System and Method for Cold Cracking Under a Condition of Modified Density of Physical Vacuum

This application is a Continuation in Part of U.S. patent application Ser. No. 17/691,369, filed on Mar. 10, 2022, the entire content of each of which is hereby incorporated by reference in their respective entirety.

Embodiments of the present invention generally relate to a system and method of processing hydrocarbon liquids with a colloidal structure, or mineral oils containing ferromagnetic components, using mechanical processing under conditions of a modified density of physical vacuum and carrying out a chain free-radical chemical reaction. The technological purpose is to change a hydrocarbon structure of the liquids, and increase a proportion of lighter molecular weight components.

Heavy crude oil or extra heavy crude oil is any type of crude oil which does not flow easily. It is referred to as “heavy” because its density or specific gravity is higher than that of light crude oil. Heavy crude oil has been defined as any liquid petroleum with an American Petroleum Institute (“API”) gravity less than 20°. Extra heavy oil is defined with API gravity below 10.0° API (i.e. with density greater than 1000 kg/mor, equivalently, a specific gravity greater than 1).

In contrast, light crude oil is liquid petroleum that has a low density and flows freely at room temperature. It has a low viscosity, low specific gravity and high API gravity due to the presence of a high proportion of light hydrocarbon fractions. Light crude oil 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 and after the transportation cost of petroleum products.

Sweet crude oil is a type of petroleum that contains less than about 0.5% sulfur, compared to a higher level of sulfur in sour crude oil. Sweet crude oil contains small amounts of hydrogen sulfide and carbon dioxide. High quality, low sulfur crude oil is commonly used for processing into gasoline and is in high demand, particularly in the industrialized nations. “Light sweet crude oil” is the most sought-after version of crude oil as it contains a disproportionately large amount of these fractions that are used to process gasoline (naphtha), kerosene, and high-quality diesel fuel.

The amount or volume of light crude products naturally present in crude oil worldwide is not sufficient to cover the worldwide consumption of various fuels. Therefore, technologies referred to as “cracking” have been developed and are necessary to maximize the light product yield from crude oil. Cracking is the process whereby complex organic molecules (heavy hydrocarbons) are broken down into shorter molecules (light hydrocarbons), predominantly by the breaking of carbon-carbon bonds by the use of mechanical action and catalysts.

Shortfalls of conventional cracking processes used in refineries include a relatively low yield of hydrocarbons having a short chain length, and a relatively high combination of temperature and pressure needed to realize the process at a commercially feasible rate. Cracking transfers energy to all degrees of freedom of the molecular compounds in a liquid medium such as crude oil. Conventional cracking processes can be separated into two categories of cracking processes: thermal cracking and catalytic cracking. Thermal cracking is expensive and is based on heating the entire volume of the liquid medium to a high temperature (e.g., above 350 degrees C.). Catalytic cracking requires the use of expensive catalysts, requiring large amount of energy for the production and regeneration of the catalysts.

Thus, there is a need for a cracking process that is able to produce relatively higher yields of hydrocarbons having short chain lengths, restructuring the colloidal structure of oil materials with a decrease in viscosity and at a relatively lower combination of temperature and pressure in order to realize the process at a commercially feasible rate.

Embodiments of the present invention generally relate to a system and procedure for treatment of liquids, in particular a colloid hydrocarbon medium mineral oil or a hydrocarbon polymer, in order to the increase the content of light, low-boiling range fractions with a decrease in viscosity. The energy needed to crack the liquids is derived from acoustic fields induced by a rotor of a pump acoustic field generator (PAFG) and having a wide acoustic spectrum in the range up to hundreds of kHz by the mechanism of a two stage stochastic resonance, this effect under conditions of a moderate temperature increase and a modified density of physical vacuum created by a physical vacuum action source unit (VASU) dissociates C—C bonds with the launch of a free-radical chemical chain reaction breaking chemical bonds underlying the cracking process of hydrocarbons.

Embodiments change the hydrocarbon structure of the colloid hydrocarbon medium, including an increase of a proportion of lighter molecular weight components due to: (1) breaking of carbon-carbon bonds due to frequency processing, under conditions of modified density of physical vacuum; (2) chemical free radical chain reaction; and (3) decrease in viscosity due to reorganization of the colloidal hydrocarbon medium.

