EP4108737A1 - Method for improving quality and stability of pyrolisis oils obtained from waste - Google Patents

Method for improving quality and stability of pyrolisis oils obtained from waste Download PDF

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Publication number
EP4108737A1
EP4108737A1 EP21382561.5A EP21382561A EP4108737A1 EP 4108737 A1 EP4108737 A1 EP 4108737A1 EP 21382561 A EP21382561 A EP 21382561A EP 4108737 A1 EP4108737 A1 EP 4108737A1
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Prior art keywords
waste
pyrolysis
ppm
adsorption
hydrotreatment
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EP21382561.5A
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German (de)
French (fr)
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Juan Pedro GÓMEZ MARTÍN
Sergio SEDANO SANTAMARÍA
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Neoliquid Advanced Biofuels And Biochemicals SL
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Neoliquid Advanced Biofuels And Biochemicals SL
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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
    • C10G1/002—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
    • C10G1/10—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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/42—Catalytic treatment
    • C10G3/44—Catalytic treatment characterised by the catalyst used
    • C10G3/45—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof
    • C10G3/46—Catalytic treatment characterised by the catalyst used containing iron group metals or compounds thereof in combination with chromium, molybdenum, tungsten metals or compounds thereof
    • 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
    • C10G3/00—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids
    • C10G3/50—Production of liquid hydrocarbon mixtures from oxygen-containing organic materials, e.g. fatty oils, fatty acids in the presence of hydrogen, hydrogen donors or hydrogen generating compounds
    • 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
    • C10G45/06—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 containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—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 containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
    • 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
    • C10G45/10—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 containing platinum group metals or compounds thereof
    • 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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10B—DESTRUCTIVE DISTILLATION OF CARBONACEOUS MATERIALS FOR PRODUCTION OF GAS, COKE, TAR, OR SIMILAR MATERIALS
    • C10B53/00—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form
    • C10B53/07—Destructive distillation, specially adapted for particular solid raw materials or solid raw materials in special form of solid raw materials consisting of synthetic polymeric materials, e.g. tyres
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1003—Waste materials

Definitions

  • the present invention relates to a method for transforming pyrolysis oils originating from microwave-assisted (or non-assisted) thermal pyrolyses into stable, quality products which can be used in the chemical industry and in fuel and biofuel production.
  • Pyrolysis oils are obtained by means of pyrolysis of municipal and industrial waste. Waste is usually formed by variable mixtures of plastics of different nature and composition, with other waste originating from materials such as paper and cardboard, food waste, wood, plant waste, textile waste, etc. Pyrolysis is capable of treating mixtures of composite materials and various compositions.
  • pyrolysis oils Due to the variable composition of the waste, pyrolysis oils are formed by mixtures of many linear and branched, aromatic and aliphatic hydrocarbon compounds containing therein alkanes and alkenes, many of which have very highly reactive dienes. This diverse chemical composition leads to the instability of pyrolysis oils and to the composition of said oils evolving over time.
  • This heterogeneous hydrocarbon mixture has, additionally, a series of oxygenated products with variability in functional groups, in addition to compounds with sulphur, chlorine, nitrogen, phosphorus, silicon and some metals.
  • These oils must be treated and purified so that they have controlled quality and stability and can be used in processes of the chemical and petrochemical industry to enable plastic waste to be chemically recycled.
  • Pyrolysis reactions produce a mixture of organic substances made up of aliphatic and aromatic hydrocarbons, along with a large variety of organic compounds in which heteroatoms such as N, S, Cl, Si, P, Ca, K, Fe, Zn, etc., are present.
  • pyrolysis liquids are characterised as heterogeneous mixtures with a significant presence of particles of various sizes, comprised between 2 and 500 micra, heavy compounds formed by hydrocarbons with molecular chains exceeding C19, and diolefin compounds, which are unstable over time due to their reactivity. These mixtures are often decanted and distilled to remove heavy components and suspended particles. These operations generate unstable, poor-quality liquids that evolve within a few hours, generating phases and compounds which complicate their subsequent use.
  • the heterogeneity of the composition causes undesirable components to be unevenly distributed between the different obtained fractions with the distillation or fractionation operations. This lack of quality and homogeneity greatly complicates the industrial utilisation of these mixtures.
  • Decomposition by means of biomass pyrolysis produces a series of organic compounds with various functional groups including, among others, alcohols, ketones, aldehydes and carboxylic acids. These compounds react with one another while at the same time undergo oxidation reactions that change the composition of the obtained liquids.
  • the organic compounds give an acidic character and are largely responsible for the corrosion exhibited by pyrolysis liquids.
  • pyrolysis oils Today, treatments for improving and stabilising pyrolysis oils include the treatment thereof in large and expensive, high-temperature and pressure installations for performing hydrodeoxygenations and hydrodesulphurisations in batch or continuous processes. They are also used in catalytic cracking processes with zeolites at high temperatures or hydrogenation processes with metal catalysts of the Ru, Pd, Co, Mo, Zn, Ni, type, etc., supported on carbon, aluminas, or silica-alumina. These processes involve very expensive investment and operations and are highly sensitive to the contamination present in pyrolysis oils. Another problem of these processes is that they are developed at petrochemical scales, so they can neither be adapted to nor used at smaller scales in pyrolysis plants.
  • the present invention relates to a method for improving pyrolysis oils which include (or consist of) hydrocarbons and have been previously obtained from municipal or industrial solid waste, mixture of plastics, paper, cardboard, textile and biomass.
  • This method enables the subsequent use of these pyrolysis oils (hydrocarbons) in the chemical industry, facilitating circular economy, or in the fuel industry, reducing the carbon footprint thereof.
  • pyrolysis oils as the starting point, operations can be carried out on the waste, such as: selection and treatment of raw material (municipal solid waste and industrial waste); and pyrolysis: a thermochemical process performed in a specific pyrolysis reactor.
  • the pyrolysis oils are obtained as a starting point of the present invention, they are subjected, according to the present invention, to one or more of the following operations to improve their quality, as will be explained below:
  • the present invention relates particularly to a method for improving liquid pyrolysis oils which comprise (or consist of) hydrocarbons and have been obtained from waste preferably comprising between 15% and 85% by weight of plastics, and which comprises one or more of the following operations:
  • the operations comprise, or consist of, adsorption followed by hydrotreatment.
  • the pyrolysis oils on which this method can be applied are organic liquids obtained from the pyrolysis of municipal or industrial solid waste, mixture of plastics, paper, cardboard, textile and biomass, by means of, for example, the methods described in any of patents:
  • the present invention comprises a series of innovations intended for transforming pyrolysis oils obtained from a raw material (plastic waste and others: paper, cardboard, textile, biomass) into hydrocarbons which meet the specifications required in the chemical and/or fuel manufacturing industry.
  • the invention is developed for obtaining, starting from liquid oils obtained by means of the pyrolysis of a mixture of waste (thermochemical process), high-quality liquid hydrocarbons which can be used in the petrochemical industry and in fuel manufacture, and to that end the contaminant content of the obtained hydrocarbons must be as low as that shown in the following table: MAXIMUM Chlorine ppm 10 Bromine ppm 1 Iron ppm 10 Zinc ppm 0.5 Sodium ppm 5 Phosphorus ppm 5 Silicon ppm 1 Acidity (TAN) mgKOH/g 2
  • MSW municipal solid waste
  • IW industrial waste
  • residual biomass residual biomass
  • the solid waste Before processing the waste according to the treatment of the invention, the solid waste is subjected to a drying treatment to reduce moisture to values below 1%, given that this property varies in each batch of waste to be processed as it depends on hard-to-control factors such as: waste origin and waste transport and storage system. As such, if needed, to a mixture with other waste to homogenise pyrolysis reactor feeding.
  • pyrolysis oils are obtained from a thermochemical treatment carried out in a pyrolysis reactor designed and built to operate under co-pyrolysis conditions, in other words, allowing biomass waste materials and plastic waste to be co-processed at the same time. Both waste materials are in variable mixtures in the MSW and IW.
  • Solid organic matter can be converted into liquids by means of pyrolysis processes. These processes are characterised by the performance of thermochemical cracking reactions under anoxia, i.e., oxygen-free, conditions or under conditions with oxygen concentrations always below the stoichiometric amount.
