US20090032384A1

US20090032384A1 - Method and Device for Processing Products that Contain Hydrocarbons

Info

Publication number: US20090032384A1
Application number: US11/988,571
Authority: US
Inventors: Werner Hasenkrug
Original assignee: CARBO TEC GmbH
Current assignee: CARBO TEC GmbH
Priority date: 2005-07-11
Filing date: 2006-07-10
Publication date: 2009-02-05
Also published as: WO2007006280A2; EP1904604B1; ATE521681T1; EP1904604B8; EP1904604A2; WO2007006280A3; BRPI0613063A2; JP2009500504A; DE112006002434A5; JP2011246721A; JP4981043B2

Abstract

The invention relates to a method and a device for preparing products containing hydrocarbons by pyrolysis, especially for preparing old tires and/or comparable rubber products, and plastics and the like. According to the method: once the reactor (2) has been loaded, it is inserted into a thermal furnace (1); the reactor (2) is heated, during a first stage, to a temperature of between 80 and 120° C., which is maintained over a period of approximately 20 minutes, and nitrogen is blown into the reactor (2) during a second stage running in parallel; the humidity and oxygen contents are reduced in the reactor (2); the temperature is increased again in the reactor (2), during the subsequent process stages, to between 360 and 420° C. over a period of between 1 and 2 hours; the process temperature is briefly increased during the subsequent stage, to 480° C. and up to a maximum of 600° C., for a period of between 10 and 60 minutes; following pyrolysis, the pyrolysis gas is drawn off the reactor (2) and supplied to a cooling and relaxing module (4), while the carbon deposited in the bottom of the reactor (2) is sucked up and the metallic components are removed from the reactor (2). The inventive method is carried out by means of a device consisting of at least one reactor (2) that can be inserted into the thermal furnace (1). According to the invention, the bottom (18) of a reactor (2) has a concave shape, the cover (17) is embodied with a guiding projection (28) which engages with a cover receiving element (22) in the closed state, and reflectors (30) and edge reflectors (31) are formed on the inner side of the cover (17).

