at CREC-UWO laboratory. The reactor was connected to a vacuum box through a four-port valve. The cracked products were removed from the Riser Simulator at the end of the pre set reaction period. A time/actuator assembly linked to the feed injection system controlled the four-port valve. The vacuum system was connected to a manually operated six-port sampling valve. This sampling valve was connected on-line to the gas chromatograph. Furthermore, the Riser Simulator reactor and the vacuum box were equipped with pressure transducers to monitor the pressure during and after the reaction periods. Both the reactor and the vacuum system were supplied by separated heating systems and both were well insulated. The feed injecting system includes a gas tight syringe connected to switches to control the timer/actuator assembly on the four port valve and the data acquisition system. The data acquisition system allowed monitoring the change of pressure with time from both the reactor and the vacuum box. A schematic diagram of the experimental setup is given in Fig. 4.4. All main parts of the set-up will be discussed in detail in the following section

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4.5.1.1

Riser Simulator

The novel Riser Simulator is the center of the experimental setup for catalytic cracking testing. This reactor was designed and manufactured at CREC-UWO. The Riser Simulator was made out from lnconel, which is a high temperature nickel alloy. The reactor consists of four main components: the reactor shells, the catalyst basket, the impeller, and the impeller drive-housing unit. The reactor is composed of two shells, the top and bottom sections. While the top shell is fixed on the steel reactor support frame, the lower shell is removable. The lower shell is attached to the upper shell section by means of a series of eight bolts and nuts. The upper shell also includes the impeller, which is operated by an electric belt-driven motor. A manual motor controller adjusts the speed of the impeller. The top shell also contains three ports, two of which are connected to the four ports valve. The third port is hooked up to the reactor pressure transducer.

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INJECTION PORT V1
4 PORT VALVE RISER SIMULATOR

V3 Ar

Air

H2

2 3 4 8 GC - MS

P1

T 7 6 5
6 PORT VALVE

MFC
VACUUM BOX

V4

V2

P2

VENT V5

VACUUM

He

N2 (L)

Fig 4.4: Schematic diagram for the experimental setup.

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The lower reactor shell includes both the injection port and the catalyst basket. The catalyst basket is designed to fit inside the annular space of the bottom shell. The catalyst basket contains top and bottom porous inconel disks, and this prevents the catalyst from being entrained out of the basket into the other sections of the reactor. Furthermore, this design allows free gas motion through the basket. The porous disks are kept in place in the catalyst basket by two snap rings. The two shells are tightly secured using a flexitallic gasket pressure seal manufactured out of an inconel graphite composite material. Each of the shells has its own sets of heaters. The bottom section contains four cartridge heaters each heaters having a resistance of around 29 . Because of the high temperature involved in the system, the top section of the Riser Simulator, including the impeller shaft and packing gland assembly, needs heat dissipation. With this end a cooling system is implemented utilizing cold tap water as the coolant. Figure 4.5 shows a cross-sectional view of the Riser Simulator. A comprehensive description of the construction and operation of this novel unit are given by Kraemer (1987) and Pruski (1996).

4.5.1.2

Injector system

The injector system consists of a gas tight glass syringe, which is fitted with a parallel threaded support rod and a threaded disc placed between two nuts limiting the motion of the syringe plunger. The disc is fixed at the support rod, allowing the syringe to intake, for every injection, a fixed amount of feedstock from the reservoir chamber. The injector system contained two electrically actuated microswitches fixed at opposite ends of the sliding support rod. While one of

28

the switches controls the data acquisition system, the other controls the timer/actuator assembly of the four-port valve.

Fig 4.5: A schematic diagram for the Riser Simulator.

29

In the sample position of the three-way valve, the syringe is attached to the feedstock (gas oil and/or model compound) container. The syringe fills the required feedstock amount when the plunger is pulled all the way back. Meanwhile, the plunger presses against one of the switches, preventing data acquisition pressure signals. The feed syringe is connected to its needle. Thus, when the plunger is pushed all the way forward, the feed sample is delivered to the reactor. At this point, the micro-switch is released, hence initiating the data acquisition program. Moreover, when the plunger is fully pushed forward, presses against another switch connected to the timer/actuator assembly of the 4-port valve. Consequently, the timer starts to count down the pre-set reaction time, upon which the timer would activate the actuator. The 4-port valve is then opened by the actuator, equalizing the pressure between the reactor and the vacuum box, thereby terminating the reaction.

