Hydrocarbon processing dewaxing

H. Franz, Urea Dewaxing Process Can Yield Normal Paraffins, Hydrocarbon Processing 44(9) 183-184 (1965). 

Urea has the remarkable property of forming crystalline complexes or adducts with straight-chain organic compounds. These crystalline complexes consist of a hoUow channel, formed by the crystallized urea molecules, in which the hydrocarbon is completely occluded. Such compounds are known as clathrates. The type of hydrocarbon occluded, on the basis of its chain length, is determined by the temperature at which the clathrate is formed. This property of urea clathrates is widely used in the petroleum-refining industry for the production of jet aviation fuels (see Aviation and other gas-TURBINE fuels) and for dewaxing of lubricant oils (see also Petroleum, refinery processes). The clathrates are broken down by simply dissolving urea in water or in alcohol. 

Lubricants. Petroleum lubricants continue to be the mainstay for automotive, industrial, and process lubricants. Synthetic oils are used extensively in industry and for jet engines they, of course, are made from hydrocarbons. Since the viscosity index (a measure of the viscosity behavior of a lubricant with change in temperature) of lube oil fractions from different cmdes may vary from +140 to as low as —300, additional refining steps are needed. To improve the viscosity index (VI), lube oil fractions are subjected to solvent extraction, solvent dewaxing, solvent deasphalting, and hydrogenation. Furthermore, automotive lube oils typically contain about 12—14% additives. These additives maybe oxidation inhibitors to prevent formation of gum and varnish, corrosion inhibitors, or detergent dispersants, and viscosity index improvers. The United States consumption of lubricants is shown in Table 7. 

Catalysis. As of mid-1995, zeoHte-based catalysts are employed in catalytic cracking, hydrocracking, isomerization of paraffins and substituted aromatics, disproportionation and alkylation of aromatics, dewaxing of distillate fuels and lube basestocks, and in a process for converting methanol to hydrocarbons (54). 

Catalytic Dewaxing Also called CDW. A hydiocracking process for removing waxes (linear aliphatic hydrocarbons) from petroleum streams by converting them to lower molecular weight hydrocarbons. The catalyst is a synthetic mordenite. Developed by BP two units were operating in 1988. 

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. 

MDDW [Mobil Distillate DeWaxing] A process for removing waxes (long-chain normal paraffins) from petroleum fractions by cracking over the zeolite ZSM-5. The waxes are converted to liquid hydrocarbon fuels. Twenty one units were operating in 1990. 

MLDW [Mobil lube dewaxing] A catalytic process for removing waxes (long-chain linear aliphatic hydrocarbons and alkyl aromatic hydrocarbons) from lubricating oil. Developed by Mobil Research Development Corporation and operated at Mobil Oil refineries since 1981. Eight units were operating in 1991. 

Dewaxing (Figure 4.17) processes also produce heater stack gas (carbon monoxide, sulfur oxides, nitrogen oxides, and particulate matter) as well as hydrocarbon emission such as fugitive propane and fugitive solvents. Steam stripping wastewater (oil and solvents) and solvent recovery wastewater (oil and propane) are also produced. The fugitive solvent emissions may be toxic (toluene, methyl ethyl ketone, methyl isobutyl ketone). 

Liquid propane is employed as the solvent in this process. The use of a petroleum fraction as a solvent for dewaxing is desirable from the standpoint of the availability and cost of solvent, and the higher boiling hydrocarbon fraction has been employed many years for dewaxing of residual stocks. 

In the petroleum industry, dewaxing solvents are separated by ultrafiltration from dewaxed oils by chemically resistant membranes made from polysulfone or polyimide. In a related process, pentane is separated from deasphalted heavy oil under conditions intermediate between reverse osmosis and ultrafilttation (ca. 15 bar applied pressure). High-molecular-weight hydrocarbons in the oil form a gel layer on the surface of a polysulfone support membrane. This gel restricts passage of heavier hydrocarbons but not pentane, which is recovered as permeate. To separate other hydrocarbon mixtures that do not contain gel-forming components, polymeric additives would be used as a rejecting barrier substitute. 

SDW [Solvent DeWaxing] A general term for processes that remove linear paraffinic hydrocarbons from petroleum fractions by solvent extraction. 

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]. 

These earlier studies have been instrumental in explaining why ZSM-5 deactivates more slowly than larger or smaller pore zeolites. However, few of these studies have considered the performance of a ZSM-5 catalyst in processing complex hydrocarbon mixtures truly representative of refinery streams. This paper examines the deactivation of a ZSM-5 catalyst in dewaxing a series of lube raffinates with different compositions and boiling ranges. 

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