WO2018216031A1 - System for re-conversion of plastics into different petro chemicals and method thereof - Google Patents

Abstract

Disclosed is a system (100) and method (200) for re-conversion of plastics into different petrochemical liquids and gaseous hydrocarbons. The system (100) mainly comprises of a reactor (22), a burning chamber (23), a feeding unit and a gas collection and cooling unit. The plastic material in granular form along with 2% manganese sulfate as a catalyst is loaded into the reactor (22) along with a catalyst and heated to first de-polymerize and then form a gaseous mixture of petrochemical compounds. The reactor (22) is insulated in such a way that the de-polymerization takes place in absence of oxygen thereby producing a peculiar quality of mixture of petrochemical liquids along with hydrocarbon gases. The petrochemical liquid obtained in the process is used as fuel and fuel additive. The system is preferably used for plastics not containing oxygen or chlorine in their molecular structure.

Description

SYSTEM FOR RE-CONVERSION OF PLASTICS INTO DIFFERENT PETRO CHEMICALS AND METHOD THEREOF

Field of the invention The present invention generally relates to recycling process of waste plastic material, and in particular it relates to a system and process for de-polymerization of plastic into its original form of petro chemicals.

Background of the invention

The today's world is producing and consuming huge quantities in millions of tons of different types of polymers made from petro products popularly known as plastics due to various advantages. These plastics after effective use being inert in nature do not degrade even after 25 years when left in nature. This un-degraded plastic finds way into nature threatening the eco balance and thus is a danger to almost all animals in one or the other way including aquatic flora. Various processes are developed for usage of waste as well as end of life plastics all over the world and are in use for almost all types of plastics to be converted into liquids which are used for burning purposes.

Hence, there is a need to provide a system and process for conversion of plastics in its original form of petro chemicals and thus overcomes the above mentioned drawbacks of the prior art.

Objects of the invention

An object of the present invention is to produce better quality petro chemicals by way of de -polymerization of waste plastics in a continuous or by semi-continuous batch process. Another object of the present invention is to utilize the waste plastic to produce petrochemicals and gases to fulfill various energy needs and reduce the nuisance of plastic waste. Yet another object of the present invention is to produce good quality fuel having high calorific value.

Still another object of the present invention is to produce fuel additives to alter the quality of the diesel/petrol being used as a fuel in various engines in such a way that enhances the performance of the engine. Summary of the invention

The present invention discloses a system and method for re-conversion of plastics into different petrochemical liquids and gaseous hydrocarbons. The system mainly comprises of a reactor, a feeding unit and a gas collection and cooling unit. The plastic material in granular form or similar form of small pieces to enable smoother loading in the reactor) is loaded into the reactor along with a catalyst, through the feeding unit. The catalyst used in the process is preferably a manganese sulfate catalyst which is recoverable and stable up to 800^eC temperature. The feeding unit is designed in such a way that its temperature is always maintained below 50^eC, so as to avoid pre melting of plastic material and chocking of pipe holding the material. Plastic material is heated in the reactor in energy efficient way. Half cut fire tubes surrounding the reactor permit the longer passage of exhaust gases through them, thereby facilitating an efficient heat energy transfer for breaking of hydrocarbon molecules. The plastic material is heated to de-polymerize and form a gaseous mixture of petrochemical compound. The reactor is fitted with a delivery pipe for carrying the gaseous mixture of petroleum products to the gas condensation unit. The delivery pipe has height greater than the reactor. The gaseous mixture of petroleum products containing heavy and lightweight polymer particles rises through the delivery pipe, wherein heavy polymer particles settle back in the reactor and lightweight polymer particles remain in the gaseous mixture which is then collected in a seal box by downward displacement of liquid therein. When the reactor charged with plastic material is heated, the inside air and water vapors are escaped out through the seal box thereby diluting the oxygen concentration inside the reactor and facilitating the de-polymerization of plastic material. The gaseous mixture rising to the top of the delivery pipe and passing through the seal box creates a positive pressure inside the reactor thereby producing a peculiar quality of combination of petrochemical liquids along with all hydrocarbon gases (CI to C4). The gaseous mixture of petrochemicals is cooled and the condensed liquid is separated from uncondensed gas. The uncondensed hydrocarbon gases are consumed for heating the reactor whereas the petrochemical liquid is used as a fuel or fuel additive.

Brief description of the drawings

The objects and advantages of the present invention will become apparent when the disclosure is read in conjunction with the following figures, wherein Figure 1 shows a system for converting plastic into different petrochemicals, in accordance with the present invention;

Figure 2 shows a horizontal cross sectional view of a reactor of the system for converting plastic into different petrochemicals, in accordance with the present invention; Figure 3 shows a vertical cross sectional view of the reactor of the system for converting plastic into different petrochemicals, in accordance with the present invention;

Figure 4 shows a flowchart illustrating a process of converting plastic into different petrochemicals, in accordance with the present invention; Figure 5 shows a laboratory scale system for converting plastic into different petrochemicals in accordance with the present invention; and

Figure 6 to Figure 12 show the FT-IR spectra of various standard and experimental samples. All the spectra are explained separately in the detailed description. Detailed description of the invention The foregoing objects of the present invention are accomplished and the problems and shortcomings associated with the prior art, techniques and approaches are overcome by the present invention as described below in the preferred embodiment.

The present invention provides a system for converting plastics into liquid petro chemicals, methane and other hydrocarbon gases, and a method thereof. These liquids find application in adding to conventional diesels and other fuels used in internal combustion engines for increase of their performance. The system of present invention is a self containing system for producing petrochemical liquid and gaseous hydrocarbons from a plastic material that does not contain oxygen or chlorine in its molecular formula. When the plastic contains oxygen or chlorine, it is treated for removal of oxygen or chlorine after de-polymerization process using known methods of the existing art and then it is used in the system for producing petrochemical liquid and gaseous hydrocarbons. The plastic, in the present invention, is mixed with 1% to 10% w/w of manganese sulfate catalyst and the mixture heated in a reactor without exposing it to outside air or oxygen to produce a gaseous mixture of petroleum products. The reactor is fitted with a delivery pipe for carrying the gaseous mixture of petroleum products to the gas condensation unit. The delivery pipe has height greater than the reactor. The gaseous mixture of petroleum products containing heavy and lightweight petroleum products along with polymer particles rises through the delivery pipe, wherein heavy polymer particles settle back in the reactor and lightweight polymer particles remain in the gaseous mixture. The gaseous mixture is condensed to give a mixture of uncondensed hydrocarbon gas and petrochemical liquid. Uncondensed hydrocarbon gas is consumed as fuel for burning the plastic material while the petrochemical liquid is used as fuel or fuel additive in the vehicle.

