JP2015518510A - Apparatus and method for recovering higher amounts of pure terpenes and terpenoids from scrap polymers and elastomers - Google Patents

Abstract

An apparatus and method for vacuum pyrolysis of finely chopped scrap material, such as tires, to produce pyrolysis oil from which valuable terpenes such as limonene and plegon can be extracted and refined The apparatus includes a pyrolysis chamber, a cooling device, a first distillation column (43), and a second distillation column (59) for recovering terpenes and terpenoids from the pyrolysis oil. The two columns are used at two pressures: atmospheric pressure and reduced pressure (strong vacuum). The vapor from the first distillation column is condensed by flowing through a small hole (53) (Joule-Thomson treatment). The resulting product mixture containing terpenes and terpenoids may be irradiated by a broad spectrum ultraviolet lamp so that the concentration of some terpenes such as isopulegol increases while other materials such as toluene can decrease. .

Description

  The present invention relates to the recovery of terpenes and terpenoids from the pyrolysis of polymers and elastomers.

  The continued accumulation of used tires is one of the most serious solid waste problems facing industrialized countries. North America is estimated to dispose of about one used tire per person per year. While incineration of tires is expensive and complex, the accumulation of used tires is a growing concern. Also, the potential for tire fires at these sites poses an ever-increasing threat to the environment. On the other hand, tire means a source of energy and chemicals. By pyrolysis, it is possible to recover useful products in an environmentally friendly manner.

  The presence of terpenes in “Py-oil” or rubber pyrolysis oil has been known for decades. However, the concentration is low. Attempting to separate the terpenes via distillation is counterproductive because the heat required for distillation results in the decomposition of the most valuable terpenes such as limonene. Simply reducing the pressure of distillation results in very high costs from large columns and long process residence times. In addition, there is a great difficulty in separating odorous mercaptans, and there is complexity due to sulfur, moisture and solids.

  This section provides an overview of the disclosure and is not an exhaustive disclosure of its full scope or all its features.

  According to various embodiments of the present invention, the present invention is a component for vacuum pyrolysis of scrap tires for producing pyrolysis oils containing compounds such as dl-limonene and progen, which are expensive in the market. Regarding the mounting system.

  The technology described here provides a combination of an entirely new concept and a concept that extracts value from oil derived from the pyrolysis of scrap while preserving valuable carbon black solids. This combination is high in expensive fragrances and essential oils, known for their unique solvent properties, their usefulness as drug precursors, their ability to mask odors, and “green” characters in final disposal Bring concentration. The most obvious example of the use of these processes is the recovery of terpenes and terpenoids from the pyrolysis of scrap tires. It achieves the most valuable recovery from the oil, the solid (carbon black and metal) and the gas (light hydrocarbons).

  The technology described here provides a combination of an entirely new concept and a concept that extracts value from oil derived from the pyrolysis of scrap while preserving valuable carbon black solids. This combination is high in expensive fragrances and essential oils, known for their unique solvent properties, their usefulness as drug precursors, their ability to mask odors, and “green” characters in final disposal Bring concentration. The most obvious example of the use of these processes is the recovery of terpenes and terpenoids from the pyrolysis of scrap tires. It achieves the most valuable recovery from the oil, the solid (carbon black and metal) and the gas (light hydrocarbons).

  Scrap rubber or similar materials are heated under vacuum and in the presence of compounds that decompose into active species upon heating and promote desulfurization and decomposition of the polymer and elastomer in the scrap. As the temperature of the feed-catalyst mixture is further increased, valuable compounds are vaporized. The reactor is designed so that the exhaust holes for carrying away steam are in the immediate area, but at the point in the reaction, the catalyst is decomposed and the catalyst species is in direct contact with the molten material. Has been. Therefore, the catalyst precursor cannot be carried away by leaking steam.

In the accompanying drawings forming part of the above specification,
FIG. 1 shows a diagram of one embodiment of the present invention for a continuous reactor process: FIG. 2 shows a system diagram of one embodiment of the present invention for batch reactor processing: FIG. 3 shows a system diagram of one embodiment of the present invention for a contactor / separator system: FIG. 4 shows a system diagram of one embodiment of the present invention for processing using ultraviolet light. Like reference characters and numbers indicate like steps or parts throughout the respective diagrams of the drawings. While one embodiment of the present invention has been described in the above referenced drawings and the following description, it should be understood that the above described embodiment is merely one preferred implementation provided for illustrative purposes only. It is an example of an embodiment, and various modifications of the structure can be used in the manufacturing process in order to make the most advantageous use of the invention according to the circumstances that can occur without departing from the spirit and intent of the invention. And should only be limited by the claims contained herein.