Description

The invention relates to a method and a device for processing products that contain hydrocarbons by means of pyrolyzation, particularly for processing old tires and/or comparable rubber products, as well as plastics and the like.
Pyrolytic methods and systems as well as devices for processing products that contain hydrocarbons are generally known; they can be used to make reusable materials available from trash, substances, and waste products.
For example, fluidized bed reactors are known, as are pyrolysis flow-through ovens, i.e. fluidized bed ovens, in which the pyrolysis material is pyrolyzed either in whole pieces or in comminuted form.
Fluidized bed reactors are known from DE 26 58 371 C2 and DE 35 45 954 A1, in which the starting substances are introduced into the oven from above and pyrolyzed, while the gaseous substances are drawn off toward the top and the solid substances are discharged towards the bottom.
The structure of these devices is relatively complex, and because of the use of a sand/cement clinker bed with a correspondingly radially introduced fluidized gas, it is often problematic to maintain the appropriate flow conditions in the fluidized bed, and it can easily be brought out of equilibrium by material masses that are introduced.
Pyrolysis flow-through ovens, i.e. fluidized bed ovens, in which the pyrolysis material is pyrolyzed either in whole pieces or in comminuted form, are described, for example, in DE 44 47 357 A1 and DE 29 25 202 A1.
The disadvantage of these flow-through ovens is that they possess an extremely complicated construction, are designed for a specific type of material and/or size, in each instance, and cannot easily be refitted for different types of materials.
A method and a device for pyrolyzation of waste products that contain hydrocarbons, particularly of old tires, has become known from DE 198 34 596 C1, in which the material to be pyrolyzed is introduced into a pyrolysis oven and pyrolyzed at 500° C. In this connection, the old tires to be treated are introduced into a pyrolysis oven in whole pieces, by way of an accommodation device, whereby the device is supposed to seal the oven off tightly, at the same time.
In this process, the starting material to be treated is immediately removed from the oven once the intended pyrolysis temperature has been reached, and foreign substances such as metals are removed.
Using this method of procedure, the process of pyrolysis, which is what is actually intended, is interrupted, and this has a disadvantageous effect on the pyrolysis itself, and is not justifiable from an energy point of view, since part of the waste heat remains unutilized and is not passed to further use.
Another method for the pyrolyzation of products that contain hydrocarbons became known from DE 103 09 530 A1, which is supposed to relate to an industrial process in which products that contain hydrocarbons, for example old tires, are pyrolyzed at specific temperatures, at a temperature of up to approximately 600° C., step by step, at dwell times established as a function of the starting material. It is true that in this connection, the process of pyrolysis is completed, but this method is not suitable for industrial use, since the prevailing high temperatures also have a harmful effect on other content substances.
With this background, the invention sets itself the task of developing a method for processing products that contain hydrocarbons, particularly old tires and/or comparable rubber products, by means of pyrolyzation, with which the products used can be treated on an industrial scale, and the reaction products can be passed to efficient utilization, whereby at the same time, it is a task of the invention to develop a device for implementing the method.
According to the invention, this task is accomplished with the characteristics of claims 1 and . . . . Specific embodiments and advantageous solutions are indicated in the dependent claims.
In recognition of the fact that it is not appropriate to our times to continuously waste new, non-renewable raw materials in diverse industrial processes, if technical possibilities exist for making available qualitatively equivalent secondary products for these processes, an industrial method and a device for the efficient separation of old materials that contain hydrocarbons, for example old tires, were created, according to the invention, in order to process the old products, on the one hand, and to recover the materials inherent in them, such as pyrolysis oil, carbon, and steel enclosed in the old tires, and to pass these recovered reusable materials on to re-use.
The method presented for processing products that contain hydrocarbons is a pyrolysis method that works without pressure in the low-temperature range, as a closed system, and because of the closed system, the discharge of pollutants into the atmosphere is prevented.
The method created is characterized in that after the waste products that contain hydrocarbons and are to be treated, the input, have been placed into a reactor and the latter was placed into a thermal oven, the pyrolysis process takes place in such a manner that nitrogen is introduced into the interior of the reactor, the temperature curve runs in the range from 80 to 120° C. during the removal of oxygen, and this process is carried out over a time span of approximately 20 min.
Subsequently, a temperature increase in the thermal oven takes place, in such a manner that a process temperature in the range of 360 to 420° C. occurs in the reactor, and this process state is maintained over a time period of 1 to 2 h.
Afterwards, a short-term increase in process temperature to 480 to 600° C. takes place for a time period of 10 to 60 min, in order to allow the pyrolysis process to take place completely within the reactor, without undesired waste products being able to settle in the reactor. The process gases obtained during the pyrolysis process are passed out of the reactor and passed to a cooler having a relaxer.
The subsequent method steps relate, for one thing, to the treatment of the pyrolysis gas that is obtained, and, for another, to the collection and treatment of the carbon that has formed in the reactor.
The process gas introduced into the cooler is cooled and relaxed, so that as a result of the condensation that takes place, a pyrolysis oil is obtained, which is subjected to separation in a subsequent method step, by means of distillation, centrifugation, or filtering. Depending on the further use of the pyrolysis oil that is obtained, there is the possibility of passing it to a main tank for intermediate storage, with subsequent quality control; delivery for further use of the pyrolysis oil can then take place from this tank.
The other method step, which takes place in parallel, now proceeds in such a manner that after controlled cooling of the reactor, the latter is removed from the thermal oven and opened up, in order to be able to remove the waste products situated in the reactor, together with the accommodation device for the waste products, here old tires.
Subsequently, emptying of the reactor takes place, in a preferred embodiment, by way of suctioning out the reactor contents. This is followed by cooling of the carbon and separation of carbon and the metal residues, whereby the two waste product residues are stored separately, in order for them to be able to be passed to further use from there.
In this connection, it is particularly advantageous if the carbon is also subjected to deodorization, in order to remove the odor-causing components inherent in the carbon from it.
The device according to the invention, for carrying out the method for processing waste products that contain hydrocarbons, is characterized, in its totality, by a reactor in which the pyrolysis process takes place, and which is moved into, i.e. inserted into a thermal oven for these process procedures, whereby the reactor or the reactors that are placed into the thermal oven are charged with the goods to be treated, here, old tires.
The device according to the invention, the reactor, is suitable, on the basis of its very simple structure, for being used in existing systems, but a prerequisite in this connection is that the thermal oven is suitable, in terms of its design configuration, for accommodating one or more reactors according to the invention. In this connection, of course, the thermal oven must be equipped with appropriate technical equipment so that the prerequisites for carrying out pyrolysis are met.
It is essential to the invention, in terms of the device, that the latter is configured as a functional module in the form of a pyrolysis reactor, which consists of a container having a lid that can be closed, which container possesses a particularly configured bottom, and that reflectors shaped by the reactor are disposed on the inside of the lid.
In this connection, it is part of the invention that the reactor is configured with corresponding connectors, by way of which feed and drain lines can be connected, which lines are passed through the thermal oven and can subsequently be connected with the downstream functional units, outside of the thermal oven, i.e. can be connected with the latter.
Thus, the reactor is configured, in its lower region, with a connector for a feed line for nitrogen. Above the lid of the reactor, the latter has a connector piece to which the gas drain pipe is connected, in which a valve is provided, and the gas line pipe makes a transition into a connector piece, by means of which the connection to the cooling and relaxation model is produced.
It is furthermore part of the invention that in addition to the reflectors provided on the inside, edge reflectors are disposed in the interior of the lid of the reactor, which are configured with specific shapes that correspond, to the greatest extent possible, to the shapes of the reflectors disposed on the lid.

