WO2010068139A1

WO2010068139A1 - Method for processing carbon- and/or hydrocarbon-containing products and reactor for implementing said method

Info

Publication number: WO2010068139A1
Application number: PCT/RU2009/000675
Authority: WO
Inventors: Максим Викторович АНИГУРКИН; Асланбек Хажмурадович АРСАМАКОВ; Грачья Пайлакович БАДАЛЯН; Денис Игоревич ДОЛМАТОВ; Алексей Васильевич ЕРУСЛAHOB; Вячеслав Александрович ПАНФИЛОВ; Павел Вениаминович ПОЛЯКОВ
Original assignee: Закрытое Акционерное Общество Научно-Производственная Компания "Интергаз"; Общество С Ограниченной Ответственностью "Мировые Экологические Стандарты"
Priority date: 2008-12-10
Filing date: 2009-12-08
Publication date: 2010-06-17
Also published as: RU2385343C1

Abstract

The inventions relate to the field of industrial processing of carbon- and/or hydrocarbon-containing products and can be used in particular for processing various types of industrial and domestic waste and for processing low-quality combustible mineral resources. In the processing method, which is carried out in a special reactor equipped with temperature sensors, a hydrocarbon synthesis and hydrogenation zone with a temperature of 250°-400°C is formed immediately behind the coking and pyrolysis zone, a temperature of 850°-1300°C is maintained in the combustion zone, chemically uncombined carbon is separated in the coking and pyrolysis zone, and said chemically uncombined carbon is treated in the combustion zone with steam with the formation of free hydrogen, which is fed to the synthesis and hydrogenation zone, subsequently effecting the synthesis and hydrogenation of hydrocarbons, wherein a vacuum is formed within the working space of the reactor and the process is carried out in the presence of a catalyst that forms part of the composition of the packing. The technical result is a reduction in the energy consumption of the process, an increase in the technological possibilities as regards controlling the chemical composition, an increase in the yield of products available for further use and an improvement in the quality of said products.

Description

METHOD OF CARBON PROCESSING-

AND / OR HYDROCARBON-CONTAINING PRODUCTS

AND REACTOR FOR ITS IMPLEMENTATION

The invention relates to the field of industrial processing of carbon- and hydrocarbon-containing products and can be used, in particular, for processing a variety of industrial and household waste, for processing low-quality combustible minerals, such as, for example, brown coal, oil shale, and the like.

The problem of processing a variety of low-quality combustible minerals, household and industrial waste, including carbon and hydrocarbon components, is very acute. A variety of methods have been developed that allow decomposing carbon- and hydrocarbon-containing products into components, however, only a certain part of them can be used for further processing, for example, as a combustible component. The rest is usually toxic waste, and in the case of the original waste - even more toxic compared to them. And although disposal of the products remaining after processing is possible, however, due to the high costs, it is economically inefficient. In addition, it should be noted one important feature of the implementation of processes for the processing of low-quality combustible minerals and the mentioned waste - they, in most existing methods, are implemented on a laboratory scale. At the transition to the industrial scale of implementation immediately affects the economic inefficiency of projects, associated primarily with the need for additional disposal of associated chemical components obtained during the main process. For this reason, the industrial processing of low-quality combustible minerals, as well as carbon and hydrocarbon-containing wastes, is not widespread.

A known method of processing solid domestic waste by gasification, implemented in a reactor with refractory lining with a length of 1600 mm and an inner diameter of 250 mm, for which a gasifying agent containing oxygen is fed countercurrently into a vertical shaft furnace, the wastes (usually mixed with lumpy fuel) are sequentially stay in the heating and drying zone, the pyrolysis zone, the combustion (oxidation) zone and the cooling zone, while the maximum temperature in the reactor is maintained within 700-1400 ⁰ C by adjusting at least m Here is the mass fraction of oxygen in the gasifying agent and / or the mass fraction of non-combustible material in the waste and / or the mass fraction of combustible material in the waste, the process being carried out periodically, for which the waste is loaded and the solid products are unloaded after shutting down the reactor [Description of the invention to the patent RF N ° 2079051 dated 1994.06.23, IPC F23G5 / 027, publ. 1997.05.10]. As a result, efficient processing of solid waste, including low-calorie, without the use of additional energy sources and with the production of environmentally acceptable (after appropriate treatment) products is ensured.

The disadvantage of this method is the high specific consumption of the oxidizing gas, which leads to the formation of an excessive amount of oxides and acid components in the product gas and the need to load additional solid lump fuel in the case of a low calorific value of the processed product, as well as its low productivity. A known method of processing combustible solid household waste, which is a modification of the method according to the patent of the Russian Federation N ° 2079051, the difference of which is that the temperature in the reactor is maintained in the range from 800 to 1300 ⁰ C, is used as a gasifying agent, mainly in a mixture with air, and the steam released during drying is included in the composition of the gasification agent [Description of the invention to RF patent N ° 2150045 from 1998.01.22, IPC ⁷ F23G5 / 027, publ. 2000.05.27]. The method provides the processing of solid waste without supplying heat from the outside with high energy efficiency, high yield of valuable products, including pyrolysis resins and combustible gas, and high overall energy efficiency of the process.

