MAXOFIN: A NOVEL FCC PROCESS FOR MAXIMIZING LIGHT OLEFINS USING A NEW GENERATION ZSM-5 ADDITIVE

Authors: Rik B. Miller - KBR Phillip K. Niccum - KBR Alan Claude - KBR Michael A. Silverman - KBR Nazeer A. Bhore - Mobil Technology Company Girish K. Chitnis - Mobil Technology Company Stephen J. McCarthy - Mobil Technology Company Ke Liu - Mobil Technology Company

Publication / Presented: NPRA Annual Meeting Date: 1998

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins Using a New Generation ZSM-5 Additive

by

Rik B. Miller, Phillip K. Niccum, Alan Claude, and Michael A. Silverman

Kellogg Brown & Root, Inc. Houston, Texas USA and

Nazeer A. Bhore, Girish K. Chitnis, Stephen J. McCarthy, and Ke Liu

Mobil Technology Company Paulsboro, New Jersey USA

Presented at: 1998 NPRA Annual Meeting San Francisco, California USA 16 March 1998

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

ABSTRACT
The Mobil-Kellogg FCC Alliance announces MAXOFIN -- a remarkably flexible FCC process that produces maximum light olefins from traditional feedstocks without resorting to severe operating conditions. MAXOFIN is based on commercially proven technology and is now available for grassroots or revamp FCC application. A new generation, higher ZSM-5 content additive and proprietary FCC hardware provide the flexibility to produce either maximum olefins or conventional fuels based on market demands. This paper shows an example where MAXOFIN can produce between 6 and 18 wt% propylene from Minas vacuum gas oil. The key features of the MAXOFIN FCC process are: # # # # A new generation, high ZSM-5 content MAXOFIN-3 additive that produces maximum light olefins without catalyst dilution No requirement for large amounts of riser steam or severe operating conditions A cost-effective ZSM-5 additive that is only now being offered to the industry Proprietary Mobil-Kellogg Hardware: T New ATOMAX-2 feed nozzles to provide superior atomization and greater riser coverage T Second Riser or lift zone for re-cracking of Naphtha T Closed Cyclones for olefin generation with minimum associated dry gas production

BACKGROUND
a. Demand for propylene increasing

Light olefins, propylene and butylenes, have long been basic building blocks for the manufacture of a variety of petrochemical products and fuels. Today, light olefins are used for the production of gasoline, polymers, antifreezes, petrochemicals, explosives, solvents, medicinals, fumigants, resins, synthetic rubber, and many other products. Propylene is second in importance to ethylene as a raw material for petrochemical manufacture. The largest source of petrochemical propylene on a worldwide basis is that produced as the primary byproduct of ethylene manufacture by thermal cracking. Ethylene plants charging liquid feedstocks typically produce about 15 wt% propylene and provide about 70 percent of the propylene consumed by the petrochemical industry. Petroleum refining, nearly all from FCC, is by far the next largest supplier of worldwide propylene production, supplying about 30 percent of the petrochemical requirement. In the U.S., FCCU's supply about one-half of the petrochemical propylene demand. AM-98-18 Page 1

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

The demand for propylene is expected to more than double, primarily driven by the rapidly increasing market for polypropylene. Propylene demand by the petrochemical industry is projected to increase more rapidly than the demand for ethylene. Since ethylene plants produce more ethylene than propylene, and furthermore, since many of the new ethylene plants in construction are based on ethane feed with no propylene co-produced, significant increases in propylene from FCC will be required to meet the increased demand. This will be accomplished by increasing FCC propylene selectivity, and by increasing the percentage of FCC propylene sent to petrochemical manufacture. Dehydrogenation of propane is expected to supply a much smaller proportion of the increased propylene demand, due to its higher production costs. Although propylene demand is high, refiners are still cautious about committing large capital investments for propylene production alone because of the large swings in propylene-fuels margins. To mitigate these risks, the MAXOFIN process can switch from a maximum propylene mode to a fuels mode to meet the marketplace demands. The key to the flexibility of MAXOFIN process is the high ZSM-5 content additive that was previously unavailable to the FCC industry. b. ZSM-5 additive evolution