The invention will be explained in greater detail below, using an exemplary embodiment. The related drawing shows, in

FIG. 1: the flow schematic for demonstrating the essential method sequence and related system parts,

FIG. 2: a fundamental diagram of the reactor,

FIGS. 3 and 4: additional embodiment variants of a reactor,

FIGS. 5 and 6: various configurations of the lid of a reactor, with assigned reflectors and edge reflectors.

The flow schematic according to FIG. 1 shows the method sequence according to the invention, with the related system components, for processing products that contain hydrocarbons, using the example of old tires, which are previously stored and are placed into accommodation devices 3 before being introduced into the reactor 2, by means of which devices the old tires to be treated are then introduced into the reactor 2, in each instance. The old tires get into the reactor 2 in the form in which they are delivered, which means that the old tires can be placed into the reactor 2 both with rims and without rims, and this does not have a negative effect on the process sequence. Once the reactor 2 has been charged with old tires, the reactor 2 is sealed to be airtight, placed into the thermal oven 1, and the necessary connections to other functional modules of the system. The thermal oven 1 is closed and brought up to temperature. During this phase, the reactor 2 is thermally started up; this takes place over a time period of approximately 20 min at a temperature curve progression from 80 to 120° C., in order to eliminate the water that is situated in the reactor. Also during this phase, nitrogen is blown into the lower region of the reactor 2, into the interior of the reactor 2, in order to remove/eliminate the oxygen situated there.
In the next process step, the thermal oven 1 is brought up to temperatures in the range of 360 to 420° C., thereby also increasing the temperatures in the reactor 2 to these values, and held over a time period of 1 to 2 h; this is followed by short-term increase of the temperatures to 480 to 600° C., this temperature range being held over a time period of approximately 10 to 60 min, in order to allow the pyrolysis to proceed completely.
The pyrolysis gases that have been released during the pyrolysis process are passed, by way of an exhaust gas line, to a cooling and relaxation module 4, in which condensation to form pyrolysis oil takes place.
In the subsequent method step, separation of the pyrolysis oil takes place in a separator 6, by means of distillation, centrifugation, or filtering.
The pyrolysis oil is then brought to subsequent quality control 7 by way of a day tank 6, which is configured for intermediate storage, and then brought to the main tank 8, and can then be passed to the delivery station 9 as needed, by way of a transport line.
If separation of the pyrolysis oil takes place by means of distillation, the pyrolysis oil is cooled down, as a precaution, before it is brought into the day tank 6 or the main tank 8, respectively.
Transport or emptying out of the reactor 2 of the other reusable materials obtained during pyrolysis takes place in such a manner that the reactor 2, in each instance, is taken out of the thermal oven 1, the lid 17 of the reactor 2 is opened, thus the reusable materials contained in it, such as carbon and metallic residues/steel wire can be transported away or taken out.
In the flow schematic according to FIG. 1, these process steps are carried out in the system module 10 that is shown as an emptying station, in which cooling of the reusable materials that are removed takes place at the same time, which are then passed on to a separation unit 11, in which separation of carbon and metallic components takes place.
The metallic residues are brought to the storage and delivery station 15, while the carbon is passed to a packaging station 14 by way of a sorting station 13, and subsequently passed to the storage and delivery station 16.
In an advantageous embodiment, deodorization 12 is provided between the separation unit 11 and the sorting station 13, in which the odor-causing components that adhere to the carbon are extracted.
FIG. 2 illustrates, in a fundamental diagram, the configuration and formation of a reactor 2, which consists of a circular basic container that possesses a bottom 18 configured in concave shape, and is configured, in its upper region, with a lid accommodation 22, in which a sealing system for airtight closing of the reactor 2 is provided, which goes into effect when the reactor 2 is closed off by means of the lid 17.
The inside of the lid 17 is configured with a guide projection 28. This guide projection 28 ensures a shape-fit connection between the lid 17 and the reactor 2. The lid 17 is furthermore configured with a central opening and a connector piece 24, to which the gas drain pipe 25 can be assigned.
Furthermore, a stirrup 23 is provided in the upper region of the lid 17, by means of which the lid 17 can be taken off the reactor 2 or set onto the reactor 2, respectively; this takes place by way of suitable lifting means.
The reactor is configured with support feet 19, preferably with three support feet 19 being selected, thereby guaranteeing the standing safety of the reactor 2, and furthermore, the ground clearance between the standing surface in the thermal oven 1 and the reactor 2 obtained in this manner has a positive effect on the process management, as will be explained in greater detail below.
