WO2023180796A1 - Liquéfaction hydrothermique catalytique de déchets plastiques, de biomasse, dans un solvant contenant de la lignine à partir d'une usine de production d'éthanol 2g - Google Patents

Liquéfaction hydrothermique catalytique de déchets plastiques, de biomasse, dans un solvant contenant de la lignine à partir d'une usine de production d'éthanol 2g Download PDF

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WO2023180796A1
WO2023180796A1 PCT/IB2022/054953 IB2022054953W WO2023180796A1 WO 2023180796 A1 WO2023180796 A1 WO 2023180796A1 IB 2022054953 W IB2022054953 W IB 2022054953W WO 2023180796 A1 WO2023180796 A1 WO 2023180796A1
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stream
biomass
feedstock
oil stream
hydrothermal liquefaction
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PCT/IB2022/054953
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Lavanya Meesala
Pedapati Chakradhar
Pramod Kumar
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Hindustan Petroleum Corporation Limited
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/40—Destroying solid waste or transforming solid waste into something useful or harmless involving thermal treatment, e.g. evaporation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/60—Biochemical treatment, e.g. by using enzymes
    • 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
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/083—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts in the presence of a solvent
    • 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
    • C10G1/08—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal with moving catalysts
    • C10G1/086—Characterised by the catalyst used
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24—Chromium, molybdenum or tungsten
    • B01J23/28—Molybdenum
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B2101/00—Type of solid waste
    • B09B2101/75—Plastic waste
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B2101/00—Type of solid waste
    • B09B2101/75—Plastic waste
    • B09B2101/77—Plastic waste containing chlorine
    • 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/14—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts
    • C10G11/18—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils with preheated moving solid catalysts according to the "fluidised-bed" technique
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • 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
    • C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
    • C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours

Definitions

  • the present invention generally relates to aprocess for preparing hydrocarbons and chemicals from waste plastics and biomass. Specifically, the present invention relates to a solvothermal process for producing high quality fuels and chemicals from a feedstock comprising combination of waste plastics and biomass using lignin containing bioliquor as a solvent for hydrothermal liquefaction with transition metal catalyst.
  • the lignin containing bioliquor of the present invention isproduced as a waste stream from 2G-ethanol manufacturing plants.
  • plastics like polyethylene, polypropylene, teflon, nylon, polyester, polyvinyl chloride, thermoplastic polyurethane, etc., have emerged as the most fundamental commodity for human-life.
  • Plastic waste is produced each year and being non-biodegradable, this plastic wastes are a huge threat to the environment in addition to the already existing pollution. Hence, there is a need to reduce the amount of plastic waste.
  • Hydrothermal liquefaction offers the advantage of pyrolyzing the waste plastics at low temperatures (may be 120 deg C to 400 deg C), and the convenience of using wet waste to form plastic crudeoil, that can be conveniently used as fuel blend with simple upgradation processes.
  • MSW Municipal solid waste
  • India also has significant amount of agricultural residues like wheat straw, rice husk and rice starw etc available which can be converted to energy source.
  • An object of the present invention is to provide a method of solvothermal process for producing high quality fuels and chemicals from a feedstock comprising of combination of biomass and waste plastics using lignin containing bio-liquor as a solvent for liquefaction.
  • Another object of the present invention is to provide a method of solvothermal process for producing high quality fuels and chemicals from a feedstock comprising of combination of biomass and waste plastics using lignin containing bioliquor as a solvent for liquefaction wherein the lignin containting liquor is formed from the acid/base pre-treatment of 2G-ethanol plant waste stream.
  • Another object of the present invention is to provide a method of solvothermal process for producing high quality fuels and chemicals from a feedstock comprising of combination of biomass and waste plastics using lignin containing bioliquor as a solvent for liquefaction yielding very good oil yieldwith assistance of transisition metal catalyst.
