PL210883B1 - Reactor for continuous processing of organic wastes, preferably the polymer wastes and method of processing them - Google Patents

Description

(12) PATENT DESCRIPTION (19) PL (11) 210883 (13) B1 (21) Application number: 384806 ^{(51) Int.Cl.}

F23G 5/00 (2006.01) F23G 7/12 (2006.01) B09B 3/00 (2006.01) (22) _{Filing date: 03/28/2008 B01J 19/18 (2006.01)}

A reactor for the continuous processing of organic waste, especially polymer waste, and the method of its treatment

(73) The right holder of the patent: (43) Application was announced: UNIVERSITY OF TECHNOLOGY OF LODZ, Łódź, PL 12.10.2009 BUP 21/09 (72) Inventor (s): MAREK STELMACHOWSKI, Łódź, PL (45) The grant of the patent was announced: 30.03.2012 WUP 03/12 (74) Representative: item. stalemate. Jolanta Dziubińska

PL 210 883 B1

Description of the invention

The subject of the invention is a reactor for continuous processing of organic waste, in particular polymer waste, and a method of its processing, intended in particular for the processing of polyolefins and rubber. The processed waste does not have to be shredded.

Many methods of processing plastic and rubber waste are known. The direction of plastic waste processing based on the use of them for the production of the starting monomers has the least defects and is the most economically and ecologically advantageous. For polyolefins and rubber, the most preferred methods are those that allow, as a result of the decomposition processes, to obtain a mixture of hydrocarbons with a chain length from C1 to C24, in which the C4 to C24 fraction should constitute the largest part, because it can be used for the production of motor fuels.

Among the various chemical and thermal methods of utilization of polymers and other organic wastes, several methods of their thermal decomposition in or on the surface of an inorganic molten medium that do not participate in the reaction are also known. These methods can lead to:

Complete annihilation of waste. They take place at high temperature (above 1000 ° C) on the surface of the molten metal (e.g. iron) with the participation of oxygen and water vapor to form useful hydrogen and a by-product which is CO2. An example is the decomposition technology called Hydromax Technology® by Alchemix Corporation (US patent 6227126, JP 2000 - 615717). The methods proposed in these solutions are very expensive and technologically difficult due to the high temperature of the process (1300 ° C). Complete destruction of the waste as a result of its oxidation with the formation of simple inorganic compounds such as CO2, H2O, NOx, etc. The process takes place in molten salts of NaCl / Na2CO3 and is known as MSO (molten salt oxidation). There are also patents related to this method (JP application 2000-48602) and commercial technologies (e.g. from Rockwell International Corporation). The process is usually recommended for the disposal of hazardous waste. This method is covered by a patent application for a process operating in a molten liquor environment (NaOH / KOH) (application WO98-EP3566). These methods only lead to the utilization of waste without the recovery of the energy and raw materials contained in it. Moreover, this method is expensive. To obtain a mixture of hydrocarbons or monomers resulting from the decomposition of organic waste or polymers in the volume of a molten metal (such as lead) or on its surface at a temperature of 350-550 ° C. This technology is, for example, described in patent application EP 90401093. It is based on a process sometimes referred to as "Clementi Process."

In the 1920s and 1940s, a method for liquefying hard coal and some organic waste was developed based on the "Clementi Process" (US patents 1709370, 1601777, 2459550). During World War II, a method of monomer recovery by decomposing polymethyl methacrylate on the surface of molten lead was also developed (Spanish patent 192909, Domingo, Cabanero, 1949). This method has never found wide industrial application. The next methods were min. the American method indicated in the patent "Method and Apparatus for thermal conversion of organic master US 342056 and in the application EP 90401093 and the Polish method indicated in the patent application No. P358773" The method of continuous processing of organic waste, especially highly contaminated plastic waste and used car and other tires motor vehicles and a device for continuous processing of organic waste, in particular car tires Known methods of utilization of polymers and other organic wastes in liquid metal are carried out in tub reactors, in which wastes move in a molten medium on belt or chain conveyors in a horizontal system. The conveyor belt is immersed in molten metal. When the conveyor belt is moved, the waste is melted, and the undissolved and not decomposed solids are carried out of the tub by the conveyor.

The reactor for continuous processing of organic waste is in the form of a vertical tubular reactor of any shape of pipes and tube cross sections, positioned vertically and / or obliquely, placed in the heating jacket, and has a flow system between the pipes in the form of at least one overflow opening or a gap between the inner tube transport and injection of waste through the external pipe of the outflow of molten waste and solids. The reactor has a waste loading port and its feeder to the inner tube, in which the device transporting organic waste downwards is in the form of a piston or a screw conveyor with cutting edges, as well as the reactor has pollution removal ports and a control and measurement system - gas phase, molten metal and the heating medium.