The disadvantage of this method is the presence of an excess of chemically unbound carbon in the solid residue at the outlet of the reactor, a high content of water, oxides and acid components in the product gas, which makes its full use ineffective. In addition, when implementing the method, there are significant heat losses with flue gases and it is characterized by low productivity.

A known method of processing condensed fuels, which is a modification of the method according to RF patent N ° 2079051, for which a charge consisting of combustible components and a lump of solid non-combustible material is loaded into the reactor, a gas flow is established through the charge with the supply of a gasifying agent with oxygen, steam and carbon dioxide, the products of processing are removed from the reactor, where successive sections of the aforementioned charge are sequentially located in the zones of heating, pyrolysis, coking, gasification and cooling Regulate the temperature in the combustion zone ranges from 800 to 1300 ⁰ C, was discharged from the reactor solid products, burn at least part of the gaseous, while as a gasifying agent used in the flue gas is mixed with air and steam, wherein the process control is carried out a change in the fraction of flue gas in the gasification agent [Description of the invention to the patent of the Russian Federation ÷ Ns 2152561 from 1998.01.22, IPC ⁷ F23G5 / 027, publ. 2000.07.10]. The result is the processing of condensed fuels without supplying heat from the outside with high energy efficiency, high yield of valuable products, including pyrolysis resins and combustible gas.

The disadvantage of this method is the excess amount of chemically unbound carbon in the solid residue at the outlet of the reactor, the high content of water, oxides and acid components in the product gas, which reduces the efficiency of its further use, as well as its low productivity.

A known method of disposal and destruction of solid waste, mainly hospital, containing combustible materials, including loading the waste into the gasification chamber, their initial ignition with the formation of a gasification zone, supplying a gasifying agent to it, moving the waste through the chamber, carrying out pyrolysis with a relative lack of air and subsequent afterburning pyrolysis products in the afterburning chamber with excess air, regulating the air supply depending on the temperatures in the gasification and afterburning chambers, at the withdrawal of gaseous gasification products is carried out directly from the gasification zone at a temperature not lower than 800 ⁰ C and provide heat to the gasification zone by heating the walls of the gasification chamber with exhaust gases at a temperature in the range 800-1200 ⁰ C [Description of the invention to RF patent JNo 2089786 from 1994.06.06 .23, IPC ⁶ F23G5 / 00, publ. 1997.09.10].

The disadvantage of this method is the high specific consumption of the oxidizing gas, the high temperature of the product gas at the outlet of the gasification chamber, the formation of an excessive amount of oxides and acid components in the gas at the outlet of the afterburner, the need for an additional heating source in the case of low calorific value and high humidity of the charge product to initiate and maintain the gasification process, as well as its low productivity. In addition, the method is characterized by low productivity and the impossibility of implementation in industrial volumes.

A known method of processing worn tires, including thermal decomposition at 400-600 ⁰ C with the formation of gas and vapor products and a solid carbon residue, their separation into liquid and vapor phases and a solid carbon residue, separation of the liquid phase into light and heavy fractions, grinding of the carbon residue, granulation of the carbon residue using a wetting liquid, carbonization of the carbon residue, and the gases and light resins formed in the proposed process are fed to the combustion furnaces of the reactor, carbonizer and activator [Description of the invention to the patent of the Russian Federation Jvfe 2142357 from 1998.07.03, IPC ⁶ . B29B17 / 00, CÜGl / 10, C08J11 / 02, publ. 1999.12.10]. The method reduces the volume and spectrum of emissions from the process of processing used tires.

The disadvantage of this method is its lack of performance and the need to burn its own pyrolysis gases and light resins to maintain the thermal regime of the reactor, which leads to a high consumption of oxidizing gas and the formation of an excessive amount of oxides and acid components.

A known method of processing combustible waste, such as worn tires and similar polymer waste containing rubber, by pyrolysis of the polymer component of the tire in order to obtain hydrocarbon pyrolysis products and fuel gas, for which the charge from pieces of tires or a mixture of pieces of tires with solid non-combustible material is loaded a reactor in which the maximum temperature is maintained in the range 800-1700 ⁰ C, and a countercurrent oxygen-containing gasifying agent (air) organized sequentially passing through the loaded charge of Well preheating pyrolysis zone coking zone, a combustion zone and a zone the mixture is cooled, the solid residue is unloaded from the reactor and the target processing product is discharged in the form of an aerosol containing vapors and small drops of pyrolysis resins and combustible gas with a temperature below 300 ⁰ C, while controlling the gasification agent feed rate and / or the gasification agent mass flow rate , and / or charge consumption, and / or gasification agent composition and / or charge composition [Description of the invention to RF patent Ne 2062284 from 1994.06.23, IPC ⁶ C10B49 / 04, C10B57 / 04, F23G5 / 027, publ. 1996.06.20]. The process is conducted without heat supply with high energy efficiency and high yield of products.