  • the present invention relates to a solvothermal process for producing high quality fuels and chemicals from a feedstock comprising combination of waste plastics and biomass using lignin containing liquor as a solvent for liquefaction.
  • the lignin containing liquor of the present invention is produced as a waste stream from 2G-ethanol manufacturing plants.
  • the present invention relates to a method of producing fuels and chemicals from a feedstock comprising combination of biomass and waste plastics comprising the steps of:
  • the waste plastic is selected from low density polyethylene (LDPE), high density polyethylene (HDPE), linear LDPE, polypropylene (PP), Teflon, nylon, polyester, polyvinyl chloride, thermoplastic polyurethane and combination thereof.
  • LDPE low density polyethylene
  • HDPE high density polyethylene
  • PP polypropylene
  • Teflon Teflon
  • nylon polyester
  • polyester polyvinyl chloride
  • thermoplastic polyurethane thermoplastic polyurethane and combination thereof.
  • the biomass is selected from rice straw, rice husk, saw dust, corn stover and combination thereof.
  • the acid is selected from organic acid or inorganic acids, like H2SO4, HC1, oxalic acid at different dilutions; base is selected from sodium hydroxide, KOH and C5-C6 sugar is xylose, arabinose, glucose, fructose and lignin.
  • the bioliquor stream comprises of sodium hydroxide and lignin.
  • the hydrothermal liquefaction is carried out at a temperature in the range of 120 deg C to 400 deg C.
  • the hydrothermal liquefaction is carried out at an initial pressure of batch reactor is in the range of 0.1 -0.5 MPa and an in-situ pressure generated is in the range of 10-30 MPa.
  • the hydrothermal liquefaction is carried out at a temperature in the range of 180 deg C to 350 deg C.
  • the hydrothermal liquefaction is carried out in a time ranging from 5 minutes to 120 minutes.
  • the gaseous product obtained from the liquefied product is routed for heat integration with feedstock heating.
  • the separating gas-free product stream comprises separating of bleed stream and make-up liquid which is connected with the bio-liquor for further processing.
  • the present invention relates to a purification of solid phase obtained from the gas-free product stream comprising the step of:
  • the present invention relates to amethod of upgradation oil stream obtained from the method of claim 1, wherein the upgradation methods are selected from:
  • the catalyst used in the fluid catalytic cracking unit is selected from ZSM-5, beta zeolite, y- zeolite or combination thereof.
  • Figure 1 represents process flow for the catalytic hydrothermal liquefaction of feedstock comprising combination of biomass and waste plastics.
  • Figure 2 represents process flow for upgradation of oil stream to valuable chemicals.
  • Figure 3 shows the comparative oil yield for the comparative examples and examples 1-2 of the present invention.
  • the numbers expressing quantities of ingredients, properties such as concentration, reaction conditions, and so forth, used to describe and claim certain embodiments of the invention are to be understood as being modified in some instances by the term “about.” Accordingly, in some embodiments, the numerical parameters set forth in the written description are approximations that can vary depending upon the desired properties sought to be obtained by a particular embodiment. In some embodiments, the numerical parameters should be construed in light of the number of reported significant digits and by applying ordinary rounding techniques. Notwithstanding that the numerical ranges and parameters setting forth the broad scope of some embodiments of the invention are approximations, the numerical values set forth in the specific examples are reported as precisely as practicable.
  • inventive subject matter provides many example embodiments of the inventive subject matter. Although each embodiment represents a single combination of inventive elements, the inventive subject matter is considered to include all possible combinations of the disclosed elements. Thus if one embodiment comprises elements A, B, and C, and a second embodiment comprises elements B and D, then the inventive subject matter is also considered to include other remaining combinations of A, B, C, or D, even if not explicitly disclosed.
  • hydrothermal liquefaction reactor refers to a reactor in which a solvent is used at its super critical conditions for hydrothermal liquefaction to convert any organic substance to crude oil and chemicals at moderate temperature and pressure.