4.5.1.3

4-Port and 6-port valves

The reactor is connected to the air/argon supply through a 1/8 inch 4-port valve. The other end of this valve is used to connect the reactor with the vacuum box. In both positions, there are always two paths available through the valve for the reaction products to move along. In the open position, the reaction products are transfered through the valve, into the reactor through an inlet port. Then, they move out of the reactor through an outlet port, back into the valve and finally they reach the vacuum box. In the closed position, however, the reactor is completely isolated from the rest of the system and connected to itself through two of the four ports of the valve. The sample injection valve (1/8 6-port chromatographic valve) is installed between the vacuum box and the GC. For both positions, there are always two independent loops for the gases to pass through.

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While one path connects the vacuum box to the vent/vacuum pump, the other joints the helium carrier gas with the GC detector. The position of the valve determines the path which includes the sample loop. 4.5.1.4 Vacuum System The vacuum system consists of a 485 cm3 stainless steel cylinder fixed between the 4-port and the 6-port valves. These components together with two on-off valves, two three- way valves, and two position selector valves are placed inside a heated box. The V1 valve (Fig 4.3) is connected between the air/argon gas supply bottles and the first on-off valve. This valve connects the gas bottle to the reactor and to the gas system. In addition, V1 connects to the 4-port valve through V2 (Fig 4.4). Finally, V2 allows the separation of the entire system from the gas supply. The stainless steel cylinder works as a sink for the reaction products. It has a large volume. In addition, an important pressure difference, with respect to the reactor, facilitates a quick and easy removal of reaction products as well as unreacted hydrocarbons. This rapid evacuation is needed to prevent further progress of cracking reactions after the pre-set time. The second isolation valve V3 is essential to control product sampling (Fig 4.3). This valve is set in closed position during post reaction evacuation period keeping the reaction products within a volume of set dimensions.

The second three-way valve (V4) is connected between V3 and the vacuum pump/vent line. This valve allows to incorporate or remove the vacuum pump in the path of the exhaust gases going to the fume hood. The main function of vacuum pump is to reduce the pressure within the vacuum box to around 0.5 psia (almost vacuum) 31

prior to the reaction test. Between the second isolation valve (V3) and the vent line/vacuum pump, there is a glass bottle. This glass bottle provides a lower pressure than the one in the vacuum box and an extra driving force for filling the sample loop of the 6-port valve.

4.5.1.5

Heating and Insulation

Heating tapes and insulation cover all of the connecting lines between the vacuum box and the two chromatographic valves. There are six heating tapes, each of them is connected to a Variac- type power supply. This system helps to keep the lines at high

temperature, preventing hydrocarbon condensation in the lines and valves. Furthermore, the reactor is insulated to maintain close to isothermal operating conditions. Maximum temperature deviation during experiments is only of a few degrees centigrade. 4.5.1.6 Control Devices 4.5.1.6.1 Temperature control There are two independently powered controlled heater systems. One controller keeps the reaction temperature constant at around 525C by means of four heating rods. These heaters are inserted in the bottom shell of the Riser Simulator. However, the top section of the Riser Simulator is directly heated using two smaller insertion rod heaters directly powered by Variacs.

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4.5.1.6.2

Pressure Transducers

The reactor and the vacuum box are provided by two identical Omega pressure transducers, series PX-303. Figure 4.3 shows P1 and P2 which represent the location of the reactor and the vacuum box transducers respectively. Each transducer is powered by its own power supply. Furthermore, these transducers have a calibrated span of 0-50 psia with 0.25% accuracy, 1 ms response time and a 0.5-5.5 Volt output signal range. The transducers are also equipped with protective pressure snubbers to take care of any sudden pressure spikes or fluctuations.

4.5.1.6.3

Thermocouples

Several thermocouples are mounted around the Riser Simulator reactor to accurately monitor the temperature. are fixed at the following places: Two thermocouples are connected to the reactor and the valve block. Other thermocouples

a)- Impeller shaft cooling jacket (20C-40C) b)- Upper reactor shell section (425C-475C) c)- Lines from the reactor to the 4-port valve (275C-300C) d)- 4-port valve body (225C-250C) e)- Vacuum box (350C-390C) f)- Lines between 6-port valve and vacuum box (225C-250C)

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g)- 6-port valve sampling loop (250C-275C) h)- Line from 6-port valve to GC (275C-300C) i)- Gas oil reservoir (50C-75C)

Note that the values in brackets indicate typical temperature ranges using in the various Riser Simulator ranges.

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4.6- Analytical Equipment 4.6.1 Gas Chromatograph System The GC system, used in the present study, consists of a HP5890 gas chromatograph, a HP3392A integrator, gas supply bottles and connecting lines, valves and associated wiring. The GC contains a 25 m long capillary column, an FID-type detector and a temperature controlled oven. While helium is used as the sample carrier gas, air and hydrogen are used as the gases for the FID detector. Furthermore, liquid nitrogen is used to facilitate the initial cryogenic operation of the GC temperature program. The liquid nitrogen cools the GC oven to 30C. The flow of liquid nitrogen is administered by a solenoid valve actuated from the GCs internal oven temperature controller. The HP3392A integrator allows strip chart recording as well integration of the GC detector signal. The integrator is connected to the GC via the HP-IL instrument network cabling system. A Mettler balance is used to accurately weigh the catalyst sample. A Hamilton gas tight syringe was calibrated for the different feedstock used in the present study. Analytical weights are of precision grade or calibrated against a set of certified standard weights. Availability of this balance is of major importance for good mass balance calculations.