PL 210 883 B1

The reactor according to the invention is in the form of a tube-in-tube arrangement with an inner tube having any edge end and has a flow system between the tubes in the form of through holes on the inner tube arranged in a spiral or honeycomb arrangement.

The reactor according to the invention may be in the form of a V-tube reactor, which has a dosing pipe arranged at an angle to the discharge pipe - an outer form placed vertically, and has a flow system between the pipes in at least one transverse pipe with an orifice.

The reactor according to the invention has a vertical tubular reactor system in the form of a 2-R system, in which the external pipe is divided by a partition with a gap between the pipes forming a flow system.

In the method of processing organic waste according to the invention, organic plastic waste is forced into a dosing pipe (e.g. internal or oblique) in a vertical direction from top to bottom into a column of liquid molten medium, where it is melted downwards and partially decomposed. part of the molten medium and unmelted waste flows through the overflow system to the outer tube, while the remaining parts of the charge move to the end of the inner tube and flow to the other tube, from where they flow freely to the surface of the molten medium undergoing further decomposition, the cracked products in the form of steam they flow into the system of coolers operating at different temperatures and condensing fractions of liquid decomposition products, the first cooler acting as a reflux condenser captures the insufficiently decomposed parts of the polymer in the form of hydrocarbons with high molar mass, the second cooler condenses hydrocarbons for a long time chain from C4 to C24, and in the third section of the coolers, the lightest fractions of hydrocarbons that have not condensed in the previous coolers are condensed, so that the exhaust gas stream contains only non-condensing gases and hydrocarbons with a partial pressure lower than that of their saturated vapor at the temperature of the last cooler.

The essence of the method according to the invention is to change the direction of movement of the waste feed during the introduction to the reactor and the waste flow in relation to the known solutions from horizontal to vertical and to extend their decomposition path. This eliminates the need for moving belts, rotating rollers and bearings that will corrode quickly in the molten metal.

In one embodiment according to the invention, the process takes place in the volume of a tall column of molten metal or other inorganic medium, at a temperature of 300 to 450 ° C under atmospheric pressure, and on its surface. The height of the column of the molten medium and the rate of feeding the waste depends on the type of waste. The molten medium in which the decomposition of plastics is carried out may be an alloy of tin, lead and possibly bismuth in any proportions, but with a predominance of more than 50% lead or pure lead. They can also be molten inorganic salts or metal hydroxides of the first or second group of the periodic table or mixtures thereof.

In the method according to the invention, waste polymers are processed without the need to crush them, irrespective of the type of waste, and this method is used for the thermal degradation of plastics, preferably polyolefins or rubber.

In the method according to the invention, the height of the column of the molten metal or other inorganic medium, and therefore the residence time of the materials and the resulting feed rate, depend on the type of waste.

Loading of polymer waste to the loading port can be done manually or automatically by means of a piston. From the loading port, it is introduced into the liquid metal through a feeder, which may be a piston moved by a press or an electric motor with a gear motor and an inverter. The introduction of polymer waste into the molten medium can be carried out by means of a screw conveyor, in particular having cutting edges. During the movement of waste in the molten medium, the process of partial melting and cracking takes place. The molten and partially degraded raw material in the molten metal may exit through the at least one cross tube, bore or slot into the outer tube or is pushed out at the end of the tube. Then, it is lifted by buoyancy forces to the surface of the molten metal, further decomposing into a mixture of C1-C24 hydrocarbons with a predominance of C4-C16 fractions. The decomposition products that are in the vapor phase under the reaction conditions flow out of the reactor.

The method according to the invention is carried out by means of an installation containing devices for generating a heat carrier stream, a waste feeder, a loading port of an inert melt reactor.

With an inorganic medium, a reflux condenser, a product cooler system, a control and measurement system, as well as product collectors and storage tanks.

The source of technological heat is a generator of gases produced from biomass, e.g. sawdust, wood chips, bark, energy willow, dewatered sewage sludge or other organic waste constituting a source of low-value and difficult to use energy.

The vertical pipe-in-pipe reactor used according to the invention has an inner (dosing) pipe with overflow (through) openings connecting the spaces of the inner and outer pipes, which allow the flow of liquid metal (during the injection of raw material) from the inter-pipe space to the inner pipe and they also allow the gaseous decomposition product to flow from the inner tube into the inter- tube space. Two to eight openings in the case of the reactor in a vertical arrangement (preferably four) are arranged along the tube under the cover preferably in a spiral or honeycomb arrangement. The lower end of the inner tube can be cut perpendicular to the axis or obliquely or double obliquely which allows easier flow of the partially unfolded charge from the inner tube into the outer tube.