  • thermochemical pyrolysis reaction can be developed in a pyrolysis reactor (2) according to any of patents P201331414, P201430719 or P201531858.
  • This process is characterised by performing the pyrolysis of residual biomass in the presence of residual plastics.
  • the residual plastics act as of hydrogen donors such that they modify the composition of the pyrolysis liquids by increasing the number of hydrocarbon compounds and reducing oxygenated compounds.
  • reactors allow the thermochemical reactions to be developed under controlled conditions on heterogeneous mixtures of variable composition such as MSW and IW.
  • the pyrolysis reactions are carried out in reactors which can be induced by means of inputting energy in the form of thermal or microwave energy.
  • the residual plastics present in the reactor are at least 15% with respect to the total waste fed to the plant.
  • the percentage of plastic waste can preferably reach up to 85% of the total waste fed to the plant.
  • the present invention relates particularly to a method for improving pyrolysis oils obtained from waste and comprising one or more of the following operations:
  • the contaminant type and content of the pyrolysis oil may vary as it is obtained from waste.
  • Table I shows how the properties of the obtained pyrolysis oil vary based on the variable % of non-plastic waste.
  • pyrolysis oil such as: sulphur, density, microcarbon waste, and TAN acidity increase with the % of non-plastic waste in the pyrolysis reactor feed.
  • TAN Total Acid Number
  • TAN values of the order of 16 mg KOH/g, as shown in Figure 1 may be obtained, so a reduction of this acidity is required.
  • Chlorine content This contaminant comes from the presence of compounds such as PVC in the waste to be pyrolysed or from forestry waste having chlorine in the composition thereof, present for the most part as organic chlorine.
  • the presence of this metal may originate from the use of zinc stearate in the manufacture of polymers.
  • silicon In terms of silicon, its presence is due to the use of silicon-based mineral fillers or organic additives in the formulation of certain plastics.
  • the method of the invention comprises performing an adsorption step for adsorbing the contaminants of the pyrolysis oils which are the starting material (hydrocarbons).
  • the function of this operation is to remove the contaminants present in the pyrolysis oil, to reduce acidity and to improve colour.
  • This operation consists of providing one or more vertical columns, through which the pyrolysis oils are passed, said columns being filled with adsorbents specific for each type of contaminant.
  • the adsorbents are formed in the shape of spheres or extruded, with a size between 1 and 5 mm, in order to reduce load loss in the bed.
  • the adsorbents to be used for each type of contaminant are:
  • the method of the invention comprises performing a distillation step for distilling the pyrolysis oils which are the starting material (hydrocarbons).
  • the pyrolysis oil obtained from waste can be distilled for use both in liquid fuel manufacture: gasoline, kerosene, diesel, and marine bunker fuel, and/or as raw material in the chemical industry for manufacturing olefins and aromatics in polymer production.
  • liquid fuel manufacture gasoline, kerosene, diesel, and marine bunker fuel
  • raw material in the chemical industry for manufacturing olefins and aromatics in polymer production.
  • process diagram used by the client simple or complex petroleum refinery, or petrochemical plant: steam cracking or aromatics production
  • a different distillation cut and quality will be required in each case, for example: naphtha range (initial point-160°C) for olefin production in steam cracking plants or cut (initial point-360°C) for gasoline, kerosene and diesel production in a petroleum refinery.
  • This fractionation of the oil influences contaminant distribution, so a method for improving the quality of the mixture of hydrocarbons obtained by means of the pyrolysis of waste is also taken into consideration.
  • the method comprises distilling the pyrolysis oil, where distillation can be selected from distillation with an initial point at 160°C or initial point at 360°C.
  • the method comprises performing adsorption and distillation.
  • the method of the invention comprises performing a hydrotreatment step for the hydrotreatment of the pyrolysis oils which are the starting material (hydrocarbons).
  • a hydrotreatment process may be required to remove compounds such as sulphur, nitrogen or silicon.
  • silica can also be used as a polymerisation catalyst support, being included in the polymer matrix.
  • Organosilane compounds with general structure RSi (OR') 3 are also used to promote adhesion between polymer and inorganic fillers.
  • the starting liquid pyrolysis oils contain silicon compounds, such as organosilanes, which are to be removed by means of the method of the invention.
  • silicones in the municipal waste gives rise to compounds, such as hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane, which result from the decomposition of silicones at temperatures >400°C, and which are also to be removed.
  • silicon compounds of this type as well as other sulphur and nitrogen compounds, is possible in a hydrotreatment process in a reactor with a solid catalyst formed by a metal (Ni, Co, Pt, Pd, NiMo, CoMo, NiW) on a support (alumina, silica-alumina, activated carbon, clay), in the shape of a sphere or extruded in a size between 1 and 3 mm.
  • the operating conditions are: space velocity (oil flow rate divided by volume of catalyst) between 1 and 5 h -1 , temperature: 150-320°C, pressure: 5-40 bar, H 2 /pyrolysis oil ratio: 50-200 Nm 3 /m 3 .
  • the hydrogen used can be imported from an external source or gas from the pyrolysis process which contains hydrogen, such as the one described in the following table, can be used: %wt H 2 0.86 CH4 15.07 CO 9.86 CO 2 19.67 C2H4 5.86 C 2 H 6 3.33 C 3 H 6 19.28 C 3 H 8 6.31 C 4 H 8 19.76
  • This hydrogenation process also allows removing diolefins, styrene or rubber precursors, as well as sulphur and nitrogen compounds.
  • the treated pyrolysis oils can be used:
  • the method of the invention comprises the following steps in the indicated order:
  • a pyrolysis oil suitable for use in refinery is thus obtained. It is a pyrolysis oil which is a mixture of hydrocarbons in the distillation range of 40°C-390°C for the processing thereof in a petroleum refinery, meeting the most restrictive specifications:
  • the method of the invention comprises stabilising the pyrolysis oils which are the starting material (hydrocarbons).
  • additives are incorporated in this oil to enable maintaining its stability over time, to that end, an intermediate receptacle in which additives and stabilisers which improve the stability of the different products contained in the treated pyrolysis liquids can be metered is used.
  • the additives and stabilisers used are preferably organic compounds from the families of benzoquinones, hydroquinones, multihydroxybenzenes, alkyl derivatives of benzenes, halogenated quinones and derivatives thereof.
  • Some of the compounds used can be: 1,2-dihydroxybenzene, 1,4-benzoquinone, 2,3,5,6-tetrachlorobenzoquinone, 1,2-dihydroxy-4-t-butylbenzene, 1,2,3-trihydroxybenzene, substituted hydroquinones (2,5-di-t-butylhydroquinone and 2,5-di-t-amyl-hydroquinone, and halogenated hydroquinones), alkyl derivatives of phenols (2,6-di-t-butyl-4-methylphenol) t-butylpyrocathecol (1,2-dihydroxy-4-t-butylbenzene), and derivatives from the family of amines such as: phenylenediamine,
  • the metering of the indicated stabilisers acting as inhibitors varies based on the composition of the functional groups causing instability in the pyrolysis oil. As a general rule, a metering range comprised between 20 and 2000 ppm of the mixture to be inhibited can be established.
  • the method selectively stabilises organic compounds in a highly efficient manner by means of using different treatment processes which can be directly developed into output liquid pyrolysis oils of the pyrolysis and co-pyrolysis reactors (starting oils).
  • liquid pyrolysis oils refers to a mixture of:
  • EXAMPLE 1 Pyrolysis oil halogen and acidity TAN reduction.
  • pyrolysis oil obtained in a conventional manner 500 g of pyrolysis oil obtained in a conventional manner, for example, according to the description of one of patents ES2532552 , ES2551512 or ES2618857 , and 17 g of adsorbent were loaded in a stirred tank reactor, and it was maintained at 250 rpm and 40°C for 48 h in order to determine the elimination of acidity and halogens (CI, Br) present in the pyrolysis oil.