  • the hydrothermal liquefaction process is conducted in a batch type autoclave reactor, that can sustain temperatures upto 500 deg C and pressures upto 32MPa, fitted with an electrically heated furnace, high temperature thermocouple, stirrer, and pressure gauge.
  • the reactor material can be stainless steel (SS3316) and the volume of reactor is anywhere between 0.5 to 1.2 L.
  • the reactor used in this study was a 0.5 L high temperature and high pressure stirred reactor (Parr 4575) with Parr 4848B reactor controller obtained from Parr Instrument Co., Moline, IL, US.
  • transition metal catalyst refers to a catalyst as prepared in the the patent applications, US20210339235A1 and WO2018235094A1.
  • the transition metal catalyst can be oil soluble catalyst or water soluble catalyst and in the form of powder.
  • the liquefaction of polyolefins begins with the depolymerization reactions that involve the cleavage of C-C or C-H bonds to form oligomers that undego P- scission reactions to give rise to olefins, which on cyclization form cyclic hydrocarbons. These cyclics, on dehydrogenation further give rise to aromatics. There is a possibility of some aromatics undergoing undesirable reactions to form polycyclic aromatic hydrocarbons that are the major precursors for solid char. The biomass liquefaction in the presence of transition-metal catalyst gave more phenolics, and aromatics. Unexpectedly, the coliquefaction of feedstock comprising combination of waste plastic and biomass resulted in high olefins and naphthenes in the present invention.
  • the present invention relates to a method of producing fuels and chemicals from a feedstock comprising combination of biomass and waste plastics comprising the steps of:
  • the figure 1 shows the flow scheme for the catalytic hydrothermal liquefaction of waste plastic and biomass in the presence of solvent and a transition metal catalyst to valuable chemicals and fuels in accordance with the present disclosure.
  • the feedstock comprising combination of biomass and waste plastic is stored or mixed in the feed hopper combined with feeder(3) which is introduced into the hydrothermal liquefaction reactor (HTL) reactor (4).
  • HTL hydrothermal liquefaction reactor
  • the lignocellulosic biomass is initially processed in the biomass pretreatment unit (1) where acid/base pre-treatment occurs and then, the C5-C6 sugars (b), constituting cellulose and hemicellulose are sent into a fermenter (2), where the ethanol (c) is the main product along with a lignin containing liquor stream (d).
  • This bio-liquor (d) is composed of sodium hydroxide and lignin and is passed to the hydrothermal liquefaction reactor (HTL) reactor (4) comprising of mixed feedstock.
  • HTL hydrothermal liquefaction reactor
  • a transition-metal catalyst (e) is added in to the HTL reactor.
  • the liquefaction takes place at a temperature in the range of 120 deg C to 400 deg C and at a pressure in the range of 120-300 bar, and for a residence time 5 min to 120 min to obtain a liquefied product (mixture of solid char, aqueous phase and oil phase) (f).
  • This liquefied product (f), obtained during the hydrothermal liquefaction is sent into a product collector vessel (5), where the gaseous product (g) may be collected, may be sent to vent, may be routed for heat integration with feedstock heating.
  • the gas -free product stream (i) is sent into a liquid- solid separator (6), where there may be a single stage or multistage separation procedures.
  • the mixed plastic and biomass crude stream (j) is separated from the solid phase (n) and the aqueous phase (k).
  • a bleed stream (1) and make-up liquid (h) are also separated.
  • the oil phase (j) can be purified or processed in (7) and final oil (m) can be sent for upgradation or blending into drop in fuel/ co-processed in refinery units like fluid catalytic cracking or hydrocracking/ hydrotreater.
  • the solid phase (n) is sent into a purification unit (8), where the solid phases is purified and the raw char stream(o) is sent into solid char upgradation unit (9) to obtain a final product which can be used as a catalyst support (p) or for bio-remediation aid(q).
  • the solid char upgradation unit can use steam, KOH or any other activation agent for improving surface area and physical propertirs of raw char stream.
