Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 3.2

DEEP CATALYTIC CRACKING, THE NEW LIGHT OLEFIN GENERATOR

Warren S. Letzsch
DCC Program Manager Stone & Webster Inc. Houston, Texas

BASIS
The fluid catalytic cracking (FCC) unit is the most important and widely used heavy oil conversion process in the modern refinery. Historically, the FCC unit has operated in maximum gasoline and maximum distillate modes, depending on seasonal product demands and refinery locale. Recently, with the advent of reformulated gasoline requirements, the FCC unit has been increasingly required to operate in the maximum olefin mode. Light isoolefins, isobutylene and isoamylene, from the FCC unit are necessary feedstocks for methyl tertiary butyl ether (MTBE) and tertiary amyl methyl ether (TAME) oxygenated reformulated gasoline blending components. Increased alkylate demand to meet reformulated gasoline requirements also necessitates an increase in light olefins. At the same time as these changes are occurring in the refining industry, the petrochemical industry is experiencing increased demands for propylene for the manufacture of polypropylene products. Nearly one-half of the propylene used by the chemical industry is obtained from refineries, and the remainder comes from steam cracking (SC).1 As a result, the demand for propylene from both FCC units and SC units is rising. Since SC units produce ethylene as the primary product, a catalytic process is more suitable for making propylenes and butylenes. The demand for propylene, both as an alkylation feed and for polypropylene production, is expected to continue growing well into the 21st century. More isoolefins are also needed for those locations where MTBE and TAME can be used in the gasoline pool. This places a considerable strain on the FCC unit and SC unit in order to meet the demand. Obviously, a need for an economical light olefin generating process is required to meet these demands for light olefins (C3 through C5). To this end, Stone & Webster has entered into an agreement with the Research Institute of Petroleum Processing (RIPP) and Sinopec International, both located in the Peoples Republic of China, to exclusively license RIPPs Deep Catalytic Cracking (DCC) technology outside China. DCC is a fully commercialized process, similar to FCC, for producing
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DEEP CATALYTIC CRACKING, THE NEW LIGHT OLEFIN GENERATOR 3.36

CATALYTIC CRACKING

light olefins (C3 to C5) from heavy feedstocks such as gas oils and paraffinic residuals. Stone & Websters proven position in FCC technology and steam cracking is a natural complement to DCC technology. Numerous DCC units have been put in commercial service. Table 3.2.1 is a list of all DCC units operating at present. Figure 3.2.1 shows the unit built in Thailand currently operating at about 18,000 B/D and producing about 150,000 MTA of propylene.

PROCESS DESCRIPTION
DCC is a fluidized catalytic process for selectively cracking a variety of feedstocks to light olefins. A traditional reactor/regenerator unit design is employed with a catalyst having physical properties much like those of FCC catalyst. The DCC unit may be operated in one of two modes: maximum propylene (type I) and maximum isoolefins (type II). Each operational mode employs a unique catalyst and operating conditions. DCC reaction products are light olefins, high-octane gasoline, light cycle oil, dry gas, and coke. A small amount of slurry oil may also be produced. DCC maximum propylene operation (type I) employs both riser and bed cracking at severe reactor conditions. Maximum isoolefin operation (type II) utilizes riser cracking, as does a modern FCC unit, at slightly milder conditions than a type I operation. Figure 3.2.2, a process flow diagram of a type I DCC process, serves as a basis for the process description. (Note that the only difference between the type I and type II designs is an extended riser with a riser termination device above the reactor bed level.) Fresh feed is finely atomized by steam and injected into the riser through Stone & Webster proprietary FCC feed injection nozzles over a dense phase of catalyst. The atomized oil intimately mixes with the catalyst and begins to crack into lighter, more valuable products. A good feed injection system is required for DCC, just as for FCC operations, to ensure rapid oil vaporization and selective catalytic cracking reactions. Riser steam is injected just above the feed injection point to supplement feed dispersion and stripping steam in order to achieve optimal hydrocarbon partial pressure for the DCC operation. Simple steam injection nozzles are employed for riser steam injection. (Steam requirements for DCC type II operation are considerably less and may not need additional steam injection nozzles.)