In another aspect, the invention provides a method for re-converting the plastic bags and other similar plastic items found in the municipal waste into petrochemical liquids. The present invention is illustrated with reference to the accompanying drawings, throughout which reference numbers indicate corresponding parts in the various figures. These reference numbers are shown in bracket in the following description. The major components of the system (100) along with various other components are listed in the Table I below:

Table I

Referring to figures 1 - 4, a system (100) and process (200) of re-conversion of plastics into different petro chemicals, in accordance with the present invention is shown. The process (200) is both continuous as well as semi continuous commercial process. Specifically, the process (200) is for conversion of various petroleum based polymers like polyethylene (PE), cross linked polyethylene (XLPE), polypropylene (PP), polystyrene (PS) and host of other similar polymers popularly known as the plastics into light, medium and heavy liquids and gaseous hydro carbons of different properties in presence of different catalysts.

The catalysts suitable for the process are mixed in either solo or two or more of them (up to five) in any proportion. The catalysts include but not limited to Manganese Sulfate, Manganese chloride, Sodium Acetate, Ammonium Acetate, Sodium Formate, Ammonium Formate, Sodium Propionate, Magnesium chloride, Calcium chloride, Sodium chloride, Ammonium chloride, Sodium Sulfate, Ammonium Sulfate, Magnesium Sulfate, Calcium Sulfate, Sodium phosphate, Ammonium phosphate, Magnesium phosphate, Manganese phosphate, Calcium phosphate, Sodium butyrate, Hydrogen Borate, Carbon(Graphite) Among the above list, Manganese sulfate was found to be the most effective catalyst for converting the plastic waste into petrochemical liquids of superior quality. Manganese sulfate in a crystal form is stable up to the temperature of 800^eC. As such, it can be used continuously over a broad temperature range. In an embodiment, quantity of manganese sulfate crystals mixed with the raw material ranges from 1% to 10% w/w, preferably from 2% to 5% w/w and most preferably 2% w/w.

Figure 1 shows a system (100) for converting various petroleum based polymers into light, medium and heavy liquids and gaseous hydro carbons of different properties in presence of different catalysts. The system (100) includes a reactor with arrangements for gas burning, insulation and jacket, feeding unit and a gas collection and cooling unit as major components.

The reactor (22) is mounted on a trolley to facilitate the movement. Below the reactor (22), in the burning chamber (23), are two burners: main burner (1A) and standby burner (IB). While the main burner (1A) provides the heat energy required from external source by burning of either CNG or LPG, the standby burner (IB) utilizes the gases generated from the process (200) achieving two purposes the requirement of energy from external source is eliminated or reduced and the probable pollution from various flue gases generated in the depolymerization process is avoided, as these gases are burned in the burning chamber (23) at a temperature above 800°C. It also possible to use liquid fuels by simply modifying the burner and associated fuel handling system. This fuel can also be the liquid derived from the earlier process instead of gaseous fuels like CNG or LPG.

While burning chamber (23) has small holes on the outer cover to facilitate the passage of air required for fuel burning, additional compressor and air- gas or air liquid fuel control system along with temperature indicator and manual control or electronic controller, electrical proportionate controllers/actuators can be used (not shown) for controlling the process parameters by controlling the temperature. On top of the reactor (22) is provided with a inlet port (21) and high temperature gasket for ease of reactor opening for maintenance. The loading system comprises of two valves (6a, 6b) with a holding tube in between them to hold the raw material.

First, the hopper (7) is filled with raw material in the granular form mixed with catalyst by keeping both the valves (6a, 6b) closed. The raw material is fed by opening top valve (6a) first and allowing the material to fall in the central tube. The top valve (6a) is closed and bottom valve (6b) is opened so that the material is delivered in the reactor (22) without exposing the reactor (22) to outside environment and reactor temperature completely. (This feeding process is not required for the first time the plant is being started as is at room temperature.) The entire system of loading raw material is kept cool by means of a cooling jacket (5) and copper pipes surrounding valves. This arrangement helps the loading of raw material for second batch after completion of first batch or can be used to load the raw material even during the progress of batch without disturbing the process. The cooling system provides two functions: 1. Protection of valves (6a, 6b) as they are directly connected to reactor (22) by means of flange (21) hence these valves may be subjected to around 400°C (or more depending on process settings) during the operation of plant. By using the cooling system these valves are never exposed beyond 50°C. This allows us to use even ordinary ball valves eliminating the use of costly high temperature valves. 2. As the entire feeding system temperature is kept below 50°C by means of cooling system, the raw material does not melt in the holding pipe or even inside the valves (6a, 6b) during the feeding due to which chocking of pipes and valves is avoided in subsequent batches.

Fig.2 shows the cross section of the reactor (22) and Fig. 3 shows the constructional details for the same. A special construction of half cut inclined fire tubes (19) welded to the shell permits the flue gases to pass through them for slightly longer time for better transfer of energy and higher temperature on top side of the reactor which facilitates the higher rate of breaking of hydrocarbon molecules to much smaller size. Outer cover for the tubes facilitates the collection of exhaust gases and releasing them away from the plant. This allows the heat transfer more efficiently and raises the reactor temperature faster. The reactor (22) is covered by fibrous reactor insulation (16) of glass wool which is finally jacketed by means of reactor outer jacket (15) of steel sheets to prevent loss of heat and damage to insulation. The insulation (16) and the outer jacket (15) provide better energy management and reduction of losses and protection to the operators due to near ambient temperature of reactor outer jacket skin. An exhaust gas collection box (20) collects the flue gases and delivers them to a delivery pipe (8).

