Catalysts additives

Historically, the isomerization catalysts have included amorphous siUca-aluminas, zeoHtes, and metal-loaded oxides. AH of the catalysts contain acidity, which isomerizes the xylenes and if strong enough can also crack the EB and xylenes to benzene and toluene. Dual functional catalysts additionally contain a metal that is capable of converting EB to xylenes. 

Uncatalyzed addition of hydrochloric acid is accompanied by replacement of one hydroxyl group, giving high yields of 2,4-dichloro-2-buten-l-ol (58) with mercuric or cupric salt catalysts, addition occurs without substitution (59,60). 

Gels. Fluorosihcone fluids with vinyl functionahty can be cured using the platinum catalyst addition reactions. The cure can be controlled such that a gel or a soft, clear, jelly-like form is achieved. Gels with low (12% after 7 d) swell in gasoline fuel are useflil (9) to protect electronics or circuitry from dust, dirt, fuels, and solvents in both hot (up to 150°C) and cold (down to —65° C) environments. Apphcations include automotive, aerospace, and electronic industries, where harsh fuel—solvent conditions exist while performance requirements remain high. 

Shell Higher Olefins Process (SHOP). In the Shell ethylene oligomerization process (7), a nickel ligand catalyst is dissolved in a solvent such as 1,4-butanediol (Eig. 4). Ethylene is oligomerized on the catalyst to form a-olefins. Because a-olefins have low solubiUty in the solvent, they form a second Hquid phase. Once formed, olefins can have Htfle further reaction because most of them are no longer in contact with the catalyst. Three continuously stirred reactors operate at ca 120°C and ca 14 MPa (140 atm). Reactor conditions and catalyst addition rates allow Shell to vary the carbon distribution. 

The equivalent nickel content of the feed to the FCCU can vary from <0.05 ppm for a weU-hydrotreated VGO to >20 ppm for a feed containing a high resid content. The nickel and vanadium deposit essentially quantitatively on the cracking catalyst and, depending on catalyst addition rates to the FCCU, result in total metals concentrations on the equiUbrium catalyst from 100 to 10,000 ppm. 

Since the catalyst is so important to the cracking operation, its activity, selectivity, and other important properties should be measured. A variety of fixed or fluidized bed tests have been used, in which standard feedstocks are cracked over plant catalysts and the results compared with those for standard samples. Activity is expressed as conversion, yield of gasoline, or as relative activity. Selectivity is expressed in terms of carbon producing factor (CPF) and gas producing factor (GPF). These may be related to catalyst addition rates, surface area, and metals contamination from feedstocks. 

In addition to the fixed capital investment needed to purchase and install process equipment and auxiliaries, there is a continuous expenditure referred to as operating cost, which is needed to operate the process. The operating cost (or manufacturing cost or production cost) includes raw materials, mass-separating agents, utilities (fuel, electricity, steam, water, refrigerants, air, etc.), catalysts, additives, labor, and maintenance. The total annualized cost of a process is defined as follows ... 

Entry Substrate Catalyst Additive Solvent trans. cis ee (%) Referenee... 

A small amount of nickel in the FCC feed has a significant influence on the unit operation. In a clean gas oil operation, the hydrogen yield is about 40 standard cubic feet (scf) per barrel of feed (0.07 wi /r ). This is a manageable rate that most units can handle. If the nickel level increases to 1.5 ppm, the hydrogen yield increases up to 100 scf per barrel (0.17 wt%). Note that in a 50,000 barrel/day unit, this corresponds to a mere 16 pounds per day of nickel. Unless the catalyst addition rate is increased or the nickel in the feed is passivated (see Chapter 3), the feed rate or conversion may need to be reduced. The wet gas will become lean and may limit the pumping capacity of the wet gas compressor. 

A higher catalyst addition rate dilutes the concentration of metals and allows less time for the vanadium to get fully oxidized. 

These contaminates originate largely from the heavy (1,050-t- °F/ 566-t- °C), high-molecular weight fraction of the FCC feed. The quantity of these metals on the E-cat is determined by their levels in the feedstock and the catalyst addition rate. Essentially, all these metals in the feed are deposited on the catalyst. Most of the iron on the E-cat comes from metal scale from piping and from the fresh catalyst. 

B = Catalyst addition rate, pounds of catalyst per barrel of feed... 

Figure 3-14 is the graphical solution to the above equation and can be employed to estimate metals content of the E-cat, based on feed metals and catalyst addition rate. 

Figure 3-14. Catalyst metals content versus catalyst addition rate for 22°API Gravity Feed. (Source Katalystics Regional Technology Seminar, New Orleans, Louisiana, December 15, 1998.)...

The amount of fresh catalyst added is usually a balance between catalyst cost and desired activity. Most refiners monitor the MAT data from the catalyst vendor s equilibrium data sheet to adjust the fresh catalyst addition rate. It should be noted that MAT numbers are based on a fixed-bed reactor system and, therefore, do not truly reflect the dynamics of an FCC unit. A catalyst with a high MAT number may or may not produce the desired yields. An alternate method of measuring catalyst performance is dynamic activity. Dynamic activity is calculated as shown below ... 

Adding ZSM-5 catalyst additive is another process available to tlie refiner to boost production of light olefins. ZSM-5 at a typical concentration of 0.5 to 3.0 wt% is used in a number of FCC units to increase the gasoline octane and light olefins. As part of the cracking of low octane components in the gasoline, ZSM-5 also makes C. C4, and Cj olefins (see Figure 6-2). Paraffinic feedstocks respond the most to ZSM 5 catalyst additive.. 

Increasing catalyst activity by increasing fresh catalyst addition or fresh catalyst activity... 

Check Fresh Catalyst avsIlabiHty source Verity Catalyst addition rate... 

FCC feed hydrotreating Gasoline end point reduction FCC gasoline hydrotreating Catalyst additives Bio-catalytic desulfurization... 

Catalyst additives can reduce FCC gasoline sulfur by about 15%. They work by converting mercaptan, thiophene, etc., to H S. A secondary benefit of the additives is an approximate 10% reduction in the LCO sulfur. 

Improvements in the developments of catalyst additives for reducing gasoline sulfur and NO emission... 

Increasing use of catalyst additives to reduce gaseous emissions and to maximize light olefins. 

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