ES2355454B1 - CONTINUOUS SYSTEM AND PROCEDURE FOR RECYCLING MATERIALS DERIVED FROM OIL BY WET. - Google Patents

Abstract

System and continuous process of recycling of petroleum-derived materials by means of wet roads. # A system and a procedure of recycling of out-of-use tires that works continuously, without the need for stops, and which allows to obtain several products with high purity are described. Among these obtainable products is a liquid hydrocarbon with characteristics similar to petroleum oil.

Description

System and continuous procedure of recycling of petroleum-derived materials by wet way.

Object of the invention

The present invention relates to a system and method for recovering hydrocarbons by wet means from the recycling of tires, non-metallic components of vehicles, non-metallic fractions of electrical and electronic equipment, and the like.

The object of the invention consists of an out-of-use tire recycling system that includes a wet extraction path in a continuous system, that is, in a system where tires are continuously introduced and a product with characteristics similar to crude oil is extracted from Petroleum.

Background of the invention

Today there is a need and dependence on hydrocarbons as a means of combustion in engines and generators, these resources are scarce and an optimization of them is necessary. Among the many possibilities that can be found today is the recycling of composite materials that, once processed, will result in a series of products that include higher or lower quality hydrocarbons.

Some of these types of processes are widely documented in the state of the art, such as:

International patent application WO03052029 describes a method and installation for the recycling of tires in a reactor with used car oil. This method has the disadvantage that it is not a continuous process and that, therefore, when it finishes it has to stop and cool down to start a new cycle. This embodiment is known as a bath or batch.

International patent application WO9909092, which describes a reprocessing or recycling of polymer products in a reactor with vegetable oil. This method has the disadvantage that it is not a continuous process and that, therefore, at the end of the process it has to stop and cool down to start a new cycle, just like the previous one.

US patent US4384151 and its French equivalent FR2490992 which describe a tire recycling process in a single reactor and which uses oil mixed with the oil product of the recycling itself. Like the previous ones it is not a continuous process, but in batches, where a load of tires is introduced and pulled over by means of oil sprinklers (external and internal mixed) and previously heated.

The international patent application WO9408768 describes a system with two tanks connected to each other, where the tires are immersed in a first tank, inside liquid rubber, and heated so that the rubber of the wheels dissolves in them. Prior to this, the gums have been preheated in a tank for this purpose. At the end it is a closed circuit system where the result of the dissolution is used for heater fuel and as a solvent for the wheels. The main problem of this system is that it does not work continuously, therefore, the change of wheels implies the stoppage and cooling of the plant.

European patent EP0652275 describes a reactor with inlet, outlet and heating means where the wheels are mixed with oil, heated and passed through a sieve, in the same way there is an auger screw mechanism that transports the recovered material (metal) to an exit. This system presents the problem of all the previous ones: it is not a system of continuous feeding and extraction, just like the previous methods described.

The publication of the Spanish patent application with publication number ES2277799 describing a system and a procedure for the recycling of tires in a continuous system, that is, in a system where tires are continuously introduced and the resulting products are extracted. These resulting products are diesel, carbon black and steel; One of the drawbacks of this invention is the need for a subsequent desulfurization process of the product obtained. This described system does not appear to be watertight, it describes a system with the placement of a tilting valve which allows gas outflows and even the entry of air into the reactor is allowed.

In US patent US4938278 where a system and method of obtaining hydrocarbons by dry route is described using pyrolysis of used motor oils, tars or other similar waste products in a horizontal reactor (HSPR) and subsequently in an inclined reactor ( ISPR). The carbon black extraction process is carried out dry and the distillation process and the solids obtained are carried out in two different reactors which lengthens the process. In the HSPR the pyrolysis of the products takes place while in the ISBR the solids obtained from the HSPR are processed.

In English patent GB 2301112, use is also made of transport systems based on auger mechanisms, whereby seals can occur in the system.

Description of the invention

The object of the invention is a wet tire recycling system and a method that makes use of said system. By means of said system, hydrocarbon can be obtained, both in liquid and gaseous state; said liquid hydrocarbon being assimilable to an oil crude.

