WO2011068437A1

WO2011068437A1 - Method for the pyrolysis of a raw material containing organic compounds

Info

Publication number: WO2011068437A1
Application number: PCT/RU2010/000685
Authority: WO
Inventors: Алексей Владимирович КУЛИКОВ; Андрей Андреевич ВОРОБЬЕВ; Игорь Леонидович ЗОБИН
Original assignee: Kulikov Alexey Vladimirovich; Vorobyev Andrey Andreevich; Zobin Igor Leonidovich
Priority date: 2009-12-04
Filing date: 2010-11-19
Publication date: 2011-06-09
Also published as: RU2009145975A

Abstract

The invention relates to the processing of raw materials containing organic compounds. The method for the pyrolysis of a raw material containing organic compounds comprises preparing and feeding a raw material into a reactor through a sluice-type loading chamber in which said material is preliminarily subjected to vacuum and separated from the thermal processing area and from the environment, carrying out the pyrolysis by indirect heating at a temperature of 450-500° C using a heat carrier fed into the reactor while removing of the solid phase thus formed by separating the liquid and gaseous phases containing carbon and hydrocarbons, and discharging the solid substances resulting from the pyrolysis through a sluice-type unloading chamber provided in the lower portion of the reactor. The pyrolysis method comprises using at least one reactor comprising dual walls, a preliminarily-heated heat carrier being fed into the gap between them. The heat carrier is heated using a heating boiler that is isolated from the reactor. The technical result is the uniformity of the heating of the reactor walls and thus an increase in the productivity and stability of the pyrolysis process.

Description

The method of pyrolysis of organo-containing raw materials

Technical field

The invention relates to the field of processing of organo-containing raw materials, in particular coal, shale, peat, wood, crop products, animal waste, industrial, municipal waste, with the aim of extracting various types of liquid and solid fuels and is intended primarily for the processing of worn, damaged or rejected during production car tires, waste rubber products, etc.

State of the art

Organ-containing raw materials that have spent their resources make up a significant share of human products polluting the environment. The most acute problem is the disposal of worn tires, especially large ones, only a small part of which are recycled, as a result of which a huge number of them accumulate in landfills.

The simplest example of the recycling of rubber products is their incineration, which is widely used especially in relation to worn tires. However, such disposal will significantly pollute the environment.

Full utilization of used tires and other rubber products is necessary, on the one hand, to reduce and eliminate storage costs accumulated stocks of these products resulting from the life of humanity. These reserves, due to the particular chemical structure, pose a serious danger to the ecological balance in the environment. On the other hand, the materials that make up these products are valuable raw materials for the production of various substances, structures, products, and their secondary use would ensure the economical and rational use of a number of natural resources: cellulose, rubbers (rubber), ores of ferrous metals, energy resources. Since these materials are contained in recyclable materials as separate mechanically interconnected components, the most important requirement is the use of technologies that would ensure only the destruction of these mechanical bonds without affecting chemical properties.

One of the processing methods is the high-temperature decomposition of rubber products without air access - pyrolysis, which allows the production of soot from tire rubber, as well as a number of liquid and gaseous organic substances that can be used in the chemical industry and energy. High-temperature decomposition of rubber products can be carried out by direct pyrolysis on the processed raw materials, when they are burned in the reactor, directly exposed to the flame, or by indirect pyrolysis, when the processed raw materials are heated through the wall of the reactor in which they are processed. An example of direct pyrolysis is the method of processing organic raw materials into fuel components described in RF patent Zh. 182684. According to the description, pre-briquetted and dried to a moisture content of 15% raw material is fed to a receiving hopper using a loading device, from which it then enters into the pyrolysis reactor in portions through the airlock feed batcher. The pyrolysis reactor is equipped with an annular combustion chamber located in its lower part, the inlet of which is equipped with a burner with a device for ionization and arc ignition of the introduced fuel components, and the outlets are made radial and placed around the perimeter of the pyrolysis reactor working zone. The flue gas enters the bottom pyrolysis reactor through radial outlets, washes the feed coming from above through the airlock feed batcher, ensuring its uniform heating to the sublimation temperature of volatile components. The return gas is supplied in an increased concentration with respect to air in order to ensure complete combustion of the oxygen contained in the air. The flue gas obtained as a result of combustion, which does not contain oxygen, consists mainly of nitrogen, which is not involved in combustion but is the main heat carrier, residues of pyrolysis gas, carbon dioxide, and other combustion products.