  • the waste plastics can be selected from be low density polyethylene (LDPE), high density polyethylene (HD PE) linear LDPE, polypropylene (PP), polyethylene terephthalate (PET), Teflon, nylon, polystyrene, polyester, polyvinyl chloride, thermoplastic polyurethane or combination thereof.
  • the feedstock of waste plastics can be polypropylene (PP), Polyethylene Terephthalate (PET), Teflon, nylon, polyester, polyvinyl chloride or combination thereof.
  • the biomass for feedstock is selected from any of the different kinds of lignocellulosic biomass categories - hardwood, softwood, grasses and agricultural wastes.
  • biomass are poplar, oak, eucalyptus, pine, douglas fir, spruce, wheat straw, barley hull, barley straw, rice straw, rice husks, oat straw, ray straw, corn cobs, corn stalks, sugarcane bagasse, sorghum straw, grass, switch grass and so on or combination thereof.
  • the biomass for feedstock is selected from rice straw, rice husk, saw dust, com stover, wheat straw, com cobs, bagasse, municipal solid waste and combination thereof.
  • the bioliquor stream can be formed from the acid/base pre-treatment of 2G-ethanol plant waste stream, as a solvent for the process, that aids in improving the plastic crude oil yield, and also producing alcohols, olefins, naphthenes and paraffins in ranges that are useful for being used for lube oil preparation, bitumen blending, surfactants, detergents, fuels and petrochemical feedstock and so on.
  • the transition metal based oilsoluble catalyst or powdered catalyst is in the concentration of 1-20 wt% of solids loading for enhancing the quality of the crude towards fuel oils and lubricating oils.
  • the bio-liquor stream comprises of 1% to 10 wt % sodium hydroxide (NaOH) and lignin about 2 to 30 wt% and can be associated with lignin concentration step using multi effect evaporation.
  • the liquefaction takes place at a temperature in the range of 120 deg C to 400 deg C.
  • the liquefaction takes place at apressure in the range of 2 to 30 MPa.
  • a pressure in the range of 15 to 25MPa More preferably, at apressure in the range of 20 to 25MPa.
  • the reacting bio-liquor stream in the hydrothermal liquefaction reactor is carried out in a time ranging from 5 minutes to 120 minutes. Preferably, in a time ranging from 10 minutes to 60 minutes. More preferably, in a time ranging from 10 minutes to 20 minutes.
  • the catalyst used in the liquefaction can be present in the concentration range of 0.1-10 wt% of solids loading for enhancing the quality of the plastic crude towards fuel oils and lubricating oils.
  • the method of converting of mixed feedstock of biomass to fuels and chemicals provides oil stream in range of 65% to 75% yield.
  • the method of converting of mixed feedstock of biomass to fuels and chemicals produces valuable fuel compounds, olefins and aromatics.
  • the fuels and chemicals are selected from the aromatic, alcohol, alkane, alkene, cycloalkane, phenols and ketonic.
  • the method of converting of mixed feedstock to fuels and chemicals produces olefins, and naphthenes that are useful for lube oil preparation, bitumen blending, surfactants, detergents, fuels and petrochemical feedstock and the like.
  • the method of converting of mixed feedstock to fuels and chemicals produces valuable chemicals in significantly higher quantity.
  • the present invention relates to a method of upgrading the crude oil stream, wherein the upgradation methods are selected from:
  • figure 2 shows the flow scheme of upgradation techniques for the products obtained from the solvothermal synthesis of waste plastics in the presence of bio-liquor solvent.
  • the oil stream (j) can be purified or processed in unit (2a) .
  • Unit (2a) can be a coprocessing unit, where the oil stream mixed with petroleum fractions like vacuum gas oil and heavy gas oil and processed to obtain the upgraded fuels or chemicals.
  • unit (2a) can be a hydrotreating unit for converting crude oil stream into diesel/jet range fuels.
