WO2023209725A1 - Production de biocarburants à partir de déchets plastiques - Google Patents

Production de biocarburants à partir de déchets plastiques Download PDF

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WO2023209725A1
WO2023209725A1 PCT/IN2023/050251 IN2023050251W WO2023209725A1 WO 2023209725 A1 WO2023209725 A1 WO 2023209725A1 IN 2023050251 W IN2023050251 W IN 2023050251W WO 2023209725 A1 WO2023209725 A1 WO 2023209725A1
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thermal cracking
stage
hydrocarbons
biofuels
long chain
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PCT/IN2023/050251
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English (en)
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Aman Singla
Yashpal JAIN
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Aman Singla
Jain Yashpal
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Publication of WO2023209725A1 publication Critical patent/WO2023209725A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of thermal cracking in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G9/26—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with discontinuously preheated non-moving solid material, e.g. blast and run

Definitions

  • the present disclosure relates to methods and systems having non-catalytic two stage continuous thermal cracking process using plug flow type, electrically heated, tubular coiled thermal cracking reactors for production of biofuels having maximum yields of ⁇ Cis molecular size hydrocarbons from a feedstock comprising all types of polypropylenes and polyethylenes segregated separately or collectively from waste plastics.
  • Biofuels offers the answer for ever-worsening fuel problem (from non-renewable sources) and management/handling of waste plastics.
  • Biofuels can be derived from natural renewable resources, exhibits similar fuel properties and results in substantially less environment damaging emissions.
  • biofuels can also be produced from some of the majorly used waste plastics such as polypropylenes and polyethylenes.
  • the biofuels produced from waste plastics such as polypropylenes and polyethylenes exhibit excellent liquid fuel characteristics and can be replaced with conventional petroleum-based fuels.
  • biofuels produced from renewable resources and waste plastics such as polypropylenes and polyethylenes fit in perfectly as the ideal substitutes for conventional petroleum products, and to reduce wastes and cost(s) associated thereof, there is still a need to devise effective methods and systems for production of biofuels wherein the processes are efficient, cost effective, facilitate easy plant setup.
  • the process description of the present disclosure overcomes the drawbacks of the prior art(s) and offers an improved and economical way of biofuel production from waste plastics producing higher yields of ⁇ Cis molecular size hydrocarbons as is desired for its usage as fuels, replacing petroleum fuels by providing non-catalytic two stage thermal cracking process using plug flow type, electrically heated, tubular coiled thermal cracking reactors.
  • the present disclosure also provides a mechanism for the continuous removal of physically inseparable inorganic impurities present in the feedstock as filler (calcium salts) and some other left-over impurities present during the segregation process of waste plastics, which is the foremost challenge in the conversion of waste plastics into liquid hydrocarbons of desired molecular size. Further, the present disclosure also provides a mechanism for the saturation of olefins and removal of organic impurities present in the biofuels.
  • the present disclosure relates to methods and systems for converting polypropylenes and polyethylenes constituents of waste plastics into ⁇ Cis molecular size hydrocarbons as biofuels by non-catalytic two stage thermal cracking process using plug flow type, electrically heated, tubular coiled thermal cracking reactors and providing higher yields of ⁇ Cis molecular size hydrocarbons.
  • the method provides solution for continuous removal of physically inseparable inorganic impurities present in the feedstock as filler and some other left-over impurities present during a segregation process of the waste plastics.
  • Desired feedstock of up to 5 millimeter (mm) size containing polypropylenes and polyethylenes components is segregated from mixed waste plastics.
  • the feedstock is melted through single or double screw extruders to generate homogeneous molten liquid mass from the feedstock at a discharge header of the single or double screw extruders.
  • the molten liquid mass from the discharge header of the single or double screw extruders is fed to a stage 1 thermal cracking reactor for partial thermal cracking reactions conducted at temperatures of up to 450 °C and pressure of up to 20 bar to receive thermally cracked products having hydrocarbon chain length of up to ⁇ C30.
  • Stage 1 thermal cracking products are separated into non-condensable gases, olefinic liquid biofuels having carbon chain length of ⁇ Cis and long chain hydrocarbons having carbon chain length of up to ⁇ C30 along with inorganic impurities composed of calcium carbonate as major impurities.