  In the following description, numerous specific details are set forth, such as a number of preferred embodiments, specific components, apparatus, example methods, etc., in order to provide a thorough understanding of embodiments of the present disclosure. . Those skilled in the art will appreciate that these specific details need not be employed and should not be construed to limit the scope of the present disclosure. In developing any actual implementation, a number of implementation specific decisions must be made to achieve the developer's specific objectives, such as meeting system-related and business-related constraints. Such development efforts may be complex and time consuming, but nonetheless are common tasks for those skilled in the design, fabrication, and manufacturing.

  At least one preferred embodiment of the present invention is illustrated in the drawings and diagrams included in this specification. More specifically, some preferred embodiments of the present invention generally provide for various pyrolysis oils from which valuable compounds can be extracted, such as FIGS. And 3 and disclosed.

  In that embodiment, two distillation columns are used; the first is atmospheric or slightly higher and the second is a violent vacuum. In addition, this treatment demonstrates the addition of a small amount of oxidant that does not contain new elements and that it is added only to the final purification step. Carbon chain length mercaptans in organic liquids downstream of the pyrolysis of rubber can be removed by the addition of oxidants, but the amount of oxidizer required is quite large and the specific oxidizer required is expensive. is there. Also, a significant amount of new material cannot be introduced without other negative consequences such as disposal costs or a reduction in the value of the remaining material. The above problem is easily addressed here by adding a small amount of a specific oxidant to a small volume stream containing terpenes and terpenoids.

General processing theory Catalyst / additive:
The addition of a catalyst to the thermal decomposition of rubber is optional. Some researchers argue that a catalyst is not necessary or even undesirable for the pyrolysis of rubber; other researchers argue that the entire group of materials can provide a catalytic effect. However, as the technology is scaled up to commercial scale and implementation is switched from “batch” to “continuous”, the catalytic effects observed in laboratory bench scale batch tests often disappear. The approach here is to produce the catalyst species in situ, i.e. change the relatively inert material to the optimum temperature and reactant conditions for the optimum temperature to utilize the catalyst. Due to the request. The optimal catalyst to achieve this is a Group 1 element such as sodium or potassium. The compounds that have the most ability to carry Group 1 elements to high temperatures are carbonates or bicarbonates. Therefore, for scrap rubber containing raw materials, potassium carbonate is the optimal material for bringing K + ions directly into the mixture and bringing the rubber and polymer and elastomer materials into close contact.

B. Reactor Design Full size commercial processing equipment can be “batch” or “continuous”. In any case, when the temperature reaches the point where the rubber melts, there is an additive that is a catalyst precursor, the additive is decomposed to release the catalyst species, and the organic vapor is the precursor. The reactor must be designed so as not to carry away additives or valuable carbon black. This is accomplished differently in continuous and batch systems.

  In a continuous system, feed materials such as scrap rubber and catalyst / additives are mixed and fed via a screw system. As the mass passes through the heated reactor, the temperature increases. The steam exhaust hole is located just beyond the point where the rubber melts and the additive is decomposed to yield the catalyst.

  In the batch system, the catalyst / additive is placed in a container on the rubber placed inside the reactor. As the temperature rises, the contents of the container are released and the contents are dispersed on the rubber, which reaches the melting temperature.

  In either a batch or continuous system, the additive is in contact with the molten rubber just as the additive is decomposed to release the Group 1 ions of the catalyst. However, this additive degradation adhesion occurs before the leaking organic vapor carries away the additive material.

C. Recovery / Purification Compounds that are distilled at very close temperatures can also be separated by working at different pressures. In this operation, two columns are used at two pressures, for example atmospheric pressure and a so-called “violent” vacuum. As the pressure in a column progresses above the column, it changes from high pressure to low pressure, and the pressure difference is achieved by an additional pressure drop in the distillation tray and / or packing. By using the concept of Joule-Thomson expansion between two columns, significant simplification and great improvement is achieved. This results in an abrupt change in pressure and immediate condensation of a small population of compounds present due to a temperature drop. In this way, small populations can be easily separated at a much reduced pressure, with much less work at once. Carbon chain length mercaptans in organic liquids downstream of the pyrolysis of rubber can be removed by the addition of oxidants, but the amount of oxidizer required is quite large and the specific oxidizer required is expensive. is there. A significant amount of new material cannot be introduced without other negative consequences such as disposal costs or a reduction in the value of the remaining material. The above problems are easily addressed here by adding a small amount of a specific oxidant, sodium or potassium percarbonate to a small volume stream containing terpenes and terpenoids. Sodium percarbonate is a major component of existing consumer products sold in large quantities.

