The urea extraction crystallization is a process for separating linear paraffins (n-paraffins, n-alkanes) from hydrocarbon mixtures through the formation of urea-n-paraffin-clathrates. The process is primarily used to lower the pour point of petroleum products, by-products of the process are n-paraffins in high purity. The method may also applied for the separation of fatty acids and fatty alcohols. In addition to urea also thiourea is used in the process.
In 1939 German chemist Friedrich Bergen was trying different extractants to separate serum proteins from milk at low temperature. When he tried urea, he noticed that something weird was going on with milk lipids. A treatment with octanol serendipitously revealed that it combines with urea in large crystals. Bergen investigated different lipids, alkanes and alcohols and found out that at least six carbon atoms are required, and that branched hydrocarbons don't participate in the phenomenon. [2]
Not being an expert in hydrocarbons and urea, he cooperated with Matthias Pier from BASF/IG Farben and then with Wilhelm Schlenk, filing for patents [3] [4] [5] with the latter in 1940, which were awarded in 1953. They didn't publish their findings until 1949 [6] because German authorities classified the discovery during the World War II, [7] but the patent applications were confiscated by Allies' Technical Oil Mission after the war [8] so Sonneborn was able to put a pilot oil dewaxing plant in Petrolia, Pennsylvania into operation already in 1950. [7] [9] DEA AG followed the suit in 1954 and Standard Oil in 1956, [7] and worldwide research in the topic took off in the 1950s. [10]
In addition to the n-alkanes are also unbranched fatty acids with more than four carbon atoms, their esters and unbranched fatty alcohols can migrate into the channels of the crystallized urea and form a clathrate.
A deviation from the linear molecular geometry, for example, by C=C-double bonds in the molecule, leads to a less stable inclusion compound. Thus stearic acid (C18: 0) forms more stable urea adducts compared to oleic acid (C18: 1 cis -9) or linoleic acid (C18: 2 cis -9, cis -12). A branching in the fatty acid molecule or an autoxidation result in a large deviation from the straight-chain molecular structure, so that these compounds do not form urea adducts. This is used as part of the fatty acid analysis and for the separation or enrichment of specific fatty acids. [11]
For the separation of n-paraffins from other hydrocarbon compounds, urea is added with an approximately 20-fold molar excess. The urea crystallizes in a hexagonal crystal structure with about 5.5 to 5.8 Å wide channels. In these channels the n-paraffins are included. If the concentration of n-paraffins in the mixture is too high, the mixture is diluted with a solvent.
In general, the reaction proceeds according to the scheme:
The equilibrium of the reaction is dependent on the concentrations of the reactants, the solvent and the temperature. [12] The necessary quantity of urea for the formation of inclusion compounds varies from about 1 to 0.8 mole of urea per methyl- and methylene group in a carbon chain. [12] The urea is added as a supersaturated aqueous solution to compensate for losses due to adduct formation during the process. In order to avoid a too high concentrations of adducts in the dewaxed oil a solvent such as methyl isobutyl ketone or methylene chloride is used for dilution. The ratio of oil to water phase is about 1 to 0.5. The mixing of the oil and water phases occurs at slightly elevated temperatures of about 35 °C. In the course of the reaction the mixture is cooled to room temperature. Lower temperatures are advantageous for the formation of inclusion complexes. [12]
The urea-paraffin-adduct can be filtered off and thereby separated from the iso-paraffins and other non-paraffinic components. By washing with a solvent a solid adduct residue is obtained. The washing of the clathrates with hot water at about 75 °C breaks up the clathrates and releases the paraffins. The obtained n-paraffins have a purity of about 99%. Losses of urea are small, the hot urea solution can be returned directly back into the process.
In organic chemistry, an alkane, or paraffin, is an acyclic saturated hydrocarbon. In other words, an alkane consists of hydrogen and carbon atoms arranged in a tree structure in which all the carbon–carbon bonds are single. Alkanes have the general chemical formula CnH2n+2. The alkanes range in complexity from the simplest case of methane, where n = 1, to arbitrarily large and complex molecules, like pentacontane or 6-ethyl-2-methyl-5-(1-methylethyl) octane, an isomer of tetradecane.
In organic chemistry, a hydrocarbon is an organic compound consisting entirely of hydrogen and carbon. Hydrocarbons are examples of group 14 hydrides. Hydrocarbons are generally colourless and hydrophobic; their odor is usually faint, and may be similar to that of gasoline or lighter fluid. They occur in a diverse range of molecular structures and phases: they can be gases, liquids, low melting solids or polymers.
Paraffin wax is a soft colorless solid derived from petroleum, coal, or oil shale that consists of a mixture of hydrocarbon molecules containing between 20 and 40 carbon atoms. It is solid at room temperature and begins to melt above approximately 37 °C (99 °F), and its boiling point is above 370 °C (698 °F). Common applications for paraffin wax include lubrication, electrical insulation, and candles; dyed paraffin wax can be made into crayons.
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Petroleum geochemistry is a branch of geochemistry which deals specifically with petroleum and its origin, generation, and accumulation, as well as its extraction, refinement, and use. Petroleum, also known as crude oil, is a solid, liquid, and/or gaesous mix of hydrocarbons. These hydrocarbons are from the burial and metamorphosis of organic matter from millions of years ago; the organic matter is from marine animals, plants, and algae. Petroleum is extracted from the Earth, refined, and used as an energy source.
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The Bergius process is a method of production of liquid hydrocarbons for use as synthetic fuel by hydrogenation of high-volatile bituminous coal at high temperature and pressure. It was first developed by Friedrich Bergius in 1913. In 1931 Bergius was awarded the Nobel Prize in Chemistry for his development of high-pressure chemistry.
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1-Octene is an organic compound with a formula CH2CHC6H13. The alkene is classified as a higher olefin and alpha-olefin, meaning that the double bond is located at the alpha (primary) position, endowing this compound with higher reactivity and thus useful chemical properties. 1-Octene is one of the important linear alpha olefins in industry. It is a colourless liquid.
Desulfatibacillum alkenivorans AK-01 is a specific strain of Desulfatibacillum alkenivorans.
Sulfolene, or butadiene sulfone is a cyclic organic chemical with a sulfone functional group. It is a white, odorless, crystalline, indefinitely storable solid, which dissolves in water and many organic solvents. The compound is used as a source of butadiene.
Crude oil is extracted from the bedrock before being processed in several stages, removing natural contaminants and undesirable hydrocarbons. This separation process produces mineral oil, which can in turn be denoted as paraffinic, naphthenic or aromatic. The differences between these different types of oils are not clear-cut, but mainly depend on the predominant hydrocarbon types in the oil. Paraffinic oil, for example, contains primarily higher alkanes, whereas naphthenic oils have a high share of cyclic alkanes in the mixture.
Winterizationof oil is a process that uses a solvent and cold temperatures to separate lipids and other desired oil compounds from waxes. Winterization is a type of fractionation, the general process of separating the triglycerides found in fats and oils, using the difference in their melting points, solubility, and volatility.
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Photochlorination is a chlorination reaction that is initiated by light. Usually a C-H bond is converted to a C-Cl bond. Photochlorination is carried out on an industrial scale. The process is exothermic and proceeds as a chain reaction initiated by the homolytic cleavage of molecular chlorine into chlorine radicals by ultraviolet radiation. Many chlorinated solvents are produced in this way.