  • CI, Br acidity and halogens
  • the pyrolysis oil used in this example has the following properties:
  • the following table shows the reduction of TAN for each element (CI, Br) depending on the adsorbent used (CuO/ZnO/Al 2 O 3 -SiO 2 ; Bentonite/MgO; gamma-AL 2 O 3 ; CaO/AL 2 O 3 ; attapulgite), where each column describes the result of an experiment in which 17 g of each of the adsorbents indicated in the table are applied.
  • the columns used for each of the adsorbents are conventional and a stirred tank reactor, which constitutes standard adsorption or reaction equipment, was used.
  • the pyrolysis oil used in this example as a starting product was obtained according to the method described in one of the aforementioned Spanish patents and has the following properties:
  • Colour improvement can also be obtained by subjecting the pyrolysis oil to turbulent agitation followed by filtration with clay or carbonaceous material.
  • the adsorption device may consist of several columns, each loaded with a type of adsorbent, or a single column with several adsorbent beds to enable adsorbing each of the contaminants that are present.
  • a double configuration consisting of an operating column and another parallel, replacement column with the same adsorbent for use thereof when the operating bed is saturated, can also be used.
  • the operating conditions can be:
  • This adsorption process can be performed by means of adsorption bed devices or by means of two consecutive processes of adding adsorbents to a tank, followed by turbulent agitation and separation by means of filtration.
  • This example shows how distillation (in a conventional column) at atmospheric pressure of the pyrolysis oil, with a distillation curve as indicated below: Initial point: 40°C, and end point: 360°C, allows producing fractions with a lower contaminant content.
  • a light fraction 40°C-200°C
  • a heavy fraction 200°C-360°C
  • some elements such as: calcium, iron, sodium, phosphorus, tin, and zinc, are concentrated in the heavy fraction of the pyrolysis oil (>200°C), reducing the contaminant content in the light fraction, with the exception of silicon.
  • This result that is obtained is due to the type of organometallic compound formed by each contaminant during the pyrolysis process.
  • the distillation process can be performed with a distillation column with a conventional, inert distillation filler, or with a mixed filler which has, in addition to an inert material, a contaminant trap like the ones mentioned above.
  • waste originating from a municipal solid waste treatment plant, which is a mixture of 94% plastics (polypropylene, film bags, PET, textile and others) with 6% cardboard, was used.
  • This waste is first dried, pyrolysed and distilled to produce a crude pyrolysis oil with a distillation range of 40°C-390°C, which is processed, according to the present invention, in the adsorption and hydrotreatment processes, producing a pyrolysis liquid with the following properties and contaminant levels:
  • the starting material used in this Example 6 is the solid waste identified above as waste 2 in the brief description of the invention.
  • the properties of the pyrolysis liquid before distillation and after passing through the preceding adsorption and hydrotreatment processes are: Input Adsorption Figure 4 Output Hydrotreatment Figure 4 Sulphur, ASTM-D 4294, ppm 200 136 Acidity (TAN) ASTM-D 664; mg KOH/g 5 ⁇ 2 YIELD (%wt) Naphtha (IP-150°C) 55 55 Distillate (150-360°C) 45 45 Water (Karl Fischer); %wt 0.1 0.09 Chlorine ASTM 7539, ppm 177 ⁇ 20 Ca, ppm 7 ⁇ 1 Fe, ppm 7 ⁇ 1 P, ppm 2 ⁇ 1 K, ppm 2 ⁇ 1 Na, ppm 4 ⁇ 1 Zn, ppm 2 ⁇ 1 Si, ppm 10 ⁇ 5
  • Waste which is a mixture of plastics and other waste was used as a starting material in this example, whereas only mixtures of plastic waste were used in most part in the preceding examples.
  • the end product achieves suitable specifications based on the final purpose of the pyrolysis oil such as: a feed for a steam cracker plant, aromatics production plant, refinery process units: distillation, hydrotreatment, or catalytic cracking, as well as for fuel formulation.
  • EXAMPLE 8 Influence of the % of non-plastic waste on the properties of the pyrolysis oil after improvement processes using a diagram shown in Figure 3.
  • Case A ⁇ 30% of non-plastic waste (paper+cardboard+biomass+textile).
  • PYROLYSIS OIL Plastic Waste (%wt) 30-50 Other Waste: Paper/cardboard/biomass/textile 50-70 Density at 15°C ASTM-D 4052; g/cm 3 0.862-0.885 Sulphur, ppm 175-260 Acidity (TAN) ASTM-D 664; mg KOH/g ⁇ 2 YIELD (%wt) Light fraction (IP-150°C) 50-60 Heavy fraction (150 + °C) 50-40 Water (Karl Fischer); %wt ⁇ 0.1 Chlorine ASTM 7539, ppm ⁇ 20 FlashPoint, °C ⁇ 40 °C Ca, ppm ⁇ 1 Fe, ppm ⁇ 1 P, ppm ⁇ 5 K, ppm ⁇ 1 Na, ppm ⁇ 1 Zn, ppm ⁇ 1 Si, ppm ⁇ 25
  • EXAMPLE 10 Stability measured according to the ASTM D525 standard.
  • the test consists of applying pressure with O 2 on a 50 ml sample of starting liquid pyrolysis oil at 100°C, and measuring the time in which a specific lowering of O2 pressure occurs as a result of oxidation reactions.
  • commercial gasoline has a minimum value fixed for this test of 360 minutes.

Abstract

The method comprises one or more of the following operations: Adsorption; Liquid phase distillation; Hydrotreatment; Pyrolysis oil stabilisation. Adsorption preferably comprises passing the pyrolysis oils through one or more columns filled with adsorbents selected from one or more of the following: chlorine absorbent; carboxylic acid adsorbent; sulphur adsorbent; metal adsorbent; nitrogenated compound adsorbent; activated carbon; activated clay. The method preferably comprises adsorption and hydrotreatment. It enables transforming pyrolysis oils, obtained from a raw material (plastic waste and others: paper, cardboard, textile, biomass) and containing hydrocarbons, into a mixture in which the hydrocarbons meet the specifications required in the chemical and/or fuel manufacturing industry.

Description

    Technical field
  • Improvement of the quality and stability of liquids originating from the co-pyrolysis of waste formed by mixtures of residual plastics and other waste such as: cardboard, paper, textile and biomass.
    • Background of the invention
  • The present invention relates to a method for transforming pyrolysis oils originating from microwave-assisted (or non-assisted) thermal pyrolyses into stable, quality products which can be used in the chemical industry and in fuel and biofuel production.
  • Pyrolysis oils are obtained by means of pyrolysis of municipal and industrial waste. Waste is usually formed by variable mixtures of plastics of different nature and composition, with other waste originating from materials such as paper and cardboard, food waste, wood, plant waste, textile waste, etc. Pyrolysis is capable of treating mixtures of composite materials and various compositions.
  • Due to the variable composition of the waste, pyrolysis oils are formed by mixtures of many linear and branched, aromatic and aliphatic hydrocarbon compounds containing therein alkanes and alkenes, many of which have very highly reactive dienes. This diverse chemical composition leads to the instability of pyrolysis oils and to the composition of said oils evolving over time.
  • This heterogeneous hydrocarbon mixture has, additionally, a series of oxygenated products with variability in functional groups, in addition to compounds with sulphur, chlorine, nitrogen, phosphorus, silicon and some metals. These oils must be treated and purified so that they have controlled quality and stability and can be used in processes of the chemical and petrochemical industry to enable plastic waste to be chemically recycled.
  • Pyrolysis reactions produce a mixture of organic substances made up of aliphatic and aromatic hydrocarbons, along with a large variety of organic compounds in which heteroatoms such as N, S, Cl, Si, P, Ca, K, Fe, Zn, etc., are present.
  • Three fundamental fractions are obtained depending on the composition of the processed raw materials, the type of pretreatment, reactor configuration and design, pyrolysis reaction conditions, the presence or absence of catalysts: a solid fraction made up of carbonaceous materials and inorganic elements, a non-condensable gas fraction and a liquid fraction originating from condensable gases.