For the transport of the reactor 2, and for placement of the reactor 2 into and removal from the thermal oven 1, holders 21 are provided on its outer circumference, at which corresponding attachment parts of hoists can be attached.
In the lower region of the reactor 2, above the bottom 18, one or more feed line connectors 20 are provided, by way of which the nitrogen is passed into the interior of the reactor 2. It is advantageous if valves are provided in these feed line connectors 20, which prevent contaminants from entering into the reactor 2, for one thing, and content substances exiting from the reactor 2, for another thing.
The gas drain line 25 is also equipped with a valve 26, which can be turned on and off and thus can be used to act on the process management, here the exit of the pyrolysis gas.
The connector piece 27 of the gas drain line 25 serves for making a proper connection to the subsequent cooling and relaxation module 4.
It is also evident from the representation according to FIG. 2 that the inside of the lid 17 is equipped with another functional component, in addition to its guide projection 28. This component is a specially shaped reflector 30, which is attached to the lid 17 by way of holders 29.
The reflector 30 can be configured in planar, concave, conical, pyramidal, or similar shape, as partially shown in FIGS. 5 and 6.
The arrangement of a reflector 30 and its special design configuration have a positive effect on the pyrolysis process that takes place in the reactor 2, since a lid 17 configured according to the invention, in the broadest sense, with its guide projection 28 and the related reflector 30, represents a reaction container lid that has a positive effect on the process management within the reactor 2. In particular, this lid 17 brings about vacuum-tight closing of the reactor 2, and good circulation of the material to be treated within the reactor 2, thereby achieving a particularly uniform treatment of the pyrolysis material.
Thus, rising particles of the pyrolysis material are deflected when they hit the reflector 30, in accordance with its configuration, and passed back into the pyrolysis material.
Two additional embodiments of a reactor 2, including the related lid 17, are shown in FIGS. 3 and 4.
Thus, FIG. 3 shows a reactor 2 that is configured with a bottom 18 configured in planar manner. The reactor 2 itself, as was already described above and shown in FIG. 2, is configured with support feet 19, in order to have the required ground clearance from the standing surface in the thermal oven 1.
In this configuration, the lid 17 is configured in analogous manner to FIG. 2, in that a reflector 30 configured in concave shape is provided on the underside of the lid 17.
In the case of the embodiment variant of the reactor 2 shown in FIG. 4, the reactor 2 is configured with a bottom 18 in concave shape, analogous to the embodiment according to FIG. 2, whereby, as is evident from FIG. 4, the guide projection 28 of the lid 17 is also configured in concave shape. The concave shape of the guide projection 28 corresponds to the concave shape of the reflector 30, but is continued beyond the outer circumference of the reflector 30, so that the pyrolysis chamber within the reactor 2 is shaped, even in the region of the lid, in such a manner that particularly uniform drying of the pyrolysis material is achieved by means of the circulation of the pyrolysis material.
In order to be able to configure this circulation process in optimal manner, it is advantageous to dispose edge reflectors 31 on the inside of the lid 17, in each instance, in addition to the reflector 30 that is provided, as shown in FIGS. 5 and 6.
These edge reflectors 31 are provided below the reflector 30, in each instance, and are configured in such a manner that they are configured with a very large central opening, so that the effect of the reflectors 30 is not restricted. This means that the edge reflectors 31 only cover the intermediate gap between the outer circumference of the reflectors 30 and the inside wall of the reactor 2.
Thus, FIG. 5 a shows a lid 17 having a guide projection 28 configured in concave shape, and an assigned planar reflector 30, as well as an edge reflector 31 configured in the shape of a truncated cone.
FIG. 5 b shows a lid 17 having a guide projection 28 configured in planar manner, and an assigned planar reflector 30, to which an edge reflector 31 configured in the shape of a truncated cone is also assigned.
The representation according to FIG. 5 c corresponds to the configuration according to FIG. 5 b, in terms of the configuration of the lid 17 and of the guide projection 28, as well as of the edge reflector 31, but the reflector 30 is configured in concave shape.
The lid 17 shown in FIG. 5 d corresponds to that of FIG. 5 a with regard to the configuration of the guide projection 28 and of the edge reflector 31, but here, the reflector 30 is configured in concave shape.
FIGS. 6 a to 6 b show lids 17 having guide projections 28 in which the guide projections 28 are concave, the reflector 30 is planar, and the edge reflector 31 is in the shape of a truncated cone—FIG. 6 a—the guide projection 28 is planar, the reflector 30 is planar, and the edge reflector 31 is in the shape of a truncated cone—FIG. 6 b—the guide projection 28 is planar, the reflector 30 is concave, the edge reflector 31 is in the shape of a truncated cone—FIG. 6 c—and in FIG. 6 d, the guide projection 28 is concave, the reflector 30 is also concave, and the edge reflector 31 is in the shape of a truncated cone.