The delivery pipe (8) which is having height of at least 300 mm more than the height of reactor (22) is connected to a primary seal box (10). The primary seal box (10) is filled up to over flow level with fresh water (for first batch) or liquid derived from the process (for subsequent batches) at the start of every batch i.e. every time the raw material is loaded in reactor (22) and during the process. Once the mixture is filled to desired capacity i.e. up to 80-90% (V/V) of reactor capacity both the valves (6a, 6b) are closed. The reactor charged with the mixture is heated up to 300^eC to 350^eC. The water vapors and the inside air escape out through the primary seal box (10) between temperature range of 80^eC to 100^eC thereby diluting the oxygen concentration inside the reactor (22). Between the temperature of 250^eC to 300^eC, the plastic waste melts and starts evaporating. In the temperature range of 300^eC to 350^eC, the gaseous mixture of petroleum products containing lightweight and heavy petrochemicals and polymer particles rises through the delivery pipe (8). Due to the peculiar height given to the delivery pipe (8), the heavy polymer particles settle back in the reactor (22) while light polymer particles pass to the primary seal box (10) along with the gaseous mixture of petroleum products.

Gaseous mixture of petroleum products from the reactor (22) in collected in the primary seal box (10) by downward displacement of liquid therein and is further delivered to the gas condensation unit (11) through the outlet pipe (12). Bubbling of the gaseous mixture of petroleum products into water/liquid filled primary seal box (10) creates a positive pressure inside the reactor (22), and the inside pressure of the reactor is maintained between 100 to 150 mm of water column.

The gas condensation unit (11) is filled with fresh water and cooling tower fan and pump (9) is started before the start of the process. In the gas condensation unit (11), the gas is cooled and condensed to liquid form. The gas liquid separator (17) separates the liquid part and is collected in a liquid collection tank (18) while the uncondensed gas is collected in a gas receiver (14) which is pressurized and fed into burning chamber (23) through standby burner (IB).

A first bypass line (28a) is provided for carrying the excess liquid from the primary seal box (10) to a secondary seal box (13), which is filled up to over flow level with fresh water (for first batch) or liquid derived from the process (for subsequent batches) at the start of every batch i.e. every time the raw material is loaded in reactor (22) and during the process. When the liquid is not required, the gas coming out from the primary seal box (10) is directly delivered to the gas receiver (14) through a second bypass line (28b), which is further pressurized and fed into burning chamber (23) through standby burner (IB) or is used as a fuel for other energy applications by transporting the same through insulated pipes.

Figure 4 shows a process (200) for converting various petroleum based polymers into light, medium and heavy liquids and gaseous hydro carbons of different properties in presence of different catalysts.

To start the process, at step (210), initially the primary seal box (10) is filled with any one liquid selected from water and petrochemical liquid, the gas condensation unit (11) is filled with water, the cooling tower fan (9) is switched ON and water recirculation there through is started. Water recirculation through the cooling jacket (5) of feeding unit is also started.

In step (220), the top valve (6a) and the bottom valve (6b) of holding pipe (5) are closed and the plastic material along with the catalyst is loaded in the feeding hopper (7). The catalyst is preferably a manganese sulfate catalyst in 1 % w/w to 10% w/w proportion.

Further, the top valve (6a) is opened and the plastic material along with the catalyst is allowed to fall into holding pipe (5). The top valve (6a) is then closed and the bottom valve (6b) is opened to allow the plastic material and catalyst to fall into reactor (22). The bottom valve (6 a) is then closed to avoid the atmospheric air entering into the reactor (22).

After loading of the plastic material, at step (230), temperature of the reactor (22) is increased by heating it gradually. Around 100^eC temperature, the water vapors and the air inside the reactor escapes through the delivery pipe (8) and the primary seal box (10) thereby diluting the oxygen concentration inside the reactor (22) to an extent that it is not a hindrance to de-polymerization process of plastic present therein. The process of de-polymerization starts at around 300-350°C. i.e. after the plastic starts boiling the plastic vapors are broken down in the presence of heat and catalyst and gets converted into gaseous mixture of petroleum products from Methane and other gas to other fuels.

At step (240), the gaseous mixture of petroleum products rises to top by delivery pipe (8), and gets collected in the primary seal box (10). The gaseous mixture of petroleum products containing lightweight and heavy polymer particles rises through the delivery pipe (8). Due to the peculiar height given to the delivery pipe (8), the heavy polymer particles settle back in the reactor (22) while light polymer particles pass to the primary seal box (10). As the gaseous mixture gets collected in the primary seal box (10), a positive pressure is created inside the reactor (22) and it is maintained between 100 to 150 mm of water column. This environment inside the reactor (22) produces a peculiar quality of combination of petrochemical liquids along with all gases (CI to C4).

The gaseous mixture of petroleum products, at step (250), passes through the gas condensation unit (11) to form a mixture of petro chemical liquid and gaseous hydrocarbons. At step (260) it passes through the gas-liquid separator (17) where the gas and petrochemical; liquid are separated. The condensed petro chemical liquid is collected in liquid collection tank (18) while uncondensed gaseous hydrocarbons like CI to C4 (Refer Gas chromatograph table) are collected in gas receiver (14) and pumped back into burning chamber (23). Thus there are different zones in the total plant with different temperatures and pressures. The raw materials used in the different experiments were either used individually or in mixed proportion (0% to 100%) in any combination polyethylene, cross linked polyethylene, polypropylene, polypropylene co polymer, polystyrene, PET and PVC etc. PET material contains (¾ which tends to oxidize the product gases , thereby reducing the yield. Thus if reduced output is acceptable then it can also be used along with other raw material. In case of PVC the presence of chlorine makes the handling of produced gases difficult hence if glass lining of all internal surfaces and separation of chlorine and converting it to inert material is done the above process can be used for all types of polymers these processes of converting chlorine to its inert chemical at elevated temperature are available in prior art.