  • Inorganic impurities are separated from the long chain hydrocarbons having carbon chain length of up to ⁇ C30 before stage 2 thermal cracking reactions of the long chain hydrocarbons using filtration alone through a filter media having a pore size varying from 0.5 micrometer (pm) to 10 pm or filtration followed by hot water rinsing or only with hot water rinsing.
  • Cleaned long chain hydrocarbons are pumped to a stage 2 thermal cracking reactor for optimum thermal cracking reactions of the long chain hydrocarbons at temperatures of up to 650°C and pressure of up to 50 bar to receive a maximum output of ⁇ Cis hydrocarbons.
  • Stage 2 thermal cracking products are separated into non-condensable gases, olefinic liquid biofuels having carbon chain length of ⁇ Cis and pitch.
  • Olefinic liquid biofuels received from stage 1 and stage 2 thermal cracking reactions are saturated and organic impurities that includes at least one of organic chlorides, nitrogen, sulphur, or oxygen are removed by hydrogenation reactions of the olefinic liquid biofuels.
  • Hydrogenation reactions are conducted in the presence of Ni catalyst or any other metal catalyst of Group VIII metals of the periodic table to obtain paraffinic biofuels as a final product. After hydrogenation, the paraffinic biofuels are separated as per a specific use having a desired molecular size and a boiling point using a separate fractional distillation column.
  • Figure 1 illustrates an exemplary process plant for segregating and pre-treating waste plastics according to the present disclosure.
  • Figure 2 illustrates an exemplary process plant for partial thermal cracking of a feedstock according to the present disclosure.
  • Figure 3 illustrates an exemplary process plant for thermal cracking of cleaned long chain hydrocarbons and hydrogenation of the thermally cracked biofuels according to the present disclosure.
  • the present disclosure relates to methods and systems having non-catalytic two stage continuous thermal cracking process using plug flow type, electrically heated, tubular coiled thermal cracking reactors for production of biofuels having higher yields of ⁇ Cis molecular size hydrocarbons from a feedstock comprising all types of polypropylenes and polyethylenes segregated separately or collectively from waste plastics.
  • biofuels refers to a liquid substance that is used as a fuel or an intermediate for production of plastic polymers, which is produced from polypropylenes and polyethylenes constituents of waste plastics.
  • the word “biofuels” produced from waste plastics may be traced backwards for its nomenclature as - polypropylenes and polyethylenes segregated from waste plastics used as a feedstock for the production of biofuels are produced by the polymerisation of propylene orethylene gas, which is produced from thermal cracking of a desired quality of hydrocarbons such as Naphtha, which is produced from the crude petroleum oils and the crude petroleum oils are produced from the decomposition of plants and animals which are biological in nature.
  • maximum yield refers to a maximum amount of product that could be formed from given amounts of reactants.
  • reduced flow refers to a flow that is optimum for a reaction in a reactor.
  • desired size refers to a size of the hydrocarbon according to an application or use.
  • the process of the present disclosure facilitates the use of polypropylenes and polyethylenes constituents segregated from waste plastics for biofuel production.
  • the polypropylenes and polyethylenes may be used separately as an independent feedstock or may be used in combinations of each other.
  • the polyethylenes include all their sub categories such as ultra-high-molecular- weight polyethylene (UHMWPE), ultralow molecular weight polyethylene (ULMWPE), high molecular weight polyethylene (HMWPE), high density poly ethylene (HDPE), cross-linked polyethylene (XLPE), medium-density polyethylene (MDPE), linear low-density polyethylene (LLDPE), low density polyethylene (LDPE), and very low density polyethylene (VLDPE).
  • UHMWPE ultra-high-molecular- weight polyethylene
  • ULMWPE ultralow molecular weight polyethylene
  • HMWPE high molecular weight polyethylene
  • HDPE high density poly ethylene
  • XLPE cross-linked polyethylene
  • MDPE medium-density
  • feedstock includes all types of polypropylenes and polyethylenes segregated from the waste plastics. During segregation, the feedstock may contain some of non-desirable components of the waste plastics such as polyvinyl chloride, polyethylene terephthalate (PET) etc. but a concentration of the non-desirable components in the feedstock is required to be minimal and it may be limited to up to 5 % or up to 1% or up to 0.1%.