Some Preferred Embodiments of the Invention Referring again to FIG. 1, one embodiment of the present invention is disclosed that provides continuous reactor process B.

  Finely chopped scrap material 1, such as automobile tires after being washed and dried, is supplied to a storage container 3 covered with nitrogen. The finely chopped scrap material 1 flows from a nitrogen-covered storage container 3 through a vacuum sealing valve 5 (also called a “double dump” valve), at which point additive / catalyst precursor is added. Added. The finely chopped scrap material 1 and additive / catalyst enter a tubular reactor 7 with a helical screw 9 that rotates slowly between about 0.2 and about 2.0 rpm, and the finely chopped material And the additive / catalyst precursor mixture is conveyed through the tubular reactor, which is a heated band 11, which is electrically heated.

  At about 15% of the length of the tubular reactor 7, the finely chopped material 1 reaches its melting point. The organic vapor 21 released from the molten finely chopped material 1 is drawn out from a first outlet 25 on the tubular reactor 7. The temperature continues to rise until the temperature of the shell near the outlet is about 450 degrees Celsius. The finely chopped material 1 continues to be decomposed / desulfurized, and as the finely chopped material travels toward the outlet end 13 of the tubular reactor 7, the organic material and the remaining moisture are the finely chopped material. Drawn from one solid. Here, the remainder of the organic material drawn from the finely chopped material 1 is pulled away through the vapor port 15 and the solid 19 is removed at the solid outlet 17. The solid 19, which is generally about 80 + wt% carbon black, goes elsewhere for further final processing and processing for sale. The organic vapor 21 enters the contactor / separator D where the initial condensation of the organic vapor occurs, in some embodiments, using a precooled liquid material oil spray. From this point in the process, the recovery process is the same in either a continuous system or a batch recovery system.

  Referring to FIG. 2, another embodiment of the present invention that provides a batch reactor process C is disclosed.

  Whole tires, in particular whole big, off-road and heavy equipment tires 27 are put into a large vacuum-sealed furnace 29. The vacuum sealing furnace 29 is evacuated using a vacuum pump 31. The heating of the sealing furnace 29 is started by operating the heating device 33. Of course, the heating device 33 may be either an electric heater or a suitable gas burner. Once a suitable low pressure of about 0.1 atmosphere is achieved, the pressure valve 35 operably connected to the vacuum pump 31 is closed and the pressure gauge is maintained to maintain the proper low pressure required for processing. 37 is monitored.

  When the furnace temperature reaches 200 degrees Celsius, the additive / catalyst located in the storage container 39 is released and distributed on the whole tire 27 in the furnace 29. When the pressure in the downstream system, particularly the spray tower 41 (FIG. 1) is reached, the release valve 41 (FIG. 2) is slowly opened. This allows the organic vapor 21 to flow to the contactor / separator D. The above operation is continued until no further organic vapor 21 flows towards the contactor / separator D, which is indicated by the decrease shown in the pressure gauge 37. Upon completion of the batch operation, the heating device 33 is turned off, the valves 35 and 41 are closed, and the furnace 29 is cooled. Once cooled, the remaining carbon black, ash and metal wires are collected and removed from the furnace 29.

Recovery and Purification The overall recovery of the valuable terpene material is achieved by charging the liquid oil, the result of which forms the batch or continuous work process described above. In this embodiment, contactor / separator system D (FIG. 3) is used for recovery and purification of the terpene material. In the recovery and purification process, the liquid oil enters the first distillation column 43 where the liquid oil travels downward due to gravity. A preferred internal component for the first distillation column 43 is a filter tray 45. In smaller systems having an inner diameter that is less than about 20 centimeters to less than about 30 centimeters, the filter tray 45 will be a Snyder type floating ball design. In larger columns having an inner diameter of about 2 centimeters to about 3 centimeters, the filter tray 45 is a bubble cap or “top hat” design rather than a sieve tray, but the sieve tray is still a larger column. May be used in the upper part of the. Regardless of which tray is employed, the vapor in the first distillation column 43 rises naturally, and the liquid falls due to the action of gravity. Heat is supplied to the first distillation column 43 by a reboiler 47, which is usually steam heating in larger systems and heated by electricity in smaller systems. In an integrated plant, waste heat from unrelated sources may also be used to provide the necessary heat. However, regardless of the heat source, the bottom 49 of the first distillation tube column 43 is approximately 200 degrees Celsius.