In the system object of the invention maintains the tightness during the entire process of separation of carbon black and the wire. In other systems that make use of tilting valves, outflows of gases can occur, and it is also possible that at some point air enters the interior of the reactor.

The treatment of out-of-use tires (referred to by its acronym NFU hereinafter) consists in causing its dissolution in mineral oils at medium temperature, transforming the tires into a liquid hydrocarbon. Typical proportions of the process are 50% by weight of tires and 50% of mineral oils, to obtain 80% of liquid fraction, 10% carbon black and 10% steel. The NFU dissolution process is carried out at medium temperatures and at atmospheric pressure. This process must be followed subsequently by a distillation of the product obtained in the solution, in order to achieve greater purification of inorganic fillers and metal oxides (mainly zinc oxide, which is used as a rubber stabilizer) that contains synthetic rubber. .

The system object of the invention allows a continuous process, without it being necessary to stop the system at any time using consecutive heating-cooling cycles, obtaining greater thermal effectiveness, thus achieving an optimum and significantly higher productivity rate with respect to the currently known systems. Likewise, the aforementioned system has an air recirculation, with the purpose of optimizing the process energetically allowing the hot air to enter the system at various points, it should be noted that it is “air” and not gases as in other systems , because in the proposed system atmospheric air is used at a sufficient temperature to provide heat to the system.

The system object of the invention does not make use of tilting valves so there is no possibility of leaks of volatile contaminants to the outside, the system is hermetic and ecologically sustainable.

Likewise, the product obtainable through it is a quality recycled product, since both carbon black and steel have a minimum amount of impurities possible. In this way a hydrocarbon assimilable to a crude oil is produced, said hydrocarbon can be found in Liquid or gaseous form free of inorganic pollutants present in metal oxides and that does not require a subsequent desulfurization process, a process that is necessary in current systems and procedures.

During the dissolution stage of the process, the elastomer is broken down into smaller hydrocarbons, which are recovered later in the process. The solid residue consists of carbon black, the inorganic components of the tire and steel. In this way, the chopped gums are fed into the dissolution reactor, which is heated by its external part, after which the tire is progressively soaked and decomposes into hydrocarbons due to the reactions that take place during dissolution. Said reactor is a parallelepiped shaped, in which the mixture of tires and oil enters inside and the dissolution reactions begin to take place. These reactions are produced by using only a drive system, thus avoiding the need for the presence of endless screws inside and avoiding the turn of the materials. As the materials advance in the circuit defined by the system, dissolution-distillation is produced, by generation of gases and vapors.

One of the most notable differences of the system and the process objects of the invention is the extraction that is carried out once the separation of carbon black and the wire is undertaken; It should be noted that the system object of the invention is based on an arrangement that, unlike others, comprises a single reactor, in which the two actions to be performed are produced: dissolution-distillation.

Said extraction is carried out with a system that maintains the watertightness of the entire process, since the extraction is carried out by means of a wet route and dispenses with the use of tilting valves such as the one used in ES2277799 that performs an extraction by dry means. In order for the aforementioned wet extraction to be carried out efficiently, an additional energy contribution is necessary.

Likewise, there is a conduit designed to cool the system in charge of preventing the evaporation of the water present in the tank when the black mixture of smoke and iron comes into contact with it.

The system object of the invention comprises at least the following elements:

-

a reception hopper, consisting of a cylindrical or essentially rectangular body in its plan and trapezoidal in its elevation, with the lower part thereof narrower than its upper part and with one of its sides inclined to, thus, favor the introduction of petroleum-derived materials, such as NFU out-of-use tires in both the hopper and the trombone itself;

-

means for introducing solvent oil into the NFU receiving hopper;

-

means for introducing the chopped tire into the hopper, selected from the following: hydraulic, by feeding belt or a tire introduction system soaked from the storage hopper to the trombone.

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a hot gas inlet to the trombone;

-

several hot gas outlets from the trombone;

-

heating means, which in turn comprise at least:

-

a biomass hopper;

-

a biomass furnace;

-

several heat exchangers, located in the hot gas inlet path of the trommel.

The dissolution-distillation trommel, has two distinct zones: a first dissolution zone, more inclined with respect to the horizontal and a second distillation zone, It should be noted that the materials that make up the trommel do not suffer dilation-contraction cycles, which They can shorten their lifespan.