  • non-desirable components of the waste plastics such as polyvinyl chloride, polyethylene terephthalate (PET) etc.
  • PET polyethylene terephthalate
  • the embodiments related to methods and systems for the conversion of polypropylenes and polyethylenes constituents of the waste plastics into biofuels comprises as under: i.
  • One of the biggest challenges for production of biofuels from the waste plastics is to have an economically self-sustainable mechanism for the waste plastics collection and their segregation to obtain the desired feedstock.
  • Domestic and commercial waste plastics, especially packaging plastic wastes generation and its quantum is directly linked with the human population inhabitation, and a type of human population etc.
  • Industrial waste plastics generation such as laminations plastic wastes from waste paper-based paper industries is concentrated at a point but a same type of industries generating the wastes are never located nearby. Further, a density of the waste plastics is very low even in baled form.
  • waste plastics needs to be collected and segregated at a short radial distance from the waste plastics to biofuels facility.
  • one of the most feasible solutions for the production of biofuels from the waste plastics is have small to medium sized plants ranging from 20 tons per day (TPD) to up to 100 TPD at any one location located nearby a source of waste plastics generation.
  • TPD tons per day
  • thermal cracking reactors or thermal cracking furnaces or pyrolysis furnaces are operational using oil or gas fired heaters in petroleum refineries for the processing of crude oils and its by-products and in petrochemical industries for the production of hydrocarbon gases such as propylene and ethylene gas from various feedstocks ranging from crude oil to naphtha.
  • Most of existing thermal cracking reactors are based on oil or gas fired heaters which are mounted on floors or walls of reactor furnaces and have tubular heat exchanging coils varying in diameter range from 25 millimeter (mm) to 150 mm, placed in a horizontal or vertical geometry.
  • thermal cracking reactors Most of the existing oil/ or gas fired heaters based thermal cracking reactors have been designed for turbulent flows in the coils and operates at higher liquid feed rate with an approximate range varying from 25 metric tons/hour (MT/hour) to up to 4000 MT/hour.
  • the large-scale thermal cracking reactors based on oil/gas fired heaters have practical limitations for their use in the production of biofuels from the waste plastics due to their size and operating conditions required to be maintained for their use.
  • an electrically heated, plug flow type, non-catalytic and non-fluidized tubular thermal cracking reactor for stage 1 and stage 2 thermal cracking reactions has been designed.
  • Mineral insulated heat trace type electrical heaters will be installed at an outer surface of tubular coils of the tubular thermal cracking reactors with tube diameter ranging from 25 mm to 100 mm.
  • Mineral insulated heat trace type electrical heaters will be installed in a spiral or any other form providing heat flux in a range from 4.0 to 10.0 kilowattXmeter 2 to the tubular thermal cracking reactors.
  • the tubes or tubular coils in the stage 1 and stage 2 thermal cracking reactors may be installed in a vertical or horizontal or inclined direction.
  • stage 1 and stage 2 thermal cracking reactors may comprise a provision for intermediate steam insertion for maintaining the desired flow conditions.
  • provision is to be understood for performing a particular process step and to be understood as including all physical articles (example pipelines, pumps, compressors, valves etc) that would be considered by a person skilled in the art in order to be able to perform this process step.
  • desired flow conditions is to be understood as reaction conditions that are optimum for performing a reaction.
  • Mineral insulated heat trace type electrical heated thermal cracking reactors will have the distinctive advantage for (i) precise temperature control in different sections of the tubular thermal cracking reactors, (ii) maintenance of desired vapor liquid ratio in the tubular thermal cracking reactors with varied temperature pressure combinations to keep the inorganic impurities suspended in the fluid, (iii) flexibility in a design of a size of a process plant for production of biofuels from the waste plastics, (iv) flexibility of operating the process under desired flow conditions, (v) no requirements of any external catalyst or media for heat transfer or conducting thermal cracking reactions in the process. ii.