TABLE 3.2.1 Location Jinan, China Jinan expansion Anqing, China Daqing, China Jinmen, China TPI, Thailand Shenyang, China Jinzhou, China Urumchi, China

DCC Commencement Status Feed, MTA* 60,000 150,000 400,000 120,000 800,000 900,000 400,000 300,000 800,000 Start-up 1990 1994 1995 1995 1997 1997 1998 1999 1999 DCC type I I and II I I II I II I II

*MTA metric tons per year. Design by Stone & Webster Engineering Corporation.

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DEEP CATALYTIC CRACKING, THE NEW LIGHT OLEFIN GENERATOR

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FIGURE 3.2.1

DCC unit at TPI refinery, Thailand.

Slurry recycle is injected, if required, just above the riser steam nozzles. This recycle stream is not required to increase overall conversion but rather to optimize the unit heat balance, as a large slurry reaction product is coke. At the top of the riser, catalyst, steam, and hydrocarbon pass through a riser terminator located below the reactor bed. Conversion of the DCC feedstock can be regulated by adjusting the catalyst bed height (hydrocarbon weight hourly space velocity) above the riser distributor, the catalyst circulation rate, and/or the reactor temperature. Two-stage highefficiency reactor cyclones remove entrained catalyst from the reactor vapors. Products, inerts, steam, and a small amount of catalyst flow from the reactor into the bottom of the main fractionator to begin product separation. The regenerated catalyst slide valve controls the reactor bed temperature by regulating the amount of hot regenerated catalyst entering the riser. Nominal reactor temperatures and pressures are listed in Table 3.2.2.

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DEEP CATALYTIC CRACKING, THE NEW LIGHT OLEFIN GENERATOR 3.38

CATALYTIC CRACKING

FIGURE 3.2.2

Maximum propylene DCC unit (type I) process flow diagram.

The stripper portion of the reactor vessel uses baffles to create multiple stages. Steam from the main steam ring fluidizes the catalyst bed, displaces the entrained hydrocarbons, and strips the adsorbed hydrocarbons from the catalyst before it enters the regeneration system. A steam fluffing ring, located in the bottom head of the stripper, keeps the catalyst properly fluidized and ensures smooth catalyst flow into the spent catalyst standpipe. An alternative to the baffled stripper is the use of packing to create the staging. Spent catalyst leaves the stripper through a slanted standpipe. Aeration taps, located stepwise down the standpipe, serve to keep the catalyst aerated and replace the gas volume
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DEEP CATALYTIC CRACKING, THE NEW LIGHT OLEFIN GENERATOR

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3.39

lost by compression. The spent catalyst slide valve, located near the point where the standpipe enters the regenerator, maintains proper bed level in the reactor/stripper. Reactor bed level is optimized with respect to conversion and unit operability. Spent catalyst is dispersed inside the regenerator by a catalyst distributor just above the combustion air rings. Combustion air rings provide even air distribution across the regenerator bed, resulting in proper fluidization and combustion. The regenerator operates in a full combustion mode with approximately 2 vol % excess oxygen. Regenerator flue gases
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DEEP CATALYTIC CRACKING, THE NEW LIGHT OLEFIN GENERATOR 3.40

