RU2246525C1 - Method of destruction of organic compounds and plant for processing petrochemical wastes - Google Patents

Abstract

FIELD: destructive processing of organic compounds; chemical, petrochemical and other industries; decontamination and utilization of hydrocarbon wastes.

SUBSTANCE: proposed method includes action on organic raw material by acoustic and electromagnetic fields. Working parameters of wave fields are selected in such way that resonance frequency of oscillation of molecules of organic compound is ensured. Then raw material is subjected to heat treatment at temperature of 140-380 C which causes active destruction of organic compounds, especially high-molecular hydrocarbons. Proposed method may be used for processing different organic wastes at selective action at low temperatures and conversion for obtaining quality finished product.

EFFECT: enhanced efficiency.

7 cl, 1 dwg, 1 tbl

Description

The invention relates to processes for the destruction of organic compounds and can be used in chemical, petrochemical, oil refining and other industries, as well as for the disposal and disposal of hydrocarbon waste. The method consists in a complex effect on high molecular weight hydrocarbons, mainly with the number of carbon atoms more than 16 (C16), by acoustic and electromagnetic fields in the working area, hereinafter referred to as the activation zone. As sources of the wave field, electromagnetic and mechanical generators are used, the operating parameters of which (frequency, power, amplitude of modulating pulses) are selected depending on the technological task taking into account the physicochemical characteristics of the raw material. The transition of high molecular weight hydrocarbons to an excited state due to resonant absorption of energy allows their selective cracking to be carried out at temperatures of 260-280 ° C by heating in a heating and reaction furnace in both cyclic and continuous modes. Technological stages of the destructive processing of high molecular weight hydrocarbons include: 1. Resonant excitation of the feedstock in the activation zone; 2. Heating of activated raw materials in a heating and reaction furnace to a temperature of selective decomposition; 3. Separation or rectification of selective cracking products; 4. Stabilization and purification of oil products recovered at the separation (rectification) stage; 5. Separation of the highly viscous part (tar) from the bottom residue and return of unreacted raw materials (recycling) to the activation zone.

The invention relates to processes for the destruction of organic compounds and can be used in the petrochemical, chemical and other industries, as well as for solving the tasks of neutralization and disposal of hydrocarbon waste in compact plants with a capacity of 3 thousand tons per year or more.

It is known that the first industrial installations for the destruction of hydrocarbons (pyrolysis) were built in 1875. The first patent on thermal cracking technology was obtained by V. Shukhov and S. Gavrilov in 1891. Cracking refers to a combination of decomposition and condensation reactions of hydrocarbons occurring at the molecular level. It is believed that the thermal decomposition of hydrocarbons occurs according to a radical-chain mechanism (Magaria RZ, Mechanism and kinetics of homogeneous thermal transformations of hydrocarbons. M: Chemistry, 1970, 186 pp.). Modern research methods make it possible to fairly accurately establish the composition of the products of decay and further conversion of hydrocarbons in thermocatalytic processes (E.V. Smidovich. Cracking of crude oil and processing of hydrocarbon gases. M: Chemistry, 1980, 323 pp.). In addition to thermal cracking, other hydrocarbon destruction methods are proposed:

- radiation-thermal, in the outer shell of the core of a nuclear reactor (RF patent No. 21116330, C 10 G 15/00 from 2000 [1]);

- a laser beam with a power of 30-50 W with a wavelength of 0.248-0.355 μm (RF patent No. 2039789, C 10 G 15/08 [2]);

- plasma-chemical pyrolysis of gaseous hydrocarbons (patent No. 2202593, C 10 G 15/08 [3]).

As follows from the description, the results of the work described in these patents were obtained in laboratory conditions and have not yet received industrial use.