  • Segregation steps involved in the preparation of the desired feedstock constituting all types of polypropylenes and polyethylenes includes - shredding of the waste plastics, density separation of desired raw materials using a sink float method with water as a medium (density of water may be altered by adding salts such as sodium chloride to achieve the desired density separation), dewatering of segregated plastics by compaction, second stage shredding and density separation of desired raw materials using the sink float method with water as the medium, second stage dewatering of segregated plastics by compaction, hot air drying of the dewatered material and finally further shredding of segregated raw material to generate a homogeneous density feedstock having a desired size of up to 5 mm.
  • the feedstock preparation can be made as a part of the overall thermal cracking process or it may be split, outsourced and got done by developing ancillary waste plastics segregators by providing them the desired specifications/requirements of the feedstock.
  • ancillary waste plastics segregators by providing them the desired specifications/requirements of the feedstock.
  • Melting of feedstock will be done in screw extruders having single or double screw, commonly used for melting of plastics. Depending upon a size of the plant for the production of biofuels from the waste plastics, there may be a single or multiple number of extruders joined together through a common discharge header of the extruder(s).
  • Desired back pressure of up to 50 bars to the molten liquid mass at an outlet of discharge header may be attained by the extruders or by putting up a positive displacement metering pump at the outlet of the discharge header connected with the stage 1 thermal cracking reactor. Temperature at the outlet of the discharge header may be maintained between 200 °C to 300 °C or between 220 °C to 250 °C. iv.
  • the molten mass in the liquid form produced at the discharge header of the extruder(s) will be conveyed to the stage 1 thermal cracking reactor for conducting the stage 1 thermal cracking reactions of the molten liquid mass.
  • stage 1 thermal cracking reactor will be a plug flow type, electrically heated tubular reactor with tube diameter ranging from 25 mm to 100 mm.
  • Partial thermal cracking reactions will be carried out in the stage 1 thermal cracking reactor within a pressure range of up to 20 bars and a temperature range of up to 450 °C.
  • Stage 1 thermal cracking reactions may be conducted under the pressure range of 1.5 to 5 bars or from 3 to 20 bars and temperature range of 380 °C to 410 °C or from 400 °C to 450 °C so as to receive thermally cracked products having hydrocarbon chain length of up to ⁇ C30 or up to ⁇ C24 or may be up to ⁇ C21.
  • Two phase flow will be maintained during the stage 1 thermal cracking reactions with a composition of fluid having liquid contents in a range of 10 to 90 % or between 40 to 70 %. Two phase flow is to be understood as a flow with two distinct phases.
  • the mixed phase fluid at an outlet of stage 1 thermal cracking reactor will be having liquid hydrocarbons, vapors and solid particles as inorganic impurities, generated during the stage 1 thermal cracking reactions of the molten liquid mass.
  • the mixed phase fluid from the outlet of the stage 1 thermal cracking reactor may be discharged into a heat and mass transfer equipment such as a fractional distillation column, shell and tube heat exchangers etc.
  • Long chain hydrocarbons containing inorganic impurities as stated will be collected in a receiver vessel for further treatment for the separation of hydrocarbons from inorganic impurities.
  • Some quantity of hydrocarbons ranging from ⁇ Cis and > C12 may be added in the long chain hydrocarbons containing inorganic impurities for its dilution.
  • the quantity of hydrocarbons ranging from ⁇ Cis and > C12 that may be added to long chain hydrocarbons containing inorganic impurities may range from 1 % to 50 % of the long chain hydrocarbons.
  • calcium salts such as calcium carbonate as filler is added along with the virgin polymers varying in proportion from 1 % to 30 % or any other percentage, decided by the manufacturers at the time of production.
  • Calcium carbonate used as filler during the production of various plastic products from virgin polypropylenes and polyethylenes polymers is added to improve their physical properties, for providing colour to polymers and for the cost reduction of products.
  • the precipitation of calcium carbonate and inorganic impurities on the surface of the thermal cracking tubular coils leads to (i) clogging of the thermal cracking tubular coils due to the reduction in surface area of the thermal cracking tubular coils and (ii) absorption of oil contents on the surface of the precipitation and thereby creating coking in the thermal cracking tubular coils.