Mixed waste collected from municipal solid waste often has a large component of plastic bags of various sizes and material but the processing of the same is a challenge as it is almost soaked in dirt and other organic material which cannot be removed without lengthy process of size reduction and then drying, water washing, re -drying, etc, even after which the entire material is rarely clean. Plastic bags from the municipal waste are reconverted into petrochemical liquids using a process (300). Process (300) comprises of : collecting the plastic bags in the municipal waste and sun drying to clean the dirt adhering thereto; heating the cleaned plastic bags in a open aluminum pan to a temperature ranging from 300^eC to 350^eC to first evaporate the water content and then to melt the plastic; adding 2% to 5% w/w of ammonium acetate catalyst to the molten plastic; closing the aluminum pan with a lid and allowing the mixture of molten plastic and ammonium acetate mixture to cool to 100^eC; transferring the molten plastic and ammonium acetate mixture into a open tray to cool down to room temperature to form a sticky paste containing oil, wax and unreacted plastic; and filtering the sticky paste and separating the oil, wax and unreacted plastic by processing the filtered sticky paste with hot liquid separation.

The process (300) shows promising future for treatment of huge loads of plastic laying in open at various places including sea beds. The sticky paste obtained in the process (300) can be used as a raw material for making products like lubricants, shoe polish, car and tyre polish etc or it can be used as a fuel in the solid fuel heaters and boilers. The unreacted plastic is again heated with the next batch. The process (300) being so simple can be carried out even at a remote place or even on boats etc which are clearing the sea garbage. Though the experiment was not carried out in semi aerobic condition still the de -polymerization was carried out so if the process is carried out in anaerobic condition the resultant product will have excellent quality. The invention is further illustrated hereinafter by means of examples. These examples are merely a way of illustrations of the present invention and are not intended to be a limitation of the invention.

Experiment No 1

Figure 5 shows a small lab scale reactor system (50) having volumetric capacity of approx. five liters, made out of ms pipe of 3 mm thick with welded bottom and flanged top with cover along with opening on top one large 50 mm NB with screwed sealed cap for loading of material and other on top sideways 8 mm ms pipe connected with valve with cooling arrangement and rubber tube for collection of product as shown in fig 5. The major components of the conversion plant along with various other components are given in the Table II as shown below:

Table II

Following raw materials were procured from local scrap dealer and tested for the depolymerization with selective catalyst:

• LLDPE i.e. linear low density polyethylene

• HDPE i.e. High density polyethylene

• XLPE i.e. Cross linked polyethylene

• PP i.e. Polypropylene · PPCP (PE) i.e. Polypropylene co-polymered with Polyethylene commercial grade

• PS i.e. Polystyrene

Experiments were carried out by using one hundred gms of raw material each from the above were taken into the reactor along with 2 gms. (2% wt/ wt) of catalyst and the reactor was sealed and heating was started. The outlet of reactor pipe was immersed in water to ensure the air does not enter back into reactor during the start of process. As the temperature starts raising such that the air inside the reactor starts to expand and escape out there by maintaining the pressure inside the reactor. As the temperature rises further and reaches the 100°C mark the moisture of the raw material as well as the catalyst starts evaporating and the entire free space in the reactor gets filled up due to which the oxygen level inside the reactor is depleted to such an extent that it does not hamper the depolymerization process in anaerobic condition.

The vapors so produced were collected in top portion and were cooled down to room temperature by means of water jacket. The liquid was collected against the water pressure in a measuring flask. As the liquid so collected was lighter than water all the liquid floated on top of water sealing and was collected and measured for quantity and specific gravity after the completion of the experiment. The same in tabled separately as Table III below:

TABLE-III

Liquid derived from Exp. No. 1 was added to fuel tank with Diesel procured from local market (BSIII). The percentage of this liquid i.e. additive was up to 5 % max. Results are listed in Table IV below: TABLE- IV

All the users also reported increase in the engine torque and reduction in vibrations as well as noise produced by engine. From the above experiments it was observed that the product derived from PP and PE was most promising as far as output is produced. The same liquid derived and used for above experiments was also tried on two stroke as well as four stroke petrol engines which showed comparable results hence it can be said that the process is suitable for all types of I.C. engines

Experiment No. 2.

Polypropylene (PP) which gave better results was chosen for the batch scale machine as described in Fig 1. (approx. gross volume 75 liters.) A batch of 25 kg of polypropylene waste in the form of granules procured from the local market was mixed with 500 gms of Manganese sulfate catalyst was loaded through the hopper (7) by opening both the valves (6a, 6b) as the reactor (22) was at room temperature. After filling up of reactor (22), all the water seals were filled up with water up to the desired level and the reactor main burner (1A) was started to raise the temperature. With the rise in temperature, air inside the reactor (22) started expanding and the water seals started releasing the air, confirming no leakage in the reactor (22) and associated system (100). As the temperature reached around 100°C, water present in reactor (22) started vaporizing which occupied the head space driving the air out of system. With the increasing temperature, de- polymerization of PP produced different petrochemicals in vapor form. Vapors were condensed, gases like methane, propane, etc were collected and fed back into burner by gas blower and the liquid was trapped and collected in separate tank. The collected liquid was kept in standing form in so that water escaped from seal was separated and filtered for other pollutants. The collected liquid was tested for compatibility with regular motor fuel (diesel). The results are presented in Table V below:

TABLE-V

The above liquid was found to be same as that derived from exp no 1 and was compatible with the regular diesel hence we conducted the experiment on some passenger cars. Some of the very popular brands available locally were selected and base data for 15 days was collected by using the vehicles with std. diesel. The diesel made available from local market (BS3/BS4) was used for the experiment.