CATALYTIC CRACKING

exit through two-stage high-efficiency regenerator cyclones which remove entrained catalyst from the flue gas. Typical regenerator temperature is near 700C. Regeneration/reactor differential pressure is controlled by a flue gas slide valve. Hot regenerated catalyst is withdrawn from the regenerator, just below the regenerator bed level, into a catalyst withdrawal well. The withdrawal well allows the catalyst to deaerate properly to standpipe density before entering the vertical regenerated catalyst standpipe. A small air ring located in the withdrawal well serves to maintain proper catalyst fluidization. Aeration taps, located stepwise down the standpipe, replace gas volume lost by compression. Catalyst passes through the regenerated catalyst slide valve, which controls the reactor temperature by regulating the amount of hot catalyst entering the riser/reactor section. A straight vertical section below the feed nozzles stabilizes the catalyst flow and serves as a reverse seal, preventing oil reversals into the regenerator. The DCC gas recovery section employs a low-pressure-drop main fractionator design with warm reflux overhead condensers to condense the large amounts of steam used in the converter. A large wet gas compressor is required, relative to FCC operation, because of the high amounts of dry gas and liquefied petroleum gas (LPG). The absorber and stripper columns, downstream of the wet gas compressor, are specifically designed for enhanced C3 recovery at relatively low gasoline rates. Following the traditional debutanizer and depropanizer for contaminant removal, a deethanizer and C3 splitter are required to produce polymer-grade propylene. For DCC units in or near a petrochemical process, a cryogenic ethylene recovery unit utilizing Stone & Websters Advanced Recovery System (ARS) technology may be of interest for ethylene recovery and essentially complete propylene recovery. For a grassroots petrochemical plant, the gas recovery system can be optimized using Stone & Websters maximum olefin recovery (MOR) technology, saving considerable investment capital. The flue gas handling system, downstream of the DCC regenerator, requires considerations no different from those of an FCC system. It consists of a flue gas slide valve to control the differential pressure between the reactor and regenerator followed by an orifice chamber. Heat is recovered by a flue gas cooler in the form of high-pressure superheated steam. Depending on local particulate emission specifications, the system may contain a third-stage cyclone separator upstream of the flue gas slide valve or an electrostatic precipitator (ESP) upstream of the stack. SOx or NOx emission requirements may necessitate a flue gas scrubber or SOx-capturing catalyst additive to reduce SOx emissions and/or a selective catalytic reduction (SCR) process for NOx removal.

CATALYST
The most critical part of the DCC process is the catalyst. RIPPs research and development efforts have resulted in the development of several proprietary catalysts, each with unique zeolites. All catalysts have physical properties similar to those of FCC catalysts. The catalyst designated CRP-1 was developed for use in the DCC maximum propylene operation (type I). CRP has a relatively low activity to ensure high olefin selectivity and low hydrogen-transfer reactions. The catalyst also exhibits a high degree of hydrothermal stability and low coke selectivity. CS-1 and CZ-1 were developed to produce high isobutylene and isoamylene selectivity as well as propylene selectivity. Again, these catalysts are low hydrogen-transfer catalysts with good hydrothermal and coke-selective properties. All three types of catalyst are currently manufactured by Qilu Petrochemical Companys catalyst facility in China. Stone & Webster has qualified suppliers outside of China.

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DEEP CATALYTIC CRACKING, THE NEW LIGHT OLEFIN GENERATOR

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FEEDSTOCKS
The DCC process is applicable to various heavy feedstocks for propylene and isoolefin production. Feedstocks include wax, naphtha, thermally cracked gas oils, vacuum gas oils, hydrotreated feeds, and residual oils. Paraffinic feedstocks are preferred; however, successful pilot-plant trials have also been performed with naphthenic and aromatic feeds, although the olefin yields are significantly lower due to their lower hydrogen contents.

OPERATING CONDITIONS
A range of typical operating conditions for both type I (maximum propylene) and type II (maximum isoolefins) are shown in Table 3.2.2. Also indicated are typical FCC and SC operating conditions for comparison. A more severe reactor temperature is required for the DCC process than for FCC. Type II DCC reactor temperature is less severe than type 1, to increase isoolefin selectivity, but still more than FCC. Steam usage for DCC operations is higher than for FCC, but considerably less than for SC. DCC catalyst circulation rates are higher than FCC operations, while regenerator temperatures are similar or lower.

DCC PRODUCT YIELDS

DCC Maximum Propylene (Type I) A typical DCC maximum propylene yield slate for a Daqing (paraffinic) VGO is shown in Table 3.2.3. For comparison purposes, FCC and SC maximum olefin yields for the same feedstock are also shown in Table 3.2.3. Propylene is abundant in the DCC LPG stream and considerably higher than that for FCC. DCC LPG also contains a large amount of butylenes where the isobutylene fraction of the total butylenes is higher than that for FCC (38 to 42 wt % versus 17 to 33 wt %).2 Subsequent MTBE production is enhanced over FCC operations because of the additional available isobutylene. These high olefin yields are achieved by selectively overcracking naphtha. Large amounts of dry gas are produced by the DCC type I process because of the severe reactor temperature. DCC dry gas is rich in ethylene, which can be recovered for petro-