The disadvantage of this method is that, firstly, it does not ensure the tightness of the reactor during operation, which can lead to the ingress of gaseous products of pyrolysis into the environment or to the fact that atmospheric oxygen with air can get into the working area, which can cause ignition of gaseous pyrolysis products. Secondly, due to the introduction of combustion products into the reaction zone in the gas phase of the pyrolysis products, the concentration of carbon dioxide will increase, which can lead to the attenuation of the flame in the burner and, as a result, the reaction will die out. In addition, the use of a packed column leads to the fact that the latter, due to the grinding of the nozzle rings, quickly clogs and requires frequent flushing, which complicates the operation of the installation.

There is also a known method for the pyrolysis of hydrocarbon feedstocks described in RF patent N ° 20781 1 1. A device for implementing this method comprises upper and lower parts connected by a conical connector to the sealing rings. In the cavity of the upper part of the furnace, a pyrolysis chamber is vertically mounted. The furnace is equipped with an annular tray with a pipe for the removal of liquid pyrolysis products. The method is carried out cyclically: the upper part of the furnace is lifted by a lifting device, a tire package is loaded into the pyrolysis chamber, then the upper part is returned to its place and detachable connections are fixed. Next, hot gases are supplied from the combustion device between the walls of the furnace and the pyrolysis chamber, and the tires are decomposed according to a predetermined mode, followed by unloading the solid residue from the pyrolysis chamber in the reverse order.

The disadvantage of this method is the cyclical operation and high energy losses associated with the need for periodic heating of the furnace to operating temperature after the next loading of tires and subsequent cooling during unloading of the solid phase of the degradation products. There is also a method of thermal processing of worn tires, described in the patent of the Russian Federation .L39187. Worn tires or used rubber products through a sealed feeder are loaded into the reaction chamber, which is a metal casing lined with refractory material from the inside. Reducing gas from the generator is supplied to the lower part of the chamber through a system of holes at a temperature of 550-800 ° C. Gaseous products of the decomposition reaction of tires containing vapors of hydrocarbon compounds from C ₂ to C ₅ and hydrocarbon gases from C ₅ to C _{\ 2} in a mixture with reducing gas with a temperature of 240-350 ° C are removed from the upper part of the reactor and fed to combustion devices, or for the separation of liquid and gaseous fractions. Solid products containing carbon black and mineral components of rubber compounds (zinc dioxide, chalk, ground sulfur, etc.) are additionally treated with superheated water vapor after pyrolysis is completed and removed through a sealed feeder to a cooled hopper, where the solid residue is separated into carbon black and metal.

From German patent application N ° 2404800, a method for pyrolysis of whole tires is known, which is carried out by heat treatment by indirect heating and significant gas impermeability. Gaseous products released during heating are carried out and rectified in a co-operating continuous process and various solids are removed. Before entering into the heat treatment zone, each tire passes through an oil bath and into during further advancement to the upper part of the heat treatment zone, it is drained, dried and heated.

The disadvantages of this method is that part of the oil in the bath is captured by each subsequent tire, is not completely drained (drains) and enters the heat treatment zone with oil residues, which leads to additional energy costs for oil pyrolysis. In fact, there is no heating of the tires, since heat is used to heat the oil film that covers the tires. There is no guarantee that as a result of the tires passing through the oil bath there will be no additional oxygen flow, which is absolutely undesirable, since it interferes with the flow of the process. The disadvantage of this invention is the high energy costs due to the use of an external source of hydrocarbons for reducing gas and steam.

