Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 8.5

UOP CATALYTIC DEWAXING PROCESS

Hemant Gala
UOP LLC Des Plaines, Illinois

INTRODUCTION
The UOP Catalytic Dewaxing process, formerly known as the Unicracking* /DW* process, is a fixed-bed process for improving the cold flow properties of various hydrocarbon feedstocks. The process is applied for improving the pour point of lube oil base stocks (LOBSs) and middle distillates, cloud point of diesel fuel, and freeze point of jet fuel. These properties are critical for the low-temperature performance of these products. The cold flow properties are strongly related to the normal and near-normal (minimally branched) paraffins present in these LOBSs and fuels. As the concentration of the normal and near-normal paraffins increases in these hydrocarbon feedstocks, their pour point, cloud point, and freeze point temperatures increase. The cold flow property temperatures also increase with the molecular weight (chain length) of the paraffins. The UOP Catalytic Dewaxing process improves the cold flow properties by selectively cracking the longchain normal and near-normal paraffins from the hydrocarbon steams. The Catalytic Dewaxing process operates across a rather narrow range of design parameters. The primary roles are LOBS dewaxing and middle-distillate flow property improvement. At the same time, the process deep-hydrotreats kerosene or diesel fuel to remove sulfur and nitrogen and also saturates aromatic compounds. Key process features of the Catalytic Dewaxing process include

Excellent product stability Excellent product color Constant product quality throughout a catalyst cycle Minimum viscosity reduction compared to other dewaxing processes Long catalyst cycle life Flexibility to produce lube stocks and process distillates in the same unit

*Trademark and/or service mark of UOP. *Trademark and/or service mark of UOP.

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PROCESS DESCRIPTION
The Catalytic Dewaxing process uses a dual-function, non-noble-metal zeolite catalyst to selectively hydrocrack the long-chain paraffinic components in the feedstock. Typically, the first stage of the process involves hydrotreatment of the incoming feedstock through olefin saturation, desulfurization, and denitrification reactions. Pretreating protects the dewaxing catalyst and provides a feed with a low organic sulfur and nitrogen content, which improves the hydrocracking performance. Pretreatment of the feed may not be necessary if the feed is relatively free of organic sulfur and nitrogen. The process uses two kinds of catalysts. The first is a high-activity desulfurization and dentrification catalyst, which gives an optimum balance between process objectives and cost. The second, a proprietary dewaxing catalyst, selectively cracks straight-chain paraffins. The zeolite support used for the dewaxing catalyst has a pore size that selectively allows the normal and near-normal paraffins to enter the pore structure at the expense of highly branched paraffins. As a result, the rate of cracking for the normal and near-normal paraffins is much higher than that for the branched paraffins. The very selective reduction of the long-chain paraffins thus achieved improves the cold flow properties of the hydrocarbon feedstock. The flexible catalyst system of pretreat and dewaxing catalyst enables a refiner to vary the feedstocks and contaminants without affecting product quality or run length. UOP has several highly active, long-lived Catalytic Dewaxing catalysts. Process objectives determine the type of catalyst used in a particular unit. Catalytic Dewaxing catalysts typically last 6 to 8 years. During that time, they are regenerated as needed. Typical cycles last 2 to 4 years between regenerations.

PROCESS FLOW
Figure 8.5.1 shows a simplified process flow for a typical Catalytic Dewaxing unit. Fresh feed is preheated and combined with hot recycle gas. The mixture enters the first reactor for treating by a high-activity denitrogenation-desulfurization catalyst, which converts organic nitrogen and sulfur to ammonia and hydrogen sulfide. The reactions are exothermic and cause a temperature rise in the reactor. The reactions are maintained at as low a temperature as possible to maximize catalyst life. Figure 8.5.1 shows two reactors for simplicity. In an actual design, both the pretreat and the dewaxing catalysts an be loaded in a single reactor. The choice of one versus two reactors depends on the feed rate to the unit, reactor size limitations (if any), operational flexibility desired, etc. The effluent from the pretreat section is cooled with cold quench gas before entering the dewaxing section, which contains one of UOPs highly selective Catalytic Dewaxing catalysts. These active catalysts function well in the presence of ammonia and hydrogen sulfide. As the feed flows over the dewaxing catalyst, long-chain normal paraffins are selectively cracked into smaller molecules, thereby improving the desired cold flow property of the feed. The average temperature in the dewaxing section is adjusted to obtain the targeted improvement in the cold flow property. Dewaxing reactions are exothermic and must be closely controlled because the dewaxing catalyst is sensitive to temperature. As in the pretreater section, reactor temperatures are maintained as low as possible. In the dewaxing section, this low temperature not only prolongs catalyst life, but also maximizes liquid yields and helps maintain control. In both reactors, temperature is controlled by the injection of cold, hydrogen-rich recycle gas at predetermined points. A unique combination of patented internals allows for sufficient mixing of recycle gas with the hot reactants emerging from the previous catalyst bed and the effective distribution of the quenched mixture to the top of the next catalyst bed.

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UOP CATALYTIC DEWAXING PROCESS

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FIGURE 8.5.1

Catalytic Dewaxing process.