  • Unit (2a) can also be a fluid catalytic cracking unit, where crude oil streamcan be cracked in presence of catalysts like zeolites (ZSM-5, beta zeolite, y- zeolite etc) to light olefins and gasoline additive compounds.
  • Unit (2a) can also be a steam cracking unit, where crude oil stream can be steam cracked to produce ethylene and propylene
  • the updgradation of oil stream (j) comprising the step of purifiying oil stream (j) in unit (2a) to obtain purified oil stream.
  • the updgradation of oil stream (j) comprising the steps of:
  • the biomass used in the present invention is procured from the local animal feed market in Devangonthy, Bengaluru.
  • Biomass waste used is secured from the agriculture fields in the neighboring rural areas of the city.
  • the agriculture waste usually consists of rice husk, or rice straw etc.
  • the agriculture waste is used directly in the experimentations without any pre-treatment or pre-processing stages.
  • Bio-liquor is produced as a waste stream from the 2G-ethanol plants. This is further sent for acid pre-treatment so as to concentrate the lignin content in the stream.
  • Sulfuric acid (2 g) is taken for about 200 ml of untreated bioliquor. This solution is made up to 600 ml using water. Around 150 g biomass is added to this solution and is soaked for 30min to 1 hour. The soaked liquor is then cooked in a reactor for 15 to 30 min at a temperature of 200 deg C. Later, after it cools down, residue is squeezed manually, and the waste liquor of about 400 ml is produced which is disposed. Now, the solid residue which is containing about 200 ml liquor is taken, and to this, about 2% sodium hydroxide solution is added. For 1 eq of the solid residue, an equal amount of sodium hydroxide solution is added and left for some time.
  • bio-liquor solution obtinaed is used as a low cost fuel, but, in this innovation, it is being used as a solvent for the hydrothermal liquefaction of biomass, as the linin content in the liquor aids in forming very useful bio-crude oil, that can be further used as a diesel or gasoline blend.
  • the metal precursor about 100g molybdic acid is taken and a solution is prepared. To this, 100g of 2-ethyl hexanoic acid (first additive) solution was added and refluxed at 180 °C for 4 hours to obtain the dark black color salt. The salt obtained was cooled and re-dissolved in 150 g of 2-ethyl hexanol (second additive) and heated with reflux at 180 °C for 12 hours to obtain the Mo(O), (2-ethyl hexanoate)2-ethyl hexanolate). About 340g was produced with the Mo percentage around 14 %.
  • the reactor is kept at the desired temperature for residence time of 15 minutesat the pressures of 23-25 MPa.
  • the autoclave is immediately cooled to room temperature with an external cooling bath. After the gas samples were collected for analysis using gas bags, the pressure was released from the reactor through vent.
  • the contents of the reactor and the stirrer are washed thoroughly with a solvent dichloromethane for three times.
  • the mixture was filtered with the help of buchner filter funnel, to remove the solids from the liquid phase. Two layers are observed in the separating funnel, where the oil stream is separated from the aqueous stream. Oil stream is extracted from the liquid samples by separating the solvent in a rotary vacuum evaporator (Buchi Rotavapor).
  • the compounds obtained in the oil stream is given in the table 1 below.
  • Example 2 [0086] Biomass (rice husk (RH)); Waste plastic (polypropylene (PP)); Solvent
  • Table 2 List of all major compound
  • Table 2a List of all major chemical group compounds
  • Biomass (rice husk (RH)); Waste plastic (polypropylene (PP)); Solvent (water) and No Catalyst
  • Comparative example -2 (CE-2): [0090] Biomass (rice straw (RS)); Waste plastic (polypropylene (PP)); Solvent (water) and No Catalyst
  • XSR % (Weight of Solid Residue x 100) / Weight of feedstock — (1)
  • XOIL % (Weight of Oil x 100) / Weight of feedstock - (2)
  • the process of present invention provides high yield of the oil stream when compared to the comparative examples.
  • the final product may have organic compounds which may have dissolved in aquoues phase which resulted in low oil yield in the comparative examples.
