Source: HANDBOOK OF PETROLEUM REFINING PROCESSES

CHAPTER 1.7

CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP)

Mark L. Gravley
ConocoPhillips Fuels Technology Bartlesville, Oklahoma

INTRODUCTION
During the late 1930s, Phillips Petroleum Company researchers discovered the benefits of using hydrofluoric acid to catalyze the synthesis of high-octane fuels from a broad range of low-value C3, C4, and C5 feedstocks. This research, as well as pilot-plant data, led to the commercialization of the HF Alkylation process at Phillips Borger, Texas, refinery in 1942 to provide aviation gasoline during World War II. Since that time, alkylate has been, and continues to be, a valuable high-octane blending component for gasoline, as evidenced by its importance in refineries around the world. ConocoPhillips has built 11 HF Alkylation units in its own refineries and has licensed over 100 grassroots units. Today, worldwide alkylation capacity exceeds 1.81 million bbl/day, with HF-based processes accounting for approximately 57 percent of the total. Isobutane alkylate is an important component of modern fuels, due to the high-octane, clean-burning characteristics as well as the low vapor pressure and absence of sulfur, olefins, or aromatics. Alkylation is receiving renewed attention by refiners contemplating the replacement of MTBE in gasoline.

CHEMISTRY
Alkylation occurs when isobutane reacts with olefins in the presence of hydrofluoric acid as the catalyst to produce branched paraffins. In simplest terms, those reactions are

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CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP) 1.80

ALKYLATION AND POLYMERIZATION

Propylene Isobutylene 1-Butene 2-Butene

isobutane 2,3-dimethylpentane isobutane 2,2,4-trimethylpentane isobutane 2,2-dimethylhexane

isobutane 2,2,4- and 2,3,4-trimethylpentane isobutane C9H20 (various isomers)

Amylene

The trimethylpentanes are the preferred reaction products because they generally have the highest octane value. In practice, however, the reactions are not so simple. Reactions involving isomerization, hydrogen transfer, dimerization, polymerization, -scission (or cracking), and disproportionation lead to a range of products. Furthermore, these side reactions produce substantial quantities of trimethylpentanes even when propylene or amylenes are the olefin feed. Polymerization produces conjunct polymers, which are complex, cyclic molecules, and this material is known as acid-soluble oil (ASO). The reactions are also affected by the dispersion of hydrocarbons in the acid, the reaction temperature, the ratio of isobutane to olefin in the reaction zone, and the presence of water and ASO in the circulating acid. Since the hydrocarbon feeds are only slightly soluble in the HF acid, the reaction is enhanced by dispersing the hydrocarbons in the acid. Improved dispersion, i.e., smaller droplets of hydrocarbon, results in an alkylate product with more of the desired trimethylpentanes and lower amounts of the undesirable lighter and heavier compounds. Lower reaction temperature also favors the desired reaction products. A large excess of isobuteneabove the stoichiometric amountalso favors the production of higher amounts of trimethylpentanes. Thus, the purity of isobutane in the recycle stream has an effect on alkylate quality, and buildup of C5 components in this stream should be avoided. Small amounts of water enter the alkylation unit in the olefin and isobutane feeds. The water is allowed to accumulate in the acid phase and is found to be beneficial in that it produces alkylate with higher concentration of C8 components and thus higher octane. Water in the HF is beneficial at levels up to about 3 to 4 wt %. However, water contents above about 2.0 percent generally have a detrimental effect on corrosion rates in the unit and are avoided.

DESCRIPTION OF THE CONOCOPHILLIPS HF ALKYLATION PROCESS

Isobutane reacts with propylene, butenes, and/or amylenes in the presence of hydrofluoric acid to produce a high-octane alkylate for motor gasoline. The reactions produce a variety of products, primarily C8 branched paraffins, with lesser amounts of C7 and C9 branched paraffins and small amounts of lighter and heavier paraffins. For best operation, the following feedstock contaminant levels are recommended: Sulfur20 wt ppm maximum Water20 wt ppm maximum Butadiene3000 wt ppm maximum C6 0.1 LV % maximum Oxygenates (MTBE, dimethyl ether, etc.)30 wt ppm maximum An alkylation unit will operate with feed contaminant at higher than the levels indicated above, but the adverse consequences are higher acid consumption, higher production of