The headings used herein are for organizational purposes only and are not meant to be used to limit the scope of the description or the claims. To facilitate understanding, like reference numerals have been used, where possible, to designate like elements common to the figures.

As used throughout this application, the word “may” is used in a permissive sense (i.e., meaning having the potential to), rather than the mandatory sense (i.e., meaning must). Similarly, the words “include”, “including”, and “includes” mean including but not limited to.

The modifier “about” when used with a range (e.g., “about X to Y”) should be understood to apply to both ends of the range (i.e., equivalent to “about X to about Y”) unless a different meaning is clearly indicated explicitly or by the context of usage.

Embodiments of the present invention generally relate to a procedure for the treatment of a liquid, in particular a colloid hydrocarbon medium, mineral oil or the like (generically, “hydrocarbon liquid” or “colloidal hydrocarbon liquid”), in order to increase the content of light fractions having a lower boiling point, and to change the colloidal structure of the hydrocarbon liquid including a decrease in viscosity.

Embodiments provide a method and system designed to destabilize, weaken, shear or even crack up molecular bonds in liquids, for example, a colloid hydrocarbon medium, mineral oils or related substances, in order to thus receive, in the course of the subsequent refining process, an increased portion of short chains and low-boiling point fractions. Weakening or destabilizing the molecular bonds may mean, for instance, that the molecular bonds enter an unstable energy state, i.e., a state higher than the minimum energy. At such a higher energy state, the molecular bonds are susceptible to breaking upon addition of a lesser amount of energy compared to molecular bonds not at the higher energy state.

In quantum-mechanical analysis, a predetermined volume of hydrocarbon liquid (e.g., crude oil, fuel oil, etc.) may be analyzed as a quantum-mechanical system that behaves as a single molecule having molecular bonds that are tightened by strong covalent bonds. In this analysis, the quantum-mechanical system is not describable using exact chemical formulas, nor by constants like melting and boiling points, dielectric permittivity, dipole moment, loss angle, electrical conduction, heat content (enthalpy) ΔH°, ΔS, and so forth.

If this quantum-mechanical system is excited by imparting an intensive energy in substantially any form, then the quantum-mechanical system becomes unstable, and various processes will occur like destruction, breakage and re-forming/redistribution of molecular bonds, division of the quantum-mechanical system into low-molecular and high-molecular compounds. Characterizing the resulting compounds as linear, cyclic, aromatic etc., is not meaningful because, under the quantum analysis, it is the state of the quantum-mechanical system under conditions of force fields of the environment that is meaningful, rather than the compositions of the various compounds within the quantum-mechanical system.

Crude oil or fuel oil is not a physical mixture, and the processing of it is not a physical process of reforming, remixing, and the like. Rather, processing of crude oil or fuel oil is a chemical reaction which can be represented by Equation (1) below:

where ΔH is a change of the heat content in the system (i.e., an enthalpy or a reaction energy). A positive change in heat content may be released as thermal energy and/or other forms of energy (e.g., photons). A negative change in heat content is accounted for by an infusion of an external source of energy.

Embodiments utilize technology based on a free radical chemical chain reaction, which causes the cold cracking of hydrocarbon polymers in a liquid (e.g., crude oil) and the restructuring of the liquid (i.e., changing the molecular compound composition) due to excitation of vibrational degrees of freedom of molecules, while modifying the physical vacuum density inside the reactor. The cold cracking is operable at least within a temperature range of 70 degrees Celsius or lower to 150 degrees Celsius or lower. In some embodiments, the cold cracking is operable within a temperature range of at least 70 degrees Celsius to 100 degrees Celsius or lower. Embodiments result in improved quality as indicated by composition, viscosity, and density, achieved by processing the liquid.

The physical basis for the types and sequences of processes operating on the liquid is a one-stage or two-stage stochastic resonance (“SR”) between and among: (1) the apparatus and system performing the process steps as a single oscillatory system, and (2) the molecular components in the liquid. The single oscillatory system refers to components that are coupled such that they respond in a “normal mode” to oscillatory vibrations described herein. The single oscillatory system includes the PMVR plus its physical support and bracing, a hydrodynamic mixer and mixing chamber, associated piping between components, pumps to move around the hydrocarbon liquid during processing, and hydrocarbon feedstock.