Mobil invented ZSM-5 zeolite in 19721. Since its invention, ZSM-5 has been commercially used in a wide variety of catalytic applications including petrochemicals (ethylbenzene, xylene isomerization, etc.), synthetic fuels (Methanol to Gasoline), and petroleum upgrading (lube and distillate dewaxing, gasoline octane enhancement, etc.). In 1983, Mobil demonstrated that ZSM-5 increased gasoline octane in a moving bed Thermofor Catalytic Cracking (TCC) Unit2. In 1986, GRACE-Davison, working with Mobil, developed the first ZSM-5 additive for use in FCC. Mobil licensed GRACE and other catalyst manufacturers to market and sell ZSM-5 additives containing 25 wt% or less ZSM-5 crystal for use in fluid and moving bed cracking processes. Within a few years, the industry embraced ZSM-5 additives for octane enhancement and maximizing alkylate. More recently the industry has looked to ZSM-5 additives for incremental production of propylene from FCC. However, current ZSM-5 additives are best suited for increasing FCC propylene yield by 50-100%. Extensive pilot plant studies by Mobil, GRACE, and others show that further increases in propylene (up to 300%) require an additive with more than 25 wt% ZSM-5 crystal content to minimize dilution of the base catalyst activity3. Mobil conducted commercial trials of its own proprietary high ZSM-5 additive as early as 1992, validating this approach. With propylene demand increasing, Mobil will now allow catalyst manufacturers to produce high ZSM-5 content additives pursuant to Mobils patent position. The MAXOFIN FCC process couples these new additives with proprietary hardware to produce either maximum olefins or conventional fuels, as the market demands, from traditional FCC feedstocks without resorting to severe operating conditions. AM-98-18 Page 2

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

DESCRIPTION OF KEY MAXOFIN FEATURES

The MAXOFIN process brings together a new generation high ZSM-5 content additive and proprietary FCC hardware to economically produce high yields of light olefins from traditional FCC feedstocks such as gas oils, deasphalted oil, and residual oil feedstocks. All these features are commercially proven and provide flexibility to alternate between light olefin maximization and traditional maximum gasoline operations. The next few sections provide details of the MAXOFIN technology. a. MAXOFIN-3 Additive

The MAXOFIN process is built around a family of proprietary additive formulations containing higher levels of ZSM-5 than previously available. The formulation can be tailored to the refiners needs based on the extensive data base compiled by Mobil during ZSM-5 development. The result is a new generation of additives that exhibit superior activity, high propylene selectivity, and excellent attrition resistance. Furthermore, these additives exploit the synergies with the Mobil-Kellogg hardware to produce maximum propylene from FCCUs. Table 2 shows a comparison between conventional ZSM-5 additives and MAXOFIN-3 additive at the same crystal level in the inventory. The large amount of conventional additive would dilute the base catalyst activity and produce lower conversion, higher bottoms yield, and fewer C6+ gasoline olefins. It is the C6+ gasoline olefins that subsequently react over ZSM-5 to produce propylene and butylenes.

TABLE 2: MAXOFIN-3 Additive Achieves High Propylene Yield Without Significant Conversion Penalty
Additive MAXOFIN-3 Additive Conventional Additive Propylene yield, wt% Base -1.2 Catalyst MAT Activity Base -4.0

b.

ATOMAX-2 Feed Injection System

The feed injection system plays a key role in the yield performance of the MAXOFIN process because a large fraction of the ZSM-5 cracking precursors, C6-C12 olefins, is formed in the feed-catalyst mixing zone. By minimizing bacmixing in the riser, an efficient feed injection system protects the C 6-C12 olefins from deleterious bimolecular hydrogen transfer and makes them available for ZSM-5 to crack into light olefins.