The reactor according to the invention can form a tube-in-tube arrangement in a vertical configuration, the inner (dosing) tube with any end of the bottom edge having a flow system to the outflow (outer) tube in the form of through holes on the inner tube arranged in a spiral or in a honeycomb arrangement.

In the case of a "V-tube" reactor, with pipes arranged obliquely to each other, the role of flow openings between the dosing and discharge pipes is played by at least one pipe connection between the feedstock feed pipe and the cracking product discharge pipe. Instead of one pipe, connections can be made with two pipes, the flow of the molten metal takes place with one pipe, and the vapor phase flows through the other one located above the surface of the molten metal. In the case of a single pipe connection, the pipe cross-section must not be completely filled with molten metal to allow the flow of the gaseous fraction.

The reactor according to the invention comprises a system in which the dosing pipe (corresponding to the inner pipe in the pipe-in-pipe arrangement) is placed at an angle to the vertical discharge pipe (outer) and has a flow system in the form of at least one transverse pipe between the pipes.

In the case of the "2-R" reactor, the pipes arranged parallel to each other, the parallel dosing and discharge pipes are connected by a gap or a series of openings also allowing the media to flow between the pipes. In this reactor, a system of vertical parallel pipes (with different cross-sections) was divided by a partition with a slot or openings forming the media flow system between the pipes, and the reactor was divided into an outflow pipe (corresponding to the outer pipe) and a dosing pipe (corresponding to the inner pipe).

The elements of the reactor in contact with molten metal are made of acid-resistant and heat-resistant steel, and resistant to electrolytic corrosion in contact with molten tin. The walls of the heating mantle are made of heat-resistant steel. The remaining elements of the reactor's devices are made of acid-resistant steel. The walls of the heating mantle are insulated from the outside with ceramic materials or other insulating materials with high temperature resistance, e.g. fabrics made of glass fiber resistant to high temperatures.

The cross-sections of the reactor tubes can be any, for example - oval, circular, rectangular, elliptical.

The installation for the implementation of the invention may constitute a series of integrated versions of reactors and auxiliary devices, set up depending on the type and type of waste processed into modules with a specific capacity, controlled by a simple control and measurement system. The modularity of the construction and the interchangeability of devices allows for the compilation of individual elements of the installation depending on the type of waste and the size of the stream of processed waste.

In the case of cracking of waste containing non-meltable solid waste, it is periodically removed while the feed of the raw material through the port to which the steam injector is connected is turned off.

During the degradation of the rubbers of the main component of tires, a minimum amount of sulfur is transferred to the liquid product, which in turn can form gaseous products, non-condensing sulfur compounds. The non-liquefied gaseous product must be desulfurized prior to discharge for combustion or the gaseous stream after combustion.

PL 210 883 B1

When using the "2-R" type reactor, the top section for the reactor version for processing whole tires - the tire conveyor moves in 2 planes: vertical - tire immersion and horizontal - tire shift from the dosing tube to the discharge tube (from position X to position Y. Bottom section for processing other waste The tube-in-tube dosing system (2) is the same as the tube-in-tube reactor, and the waste conveyor is a screw conveyor.

The solution according to the invention makes it possible to carry out the process of melting waste and cracking in one device, the whole process is faster, does not require a catalyst, mixing and grinding. The solution according to the invention, thanks to the simplified structure of the device, is less emergency.

The solution according to the invention is shown in the non-limiting drawings. Fig. 1 shows a longitudinal sectional view of a tube-in-tube reactor, Fig. 2 shows a longitudinal section of a V-tube reactor, Fig. 3 shows a longitudinal and cross section of a baffle reactor, 4, longitudinal and cross-section of a reactor with two parallel pipes, FIG. 5, a technological diagram of a plant for continuous thermal degradation of waste polymers in a liquid-metal pipe-in-pipe reactor, where (31) means a reactor, (32) a heating jacket, (33) pumps, (34) reflux condenser (35) trap type cooler, (36) aftercooler, (37) end product tank, (38) circulating water buffer tank, (39) apparatus venting gas scrubber, (40) process control computer, (41) biomass gasifier and furnace, (A) waste polymer raw material stream, (B) product vapor stream, (C) primary liquid product stream, (D) downstream liquid product stream, E product gas stream ( non-condensing) for combustion ania, (F) exhaust gas stream from venting, (G) pollutant stream from waste after degradation, (H) biomass stream for gasification, (I) cooling water supplement, (J) cooling water drain, (K) final product stream (L) drain the contents of the scrubber.