  • Today, pyrolysis liquids are characterised as heterogeneous mixtures with a significant presence of particles of various sizes, comprised between 2 and 500 micra, heavy compounds formed by hydrocarbons with molecular chains exceeding C19, and diolefin compounds, which are unstable over time due to their reactivity. These mixtures are often decanted and distilled to remove heavy components and suspended particles. These operations generate unstable, poor-quality liquids that evolve within a few hours, generating phases and compounds which complicate their subsequent use. The heterogeneity of the composition causes undesirable components to be unevenly distributed between the different obtained fractions with the distillation or fractionation operations. This lack of quality and homogeneity greatly complicates the industrial utilisation of these mixtures.
  • Decomposition by means of biomass pyrolysis produces a series of organic compounds with various functional groups including, among others, alcohols, ketones, aldehydes and carboxylic acids. These compounds react with one another while at the same time undergo oxidation reactions that change the composition of the obtained liquids. The organic compounds give an acidic character and are largely responsible for the corrosion exhibited by pyrolysis liquids.
  • Depending on the type of plastic waste and the type of residual biomass, simple or complex aromatic organic compounds derived from the partial decomposition of lignin present in lignocellulosic or plastic polymer waste are obtained.
  • Today, treatments for improving and stabilising pyrolysis oils include the treatment thereof in large and expensive, high-temperature and pressure installations for performing hydrodeoxygenations and hydrodesulphurisations in batch or continuous processes. They are also used in catalytic cracking processes with zeolites at high temperatures or hydrogenation processes with metal catalysts of the Ru, Pd, Co, Mo, Zn, Ni, type, etc., supported on carbon, aluminas, or silica-alumina. These processes involve very expensive investment and operations and are highly sensitive to the contamination present in pyrolysis oils. Another problem of these processes is that they are developed at petrochemical scales, so they can neither be adapted to nor used at smaller scales in pyrolysis plants.
  • To enable assuring a controlled quality of pyrolysis oils and their fractions, innovation consisting of a series of treatment processes which allow assuring the quality of the improved mixture and fractions thereof is needed. Pyrolysis or co-pyrolysis oils from plastic waste and other waste, such as biomass, have a complex and variable composition compared to the hydrocarbon streams in conventional refineries, such they require an innovation in the treatment and design of the equipment for treating same and for improving quality and stabilisation.
  • An innovation which allows small-scale improvement and stabilisation and does not require large, expensive installations in terms of investment and operation is needed.
    • Description of the invention
  • The present invention relates to a method for improving pyrolysis oils which include (or consist of) hydrocarbons and have been previously obtained from municipal or industrial solid waste, mixture of plastics, paper, cardboard, textile and biomass.
  • This method enables the subsequent use of these pyrolysis oils (hydrocarbons) in the chemical industry, facilitating circular economy, or in the fuel industry, reducing the carbon footprint thereof.
  • To obtain the mentioned pyrolysis oils as the starting point, operations can be carried out on the waste, such as: selection and treatment of raw material (municipal solid waste and industrial waste); and pyrolysis: a thermochemical process performed in a specific pyrolysis reactor.
  • Once the pyrolysis oils are obtained as a starting point of the present invention, they are subjected, according to the present invention, to one or more of the following operations to improve their quality, as will be explained below:
    • Operation 1. Adsorption.
    • Operation 2. Distillation. Distillation of the obtained liquid phase.
    • Operation 3. Hydrotreatment.
    • Operation 4. Pyrolysis oil stabilisation.
  • The present invention relates particularly to a method for improving liquid pyrolysis oils which comprise (or consist of) hydrocarbons and have been obtained from waste preferably comprising between 15% and 85% by weight of plastics, and which comprises one or more of the following operations:
    • adsorption;
    • liquid phase distillation;
    • hydrotreatment;
    • pyrolysis oil stabilisation.
  • As will be explained below, in a more preferred example of the invention, the operations comprise, or consist of, adsorption followed by hydrotreatment.
  • The pyrolysis oils on which this method can be applied are organic liquids obtained from the pyrolysis of municipal or industrial solid waste, mixture of plastics, paper, cardboard, textile and biomass, by means of, for example, the methods described in any of patents:
    • ES2532552 (P201331414). "Method and device for obtaining hydrocarbons".
    • ES2551512 (P201430719). "Method for obtaining hydrocarbons from waste and/or biomass and installation for implementing said method".
    • ES2618857 (P201531858), "Thermochemical method and installation for transforming polymer materials".
  • The present invention comprises a series of innovations intended for transforming pyrolysis oils obtained from a raw material (plastic waste and others: paper, cardboard, textile, biomass) into hydrocarbons which meet the specifications required in the chemical and/or fuel manufacturing industry.
  • The invention is developed for obtaining, starting from liquid oils obtained by means of the pyrolysis of a mixture of waste (thermochemical process), high-quality liquid hydrocarbons which can be used in the petrochemical industry and in fuel manufacture, and to that end the contaminant content of the obtained hydrocarbons must be as low as that shown in the following table:
    MAXIMUM
    Chlorine ppm
    10
    Bromine ppm 1
    Iron ppm 10
    Zinc ppm 0.5
    Sodium ppm 5
    Phosphorus ppm 5
    Silicon ppm 1
    Acidity (TAN) mgKOH/g 2
  • The raw materials with which the pyrolysis oils, used as a starting point, are obtained are municipal solid waste (MSW), industrial waste (IW) and residual biomass. It should be pointed out that the composition of MSW and IW varies greatly and they are generally heterogeneous mixtures of materials in which biomass is present in the form of paper and cardboard, textile materials, wood waste, etc.
  • The following table shows an example of the variety of polymers and other materials forming part of the waste mixture from which there are obtained, by means of pyrolysis, liquid oils which can be processed in the method object of the invention. Municipal Solid Waste composition (waste 1).
    Material % Weight
    Fine fraction (<10 mm) 0.08
    Organic matter 0
    Plant fraction 0.9
    Wood 3.9
    Paper 1.5
    Cardboard 6.48
    Plastic mixture 0.09
    Natural HDPE 0.3
    Coloured HDPE 0.82
    Natural PET 0.84
    Coloured PET 0.06
    PP 48.7
    PS 3.79
    EPS 4.16
    Film (Bags) 23.05
    Industrial film 3
    Tetra-brik 0.22
    Textile 1.58
    Ferric materials 0.14
    Aluminium 0.13
    PVC 0.26
    Total 100
    HDPE: High-density polyethylene; PET: Polyethylene terephthalate; PP: Polypropylene; PS: Polystyrene; PVC: Polyvinyl chloride; EPS: Expanded polystyrene.
  • The following table shows the contaminants most commonly found in waste of this type. Contaminants found in municipal/industrial solid waste (waste 2)
    WASTE TYPE SOLID WASTE
    Moisture (%) 12 0.75
    Ash 815°C, % 23 13.9
    C, % 52.9 60.2
    H, % 6.2 8.65
    N, % 0.51 0.44
    S, % 0.03 0.04
    Cl, ppm 240 470
    Ca, % 19 8
    Fe, ppm 1877 1004
    Si, ppm 2422 2329
    Mg, ppm 1101 813
    Na, ppm 691 500
    Zn, ppm 656 383
    P, ppm 603 409
    K, ppm 1300 668
    Mn, ppm 29 20
  • Before processing the waste according to the treatment of the invention, the solid waste is subjected to a drying treatment to reduce moisture to values below 1%, given that this property varies in each batch of waste to be processed as it depends on hard-to-control factors such as: waste origin and waste transport and storage system. As such, if needed, to a mixture with other waste to homogenise pyrolysis reactor feeding.
    WASTE POLYPROPYLEN E (PP) CSR (Plastic waste mix) MIXTURE: 10%wt PP+ 90%wt CSR
    Moisture, % 3.1 0.7 0.94
  • As indicated above, pyrolysis oils are obtained from a thermochemical treatment carried out in a pyrolysis reactor designed and built to operate under co-pyrolysis conditions, in other words, allowing biomass waste materials and plastic waste to be co-processed at the same time. Both waste materials are in variable mixtures in the MSW and IW.
  • Solid organic matter can be converted into liquids by means of pyrolysis processes. These processes are characterised by the performance of thermochemical cracking reactions under anoxia, i.e., oxygen-free, conditions or under conditions with oxygen concentrations always below the stoichiometric amount.
