Crude oil contains four different hydrocarbons including paraffins, napthenes, aromatics, and asphaltenes. Paraffins, or alkanes, are saturated hydrocarbons that consist only of hydrogen and carbon atoms, having the general formula CnH2n+2. All bonds are single bonds, and the carbon atoms are not joined in cyclic structures but instead form a simple chain. They make up from about 15 to about 60% of crude oil, and on average about 30%. Resins or naphthenes, otherwise known as cycloalkanes, are alkanes that have one or more rings of carbon atoms in the chemical structure of their molecules. They make up from about 30 to about 60% of crude oil, and on average about 49%. Aromatics, or arenes, are hydrocarbons with alternating double and single bonds between carbon atoms forming rings. Aromatics make up from about 3 to about 30% of crude oil, and on average about 15%, See Antonio Cardenas et al., US 20130264247 patent application by Nano Dispersions Technology Inc (NDT patent) which is incorporated herein as a reference,
Asphaltenes consist primarily of carbon, hydrogen, nitrogen, oxygen, and sulfur, as well as trace amounts of vanadium and nickel. The C:H ratio is approximately 1:1.2, depending on the asphaltene source. Asphaltenes are defined operationally as the n-heptane (C7H16)-insoluble, toluene (C6H5CH3)-soluble component of a carbonaceous material such as crude oil, and are the sticky, black, highly viscous residue of distillation processes. They make up the remainder of crude oil, and on average from about 3 to about 10% of the crude oil; however heavy oils can contain 10% or more, with a high C:H ratio. Due to the aggregation of asphaltenes, they are the most significant contributor to the viscosity of crude oil affecting its viscosity. Light crude oil is liquid petroleum that has low viscosity, low specific gravity, and high API (American Petroleum Institute) gravity due to the presence of a high proportion of light hydrocarbon fractions. API gravity is calculated by dividing 141.5 by the fluid's specific gravity and subtracting 131.5. The New York Mercantile Exchange (NYMEX) defines light crude oil for domestic U.S. oil as having an API gravity between 37° API (840 kg/m3) and 42° API (816 kg/m3), while it defines light crude oil for non-U.S. oil as being between 32° API (865 kg/m3) and 42° API (816 kg/m3). The National Energy Board of Canada defines light crude oil as having a density less than 875.7 kg/m3 (more than 30.10 API). The Mexican state oil company, Pemex, defines light crude oil as being between 27° API (893 kg/m3) and 38° API (835 kg/m3). Unlike light crude oil, heavy crude oils are generally not pumpable due to the high viscosity. Therefore, it is advantageous to remove the higher viscosity products, i.e. asphaltenes, in order to pump the remaining, lighter de-asphalted crude oil. Light crude oil is also desired over heavy crude oil because it receives a higher price than heavy crude oil on commodity markets because it produces a higher percentage of gasoline and diesel fuel when converted into products by an oil refinery (see more in NDT patent).
Sonication is the act of applying sound energy to agitate particles in a sample, for various purposes. Ultrasonic frequencies (>20 kHz) are usually used, leading to the process also being known as ultrasonication or ultra-sonication “Sonication” and “low frequency acoustic sonication” refer hereinafter inter alia and in a non-limiting manner to methods whereby a material is subjected to low frequency acoustic vibration. Devices for producing such vibration, “sonicators”, are disclosed in, for example, U.S. Pat. Nos. 4,941,134 and 5,005,773 (Nyberg et al.). Unlike ultrasonic devices, these low frequency sonic reactors are reducible to large scale commercial practice (e.g. 20 kilowatt sonicator modules) and can achieve HCO deasphalting at low solvent:HCO doses (with ultra-low residence times in the sonicator (e.g. less than 120 seconds), see Petrosonic patent below, which is incorporated herein as a reference.
EP 1276833 patent application by Foxboro NMR, Ltd. which is incorporated herein as a reference discloses a method for blending two or more constituents into a petroleum mixture employs nuclear magnetic resonance to obtain real-time estimates of selected properties of at least one of the constituents. A multivariate controller processes these estimates to determine the relative amounts of each constituent that are required to form a petroleum mixture having desired values of those selected properties.
EP 2584381 patent application by a ENI S.p.A. which is incorporated herein as a reference, discloses method for predicting the properties of crude oils by the application of neural networks articulated in phases and characterized by determining the T2 NMR relaxation curve of an unknown crude oil and converting it to a logarithmic relaxation curve; selecting the values of the logarithmic relaxation curve lying on a characterization grid; entering the selected values as input data for a multilayer neural network of the back propagation type, trained and optimized by means of genetic algorithms; predicting, by means of the trained and optimized neural network, the physico-chemical factors of the unknown crude oil.