P r z k ł a d 1

The polymer, not comminuted in the form of polyolefin waste, is introduced into the reactor (31) through the loading port (3) manually or automatically and goes to the dosing pipe (internal). There, with a low linear velocity, it is introduced into the liquid metal through the feeder (4). This feeder can be a piston moved by a press or by an electric motor with a gear motor and an inverter. The transmission of rotary motion into sliding motion is achieved by a mechanical transmission, preferably toothed gear of any type. When the charge is shifted in the metering tube (2) internal for the tube-in-tube reactor, it melts at a temperature of 370 - 420 ° C and then cracks. The molten and partially decomposed raw material flows to the outer tube of the reactor (1), and then, discharged by buoyancy forces, flows onto the surface of the molten metal. During outflow and on the surface, it further decomposes into a mixture of C1-C24 hydrocarbons, with a predominance of C4 to C10 fractions. The product of decomposition of polymers in the vapor phase flows from the reactor through the port (5) to the system of three types of coolers, carrying out various tasks at different temperatures. The first condenser operating as a reflux condenser (34) is designed to return undecomposed hydrocarbon polymers of high molar mass to the reactor. In the second trap cooler section (35) the main part of the liquid product condenses. These coolers enable the safe condensation of light wax fractions (C16-C24) without the risk of clogging of the coolers. The third section of coolers (36) enables the lightest fractions to be condensed at the lowest temperature in order to trap as much of the light hydrocarbons as possible.

The tube-in-tube reactor in vertical arrangement has an inner tube (2) with overflow holes (18) connecting the spaces of the inner and outer tubes, which allow liquid metal to flow (during the injection of raw material) from the inter-tube space to the inner tube and also allow flow gaseous decomposition product from the inner tube to the inter-tube space. Two to eight openings in the case of the reactor in a vertical arrangement (preferably four) are arranged along the tube under the cover preferably in a spiral or honeycomb arrangement. This is shown in Figure 1.

The reactor (31) has a temperature control system for the vapor phase flowing out of the reactor, liquid metal, and the heating medium in the heating mantle. Measurements are made with K-type thermocouples (or other) connected to the data acquisition card, converting the analog signal into a digital signal transferred to a computer with a data acquisition program. The collected temperature data is used to control the heat flux supplied to the reactor by regulating the size of the heating flux. This control can be done manually as a result of data analysis

On a monitor screen, or automatically by coupling temperature input data with output data.

The heating medium supplied through the stub pipe (15) to the reactor and the drained pipe stub (17) may be a stream of flue gases (4) from the biomass gasification process (e.g. sawdust, bark) and then biogas combustion. Biogas resulting from biomass gasification is supplemented with a stream of gaseous decomposition products. When the device is operated in a refinery, the heat flux may be produced from the combustion of gaseous decomposition products and waste hydrocarbon streams usually burned in refinery flares (instead of biomass gasification).

P r z k ł a d 2

When using the method according to the invention, using the "V-tube" reactor, the process is the same as in the "tube-in-tube" reactor, except that the feed is dosed in the oblique tube (2) to the tube (1). It also has a feeder, either in the form of a piston or in the form of a screw conveyor, and a discharge pipe (1) for the cracking products from the reactor. Between the product discharge pipe (1) and the raw material dosing pipe (2) in their upper part there is a pipe connection (18) serving the same function as the overflow openings in the reactor from example 1 - i.e. serving as a flow opening. In a V-tube reactor, the entirety of automotive tires can be processed, then the cross-section of each tube can be rectangular corresponding to the maximum dimensions of the tires processed. Sliding tires are a piston from top to bottom into the molten metal in a metering tube at a speed proportional to the weight of the tires. Then, the decomposition products, the undecomposed rubber fragments and the remnants of the non-degradable components of the tires move to the second tube and float to the surface. Steam products leave through the product receiving port. The elemental carbon (soot) and other components, such as zinc oxide, are discharged through a port connected to the steam injector. The steel cord is removed by an independent port with a cyclically working scraper.

P r z k ł a d 3

In a reactor with two parallel tubes "2-R, one of the tubes corresponds to the dosing tube (2) in the" tube in tube "or diagonal tube (2) reactor in the" V-tube "reactor and the other to the discharge tube (1). Both pipes are placed vertically - parallel to each other and placed in the heating jacket (14). By following the process of the invention, using a "2-R" type reactor, the process is carried out in the same manner as in a tube-in-tube or V-tube reactor.

