WO2012078068A1

WO2012078068A1 - Method of converting hydrocarbon raw material by distillation

Info

Publication number: WO2012078068A1
Application number: PCT/RU2010/000755
Authority: WO
Inventors: Георгий Рамазанович УМАРОВ; Сергей Иванович БОЙЧЕНКО; Валерий Михайлович ПЕТУХОВ; Шив Викрам КХЕМКА
Original assignee: Общество С Ограниченной Ответственностью "Лаборатория Карбон"
Priority date: 2010-12-06
Filing date: 2010-12-14
Publication date: 2012-06-14
Also published as: RU2434050C1

Abstract

The invention relates to petroleum chemistry, in particular to the field of processing hydrocarbons, and can be used in the chemical and petrochemical industry for producing various petroleum products, including high-grade fuel. The method for processing hydrocarbon stock comprises feeding a feedstock into a volume for distillation with a directed stream of stock being formed and distilling the latter with target fractions being removed. The stream of stock is formed such that the stream density and moment of impulse are distributed in association with a wave function responding to the conditions of phase transition of part of the stream of stock into the positron state of Dirac's matter.

Description

METHOD FOR PROCESSING HYDROCARBON RAW MATERIAL BY REFINING METHOD

Technical field

The invention relates to petrochemistry, in particular, to the field of hydrocarbon processing, and can be used in the chemical, petrochemical industry and fuel energy to produce various petroleum products, including high-quality fuel.

State of the art

Known methods for processing hydrocarbon raw materials, in particular, heavy crude oil, to obtain the target products, suggesting its preliminary desalination and dehydration, the subsequent stage of distillation, including thermal and thermo-destructive processes with separation into fractions, the conclusion of the finished product (patent US N2 738324, cl. СВВ 55/00, 1985; US patent J \ O 295968, class C10G9 / 16, 1994; US patent 7077199, CL ЕВВ 43/243, 2006). The disadvantages of the known methods include high energy costs per unit of production and high cost of the process, because for the decomposition of heavy hydrocarbon molecules, high temperature and pressure in the distillation apparatus are maintained or hydrotreating is carried out using expensive catalysts.

Known methods for the processing of hydrocarbon raw materials, which produce various kinds of additional effects on the feed stream or coolant. In the method of processing liquid hydrocarbons according to preliminary patent KZ N ° 3410, cl. C10G 9/00, 2006 and patent EP JY "1452576, cl. C10G 33/06, 2004, the efficiency of the process of increasing the yield of light fractions and reducing energy costs is achieved by cavitation effects on the feed stream at the stage of distillation or by preliminary cavitation treatment.

Known methods for the processing of hydrocarbon raw materials in which the feed stream in the distillation reactors is subjected to mechanical activation, including according to patents EP N2 I 452 576, class SJO 33/06, 2002; RU "2102435, cl. SyUS 15/08, 1998.

The known method implemented in the reactor according to patent RU 2146525, class. C10G 1 1/10, 200 g. The method involves the supply of hydrocarbon feed to the reactor with imparting it to the flow in the directional reactor volume. Intensive flow movement allows, first of all, to eliminate stagnant zones in the distillation volume and to ensure active interaction of the processed feed stream with a heat carrier and / or catalyst, which increases the efficiency of the process. In addition, internal friction in a jet with a complex trajectory of movement is accompanied by some additional heat. However, the heat generated is not enough to significantly activate the destructive processes in hydrocarbons, and the reduction in energy costs for the refining process is small. In addition, the insufficient degree of destruction of the structure of raw materials does not guarantee a high content of light fractions and their proper quality in processed products.

Disclosure of invention

The technical result, the achievement of which the present invention is directed, is to reduce energy consumption by unit of production with an increase in the yield of light fractions and an increase in their quality by creating optimal conditions for phase transitions in the substrate constituting the initial feed stream.