It is known that there are positive results obtained at the facilities of acoustic and ultrasonic effects on oil, direct race gasoline, as well as gas oil and residual fuel oil from the output of the secondary process units, in order to obtain motor fuels:

- in the patent of the Russian Federation No. 2149886, C 10 G 32/00 of 1999 [4], a method of exposure to a sound field is described, a solenoid with a multilayer winding, with a power of 0.1-150 kW / cm and a frequency of 1-10 is used as a field generator ⁶ Hz;

- in the patent of the Russian Federation No. 2151165, C 10 G 15/08 of 1999 [5] describes a method for producing marketable petroleum products under ultrasonic treatment. Oil and fuel oil are affected by opposing ultrasonic fields with a frequency of 1-10 ⁴ kHz, a radiation intensity of 1-10 ⁴ MW / m ² at a variable pressure of 0.1-0.5 MPa;

- in the patent of the Russian Federation 2078116, C 10 G 15/00 from 1995 [6], a method for ultrasonic treatment of hydrocarbons by a rotary type activator with a radiation intensity of 1-10 MW / m ² and a static pressure of 0.2-0.5 MPa is described.

There are also patents for cracking hydrocarbon feed resulting from cavitation:

- in RF patent No. 2144550, C 10 G 15/08 of 1999 [7], a method is proposed for processing heavy hydrocarbons under the influence of an acoustic field of cavitation origin, generated by accelerating the flow to 330-350 m / s and subsequent expansion of the flow in diffusers ;

- in the patent of the Russian Federation No. 2186825, C 10 G 15/08 of 2001 [8], a method for increasing the octane number of straight-run gasolines by high-temperature pulsed exposure in a step cavitation installation is described; a multistage centrifugal pump is proposed as a generator. The processing time of the hydrocarbon mixture in the cavitator is 20-40 minutes.

Closest to the proposed method is a method of cracking oil and installation for its implementation proposed in the patent of the Russian Federation 2078116, C 10 G 15/00 from 1995 [6], where the crude oil is subjected to ultrasonic treatment, at a pressure of 0.2-5.0 MPa in the zone of a closed circulation loop, where a dispersant (water, liquid metal, hydrogen) is fed simultaneously with the raw material, then the resulting products are separated in a separation chamber. The entire installation is made in one housing, where there are combined working chambers, in each of which a centrifugal pump wheel (rotor) is installed. The described method allows to increase the yield of light petroleum products during the processing of vacuum gas oil.

In our opinion, this method has the following disadvantages:

1. the rotor, which is the cavitation generator, requires frequent replacement, as it undergoes permanent cavitation destruction,

2. unreliability of the design, as a consequence of a complex rotating mechanical system having a large number of friction nodes,

3. there is no stabilization and purification of mercaptan compounds of the final products; the gasoline obtained at this installation does not correspond to commercial quality.

4. ineffective separation system, since there is no temperature adjustment of the separation process,

5. low selectivity of the destruction process.

From the analysis of the cited patents, it follows that the cause of the destruction of hydrocarbons is the influence of wave fields mainly in the acoustic (ultrasonic) region with an energy density leading to the breaking of carbon bonds (CC) of the “skeleton” of the molecule. The identification of the resonant frequencies of combined acoustic and radio frequency electromagnetic fields, their target generation, radiation in the activation zone and subsequent absorption by high molecular weight hydrocarbons allows the destruction of these hydrocarbons at temperatures of 260-280 ° C. This is significantly lower than the temperatures currently used for cracking processes in the refining industry. The process of destruction after resonant activation occurs at atmospheric pressure without the use of catalysts, the role of which is to some extent played by the finely dispersed state present in the feedstock, especially in used oils, residues of fuel oils of various origin, inorganic impurities, including transition metal. In our opinion, the destruction of molecular bonds of carbon occurs at the moment when the frequency of the external field vibrates in resonance with the natural frequency of the vibrations of the nuclei of the carbon molecules, as a result of which the equilibrium state of the molecular bonds of carbon is disturbed, resulting in free radicals. It was experimentally established that the depth of decomposition of the source of high molecular weight raw materials (waste oils, fuel oils of various origin) and the composition of the products of destructive decomposition obtained by the described method, at equal power levels and spectra of the impact vibrations, differ significantly, than a large number of wave fields with different parameters affect the hydrocarbon mass , the more different classes of carbon compounds will undergo destruction.