The same diesel was used with 2% of above liquid as an additive and all these vehicles were used for similar period and the data was collected from these vehicles before and after use of the liquid additive. From the data collected it was observed that after the use of diesel with additive the vehicles started producing more power which was evident from the fact that the car could clear the up gradients without change of gear which was necessary earlier and at the same time the firing of the engine improved and the engine became smooth. The PUC tests conducted at regular interval on these cars showed drastic reduction in the HSU values and at the same time the per liter average also increased. From the above observation we can say that by addition of this additive in the regular diesel it can be converted into High speed diesel which only provides better torque and average with additional properties like better fuel burning, less air pollution, smoother engine running, removal of carbon deposits on engine internals, better lubrication of fuel delivery system etc. The additive is suitable for even cold climate since even after cooling the additive to -15^eC for 60 min. the additive could be poured and was not solidified due to vax content which is a very normal phenomena for a regular commercial diesel. (Pour point recorded -39^eC)

After 15 days of field trials with 2% liquid derived from above experiment- diesel additive (approx.500 KM) mixed with commercial grade BSIV diesel on similar route the pollution levels were found to be 40% to 85% less than the control and at the same time fuel efficiency increased by 10.3% to 33.2% as compared to the test run with normal diesel without additive (control). The tests were carried out on different cars with engine capacity from 1300 CC up to 2750 CC. Hence we can assume that this liquid can be used on any type of diesel engine of varying sizes and capacities. The main advantage of this liquid is that the liquid provides lubrication to even fuel pumps and other parts during running which is not possible in normal operation.

This liquid was also used in petrol engines up to 2% as a petrol additive which gave smoother engine running with less vibrations and noise.

During testing this liquid for proximate analysis it was found the liquid has three main components based on boiling point Viz. Part: less than 100^eC (up to 15% by Vol.) Part 2: 100^eC to 300^eC (up to 80% by Vol) & Part 3: above 300°C (ball Part up to 15% vol.). The first part is responsible for removal of carbon and other sticky material deposits in the engine as well as fuel path due to its low boiling point. The second part obviously contains various components of petro chemicals usually found in diesel while the third part which has very high boiling point( above 350 °C) provides lubricity to the engine particularly cylinder piston and other parts of combustion process of engine. Hence if we remove this third part by way of partial distillation it finds us in industrial lubricants engine oils etc .as additives or even carrier as this entire liquid has a pour point of -39^eC and cold filter plug point of -8^eC

The oil derived from the above experiment was used as an additive in a diesel available from local market (BS3/BS4). The diesel available in the local market and the diesel with 2% of the oil obtained in experiment no. 2 as an additive were tested in diesel engine for comparison of exhaust gases in no load condition, half load condition and full load condition. Table VI below shows comparison of exhaust gases in no load condition of engine, when diesel (D) is used as fuel and when diesel with 2% of the oil obtained in experiment no. 3 (DA) is used as fuel.

The engine was IC Engine set up under test a Research Diesel having power 3.50 kW @ 1500 rpm which is 1 Cylinder, Four stroke, Constant Speed, Water Cooled Diesel Engine, with Cylinder Bore 87.50(mm), Stroke Length l lO.OO(mm), Connecting Rod length 234.00(mm), Compression Ratio 17.50, Swept volume 661.45 (cc) natural asp. Engine.

Table VI

3 DA 38 0.96 2.04 530 17.32 140 94.5

4 D 37 0.56 1.54 1444 18.61 191 127.4

4 DA 38 0.96 2.04 530 17.43 145 95

5 D 37 0.56 1.54 1444 18.57 189 127.1

5 DA 38 0.96 2.04 537 17.51 144 95.3

6 D 37 0.56 1.54 1444 18.52 186 126.8

6 DA 38 0.97 2.03 539 17.59 136 96

7 D 37 0.56 1.54 1453 18.66 187 127.7

7 DA 38 0.97 2.02 542 17.58 126 96.4

8 D 37 0.56 1.54 1453 18.63 186 127.5

8 DA 38 0.97 2.02 542 17.49 116 95.9

9 D 37 0.56 1.54 1453 18.62 184 127.4

9 DA 38 0.97 2.03 588 17.38 110 94.9

10 D 37 0.56 1.54 1453 18.67 188 127.7

10 DA 38 0.97 2.03 594 17.32 108 94.6

11 D 37 0.56 1.54 1453 18.71 192 127.9

11 DA 38 0.97 2.03 601 17.43 119 95.1

12 D 37 0.57 1.53 1462 18.67 196 128.4

12 DA 38 0.97 2.03 601 17.46 126 95.2

13 D 37 0.57 1.53 1453 18.68 195 128.5

13 DA 38 1.04 2.02 601 17.5 129 95.4

14 D 37 0.57 1.53 1453 18.64 191 128.2

14 DA 38 1.04 2.02 601 17.54 128 95.5

15 D 37 0.57 1.53 1453 18.66 195 128.4

15 DA 38 1.04 2.02 601 17.52 124 95.5

16 D 37 0.57 1.53 1453 18.56 192 127.8

16 DA 38 0.97 2.02 604 17.46 120 95.6

17 D 37 0.56 1.54 1453 18.53 194 126.9

17 DA 38 0.97 2.02 604 17.44 122 95.5

Table VII below shows comparison of exhaust gases in half load condition of engine, when diesel (D) is used as fuel and diesel with 2% of the oil obtained in experiment no.3 (DA) is used as fuel.