Closest to the technical nature of the claimed invention, i.e. the prototype is a method of pyrolysis of a solid car tire described in the patent of the Russian Federation N ° 2358002. According to the known invention, the method of pyrolysis of whole tires is carried out by heat treatment by indirect heating with significant gas impermeability, and the released gaseous hydrocarbons are transferred to a joint condensate separation unit connected to the equipment, where they are rectified in a continuous joint process. Separated solid components are removed. Each tire is exposed pre-heating before entering the heat treatment area, and before pre-heating, the space occupied by the next tire is subjected to vacuum treatment, filled with an inert gas and separated from the heat treatment area and the environment. The heat treatment area is a cylindrical reactor, which is heated by the combustion system by means of tangentially positioned burners of the combustion chamber. To load the tire, the cap of the cylindrical reactor is lifted using an externally mounted hoist connected to the cap, and propelled forward using two pneumatic lifting cylinders. The tire is simultaneously driven to the bore of the cylindrical reactor. The technological process is carried out with the continuous supply of solid tires at a given speed and with the constant release of gaseous hydrocarbons, after which the solid components - carbon and steel wire - are transported through the lower hole of the cylindrical reactor into the water tank and unloaded for further processing.

The disadvantage of this method is that it is provided with complex hardware design of the process, caused by the presence of a complex horizontal feed conveyor system in the upper level of the reactor and located at the bottom of the exhaust conveyor system with pipelines, a complex design of the receiving chamber. Raising the cap of the cylindrical reactor to load the processed tire using an externally mounted elevator, connected to the cap, and moving forward with two lifting pneumatic cylinders also complicates the implementation of the method of processing raw materials, increases energy costs, reduces its productivity. The disadvantage of this method is also the high energy loss associated with the need for periodic heating of the furnace to operating temperature after the next loading of tires and subsequent cooling when unloading the solid phase of the degradation products. In addition, the presence of a combustion system made in the form of a combustion chamber, which covers the reactor along its height, and burners symmetrically surrounding the reactor in the lower part of the combustion chamber, do not allow uniform heating of the walls of the reactor, which, in turn, reduces the performance of the pyrolysis process , increases the risk of thermal process. Corrosion effect (metal rusting) of reactor walls may occur if they are made of ferrous metal. All this taken together reduces the efficiency of the pyrolysis of organo-containing raw materials.

Disclosure of invention

The present invention is aimed at eliminating the above disadvantages, namely, to increase the efficiency of the pyrolysis process of organo-containing raw materials, in particular coal, shale, peat, wood, crop products, animal waste, industrial, urban waste, worn, damaged or rejected in the manufacture of tires, waste production rubber-containing products by increasing processing productivity, process safety and simplifying it.

To solve the problem in a method for the pyrolysis of organo-containing raw materials by heat treatment, including the preparation and supply of raw materials to the reactor through a sluice loading chamber, in which it is previously subjected to vacuum and separated from the heat treatment area and the environment, the subsequent pyrolysis of the processed raw materials by indirect heating at temperature 450-500 ° C supplied to the reactor with a coolant with separation of the resulting solid phase, separation of liquid and vapor-gas phases, containing carbon and hydrocarbons, and the evacuation of solid substances of pyrolysis through the airlock discharge chamber located in the lower part of the reactor, according to the claimed invention, at least one reactor is used for pyrolysis, which is performed with double walls, into the space between which continuous pyrolysis is carried out the supply of preheated coolant, while the coolant is heated by means of a heating boiler, placed in isolation from the reactor.

Other differences of the proposed method is that the processed organo-containing raw materials before being fed to the reactor are either preliminarily crushed or fed to the reactor as a whole product.

Additional differences of the present invention from the prototype are that high-temperature organic materials can be fed into the space between the walls of the reactor heat carriers (BOT) or a high-temperature heat carrier in the form of a eutectic alloy.