The disadvantage of this method is the need to use water or carbon dioxide in the composition of the gasification agent, as well as the need to introduce water into the combustion and / or cooling zone to control the thermal regime, which leads to additional heat costs and a decrease in the calorific value of the product gas at the outlet of the reactor, and also the formation of an excessive amount of oxides and acid components in the product gas due to the excessively high temperature in the combustion zone.

The closest in combination of essential features of the claimed method of processing combustible carbon and hydrocarbon-containing waste is a method of environmentally friendly disposal of oil waste or sludge and other waste containing heavy, including liquid, hydrocarbons [Description of the invention to the patent of the Russian Federation N ”2116570 of 1996.09.25, IPC ⁶ F23G7 / 00, F23G7 / 05, publ. 1998.07.27]. The method includes a high-temperature layer-by-layer treatment of waste in the reactor, when an oxygen-containing agent and water vapor are supplied, burning part of the waste, pyrolysis of combustible waste constituents with the formation of gas-vapor products with a predominant content of hydrocarbons and solid residues, their cooling, removal and removal from the reactor working zone.

The disadvantages of the method is the necessity of using water as a part of the gasification agent, which leads to additional costs heat and reduce the calorific value of the product gas at the outlet of the reactor, the need to load additional solid lump fuel in the case of a low calorific value of the processed product, as well as increased oxygen consumption in the gasification agent and the formation of excessive oxides and acid components during product gas combustion. In addition, the method is implemented at the level of a laboratory experiment, which makes it impossible to evaluate its potential and technological features.

The problem to be solved by the first invention of the group and the technical result achieved is to create another environmentally friendly high-performance method for high-temperature processing of combustible carbon and / or hydrocarbon-containing products, reduce its energy capacity, expand technological capabilities in terms of controlling the chemical composition and increasing the yield of products ready for further use as well as improving their quality.

To solve the problem and achieve the claimed technical result in a method for processing combustible carbon and / or hydrocarbon-containing products, including their high-temperature layer-by-layer processing in the reactor in the presence of a nozzle when supplying an oxygen-containing agent and water vapor, burning, coking and pyrolysis of combustible components, the formation of a gas-vapor mixture and solid residues, their cooling, removal and removal from the working space of the reactor, directly behind the coking and pyrolysis zone, form a zone of synthesis and hydrogenation of hydrocarbons with a temperature of 250-400 ⁰ C, maintain a temperature of 850-1300 ⁰ C in the combustion zone, chemically unbound carbon is released in the coking and pyrolysis zone and treated with water vapor in the combustion zone with the formation of free hydrogen, which is fed into the synthesis zone and hydrogenation, sequentially carrying out the synthesis and hydrogenation of hydrocarbons, while inside the working space of the reactor form rarefaction The process and process are conducted in the presence of a catalyst, which is part of the packing.

Besides:

- additional hydrogen is introduced into the zone of synthesis and hydrogenation of hydrocarbons;

- the nozzle further comprises chemically unbound carbon;

- the nozzle is made of fly ash containing chemically unbound carbon.

Each method cited above from the prior art can be implemented on a corresponding device.

The closest in terms of the essential features of the claimed device — a reactor for processing combustible carbon and hydrocarbon-containing wastes — is a batch or continuous-cycle device for the environmentally friendly disposal of oil waste or sludge and other wastes [Description of the invention to the RF patent N ° 2116570], which includes a sealed working chamber equipped with appropriate instrumentation with located p working areas: unloading solid processing residues with an unloading window, supplying air and water vapor, heating air and water vapor, burning, coking, pyrolysis, heating waste, selection of combined-cycle products with at least one waste collection and loading channel with a gateway, moreover, each zone is equipped with temperature sensors, and the air supply and selection of combined-cycle products are equipped with pressure sensors.

This device has the same disadvantages as the method implemented on it.

The problem solved by the second invention of the group and the technical result achieved are to create an economical reactor that implements an environmentally friendly high-performance method of processing ki of combustible carbon and / or hydrocarbon-containing products according to the first invention, which provides a reduction in the energy capacity of the process, expansion of technological capabilities in the process of high-temperature waste treatment, increase the yield of products ready for further use and improve their quality.