Said dissolving trommel is an inclined rectangular, watertight and static rectangular parallelepiped, which has inside a hot oil bathtub through which the chopped tires travel, in which the dissolution begins. It is heated by its external face, in a jacket circuit, with the hot gases that come from a biomass or other combustion furnace, so that the liquid inside transmits heat to the pieces of tire that are traveling inside. To make the thermal transmission more efficient, the jacket is equipped with a system of fins that increase heat transmission. In its final part it is connected to the distillation trommel.

Only the quantity of oil-pneumatic diluted mass that will be continuously distilled in contact with the surfaces, which are at an elevated temperature, will also enter the distillation tank, as they also have a double jacket system on the outside that allows the circulation of hot gases. The jacket is equipped with a system of longitudinal fins, as well as the anterior part of dissolution, to increase heat transmission. As the product progresses, distillate vapors are generated and subsequently extracted from the trommel and condensates. At the outlet of the trommel is the connection to the reception tube of the coal-steel mixture.

The process object of the invention implements a recycling process consisting, at least, of the following stages:

1.-Introduction of NFU

2.-Soaking of the NFU, and subsequently the following processes are carried out in parallel:

2.1.-Dissolution of the tires (in this process the depolymerization of the tires begins);

2.1.1.-Distillation

2.1.2.-Separation of carbon black and steel recovered from other waste;

2.2.-Evaporation

2.2.1.-Condensation.

2.2.2.-Storage.

First of all, and by means of the NFU introduction means, these are introduced into the receiving hopper during said introduction stage to subsequently pass to the soaking stage, where the receiving hopper is partially filled with a diluting agent, preferably used oil from the recycled itself or oils derived from petroleum. In it, the NFUs are soaked in this product, starting the chemical process of dissolving the NFUs. These soaked tires are introduced into the dissolution-distillation trommel either by means of a system of hydraulic piston-type pushers or, if preferred, by means of a system of dragging by means of vanes, or conveyor belt the piston / sleeve / piston system. The lower part of the hopper is connected to this feeding system, which injects these tires into the trombone through its first dissolution zone. The chopped tires are introduced into the first area of the trombone at all times immersed in the solvent. Both in the system and in the process objects of the invention it is not necessary that both levels of oil inside the trombone and in the hopper are met.

As previously outlined in this stage of soaking, two stages take place in parallel.

In the first one, corresponding to the dissolution stage, the paste formed by the partially dissolved NFUs and the diluting agent introduced into the first zone of the trommel or dissolution zone, begin the chemical depolymerization process at a temperature that gradually increases as They are traveling inside. The level of the diluent agent in the trommel is the same as that in the hopper, since they communicate by communicating vessels with each other. The temperature is reached in the trommel thanks to the hot gases introduced in the double jacket of the same, coming from the heating means. In this zone of dissolution-distillation a temperature of 300-430ºC is reached by subsequently raising the temperature to 550ºC (the maximum temperature of distillation of the solvent agent: used automotive oil) to dry the corresponding carbon black of the accompanying solvent. This operation can be carried out on the outside of the trommel if its dimensions do not allow such an operation to be performed inside.

After this dissolution stage the process carries out the distillation stage: The paste resulting from the dissolution of the chopped tire is transported by a drag system. In this area the carbon black that exists is drying up when the oil that soaks it evaporates. And then the separation stage: Carbon black and steel (solid elements) are separated from the mixture resulting from distillation. These subsequently fall on a conveyor belt, which leads them to the magnetic separation system, each of them falling on conveyor belts that take them to different tanks.

The second stage that is carried out in parallel to the stage of dissolution after the soaking is the evaporation stage, where the volatile components generated in the process of depolymerization of the rubber of the tires evaporate due to the temperature reached inside from the zone of distillation of the trommel.

From this evaporation stage the process passes to the condensation stage where the gases generated are channeled and condensed out of the trommel. The distillation vapors leave the distillation trombone at the top. To help the distillation be more effective and faster, the liquid hydrocarbon already obtained up to injectors will be injected at the exit of the trombone and in the route of the gases through the condensation lines; the exit of said liquid hydrocarbon by the injectors will drag all the gases that are in the vicinity. Since the injection of this hydrocarbon for cooling may not be sufficient to keep the installation running continuously and with optimum yields, it is necessary to place a forced extraction system for these gases (condensable or not). In this case the extraction of all gases occurs, with the compressor, placed after the condensation system.