Table VII

2 DA 38 0.52 3.07 514 15.73 512 64.3

3 D 37 0.31 2.38 981 17.18 419 84.4

3 DA 38 0.52 3.07 514 15.78 505 64.5

4 D 37 0.31 2.39 977 17.19 421 84.1

4 DA 39 0.52 3.07 509 15.76 501 64.4

5 D 38 0.31 2.38 981 17.29 425 84.8

5 DA 38 0.53 3.03 516 15.84 501 65.3

6 D 38 0.31 2.38 981 17.24 426 84.6

6 DA 38 0.53 3.03 516 15.79 500 65.1

7 D 38 0.31 2.38 981 17.23 428 84.6

7 DA 39 0.52 3.08 508 15.58 499 63.7

8 D 37 0.31 2.37 986 17.35 429 85.3

8 DA 38 0.47 3.09 508 15.43 498 63.2

9 D 38 0.31 2.36 990 17.37 430 85.7

9 DA 38 0.47 3.09 508 15.59 502 63.8

10 D 37 0.31 2.36 990 17.39 428 85.8

10 DA 39 0.47 3.1 506 15.62 508 63.7

11 D 37 0.31 2.36 990 17.42 426 85.9

11 DA 38 0.47 3.1 506 15.61 510 63.7

12 D 38 0.31 2.35 988 17.43 422 86.3

12 DA 38 0.47 3.1 506 15.62 508 63.7

13 D 38 0.31 2.35 988 17.37 419 86

13 DA 38 0.47 3.1 506 15.66 506 63.8

14 D 37 0.31 2.34 992 17.45 416 86.6

14 DA 39 0.47 3.09 508 15.83 507 64.5

15 D 37 0.32 2.32 1000 17.49 414 87.4

15 DA 38 0.47 3.08 509 15.87 508 64.8

16 D 38 0.32 2.32 1000 17.43 413 87.1

16 DA 38 0.47 3.08 509 15.81 505 64.6

17 D 37 0.32 2.31 1004 17.4 412 87.3

17 DA 38 0.47 3.08 509 15.84 504 64.7

18 D 38 0.32 2.32 1000 17.34 410 86.8

18 DA 38 0.47 3.08 509 15.81 503 64.6 Table VIII below shows comparison of exhaust gases in full load condition of engine, when diesel (D) is used as fuel and diesel with 2% of the oil obtained in experiment no.3 (DA) is used as fuel.

Table VIII

(D or rat u re /%vol /%vol /ppm /%vol /%vol

DA) /^SC

D 37 0.56 1.82 1286 18.14 346 108.2

DA 39 1.25 3.51 505 14.78 585 53

D 38 0.56 1.82 1286 18.2 349 108.5

DA 39 1.25 3.52 504 14.79 576 52.9

D 37 0.63 1.82 1287 18.22 350 108

DA 39 1.21 3.54 503 14.89 571 53.1

D 38 0.63 1.81 1294 18.23 351 108.6

DA 39 1.13 3.55 504 14.93 570 53.4

D 38 0.63 1.81 1294 18.28 351 108.8

DA 39 1.14 3.54 509 14.94 571 53.5

D 37 0.63 1.81 1294 18.26 350 108.7

DA 39 1.14 3.54 509 14.92 574 53.4

D 38 0.63 1.81 1302 18.18 346 108.3

DA 39 1.14 3.54 509 14.9 574 53.4

D 38 0.63 1.81 1302 18.23 345 108.5

DA 38 1.14 3.54 509 14.85 574 53.2

D 38 0.63 1.81 1302 18.29 348 108.8

DA 38 1.13 3.57 505 14.74 573 52.6

D 38 0.63 1.81 1302 18.33 348 109

DA 38 1.13 3.57 509 14.76 573 52.7

D 38 0.63 1.81 1302 18.37 348 109.3

DA 39 1.13 3.57 509 14.83 576 52.9

D 38 0.63 1.81 1302 18.22 345 108.5

DA 39 1.13 3.56 510 14.89 577 53.1

D 38 0.63 1.81 1310 18.22 344 108.4

DA 39 1.13 3.56 510 14.93 579 53.2

D 38 0.63 1.81 1310 18.23 342 108.5

DA 39 1.13 3.56 510 14.95 579 53.3

D 38 0.63 1.81 1310 18.18 341 108.2

DA 38 1.13 3.55 512 14.92 591 53.3

D 38 0.63 1.81 1310 18.12 341 107.9

DA 39 1.13 3.55 512 14.92 587 53.3

D 38 0.63 1.82 1303 18.13 343 107.5

DA 39 1.13 3.55 512 14.94 587 53.4

D 38 0.63 1.82 1303 18.09 346 107.3

DA 39 1.13 3.55 512 14.95 587 53.4

D 38 0.63 1.82 1303 18.14 350 107.6

DA 39 1.14 3.54 513 14.97 588 53.5

D 38 0.63 1.82 1303 18.19 352 107.8 20 DA 39 1 .1 4 3.54 513 14.96 593 53.5

21 D 37 0.63 1 .82 1 303 18.12 354 1 07.5

21 DA 39 1 .1 4 3.54 513 14.9 596 53.4

22 D 38 0.63 1 .83 1 296 18.03 354 1 06.5

22 DA 39 1 .1 4 3.54 513 14.89 596 53.3

23 D 38 0.63 1 .83 1 296 18.1 1 359 1 06.9

23 DA 39 1 .1 4 3.54 513 14.88 596 53.3 Gas chromatograph was obtained from the GC using porapack-Q column with TCD detector and by testing the gas derived from the gas collection system after the completion of entire cooling process of exp no 2. It is the component which is in gaseous state at room temp and pressure (methane and components of LPG are observed in it) Figures 6 to 12 show the FT-IR spectra of various standard samples and the product sample obtained from experiment 2 (hereinafter "sample 2"). The main aim of running the spectra was to obtain and to find the major difference between the liquid under test and the standard diesel.

Figure 6 (FT-IR spectrum 1) is commercially available FT-IR spectrum of Diesel, whereas Figure 7 (FT-IR spectrum 2) is a FT-IR spectrum of sample 2.

Sample 2 was subjected to FTIR test in the spectral range 4000 - 400 cm . The FTIR was auto subtracted from the commercially available diesel spectrum. Then it was compared with the built in spectral library software. The Ft-IR spectrum in % transmittance is interpreted. Figure 8 shows comparison of FT-IR spectrum of standard Polyethylene and polypropylene mixture (Spectrum 2A-2) and FT-IR spectrum of sample 2 (Spectrum 2A-1). Table IX below enlists the peak values in spectrum 2A-1 and possible polymers indicated by those values.