TABLE 3.2.2

DCC, FCC, and SC Operating Conditions DCC type I max, C3 DCC type II max., isoolefins 525550 670700 1.01.4 2 (riser) 711 1015 FCC 510550 670730 1.42.1 2 (riser) 58 27 SC 760870 1.0 0.10.2 3080

Temperatures: Reactor, C Regenerator, C Reactor pressure, kg/cm2 gage Reaction times, s Catalyst/oil, wt/wt Steam injection, wt % feed

550565 670700 0.71.0 * 915 2030

*Riser residence time approximately 2 s plus 220 weight hourly space velocity (WHSV) in reactor bed.

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DEEP CATALYTIC CRACKING, THE NEW LIGHT OLEFIN GENERATOR 3.42 TABLE 3.2.3 Cracking
CATALYTIC CRACKING

Yields for DCC Type I versus FCC and Steam Wt % of feed

Component H2 Dry gas (C1-C2) LPG (C3-C4) Naphtha (C5-205C) Light cycle oil (205330C) Slurry oil (330C ) Coke Light olefins: C2 C3 C4

DCC (type I) 0.3 12.6 42.3 20.2 7.9 7.3 9.4 5.7 20.4 15.7

FCC 0.1 3.8 27.5 47.9 8.7 5.9 6.1 0.9 8.2 13.1

SC 0.6 44.0 25.7 19.3 4.7 5.7 28.2 15.0 4.1

Source: Lark Chapin and Warren Letzsch, Deep Catalytic Cracking, Maximum Olefin Production, NPRA Annual Meeting, AM-94-43, Mar. 2022, 1994.

chemical sales. Nonetheless, the DCC operation produces considerably less dry gas and more LPG than steam cracking does. The primary DCC product is propylene, whereas ethylene is the major SC component. (Steam cracking is a thermal reaction whereas DCC is predominantly catalytic.) Because of high conversion, the DCC C5 liquid products are all highly aromatic. Consequently octane values of the DCC naphtha are very high. For this yield slate, an 84.7 motor octane number, clear (MONC) and 99.3 research octane number, clear (RONC) were measured.3 DCC C5 naphtha has greater than 25 wt % benzene, toluene, and xylene (BTX) content and is a good BTX extraction candidate. Because of high diolefin content, selective hydrotreating is usually required. Selective hydrotreating can be achieved without losing octane. The coke make is somewhat higher than that in FCC operation. The higher heat of reaction required for the conversion of the feed to DCC products and the high reactor temperature add to the coke yield. The sensitivity of olefin yield for three VGO types is shown in Table 3.2.4. Daqing VGO is highly paraffinic. Arabian light is moderately aromatic, while Iranian is highly aromatic. Propylene and butylene yields are very high for paraffinic feedstocks and decrease for the most aromatic feeds. The data were generated in RIPPs 2 barrel per day (BPD) DCC pilot unit but have been commercially verified.

DCC Maximum Isoolefin (Type II) DCC type II yields are shown in Table 3.2.5. Large olefin yields are produced by overcracking naphtha at less severe conditions than for type I. The high olefin selectivity is indicative of very low hydrogen transfer rates. Butylene and amylene isomer breakdowns are shown in Table 3.2.6. Note that the isoolefins in the DCC type II operation approach their respective thermodynamic equilibrium. As a result, isobutylene and isoamylene yields are very large, each over 6.0 wt % of feed.

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DEEP CATALYTIC CRACKING, THE NEW LIGHT OLEFIN GENERATOR

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TABLE 3.2.4

DCC Type 1 Olefin Yields for Various VGO Feedstocks Daqing Arabian Light* 0.88 11.9 4.3 16.7 12.7 Iranian* 0.91 11.7 3.5 13.6 10.1

Specific gravity UOP K factor Olefin yield, wt % feed: C2 C3 C4

0.84 12.4 6.1 21.1 14.3

*Hydrotreated vacuum gas oil.