  • The thermochemical pyrolysis reaction can be developed in a pyrolysis reactor (2) according to any of patents P201331414, P201430719 or P201531858. This process is characterised by performing the pyrolysis of residual biomass in the presence of residual plastics. The residual plastics act as of hydrogen donors such that they modify the composition of the pyrolysis liquids by increasing the number of hydrocarbon compounds and reducing oxygenated compounds.
  • These reactors allow the thermochemical reactions to be developed under controlled conditions on heterogeneous mixtures of variable composition such as MSW and IW. The pyrolysis reactions are carried out in reactors which can be induced by means of inputting energy in the form of thermal or microwave energy.
  • For the suitable development of pyrolysis reactions and the quality of the products thereof, it is advisable that the residual plastics present in the reactor are at least 15% with respect to the total waste fed to the plant. The percentage of plastic waste can preferably reach up to 85% of the total waste fed to the plant. Depending on the reaction conditions developed in the pyrolysis reactor and on the equilibrium between oxygenated compounds derived from the biomass and hydrogenated compounds from the plastic waste, different qualities of solid, liquid and gaseous products will be obtained.
  • The present invention relates particularly to a method for improving pyrolysis oils obtained from waste and comprising one or more of the following operations:
    • adsorption;
    • liquid phase distillation;
    • hydrotreatment;
    • pyrolysis oil stabilisation.
  • For a suitable treatment, there is a need to take into consideration that the contaminant type and content of the pyrolysis oil may vary as it is obtained from waste. Table I shows how the properties of the obtained pyrolysis oil vary based on the variable % of non-plastic waste.
  • Properties of the pyrolysis oil such as: sulphur, density, microcarbon waste, and TAN acidity increase with the % of non-plastic waste in the pyrolysis reactor feed. Given the heterogeneity of the waste fed to the pyrolysis plant, pyrolysis oil with TAN (Total Acid Number) exceeding 2 mg KOH/g, which is the maximum limit allowed by some refinery or petrochemical installations, may be produced. In the case of having only 30% plastic waste and the rest being lignocellulosic waste, TAN values of the order of 16 mg KOH/g, as shown in Figure 1, may be obtained, so a reduction of this acidity is required.
  • On the contrary, other substances such as nitrogen, chlorine, metals, do not follow any correlation due to the existing high variability in terms of the types of plastic waste present or the percentage of other non-plastic waste. TABLE I. INFLUENCE OF THE % OF NON-PLASTIC WASTE ON PROPERTIES
    PLASTIC WASTE 93 85 70 30 0
    (%wt) 100
    PAPER/CARDBOARD/TEXTILE/BIOMASS 7 15 30 70 100
    (%wt) 0
    Density at 15°C ASTM-D 4052; 0.906 0.856 0.881 0.862 0.921 1.09
    g/cm 3 0 7 6 0 5 9
    Total sulphur 60 188 163 106 365 405
    ASTM-D 4294, ppm
    Total nitrogen 1756 1385 1351 2033 3050 190
    ASTM-D 4629, ppm
    Acidity (TAN) 0.08 0 1 5 16 26
    ASTM-D 664; mg KOH/g
    Microcarbon waste 0.68 0.9 1 2.1 10.5
    ASTM- D 4530, %wt
    Chlorine 260 45 354 320 190
    ASTM 7359, ppm
    Metals, ppm
    Ca 298 0 119 160
    Fe 185 1 10 20 <0.1
    P 6 2 10
    Na <0.2 5
    Zn 19 15 185 180 200
    Si 250 152 149 15 220
    TAN: Total Acid Number
  • The following table shows a summary of the contaminants that are most commonly found by processing waste of this type, as well as the range of variation in the composition thereof. On the other hand, the presence of non-plastic waste, such as cardboard+paper+biomass+textile, in different proportions, also contributes to the variability of the contaminant content.
  • The maximum and minimum content of each contaminant found in the crude pyrolysis oil (starting oil) samples is shown in Table II below. Table II
    Chlorine ASTM 7359, ppm 0-400
    Fluorine ASTM 7539, ppm 0-9
    Bromine ASTM 7539, ppm 0-70
    Ca, ppm 0-20
    Na, ppm 0-10
    Fe, ppm 0-18
    P, ppm 0-10
    Zn, ppm 0-220
    Si, ppm 0-300
    Acidity (TAN) 0-16
    ASTM-D 664; mg KOH/g
  • Chlorine content. This contaminant comes from the presence of compounds such as PVC in the waste to be pyrolysed or from forestry waste having chlorine in the composition thereof, present for the most part as organic chlorine. The presence of this metal may originate from the use of zinc stearate in the manufacture of polymers. In terms of silicon, its presence is due to the use of silicon-based mineral fillers or organic additives in the formulation of certain plastics.
  • According to particular embodiments, the method of the invention comprises performing an adsorption step for adsorbing the contaminants of the pyrolysis oils which are the starting material (hydrocarbons).
    • Adsorption
  • As a whole, the function of this operation is to remove the contaminants present in the pyrolysis oil, to reduce acidity and to improve colour.
  • This operation consists of providing one or more vertical columns, through which the pyrolysis oils are passed, said columns being filled with adsorbents specific for each type of contaminant. The adsorbents are formed in the shape of spheres or extruded, with a size between 1 and 5 mm, in order to reduce load loss in the bed. The adsorbents to be used for each type of contaminant are:
    • Chlorine trap: calcium, sodium or potassium carbonate supported on alumina, silica-alumina, zeolites, activated aluminas. Calcium oxide, sodium oxide, zinc oxide and copper oxide supported on alumina, silica-alumina, or zeolites. Sodium-, potassium-, calcium- or magnesium-doped bentonites.
    • Carboxylic acids (TAN reduction) trap: activated aluminas, calcium, sodium, potassium or magnesium compounds supported on alumina, silica alumina, clay, mixed copper and zinc oxides on alumina or silica/alumina, activated carbon.
    • Sulphur trap: nickel, nickel-molybdenum, nickel-tungsten in reduced or oxidised state supported on alumina or silica-alumina. Zinc and copper oxide.
    • Metal (Fe, Zn, Ca, Na, etc.) trap: macroporous alumina or silica-alumina, activated carbon, acidic resins, zeolites, activated clay or bentonites.
    • Nitrogenated compound trap: acidic aluminosilicates, polymer resins, bentonites, activated carbon, biochar, natural or activated clay.
    • Colour improvement trap: activated carbon, activated clay (clay which has been subjected to a process whereby it is converted into a solid phase capable of absorbing particles).
  • According to particular embodiments, the method of the invention comprises performing a distillation step for distilling the pyrolysis oils which are the starting material (hydrocarbons).
    • Distillation.
  • The pyrolysis oil obtained from waste can be distilled for use both in liquid fuel manufacture: gasoline, kerosene, diesel, and marine bunker fuel, and/or as raw material in the chemical industry for manufacturing olefins and aromatics in polymer production. On the other hand, depending not only on the final purpose, but also on the process diagram used by the client: simple or complex petroleum refinery, or petrochemical plant: steam cracking or aromatics production, a different distillation cut and quality will be required in each case, for example: naphtha range (initial point-160°C) for olefin production in steam cracking plants or cut (initial point-360°C) for gasoline, kerosene and diesel production in a petroleum refinery.
  • This fractionation of the oil influences contaminant distribution, so a method for improving the quality of the mixture of hydrocarbons obtained by means of the pyrolysis of waste is also taken into consideration.
  • According to particular embodiments, the method comprises distilling the pyrolysis oil, where distillation can be selected from distillation with an initial point at 160°C or initial point at 360°C.
  • According to particular embodiments, the method comprises performing adsorption and distillation.
  • According to particular embodiments, the method of the invention comprises performing a hydrotreatment step for the hydrotreatment of the pyrolysis oils which are the starting material (hydrocarbons).
    • Hydrotreatment.
  • With some pyrolysis oils and depending on their composition and on the final use, a hydrotreatment process may be required to remove compounds such as sulphur, nitrogen or silicon.
  • Particularly, in relation to silicon compounds, there is a wide range of fillers and additives which can be used in the plastics forming part of the waste used for obtaining the starting liquid pyrolysis oils, depending mainly on their intended application and on the characteristic to be improved. Silica is a rather common filler in polyolefins because it provides good properties; therefore, talc, silica and other minerals are often used as a nucleating agent in polypropylene. On the other hand, silica can also be used as a polymerisation catalyst support, being included in the polymer matrix.