The stochastic resonance is under conditions of a modified energy density of a physical vacuum, produced by a circularly-operating mechanical vibrator according to the Unruh effect discussed herein, within a pump magnetic vacuum reactor (“PMVR”) that acts on polymer macromolecules. A hydrocarbon liquid of polymer macromolecules may be referred to as a polymeric system. The area of a polymeric system operated upon by frequency fluctuations will be approximately four orders of magnitude smaller than the area of a polymeric system operated upon by a mechanical system, therefore direct resonant interaction is not feasible for a stochastic resonant system.illustrates a difference in scale of resonant frequencies between a mechanical system (a), a micelle of colloids (b) and a polymer molecule (c).

illustrate the spectra of acoustic phonons (curve “1”) and optical phonons (curve “2”). Acoustic phonons pump energy into optical phonons in this mechanism, leading to “heating” of an electron subsystem of polymers and dispersion electrons, i.e., the acoustic phonons reduce electron correlation in polymeric molecules. Electron correlation in this context refers to interaction among electrons in the electron structure of a quantum system. Correlation energy is a measure of how much the movement of one electron is influenced by the presence of all other electrons in the quantum system.

illustrate symmetry of a carbon chain.illustrates a common potential surface overlaid with a potential surface of a symmetric molecular system from molecules of different dynamic structure and with a degenerated electron subsystem.

Dissociation of carbon bonds occurs due to the Jahn-Teller effect. Interaction of ultrasound fields and acoustic phonons in the carbon chains leads to generation of optical phonons and to excitation of an electron subsystem. Shortly thereafter, the excited electron subsystem decays to release correlation energy of electrons and, hence, decreases correlation in the excited electron subsystem. This causes high anharmonicity in the excited electron subsystem.

Anharmonic electron potential (i.e., a fluctuating average field of electrons) in the carbon-chain (“CC”), depending on oscillations of nuclei, has a high level of symmetry in its nuclear system, leading to formation of vibronic states of a degenerate system (i.e., equal energy) of electron terms of covalent CC-bonds. Such electron-oscillatory states of molecules, having a different configuration of dynamics, lie on one potential surface, i.e., has identical energy as illustrated in.

The received raised electron states of these bonds with low electron correlation form antibinding σ-orbitals instead of binding σ-orbitals (). These raised vibronic states turn on repulsive states and further move according to the Jahn-Teller effect.

illustrates a change in level of high symmetry of a fragment of a CC-chain (left side) at dissociation of CC-bonds (right side).illustrates electron density of CC-bonds of a carbon chain.illustrates a change of energy of electron orbitals of C-atoms as distance between the carbon atoms changes (left side), and the levels of electron density of binding and antibinding of a C-atom (right side).

Degeneration of electron level changes the nuclear configuration according to the Jahn-Teller effect, acting to remove the electron degeneration. This condition corresponds to movements of nuclear systems that lower symmetry of a nuclear configuration.illustrates this movement, specifically a displacement of nuclei that increases the distance between them.

Degeneration is promoted by transforming electron terms of antibinding σ-orbital and electrons transitioning between s and p orbitals. This set of processes in an electron and nuclear configuration enables dissociation of CC-bond. Electron-oscillatory (i.e., vibronic) interactions underlie many chemical reactions including depolymerization reactions.

These processes under normal physical conditions (e.g., normal density of the physical vacuum) require a significant use of energy. As the energy density of the physical vacuum changes, the amount of energy used changes.

The theoretical foundations of the physical vacuum technology are presented in the works of leading physicists and are shown in the form of quantum electrodynamic phenomena known as the Casimir effect, Unruh effect, Sokolov-Ternov effects, Lamb shift (i.e., shift of electron levels), and others. During the creation of the Theory of General Relativity, Einstein introduced an additional term—the cosmological constant—denoting an existence in astronomical space of a force that prevent the compression of matter and thus the compression of the universe under the influence of gravitational forces. The force preventing the compression of matter is manifested by the concept of a “physical vacuum” as a special material medium with a special physical state and which provides a state with a negative density sign. See equation (2) below for one result of the Theory of General Relativity.