The technical result is achieved by the fact that in the method of processing hydrocarbon feedstock, comprising supplying the feedstock to the distillation volume (hereinafter referred to as the reactor) with the formation of a directed feed stream and its distillation with the selection of the target product, the flow is formed with the distribution of density and angular momentum of the feed stream in accordance with the wave function corresponding to the phase transition of part of the feed stream to the positron state of Dirac matter. The mentioned part of the feed stream is not more than 0.01% of its volume. To improve the rheological properties of the feed stream and reduce energy consumption to give it directional movement, the feed is preheated to temperatures in the range (160..440) ° С. For the same purpose, as well as to increase the life of the distillation systems, the raw materials are subjected to desalination and dehydration before and after preheating. In the second case, the processes of desalination and dehydration take place with less energy consumption and the environmental hazard of production is reduced. To increase the profitability of the process, distillation is carried out in at least two stages, for which the remainder of the raw material after selection of heavy fractions is sent to a subsequent volume for distillation or returned to the existing one.

The essence of the proposed method consists in initiating a phase transition of a part of the substrate constituting the feed stream of hydrocarbons, in the fifth state of the substance with the release of a significant amount of energy directed to the implementation destructive transformations of hydrocarbons, which in turn allows to reduce energy costs from an external source, including heat, for processing raw materials. In this case, the fifth state of matter is understood to mean the positron state of Dirac matter.

The physical foundations of the positron state of Dirac matter are described in detail in the monograph “The Principles of Quantum Mechanics by P.A.V.”, Dirac, Second Edition, Oxford, 1935 [1]. The mechanisms of the phase transition of the working medium to the fifth state of matter with the absorption or release of a large amount of energy are valid for a substrate in any state of aggregation, and are reflected in the work of G. Umarov and others. "The solution of the problems of many bodies and the mechanism of melting of solids", Melts of the USSR Academy of Sciences, 1990, -3, 25-31 [2] and are based on the fact that when a substrate is introduced into quantum mechanical resonance with the positron state of Dirac matter, polarization processes arise in the latter, accompanied by the absorption of two material particles, such as electrons and protons, and initiating the process of heat and electromagnetic (in particular, in the form of γ-radiation) energy.

The conditions for creating the mentioned quantum-mechanical resonance in the microvolume dV are based on the law of conservation of energy and angular momentum and are expressed by the following relationships:

n = 1, 2, 3 ... - quantum number

ω is the microvolume transition frequency

substrate into the fifth state of matter, equal to the oscillation frequency the motion of the center of gravity of the microvolume dV m is the mass of particles participating in the transition c is the speed of light in vacuum

and W _c = hL (2), where:

1 _s = ± 1, ± 2, ± 3 ... is the quantum number of the projection of the angular momentum of the feed stream

L = ± 1, ± 2, ± 3 ... - quantum number

projection of angular momentum,

transmitted to the fifth state h is Planck's constant

The mechanism of development of the phase transition of the substrate, including the feed stream of hydrocarbons, into the fifth state of matter includes as a necessary condition for degeneracy in the energy spectrum.

In other words, a phase transition is possible and will take place when two different states of the substrate, characterized by two different combinations of quantum numbers, have the same energy.

This condition can be expressed by the following mathematical expressions, where the following notation is accepted:

E _s Ψι (C _o ni _l) - the energy and the wave function of the feed stream as a system of moving in space and time microvolumes dV, E _2, Ψ2 (η _2, ηι ₂₎ - the energy and the wave function of the same system in the state of the phase transition in the fifth state of matter, nl, n2, ml, m2 — quantum numbers

For small volumes dV, the following expression is valid for the zero approximation of the energy of the initial state of the substrate:

where Z is the average charge of atoms making up the considered microvolume dV.

Given this equality and for

(condition of quantum mechanical resonance) the sum of the quantum numbers characterizing the system:

nl + | ml | > 0 (5) The properties of the wave functions describing the parameters of the feed stream as a system of microvolumes dV moving in space and time are described in detail in G.R.Umarov, “Correlation effects in a two-electron atom”, Eur. J.Phis. 2 (1981), p. 228 - 231. [3].