The following differences of the proposed method of pyrolysis are that the working zone of the reactor is heated by an additional element installed inside it, heated by a heat carrier.

In addition, pyrolysis can be carried out simultaneously in several reactors forming a battery pack.

Comparative analysis with the prototype shows that the claimed invention is characterized by the presence of new actions, a different order of execution in time, as well as the conditions for the implementation of actions, in particular, equipment that is used in their implementation.

A patent search showed that at present there is no known method of pyrolysis of organo-containing raw materials by heat treatment, which has the same set of essential features as the proposed one. Thus, the claimed method meets the criteria of the invention of "novelty."

When studying the level of technology known in the art, features that distinguish the claimed invention from the prototype were not identified and therefore they provide the claimed technical solution with the criterion of "inventive step".

Use for carrying out pyrolysis of organo-containing raw materials of a reactor made with double walls, into the space between which during pyrolysis they continuously supply a preheated coolant, heating the coolant by means of a heating boiler placed in isolation from the reactor will allow uniform heating of the reactor, thereby ensuring the uniformity of the products obtained in chemical composition and increasing the productivity of the process. The absence of burners for pyrolysis will increase the safety of the thermal process of decomposition of raw materials. In addition, indirect heating of the tires through the walls of the reactor without the use of burners will greatly simplify the maintenance of a constant temperature in the reactor, necessary for the process, increase the heating efficiency, and automate the heat treatment process. Pyrolysis in the absence of oxygen and steam in the coolant prevents the corrosion of the metal of the walls of the reactor. The supply into the space between the walls of the reactor of either high-temperature organic coolant (BOT) or a high-temperature coolant in the form of a eutectic alloy is carried out depending on the specific temperature regime at which the pyrolysis process occurs. This extends the technological capabilities of the proposed method. The feed into the reactor of organo-containing raw materials in the form of a whole product or previously subjected to crushing are process variants and also expand its technological capabilities. Heating the working zone of the reactor with an additional element installed inside it, heated by a coolant, will increase heat transfer during pyrolysis, thereby accelerating its flow. The use of several reactors forming a battery pack for pyrolysis will allow also increase the productivity of the process of heat treatment of rubber products. Thus, all of the above combined characteristics that are distinct from the prototype will allow, ultimately, to increase the efficiency of the process of thermal decomposition without access of air of organo-containing raw materials, including worn-out car tires.

The above proves that the combination of distinctive features from the prototype of the features makes it possible to use the claimed technical solution for the processing of organo-containing raw materials, in particular worn, damaged or rejected in the manufacture of automobile tires, waste products of rubber-containing products to obtain material suitable for reuse, for example in the form of fuel, those. it meets the criteria of the invention of "industrial applicability".

Brief Description of the Drawings

The present invention is illustrated by drawings, where figure 1 schematically shows an installation for implementing the method; figure 2 - reactor with a heating element installed inside.

The best embodiment of the invention

Organ-containing raw materials are loaded into the reactor 1 through the loading lock chamber 2: the utilized waste - automobile tires, other rubber waste, various hydrocarbon waste, including polymers. The lock chamber 2 allows the process of loading raw materials without access of oxygen. A specific example of the method, we consider the thermal processing of worn-out tires. According to the proposed invention, the tires 3 are fed into the airlock 2 as a whole product, or they are pre-crushed before being fed. After filling the chamber 2 with the processed raw material 3, it is closed with a shutter 4, separating it from the environment and the heat treatment zone of the reactor 1, and air is pumped out of it, i.e. vacuum, thereby ensuring the tightness of the reactor. Then the shutter 4 is opened and the tires 3 enter the working space of the reactor 1. The reactor is made in the form of a thermos and has double walls, into which the coolant is fed into the space (jacket) 5 between which. The coolant is preheated by means of a heating boiler 6, placed in isolation relative to the reactor 1, and it is continuously fed into the reactor. Depending on the specific temperature regime under which the pyrolysis process takes place (in our example, it is 450-500 ° C), high-temperature organic heat transfer fluids BOT (http://poliest.ltd.su/main/index- 1312.html;