The objective of the present invention is to increase the efficiency and reliability of the process of destruction of residual high molecular weight hydrocarbons with boiling points above + 360 ° C by resonant activation and subsequent cracking at a temperature of + 260-280 ° C and distillation of the formed light boiling products within the parameters of direct atmospheric distillation of oil, t. e. at temperatures up to + 360 ° C and with the receipt of light commercial oil products. The specified parameters of the process of processing high-boiling, including and spent so-called “dark” oil products into low-boiling ones, with a boiling point below 360 ° С and called “light”, are reached by preliminary processing - resonant activation - of raw materials in the activation working zone. The operating parameters of the fields in the activation zone provide the transition of the hydrocarbon molecules that underwent activation to a state with a higher energy level of the valence electron orbitals, leaving their outer electron shell and hereinafter referred to as the excited state. The level of excitation, the period of time spent in this state depends on the ratio of the energy of the acting fields, the time spent in the activation zone. The transition of a hydrocarbon molecule to an excited state is determined by the amount of energy absorbed from the energy of the fields in the activation zone. Effective absorption of wave field energy by hydrocarbon molecules occurs at frequencies, hereinafter referred to as resonant frequencies. The onset of resonant absorption of energy of external wave fields occurs when the threshold values of both the parameters of these fields and the external static pressure on the activated hydrocarbon medium are reached. The activation zone is a resonator equipped with radiating antennas of the radio frequency spectrum and an emitter of ultrasonic vibrations. Antennas and emitters are powered by special generators outside the working area. The process of resonant absorption of ultrasonic and radio frequency energy supplied to the activation zone is achieved by preliminary selection of the frequencies of the spectrum, as well as the intensity of its components. Achieving and fixing the parameters of the radio frequency and ultrasonic vibrations supplied to the antennas and emitter, respectively, is achieved by isolating and analyzing the reflected back waves from the radio frequency antennas. The minimum level of reflections during reconstruction, i.e. scanning the generator of radio-frequency oscillations at the initial moment of tuning the activation system is fixed by the microprocessor control system of the generator. This frequency is taken as the central one and in the process of further work some change occurs, deviation up and down. This increases the efficiency of the activation process, obviously related to the composition of the feed. The energy absorption of fields in the activation zone occurs most intensively by hydrocarbon molecules with the number of carbon atoms greater than C16 - C20. The state of “activation” after the release of raw materials from the activator’s working zone is also maintained for a longer period, from several hours to 10-15 days, for high molecular weight hydrocarbons. High molecular weight raw materials after resonant activation are fed into the thermal cracking reactor at a temperature of 260-280 ° C. The process of decomposition of the feedstock is characterized by a break in the feed hydrocarbon molecule in its middle part, where the binding energy between carbon atoms (...- С-С -...) is usually the smallest. Hydrocarbons containing sulfide sulfur are more likely to explode in the sulfur-carbon bond. A decrease in the proportion of hydrogen in high molecular weight hydrocarbons with any kind of cracking leads to the formation of unsaturated hydrocarbons, and the presence of sulfide sulfur leads to the formation of mercaptans. Thus, to obtain stable and most valuable light petroleum products, the process of processing the feedstock should include a chemical stabilization and purification plant for the products obtained. The cracking process at a temperature of 260-280 ° C does not allow to isolate that part of the light oil products having a boiling point from 280 ° C to 350 ° C in the vapor phase directly from the reactor. Depending on the situation, a two-stage process of stripping the obtained light fractions by raising the temperature in the reactor after the completion of cracking to 350 ° C is possible, then the process will be cyclical. Or sequential transfer of activated raw materials through the reactor and evaporation of the low-boiling fraction from it, and then to the evaporator of higher boiling fractions at the end temperature of boiling light oil products and separating the reacted residue from it. The composition of the raw materials, the level of vibrational energy supplied to the resonant activator significantly affect both the yield of light products, i.e. the proportion of reacted raw materials to the remaining part, as well as the fractional composition and chemical stability. At a level of energy input of 0.6-1.0 kW for waste oil, the yield was 65-80% with an activator productivity of 0.9-1.4 cubic meters / hour and 40-55% for long-term bitumen-like fuel oils of long-term storage. After reactivation of the used oil due to the high level of inorganic finely dispersed impurities, the decomposition process was not completed to the end and was completed at 6% VAT. The fraction of fractions with a boiling point up to 150 ° С was about 15%. The fraction with a boiling point of 150-350 ° C was 72%. Hydrocarbon gases C1-C4 during primary processing amounted to 3%. After secondary activation and subsequent cracking, their share increased to 4%, and only to 7%. The processing of long-term bituminous fuel oils of long storage was carried out after preliminary heating to a temperature of about 80 ° C and the appearance of fluidity necessary for pumping through the activation zone with a gear pump. In the process of activation and subsequent cracking in a heating and reaction furnace with a sequential increase in temperature to 260-280 ° C with fractionation of the obtained light oil products and a further increase in temperature to 360 ° C. For two activation and cracking cycles, the proportion of light products was about 65%. The proportion of gaseous products did not exceed 8%. The remainder consisted of a highly viscous tar with a dilution temperature of more than 120 ° C.