  The liquid material from the bottom 49 of the reboiler 47 is taken for sale and is close to the properties of crude oil which constitutes approximately 55% by volume of the liquid oil fed to the first distillation column 43. The residual vapor rising in the first distillation column 43 is a lighter material (shorter molecular chain or smaller molecular weight). The temperature near the top of the first distillation column 43 is about 185 degrees Celsius at 760 mmHg or 760 torr. Those residual vapors pass through the hole 53 where the vapor pressure is small, are reduced into the separator 57 and exit the top of the first distillation column 43 where the gas expands rapidly, so that they It is cooled by the Thomson effect, i.e., in an isolated state (so that there is no heat exchange with the surroundings), the change in gas or liquid when forced through a hole or porous plug. Eventually, the name is “throttling process” or Joule-Thomson process. As will be appreciated by those skilled in the art, the cooling of the condensable substance is rapid enough that the cooling causes part of the organic material of the residual vapor 51 to become liquid oil 55. A chiller assembly for lowering the temperature of the steam is provided for each distillation column 43 and 59. The liquid is richer in terpenes than vapor. The steam temperature will drop almost instantaneously or within about 1 second.

  The light liquid oil 55 from the separator 57 enters the second distillation column 59, the light liquid oil 55 passes partly quickly, and the remaining liquid oil 55 passes through a series of connecting pipes 61 by gravity. Go down. Preferred internal components 63 for the second distillation column 59 include sieve trays or structured packing. In smaller systems between about 1 centimeter and about 2 centimeters, the internal component 63 may be a tray or a Snyder type floating ball design. Heat can be supplied to the column by a second reboiler 65. In an integrated plant, if the bottom 67 of the second distillation column is about 100 degrees Celsius and ensures minimal decomposition of the terpene or terpenoid, to provide heat to the second distillation column 59 Waste heat may be used. The liquid material from the bottom of the second distillation column 59 is close to that of light crude oil. The light crude is then mixed with the bottom 49 of the first distillation column 45 and removed for sale. Auxiliary vacuum pump 71 and auxiliary liquid pump 73 are used to work overall or to evacuate the system.

  Of course, several streams or plugs 69 are removed from the second distillation column 59. Since the vapor rising in the second distillation column 59 is a light material (shorter molecular chain or smaller molecular weight), low boiling terpenes or terpenoids predominate in the upper internal component 63 of the second distillation column. It is. It is known that the top of the second distillation column 59 is generally about 85 degrees Celsius at 60 mmHg or 60 torr.

  The product mixture from the distillation process (FIG. 4) 73 may be irradiated by a broad spectrum ultraviolet lamp 75 that is fired by a voltage rising pulse. After 2 hours, 4 hours and 7 hours of exposure to UV light, a significant change in the relative concentration of terpenes and other valuable materials occurred and the appearance of product 80 was visibly dark. Sufficient cooling is required to remove excess heat from the irradiation chamber and an additional pump 79 may be required. Such excess heat carried away as the heated fluid 77 used elsewhere in the process is removed by the coolant 76 from the cooling system. Analysis by gas chromatography suggests that the concentration of some terpenes such as isopulegol has more than doubled, while other materials such as toluene can be reduced by more than 25%. This entire part of the process can be located within the distillation process.

  In the preceding description, numerous specific details are set forth, such as specific parts, devices, example methods, etc., in order to provide a thorough understanding of embodiments of the present disclosure. Those skilled in the art will appreciate that these specific details need not be employed and should not be construed to limit the scope of the present disclosure. In developing any actual implementation, a number of implementation specific decisions must be made to achieve the developer's specific objectives, such as meeting system-related and business-related constraints. Such development efforts may be complex and time consuming, but nonetheless are common tasks for those skilled in the design, fabrication, and manufacturing. The scope of the invention should be determined not by the examples shown, but by the appended claims and their legal equivalents.