  • Organosilane compounds with general structure RSi (OR')3 are also used to promote adhesion between polymer and inorganic fillers.
  • Therefore, the starting liquid pyrolysis oils contain silicon compounds, such as organosilanes, which are to be removed by means of the method of the invention.
  • On the other hand, the presence of silicones in the municipal waste gives rise to compounds, such as hexamethylcyclotrisiloxane and octamethylcyclotetrasiloxane, which result from the decomposition of silicones at temperatures >400°C, and which are also to be removed.
    Figure imgb0001
  • The removal of silicon compounds of this type, as well as other sulphur and nitrogen compounds, is possible in a hydrotreatment process in a reactor with a solid catalyst formed by a metal (Ni, Co, Pt, Pd, NiMo, CoMo, NiW) on a support (alumina, silica-alumina, activated carbon, clay), in the shape of a sphere or extruded in a size between 1 and 3 mm. The operating conditions are: space velocity (oil flow rate divided by volume of catalyst) between 1 and 5 h-1, temperature: 150-320°C, pressure: 5-40 bar, H2/pyrolysis oil ratio: 50-200 Nm3/m3. The hydrogen used can be imported from an external source or gas from the pyrolysis process which contains hydrogen, such as the one described in the following table, can be used:
    %wt
    H2 0.86
    CH4 15.07
    CO 9.86
    CO2 19.67
    C2H4 5.86
    C2H6 3.33
    C3H6 19.28
    C3H8 6.31
    C4H8 19.76
  • This hydrogenation process also allows removing diolefins, styrene or rubber precursors, as well as sulphur and nitrogen compounds.
    Once improved in terms of quality and stability, the treated pyrolysis oils can be used:
    1. 1) In cracker-type petrochemical units or the like for the production of organic base chemical products. The improved oils are a mixture of variable composition with components valuable in the chemical industry such as: benzene, toluene, ethylbenzene, p-xylene, m-xylene, O-xylene, styrene, α-methylstyrene and naphthalene.
    2. 2) For the formulation of transportation fuels, such as advanced biofuel, recycled carbon fuel, or such as fuel with a lower carbon footprint than fossil fuel.
  • In order to achieve the required quality based on the final purpose of the pyrolysis oil, one or more of the operations described above can be combined in different ways. According to a preferred embodiment, the method of the invention comprises the following steps in the indicated order:
    • adsorption; and
    • hydrotreatment.
  • A pyrolysis oil suitable for use in refinery is thus obtained. It is a pyrolysis oil which is a mixture of hydrocarbons in the distillation range of 40°C-390°C for the processing thereof in a petroleum refinery, meeting the most restrictive specifications:
    • Halogens: Chlorine, Bromine <1 ppm
    • Metals: iron, zinc, <1 ppm
    • phosphorus, silicon <5 ppm
    • sodium, potassium, calcium <1 ppm
    • Acidity TAN <2 mgKOH/g.
  • According to particular embodiments, the method of the invention comprises stabilising the pyrolysis oils which are the starting material (hydrocarbons).
    • Pyrolysis oil stabilisation.
  • Given the heterogeneity in the hydrocarbons of the pyrolysis oil, with the presence of reactive compounds such as diolefins, styrene and others, which cause the pyrolysis oil to be unstable during storage and transport, the formation of gums and sediments may occur. To prevent same, according to particular embodiments of the invention, additives are incorporated in this oil to enable maintaining its stability over time, to that end, an intermediate receptacle in which additives and stabilisers which improve the stability of the different products contained in the treated pyrolysis liquids can be metered is used.
  • The additives and stabilisers used are preferably organic compounds from the families of benzoquinones, hydroquinones, multihydroxybenzenes, alkyl derivatives of benzenes, halogenated quinones and derivatives thereof. Some of the compounds used can be: 1,2-dihydroxybenzene, 1,4-benzoquinone, 2,3,5,6-tetrachlorobenzoquinone, 1,2-dihydroxy-4-t-butylbenzene, 1,2,3-trihydroxybenzene, substituted hydroquinones (2,5-di-t-butylhydroquinone and 2,5-di-t-amyl-hydroquinone, and halogenated hydroquinones), alkyl derivatives of phenols (2,6-di-t-butyl-4-methylphenol) t-butylpyrocathecol (1,2-dihydroxy-4-t-butylbenzene), and derivatives from the family of amines such as: phenylenediamine, hydroxyamine, etc.
  • The metering of the indicated stabilisers acting as inhibitors varies based on the composition of the functional groups causing instability in the pyrolysis oil. As a general rule, a metering range comprised between 20 and 2000 ppm of the mixture to be inhibited can be established.
    • Advantages of the invention
  • Providing hydrocarbons suitable for industrial use in processes of the chemical industry or as fuels.
  • Enabling the washing of condensable and non-condensable gases, the separation of solid particles, heavy compounds present in the pyrolysis liquid, and the adsorption of heteroatoms present therein.
  • Separation treatments with solid adsorbents for the liquid fractions improve the stability and the chemical composition of pyrolysis oils.
  • The method selectively stabilises organic compounds in a highly efficient manner by means of using different treatment processes which can be directly developed into output liquid pyrolysis oils of the pyrolysis and co-pyrolysis reactors (starting oils).
  • It must be clarified that the term "liquid pyrolysis oils" refers to a mixture of:
    • hydrocarbons and oxygenated compounds distilling in the naphtha range (40-150°C); and
    • middle distillates: kerosene + diesel, distillation in the range of: 150-360°C), as described in some examples.
    Description of the figures
    • Figure 1 shows the variation of TAN with respect to the % plastic waste.
    • Figure 2 shows the colour improvement by means of treatment with activated carbon.
    • Figure 3 shows a diagram for producing improved pyrolysis oil which comprises performing the steps of:
      • drying the waste
      • thermochemical (pyrolysis) treatment,
      and according to the method of the invention performing the steps of:
      • adsorption
      • hydrotreatment
      and an improved pyrolysis oil, which is a mixture of hydrocarbons in the distillation range of 40°C-390°C, is thereby obtained for the processing thereof in a petroleum refinery, meeting the required specifications.
    • Figure 4 shows a diagram for producing an improved pyrolysis oil which comprises performing the steps shown in Figure 3, and including a distillation step, Figure 4. In this case, two different fractions are obtained: 1) a light IP-180°C fraction which can be useful in manufacturing gasolines or as a feed for petrochemical units. 2) a heavy fraction with a boiling point of between 180°C-360°C which can be used in a refinery for manufacturing diesel oils or marine fuels.
    • Figure 5 shows the diagram of an embodiment of the method, according to which there are performed the prior steps of:
      • drying the waste
      • thermochemical (pyrolysis) treatment
      and, according to the invention:
      • distillation
      • adsorption
      • hydrotreatment
      to produce only an IP-180°C fraction, whereas the 180+°C fraction is recycled to the pyrolysis reactor for additional thermal cracking.
    EXAMPLE 1. Pyrolysis oil halogen and acidity TAN reduction.
  • 500 g of pyrolysis oil obtained in a conventional manner, for example, according to the description of one of patents ES2532552 , ES2551512 or ES2618857 , and 17 g of adsorbent were loaded in a stirred tank reactor, and it was maintained at 250 rpm and 40°C for 48 h in order to determine the elimination of acidity and halogens (CI, Br) present in the pyrolysis oil.
  • The pyrolysis oil used in this example has the following properties:
    • TAN (ASTM D664): 11 mg kOH/g Cl: 700 ppm
    • Br: 40 ppm
  • The following table shows the reduction of TAN for each element (CI, Br) depending on the adsorbent used (CuO/ZnO/Al2O3-SiO2; Bentonite/MgO; gamma-AL2O3; CaO/AL2O3; attapulgite), where each column describes the result of an experiment in which 17 g of each of the adsorbents indicated in the table are applied.