Effluent from the dewaxing section is cooled by exchange with several process streams, including feed and recycle gas. The effluent is then flashed into a hot high-pressure separator, where liquid products are separated from hydrogen-rich vapors. The liquid fraction from this separator is directed to the fractionation section, and vapors are sent to a cold high-pressure separator after being cooled in reactor effluent coolers. Steam condensate or deaerated boiler feedwater is injected upstream of the reactor effluent air condensers to minimize corrosion and prevent deposition of ammonia salts. The cold-separator vapor is joined by hydrogen makeup gas to become recycle gas. Liquid hydrocarbon flows into a low-pressure separator. Flash gas from the low-pressure separator is routed to a light-ends recovery unit or to sour fuel gas. Liquid hydrocarbon from the low-pressure separator exchanges heat with the reactor effluent before flowing into the stripper in the fractionation section.

YIELD PATTERNS
The Catalytic Dewaxing process can be applied to a wide range of feedstocks for dewaxing purposes. Table 8.5.1 shows typical yields and properties for vacuum gas oil (VGO) and diesel applications.

INVESTMENT AND OPERATING EXPENSES

The capital investment associated with a Catalytic Dewaxing unit is closely related to the feedstock type and quality as well as the desired level of dewaxing for final products. The capital investment for a typical Catalytic Dewaxing unit is given in Table 8.5.2, and utilities are listed in Table 8.5.3. The unit can be designed to provide the flexibility of processing very different feedstocks in blocked mode of operation. Considerable cost savings is achieved in such a

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TABLE 8.5.1 Typical Yield and Property Patterns for Catalytic Dewaxing Process VGO feed Yields, wt %: C1C3 C4260C (500F) naphtha Dewaxed product Feed properties: API gravity Sulfur, wt ppm Nitrogen, wt ppm Viscosity, cSt at 100C (212F) Pour point, C (F) Dewaxed product properties: API gravity Sulfur, wt ppm Nitrogen, wt ppm Viscosity, cSt at 100C (212F) Pour point, C (F)
Note: API

Diesel feed 2.50 24.50 73.00 35.1 1.7 1.0 21 (70) 37.5 1.0 1.0 12 (110)

0.50 24.50 75.00 27.7 9500 690 4.25 30 (86) 27.4 20 20 3.63 20.5 (25.0)

degrees on American Petroleum Institute scale.

TABLE 8.5.2

Capital Investment 165.7 (25,000) 28.3 0.8855 0.64 380 36

Unit feed rate, m3/h (BPSD) Feedstock: API gravity Specific gravity Sulfur, wt % Nitrogen, wt ppm Estimated erected cost, million $
Note: BPSD barrels per stream day.

design by eliminating duplicate equipment that may be necessary in two stand-alone units. Some compromise in the design of some equipment may be necessary to accommodate the processing objectives of the two feeds.

COMMERCIAL EXPERIENCE
Several UOP licensed Catalytic Dewaxing plants have been put into operation or are in design. The first unit was a vacuum gas oil unit processing 10,000 BPD of shale oil to remove paraffins at Unocals shale oil plant in Parachute, Colorado. In 1988, a Unicracking/DW unit was commissioned at OMVs Schwechat refinery in Austria. This unit was designed to met two objectives: deep hydrogenation and pour point reduction of high-viscosity VGO feedstocks. During the winter months, this same unit is used to improve the pour point of diesel.1 The second catalyst cycle in the OMV Unicracking/DW unit began in July 1992 and ran for about 5 years. Both the pretreat and the dewaxing catalysts show excellent stabili-

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UOP CATALYTIC DEWAXING PROCESS

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TABLE 8.5.3

Utilities 5100 Minimal 80 (352) 4 (17.6) 20.5 (81.3)

Power, kW Steam (tracing only) Cooling water, m3/h (gal/min) Condensate, m3/h (gal/min) Fuel absorbed, million kcal/h (million Btu/h)

ty of the UOP HC-K catalyst in the pretreating reactor and UOP HC-80 catalyst in the downstream dewaxing reactor.2 What makes this stability even more impressive is the high level of contaminants that the HC-80 dewaxing catalyst is tolerating. During this cycle, the unit averaged 133 percent of the design feed rate and had typical feed sulfur and nitrogen contents of 0.9 wt % and 700 wt ppm, respectively. At these conditions, the HC-80 catalyst is routinely processing effluent directly from the pretreating reactor that contains an average of more than 100 wt ppm unconverted nitrogen with no detrimental effects. This unit easily met all OMVs processing objectives. Even at the high feed rate, the pour point of the VGO feedstock was reduced by more than 100F. The dewaxed product met all other specifications, and the yield structure was quite stable. When processing diesel, the pour point was reduced by about 35F, the cloud point was reduced by about 80F, and the diesel product had excellent color (0.5 ASTM). The products from both the VGO and diesel operations contain less than 20 ppm sulfur and less than 20 ppm nitrogen. The unit is currently in its third cycle.

BIBLIOGRAPHY
1. R. Bertram, and F. Danzinger: NPRA Annual Meeting, San Antonio, Tex., March 1994, AM-94-50. 2. D. C. Martindale, G. J. Antos, K. Baron, and R. Bertram: NPRA Annual Meeting, San Antonio, Tex., March 1997, AM-97-25.

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UOP CATALYTIC DEWAXING PROCESS

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