  It can also be seen from the above description that a number of objectives of the present invention have been achieved and other advantageous and useful results have been achieved. Since various modifications in the above arrangement can be made without departing from the scope of the invention, all matter contained in the above description or shown in the accompanying drawings is to be understood as illustrative rather than limiting. Intended to be.

  For example, "proximate", "distal", "upper", "lower", "inner", "outer", "inwardly ) '', `` Outwardly '', `` exterior '', `` interior '' and the like are used herein to refer to each of the elements in which they are shown in the accompanying drawings. The above disclosure is not necessarily limited to such positions. Terms such as “first”, “second” and other numerical terms are used herein and do not imply continuity or order unless otherwise indicated by context. .

  When introducing elements or features and exemplary embodiments, the articles “a”, “an”, “the”, and “said” may include one or more It is intended to mean that there is such an element or feature. The terms “comprising”, “including”, and “having” are intended to be inclusive and include additional elements or features other than those specifically mentioned. Means that there may be. The method steps, processes, and operations described herein are to be construed as requiring them to be performed in the specific order discussed or described, unless the order of execution is specifically indicated. Should not. Of course, additional or alternative steps may be employed.

  It should also be understood that an element may be “operatively connected”, “connected”, “coupled” to and / or from other elements. ) "," Engaged "or" engageable ", it is directly connected to and / or connected to other elements and / or It may be interlocked and there may be intervening elements. On the other hand, an element is `` directly connected '', `` directly coupled '', `` directly engaged '', `` directly engageable '' with other elements ", There are no intervening elements. Other terms used to describe the relationship between elements should be construed in the same way (eg, “between” for “between” and “just next” for “adjacent” Such).

Claims (2)

A nitrogen-covered storage container for receiving finely chopped, washed and dried automobile tires;
At least one vacuum sealing valve;
A spiral screw that rotates slowly to generate a finely chopped automobile tire and additive / catalyst mixture that can flow from the nitrogen-clad storage container;
At least one heater for heating the mixture from ambient temperature to about 450 degrees Celsius;
Into the contactor / separator from the nitrogen-sealed vacuum sealed furnace for recovering either at least one terpene or one terpenoid from a mixture having either at least one material or steam A release valve for controlling the release of any of the at least one material and steam, wherein the contactor / separator is configured to remove the at least one material after the series of solids has been removed from the mixture or Pyrolysis steam can be generated from any of the steams, the contactor / separator for cooling the assembly to reduce the temperature of the pyrolysis oil, and for reheating and cooling the mixture A first heatable distillation column and a second heatable distillation column for separating the terpene type and the terpenoid type extracted from the mixture, During the serial first heatable distillation column and said second heatable distillation column, a small hole is arranged to be working, a release valve;
For transporting the liquid and vapor products produced, transferred, recovered or purified by a device for pyrolysis of tires to form a pyrolysis oil comprising limonene and plegon A piping system;
An apparatus for pyrolysis of tires to form a pyrolysis oil containing limonene and plegon containing A nitrogen-sealed vacuum-sealed furnace for receiving automobile tires;
A heater for heating the nitrogen-covered furnace to at least about 200 degrees Celsius;
A vacuum pump for generating a vacuum in the vacuum-sealed furnace covered with nitrogen;
An additive / catalyst placed in the nitrogen-sealed vacuum-sealed furnace to be dispersed on the automobile tire;
Into the contactor / separator from the nitrogen-sealed vacuum sealed furnace for recovering either at least one terpene or one terpenoid from a mixture having either at least one material or steam A release valve for controlling the release of any of the at least one material and steam, wherein the contactor / separator is configured to remove the at least one material after the series of solids has been removed from the mixture or Pyrolysis steam can be generated from any of the steams, the contactor / separator for cooling the assembly to reduce the temperature of the pyrolysis oil, and for reheating and cooling the mixture A first heatable distillation column and a second heatable distillation column for separating the terpene type and the terpenoid type extracted from the mixture, During the serial first heatable distillation column and said second heatable distillation column, a small hole is arranged to be working, a release valve;
For transporting the liquid and vapor products produced, transferred, recovered or purified by a device for pyrolysis of tires to form a pyrolysis oil comprising limonene and plegon A piping system;
An apparatus for pyrolysis of tires to form a pyrolysis oil containing limonene and plegon containing

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