AM-98-18 Page 3

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

In 1992, Mobil and Kellogg commercialized the ATOMAX feed nozzle, which provided a significant advancement in FCC feed injection technology. Although the original ATOMAX nozzle quickly became the market leader, Mobil and Kellogg DROPLET SIZE ACROSS SPRAY were not willing to rest ATOMAX-2 vs. ATOMAX-1 on this accomplishment.
Relative Sauter Mean Diameter

In 1996, we began work to develop the nextWider Spray Angle 1.0 ATOMAX-1 generation feed nozzle. and More Uniform Avg. SMD = 1.0 Atomization A custom feed nozzle ATOMAX-2 0.8 test rig was built at the Avg. SMD= 0.57 Kellogg Technology Development Center to 0.6 evaluate nozzle prototypes. This rig incor0.4 porates a state-of-the-20 -10 0 10 20 Distance from Center of Spray, inches art Laser Dopplerimeter that can meaFigure 3 sure droplet size, velocity, and liquid flux at any point in the spray pattern. Each of these parameters is key to developing a wellintegrated feed injection system. Our successful development efforts have led to the commercialization of the ATOMAX-2 nozzle, representing a significant step forward in feed nozzle technology. As shown in Figure 3, ATOMAX-2 produces a significantly smaller Sauter mean droplet size than the industry-leading ATOMAX nozzle at all points in the fan-shaped spray. ATOMAX-2 produces a spray-averaged Sauter mean droplet size that is about 43% smaller than ATOMAX. For a given volume of spray, the new nozzle produces about six times more droplets than its predecessor!

1.2

AM-98-18 Page 4

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

c.

Second Riser for Naphtha Cracking

FCC naphtha, preferably light cat naphtha, can be re-cracked in the presence of ZSM-5, high cat-to-oil ratios, and high riser outlet temperatures to produce olefins. For clients requiring maximum olefin yields, a second riser can be installed that processes recycled naphtha and operates at a riser outlet temperature of approximately 1100F. A dual riser MAXOFIN FCC configuration is depicted in Figure 4 The combination of high temperature and high levels of ZSM-5 allow the gasolinerange light olefins and light paraffins to crack. The high riser outlet temperature and the high heat of reaction produce a cat-to-oil ratio close to 25-to-1, thus maximizing the effectiveness of MAXOFIN-3 additive.

MAXOFIN FCC with Dual Risers

Closed Cyclone System Two-Stage Stripper

CounterCurrent Regenerator

Primary Feed Riser

2nd Riser for Naphtha Recycle

At lower cost than a second riser, naphtha ATOMAX-2 Recycle can also be recycled to the "lift zone" at the Fresh Feed Naphtha Injection Injection base of the riser and below the fresh feed nozzles. This location produces the highest temperature possible in a unit with only one riser. However, in this scenario gasoline Figure 4 cracking is less than with a separate riser due to reduced residence time and inefficient gas-solid contacting. As a result, olefin yields are slightly lower and selectivity is better for lift-zone naphtha cracking than for separate-riser naphtha cracking. However, the second riser gives more operating flexibility, especially when it is desirable to maximize the distillate and light olefins with minimum gasoline produced. Thus, the choice between a lift-zone and a second riser depends on the need for operating flexibility and capital availability. d. Choice of base catalyst and feedstock

In addition to the MAXOFIN-3 additive, the propylene yield from a given feedstock can be optimized by proper choice of the base catalyst. The base FCC catalyst is optimized to minimize hydrogen transfer and produce maximum C 6-C12 olefins, which will convert to light olefins in the presence of ZSM-5. Reaction pathways4-8 for cracking over base catalyst and ZSM-5 are depicted in Figure 5.

AM-98-18 Page 5

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

The feedstock can be optimized among the available feed components. As mentioned earlier, recycle of naphtha to a second riser or lift zone can be used to produce incremental FCC REACTION PATHWAYS propylene.
for production of C3-C4 olefins with base catalyst & ZSM-5

Mobil and Kellogg have pilot plant and commercial test data on cracking streams of various unfinished gasoline streams. These include virgin naphtha, coker gasoline, visbreaker gasoline, and hydrotreated naphtha. The optimum feedstock and catalyst are identified by using a proprietary compositional FCC yield model that tracks more than 3000 components in the FCC feed and products.