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CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP)

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unwanted by-products, and possible lower octane number of the alkylate product. One feed treatment to remove butadiene is hydroisomerization, such as the ConocoPhillips Hydrisom Process. Hydroisomerization reduces butadiene (and pentadienes) to very low levels and also isomerizes 1-butene to cis- and trans-2-butene. The 2-butene isomers give higher-octane alkylate in the HF Alkylation Process. Referring to the flow diagrams in Figs. 1.7.1 and 1.7.2, we see that the olefin and makeup isobutane are typically mixed and then dried. The combined olefin and makeup isobutane are mixed with the recycle isobutane and sent to the differential gravity reactor of Phillips proprietary design. This low-pressure reactor has no moving parts, such as impellers or stirrers, nor are there any pumps to circulate the acid. The feed mixture is highly dispersed into a moving bed of liquid acid, which circulates because of the difference in density between the acid and the hydrocarbon. Total conversion of olefins to alkylate occurs very quickly. Operating conditions in the reactor are relatively mild. The temperature will typically be about 80 to 110F (27 to 43C), or only 5 to 15F (2.5 to 8C) above the cooling-water temperature. The pressure will be only slightly above that required to maintain the hydrocarbons in the liquid phaseusually in the range of 85 to 120 lb/in2 gage (590 to 820 kPa). Each alkylation design case is carefully studied in order to maximize heat recovery and minimize the isobutene/olefin ratio, while producing alkylate of sufficient octane quality to meet the refiners needs. Isobutane/olefin ratios in the range of 8 : 1 to 13 : 1 are typically used. From the reaction zone, the hydrocarbons and catalyst flow upward to the settling zone (see Fig. 1.7.3). Here, the catalyst separates as a bottom phase and flows, by gravity, on a return cycle through the acid cooler to the reaction zone, where the reaction cycle is continued. The hydrocarbon phase from the settling zone, containing propane, excess isobutane, normal butane, alkylate, and a small amount of HF, is charged to the fractionation section. Recycle isobutane, essential for favorable control of reaction mechanisms, is returned to the reactor from the fractionator either as a liquid or as a vapor. In the latter case, the latent heat of vaporization is recovered in nearby exchangers. Propane and HF are produced overhead in the fractionator. The HF phase separates in the overhead accumulator, which is shared with the HF stripper, and is returned to the acid settler. What HF remains in the propane from the fractionator is removed in the HF stripper, separates in the overhead accumulator, and is returned to the acid settler. The propane product from the HF stripper contains traces of propyl fluoride, which are removed in the propane defluorinators. The propane stream is heated and passed over alumina to remove the fluoride, yielding primarily aluminum fluoride and water with a trace of HF. The propane is sent through the KOH treater to remove the trace of HF and then to storage. A similar set of equipment may be used to treat n-butane, if it is produced as a separate product stream. The n-butane product may be blended with gasoline for vapor pressure control. Alkylate is produced as a bottoms product from the fractionation section. The alkylate product is suitable for blending in motor gasoline, but may require additional fractionation for use in aviation gasoline. To regenerate the system acid, a small slipstream of acid is fed to the acid rerun column to remove the ASO. The HF is stripped from the ASO with hot isobutane. The ASO is washed in the ASO caustic washer to remove free HF, and the ASO is disposed of, typically by burning in the reboiler furnace or blending with fuel oil. Excess water is also removed from the system acid in the acid rerun column. Auxiliary systems within the alkylation unit include Relief-gas neutralizer to remove HF from gases before being sent to the refinery flare Storage for anhydrous HF during periods when the unit is down for maintenance 3. A neutralizing system for surface drainage and sewer drainage in the acid area
1. 2.

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ACID SETTLER

HF ACID TO SETTLER

REACTOR/ RISER MAIN FRACTIONATOR

HF STRIPPER

ACID COOLER

ACID STORAGE NORMAL BUTANE PROPANE DEFLUORINATORS PROPANE PRODUCT PROPANE KOH TREATER BUTANE PRODUCT ACID SOLUBLE OIL BUTANE DEFLUORINATORS BUTANE KOH TREATER

FEED DRYERS

ACID RERUN COLUMN

ISOBUTANE FEED

OLEFIN FEED

RECYCLE ISOBUTANE

CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP)

ACID SOLUBLE OIL TO FUEL

ASO CAUSTIC WASHER

ALKYLATE PRODUCT

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FIGURE 1.7.1

Flow diagram of the ConocoPhillips HF Alkylation process.