In this way, a suction effect of the gases that are distilled and their rapid cooling is achieved. These gases are also extracted by means of forced gas extraction, such as an exhaust, and can be used as fuel in other boiler systems, etc ... At the exit of the condensation lines the products go to a tower of condensation that separates them from non-condensable gases and from there they are pumped to a tank. The non-condensable gases recovered are directed to their subsequent combustion either in a torch or in the oven. The hydrocarbon reservoir will be kept at a constant temperature between 60ºC and 80ºC.

Description of the drawings

To complement the description that is being made and in order to help a better understanding of the characteristics of the invention, according to a preferred example of practical implementation thereof, a set of drawings is attached as an integral part of said description. where, for illustrative and non-limiting purposes, the following has been represented:

Figure 1.-Shows a complete system scheme.

Figure 2a.-It shows a view where, among others, a section of the dissolving-distillation tromer can be seen.

Figure 2b.-Shows a zenith view where, among others, the dissolving-distillation trombone can be seen.

Preferred Embodiment of the Invention

In view of the figures, a preferred embodiment of the system and method objects of this invention is described below.

As can be seen in Figure 1, the recycling of out-of-use tires begins at the introduction stage by introducing the NFUs into a receiving hopper (2) using pumping means (3) and some ducts (4) in the receiving hopper (2), where the soaking stage begins. Once the solvent agent NFUs soaked from solvent storage media (7) have been soaked, they are injected into a dissolving-distillation (5), where a temperature of between 300 ° C and 430 ° C is reached, at a pressure close to Atmospheric, due to the hot gases coming from a hot air inlet (6) that circulate through a double jacket of the trommel (5) said procedure makes use of dragging means that are inside the trommel (5) that They comprise at least one vane (16) that is responsible for collecting and turning a mixture consisting of NFU and a solvent agent in the trommel (5).

The temperature generated inside the trommel (5) accelerates the dissolution of the tires in the diluting agent in the dissolution stage, within a first zone (8) of dissolving the trommel (5).

Subsequent to dissolution, and in parallel to the evaporation and condensation stages, distillation occurs in a second zone (9) of the trommel (5), and finally the wet separation between the solid products obtained as a result of the process, being these carbon black and steel that are subsequently stored. For this, the temperature is raised to 550 ° C by means of heating means (19) connected to a pipe (20) and a hot air outlet (10) both connected to the trombone (5), where the pipe (20) is connected to a conduit connected to the trommel (5) by means of the hot air inlet (6), to deliver hot air from said heating means (19); Likewise, the carbon black of the solvent that accompanies it is achieved by heating by means of heating (19) the gases that circulate through hot air outlet (10) and that come from the trombone (5) to then pass to a separation means magnetic (12) from where the mixture of carbon black and iron is carried through a cooling duct (17) to a reservoir (14).

Similarly, and in parallel there is the evaporation of volatile components, which condense in the condensation stage. In this stage the gases are channeled on the one hand to the outlet pipe of smoke outside (13) and on the other hand to condensation lines (11) these condensation lines leave the trommel

(5) where condensation begins to occur outside the trommel (5) while previously obtained hydrocarbon (or any other hydrocarbon) is injected, cooled by means of cooling means (25) and stored in a tank (24) above, by means of injectors (22) producing the cooling and condensation of the generated vapors. The condensed gases already in a liquid state reach a condensation tower (23), to which are forced gas extraction means (18) responsible for extracting gases and facilitating the condensation of gases in the condensation lines (11 ) and in said condensation tower (23), and from there they are channeled to a reservoir (24). This reservoir (24) is maintained at a constant temperature of 60 ° C, storing the final result at said temperature maintained through the use of the cooling means (25). From this tank (24), cooled liquid hydrocarbon is carried to the condensation tower (23) and to the condensation lines (11) as described above.