To solve the problem and achieve the claimed technical result, the reactor for processing combustible carbon and / or hydrocarbon-containing products includes a sealed working chamber with working zones located in the technological sequence: unloading solid processing residues with an unloading window, air and water vapor through the corresponding channels, heating of air and water vapor, combustion, coking and pyrolysis, heating of processed products, selection of a gas-vapor mixture with at least one channel ohm of selection, and a loading zone of processed products with a gateway, with each zone equipped with at least one temperature sensor, and the heating zones of air and water vapor, and selection of the gas-vapor mixture are equipped with pressure sensors, while the working chamber contains a zone equipped with additional temperature sensors synthesis and hydrogenation of hydrocarbons located directly behind the coking and pyrolysis zone.

Besides:

- the zone of synthesis and hydrogenation of hydrocarbons is configured to maintain a working temperature of 250-400 ⁰ C;

- the zone of synthesis and hydrogenation of hydrocarbons is equipped with at least two channels of additional hydrogen supply located at different levels.

The invention is illustrated by drawings, where:

- in FIG. 1 shows the design of a reactor for the processing of combustible carbon and / or hydrocarbon-containing waste - a general view;

- in FIG. 2 shows a distribution diagram of characteristic work areas in the reactor.

A method of processing combustible carbon and / or hydrocarbon-containing products is implemented on the appropriate equipment — in a reactor, which includes a sealed heat-insulated working chamber 1 with working zones located in the technological sequence: unloading solid processing residues — 2 with a discharge window 3; air supply and water vapor - 4 through channels 5; heating air and water vapor - 6; burning - 7; coking and pyrolysis - 8; heating of processed products - 9; selection of the gas-vapor mixture - 10 s, at least one channel 11 of its selection; and a zone 12 for loading processed products with a gateway (not shown conventionally), each zone being equipped with at least one temperature sensor 13 of a corresponding design, and a zone for heating air and water vapor — 6, and a selection of gas-vapor mixture — 10 (intersects with the zone 12 download processing products) - equipped with pressure sensors 14, while the working chamber 1 contains equipped with temperature sensors 15 zone 16 synthesis and hydrogenation of hydrocarbons located directly behind zone 8 of coking and pyrolysis. The reactor features are that the zone 16 for the synthesis and hydrogenation of hydrocarbons is configured to maintain a working temperature of 250-400 ⁰ C, and this zone 16 is equipped with at least two additional hydrogen supply channels 17 and 18 located at different levels.

The separation of the reactor into zones, to a certain extent, is conditional, since these zones can be displaced along the reactor within certain limits, their boundaries are not always clear and, often, processes characteristic of each of them occur at these boundaries. Nevertheless, when designing technological processes and carrying out calculations, it is more convenient to consider these zones as independent. Thus, the described reactor implements a method for the high-temperature processing of carbon and / or hydrocarbon-containing products in the presence of a nozzle with the supply of oxygen-containing a burning agent and water vapor, burning, coking and pyrolysis of their combustible components, the formation of a gas-vapor mixture and solid residues, their cooling, removal and removal from the working space of the reactor through channels 11, while synthesis zone 16 is formed directly behind coking and pyrolysis zone 8 and hydrogenation of hydrocarbons with a temperature of 250-400 ⁰ C, a temperature of 900-1300 ⁰ C is maintained in the combustion zone 7, chemically unbound carbon is emitted in the coking and pyrolysis zone 8, which is treated with steam in the combustion zone 7 with the formation of free hydrogen supplied to the zone of synthesis and hydrogenation of hydrocarbons - 16, sequentially carrying out their synthesis (conditional element 19 of zone 16) and hydrogenation (conditional element 20 of zone 16), while in the working space of the reactor form a vacuum and the process is carried out in the presence of a catalyst, which is part of the nozzle. The method features are that additional hydrogen is introduced into zone 16 of the synthesis and hydrogenation of hydrocarbons, while the nozzle additionally contains chemically unbound carbon, for example, it is made of fly ash containing some amount necessary for use in the technological process.

We analyze the materiality of the features of inventions.

When implementing a method for processing combustible carbon- and / or hydrocarbon-containing products in an appropriate reactor in a zone-separated reactor, an additional zone 16 was formed - the synthesis and hydrogenation of hydrocarbons with a temperature of 250-400 ⁰ C. The processes of synthesis and hydrogenation of hydrocarbons themselves were studied quite well and repeatedly realized in practice, in particular, the synthesis process - better known under the name "Fischer-Tropsha synthesis" [Pechuro H. S, Kapkin V.D. and Pesin O.Yu. Chemistry and technology of synthetic liquid fuel and gas. - M .; Chemistry, 1986, p. 265-307.].