Claims

1. Method for processing products that contain hydrocarbons, particularly old tires, by means of low-temperature pyrolysis, for the purpose of recovering carbon, pyrolysis oil, residual gas, and metallic components, using reactors that are accommodated in a thermal oven, wherein

after the reactor (2) has been charged, it is placed into a thermal oven (1); in a first stage, the reactor (2) is heated to a temperature in the range from 80 to 120° C., which is held over a time period of approximately 20 min, and in a second stage, which takes place in parallel, nitrogen is blown into the reactor (2), a reduction in moisture and oxygen takes place in the reactor (2); in the subsequent process steps, a further temperature increase in the reactor (2) takes place, to a range of 360 to 420° C., over a time period of 1 to 2 hours; in the subsequent method step, a short-term increase in process temperature to 480° C. to max. 600° C. takes place for a time period of 10 to 60 min, and after the pyrolysis process has been completed, the pyrolysis gas is passed out of the reactor (2) and passed to a cooling and relaxation module (4), while carbon that has settled in the bottom region of the reactor (2) is suctioned off, and the metallic components are removed from the reactor (2).

2. Method according to claim 1, wherein

the material particles that are released during pyrolysis and that rise and are suspended in the reactor (2) are circulated in controlled manner within the reactor (2), and are incorporated into the process circuit of pyrolysis that takes place.

3. Method according to one of claim 1, wherein

the hot-air feed to the thermal oven (1) and the temperatures in the reactor (2) are regulated, preferably with electronic control, and the temperature management of the thermal oven (1) and of the reactor (2) takes place by way of thermostats.

4. Method according to one of claim 1, wherein

the pyrolysis gas is transported out of the reactor (2) by way of an exhaust gas line (25).

5. Method according to one of claim 1, wherein

the old tires to be treated are inserted into the reactor (2), in each instance, in stacked form, and removed from it, by means of accommodation devices.

6. Device for carrying out the method according to claim 1, wherein

the device consists of one or more reactors (2) that can be inserted into thermal ovens (1), the bottom (18) of a reactor (2) possesses a concave shape, the lid (17) is configured with a guide projection (28), which engages into a lid accommodation (22) in the closed state, and reflectors (30) and edge reflectors (31) are disposed on the inside of the lid (17).

7. Device according to claim 6, wherein

the reactor (2) possesses support feet (19) that form a ground clearance between the bottom (18) of the reactor (2) and the standing surface in the thermal oven (1), which has a positive effect on the process management within the reactor (2).

8. Device according to claim 6, wherein

the bottom (18) preferably has a planar shape, and feed line connectors (20) are disposed in the container wall of the reactor (2), above the floor (18).

9. Device according to claim 6, wherein

a sealing system is provided in the lid accommodation (22), the lid (17) and the guide projection (28) are structured with a central bore, and the lid (17) is configured with a connector piece (24).

10. Device according to claim 6, wherein

the guide projection (28) of the lid (17) possesses a planar surface shape, or one configured in concave shape, on its inside.

11. Device according to claim 6, wherein

the reflectors (30) possess a planar, concave, conical, pyramidal or similar shape.

12. Device according to claim 6, wherein

the edge reflectors (31) possess a large-area central opening and are structured in the shape of a truncated cone, as well as concave or in similar shape, adapted to the shape of the reflectors (30).