Claims (7)

1. System (1) for the recycling of petroleum-derived materials comprising:

-

a receiving hopper (2) of NFU connected to solvent storage means (7) and from which pumping means (3) connected to conduits (4) start,

-

a dissolving-distillation trombone (5) connected to the ends of the double-jacketed ducts (4) comprising an internal finned circuit and two continuous zones differentiated from each other, a first dissolution zone (8) and a second zone (9 ) of distillation, to which hot air arrives by means of a hot air inlet (6) to raise its temperature,

-

condensation lines (11) that start from the trombone (5) adapted to facilitate the condensation of the gases coming from said trommel (5) and that in turn reach a condensation tower (23) that is located in the other end of said condensation lines (11) from which part pipes that reach a reservoir (24) leave, and the condensation lines (11) and the condensation tower (23) being connected to a plurality of injectors (22) ) responsible for injecting and recirculating hydrocarbon, cooled by means of cooling (25) and stored in the tank (24), in the condensation lines (11) and in the condensation tower (23) to facilitate the condensation of gases,

-

a pipe for exiting smoke outside (13) and a hot air outlet (10) that start from the trombone (5),

characterized in that it comprises:

-

heating means (19) that are connected to the pipe (20) and the hot air outlet (10),

-

forced gas extraction means (18) located next to the condensation tower (23) responsible for extracting gases and facilitating the condensation of gases in the condensation lines (11) and in the condensation tower (23),

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a cooling duct (17) connected after the hot air outlet (10) and before magnetic separation means (12), intended to cool a mixture of iron and carbon black from the trommel (5),

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a reservoir (14) that is located next to the magnetic separation means (12), and

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entrainment means that are inside the trommel (5) comprising at least one vane (16) that collect and turn the mixture of NFU and solvent in the trommel (5).

2. System (1) according to claim 1, characterized in that the receiving hopper (2) and the dissolving distiller (5) contain a diluting agent from the solvent storage means (24) selected from:

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tire oil, and

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other oil derived from petroleum.

3. Method that makes use of the system (1) described in any one of the preceding claims characterized in that it comprises the following steps: a.-introduction of NFU into the system (1) by means of the pumping means (3) of NFU, b.-soaking of the NFUs, once the NFUs are soaked, these are injected into the trommel (5), where a temperature of between 300ºC and 430ºC is first reached, at atmospheric pressure, due to the hot gases circulating in the double Tromel jacket (5) to then bring the temperature through the heating means (19) to 550 ° C to dry carbon black of the diluting agent, the following processes are subsequently carried out in parallel: c.1.-dissolution of the tires where the depolymerization of the NFUs comprising the following subphases begins; c.1.1.-distillation of the result of c.1 in the second zone (9) of the trombone (5),

c.1.2.

separation of carbon black and recovered iron,

c.2.

evaporation of the volatile components, the gases analyzed and condensed outside the trommel (5) being injected by means of the injectors (22) hydrocarbon obtained cold, in the condensation lines (11) and in the condensation tower (23) producing condensation of liquids in said condensate lines (11) that carry all the gases and from where condensates arrive totally or partially to the condensation tower (23) and from there they fall into the tank (24); This tank is maintained at a constant temperature of 60 ° C by means of the cooling means (25), obtaining and storing the resulting product in the tank (24) from which the hydrocarbon obtained by the injectors (22) is recycled and

d.

forced extraction of the gases present in the condensation tower (23), the condensation lines (11) and the trombone (5) through the use of the forced gas extraction means (18).

SPANISH OFFICE OF THE PATENTS AND BRAND Application no .: 200930591 SPAIN Date of submission of the application: 11.08.2009 Priority Date: REPORT ON THE STATE OF THE TECHNIQUE 51 Int. Cl.: C10G1 / 10 (01.01.2006) C08J11 / 10 (01.01.2006) RELEVANT DOCUMENTS

Category

Documents cited Claims Affected

X

EN 2277799 A1 (RECYCLING SYSTEMS AND IN S L) 16.07.2007, figures 1,2a, 2b; page 3, 1-3

line 26 - page 5, line 35; page 6, line 33 - page 7, line 30.

TO

US 6657095 B1 (RECYCLED ENERGY L L C) 02.12.2003, figures 1A, 1B, column 3, 1-3

line 12 - column 4, line 49.