TABLE 3.2.5 DCC Maximum Isoolefin Yields (Type II) Component C2 C3-C4 C5 naphtha Light cycle oil Heavy cycle oil Coke Loss Light olefins: C2 C3 C4 i-C4 C5 i-C5 Yield, wt % of feed 5.59 34.49 39.00 9.77 5.84 4.31 1.00 2.26 14.29 14.65 6.13 9.77 6.77

Source: Z. T. Li, W. Y. Shi, N. Pan, and F. K. Jaing, DCC Flexibility for Isoolefins Production, Advances in Fluid Catalytic Cracking, ACS, vol. 38, no. 3, pp. 581583.

DCC INTEGRATION
It is possible to incorporate a DCC process in either a petrochemical or a refining facility. Idled FCC units in operating facilities are particularly attractive for DCC implementation. A few possible processing scenarios are discussed. One possible scenario is utilization of a DCC unit to increase propylene production in an ethylene facility. DCC naphtha, ethane, propane, and butane could be sent to the SC unit for additional ethylene yield. It may be possible to debottleneck the existing product splitter to accommodate the DCC gaseous stream. A petrochemical facility can be designed to take whole crude oil as the feed where the naphtha goes to a steam cracker and the heavier components go to a DCC unit.

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DEEP CATALYTIC CRACKING, THE NEW LIGHT OLEFIN GENERATOR 3.44 TABLE 3.2.6
CATALYTIC CRACKING

Olefin Isomer Distribution DCC Type II Operation Equilibrium value 14.7 24.5 16.7 44.1 5.2 12.2 12.0 70.6 DCC max. isoolefin 12.8 26.7 18.6 41.9 5.2 17.6 7.9 69.3

Component, wt % Butylene isomers: 1-butene t-2-butene c-2-butene Isobutylene Amylene isomers: 1-pentene t-2-pentene c-2-pentene Isoamylene

Source: Z. T. Li, W. Y. Shi, N. Pan, and F. K. Jaing, DCC Flexibility for Isoolefins Production, Advances in Fluid Catalytic Cracking, ACS, vol. 38, no. 3, pp. 581583.

A DCC unit could be incorporated into a refining facility for polypropylene and styrene production. An example of such a processing scheme is shown in Fig. 3.2.3. Another example of DCC integration is for supporting reformulated gasoline production, as shown in Fig. 3.2.4. An ethylene recovery unit using Stone & Websters ARS technology could be incorporated into this scheme for polymer ethylene and propylene sales.

REFERENCES
1. Lark Chapin and Warren Letzsch, Deep Catalytic Cracking Maximize Olefin Production, NPRA Annual Meeting, AM-94-43, Mar. 2022, 1994. 2. C. Xie, W. Shi, F. Jiang, Z. Li, Y. Fan, Q. Tang, and R. Li, Research and Development of Deep Catalytic Cracking (DCC Type II) for Isobutylene and Isomylene Production, Petroleum Processing and Petrochemicals, no. 5, 1995. 3. L. Zaiting, J. Fakang, and M. Enze, DCCA New Propylene Production Process from Vacuum Gas Oil, NPRA Annual Meeting, AM-90-40, Mar. 2527, 1990. 4. Lark Chapin, W. S. Letzsch, and T. E. Swaty, Petrochemical Options from Deep Catalytic Cracking and the FCCU, NPRA Annual Meeting, AM 98-44. 5. Wang Yamin, Li Caiying, Chen Zubi, and Zhong Xiaoxiang, Recent Advances of FCC Technology and Catalyst in RIPP, Proceedings of 6th Annual Workshop on Catalysts in Petroleum Refining and Petrochemicals, December 1996. KFUPM, Dhahran, Saudi Arabia. 6. Andrew Fu, D. Hunt, J. A. Bonilla, and A. Batachari, Deep Catalytic Cracking Plant Produces Propylene in Thailand, Oil & Gas Journal, Jan. 12, 1998. 7. Zaiting Li, Jiang Fukang, Xie Chaogang, and Xu Youhao, DCC Technology and Its Commercial Experience, China Petroleum Processing and Petrochemical Technology, no. 4, December 2000.

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FIGURE 3.2.3 Polypropylene and styrene production scheme (EXT = aromatics extraction, HDA = hydrodealkylation, SHP 5 selective hydrogenation).

FIGURE 3.2.4

Reformulated gasoline production scheme.

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