The resulting light fractions were highly prone to oxidation. Within a few days, the color of the fractions changed from light yellow to red-brown.

The obtained light oil products had a sharp unpleasant odor characteristic of mercaptans. The sulfur content in the feed was up to 3.8%, the total sulfur content in the light fractions was 0.6%. The purification of light fractions according to the methodology of RF patent No. 2166530, С 10 С 27/00 from 2000, allowed to obtain a light yellow product that meets the standards for heating oil.

The bottom residue was used as raw material for the production of high-viscosity bitumen for waterproofing the storage tank for storm sewage from the industrial site. An increase in the energy supplied to the activation zone to 4 kW led to an increase in the yield of light fractions in one cycle, corresponding to a double activation-cracking-stripping cycle of raw materials. Significantly increased the resistance to the grinding of light fractions without the use of stabilizers and chemical cleaning. There was no visible tarring for 8 days, the smell was more responsive to gasoline of gas condensate origin. The proportion of gaseous products was not more than 8%.

Schematic diagram of the installation for the processing of used engine oil is shown in the drawing.

From the tank 1, the raw material enters the destructor apparatus 2, which consists of two autonomous blocks 2a and 2b. The apparatus 2b is made on the basis of an electromagnetic radiation generator, which can be structurally made, for example, as proposed in the patents [4], [5]. By changing the antenna field in devices of this type, it is possible to control the wavelength and power of electromagnetic exposure, which allows you to selectively affect certain groups of hydrocarbon compounds, while the wave field parameters vary in the range: frequency 1-10 ⁴ Hz, intensity 1-10 ⁴ MW / m ² . Apparatus 2a is connected by a pipeline with apparatus 2b having shutoff valves, as well as a pipeline line that allows fully or partially directing the flow to the separation unit. The apparatus 2b is made on the basis of a mechanical generator of ultrasonic vibrations, it can be rotary [6] or hydrodynamic type [7]. You can use the apparatus, structurally made according to the principle of the Laval nozzle (B. M. Yavorsky. Handbook of physics. M: Nauka, 1977, p. 339). The advantage in combining two different methods for generating a water field is as follows: 1. The ability to form a wave field for the influence of hydrocarbons on a wider spectrum, and as a result, a deeper conversion of raw materials, 2. The reliability of the installation increases, 3. the universality of work increases installation. Then, the resulting mixture of hydrocarbons is sent for separation to block 3. The hardware of the separation block can be made on the basis of standard equipment manufactured by the industry, the selection of which is based on the estimated material balance of the installation. The calculation of the heating-reaction furnace was carried out according to the method of E.V. Smidovich, “Cracking of Petroleum Raw Materials and the Processing of Hydrocarbon Gases,” Part II, pp. 34–44. M .: Chemistry, 1980. The separator separates a wide fraction of hydrocarbons with a boiling range of 35-360 ° C from a heavy oil residue, with a boiling point above 360 ° C. To stabilize the resulting cracked product in tank 4, it is treated with antioxidants, such as industrial preparations such as Agidol-1 or Agidol-12. It is well known that as a result of cracking of hydrocarbons of petroleum origin, mercaptan compounds are formed, even miserable concentrations of which are extremely negatively perceived by humans. At refineries, hydrogenation plants are used to eliminate them, in which, during catalytic hydrogenation, unsaturated hydrocarbons are saturated, sulfur compounds are destroyed and sulfur is removed in the form of hydrogen sulfide. However, the use of such an installation, with small-tonnage production, is economically disadvantageous. In the described process, the removal of mercaptan compounds from the finished product is carried out according to the method of RF patent No. 2166530, C 10 G 27/00 from 2000 in block tank 5, other methods that give a similar result can be used.