The macrokinetics of the processes of synthesis and hydrogenation of hydrocarbons are It is very complicated, since the course of synthesis and hydrogenation reactions is influenced by a large number of factors, such as, for example, pressure, temperature, composition of the initial gas (in pyrolysis products), contact time, conditions for transporting substances, amount of heat transferred, and others. These processes are present in almost all methods of waste processing, however, in these cases they are chaotic and cannot be controlled, since the synthesis and hydrogenation zone in the volumes of known reactors is clearly not allocated and is not considered as an independent zone. In the claimed method for processing combustible carbon and / or hydrocarbon-containing products, an independent zone 16 for the synthesis and hydrogenation of hydrocarbons is formed. This allowed us to raise the depth of the processing of raw materials.

The ability to maintain a temperature below 1300 ⁰ C in combustion zone 7 eliminates the formation of nitrogen oxides, while the lower temperature limit of 85O ⁰ C ensures guaranteed combustion of the processed products. A lower combustion temperature makes the process of hydrogen formation in the combustion zone 7 unstable or even impossible as a result of the reaction of the interaction of carbon with water.

In the course of synthesis and hydrogenation processes, the presence of a catalyst in the reactor volume is necessary. The most favorable case for the use of a variety of chemical processes is the use of the catalyst when it is part of the packing. Among the existing products of processing of many industries there are those where the base, neutral for the claimed process, and the presence of inclusions of the necessary metals on its surface are organically combined. Such active nozzles may include waste from the concentration of iron ore deposits, solid waste from thermal stations operating on solid fuel, and other similar products containing metallic inclusions that can act as catalysts. Zone 8 of coking and pyrolysis is certainly not divided into conditional zones — the coking zone and the pyrolysis zone — for the reason that, depending on the processed raw materials, their size and, accordingly, the ratio can vary within very wide limits, for example, for the case of processing solid household the waste pyrolysis zone will dominate the coking zone, and in the case of the processing of automobile tires - vice versa.

The evolution of chemically unbound carbon in zone 8 of coking and pyrolysis and treating it with water vapor in the combustion zone made it possible to obtain free hydrogen, which was sequentially supplied to the synthesis and hydrogenation zone (20) of vapor-gas products, also sequentially carrying out the synthesis and hydrogenation of hydrocarbons. Depending on the processed raw materials, the amount of hydrogen thus obtained may not be enough for the synthesis and hydrogenation reactions to occur, in this case, it is possible to introduce additional hydrogen into the corresponding zone of the reactor. Hydrogen is introduced in at least two levels spaced apart along the height of the reactor. This is due to the fact that hydrogen may be needed both at the stage of hydrocarbon synthesis and at the stage of their hydrogenation.

The decarburized residue of the processed products and the decarburized nozzle are removed from the reactor and can be used for a special purpose, for example, for the manufacture of building mixtures, etc.

An industrial reactor designed for the continuous processing of a variety of combustible carbon and hydrocarbon-containing products has a significant advantage over its conventionally called “laboratory” samples of small sizes - in it, due to the large surface area of the zones, it becomes impossible to clog the reactor’s internal section with various plastic ones ( resinous) substances of pyrolysis products - they simply do not have time to merge into a single volume. In this way, a situation of unhindered passage of reactor gases over the entire height of the reactor becomes possible.

In this way, the organized process of processing raw materials allowed the formation of a pressure of the order of 500-5000 Pa (50-500 mm water column) inside the reactor, which eliminates the ingress of decomposition and synthesis products into the environment. Thus, the claimed process can be considered environmentally friendly.

A method for processing combustible carbon and hydrocarbon-containing products can be implemented in a reactor, the working chamber of which, unlike typical reactors (see the prior art), contains a zone 16 for the synthesis and hydrogenation of hydrocarbons located directly behind zone 8 of pyrolysis and coking. The location of the indicated zone 16 is marked on the reactor with the corresponding conclusions of the temperature sensors 15. In zone 8, complete or partial coking of the processed products

To produce hydrogen by the reaction CO + H ₂ O = CO ₂ + H ₂ and / or C + 2H ₂ O = CO ₂ + 2H _2, air and water vapor are introduced into zone 4 through channels 5. It is advisable to separate the flow of air and water vapor into the reactor, for example, by supplying air through special channels 21, and steam through channels 22. In this case, there is no condensation of the air-vapor mixture in the pipeline on the way to the reactor, respectively, it does not require the cost of its repeated evaporation. Thus, air and water vapor, continuing to heat up on solid processing residues and cooling them, rise up into combustion zone 7 to interact with carbon and its oxide. Hydrogen released as a result of the reaction rises further up to zone 16 and is involved in the synthesis and hydrogenation of hydrocarbons. If the available hydrogen is not enough, then it must be introduced from the outside through the corresponding channels 17, 18 in the refractory walls 23 of the reactor. If hydrogen turned out to be excessive, then it is removed from the internal volume of the reactor along with other processed products. Feature of such a regime It is that at the outlet of the reactor there is no free (unbound) oxygen, which in combination with hydrogen could form an explosive mixture.

