Catalysts olefin cracking

Olefin cracking has been developed as a process to produce propylene in a highly selective manner from butenes and pentenes. Zeolites used in processes such as UOP s Olefin Cracking Process are often MFI-based in order to avoid coke buildup during the reaction, leading to longer times between catalyst regeneration (Table 12.15). 

Linear olefins are prepared by dehydrogenation of paraffins, by polymerization of ethylene to a-olefins using a triethyl aluminum catalyst (Ziegler-type catalyst), by cracking paraffin wax, or by dehydrohalogena-tion of alkyl halides. 

Modified silico-aluminate materials were investigated as candidates for inclusion in mat-ricies of FCC catalysts for cracking heavy hydrocarbons. Through thermal and chemical treatments of kaolinite is possible to gain at least 40 conversion units with respect to the base material, as well as a reduction of 75 wt.% of heavy cycle oil and a 500 % increase in high-olefinic LPG yield. 

Olefins crack more readily than paraffins since double C=C bonds are more friable under reaction conditions. Iso-paraffins and naphthenes are cracked more readily than normal paraffins, which in turn are cracked more readily than aromatics. In fact, aromatic ring compounds are very resistant to cracking, since they readily deactivate fluid cracking catalysts by blocking the active sites of the catalyst (see the next part). The reactions postulated for olefin compounds apply principally to intermediate products within the reactor system, since the olefin content of catalytic cracking feedstock is usually very low. 

Oxidic catalysts with acidic properties catalyze many industrial reactions, including the dehydration of alcohols, the hydration of olefins, cracking processes, and olefin polymerization. How does the acidity of such solids arise ... 

Thermal polymerization is not as effective as catalytic polymerization but has the advantage that it can be used to polymerize saturated materials that caimot be induced to react by catalysts. The process consists of the vapor-phase cracking of, for example, propane and butane, followed by prolonged periods at high temperature (510—595°C) for the reactions to proceed to near completion. Olefins can also be conveniendy polymerized by means of an acid catalyst. Thus, the treated olefin-rich feed stream is contacted with a catalyst, such as sulfuric acid, copper pyrophosphate, or phosphoric acid, at 150—220°C and 1035—8275 kPa (150—1200 psi), depending on feedstock and product requirement. 

Rhodium catalyst is used to convert linear alpha-olefins to heptanoic and pelargonic acids (see Carboxylic acids, manufacture). These acids can also be made from the ozonolysis of oleic acid, as done by the Henkel Corp. Emery Group, or by steam cracking methyl ricinoleate, a by-product of the manufacture of nylon-11, an Atochem process in France (4). Neoacids are derived from isobutylene and nonene (4) (see Carboxylic acids, trialkylacetic acids). 

The second step is a -scission, the breaking of a carbon—carbon bond P to the charged carbon. The sum of the two reactions is the stoichiometry of the overall cracking reaction R H — RH + olefin. R+, a relatively stable carbenium ion such as the /-butyl cation, is a chain carrier. The role of the catalyst is to donate the proton to start the chain. This is a greatiy simplified representation. 

Catalytic Pyrolysis. This should not be confused with fluid catalytic cracking, which is used in petroleum refining (see Catalysts, regeneration). Catalytic pyrolysis is aimed at producing primarily ethylene. There are many patents and research articles covering the last 20 years (84—89). Catalytic research until 1988 has been summarized (86). Almost all catalysts produce higher amounts of CO and CO2 than normally obtained with conventional pyrolysis. This indicates that the water gas reaction is also very active with these catalysts, and usually this leads to some deterioration of the olefin yield. Significant amounts of coke have been found in these catalysts, and thus there is a further reduction in olefin yield with on-stream time. Most of these catalysts are based on low surface area alumina catalysts (86). A notable exception is the catalyst developed in the former USSR (89). This catalyst primarily contains vanadium as the active material on pumice (89), and is claimed to produce low levels of carbon oxides. 

Cracking temperatures are somewhat less than those observed with thermal pyrolysis. Most of these catalysts affect the initiation of pyrolysis reactions and increase the overall reaction rate of feed decomposition (85). AppHcabiUty of this process to ethane cracking is questionable since equiUbrium of ethane to ethylene and hydrogen is not altered by a catalyst, and hence selectivity to olefins at lower catalyst temperatures may be inferior to that of conventional thermal cracking. SuitabiUty of this process for heavy feeds like condensates and gas oils has yet to be demonstrated. 

Effect of Catalyst The catalysts used in hydrotreating are molybdena on alumina, cobalt molybdate on alumina, nickel molybdate on alumina or nickel tungstate. Which catalyst is used depends on the particular application. Cobalt molybdate catalyst is generally used when sulfur removal is the primary interest. The nickel catalysts find application in the treating of cracked stocks for olefin or aromatic saturation. One preferred application for molybdena catalyst is sweetening, (removal of mercaptans). The molybdena on alumina catalyst is also preferred for reducing the carbon residue of heating oils. 

In treating cracked stocks such as steam cracked naphtha or visbreaker naphtha, which are highly olefinic in nature, nickel molybdate or nickel tungstate catalysts are generally employed. These catalysts have much higher activity for olefin samration reactions than does cobalt molybdate. 

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