Feed Component Paraffin & Side Chains

Intermediate
Cracking
r sfe ran HT

Product Paraffin C3 - C4 Olefins

Crack ing

C6 - C12 Olefins

ZSM-5
Cracking
Po lym eriz atio n

g ckin Cra

Naphthene
H Transfer

Coke
tion ensa Cond

Aromatic

Figure 5

Unlike competing processes, the MAXOFIN-3 additive and base catalyst combination obviates the need for low riser hydrocarbon partial pressure and high amounts of riser steam. e. Riser Termination (Closed Cyclones)

FEATURES OF CLOSED CYCLONES

Excellent catalyst / vapor separation 97+% of riser product vapors flow directly to overhead line Very brief vapor residence time Very little thermal cracking No dilute phase catalytic cracking Yield benefits:

The MAXOFIN process uses relatively high riser outlet temperatures to optimize the yield of propylene. In this environment, modern riser termination technology is essential.

less dry gas Closed Cyclones minimize the higher propylene yield residence time of hydrocarless bottoms yield bon vapor and catalyst in the improved coke selectivity disengager vessel. By elimClosed Cyclones inating post riser thermal and catalytic cracking, Closed CyFigure 6 clones reduce the yield of dry gas, reduce coke formation on the catalyst, and increase the yield of more valuable products, as depicted in Figure 6.

AM-98-18 Page 6

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

Closed Cyclones have been in commercial service since 1985 and have proven to minimize thermal cracking in the disengager while being both operationally and mechanically reliable. f. Dense Phase Catalyst Cooler

For processing heavy resid-containing feedstocks the MAXOFIN process offers a Dense Phase Catalyst Cooler to control regenerator temperature and optimize catalyst-to-oil ratio.

Water In Catalyst In Inner Tube Tubesheet

Water & Steam Out Tubesheet

Fluidization The unique design of the Catalyst Air system allows complete Return Scabbard -turndown by adjustment Outer Tube Slide of the catalyst circulation Valve rate through the cooler. By placing the tube bunFigure 7 - Dense Phase Catalyst Cooler dle on top of the cooler shell as shown in Figure 7, the fluidization air distributors within the cooler shell are located well below the tubes, eliminating the possibility of tube erosion and failure due to impingement of air jets. Since 1989, eleven Kellogg dense phase catalyst coolers have been licensed and three are now in operation.

MAXOFIN PROCESS EXAMPLE

a. Basis and Yields

As a case study, we have illustrated the flexibility of the MAXOFIN process by studying three different modes of operation: T T T Maximum propylene Maximum fuels An intermediate case

While this technology can be easily applied to revamp cases, the illustrations below cover a grassroot FCC processing 600-1000F TBP boiling range gas oil feed derived from Minas crude oil. The unit is designed to process 30 MBPSD of gas oil in the maximum propylene mode at 1000F riser top temperature and 400F combined feed temperature.

AM-98-18 Page 7

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

Table 3 shows that the propylene yield / fuels yield tradeoffs can be selected to suit the current market needs. For example, the propylene yield can be changed from 6.2 wt% in the fuels mode to 18.4 wt% in the maximum propylene mode. The maximum propylene case produces about 300,000 tons of propylene per year for a downstream world scale polypropylene facility.

TABLE 3: MAXOFIN Process Yields and Operating Conditions

OPERATING MODE DESCRIPTION Propylene Yield, wt.% Feed Catalyst Reactor Configuration Riser Top Temp, F Catalyst / Oil Feed Rate, MBPSD YIELDS, wt% Hydrogen Sulfide Hydrogen Methane & Ethane Ethylene Propane Propylene n-Butane i-Butane Butylenes Gasoline Light Cycle Oil Decant Oil Coke Maximum Propylene Case 18.4 VGO & Light Naphtha Recycle RE-USY + ZSM-5 Dual Riser 1000 / 1100 8.9 / 25 30.0 Intermediate Case 14.4 VGO RE-USY + ZSM-5 Single Riser 1000 8.9 30.0 Fuels Mode Case 6.2 VGO RE-USY Only Single Riser 1000 8.9 44.1