Where “Λ” is the cosmological constant

Processes in a vacuum are the cause of the expansion of the universe (according to Gliner), which is expressed by the vacuum equation of state, formulated by De Sitter in the Einstein equations he modified. Theory holds that p=−ε, which means the direct proportionality of the pressure of matter (p) to the negative energy density of the vacuum (ε).

The mechanism of induction of vacuum flows with a change in vacuum density, and the rotational motion of the material masses, is described by the angular velocity and angular displacement vector. In this situation, according to Einstein, the sign of these quantities of the physical vacuum must be reversed and the negative vector of the angular velocity and angular displacement vector of vacuum induces a vacuum flow in the direction opposite to the flow of material masses.

In quantum theory, the basic state of matter is “empty space” with a special structure, called a physical vacuum according to Dirac. The vacuum state is the ground state (i.e., the lowest level) of energy of material particles and fields. The theoretical foundations of these states are developed in and described in detail in the field of quantum electrodynamics (“QED”) and quantum chromodynamics (“QCD”).

The material sources (i.e., particles such as electrons, protons, etc.) of the field are surrounded by virtual quanta, i.e., the zero state of the electromagnetic field (“EMF”). Around the masses and electric charges are created real quanta (with a non-zero energy). An atom interacting with an electromagnetic vacuum field in the ground state is surrounded by a cloud of virtual photons. Near the field source, the boson field contributes to the field energy density.

With respect to interactions in the physical vacuum, the material field of an object acts as a source of EMF, and the internal dynamic structure of the sources is influenced by the virtual field. There is a continuous process of energy fluctuations—the creation and annihilation of pairs of virtual particles and antiparticles. Despite their virtual and ephemeral nature, they put pressure on the material media in a process known as the static Casimir effect. Along with this effect, charges are also affected by the dynamic Casimir effect, which is a transformation of physical vacuum fluctuations into real particles (in particular, photons). Classical physics considers “zero” vacuum oscillations as quasi-elastic acoustic oscillations in a continuous medium,

The interaction with a physical vacuum determines the behavior of electrons, their interaction with positive charges in an atom and an equilibrium structure of atoms and molecules that form at normal physical vacuum density.

The interaction with the physical vacuum strongly influences the electron state in the atom, in particular the properties of the electron shells of the atoms. Physical vacuum polarization, as its energy density increases, removes the degeneracy of electrical levels. Electrons can emit and absorb a virtual photon, while its interaction with the Coulomb field of the nucleus changes and it receives a pulse. This results in a decrease in the localization of the electron's wave function near the nucleus at the s-level orbital. This noticeably changes the electron's frequency near the nucleus, raising it to 1 GHz. A modification of the Coulomb field with physical vacuum polarization shifts the s-level by 25 MHz. This is manifested in the effect of splitting levels, i.e., the Lamb shift. Accordingly, a decrease in the physical vacuum density leads (i.e., increases the probability) of degeneracy of the electron levels.

According to the Unruh effect, a real mass moving with acceleration induces the appearance (i.e., changes the structure) of a physical vacuum in the surrounding space. The Unruh effect is present in any accelerating material system, such as an elementary particle, atom, molecule, crystal, solid or liquid body. The accelerating material system may include a material rotating around an axis of rotation (including uniform circular motion), which experiences radial (i.e., centripetal) acceleration. The Unruh effect, when arising from a rotating mass having a moment of rotation and radial acceleration, induces a vacuum flow, the quality and composition of which varies with the material being rotated and characteristics of the rotation. The vacuum flow, according to Einstein-de Sitter's rule, has a negative sign of the moment of rotation relative to the moment of rotation of the real mass. A directed vacuum flow is formed in the direction opposite to the moment of rotation of the real domain. This directed vacuum flow creates displacements of the vacuum environment with the formation of a region with a modified vacuum density and a region of increased vacuum density. In an area with a modified vacuum density, Lamb effects take place in the electron structure. In an area with a lower vacuum density, the effects of electron states degeneration increase, with the development of Jahn-Teller effects, with degeneration of electron levels of vibronic states of molecules.