4.5.2-Coke analyzer Coke deposited on spent catalysts is determined, in the present study, by a common combustion method. In this method, a carbon analyzer Cs-244 (Leco Corp.) is used. Oxygen is supplied to the unit directly. A small amount of the spent catalyst (0.25 g) is used for the analysis. The coke laid out on the sample during reaction experiments is burned completely converting the carbonaceous deposit into carbon 35

dioxide. The moles of carbon dioxide formed are measured, and thus the coke formed is determined. 4.6- Procedure Both CAT-LC and CAT-SC were used in the present study. The reaction conditions adopted during the present study are close to those used in an industrial FCC unit. Both catalysts were tested at four different contacts times (3, 5, 7,and 10sec). In the case of cumene, four different reaction temperature levels were used: 400, 450, 500, and 550 C. However, in the case of 1,3,5 TIPB six different temperatures were considered 350, 400, 450, 500, 525 and 550 C. In addition, for all experiments, one catalyst to oil ratio of C/O=5 was employed (feed weight =0.16g and catalyst weight=0.81g). More than three repeat runs were conducted at each experimental condition. Regarding the experimental procedure in the Riser Simulator, every experimental run uses 0.81g of catalyst in the Riser Simulator basket. The system is sealed and tested for any pressure leaks by applying special liquids around the reactor and vacuum box and monitoring any pressure changes in the system. The reactor is then heated to the reaction temperature. The vacuum box is heated to around 250 C and is evacuated at around 0.5 psi to prevent any condensation of hydrocarbons inside the box. The heating of the Riser Simulator is conducted under continuous flow of inert gases (argon) and the process usually takes around 3 hours until reaching thermal equilibrium. At this point the GC is started and its temperature lowered to 30C. This temperature is kept for 3 minute, then increased at a rate of 15C/min up to 240C. The GC is left at 240C for 1 minute, and then the temperature is increased at a rate of 40C/min up to 300C. Then, the temperature is left at 300C for 20 minutes to

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ensure that all the hydrocarbons present in the reacted gases are eluted from the capillary column.

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Composition Determine FCC Catalysts Performance, Oil & Gas Journal, Feb. 6, 45-51, (1989). Kraemer, D.W., Sedran, U., and de Lasa, H.I, Catalytic Cracking in a Novel Riser Simulator. Chem. Eng. Sci. 45(8), pp2447-2452, (1990). Kraemer, D.W., Larocca, M., and de Lasa, H.I, Deactivation of Cracking Catalysts in Short Contact Time Reactors: Alternative Models. Can. J. Chem. Eng., (1990). McElhiney, G., FCC Catalyst Selectivity Determined From Microactivity Tests, Oil and Gas J., Feb. 8, pp35-38 (1988). Moorhead, E.L., Mclean,J.B., and Cronkright, W.A. Microactivity Evaluation of FCC Catalysts in the Laboratory: Principles, Approachs and Applications In: Fluid Catalytic Cracking: Science and Technology, Magee, J.S., and Mitchell, M.M. (editors), Amesterdam: Elsevier, 1993.

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Mott, R.W., New Concept Measures Catalyst Performance, Oil and Gas J., Jan. 26, pp73-77 (1987). OConnor, P. and Hartkamp, M.B. A Microscale Simulation Test for FCC Development, Paper Presented at the Symposium on the Preparation and Characterization of catalysts before the Division of Petroleum Chemistry, Inc , American Chemical Society Meeting, Los Angeless, Sep 25-30 (1988). Sunderland, P., An Assessment of Laboratory Reactors for

Heterogeneously Catalyzed Vapor Phase Reactions, Trans. Instn. Chem. Engrs., 54, 135 (1976). Tasi, T.C., Pan, W.P., Leu, L.J. and Yu, S.T., A Procedure for Evaluation of Commercial FCC Catalyst, Chem. Eng. Comm., 78, pp97-109 (1989). Weekman, V.W., Laboratory Reactors and Their Limitations, AIChE, 20(5), pp833-840, (1974). Young, G.W. and Weatherbee, G.D., FCCU Studies with an Adiabatic Circulating Pilot Plant Unit, Paper Presented at the AIChE Annual Meeting, San Francisco, November (1989).

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