0.03 0.91 6.61 4.30 5.23 18.37 2.25 8.59 12.92 18.81 8.44 5.19 8.34

0.02 0.18 2.07 1.96 3.90 14.38 2.16 8.52 12.33 35.53 7.33 5.24 6.38

0.01 0.12 2.08 0.91 3.22 6.22 2.17 7.62 7.33 49.78 9.36 5.26 5.91

The extraordinary propylene yield is accomplished with a combination of high ZSM-5 content additive and re-cracking of gasoline in a second riser. The optimal top temperature, gasoline recycle ratio, and residence time in the second riser depends on gasoline composition, incremental propylene and gasoline prices, metals on equilibrium catalyst, and

AM-98-18 Page 8

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

FCCU constraints such as air rate, main fractionator, wet gas compressor, and gas concentration section bottlenecks. The second riser converts essentially all the gasoline range olefins and naphthenes in the recycled gasoline. Both the fresh feed riser and the gasoline re-cracking riser are operated at conventional steam rates (2-5 wt%). For purposes of the example, and to more clearly show the effects of the ZSM-5 additive and the effects of the second riser, a 1000F primary riser temperature is used for all three cases. In a commercial application, depending on unit constraints and other operating objectives, the primary riser temperature would be optimized in each case. Also listed in Table 3 is an intermediate case that provides up to 14.4 wt% propylene yield without the use of the second gasoline re-cracking riser. In this intermediate case, the increased coke yield relative to the fuels case is due to the heat requirement for C6+ olefin re-cracking and lack of hydrogen transfer. An additional 5-7 wt% propylene yield can be obtained by secondary processing of ethylene and butylenes through olefin interconversion processes, thereby producing a net propylene yield of up to 25 wt% on a fresh feed basis. b. Fuels Mode

The use of MAXOFIN-3 additive can be discontinued if market conditions change and the production of fuels becomes more economic than the productioni of propylene. The third column of Table 3 outlines a maximum fuels operating mode, which uses a conventional FCC catalyst (without ZSM-5 additive) and employs the second riser for gas oil feed. The fresh feed rate is increased to take full advantage of the available capacity of the air blower required for producing maximum propylene. For simplicity we show the incremental feed quality to be the same as the base feed. However, depending on the refiner's configuration, this incremental feed could be light gas oil, vacuum tower overflash, or vacuum tower bottoms. Detailed investigations indicate that all the equipment can be designed to operate at the extremes of both cases (high vapor loads at the top of the main fractionator for the maximum propylene case and high liquid loads for the debutanizer in the fuels operation). Although these examples show a maximum conversion FCC operation, the MAXOFIN process can also be used for providing maximum propylene in a low-conversion, highdistillate mode of operation. Distillate mode consists of low riser temperature, high feed preheat temperature, and high recycle of bottoms. c. Utilities

Mobil/Kellogg can assist in evaluations of propylene production costs for the various catalyst and hardware options. The production costs should always include the visible catalyst and AM-98-18 Page 9

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

additive expenses as well as the life cycle effect of the less visible utility costs. The life cycle costs can be significant, especially if a large amount of steam is necessary to maintain low hydrocarbon partial pressures. Surprisingly, the cost of steam may actually exceed the cost of the ZSM-5 additive! To allow a quick comparison of utilities requirements, Table 4 outlines the estimated utilities requirements for three different operating modes: 1) MAXOFIN maximum propylene case, 2) MAXOFIN fuels case, and 3) A process using 20 wt% dispersion steam. The MAXOFIN process provides high yields of propylene with only 4 wt% dispersion steam on a fresh feed basis. The cost of this steam is estimated to be approximately 7 cents per barrel of fresh feed when main fractionator condensing costs and sour water treating costs are included along with the cost of producing the steam. The cost per barrel of fresh feed would be approximately 5 times higher if 20 wt% dispersion steam were required. The difference in steam costs, approximately 28 cents per barrel, is typically more than the cost of ZSM-5 additive. Table 4 shows that consuming large amounts of dispersion and stripping steam in the converter can also lead to significant costs for condensing the steam and for treating the subsequent sour water. In addition to the increased steam consumption and production of sour water, the high dispersion steam case requires an increase in air blower capacity to burn the extra coke required to heat the dispersion steam to riser outlet temperature. The extra coke production must come at the expense of liquid product yield, a factor that has not been considered in this analysis.