HF ACID TO SETTLER

ACID SETTLER HF STRIPPER

DEPROPANIZER

REACTOR/ RISER PROPANE PRODUCT PROPANE DEFLUORINATORS PROPANE KOH TREATER

ACID COOLER

ACID STORAGE

FEED DRYERS ISOSTRIPPER

ACID RERUN COLUMN

ISOBUTANE FEED BUTANE DEFLUORINATORS ACID SOLUBLE OIL

BUTANE PRODUCT BUTANE KOH TREATER

OLEFIN FEED

RECYCLE ISOBUTANE

ACID SOLUBLE OIL TO FUEL

CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP)

ASO CAUSTIC WASHER

ALKYLATE PRODUCT

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FIGURE 1.7.2

Flow diagram of the ConocoPhillips HF Alkylation processalternate fractionation scheme.

CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP) 1.84

ALKYLATION AND POLYMERIZATION

ACID SETTLER

ACID STORAGE

REACTOR RISER

COOLING WATER OUT

HYDROCARBON FEED IN ACID OUT COOLING WATER IN FIGURE 1.7.3

ConocoPhillips HF Alkylation reactor/settler system.

A change room and storage room for cleaning and storing the protective clothing required on occasion by operating and maintenance personnel 5. Wastewater treatment system to remove more than 99 percent of the soluble fluoride in the effluent water
4.

HF Alkylation units are constructed predominately of mild carbon steel. Only the acid regeneration column and some adjacent piping are constructed of nickel-copper alloy 400 (Monel). Other than a small centrifugal pump for charging HF to the acid rerun column, no HF pumping is required in the ConocoPhillips HF Alkylation process. HF unloading from shipping containers and HF transfers from in-plant storage are accomplished by using nitrogen or other gas under pressure.

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CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP)

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WASTE TREATMENT AND DISPOSAL

Figure 1.7.4 shows the disposition of various waste streams within the alkylation unit. Nonacid gas streams are sent directly to the refinery flare system. HF-containing gases are sent first to the acid relief neutralizer, where the gases are scrubbed with an aqueous solution of sodium hydroxide for removal of HF, and then to the refinery flare. The spent caustic solutions from the acid relief neutralizer and the ASO caustic washer are sent to a mixing basin, where they are combined with calcium chloride. This mixture then flows to the precipitation basin, where the calcium fluoride precipitates out of solution. The liquid flows to the refinery wastewater system, and the solid is periodically sent to the landfill for disposal. The water from the calcium chloride precipitation system contains nominal amounts of sodium chloride and calcium chloride. Spent caustic from the KOH treaters and runoff from drains in the acid area of the plant flow to a neutralization pit and then to the refinery wastewater system. Water from nonacid drains and sewers goes directly to the refinery wastewater system. Used aluminacontaining aluminum fluoridefrom the defluorinators may be returned to the alumina supplier to be converted back to alumina.

RISK REDUCTION AND SAFETY

The following principles may be used in the HF Alkylation process to minimize risk: Minimize leak potential (few leak sites) 2. Minimize leak rate (i.e., minimum reactor/settler pressures) 3. Minimize leak duration 4. Minimize quantity released
1.