  • the precipitation and coking in the thermal cracking tubular coils create undesired differential pressures and hence shutdown of the plant at very short intervals of time.
  • calcium carbonate and other inorganic impurities must be removed continuously from the stage 1 thermal cracking reactor along with the cracked hydrocarbons. vi.
  • the fluid containing long chain hydrocarbons, inorganic impurities and a desired quantity of hydrocarbons ranging from ⁇ Cis and > C12 will be separately treated for the separation of the inorganic impurities from the hydrocarbons.
  • the separation of the inorganic impurities from the hydrocarbons may be carried out by filtration alone or filtration followed by hot water rinsing or only with hot water rinsing. Filtration may be carried out using any of a liquid filtration mechanism such as a pressure leaf filter or a hydraulic filter press or any other suitable equipment capable of filtration of liquid hydrocarbons through a filter media having a pore size varying from 0.5 micrometer (pm) to 10 pm.
  • the filtration may be carried out under hot conditions with a temperature of mixed fluid being maintained up to 200 °C or between 80 °C to 150 °C.
  • Hot water rinsing may be carried out by agitating the mixed fluid in hot water having water contents of up to 1 to 50 % and the temperature of the mixture being maintained in the range of 50 °C to 90 °C.
  • Hot water rinsing may be carried out once or multiple times depending upon the presence of impurities in the hydrocarbons.
  • Density separation or layer separation of the cleaned hydrocarbons may be carried out from water component containing impurities. Cleaned hydrocarbons separated from the inorganic impurities may be dried and collected as a feedstock for stage - 2 thermal cracking reactions. vii.
  • stage 2 thermal cracking reactor will be a plug flow type tubular reactor having electrically heated tubular coils with a tube diameter ranging from 25 mm to 100 mm.
  • the cleaned hydrocarbons may be partially heated in shell and tube heat exchangers with hot thermic oil before entering the stage 2 thermal cracking reactor.
  • Optimum thermal cracking reactions under controlled conditions will be carried out in the stage 2 thermal cracking reactor within a pressure range of up to 50 bars and a temperature range of up to 650 °C to achieve a maximum yield of ⁇ Cis hydrocarbons.
  • Stage 2 thermal cracking reactions may be conducted under the pressure range of 1.2 to 15 bars or from 2 to 25 bars and temperature range of 420 °C to 520 °C or from 440 °C to 480 °C so as to receive maximum of thermally cracked products having hydrocarbon chain length of up to ⁇ Cis.
  • Two phase flow will be maintained during the stage 2 thermal cracking reactions with the composition of fluid having liquid contents between 5 to 30 % or between 2 to 20 %.
  • the thermally cracked products from an outlet of the stage 2 thermal cracking reactor will be discharged into a fractional distillation column for the separation of hydrocarbons components into non-condensable gases, olefinic liquid biofuels having hydrocarbon chain length of up to ⁇ Cis and residual pitch.
  • the non-condensable gases generated from the stage 1 and stage 2 thermal cracking reactor may be utilised for the provision of energy required in the process in a thermic fluid heater or a steam generator or production of electrical energy.
  • the residual pitch generated from the stage 2 thermal cracking reactions may be used as source of energy in the downstream industry. ix.
  • the olefinic liquid biofuels produced during stage 1 and stage 2 thermal cracking reactions may contain some unwanted impurities such as organic chlorides, nitrogen, sulphur, and oxygen etc.
  • the source of organic impurities in the olefinic liquid biofuels may be presence of some constituents of polyvinyl chloride (PVC), polyethylene terephthalate (PET) or any other type of plastics which may be present as unwanted impurities in the feedstock during the stage 1 thermal cracking reactions.
  • PVC polyvinyl chloride
  • PET polyethylene terephthalate
  • the organic impurities need to be removed and the olefins needs to be saturated to convert them into paraffinic biofuels.
  • Saturation of olefins liquid biofuels and removal of organic impurities such as organic chlorides, nitrogen, sulphur, and oxygen may be done simultaneously with the hydrogenation of olefinic liquid biofuels.