For the processing of tires as a whole, the cross-sections of the tubes correspond approximately to the shape of vertically traveling tires. The conveyor is a piston with a catch for transporting tires. The pipes are separated by a partition (6) with a slot (18) which acts as overflow holes from the reactor from example 1 located along the entire height of the partition - allowing the free flow of molten medium and products from one pipe to another. The baffle (6) does not reach the bottom of the reactor but ends at a height greater than the diameter of the tire. The feeder moves in two vertical planes - submerging tires and horizontal - moving the tire from the dosing tube to the discharge tube (from position X to position Y). Polymer decomposition products, non-decomposed rubber fragments and residues of non-degradable tire components transferred to the second tube (1) float to the surface. Steam products leave through the product receiving port (5). The elemental carbon (soot) and other components, e.g. zinc oxide, are discharged through a port connected to the steam injector. The steel cord is removed by an independent port with a cyclically working scraper.

P r z k ł a d 4

For the processing of polyolefin waste in the "2-R version" reactor, the most advantageous pipe cross-section is the circular cross-section. One of the tubes corresponds to the dosing tube (2) and the other to the discharge tube (1). Both pipes are placed vertically, parallel to each other and placed in the heating jacket (14). By following the process of the invention, using a "2-R" type reactor, the process is carried out in the same manner as in a tube-in-tube or V-tube reactor. The conveyor placed in the pipe is a piston or a screw conveyor (4). The baffle (6) separating the tubes also has overflow openings (18) in the upper part of the reactor - between the parallel tubes, which have the same function as the overflow openings in the reactor of example 1.

Claims (6)

Patent claims 1.Reactor for continuous processing of waste containing a liquid medium, waste loading port, product receiving port, screw conveyor, characterized by being in the form of a vertical A tubular reactor, with any shape of pipes and cross-sections of pipes, arranged vertically and / or obliquely, placed in the heating jacket, and has a flow system between the pipes in the form of at least one overflow opening or a gap (18) between the inner pipe (2 ) transport and injection of waste through the outer pipe (1) of the outflow of molten waste and solids, and the reactor has a waste loading port (3) and their feeder (4) to the inner pipe (2), in which the device (4) transports organic waste downwards , is in the form of a piston or a screw conveyor with cutting edges, as well as the reactor has a port (11) for removing impurities and a control and measurement system - gas phase, molten metal and heating medium. 2. The reactor according to claim The method of claim 1, characterized in that it is in the form of a tube-in-tube arrangement with an inner tube (2) having any edge end and has a flow system between the tubes in the form of through holes (18) on the inner tube (2) arranged in a spiral or in a plaster arrangement honey. 3. The reactor according to claim The process of claim 1, characterized in that it is in the form of a V-tube reactor, which has a dosing pipe (2) placed at an angle with respect to the outflow pipe - external (1) placed vertically, and has a flow system in the form of at least one pipe between the pipes. cross tube with an opening (18). 4. The reactor according to claim 1 The method of claim 1, characterized in that the vertical tubular reactor system is in the form of a 2-R system in which the outer tube is separated by a partition (6) with a gap between the tubes (18) forming a flow system and dividing the tube into an outer discharge tube (1) and inner tube - dosing (2). 5. The reactor according to claim 1 The system of claim 1, characterized in that the vertical tubular reactor system in the 2-R system has an outer discharge pipe (1) placed parallel to the inner dosing pipe (2) and between the pipes there is a partition (6) with a slot or openings (18) constituting a system the flow of molten metal, molten and gaseous decomposition products and unmelted parts of organic waste. 6. A method of processing organic waste, especially polymer waste in a molten medium, by cracking, at a melting point of 300 to 450 ° C under atmospheric pressure, characterized in that the organic waste is forced into the inner tube - dosing (2) vertically, from above on down to the column of liquid molten medium, where they melt and partially decompose as they move downwards, part of the molten medium and unmelted waste flows through the overflow system (18) into the outer tube (1), while the remaining parts of the charge move to the end of the inner tube (2 ) then flow out to the outer pipe (2), from where they flow freely to the surface of the molten medium, undergoing further decomposition, while the cracking products in the form of steam flow to the system of coolers operating at different temperatures and condensing fractions of liquid decomposition products, the first The cooler, acting as a reflux condenser, captures the dissipation insufficiently Complex parts of the polymer in the form of hydrocarbons with high molar masses, in the second cooler, hydrocarbons with a chain length of C4 to C24 condense, and in the third section of the coolers, the lightest fractions of hydrocarbons that have not condensed in the previous coolers are condensed, so that the exhaust gas stream contains only gases non-condensing and hydrocarbons having a partial pressure lower than their saturated vapor pressure at the temperature of the last cooler.