Table IX

2 880 50-IRs Polymer2 PP, Polypropylene

3 876 51 -IRs Polymer2 PP1 , PP, polypropylene

4 871 34-IRs Polymer2 PB, Polybutene

5 852 20-IRs Polymer2 LLDPE, Low density polyet hylene

6 847 47-IF!s Polymer2 Pi nene

7 843 71 -IF!s Polymer2 VLDPE, Low density polyet hylene

8 838 19-IRs Polymer2 LDPE, Low density polyethylene

9 834 85-IF!s Polymer2 NR, Natural rubber

10 834 21 -IF!s Polymer2 LLDPE1 , Low density polyet hylene

1 1 833 68-IF!s Polymer2 95 SIS

12 827 83-IRs Polymer2 BR3, Polybutadiene

13 823 48-IF!s Polymer2 PI P, Polyisoprene

14 818 18-IRs Polymer2 Lanoli ne

15 815 16-IRs Polymer2 lonomer- 1

Figure 9 (FT-IR spectrum 2B): FT-IR spectra obtained by eliminating the spectra of sample 2 (spectrum 2) from the standard diesel spectra (spectrum 1). Observations of FT-IR test are enlisted in Table X below:

Table X

Figure 10 shows comparison of FT-IR spectrum of standard 2,3 dimethyl butane (Spectrum 2C-2) and FT-IR spectrum of sample 2 (Spectrum 2C-1). Table XI below enlists the peak values in spectrum 2C-2 and possible polymers indicated by those values.

Table XI Sr. Score Library Note found / Title

No.

1 712 2- Tutorial database 2, 3 Dimethyl butane

2 673 1- Tutorial database Octane

3 650 15- Tutorial database Chloroform

4 648 18- Tutorial database Toluene

5 641 3- Tutorial database Cyclohexane

6 637 13- Tutorial database p-Xylene

7 637 16- Tutorial database Tribromomethane

8 631 11 - Tutorial database o-Xylene

9 626 7- Tutorial database Benzene

10 618 24- Tutorial database N, N-dimetyldecylamine

11 617 21 - Tutorial database N-methylbutylamine

12 614 5- Tutorial database Cyclooctene

13 607 22- Tutorial database 2-Pipecoline

14 604 14- Tutorial database Indene

15 600 19- Tutorial database Propylamine

Figure 11 shows comparison of FT-IR spectrum of standard 2,3 dimethyl butane (Spectrum 2D-2) and FT-IR spectrum of sample 2 (Spectrum 2D-1). Table XII below enlists the peak values in spectrum 2D-2 and possible polymers indicated by those values.

Table XII

Thus, the gist of their findings is that there is a presence of these polymers (PP/PE) in the sample in liquid form itself, in addition to almost all components of diesel which is something new and not found normally. In short, plastic in liquid form, though in small quantity is observed in the liquid which is a probable reason for additional lubricity found in the engines after the treatment. Gases obtained in the above experiment were analyzed with Gas chromatography using porapack-Q column and TCD detector. The spectrum showed the presence of hydrocarbon gases in the sample. Table XIII below enlists the peak values in the gas chromatograph and possible gaseous hydrocarbons CI to C4 indicated by those values:

Table XIII

Experiment No.3. Plastic bags of different sizes and types of PP, LLDPE and PE were collected from the municipal garbage and sun dried to get rid of the dirt which could be taken off. These plastic bags were treated using the method (300) to get a sticky paste of petroleum products. 100 gm plastic was heated on LPG stove in an open aluminum pan having a lid. As soon as the plastic temperature started increasing the water started escaping from the pan soon the plastic melted at around 300 to 350°C. 2% by wt of catalyst was delivered in molten plastic stirred to mix the catalyst (Ammonium acetate) and the flame was switched off after 30 to 60 sec. with lid closed the pan was allowed to cool off up to around 100°C. The lid was opened fully, pan was emptied in an open tray and the contents were allowed to further cool down to room temperature. The liquid when cooled became sticky paste and not hard solid as plastic. The contents of this paste were tested on FTIR which showed heavy mineral oil as a major component along with wax along with small quantities of un-reacted polyethylene and polypropylene.

Fig 12 is a spectra of the sticky paste obtained in the above experiment. Spectrum shows the presence of heavy mineral oil along with unreacted plastic polymers i.e. PP and PE.

EXPERIMENT NO 4

Mixed waste collected from Municipal solid waste as in above experiment with large component of plastic bags of various sizes and material which was soaked in dirt and other organic material which cannot be removed without lengthy process of size reduction and then drying, water washing, re-drying, etc, was collected from municipal dump site.

Plastic bags and other plastic waste of different sizes and types of PP, LLDPE and PE were collected from the garbage and sun dried to get rid of the dirt which could be taken off.

This waste was then subjected to addition of catalyst from the list mentioned above with v/v percentage up to 10% and processed in an equipment as shown in fig 5 but instead of taking the product to cooling system the gases were taken out directly from outlet valve to a burning chamber. The gases continued to flow out of system till the entire plastic was consumed. These gases when tested were found to have the similar chemical properties of liquid as derived in the above experiment. This process finds huge potential in plastic waste processing at various dump sites of urban local bodies where the separation and reuse of plastic is almost impossible due to heavy contamination. The heat generated by these gases can be put to various uses like incineration of medical and other hazardous waste disposal of waste generate in abattoir incinerators used for scientific disposal of dead bodies and all uses likewise. This heat can be made available on continuous basis by treating this in a plant of suitable size like that of fig 1 by making small modifications/additions like automatic removal of rejects from bottom so as to make the plant operation a continuous one.

Advantages of the invention

• The process (200) for re-conversion of plastics into its original form of petro chemicals produces better quality petro chemicals by way of de- polymerizations .

• The process (200) converts the waste plastic into various products that can be utilized for fulfilling various energy needs.

• The process (200) produces good quality diesel like fuel having high calorific value.

• The process (200) produces fuel additives to alter the quality of the diesel and petrol being used as a fuel in various I.C. engines in such a way that enhances the performances of the engine due to presence of different chemicals and lubricants present.