To increase the yield of the final product, it is possible to supply, together with the hydrocarbon feed, to the input of the destruction unit, in an amount up to 30 volume percent, aqueous solutions of organic acids, aldehydes, ketones, alcohols, ethers, water-in-oil emulsions or mixtures thereof. This will solve the issue of recycling industrial waste, for example in the alcohol industry, processing distillation residue - a solution of “fusel” oils.

Thus, the proposed method for the destruction of organic compounds has several advantages:

- the versatility of the method, which consists in the possibility of working on various types of organic compounds;

- lack of high pressures and temperatures;

- the ability to selectively act on various types of organic compounds;

- a two-stage destruction system allows for the deep conversion of hydrocarbons;

- obtaining a high-quality final product - stabilized, odorless mercaptans and meeting the standards for commercial naphtha products;

- the ability to use standard components and assemblies manufactured in industry;

- the ability to quickly change equipment to transfer work to other raw materials, or to other process modes.

Examples of specific implementation of the method.

1. The used engine oil corresponding to GOST 21046-86 was subjected to destruction: used engine oil: 1. kinematic viscosity at 50 ° С - 2.7 mm ² / s, 2. flash point in an open crucible - 102 ° С, 3. water content - 7 wt.%. After processing the specified raw materials in a rotary disperser at 0.6 MPa, an emulsion of the water-in-oil type was obtained, which was sent to a destructor, where at a supplied energy level of 0.8 kW and an ultrasonic vibration amplitude empirically set at 8-12 μm with an electromagnetic flux power of 7 W in a feed stream of 50 l / h, a wave action was carried out until the heating and reaction furnace was completely filled with raw materials, in which, at a temperature of 380 ° C, from the vapor phase described above was obtained a wide fraction of hydrocarbons in an amount of 84 wt.% with a boiling point in the range of 37-365 ° C, the bottom residue close in composition to tars amounted to 9 wt.%, the rest was the loss of the gas phase and fur. impurities.