TO

GB 2301112 A (CALIFORNIA ENGINEERING CONSULT) 27.11.1996, figure 2; page 5, 1-3

line 12 - page 9, line 4.

TO

US 4983278 A (WESTERN RESEARCH INST & ILR SE) 08.01.1991, column 7, 1-3

line 50 - column 10, line 54.

Category of the documents cited X: of particular relevance Y: of particular relevance combined with other / s of the same category A: reflects the state of the art O: refers to unwritten disclosure P: published between the priority date and the date of priority submission of the application E: previous document, but published after the date of submission of the application

This report has been prepared • for all claims • for claims no:

Date of realization of the report 02.28.2011

Examiner A. Urrecha Espluga Page 1/4

REPORT OF THE STATE OF THE TECHNIQUE Application number: 200930591 Minimum documentation sought (classification system followed by classification symbols) C10G, C08J Electronic databases consulted during the search (name of the database and, if possible, terms of search used) INVENES, EPODOC, WPI, XPESP, NPL, TXTUS. State of the Art Report Page 2/4  WRITTEN OPINION Application number: 200930591 Date of Completion of Written Opinion: 02.28.2011 Statement

Novelty (Art. 6.1 LP 11/1986)

Claims Claims 1-3 IF NOT

Inventive activity (Art. 8.1 LP11 / 1986)

Claims Claims 1-3 IF NOT

The application is considered to comply with the industrial application requirement. This requirement was evaluated during the formal and technical examination phase of the application (Article 31.2 Law 11/1986).  Opinion Base.- This opinion has been made on the basis of the patent application as published. State of the Art Report Page 3/4  WRITTEN OPINION Application number: 200930591 1. Documents considered.- The documents belonging to the state of the art taken into consideration for the realization of this opinion are listed below.

Document

Publication or Identification Number publication date

D01

EN 2277799 A1 (RECYCLING SYSTEMS AND IN S L) 07/16/2007

2. Statement motivated according to articles 29.6 and 29.7 of the Regulations for the execution of Law 11/1986, of March 20, on Patents on novelty and inventive activity; quotes and explanations in support of this statement The object of the invention is a tire recycling process and the installation where it is carried out. Document D01 discloses a tire recycling system comprising: - an out-of-use tire receiving hopper (NFU) connected to solvent storage means (selected from pneumatic oil and another oil derived from petroleum)

-

a double jacketed trombone with a finned internal circuit comprising two continuous zones differentiated from each other, a first dissolution zone and a second distillation zone. It has means of drag (augers, pallets).

-

condensation lines that start from the trombone for the condensation of gases, with injectors and a tower of

condensation. -a channeling smoke outlet to the outside and a hot air outlet starting from the trommel -a magnetic separation means connected after the hot air outlet and a tank It also discloses the procedure that makes use of the system characterized in that it comprises the following stages:

one.

Introduction of NFU in the system

2.

Soaking of the NFU. Once soaked, they are injected into the trommel, where a temperature between 300 ° C and 430 ° C is reached at atmospheric pressure, due to the hot gases circulating through the double jacket of the trommel.

3.

Dissolution of the tires, the depolymerization of the NFUs comprising the following subphases begins;

to.

distillation of the dissolution of the NFUs with oil in the second zone of the trombone

b.

separation of carbon black and recovered iron,

4. Evaporation of volatile components (Figures 1, 2a and 2b; page 3 line 26-page 5 line 35; page 6 line 33-page 7 line 30). The differences between the technical object of claims 1 and 3 of the application and document D01 are the heating means connected to the hot air outlet that allow the temperature to be increased up to 550 ° C to dry the carbon black of the diluting agent and the means Forced extraction of gases located next to the condensation tower responsible for facilitating the condensation of gases. The introduction of heating means to force the drying of carbon black is a design option that is considered within the scope of practice of the person skilled in the art. In the same way, the presence of means of forced extraction of gases located next to the condensation tower is also a design option that the person skilled in the art would use to solve the problem. Consequently, the technical object of claims 1-3 lacks inventive activity in light of what is disclosed in D01 (Art. 8 LP). State of the Art Report Page 4/4