Zeolite catalysts petroleum fractions

Endewax [National Chemical dewaxing] A process for dewaxing heavy petroleum fractions by treatment with a catalyst which converts the long-chain hydrocarbons to shorter ones. The catalyst is a ZSM-5 -type zeolite in which some of the aluminum has been replaced by iron. Developed by the National Chemical Laboratory, Pune, India, and piloted in 1991. 

ISAL A hydrotreating process for removing sulfur and nitrogen compounds from petroleum fractions without reducing their octane values. Developed by Intevep SA, the research and technology arm of Venezuela s state petroleum company PDVSA. A proprietary zeolite catalyst first saturates the olefins and then isomerizes them to higher octane-value compounds. 

Selectoforming A process for increasing the octane rating of a petroleum fraction by selectively cracking the n-pcntanc and n-hcxanc in it. The catalyst is a metal-loaded synthetic zeolite. Developed by Mobil Corporation and first commercialized in the mid-1960s. 

In practice, short-chain alkanes and alkenes are normally used as feedstock for shape-selective catalytic formation of isooctanes at relatively low temperatures. Until the 1980s, lead alkyls (Section 18.1) were added to most automotive fuels to help suppress engine knock, but they have been phased out in North America because of the chronic toxicity of lead and lead compounds. The most commonly used nonlead antiknock additive is now methyl tert-butyl ether [MTBE CH30C(CH3)3], which is made by the reaction of methanol with 2-methylpropene, (CHs C—CH2 (see Section 7.4). The latter is obtained by catalytic cracking of petroleum fractions to give 1-butene, which is then shape-selectively isomerized on zeolitic catalysts. 

Figure 1731. Fluidized bed reactor processes for the conversion of petroleum fractions, (a) Exxon Model IV fluid catalytic cracking (FCC) unit sketch and operating parameters. (Hetsroni, Handbook of Multiphase Systems, McGraw-Hill, New York, 1982). (b) A modem FCC unit utilizing active zeolite catalysts the reaction occurs primarily in the riser which can be as high as 45 m. (c) Fluidized bed hydroformer in which straight chain molecules are converted into branched ones in the presence of hydrogen at a pressure of 1500 atm. The process has been largely superseded by fixed bed units employing precious metal catalysts (Hetsroni, loc. cit.). (d) A fluidized bed coking process units have been built with capacities of 400-12,000 tons/day.

The natural clay minerals are hydrous aluminum silicates with iron or magnesium replacing aluminum wholly or in part, and with alkali or alkaline earth metals present as essential constituents in some others. Their acidic properties and natural abundance have favored their use as catalysts for cracking of heavy petroleum fractions. With the exception of zeolites and some specially treated mixed oxides for which superacid properties have been claimed, the acidity as measured by the color changes of absorbed Hammett bases is generally far below the superacidity range. They are inactive for alkane isomerization and cracking below 100 °C and need co-acids to reach superacidity. 

For many catalysts, the major component is the active material. Examples of such unsupported catalysts are the aluminosilicates and zeolites used for cracking petroleum fractions. One of the most widely used unsupported metal catalysts is the precious metal gauze as used, for example, in the oxidation of ammonia to nitric oxide in nitric acid plants. A very fast rate is needed to obtain the necessary selectivity to nitric oxide, so a low metal surface area and a short contact time are used. These gauze s are woven from fine wires (0.075 mm in diameter) of platinum alloy, usually platinum-rhodium. Several layers of these gauze s, which may be up to 3 m in diameter, are used. The methanol oxidation to formaldehyde is another process in which an unsupported metal catalyst is used, but here metallic silver is used in the form of a bed of granules. 

Bifunctional zeolite catalysts such as platinum loaded acid zeolite catalysts are applied in several petroleum refinery operations, designated as hydroconversion processes isomerisation of light n htha, iso-dewaxing and hydrocracking of heavy fractions [4]. Most experimental investigations in academic laboratories are typically performed with pure model components or simple mixtures thereof as feedstock, and using reaction conditions under which the hydrocarbon compounds are in the vapor phase. Industrial hydroconversion processes are mostly run under three phase, or even in some cases under liquid phase conditions and with feedstocks that are extremely complex mixtures of large numbers of different hydrocarbon compounds [4]. 

As the number of important catalyst families increased in the post World War II decades, researchers began to specialize in areas such as ammonia catalysts, reforming and cracking of petroleum fractions, Ziegler-Natta catalysts, zeolites, homogeneous catalysis, and use of enzymes as industrial catalysts. Creating a unified discipline of catalysis from all these fields continues to be challenge today as it was in the past. 

The FCC process is the most important refinery process mainly for the production of gasoline from heavy petroleum fractions, such as atmospheric and vacuum gas oil (VGO). In the FCC unit, the long hydrocarbons are cracked in the 480—540°C temperature range over zeolite catalysts to smaller n- and i-parafiins, n- and i-olefins, and aromatics. Conventional FCC feedstocks are relatively aromatic, with a high sulfur and nitrogen content, in contrast to FT waxes that are highly paraffinic with extra-low aromatics content (<1 wt%) and viitually zero sulfur (<5 ppm) (see Table 18.4). The development therefore of new catalyst formulations, as well as optimization of the overall process parameters, are both very critical to optimize the yield and quality of FCC products from FT waxes. 

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