http: //www.fptl. ha / files / oborudovani e / lekcij a_6.doc), or high-temperature coolants in the form of a eutectic alloy (http://www.fptl.ru/files/oborudovanie/lekcija_6.doc; http: //www.masla- smazki.ru /common.html?thermooil), such as sodium and potassium salts. The coolant enters from the boiler 6 through a heat-insulated pipe 7 through an opening in the jacket 5 of the reactor 1, washes the walls of its working zone 8, heating them and the processed raw materials loaded into it. The spent coolant through the heat pipe 9 is returned to the boiler 6, where it is again heated. Thus, a constant operating temperature is maintained in the reactor 1.

The heated coolant entering the reactor warms the processed tires to the decomposition temperature of the raw material (450–600 ° С), as a result of which, in the absence of air access, they decompose to form a synthesized gaseous product, liquid fuel (pyrolysis oil, heating oil) and solid fraction (pyrocarbon , metal cord). Pyrolysis liquid is used as heating oil for boiler units, subsequent distillation into fractions is possible in order to obtain various petroleum products: gasoline, kerosene, diesel fuel. Pyrocarbon is used as solid fuel, a filler for the manufacture of non-critical rubber products, dye, etc. Steel cord is used for further remelting.

The resulting solid phase — carbon black and metal cord — is collected in the lower part of the reactor 1, from where it is evacuated through the discharge lock chamber 10 located in the lower part of the reactor 1.

One of the embodiments of the claimed invention is the use for pyrolysis of several reactors 1 forming a battery unit (not shown in the drawing), which will improve the performance of the process of heat treatment of rubber products. For the thermal processing of crushed automobile tires in order to accelerate the pyrolysis process by increasing heat transfer, the working zone of the reactor 1 can be heated additionally installed inside it a tubular element 1 1 (for example, a coil), heated with a coolant.

Industrial applicability

The claimed invention allows to increase the efficiency of the pyrolysis process of organo-containing raw materials, including worn tires and other rubber products, by increasing its productivity, expanding technological capabilities, and ensuring the homogeneity of the products obtained in chemical composition. The absence of burners for pyrolysis will increase the safety of the thermal process of decomposition of raw materials. The inventive method is easy to use.

Claims

Claim

1. The method of pyrolysis of organo-containing raw materials by heat treatment, including the preparation and supply of raw materials to the reactor through the airlock loading chamber, in which it is previously subjected to vacuum and separated from the heat treatment and the environment, the subsequent pyrolysis of the processed raw materials by indirect heating at a temperature of 450- 500 ° C supplied to the reactor with a coolant with separation of the formed solid phase, separation of the liquid and vapor-gas phases containing carbon and hydrocarbons, and EVA the solidification of pyrolysis solid substances through the airlock discharge chamber located in the lower part of the reactor, characterized in that at least one reactor is used for pyrolysis, which is performed with double walls, into the space between which the preheated coolant is continuously fed, wherein the coolant is heated by means of a heating boiler placed in isolation from the reactor.

2. The method according to claim 1, characterized in that the processed organo-containing raw materials are first crushed before being fed to the reactor.

3. The method according to claim 1, characterized in that the processed organo-containing raw materials are fed into the reactor as a whole product.

4. The method according to claim 1, characterized in that high-temperature organic coolants are fed into the space between the walls of the reactor.

5. The method according to claim 1, characterized in that in the space between the walls of the reactor serves high-temperature coolant in the form of a eutectic alloy.

6. The method according to claim 1, characterized in that the working zone of the reactor is heated by an additional element installed inside it, heated by a heat carrier.

7. The method according to claim 1, characterized in that the pyrolysis is carried out simultaneously in several reactors forming a battery unit.