The Unruh effect is an example of a vacuum and magnetic influence. To increase the Unruh effect generated by a rotating material (the rotating material being, e.g., a rotating source substance or composition thereof, generically “source substance”) upon a target substance being processed (the target substance being, e.g., crude oil or other hydrocarbon), the material to rotate is selected according to principles of its resonant interaction with oil.

The selection principles for the rotating material include, first, that the rotating material should include molecules (or molecule groups) whose concentration should increase in the processed material during processing. Second, the rotating material should include ionic and low-molecular components that are part of the solvate shells of the colloidal system of the target substance. The process may operate with unregulated or loosely regulated temperature and pressure conditions in the PMVR. Third, the rotating material should have predetermined IR and/or Raman absorption and emission bands that coincide with the bands of the target substance. For example, the rotating material will have a greater beneficial effect upon the target substance as the IR and/or Raman spectrum of the rotating material better matches or correlates with the IR and/or Raman spectrum of the target substance (or processed product thereof). Each target substance may have a respective source substance that acceptably matches the target substance. An acceptable match of the source substance may be selected or prepared according to predetermined Infrared (IR)/Raman vibrational spectra criteria. The resulting source substance forms a vacuum flow that has increased effect upon the respective target substance, compared to a vacuum flow from non-matching source substances.

In one embodiment, the source substance may be a hydrocarbon colloidal substance having an IR/Raman spectrum wavenumber shift of about 400 cmto about 4,000 cm.

As known in the art, Raman spectroscopy is a form of vibrational spectroscopy, much like infrared (IR) spectroscopy. However, whereas IR bands arise from a change in the dipole moment of a molecule due to an interaction of light with the molecule, Raman bands arise from a change in the polarizability of the molecule due to the same interaction. This means that these observed bands (corresponding to specific energy transitions) arise from specific molecular vibrations. Moreover, molecular vibrations can be one type of molecular motion in which there is a change in the position of the atoms relative to one another. Molecular vibrations can be the periodic motion of atoms within a molecule. The atoms can oscillate around their equilibrium positions and maintain the molecule's center of mass. Such vibrations can be visualized as atoms connected by springs with different types of vibrations that include stretching and bending. When the energies of these transitions are plotted as a spectrum, they can be used to identify the molecule as they provide a “molecular fingerprint” of the molecule being observed. Certain vibrations that are allowed in Raman are forbidden in IR, whereas other vibrations may be observed by both techniques although at significantly different intensities thus these techniques can be thought of as complementary. Thus IR and Raman spectroscopy have similar effects upon a target hydrocarbon for the purpose of cracking molecular hydrocarbon chains.

Raman scattering of a photon by a molecule can occur with a change in vibrational, rotational or electronic energy of the molecule. Embodiments herein are concerned primarily with the vibrational Raman effect. The difference in energy between an incident photon and a corresponding Raman scattered photon is equal to the energy of a vibration of the scattering molecule. The Raman effect arises when a photon is incident on a molecule and interacts with the electric dipole of the molecule. It is a form of electronic (more accurately, vibronic) spectroscopy, although the spectrum contains vibrational frequencies. In classical terms, the interaction can be viewed as a perturbation of the molecule's electric field. In quantum mechanical terms the scattering can be described as an excitation to a virtual state lower in energy than a real electronic transition with nearly coincident de-excitation and a change in vibrational energy. In the Raman effect the electron excited in the scattering process decays to a different level than that where it started and is termed inelastic scattering.

Numerically, the energy difference between the initial and final vibrational levels, or Raman shift in wave numbers (cm), is calculated as the difference in the reciprocal of incident and scattered wavelengths, in which incident and scattered refer to the wavelengths (in cm) of the incident and Raman scattered photons, respectively.

The vibrational energy is ultimately dissipated as heat. At room temperature the thermal population of vibrational excited states is low, although not zero. Therefore, the initial state is the ground state, and the scattered photon will have lower energy (longer wavelength) than the exciting photon. A small fraction of the molecules are in vibrationally excited states. Raman scattering from vibrationally excited molecules leaves the molecule in the ground state.