A situation is possible where, to obtain additional hydrogen, it is possible to use a nozzle containing chemically unbound carbon (and metals - catalysts) in advance, which can be used in the combustion zone 7 for the reaction of interaction with water to occur. It is possible to make such a nozzle from fly ash, for example, TPP, by decarburizing it in the reactor for the purpose of further independent processing.

As a result, in the exit zone 10, the gas-vapor mixture contains pyrolysis and synthesis products such as isoprene, dipentene, C ₄ -C ₈ hydrocarbons that make up the gasoline fraction, C ₉ -Ci ₂ hydrocarbons that make up the kerosene fraction and light gas oil fraction, as well as entrained gas in the form of drops, high-boiling compounds and other substances, the composition of which depends on the feedstock and the catalysts used. The listed products are removed from the reactor through the appropriate selection channels 11 for direct use or subsequent processing.

A method for processing combustible carbon- and hydrocarbon-containing products will first be considered for the case of their loading into a continuous reactor and their further movement from top to bottom with the complete decomposition of high molecular weight organic compounds and the conversion of carbon-containing inorganic to carbon monoxide and hydrogen with the inert components unchanged and further sequential synthesis of hydrocarbons from the obtained carbon monoxide and hydrogen and their further hydrogenation with the acquisition of specified chemical voystv. Such a presentation of information on inventions will most fully illustrate the operation of the reactor.

Processing products with a nozzle containing a catalyst (iron, iron oxides, etc.) through the gateway enter the zone 12 of the reactor load with temperature of 20-50 ° C and sequentially pass zone 9 of the heating of the processed products (which includes the zone 10 of the selection of the gas mixture) with a temperature of 150-250 ⁰ C, zone 16 of the synthesis and hydrogenation of hydrocarbons with a temperature of 250-400 ⁰ C, zone 8 of pyrolysis coking with a temperature of 350-850 ⁰ C, combustion zone 7 with a temperature of 850 -1300 ⁰ C, heating zone 6 involved in the process of processing air and steam to a temperature of 800-1000 ⁰ C ₅ zone 4 of air and steam with a temperature of 20-140 ⁰ C, and zone 2 of the discharge of solid processing residues with a temperature of 20-60 ⁰ C.

In zone 8 of pyrolysis and coking, the processed products are decomposed into constituent unstructured hydrocarbon fragments, which rise up and give up heat to the newly incoming processed products and fall into zone 16 of the synthesis and hydrogenation of hydrocarbons, forming mainly saturated (saturated hydrocarbons). If necessary, additional hydrogen is supplied to the synthesis and hydrogenation zone 16 from the outside. After all the planned processes have passed, the resulting vapor-gas mixture containing droplets of high-boiling liquid is cooled, giving heat to the loaded solid waste and, with a temperature of 190-240 ⁰ C, is removed outside the reactor for further processing.

We will consider the specific methods for processing combustible carbon- and hydrocarbon-containing products, including various wastes, depending on their classification, using the following examples.

Example 1

Worn car tires are subject to recycling.

A mixture consisting of 1600 kg / h of cut pieces of tires made of isoprene rubber with linear dimensions of 20-100 mm and 1600 kg / h of nozzles with linear dimensions of 25-100 mm containing a catalyst in the form of iron and iron oxides is fed into a continuous reactor.

The quantitative composition of the components included in tires made of isoprene rubber, the following, kg / h: isoprene rubber - 776; metal cord - (stainless steel type Xl 8Hl OT) - 310; chemically unbound carbon - 310; oxygen adsorbed - 30; hydrogen adsorbed - 10; softeners (vegetable oils, wax, higher acids) - 128; sulfur - 30; metal oxides - 6.

The quantitative composition of the components included in the nozzle is as follows, kg / h: chamotte -1550; catalyst (iron, magnetite, hematite) - 50.

As a gasification agent, air is supplied to the corresponding zone of the reactor in an amount of 2300 nm / h or 2967 kg / h, including nitrogen - 2255 kg / h and oxygen - 712 kg / h.

The temperature in the combustion zone does not exceed 1100 ⁰ C.

To produce hydrogen by the reaction C + 2H ₂ O → Cθ ₂ + 2H ₂ t and / or CO + + H ₂ θ → Cθ ₂ + H ₂ T, water vapor is supplied together with air in an amount of 180 kg / h.

Additionally, in the zone 16 of the synthesis and hydrogenation of hydrocarbons serves hydrogen in an amount of about 60 kg / h.

The gas-vapor products leaving the reactor with a temperature of 24O ⁰ C and the hydrocarbons contained in them are separated into liquid and gas components, which is carried out sequentially in a cyclone and condensers cooled by water with an initial temperature of about 18 ⁰ C.