  • the olefinic liquid biofuels in the liquid phase will be reacted with hydrogen gas in the presence of Ni catalyst or any other metal catalyst of Group VIII metals of a periodic table in a hydrogenation reactor.
  • the hydrogenation reactions will be carried out under hydrogen pressure with a gas pressure range varying from 2 to 50 bar (0.2MPa to 5MPa) and temperature of the fluid in the hydrogenation reactor varying from 120 °C to 250 °C. x.
  • the hydrogenated biofuels may be passed through another fractional distillation column operated under vacuum for the separation of products as per specific use, based on their carbon chain length and boiling points.
  • the present disclosure will now be illustrated in greater detail with reference to an example, but the present disclosure should not be interpreted as being restricted thereto.
  • the following is the example that is described in detail about the method of production of biofuels from waste plastics.
  • the source of waste plastics may be industrial, commercial or residential waste plastics.
  • FIG 1 illustrates an exemplary pretreatment plant (10) for segregating and pretreating of the waste plastics
  • the pretreatment plant (10) includes a shredder (115), a first sink float tank (120), a first screw press (135), a granulator (140), a second sink float tank (145), a second screw press (155), and a hot air dryer (160).
  • Segregation and pretreatment of the waste plastics was conducted as under; a) 2 MT of waste plastics consisting of mixed polypropylene and polyethylene (packaging material) (110) was procured.
  • the waste plastics contained physically separable impurities like sand particles, paper, some quantity of PVC, PET etc.
  • b) The waste plastics was shredded in a coarse shredder (115) and the size of the waste plastic was reduced to around 25 mm.
  • the coarse shredded material was washed in the first sink float tank (120) using water. Density of water was maintained at 1050 kilogram/metre 3 (kgs/m 3 ) by adding sodium chloride (125) in the first sink float tank (120).
  • the main objective of the partial thermal cracking of feedstock in the electrically heated, plug flow type stage 1 thermal cracking tubular reactor was to convert the waste plastics into (i) a desired product comprising olefinic liquid biofuels having carbon chain length of ⁇ Cis, and (ii) long chain hydrocarbons having carbon chain length of up to ⁇ C30 along with continuous and complete removal of CaCOs from the stage 1 thermal cracking reactor without any significant coke formation so as to run the stage 1 thermal cracking process continuously for long run lengths without any shutdown.
  • Figure 2 illustrates an exemplary process plant (20) for partial thermal cracking of feedstock.
  • the process plant (20) includes an extruder (170), a stage 1 thermal cracking reactor (175), a first distillation column (180), a first filter press (195), and an agitated vessel (210). Stage 1 thermal cracking process operations were conducted as under; a) The prepared feedstock (165) was continuously fed into a screw type melt extruder (170) @ 10 kgs/hour. Temperature at the discharge header of the screw type melt extruder (170) was maintained @ 250 °C. Molten liquid mass from a discharge header outlet was pumped into stage - 1 thermal cracking reactor (175).
  • Stage 1 thermal cracking reactor (175) used in the process was a plug flow type, electrically heated with mineral insulated heat trace type electrical heaters, having vertical coils of 50 mm NB (nominal bore). Two phase flow was maintained at the outlet of the stage 1 thermal cracking reactor (175) with the fluid having around 70 % liquid in it for carrying out the continuous and complete removal of CaCCh as suspension in the liquid.
  • the outlet parameters of the stage 1 thermal cracking reactor (175) were maintained as under;
  • Long chain hydrocarbons (190) is cleaned in a long chain hydrocarbons cleaning unit.
  • the long chain hydrocarbons cleaning unit includes, but not limited to, the first filter press (195), and the agitated vessel (210).
  • Long chain hydrocarbons (190) having molecular size > Cis and ⁇ C30 were collected from a bottom of the first distillation column (180), passed through a condenser to maintain temperature of up to 200 °C and sent to the first filter press (195) for the removal of CaCCh from the long chain hydrocarbons (190).
  • CaCCL with some oil constituents was recovered as cake (200) whereas clear hydrocarbons were recovered as filtrate (205). 150 kgs.