    Element (ppm) CuO/ZnO/Al2O3-SiO2 Bentonite/MgO gamma-Al2O3 CaO/Al2O3 Attapulgite
    Cl 42.86% - 28.57% 14.29% -
    Br 25.00% 5.70% 25.00% 50.00% 11.00%
    % of TAN reduction 76.0% 70.6% 84.3% 97.8% 6.8%
    • EXAMPLE 2. Pyrolysis oil metals and acidity TAN reduction.
  • 500 g of pyrolysis oil and 17 g of adsorbent were loaded into a stirred tank reactor, and it was maintained at 250 rpm and 40°C for 24 hours in order to determine the elimination of acidity and metals present in the pyrolysis oil.
  • In this example, the columns used for each of the adsorbents are conventional and a stirred tank reactor, which constitutes standard adsorption or reaction equipment, was used.
  • The pyrolysis oil used in this example as a starting product was obtained according to the method described in one of the aforementioned Spanish patents and has the following properties:
    • TAN (ASTM D664): 6 mg kOH/g
    • Fe: 131 ppm
    • Sn: 2 ppm
    • Zn: 344 ppm
    • Na: 4 ppm
    • Ca: 5 ppm
    • P: 8 ppm
    Al2O3 Al2O3 Activated carbon Activated carbon Activated carbon
    Adsorbent 1 2 1 Zeolite 2 3
    Surface 121 251 650 360 1100 1900
    Specific surface (m2/g)
    BET method: ASTM D3663-20
    Fe (ppm) 79 76 112 72.9 73.1 30.7
    Sn (ppm) 1 1 1 2 2 1
    Zn (ppm) 228 145 313 281 252 81.01
    Na (ppm) 1 1 1 2 2 4
    P (ppm) 8 8 8 9 8 7
    Ca (ppm) 4 2 3 4 4 2
    % of TAN reduc. 18.6% 32.5% 25.5% 29.3% 4.5% 18.8%
    EXAMPLE 3. Pyrolysis oil colour improvement.
  • 2 kg of activated carbon with a specific surface of 1500 m2/g (BET Method: ASTM D3663-20) were loaded in a conventional column, and 50 l of pyrolysis oil were circulated with a flow rate of 50 l/h. After a first pass, the pyrolysis oil was passed again at 50 l/h up to 4 times more, an improvement in the colour of the oil being observed as a result of the adsorption of compounds such as: gums, carbon fines, nitrogenated compounds, as can be seen in Figure 2.
  • The identification of colour-producing compounds in these liquids is extremely complex because these liquids can have more than 300 different chemical compounds with some of them at ppm levels, hence the difficulty in identifying responsible compounds, such that the removed contaminants are identified by means of visual identification.
  • Colour improvement can also be obtained by subjecting the pyrolysis oil to turbulent agitation followed by filtration with clay or carbonaceous material.
  • The adsorption device may consist of several columns, each loaded with a type of adsorbent, or a single column with several adsorbent beds to enable adsorbing each of the contaminants that are present.
  • A double configuration, consisting of an operating column and another parallel, replacement column with the same adsorbent for use thereof when the operating bed is saturated, can also be used.
  • The operating conditions can be:
    • Ascending or descending flow.
    • Space velocity: defined as the flow rate of the liquid divided by the volume of the bed, which can range between 0.5 and 5 h-1.
    • Linear velocity: defined as the flow rate of the liquid divided by the section of the column, between 1 and 1.5 cm/s, in order to ensure that the solid bed is completely wet.
    • Temperature: 20-250°C.
    • Pressure: 5-20 bar.
  • This adsorption process can be performed by means of adsorption bed devices or by means of two consecutive processes of adding adsorbents to a tank, followed by turbulent agitation and separation by means of filtration.
    • EXAMPLE 4. Contaminant distribution in pyrolysis oil distillation.
  • This example shows how distillation (in a conventional column) at atmospheric pressure of the pyrolysis oil, with a distillation curve as indicated below: Initial point: 40°C, and end point: 360°C, allows producing fractions with a lower contaminant content. There was obtained in this example a light fraction: 40°C-200°C, and a heavy fraction: 200°C-360°C, and it is observed that some elements such as: calcium, iron, sodium, phosphorus, tin, and zinc, are concentrated in the heavy fraction of the pyrolysis oil (>200°C), reducing the contaminant content in the light fraction, with the exception of silicon. This result that is obtained is due to the type of organometallic compound formed by each contaminant during the pyrolysis process.
    DISTILLATION
    Pyrolysis oil
    40°C-200°C 200°C-360°C
    ppm ppm ppm
    Ca 3.4 0.3 7.0
    Fe 71 <0.2 143.6
    Na 0.9 <1.1 4.2
    P 8.4 <1.7 31.2
    Si 115 123.9 41.1
    Sn 1.6 <0.4 0.9
    Zn 344 <0.3 477.1
  • The distillation process can be performed with a distillation column with a conventional, inert distillation filler, or with a mixed filler which has, in addition to an inert material, a contaminant trap like the ones mentioned above.
    • EXAMPLE 5. Improvement of the pyrolysis oil using a process diagram according to Figure 3.
  • The waste described above as waste 1, originating from a municipal solid waste treatment plant, which is a mixture of 94% plastics (polypropylene, film bags, PET, textile and others) with 6% cardboard, was used.
  • This waste is first dried, pyrolysed and distilled to produce a crude pyrolysis oil with a distillation range of 40°C-390°C, which is processed, according to the present invention, in the adsorption and hydrotreatment processes, producing a pyrolysis liquid with the following properties and contaminant levels:
    • ADSORPTION PROCESS. OPERATING CONDITIONS:
    • Space velocity: 1 h-1,
    • Temperature: 80°C,
    • Pressure: 5 bar,
    • 4-Bed adsorption column:
      • Bed 1: Zeolite 13X
      • Bed 2: Polymer resin.
      • Bed 3: Gamma-alumina
      • Bed 4: Activated carbon
    • HYDROTREATMENT PROCESS. OPERATING CONDITIONS:
    • Space velocity: 3 h-1,
    • Temperature: 300°C,
    • Pressure: 40 bar,
    • H2/pyrolysis oil ratio: 200 Nm3/m3
    • Catalyst: Cobalt-molybdenum on alumina. Before feeding the pyrolysis liquid to the reactor, the catalyst is sulphurised following the methods already described in the state of the art of sulphurisation with catalysts of this type.
    Output Liquid Pyrolysis Figure 3 Output Liquid Hydrotreatment. Figure 3
    Density at 15°C ASTM-D 4052; g/cm3 0.8575 0.8569
    Sulphur ASTM-D 4294, ppm 190 95
    Nitrogen ASTM-D 4629, ppmw 1390 695
    Total Acid Number (TAN) ASTM-D 664;mg KOH/g 2 0
    Water (Karl Fischer); %wt 0.098 0.01
    Chlorine ASTM 7359, ppm 41 <10
    Fe 4 1
    Ca <1 <1
    Si 132 <1
    Ni 5 0.5
    P 6 3
    Zn 15 <5
    EXAMPLE 6. Improvement of the pyrolysis oil using a process diagram according to Figure 4.
  • The starting material used in this Example 6 is the solid waste identified above as waste 2 in the brief description of the invention.
  • Reduction of the contaminants present in this solid waste 2 and processing according to the diagram of Figure 4 are shown, in which, after a drying and pyrolysis process, the produced liquid (pyrolysis oil) is subjected, as a starting point of the present invention, to the processes described in Examples 1 and 2 (adsorption) and hydrotreatment in a reactor with solid catalyst, formed by nickel and molybdenum sulphur, on an alumina support, in an extruded form with a particle size between 1 and 3 mm. The operating conditions of the hydrotreatment are: space velocity between 1 and 5 h-1, temperature: 250°C, pressure: 20 bar, H2/pyrolysis oil ratio: 200 Nm3/m3.