After the condensation system, the gas component, the amount of which will be 3598 kg / h, will have the following composition,% of the mass:

N ₂ - 62.67; CO ₂ 25.89; H ₂ O - 5.92; СО - 1.68;

H ₂ S + SO ₂ - 1.67; H ₂ - 0.06; CH ₄ - 2.11 After the condensation system, the liquid component was analyzed on a Kristallux-4000M chromatograph with two flame-ionization detectors and a 30 m long quartz capillary column with an inner diameter of 0.53 mm. The sample volume was 1 mm, under the following conditions:

- detector temperature - 300 ⁰ C;

- evaporator temperature - 300 ⁰ C;

- column temperature: initial - 6O ⁰ C, final - 15O ⁰ C;

- capillary column pressure - 1 atm;

- sweep speed - 10 ° C / min;

- carrier gas flow rate (nitrogen): 30 smVmin, 60 cm ³ / min and 29 smVmin;

- air consumption - 500 cm ³ / min;

- hydrogen consumption - 60 cmVmin.

The results of chromatographic analysis are summarized in the Table. Thus, the liquid component, the amount of which was 870 kg / h, has the following composition,% of the mass:

- fraction Cs - C ₁ O - 30;

- fraction Cu - Ci _b - 40;

- fraction Ci ₇ and above - 30.

The output stream of solid residues from the discharge zone of the reactor amounted to 1936 kg / h in quantity and its structure includes: nozzle - 1600; metal cord - 320; carbon-containing (soot) - 10; metal oxides - 6.

Example 2 (comparative).

As in the previous example, a mixture consisting of 1,600 kg / h of cut pieces of tires made of isoprene rubber with linear dimensions of 20-100 mm and 1,600 kg / h of nozzle is fed into a continuous reactor. The difference 19 is in the qualitative composition of the nozzle - its only component is chamotte, which has linear dimensions of 25-100 mm, while no catalyst in the packing.

As a gasification agent, air is also fed into the reactor in an amount of 2300 nmVh.

The temperature in the combustion zone is not higher than 1100 ⁰ C.

The gas-vapor products leaving the reactor with a temperature of 200 ^° C and the hydrocarbons contained in it are separated into liquid and gas components.

After the condensation system, the gas component, the amount of which is 3889 kg / h, has the following composition,% of the mass:

N ₂ - 58.00; CO ₂ - 9.30; H ₂ O - 2.60; СО - 27.50;

H ₂ S + SO ₂ - 1.50; H ₂ - I ₅ IO

After the condensation system, the liquid component, the amount of which is 320 kg / h, has the following composition by chromatographic analysis,% of the mass:

- fraction C ₅ - C ₉ - 40;

- Xu fraction - Ci ₆ - 30;

- fraction Ci ₇ and above - 30

The output stream of solid residues from the discharge zone of the reactor is similar in quantity to Example 1.

Example 3

The feedstock for processing in the reactor is household waste with a density of 200-300 kg / m ³ , including the following components,% of the mass: paper - 47.0; food waste - 29.0; textile - 5.0; glass and stones - 4.9; metal - 4.5; plastic - 2.0; leather and rubber - 1.8; wood - 1.0; bones - 0.5; screening less than 15 mm - 4.5; other - 0.4.

The composition of the working mass,% of the mass: water - 39.65; ash content - 18.43; carbon 21.36; oxygen - 17.52; sulfur - 0.13; hydrogen 2.80; nitrogen - 0.13

After pressing the working mass, briquettes with dimensions of 150x150x150 mm were obtained, of the following composition,% of the mass: water - 20.00; ash content - 24.40; carbon 28.32; oxygen 23.23; sulfur - 0.17; hydrogen - 3.71; nitrogen - 0.17

1600 kg / h of briquettes and 1600 kg / h of nozzles with linear dimensions of 25-100 mm containing a catalyst in the form of iron and iron oxides are loaded into a continuous reactor.

A gasifying agent is supplied to the air supply zone, in which air is used in an amount of 2064 kg / h (1600 nm ³ / h) and water vapor in an amount of 200 kg / h, and 30 kg of hydrogen in the synthesis and hydrogenation of hydrocarbons /hour.

The combustion process is carried out at a temperature of about 1000 ⁰ C.

The gas-vapor products leaving the reactor with a temperature of 190 ^° C and the hydrocarbons contained in them are separated into liquid and gas components, which is carried out sequentially in a cyclone and condensers cooled by water with an initial temperature of about 18 ° C.

After the condensation system, the gas component, the amount of which is 2694.5 kg / h, has the following composition,% of the mass:

N ₂ - 60.50; CO ₂ 37.85; H ₂ O - 1.50; СО - 0.05;

H ₂ S - 0.05; H ₂ - 0.05

After the condensation system, an organic liquid component in the amount of 320 kg / h was obtained, containing a mixture of hydrocarbons C ₆ - Syu (including octane, benzene, xylene isomers).