One step to reduce risk is the elimination of any pumps for circulating HF catalyst through the reactor system. By eliminating rotating equipment, potential packing and seal failures associated with the equipment were eliminated, along with the dangers of frequent maintenance exposure. Without the acid pump, isolation valves were no longer required in the reactor/settler circulation system. Elimination of the acid pump allows the acid settler to operate at a minimum pressure, which minimizes the leak rate. The result is that for more than 40 years the reactor circuit design has only welded joints (built to pressure vessel codes) for joining the reactor and acid return pipes to the acid cooler and acid settler. No flanges are used to join these pipes, so these potential leak or failure sites do not exist. This is important since more than 90 percent of the HF on-site is contained in this circuit alone. Risk is further reduced by using such features as remote isolation valves, rapid acid transfer (transfer to secure storage in less than 10 minutes), and inventory compartmentalization. For units with multiple acid coolers, the bottom portion of the acid settler is divided into compartments to reduce the amount of acid that could be released in the event of a major leak. The compartments segregate the acid in each acid cooler/reactor circuit such that the maximum amount of acid which could be released from a leak in one acid cooler or reactor section is only slightly more that that contained in each compartment. The rapid transfer of acid to secure storage is done by gravity flow; i.e., no pumping is required, and it has been accomplished in as little as 90 seconds. These features reduce risk by reducing both the duration of a leak and the amount of acid that could be emitted in the event of a leak. Water spray mitigation systems may also be employed to improve safety. Water sprays can be used to knock down airborne HF from small leaks and, to some extent, isolate hydrocarbon leaks from ignition sources.

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NONACID RELIEF NONACID PUMP VENTS NONACID GAS VENTS REFINERY FLARE (GASES) ACID RELIEF NEUTRALIZER NaOH NaOH CALCIUM CHLORIDE SODA ASH SPENT CAUSTIC MIXING BASIN SPENT CAUSTIC NEUTRALIZATION PIT CALCIUM FLUORIDE PRECIPITATION FACILITY (LIQUID) REFINERY WASTEWATER SYSTEM (LIQUID)

HF SERVICE RELIEF HF SERVICE PUMP VENTS VENT GAS ABSORBER VENT

SPENT CAUSTIC FROM ASO WASHER

SPENT CAUSTIC FROM KOH TREATERS STORM SEWERS AND DRAINS IN THE ACID-CONTAINING AREA

(SOLID) LANDFILL

CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP)

NONACID STORM SEWERS AND DRAINS

SPENT ALUMINA FROM ALUMINA TREATERS

RECYCLE TO MANUFACTURER

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FIGURE 1.7.4

Waste disposalConocoPhillips HF Alkylation process.

CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP)

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A quantitative risk assessment was performed on a large (15,000 BPSD) HF Alkylation unit located in hypothetical rural and urban locations with up to 400,000 people in a 36mi2 area around the refinery. Risk is site-specific and cannot be easily calculated for a particular location. However, even in the highest population area studied, the current 15,000 BPSD design achieved a Societal Risk Index (SRI) of 0.098well within the Dutch standards limit of 0.2, which is the strictest in the world. Individual risks for fatality due to being struck by a falling aircraft are said to be 10,000 times higher than the level of risk that the Dutch standard calls unacceptable. No U.S. HF alkylation site has as many people living nearby as the case where the process measured the 0.098 SRI value. The ReVAP (for Reduced-Volatility Alkylation Process) is very similar to conventional HF Alkylation with the exception that a vapor pressure suppression additive is blended with the HF acid. Mobil Oil Corporation and Phillips Petroleum Company developed the ReVAP technology jointly in the early 1990s. Based upon bench-scale, pilot-plant, and demonstration plant tests, each company commercialized the ReVAP technology in 1997 in one of its own refineries, where the units continue to operate. The additive is a nonvolatile, nonodorous, low-toxicity material that is completely miscible in the acid phase, but has very limited affinity to other hydrocarbons, including acidsoluble oil. These unique physical properties of the additive reduce the volatility of the acid significantly at ambient conditions. Furthermore, the additive is compatible with the metallurgy of existing HF Alkylation units. When the additive is mixed with HF acid, it mitigates an acid leak in three ways: by (1) reducing the flash atomization of the acid, (2) reducing the vapor pressure significantly, and (3) diluting the acid. This is a passive mitigation system in that it is always effective and requires no intervention by an operator. Traces of the additive accumulate in the heavier unit products of ASO and alkylate. The ASO is removed from the system acid in the acid rerun column in the normal manner. The ASO is then sent to a simple and efficient recovery system where the ASO and additive are separated. The additive is returned to the reactor, and the ASO is sent to the ASO caustic washer and treated in the normal manner. Additive is separated from alkylate, recovered, and returned to the reactor. Figure 1.7.5 indicates the modifications required in an existing HF Alkylation unit to convert to the ReVAP technology. The ReVAP technology has the added benefit of reducing the consumption of HF and caustic, relative to the conventional HF Alkylation process. ReVAP increases the efficiency of separation of ASO and HF, thus reducing the loss of HF, which translates to lower caustic consumption as well.