The available publications “NMR properties of petroleum reservoir fluids” by G. J. Hirasaki, Sho-Wei Lo, Y. Zhang (currently available in http://www.researchgate.net/publication/10670196_NMR_properties_of_petroleum_reservoir_fluids/links/00b7d52a880594cfa5000000.pdf); and Maddinelli, G., L. Del Gaudio, and U. Cornaro. “Characterization of petrochemical products by the application of a mobile NMR instrument.” Magnetic Resonance Imaging 25.4 (2007): 571, are incorporated herein as a reference
US 20120305383 by Sorokin (Sorokin patent) which is incorporated herein as a reference discloses a process and a device, for the treatment of crude oil, component(s) of crude, or mixtures thereof, to convert components of said hydrocarbon liquid to products having boiling points that are lower than the boiling points of said components prior to treatment. The process comprises subjecting crude to be treated to ultrasound vibrations and to an electromagnetic field emitted by a an electromagnetic field generator; wherein the electromagnetic field emitted by said electromagnetic field generator comprises a component of electromagnetic field modulated by an electromagnetic field emitted from the crude to be treated on the exposure thereof to ultrasound vibrations. Sorokin patent is concerned with a method and a device for the processing of crude oil, components of crude, or mixtures thereof to increase the light hydrocarbon content thereof. Thus, Sorokin suggests a process for the treatment of crude oil, component(s) of crude, or mixtures thereof, wherein the novel concept is that the electromagnetic field emitted by an (a) electromagnetic field generator or (b) a ultrasound generator comprises a component of electromagnetic field modulated by an electromagnetic field emitted from the crude to be treated on the exposure thereof to ultrasound vibrations.
WO 2013110944 patent application by Nov Downhole Eurasia Limited and University Of Nottingham (Nov patent) which is incorporated herein as a reference discloses an apparatus for separating a hydrocarbon content from a material matrix comprises the hydrocarbon content and a water content, the apparatus comprising: a material feeder arranged to feed material through a treatment chamber, the treatment chamber comprising a window which is substantially transparent to microwaves; a microwave emitter arranged in use to expose feed material in the treatment chamber to microwaves via the window in order to cause rapid heating of at least part of the water content of the matrix to form steam, so as to remove at least part of the hydrocarbon content from the matrix; wherein the material feeder and treatment chamber are arranged so that in use, the treatment chamber is substantially filled with material matrix. The problem to solve of the invention is that hydrocarbons are often mixed within a matrix of other solid materials such as sand, soil or rock, and it is frequently desirable to separate or remove the hydrocarbons from such a matrix. For example, a substantial fraction of the world's hydrocarbon reserves are to be found in oil sands and in order to extract the oil, it must first be separated from the sand with which it is mixed.
US 20130277275 by Petrosonic Energy Inc. (Petrosonic patent) discloses a method for treating heavy crude oil (HCO) which includes the steps of combining the HCO with an alkane containing solvent to form an HCO/solvent mixture, sonicating this mixture at audio frequency to precipitate asphaltenes from the HCO/solvent mixture, and separating the precipitated asphaltenes from the HCO/solvent mixture.
Similarly, U.S. Pat. No. 8,323,479 patent discloses a process for converting heavy sulfur-containing crude oil into lighter crude oil with lower sulfur content and lower molecular weight is provided. The process is a low-temperature process using controlled cavitation. Patent application US2002125174 describes a method for decreasing the viscosity of crude oils and residuum utilizing a combination of acid and sonic treatment. Patent application US2013213795A describes conversion of heavy fossil hydrocarbons (HFH) to a variety of value-added chemicals and/or fuels can be enhanced using microwave (MW) and/or radiofrequency (RF) energy. Variations of reactants, process parameters, and reactor design can significantly influence the relative distribution of chemicals and fuels generated as the product. In one example, a system for flash microwave conversion of HFH includes a source concentrating microwave or RF energy in a reaction zone having a pressure greater than 0.9 Atm., a continuous feed having HFH and a process gas passing through the reaction zone, a HFH-to-liquids catalyst contacting the HFH in at least the reaction zone, and dielectric discharges within the reaction zone. The HFH and the catalyst have a residence time in the reaction zone of less than 30 seconds. In some instances, plasma forms in or near the reaction zone. U.S. Pat. No. 5,181,998 patent describes low value hydrocarbons can be upgraded by contact with the products formed during irradiation of a hydrogen donor using microwave energy in the presence of at least one plasma initiator. All those patents and applications are incorporated herein as a reference.
It is hence still a long felt need to provide industrial scale, inline, online accurate NMR-based systems for crude oil enhancement and to methods thereof.