The output stream of solid residues from the discharge zone of the reactor amounted to 2020 kg / h in quantity and its structure includes, kg / h: nozzle - 1600; mineral raw materials - 320; metal - 90; sulfur-containing compounds - 10. Example 4

Brown coal of the Moscow Region basin of the following composition is used as the initial raw material,% of the mass: water - 32.00; ash content - 21.00; carbon 28.70; oxygen - 9.00; total sulfur - 2.70; hydrogen - 2.20; nitrogen - 0.60

2000 kg / h of brown coal briquettes with linear dimensions of 150-100 mm and 2000 kg / h of packing with linear sizes of 75-100 mm containing a catalyst in the form of iron and iron oxides are loaded into a continuous reactor.

Gasification agent (air) is supplied to the reactor’s air supply zone in the amount of 3870 kg / h or 3000 nmVh and water vapor in the amount of 300 kg / h, and hydrogen in the amount of 30 kg / h to the zone of hydrocarbon synthesis and hydrogenation. The combustion process is carried out at a temperature not exceeding 1100 ⁰ C.

After the condensation system, the gas component, the amount of which is 4602 kg / h, has the following composition,% of the mass:

N ₂ - 64.8; CO ₂ 31.88; H ₂ O - 2.17; CO 0.2;

H ₂ S + SO ₂ - 0.75; H ₂ - 0.2

After the condensation system, the organic liquid component was obtained in an amount of 293 kg / h, containing a mixture of C ₆ -Ci _S hydrocarbons (β including octane, benzene, xylene isomers, decane, n-hexadecane).

The output stream of solid residues from the discharge zone of the reactor amounted to 2665 kg / h in quantity and its structure includes, kg / h:

- nozzle - 2000; - powder mineral raw materials - 420;

- sulfur-containing compounds - 25.

It should be noted that the nozzle mentioned in Examples 1, 3 and 4 can be made of fly ash, for example, the Cherepetskaya state district power station of the Tula region or other power plants. In addition to the neutral base, fly ash contains a sufficient amount of iron oxides. It also contains alumina (Al ₂ O ₃ ), which is a promoter of catalysts based on iron oxides.

Other combustible carbon and / or hydrocarbon containing products are processed similarly to the examples given.

As a result of the solution of the set tasks, an environmentally friendly high-performance method for high-temperature processing of combustible carbon and / or hydrocarbon-containing products and a reactor for its implementation were created, the energy capacity of the process decreased, technological capabilities expanded in terms of controlling the chemical composition and increasing the yield of products ready for further use, and their quality also improved.

CHROMATOGRAPHIC ANALYSIS RESULTS

Table

Claims

CLAIM

1. A method of processing combustible carbon and / or hydrocarbon-containing products, including their high-temperature layer-by-layer processing in the reactor in the presence of a nozzle when supplying an oxygen-containing agent and water vapor, burning, coking and pyrolysis of combustible components, the formation of a gas-vapor mixture and solid residues, their cooling , retraction and removal from the reactor working space, characterized in that immediately after the pyrolysis and coking zone is formed, and hydrogenation of hydrocarbon synthesis zone at a temperature of 250-400 ⁰ C, in ZA not support combustion temperature of 850-1300 ⁰ C, and pyrolysis in the carbonization zone is isolated chemically uncombined carbon in the combustion zone and it is treated with steam to form free hydrogen which is fed to the synthesis zone and the hydrogenation successively carrying out the synthesis and hydrogenation of hydrocarbons, the inside the working space of the reactor form a vacuum and the process is conducted in the presence of a catalyst, which is part of the nozzle.

2. The method according to p. 1, characterized in that additional hydrogen is introduced into the zone of synthesis and hydrogenation of hydrocarbons.

3. The method according to claim 1, characterized in that the nozzle further comprises chemically unbound carbon.

4. The method according to claim 1, characterized in that the nozzle is made of fly ash containing chemically unbound carbon.

5. A reactor for the processing of combustible carbon and / or hydrocarbon-containing products, including a sealed working chamber with working areas arranged in a technological sequence: unloading solid processing residues with an unloading window, supplying air and water vapor through appropriate channels, heating air and water vapor , combustion, coking and pyrolysis, heating of processed products, a gas-vapor mixture with at least one sampling channel and a loading zone for processed products with a gateway, each zone being equipped with at least one temperature sensor, and air and water vapor heating zones and a gas-vapor mixture are equipped with pressure sensors, at the same time, the working chamber contains a zone for synthesis and hydrogenation of hydrocarbons equipped with additional temperature sensors located directly behind the coking and pyrolysis zone.

6. The reactor according to claim 5, characterized in that the zone of synthesis and hydrogenation of hydrocarbons is configured to maintain a working temperature of 250-400 ⁰ C.

7. The reactor according to claim 5, characterized in that the zone for the synthesis and hydrogenation of hydrocarbons is equipped with at least two channels for additional supply of hydrogen located at different levels.