Catalytic refining

The viscous fractions of crude oil often contain metals such as iron, nickel, and vanadium. Catalytic refining processes are often sensitive to metal contamination and, therefore, the type and quantity of metals must... 

Without doubt, the most important asphaltene reactions, in the current context, are thermal reactions and the manner in which they relate to thermal and catalytic refining options. It is known that asphaltenes will produce significant quantities of distillable liquids in thermal processes, but the production of significant quantities of coke has always been an issue (I). 

The growing importance of hydrogen is the outcome of the development of catalytic refining processes, especially desulfurization and hydrocracking, and of the rise in the production of ammonia, methanol and certain intermediates (cyclohexane by benzene hydrogenation) in chemical synthesis. 

Table 1 Some characteristics of the principal petroleum fractions. Contribution of the various hydrocarbon families to these characteristics. Qualities of the fractions produced by three typical catalytic refining processes (cracking, hydrocracking, hydroisomerization)... 

There are little or no olefins in crude oil or straight run (direct from crude distillation) products but they are found in refining products, particularly in the fractions coming from conversion of heavy fractions whether or not these processes are thermal or catalytic. The first few compounds of this family are very important raw materials for the petrochemical Industry e.g., ethylene, propylene, and butenes. 

Following certain refining processes like catalytic cracking, sizeable amounts of nitrogen can appear in light cuts and cause quality problems such as instability in storage, brown color, and gums. 

For the refiner, the reduction in benzene concentration to 3% is not a major problem it is achieved by adjusting the initial point of the feed to the catalytic reformers and thereby limiting the amount of benzene precursors such as cyclohexane and Cg paraffins. Further than 3% benzene, the constraints become very severe and can even imply using specific processes alkylation of benzene to substituted aromatics, separation, etc. 

H2S is found with the reservoir gas and dissolved in the crude (< 50 ppm by weight), but it is formed during refining operations such as catalytic cracking, hydrodesulfurization, and thermal cracking or by thermal decomposition of sulfur[Pg.322]

The development of catalytic converters for combustion of unburned hydrocarbons prohibits a return to lead compounds and henceforth refiners are turning to oxygenated compounds that must be used as a gasoline component therefore, in amounts much greater than those of lead compounds. 

Catalytic cracking is a key refining process along with catalytic reforming and alkylation for the production of gasoline. Operating at low pressure and in the gas phase, it uses the catalyst as a solid heat transfer medium. The reaction temperature is 500-540°C and residence time is on the order of one second. 

Simple conventional refining is based essentially on atmospheric distillation. The residue from the distillation constitutes heavy fuel, the quantity and qualities of which are mainly determined by the crude feedstock available without many ways to improve it. Manufacture of products like asphalt and lubricant bases requires supplementary operations, in particular separation operations and is possible only with a relatively narrow selection of crudes (crudes for lube oils, crudes for asphalts). The distillates are not normally directly usable processing must be done to improve them, either mild treatment such as hydrodesulfurization of middle distillates at low pressure, or deep treatment usually with partial conversion such as catalytic reforming. The conventional refinery thereby has rather limited flexibility and makes products the quality of which is closely linked to the nature of the crude oil used. 

Cracking (Section 2 16) A key step in petroleum refining in which high molecular weight hydrocarbons are converted to lower molecular weight ones by thermal or catalytic carbon-carbon bond cleavage... 

Catalytic Processes. A second group of refining operations which contribute to gas production are the catalytic cracking processes, such as fluid-bed catalytic cracking, and other variants, in which heavy gas oils are converted into gas, naphthas, fuel oil, and coke (5). 

Reduction of metal oxides with hydrogen is of interest in the metals refining industry (94,95) (see Metallurgy). Hydrogen is also used to reduce sulfites to sulfides in one step in the removal of SO2 pollutants (see Airpollution) (96). Hydrogen reacts directiy with SO2 under catalytic conditions to produce elemental sulfur and H2S (97—98). Under certain conditions, hydrogen reacts with nitric oxide, an atmospheric poUutant and contributor to photochemical smog, to produce N2 ... 

Other routes for hydroxybenzaldehydes are the electrolytic or catalytic reduction of hydroxybenzoic acids (65,66) and the electrolytic or catalytic oxidation of cresols (67,68). (see Salicylic acid and related compounds). Sahcylaldehyde is available in drums and bulk quantities. The normal specification is a freezing point minimum of 1.4°C. 4-Hydroxybenzaldehyde is available in fiber dmms, and has a normal specification requirement of a 114°C initial melting point. More refined analytical methods are used where the appHcation requires more stringent specifications. 

Liquid Fuels. Liquid fuels can be obtained as by-products of low temperature carbonization by pyrolysis, solvent refining, or extraction and gasification followed by catalytic conversion of either the coal or the products from the coal. A continuing iaterest ia Hquid fuels has produced activity ia each of these areas (44—46). However, because cmde oil prices have historically remained below the price at which synthetic fuels can be produced, commercialization awaits an economic reversal. 

Low temperature filtration (qv) is a common final refining step to remove paraffin wax in order to lower the pour point of the oil (14). As an alternative to traditional filtration aided by a propane or methyl ethyl ketone solvent, catalytic hydrodewaxing cracks the wax molecules which are then removed as lower boiling products. Finished lubricating oils are then made by blending these refined stocks to the desired viscosity, followed by introducing additives needed to provide the required performance. Table 3 Usts properties of typical commercial petroleum oils. Methods for measuring these properties are available from the ASTM (10). 

Refinery Production. Refinery propylene is formed as a by-product of fluid catalytic cracking of gas oils and, to a far lesser extent, of thermal processes, eg, coking. The total amount of propylene produced depends on the mix of these processes and the specific refinery product slate. For example, in the United States, refiners have maximized gasoline production. This results in a higher level of propylene production than in Europe, where proportionally more heating oil is produced. 

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