• The process (200) produces petrochemicals which can be further refined and separated and processed for various applications and also as a base material for lubricants oils greases etc. The foregoing descriptions of specific embodiments of the present invention have been presented for purposes of illustration and description. They are not intended to be exhaustive or to limit the present invention to the precise forms disclosed and obviously many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the present invention and its practical application and to thereby enable others skilled in the art to best utilize the present invention and various embodiments with various modifications as are suited to the particular use contemplated. It is understood that various omissions and substitutions of equivalents are contemplated as circumstances may suggest or render expedient, but such omissions and substitutions are intended to cover the application or implementation without departing from the spirit or scope of the claims of the present invention.

Claims

A system (100) for re-conversion of plastics into different petrochemical liquids and gaseous hydrocarbons, the system (100) comprising: a reactor (22) fitted with a feeding hopper (7) through a holding pipe (4) configured with a top valve (6a) and a bottom valve (6b) and covered by a cooling jacket (5); the reactor (22) having a plurality of half cut fire tubes (19) welded in inclined way on the outer surface thereof permitting the passage of exhaust gases there through for efficient heat energy transfer; a delivery pipe (8) configured thereon having a height of at least 300 mm more than the height of reactor (22); and a burning chamber (23) there below for supplying heat energy thereto; wherein a mixture of plastic and 1 % w/w to 10% w/w of manganese sulfate catalyst is charged into the reactor (22) through the holding pipe (4) maintained at temperature below 50^eC; exposure of mixture to the outer environment is avoided by closing bottom valve (6a); and the reactor (22) is heated to the temperature of 300^eC to 350^eC to first escape the inside air and water vapors out through the delivery pipe and then melt the plastic to produce a gaseous mixture containing heavy and lightweight polymer particles to rise through the delivery pipe (8) wherein heavy polymer particles settle back in the reactor (22) and lightweight polymer particles remain in the gaseous mixture; a primary seal box (10) filled to overflow level with any liquid selected from water and the petrochemical liquid for receiving the gaseous mixture of petroleum products from delivery pipe (8) by downward delivery method, wherein the gaseous mixture passing through the primary seal box (10) creates a positive pressure inside the reactor (22) and the inside pressure of the reactor is maintained between 100 to 150 mm of water column; a gas condensation unit (11) receiving the gaseous mixture from the primary seal box (10) through an outlet pipe (12) to form a mixture of petrochemical liquid and gaseous hydrocarbons; and a gas-liquid separator (17) for separating the petrochemical liquid and gaseous hydrocarbons, collecting the petrochemical liquids in a liquid collection tank (18), and collecting the uncondensed gas in a gas receiver (14).

The system (100) as claimed in claim 1 , wherein the plastic material is selected from polyethylene, cross linked polyethylene, polypropylene, polypropylene co polymer, polystyrene, polyvinyl chloride and polyethylene terephthalate.

The system (100) as claimed in claim 1 , wherein the catalyst is in the range of 2% w/w to 5% w/w of plastic.

The system (100) as claimed in claim 1 , wherein the catalyst is partly recovered after completion of the process.

The system (100) as claimed in claim 1 , wherein the gas collection and cooling unit comprises of a secondary seal box (13) connected to the primary seal box (10) by a first bypass tube (28a) for collecting the excess liquid there from.

The system (100) as claimed in claim 1 , wherein a second bypass tube (28b) is provided for collecting the uncondensed gaseous mixture from the outlet pipe (12) into the gas receiver (14) for directly supplying to the burning chamber (23) as a fuel. The process (200) for re-conversion of plastics into different petrochemical liquids and gaseous hydrocarbons using the system (100) as claimed in claim 1 , the process (200) comprising of the steps: cutting the plastic waste into pieces; mixing the cut plastic waste with a manganese sulfate catalyst in a proportion ranging from 1% w/w to 10% w/w; filling the primary seal box (10) with any liquid selected from water and petrochemical liquid and starting cooling system of holding pipe (4) and gas condensation unit (11); closing a bottom valve (6b) of holding pipe (5) and loading the waste plastic and catalyst mixture therein through a feeding hopper (7) and then closing the top valve (6a) opening the bottom valve (6b) to allow the plastic material and catalyst mixture to fall into reactor (22) and closing the bottom valve (6a) thereby inhibiting the outside air entering into the reactor (22); heating the plastic material and catalyst mixture in the reactor (22) upto 350^eC, wherein water vapors and the inside air escape out through the primary seal box (10) between temperature range of 80^eC to 100^eC thereby diluting the oxygen concentration inside the reactor (22), plastic waste melts and starts evaporating between temperature range of 250^eC to 300^eC, the gaseous mixture of petroleum products containing light and heavy polymer particles rises through the delivery pipe (8) between temperature range of 300^eC to 350^eC, heavy polymer particles settle back in the reactor(22) and light polymer particles pass to the primary seal box (10) along with the gaseous mixture of petroleum products; collecting the gaseous mixture of petroleum products in the primary seal box (10) by downward displacement of the liquid therei, wherein the gaseous mixture passing through the primary seal box (10) creates a positive pressure inside the reactor (22) and the inside pressure of the reactor is maintained between 100 to 150 mm of water column; passing the gaseous mixture of petroleum products through the gas condensation unit (11) to form a mixture of petrochemical liquid and uncondensed gaseous hydrocarbons; separating the petrochemical liquid from uncondensed gaseous hydrocarbons, collecting the petrochemical liquid in a liquid collection tank (18) and collecting the gaseous hydrocarbons in the gas receiver (14).

A process (300) for re-conversion of municipal plastic waste into different petrochemical liquids, the process (300) comprising: collecting the plastic bags in the municipal waste and sun drying to clean the dirt adhering thereto; heating the cleaned plastic bags in a open aluminum pan to a temperature ranging from 300^eC to 350^eC to first evaporate the water content and then to melt the plastic; adding 2% to 5% w/w of ammonium acetate catalyst to the molten plastic; closing the aluminum pan with a lid and allowing the mixture of molten plastic and ammonium acetate mixture to cool to 100^eC; transferring the molten plastic and ammonium acetate mixture into a open tray to cool down to room temperature to form a sticky paste containing oil, wax and unreacted plastic; and filtering the sticky paste and separating the oil, wax and unreacted plastic by processing the filtered sticky paste with hot liquid separation.