HF alkylation

HF All lation. The HF alkylation process was developed ia the late 1930s and commercialized ia the 1940s. Initially, the growth rate of capacity was lower than for H2SO4, but by the 1980s, the capacity was approximately equivalent. 

The modern HF alkylation processes are also differentiated primarily by the reactor system that is used. The Phillips process employs a gravity acid circulation system and a riser reactor (19). The UOP process uses a pumped acid circulation system and an exchanger reactor (20). 

Table 1. HF Alkylation Products from Pure Butene Isomers ...

The following HF alkylation reactions are based on straight-chain olefins. A similar chemistry can be written for the branched-chain process. The main reaction is the alkylation of benzene with the straight-chain olefins to yield a linear alkylbenzene ... 

Property AlCl alkylate HF alkylate Detal alkylate ... 

Figure 11.4-2 shows process flows for an HF alkylation unit. The three sections are 1) reaction, 2). settling and 3) fractionation. In the reaction section isobutane feed is mixed with the olefin feed (usually propylene and butylene) in approximately a 10 or 15 to 1 ratio. In the presence of the HF acid catalyst the olefins react to form alkylate for gasoline blending. The exothermic reaction requires water cooling. The hydrocarbon/HF mixture goes to the settling... 

Ni-Cr-Mo Ni-Mo Ni-Cu Chlorination processes Processes involving HCl and nonoxidising acidic chlorides Production and Distillation columns containing acidic chlorides HF alkylation Fluorination Applications where no pitting and no loss of reflectivity are necessary Valves, Bleaching operations Handling Pickling of... 

FIG. 14 Flow diagram of the HF alkylation process. R, reactor AS, acid settler HR, HF regenerator HS, SF stripper BC, benzene column PC, paraffin column RR, rerun column AT, aluminia treater VE, vacuum ejector. 

As a result of alkylation LAB is obtained with a clearly changed composition in comparison with the use of chloroparaffin. With respect to the dialkyl-tetralin content, values are obtained which are comparable to LAB from the HF alkylation process (same olefin base) (Table 11). Another important difference is the 2-phenylalkane content. The isomer distribution depends on the catalyst. The reaction between straight /z-chloroparaffins or n-olefins with benzene in the presence of aluminum chloride leads to the same isomer distribution. In both cases the 2-phenylalkane content is predominant compared to the 3-, 4-, and 5-phenylalkanes. If hydrogen fluoride is used as catalyst the 2-phenylalkane... 

The effect of carbon chain length and high vs. low 2-phenyl isomer distribution on viscosity and solubility (cloud/clear point) of a liquid hand dishwashing formulation is shown in Table 5. Two sets of pure LAS homolog samples ranging from Cl0 to Cl3 were prepared. All samples were prepared with pure olefins, but one set was produced with an HF alkylation catalyst (low 2-phenyl) and the other set was alkylated with A1C13 (high 2-phenyl). Each LAB... 

If some of the alkyl ligands in Ti, Zr, or Hf alkyls are replaced by halogen atoms, the following types of transition metal centers are obtained ... 

SOFT [Split-olefin feed technology] An improved version of Phillips HF alkylation process. 

The use of a single-stage CSTR for HF alkylation of hydrocarbons in a special forced-circulation shell-and-tube arrangement (for heat transfer) is illustrated by Perry et al. (1984, p. 21-6). The emulsion copolymerization of styrene and butadiene to form the synthetic rubber SBR is carried out in a multistage CSTR. 

The alkylation reaction is initiated by the activation of the alkene. With liquid acids, the alkene forms the corresponding ester. This reaction follows Markovnikov s rule, so that the acid is added to the most highly substituted carbon atom. With H2S04, mono- and di-alkyl sulfates are produced, and with HF alkyl fluorides are produced. Triflic acid (CF3S020H) behaves in the same way and forms alkyl triflates (24). These esters are stable at low temperatures and low acid/hydrocarbon ratios. With a large excess of acid, the esters may also be stabilized in the form of free carbenium ions and anions (Reaction (1)). 