  • stage - 1 partial thermal cracking process was operated continuously for more than 7 days i.e., 170 hours @ 10 kgs/hour of feed and there was no shutdown of the process due to either retention of CaCCT or due to coke formation within the stage 1 thermal cracking reactor (175).
  • stage 1 thermal cracking reactor (175) was inspected and a surface of the stage 1 thermal cracking reactor (175) was found clean without any significant attached impurities.
  • Stage - 2 thermal cracking of cleaned long chain hydrocarbons (In accordance with Figure - 3) The main objective of the stage 2 thermal cracking of cleaned long chain hydrocarbons was to achieve maximum yield of ⁇ C18 hydrocarbons.
  • Figure 3 illustrates an exemplary process plant (30) for thermal cracking of cleaned long chain hydrocarbons and hydrogenation of the thermally cracked biofuels.
  • the process plant (30) includes a stage 2 thermal cracking reactor (225), a second distillation column (230), a hydrogenator reactor (245), hydrogen cylinders (250), a second filter press (255), and a third distillation column (260).
  • Stage 2 thermal cracking process operations were conducted as under; a) Cleaned long chain hydrocarbons (220) having molecular size > Cis and ⁇ C30 was pumped into a stage 2 thermal cracking reactor (225) @ 10 kgs/hour. Plug flow type, electrically operated stage 2 thermal cracking reactor (225) having vertical coils of 50 mm NB was used for the optimum thermal cracking of the long chain hydrocarbons (220) having molecular size > Cis and ⁇ C30. Two phase flow was maintained at an outlet of the stage 2 thermal cracking reactor (225) with fluid having ⁇ 20 % liquid contents. b) The outlet parameters of the stage 2 thermal cracking reactor (225) were maintained as under;
  • stage 2 thermal cracking process was operated continuously for more than 3 days i.e., 83 hours @ 10 kgs/hour of feed and there was no shutdown of the process due to coke formation in the stage 2 thermal cracking reactor (225).
  • the filtrate was distilled in the third distillation column (260) operated at 0.5 Bar pressure (Gauge Pressure).
  • the top-level temperature of the third distillation column (260) was maintained at 330 °C to recover only up to ⁇ Cis hydrocarbons.
  • the vapors from a top of the third distillation column (260) were condensed in a condenser and the final distilled paraffinic biofuels (265) having molecular size of ⁇ Cis were collected as final product. 1400 kgs. or 1750 liters of paraffinic biofuels (265) was received as final product.

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  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente divulgation concerne des procédés de conversion de constituants polypropylènes et polyéthylènes de déchets plastiques en des hydrocarbures de taille moléculaire ≤ C18, en tant que biocarburants par un procédé de craquage thermique en deux étages, continu, non catalytique, à l'aide de réacteurs de craquage thermique à tubes enroulés, à chauffage électrique, à écoulement bouchon, et pour obtenir des rendements plus élevés en hydrocarbures paraffiniques de taille moléculaire ≤ C18. Le procédé fournit également une solution à l'élimination continue d'impuretés inorganiques physiquement non séparables tels que le carbonate de calcium présent comme charge dans une charge d'alimentation, en assurant une durée d'exploitation longue et continue d'un procédé sans aucune interruption.
PCT/IN2023/050251 2022-04-25 2023-03-16 Production de biocarburants à partir de déchets plastiques WO2023209725A1 (fr)

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Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
FAHIM IRENE, MOHSEN OMAR, ELKAYALY DINA: "Production of Fuel from Plastic Waste: A Feasible Business", POLYMERS, vol. 13, no. 6, pages 915, XP093106800, DOI: 10.3390/polym13060915 *
JUWONO H, NUGROHO K A, ALFIAN R, NI’MAH Y L, SUGIARSO D, HARMAMI: "New generation biofuel from polypropylene plastic waste with co-reactant waste cooking oil and its characteristic performance", JOURNAL OF PHYSICS: CONFERENCE SERIES, INSTITUTE OF PHYSICS PUBLISHING, GB, vol. 1156, 1 January 2019 (2019-01-01), GB , pages 012013, XP093106799, ISSN: 1742-6588, DOI: 10.1088/1742-6596/1156/1/012013 *

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