This wave function is modeled as follows:

n _s t _s - normalized spherical function that describes the angular part of the wave function

1 _C , w _b - _with orbital and magnetic

quantum numbers

i — imaginary unit

R is the modulus of the distance vector

electrons

φι - angular variable in parabolic coordinates

θ, 92 - angular variables in spherical coordinates The functions φ (η) and φ (ξ) describe the oscillations of the oscillator in parabolic coordinates and are represented by the following expression:

and the radial component of the wave function is the following expression:

N _n , _mi , N _n , i _c are normalization factors determined by relations of the form:

tF | - degenerate hypergeometric function,

ω is the frequency describing

oscillating

center of gravity movements

considered microvolumes of raw materials

Ζ is the average charge of atomic nuclei,

constituents

microvolume under consideration dV R is the radius vector module describing the average dipole moment

microvolume under consideration dV. Thus, the wave function of the transition state of the system as a stream of microvolumes moving in space and time is described by the corresponding linear combination of wave functions of the form (6) under conditions (4) and (5):

constant values

It follows that the distribution of the density of the microvolume of the feed stream and the angular momenta for quantum-mechanical resonance with the positron state of Dirac matter must correspond to the following conditions:

H is the Hamiltonian of the system

M - momentum operator

m is the average mass of the molecule

feed stream

In certain parts of the reactor volume, the density of the feed stream p and the momentum M are described as follows:

T is the characteristic process time

t - current time

to is the point in time at which

breaks in intermolecular bonds - pre-exponential

factors

Thus, as a result of the quantum-mechanical resonance of the substrate with the positron state of Dirac matter, the prerequisite for which is the formation of a stream in the reactor with the above conditions fulfilled (12, 13, 14), physicochemical activation of hydrocarbon destruction processes occurs due to their own energy resources substrate. The result of the activation and the process of energy release described above is the breaking of hydrocarbon bonds of different strengths and the separation of the feed stream into fractions with different boiling points. The heavy part of the feed stream with a high boiling point in a volume of up to 10% of the total volume is discharged from the reactor as the target product, for example, tar. The selected product containing light fractions can be sent for reprocessing in an existing reactor or in an additional one. This operation can be repeated repeatedly.

Best Mode for Carrying Out the Invention The possibility of implementing the inventive method is confirmed experimentally on the installation, the functional diagram of which is presented in the attached drawing.

The installation contains a main unit - a reactor (volume for distillation of hydrocarbon feedstocks) 1, a feed system for the feedstock and coolant 2, a device for extracting the target product 3 and 4, a feedstock pretreatment device 5. The reactor itself is a volume with a jet forming device placed in it . The reactor is equipped with an inlet pipe that communicates with the feed system and coolant, and output for communication with devices for the removal of target products: light and heavy fractions. The jet forming device is a set of distributed in the reactor volume and variously oriented pipelines with different flow sections. Each of the pipelines has a specific configuration unique to it, corresponding to the wave function presented above, which describes the state and properties of the feed stream at each point in the volume at any given time. Perforations are made in the walls of the pipelines, communicating the internal cavities of the pipelines with the reactor volume. The shape, size and relative position of the elements of the jet forming device are determined by calculation and experimentally based on the requirements for the target product, nature, physico-chemical properties and composition of the feedstock and a number of its other thermodynamic parameters, as well as requirements for the final product. The feed supply system is a device for pumping the flow of raw materials and controlling its speed, and the selection system is based on the principle of separation of fractions according to their specific gravity. The method is as follows.