Patents assigned to Mobil (217) describe the use of boron trifluoride supported on several porous carriers. BF3 supported on silica was found to exhibit a slightly higher performance with added water in the alkylation of a mixed alkene feed at 273 K. It was also shown that self-alkylation activity was considerably lower than that with HF as catalyst. Another patent (218) describes the use of a pillared layered silicate, MCM-25, promoted with BF3 to give a high-quality alkylate at temperatures of about 273 K. BF3 was also supported on zeolite BEA, with adsorbed water still present (219). This composite catalyst exhibited low butene isomerization activity, which was evident from the inferior results obtained with 1-butene. At low reaction temperatures, the product quality was superior to that of HF alkylate. 

At the heart of the UOP HF alkylation unit is a vertical reactor-heat exchanger, shown in Fig. 14. The isobutane-alkene mixture enters the shell of the reactor through several nozzles, and HF enters at the bottom of the reactor. The reaction heat is removed by cooling water, which flows through cooling coils inside the reactor. After phase separation in the settler, the acid is recycled to the reactor. The hydrocarbon phase together with a slipstream of used acid and makeup isobutane is sent to the isostripper , where the alkylate product, n-butane, and isobutane are separated. The isobutane is recycled to the reactor. During normal... 

HF alkylation an alkylation process whereby olefins (C3, C4, C5) are combined with isobutane in the presence of hydrofluoric acid catalyst. 

Hydrofluoric acid (HF) alkylation units have small acid remn units to purify the acid for reuse. HF units do not have a spent acid or spent caustic waste stream. Any leaks or spills that... 

Table 1. World-Wide Cost of Clean-Up and Make-Up in HF Alkylation.

Although not a separate process, isomerization plays an important role in pretreatment of the alkene feed in isoalkane-alkene alkylation to improve performance and alkylate quality.269-273 The FCC C4 alkene cut (used in alkylation with isobutane) is usually hydrogenated to transform 1,3-butadiene to butylenes since it causes increased acid consumption. An additional benefit is brought about by concurrent 1-butene to 2-butene hydroisomerization. Since 2-butenes are the ideal feedstock in HF alkylation, an optimum isomerization conversion of 70-80% is recommended.273... 

It is advantageous to pretreat butene feeds before alkylation.294-298 1,3-Butadiene is usually hydrogenated (to butenes or butane) since it causes increased acid consumption. The additional benefit of this process is that under hydrogenation conditions alkene isomerization (hydroisomerization) takes place, too. Isomerization, or the transformation of 1-butene to 2-butenes, is really attractive for HF alkylation since 2-butenes give better alkylate (higher octane number) in HF-cata-lyzed alkylation. Excessive 1,3-butadiene conversion, therefore, ensuring 70-80% isomerization, is carried out for HF alkylation. In contrast, approximately 20% isomerization is required at lower butadiene conversion for alkylation with H2SO4. 

Further improvements in alkylation can be achieved when an MTBE unit (acid-catalyzed addition of methanol to isobutylene to form tert-butyl methyl ether) is added before the alkylation unit.299 The MTBE unit removes the lowest-octane-producing isomer, isobutylene, from the C4 stream (and produces a very-high-octane number component, MTBE). The H2S04 alkylation unit then can be operated under better conditions to produce an alkylate with a somewhat increased octane number (0.75-1). Higher acid consumption, however, may be experienced as a result of methanol, MTBE and dimethyl ether impurities in the olefin feed. The combination of MTBE with HF alkylation offers no apparent advantages. 

Over the years H2S04 alkylation capacity has declined relative to HF alkylation.303,304 Reasons for this trend are a significantly lower acid consumption, overall lower operation costs, and less expensive regeneration plant cost and operating expenses of the HF alkylation process. Because of the mentioned environmental hazard associated with anhydrous HF and the need for further improvement of alkylate quality, improved technologies for sulfuric acid alkylation emerged, although it is improbable that there will be a major turnback to sulfuric acid alkylation. 

The early experimental work showed that the alkylation reactions could be carried out thermally and by using hydrofluoric acid or aluminum chloride as catalysts. Successful processes were developed with the hydrofluoric acid catalyst, and the first commercial HF unit started up on Christmas Day 1942, having a capacity of 1950 BPD (3). Other commercial HF alkylation units followed quickly. The thermal and aluminum chloride-catalyzed alkylation processes had limited commercial acceptance. 

The ranges of operating conditions normally used in commercial H2S04 and HF alkylation processes are shown in Table I. Both processes operate in the liquid phase at relatively low temperatures. For the best... 

---