  • The properties of the pyrolysis liquid before distillation and after passing through the preceding adsorption and hydrotreatment processes, according to Figure 4, are:
    Input Adsorption Figure 4 Output Hydrotreatment Figure 4
    Sulphur, ASTM-D 4294, ppm 200 136
    Acidity (TAN) ASTM-D 664; mg KOH/g 5 <2
    YIELD (%wt)
    Naphtha (IP-150°C) 55 55
    Distillate (150-360°C) 45 45
    Water (Karl Fischer); %wt 0.1 0.09
    Chlorine ASTM 7539, ppm 177 <20
    Ca, ppm 7 <1
    Fe, ppm 7 <1
    P, ppm 2 <1
    K, ppm 2 <1
    Na, ppm 4 <1
    Zn, ppm 2 <1
    Si, ppm 10 <5
    • EXAMPLE 7. Properties of IP-200°C distillate using a diagram process according to Figure 5.
  • Figure 5 shows the process diagram for producing only an IP-200°C (IP = initial point) fraction, whereas the 200+°C fraction is recycled to the pyrolysis reactor for additional thermal cracking.
  • Waste which is a mixture of plastics and other waste (paper, cardboard, etc.) was used as a starting material in this example, whereas only mixtures of plastic waste were used in most part in the preceding examples.
  • This example shows the properties of the IP-200°C fraction obtained according to the process diagram of Figure 5 and using waste with 85%wt of a mixture of plastics and 15%wt of other waste: cardboard, paper, biomass and textile.
    MIXTURE OF 85% PLASTICS + 15% OTHER WASTE: Paper/Cardboard/Biomass/Textile
    Density at 15°C ASTM-D 4052; g/cm3 0.855
    Sulphur ASTM-D 4294, ppm <50
    Nitrogen ASTM-D 4629, ppm 480
    Acidity (TAN) ASTM-D 664; mg KOH/g <1
    1% 50
    50% 139
    95% 195
    PF 200
    CHEMICAL COMPOSITION
    Olefins (%wt) 20.4
    Aromatics (% wt) 75.0
    Paraffins+Napthenes (%wt) 4.6
    Chlorine ASTM 7539, ppm <5
    Ca, ppm <1
    Fe, ppm <1
    P, ppm <1
    K, ppm <1
    Na, ppm <1
    Zn, ppm <1
    Si, ppm <5
  • With the proposed process diagrams, the end product achieves suitable specifications based on the final purpose of the pyrolysis oil such as: a feed for a steam cracker plant, aromatics production plant, refinery process units: distillation, hydrotreatment, or catalytic cracking, as well as for fuel formulation.
    • EXAMPLE 8. Influence of the % of non-plastic waste on the properties of the pyrolysis oil after improvement processes using a diagram shown in Figure 3.
  • The following example shows two cases with two different non-plastic waste contents (paper+cardboard+biomass+textile). Case A: <30% of non-plastic waste (paper+cardboard+biomass+textile).
    PYROLYSIS OIL
    Plastic Waste (%wt) 70-90
    Other Waste: Paper/cardboard/biomass/textile 10-30
    Density at 15°C ASTM-D 4052; g/cm3 0.846-0.882
    Sulphur, ppm 20-100
    Acidity (TAN) ASTM-D 664; mg KOH/g <1
    YIELD (%wt)
    Light fraction (IP-150°C) 50-60
    Heavy fraction (150+°C) 50-40
    Water (Karl Fischer); %wt <0.1
    Chlorine ASTM 7539, ppm <20
    FlashPoint, °C <40 °C
    Ca, ppm <1
    Fe, ppm <1
    P, ppm <5
    K, ppm <1
    Na, ppm <1
    Zn, ppm <1
    Si, ppm <10
    Case B: > 50% of non-plastic waste (paper+cardboard+biomass+textile).
    PYROLYSIS OIL
    Plastic Waste (%wt) 30-50
    Other Waste: Paper/cardboard/biomass/textile 50-70
    Density at 15°C ASTM-D 4052; g/cm3 0.862-0.885
    Sulphur, ppm 175-260
    Acidity (TAN) ASTM-D 664; mg KOH/g <2
    YIELD (%wt)
    Light fraction (IP-150°C) 50-60
    Heavy fraction (150+°C) 50-40
    Water (Karl Fischer); %wt <0.1
    Chlorine ASTM 7539, ppm <20
    FlashPoint, °C <40 °C
    Ca, ppm <1
    Fe, ppm <1
    P, ppm <5
    K, ppm <1
    Na, ppm <1
    Zn, ppm <1
    Si, ppm <25
    • EXAMPLE 9. Stability measured according to the EN15751 standard
  • This example shows the improvement of the stability of the formulation of a mixture of diesel and biodiesel (fatty acid methyl ester, "FAME") with the output pyrolysis oil of the pyrolysis reactor, without any subsequent treatment for improving same. In these mixtures, stability is determined by means of the EN15751 standard, which deems the product to be stable when it gives a result above 20 hours.
    MIXTURE STABILISING ADDITIVE EN15751 (hours)
    93% Diesel + 7% Fame NO 28
    92% Diesel + 7% Fame + 1% Pyrolysis oil NO <0.1
    92% Diesel + 7% Fame + 1% Pyrolysis oil 3000 ppm >48
    • EXAMPLE 10. Stability measured according to the ASTM D525 standard.
  • The test consists of applying pressure with O2 on a 50 ml sample of starting liquid pyrolysis oil at 100°C, and measuring the time in which a specific lowering of O2 pressure occurs as a result of oxidation reactions. As a reference, commercial gasoline has a minimum value fixed for this test of 360 minutes.
    ASTM D525, >360 min
    Pyrolysis oil 120 min
    Pyrolysis oil + 1000 ppm stabilising additive 960 min

Claims (15)

  1. A method for improving pyrolysis oils obtained from waste, wherein the process starts from, as a starting material, liquid pyrolysis oils which contain, or consist of, hydrocarbons, and have been obtained from waste; the method being characterised in that it comprises one or more of the following operations:
    - adsorption;
    - liquid phase distillation;
    - hydrotreatment;
    - pyrolysis oil stabilisation.
  2. The method according to claim 1, wherein the operations include adsorption.
  3. The method according to claim 2, wherein the adsorption comprises passing the pyrolysis oils through one or more columns filled with adsorbents selected from one or more of the following:
    - chlorine absorbent
    - carboxylic acid adsorbent
    - sulphur adsorbent
    - metal adsorbent
    - nitrogenated compound adsorbent
    - activated carbon
    - activated clay.
  4. The method according to any of claims 1-3, wherein the operations include hydrotreatment.
  5. The method according to claim 4, wherein the operations comprise, or consist of, adsorption followed by hydrotreatment.
  6. The method according to any of claims 4-5, wherein the hydrotreatment comprises treating the pyrolysis oil with hydrogen in a reactor with solid catalyst, formed by a metal on a support in the shape of a sphere or extruded in a size between 1 and 3 mm, such that compounds derived from silicone decomposition are removed.
  7. The method according to any of claims 1-6, wherein the waste comprises one or more types selected from: municipal solid waste, industrial waste and biomass.
  8. The method according to claims 1-7, wherein the waste comprises one or more types selected from: plastics, paper, cardboard, textile, biomass.
  9. The method according to claim 4, wherein the waste comprises between 15% and 85% by weight of plastics.
  10. The method according to any of claims 1 to 9, wherein the operations comprise distillation, preferably with an initial point at 160°C or with an initial point at 360°C.
  11. The method according to claim 10, wherein the operations comprise adsorption, followed by distillation and by hydrotreatment.
  12. The method according to one of claims 1-11, wherein the operations comprise a pyrolysis oil stabilisation operation by means of metering at least one additive, or at least one stabiliser, or combinations thereof.
  13. The method according to claim 12, wherein the stabiliser is selected from organic compounds from the families of benzoquinones, hydroquinones, multihydroxybenzenes, alkyl derivatives of benzenes, halogenated quinones and derivatives thereof.
  14. The method according to claim 12 or 13, wherein the stabiliser is selected from 1,2-dihydroxybenzene, 1,4-benzoquinone, 2,3,5,6-tetrachlorobenzoquinone, 1,2-dihydroxy-4-t-butylbenzene, 1,2,3-trihydroxybenzene, substituted hydroquinones, alkyl derivatives of phenols, t-butylpyrocathecol and amine derivatives.
  15. The method according to any of claims 12-14, wherein the additive is an inhibitor which is added in an amount comprised between 20 and 2000 ppm by weight with respect to the weight of the mixture to be inhibited.
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