The feed stream, previously heated before it enters the reactor to improve its rheology and desalted and dehydrated by known methods to reduce reactor design requirements, is fed to the latter through the feed system and the inlet pipe and enters the pipelines of the jet forming device. Simultaneously with the feedstock, a coolant is supplied to the reactor. In the said device, the feed stream acquires directional movement through pipelines, breaking up into separate jets. The configuration of the pipelines and their relative orientation provides unidirectional, counter-directional or cross-directional movement of the jets. Penetrating into the reactor volume through perforations in the walls of pipelines, parts of the flow interact with each other. In the process of complex directional movement, part of the feed stream undergoes a change in density and angular momentum. The distribution of the density and angular momentum in accordance with the wave function corresponding to the conditions for the transition of a part of the flow to the fifth state of Dirac matter is guaranteed by the shape and size of the elements of the jet forming device and their relative position. Providing the conditions for the mentioned transition of more than a small (not more than 0.01%) part of the feed stream can cause a significant release of energy, which will lead to uncontrolled process. The thermomechanical effect on the feed stream, initiated by the energy released during this process, causes destructive processes and redistribution of the processing components in it: light hydrocarbons, which are removed from the reactor as target products, and heavy oil residue. Target products can be used both independently and sent for re-processing in subsequent reactors or returned to the existing one. The number of stages of distillation is determined by the tasks.

The percentage yield of light fractions depends on the physicochemical characteristics of the raw materials, the requirements for the target product, and may be higher than when using already known methods. This figure is determined empirically in the distillation of highly viscous oil in the above device.

The table below shows the results of an experiment on the separation of the original oil by the present method in an industrial installation with a capacity of 1,500 tons per year.

The proportions of gasoline, diesel and jet fuel can be changed within 20-30% of the mass of gasoline, 40-60% of the mass of diesel fuel, 10-30% of the mass of heavy residues without compromising the quality of the resulting products. As a result of the application of the proposed method it is noted that the redistribution of components occurs: most of the resins, asphaltenes, heavy metals go into a heavy residue. This greatly facilitates the working conditions of equipment for producing fuels, and also removes the severity of the environmental problems of oil refining.

It was also noted that the fraction of light hydrocarbons obtained by the claimed technology exceeds the fraction of distillates produced by traditional technology, and the heavy fraction, into which the bulk of the impurities harmful to light fractions passes, can be used as raw material for production in its physical and technological properties high quality road surfaces.

The quality of the oil processed by the claimed method was also evaluated by the integrated indicator (K) calculated according to the method described in the work of V. Degtyarev. “On the Bank of Oil Quality”, Oil industry, 1997, Z, p. 62-63. Calculations showed that a comprehensive indicator of the quality of the refined oil was K _lane ⁼ 0.455 with an initial oil index of K _ref = 2.92. Deviation of a comprehensive quality indicator from one to a downward direction leads to a reduction in the cost of its processing.

The most effective method in the processing of "secondary" raw materials, including fuel oil and used engine oil, in order to obtain diesel fuel. In the latter case, the claimed method, perhaps the only possibility of its processing. In addition to reducing energy costs for processing, the method allows to improve the quality of the target product, since the phase composition of the obtained fractions is significantly better than those obtained by known methods and meets European standards. This is ensured by the depth of destructive processes in hydrocarbons. By varying the parameters of the jet forming device, it is possible to obtain an additional technical result when implementing the method:

- increase the range of target fractions;

- allocation of fractions of a given composition;

obtaining fractions suitable for direct use as fuel.

Industrial applicability

The claimed method of processing hydrocarbon raw materials is characterized by a high ratio of the output of the most valuable target fractions to energy costs, processing costs and losses of raw materials. The method can be used for deep, waste-free, environmentally friendly processing of all types of liquid raw materials, including high-viscosity oil with a high content of sulfur, salts, resins and other impurities.

Claims

Claim

1. A method of processing hydrocarbon feedstock, comprising supplying feedstock to a distillation volume with the formation of a directed feed stream and distillation with the selection of target fractions, characterized in that the flow is formed by providing a distribution of the flow density of the feedstock and the angular momentum in accordance with the wave function corresponding to conditions for the phase transition of a part of the feed stream to the positron state of Dirac matter.

2. The method according to p. 1, characterized in that the said part is not more than 0.01% of the total volume of the feed stream.

3. The method according to claim 1, characterized in that the feedstock is preheated.

4. The method according to p. 1, characterized in that the feedstock is preliminarily subjected to desalination and dehydration.

5. The method according to p. 1, characterized in that it is carried out in at least two stages.