CONCLUSIONS
As worldwide demand for polypropylene has increased, refiners have looked to FCC to produce incremental propylene for petrochemical feedstock. The Mobil-Kellogg MAXOFIN FCC process, based on a new MAXOFIN-3 ZSM-5 additive and proprietary hardware technology features, is available for maximizing the production of light olefins from FCC feedstocks. The key feature of this technology is its flexibility to respond to market demands by effectively operating in maximum olefin mode, maximum fuels mode, or anywhere between. The MAXOFIN FCC process can produce propylene yields approaching 20 wt% of feed while retaining the ability to operate as a conventional fuels FCC. This flexibility is provided by using the highly active MAXOFIN-3 additive and FCC hardware components designed for maximum operating flexibility. Mobils extensive database can be used to optimally match the selection of FCC feedstock components, base FCC catalyst, and MAXOFIN-3 additive.

AM-98-18 Page 10

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

REFERENCES
1. 2. 3. 4. 5. 6. 7. 8. R.J. Argauer and G.R. Landolt; US Patent 3,702,886; Nov 14, 1972 to Mobil. C.D. Andersen, F.G. Dwyer, G. Koch, P. Niiranen; 9th Ibero American Symp. Catal.; Lisbon, Portugal; 1984. Y.G. Adewuyi, J. Klocke, J.S. Buchanan; Appl. Catal. A,131 (1995), 121. J. S. Buchanan and Y. G. Adweyi, Applied Catalysis, 134 (1996) 237. D. A. Pappal and P. H. Schipper, ACS Symposium Series 452, 1990. R. J. Madon, J. Catal. 73 (1991) 275. J. S. Buchanan, Appl. Catal. 74 (1991), 83. P.H. Schipper, F.A. Dwyer, P.T. Sparrell, S. Mizrahi, S.P. Donnelly, J.A. Herbst; ACS Symp. Series 375 (1982) 364.

AM-98-18 Page 11

MAXOFIN: A Novel FCC Process for Maximizing Light Olefins

TABLE 4: Estimated Utilities

OPERATING MODE Max Propylene Case Feed Rate, BPSD Dispersion Steam, wt% Fresh Fd High Pressure Stm (600 psig) Production, lb/hr Flue Gas Cooling Consumption, lb/hr Air Blower Turbine Wet Gas Comp. Turbine C3 Drier Med Pressure Stm (250 psig) Production, lb/hr Main Frac P/As Consumption, lb/hr Converter Main Frac Stripping Amine Stripper Low Pressure Stm (50 psig) Consumption, lb/hr VRU Reboilers Condensate Return, gpm Boiler Feedwater, gpm Cooling Water, gpm (20E F rise) Main Frac Wash Water, gpm Sour Water Produced, gpm Electric Power, kW Main Frac Ovhd Duty, MMBtu/hr (244,000) 894 264 54,500 60 121 2,300 126 (152,800) 619 286 42,100 85 141 2,100 138 (244,000) 903 305 55,700 60 241 2,500 192 (28,800) (1,600) (600) (26,000) (2,400) (300) (89,000) (1,600) (600) 30,000 34,400 45,700 (99,300) (91,700) (11,700) (99,300) (50,500) (6,600) (103,600) (91,700) (11,700) 98,000 104,600 102,300 30,000 4.0 Fuels Mode Case 42,350 3.0 High Dispersion Steam Case 30,000 20.0

AM-98-18 Page 12