2. Decompositions were made of bituminous fuel oil from an open storage with a shelf life of 60 years, which can be characterized as ultrahigh-viscosity plastic-like oil sludge. After preliminary heating to 80 ° C and sludge during the day at a constant above temperature, 40 wt.% Water was separated. The separated hydrocarbon mass was fed into the dispersant and then to the destructor, where in the recirculation mode, with parameters corresponding to the described method, it was processed for 120 minutes at a temperature of 80-120 ° C, an amplitude of ultrasonic vibrations of 10 μm and an electromagnetic power of 7 W. After processing in a heating and reaction furnace at a temperature of 380 ° C, a hydrocarbon fraction was obtained with a boiling point of 32-360 ° C in an amount of 63 wt.%. In practice, the proposed technology was implemented in a pilot installation for the processing of used motor oils. The plant productivity is 0.7 m ³ / hour for raw materials, which is a mixture of used motor oils, purified from mechanical impurities. Power consumption (total) - 17 kW / h. The yield of a wide fraction of hydrocarbons is 82-85 wt.%, The bottom residue is tar with a boiling point above 365 ° C. Attendants - 2 people. The unit is universal and can operate both on heavy, highly viscous petroleum products, and on used oils and high molecular hydrocarbons. The heating of the heating-reaction furnace was carried out by burning the gas oil obtained at this installation. A light gasoline fraction of 37-140 ° C and a gas oil fraction of 140-365 ° C were isolated, the fractional composition of which is given in Table 1. The structural group hydrocarbon composition of the gas oil fraction and feedstock, used oil was determined by liquid chromatography according to the VNIITU method chromatograph XJ-1, the results are shown in table 1. From the above analysis results, the fact of destruction of hydrocarbons when exposed to it as described above is obvious.

Table 1 Specifications Raw materials (used engine oil) Gasoline fraction Gas oil 1. Fractional composition. The beginning kip. ° C
Boils,% vol. 250 ° C. 39.0 ° C 120.0 ° C 10% 65.0 ° C 131.0 ° C thirty% 83.5 ° C 197.0 ° C 60% 111.0 ° C 272.0 ° C 97% 187.0 ° C 365.0 ° C 2. The structural group composition, wt.% 2.1 Paraffin-naphthenic hydrocarbons 62 64.8 2.2 Aromatic hydrocarbons: - monocyclic 16.1 15.4 - bicyclic 10.5 14.0 - polycyclic 3,5 3.6 - resinous 5.9 2.2 2.4 Asphaltenes 2.0 - 3. Density at 20 ° C, g / cm ³ 0.739 0.831

Claims (7)

1. The method of destruction of organic compounds and / or compounds, including the simultaneous or sequential exposure of the degradable raw materials by wave electromagnetic and acoustic fields with energy and frequencies corresponding to the resonant frequencies and / or vibration frequency of molecules of the degradable organic compounds and / or compounds with subsequent temperature exposure in atmospheric distillation limits. 2. The method according to claim 1, characterized in that the preparation of raw materials for destruction in order to reduce the activation potential of the decomposition of organic compounds is achieved by simultaneously superimposing a spectrum of electromagnetic waves on acoustic wave vibrations arising from cavitation, excited by various sources of wave energy generated by two and more different generators, while the selection of frequencies of electromagnetic waves is performed automatically at the minimum level of the reflected signal from the radiation boiling antennas resulting from sequential changes the oscillation frequency electromagnetic generator under control of the microprocessor, the selection and the measurement of the reflected signal is also produced by the microprocessor. 3. The method according to claim 1, characterized in that the wave-activated hydrocarbon feed is degraded in a heating and reaction furnace at temperatures up to 280 ° C, both in the presence of a catalyst and without it. 4. The method according to claim 2, characterized in that when the wave action on high molecular weight hydrocarbons as described above, the viscosity index decreases by a value from 0.5 to 45% of the initial value. 5. The method according to claim 2, characterized in that when the wave action on organic compounds and / or the compound as described above, the effect of destructive decomposition up to 280 ° C is maintained for up to 30 days, while the depth of destruction is reduced and the amount of light hydrocarbons is reduced accordingly . 6. Installation for the processing of oil raw materials, characterized in that the destruction unit is made on the basis of two or more independently working wave field generators, and one electromagnetic generator with radiating antennas in the resonator through which the raw material is pumped, with built-in magnetostrictive and / or a piezoelectric acoustic emitter, another rotational and / or hydrodynamic type cavitation acoustic generator, structurally constructed according to the principle of a Laval nozzle with acoustic resonators. 7. Installation according to claim 6, characterized in that the heating and reaction furnace is equipped with a device for introducing superheated steam and a collection of petroleum products with a boiling point above 380 ° C and a device for removing them from the heating and reaction furnace.