  • the present invention provides a method of converting of mixed feedstock of biomass to fuels and chemicals which gives high yield of oil stream.
  • the present invention provides a method of converting of mixed feedstock of biomass to fuels and chemicalswhich gives high yield of olefins and naphthenes.
  • the method of present invention shows synergestic effect and results in high yield of oil compared to when biomass and plastics are treated independently.
  • the method present invention can be utilized for conversion of MSW which is hard to seggreagte from plastics.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • General Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Biochemistry (AREA)
  • Physics & Mathematics (AREA)
  • Thermal Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

La présente invention concerne un procédé solvothermique pour produire des combustibles et des produits chimiques de haute qualité à partir d'une charge d'alimentation comprenant une combinaison de déchets plastiques et de biomasse à l'aide d'une liqueur contenant de la lignine en tant que solvant pour la liquéfaction conjointement à l'utilisation d'un catalyseur de métal de transition. La liqueur contenant de la lignine de la présente invention est produite en tant que flux de déchets à partir d'usines de production d'éthanol 2G.
PCT/IB2022/054953 2022-03-25 2022-05-26 Liquéfaction hydrothermique catalytique de déchets plastiques, de biomasse, dans un solvant contenant de la lignine à partir d'une usine de production d'éthanol 2g WO2023180796A1 (fr)

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WO2018096103A1 (fr) * 2016-11-25 2018-05-31 Cambridge Enterprise Limited Photocatalyseur et procédés photocatalytiques
US20200165526A1 (en) * 2017-07-13 2020-05-28 Envirollea Inc. Process for producing liquid fuel from waste hydrocarbon and/or organic material, reactor, apparatus, uses and managing system thereof
WO2020223335A1 (fr) * 2019-04-30 2020-11-05 Xyleco, Inc. Éthylène d'origine biologique pour la production de polymères d'origine biologique, de copolymères et d'autres composés chimiques d'origine biologique

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Publication number Priority date Publication date Assignee Title
US4013543A (en) * 1975-10-20 1977-03-22 Cities Service Company Upgrading solid fuel-derived tars produced by low pressure hydropyrolysis
US9200207B2 (en) * 2011-05-31 2015-12-01 University Of Central Florida Research Foundation, Inc. Methods of producing liquid hydrocarbon fuels from solid plastic wastes
WO2018096103A1 (fr) * 2016-11-25 2018-05-31 Cambridge Enterprise Limited Photocatalyseur et procédés photocatalytiques
US20200165526A1 (en) * 2017-07-13 2020-05-28 Envirollea Inc. Process for producing liquid fuel from waste hydrocarbon and/or organic material, reactor, apparatus, uses and managing system thereof
WO2020223335A1 (fr) * 2019-04-30 2020-11-05 Xyleco, Inc. Éthylène d'origine biologique pour la production de polymères d'origine biologique, de copolymères et d'autres composés chimiques d'origine biologique

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ADEGOKE SAMUEL OLUWAFIKAYO, ADELEKE ADEKUNLE AKANNI, IKUBANNI PETER PELUMI, NNODIM CHIEBUKA TIMOTHY, BALOGUN AYOKUNLE OLUBUSAYO, F: "Energy from biomass and plastics recycling: a review", COGENT ENGINEERING, vol. 8, no. 1, 1 January 2021 (2021-01-01), XP093094711, DOI: 10.1080/23311916.2021.1994106 *
AHAMED KAMEEL NURUL IZZAH, WAN DAUD WAN MOHD ASHRI, ABDUL PATAH MUHAMAD FAZLY, MOHD ZULKIFLI NURIN WAHIDAH: "Influence of reaction parameters on thermal liquefaction of plastic wastes into oil: A review", ENERGY CONVERSION AND MANAGEMENT: X, vol. 14, 1 May 2022 (2022-05-01), pages 100196, XP093094709, ISSN: 2590-1745, DOI: 10.1016/j.ecmx.2022.100196 *
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