YIELD AND PRODUCT PROPERTIES

Based on processing typical butenes produced by fluid catalytic cracking (FCC) and supplemental isobutane, Tables 1.7.1 and 1.7.2 give the premises for ConocoPhillips HF Alkylation process economics for a unit with the ReVAP technology producing 6000 bbl/day of alkylate.

ECONOMICS
The estimated capital cost for a plant producing 6000 bbl/day of alkylate indicated in the above material balance, utilizing the flow scheme in Fig. 1.7.1, including the auxiliary systems indicated in the section Description of ConocoPhillips HF Alkylation Process, with the ReVAP technology is $24.8 million. This cost is for a U.S. Gulf Coast location, second quarter, 2002. Initial catalyst cost, royalty, escalation, and contingency have been excluded.
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CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP) 1.88

ALKYLATION AND POLYMERIZATION

RECYCLE ISOBUTANE FEED REACTOR SECTION (EXISTING) PRODUCT SEPARATION (EXISTING)

ACID REGENERATION (EXISTING, POSSIBLE MODIFICATIONS REQUIRED)

ADDITIVE RECOVERY FROM ALKYLATE (NEW)

ALKYLATE

ADDITIVE EXPORT (IF REQUIRED) ADDITIVE RECOVERY FROM ASO (NEW)

ASO TO TREATMENT

ADDITIVE RECYCLE
FIGURE 1.7.5 Modifications for adding ReVAP to an existing HF Alkylation unit.

Table 1.7.1 Component

Material Balance, BPSD Olefin feed 153 115 2380 702 3068 20 56 2 0 0 6496 Makeup isobutene 0 7 1446 37 0 0 0 0 0 0 1490 Propane product 0 146 2 0 0 0 0 0 0 0 148 Butane product 0 0 38 571 0 0 0 26 0 0 635 Alkylate product 0 0 0 168 0 0 0 42 5790 0 6000 Acidsoluble oil 0 0 0 0 0 0 0 0 0 8 8

Propylene Propane Isobutane n-Butane Butenes 1,3-Butadiene Pentenes Pentanes Alkylate Acid-soluble oil Total

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CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP)

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Table 1.7.2

Product Properties 0.70 5.0 95.6 94.1 0 5 wt ppm 104 176 212 257 383

Specific gravity at 15C Reid vapor pressure, lb/in2 Research octane number, clear Motor octane number, clear Olefin Sulfur ASTM D-86 Distillation, F Initial boiling point 10 50 90 Final boiling point

Estimated Utilities Consumptions (Fig. 1.7.1 Flow Scheme), per 1000 bbl of Alkylate, Including ReVAP Technology Electricity (operating), kW Cooling water, million Btu Low-pressure steam (50 lb/in2 gage), million Btu Medium-pressure steam (170 lb/in2 gage), million Btu Fuel gas (absorbed), million Btu 77.4 15.1 0.6 1.4 10.0

Estimated Chemicals Consumptions, per 1000 bbl of Alkylate Anhydrous HF, lb NaOH, lb KOH, lb CaCl2, lb Defluorinator alumina, lb ReVAP additive (if used), lb 70100 47 9.3 79 11 4

Maintenance and Labor Costs Operating labor Laboratory labor Maintenance (materials plus labor) 2 persons per shift 1 person per day (8 h) 3% of investment per year

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CONOCOPHILLIPS REDUCED VOLATILITY ALKYLATION PROCESS (ReVAP) 1.90

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BIBLIOGRAPHY
Hutson, Jr., Thomas, and Richard S. Logan: Estimate Alky Yield and Quality, Hydrocarbon Processing, September 1975, pp. 107110. Lew, Lawrence E., Martyn E. Pfile, and Larry W. Shoemaker: Meet the Greater Demand for High Octane Blending Agents with HF Alkylation, Fuel Reformulation, March/April 1994. Randolph, Bruce B., and Keith W. Hovis: ReVAP: Reduced Volatility Alkylation for Production of High Value Alkylate Blendstock: Year 4, NPRA Annual Meeting, Mar. 1719, 2002, San Antonio, Tex., Paper AM-02-20.

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