WO2018104401A1 - Processus de conversion par craquage de plastique en gaz, combustibles liquides et cires - Google Patents

Processus de conversion par craquage de plastique en gaz, combustibles liquides et cires Download PDF

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Publication number
WO2018104401A1
WO2018104401A1 PCT/EP2017/081731 EP2017081731W WO2018104401A1 WO 2018104401 A1 WO2018104401 A1 WO 2018104401A1 EP 2017081731 W EP2017081731 W EP 2017081731W WO 2018104401 A1 WO2018104401 A1 WO 2018104401A1
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Prior art keywords
plastic
mixture
cracking
process according
catalyst
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PCT/EP2017/081731
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English (en)
Inventor
Stéphane STREIFF
Dominique Balthasart
Marco Piccinini
Avelino Corma
Miriam CERRO-ALARCÓN
Jesús MENGUAL
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Solvay Sa
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Application filed by Solvay Sa filed Critical Solvay Sa
Priority to JP2019529859A priority Critical patent/JP2020513453A/ja
Priority to KR1020197019255A priority patent/KR20190092487A/ko
Priority to EP17817700.2A priority patent/EP3551726A1/fr
Priority to US16/466,788 priority patent/US20190345393A1/en
Priority to CN201780003036.7A priority patent/CN108603122A/zh
Publication of WO2018104401A1 publication Critical patent/WO2018104401A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils 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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/06—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for spark ignition
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • 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
    • 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
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/04—Diesel oil
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/08—Jet fuel
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2200/00—Components of fuel compositions
    • C10L2200/04—Organic compounds
    • C10L2200/0461—Fractions defined by their origin
    • C10L2200/0469—Renewables or materials of biological origin
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/023—Specifically adapted fuels for internal combustion engines for gasoline engines
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/02—Specifically adapted fuels for internal combustion engines
    • C10L2270/026—Specifically adapted fuels for internal combustion engines for diesel engines, e.g. automobiles, stationary, marine
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2270/00—Specifically adapted fuels
    • C10L2270/04—Specifically adapted fuels for turbines, planes, power generation
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
    • C10L2290/00—Fuel preparation or upgrading, processes or apparatus therefore, comprising specific process steps or apparatus units
    • C10L2290/54—Specific separation steps for separating fractions, components or impurities during preparation or upgrading of a fuel
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P30/00—Technologies relating to oil refining and petrochemical industry
    • Y02P30/20—Technologies relating to oil refining and petrochemical industry using bio-feedstock

Definitions

  • the present invention relates to a process for converting a mixture comprising plastic and at least one oxygenated compound into gases, liquid fuels and waxes by cracking.
  • the process comprises a deoxygenation step and subsequently a cracking step during which the mixture is subjected to cracking conditions for obtaining a product stream containing said gases, liquid fuels and waxes.
  • the volatile compounds can be either relatively high-boiling liquid hydrocarbons useful as fuel oils or fuel oil supplements or light- to medium-boiling carbon atoms useful as gasoline-type fuels or as other chemicals. Furthermore, the volatile compounds can be or at least can include waxes.
  • a process for converting oxygenated hydrocarbons into hydrocarbons is described in US 4,308,411. This process starts from solid waste, including cellulosic materials, from which an inorganic fraction is separated. The organic fraction is dried and then pyrolyzed at a temperature of from about 300°C to about 800°C, such as 550°C in the examples. The thus obtained vapor comprising oxygenated hydrocarbons is separated and subsequently the oxygenated hydrocarbons are contacted with a crystalline aluminosilicate zeolite for conversion into hydrocarbons. While this process allows for the reduction of oxygenated hydrocarbons, it has the drawback that the organic fraction of the solid waste first has to be pyrolyzed at high temperature. At such high temperature, the plastic in the solid waste also depolymerizes and the
  • depolymerization products can react with the oxygenized compounds resulting in an undesired high oxygen content of the obtained gases, liquid fuels and waxes.
  • the present inventors now found that oxygenated compounds can be removed from a mixture comprising plastic and the oxygenated compounds at a rather low temperature. Additionally, the inventors found that the density of the condensate of the gas stream obtained from the heated mixture is a suitable marker for determining the end of the deoxygenation process. At the beginning of the process, the density of the condensate is high. During deoxygenation the density of the condensate decreases. At a certain density a substantial amount of the undesired oxygenated compound has been removed from the mixture so that during the subsequent cracking step a product stream containing gases, liquid fuels and waxes of high quality and low oxygen content is obtained.
  • the present invention therefore relates to a process for converting a mixture comprising plastic and at least one oxygenated compound into gases, liquid fuels and waxes by cracking, the process comprising :
  • a deoxygenation step which is conducted by heating the mixture to a temperature of at least 200°C for a period until the condensate of the gas stream obtained from the heated mixture has a density of about 0.94 g/cm 3 or lower; and subsequently to the deoxygenation step a cracking step during which the mixture is subjected to cracking conditions for obtaining a product stream containing said gases, liquid fuels and waxes.
  • the gasoline fraction contains compounds having a low boiling point of for example below 150°C. This fractions includes compounds having 5 to 9 carbon atoms.
  • the kerosene and diesel fraction has a higher boiling point of for example 150°C to 359°C. This fraction generally contains compounds having 10 to 21 carbon atoms.
  • the even higher-boiling fractions are generally designated as heavy cycle oil (or HCO) and waxes. In all these fractions, the compounds are hydrocarbons which optionally comprise heteroatoms, such as N, O, etc.
  • “Waxes” in the sense of the present invention therefore designate hydrocarbons which optionally contain heteroatoms. In most cases, they are solid at room temperature (23°C) and have a softening point of generally above 26°C. A definition of the obtained fractions is provided in the experimental section below.
  • a plastic is mostly constituted of a particular polymer and the plastic is generally named by this particular polymer.
  • a plastic contains more than 25 % by weight of its total weight of the particular polymer, preferably more than 40 % by weight and more preferably more than 50 % by weight.
  • Other components in plastic are for example additives, such as fillers, re- enforcers, processing aids, plasticizers, pigments, light stabilizers, lubricants, impact modifiers, antistatic agents, inks, antioxidants, etc.
  • a plastic comprises more than one additive.
  • Plastics used in the process of the present invention include polyolefms and polystyrene, such as high-density polyethylene (HDPE), low-density polyethylene (LDPE), ethylene-propylene-diene monomer (EPDM),
  • HDPE high-density polyethylene
  • LDPE low-density polyethylene
  • EPDM ethylene-propylene-diene monomer
  • polypropylene PP
  • PS polystyrene
  • Mixed plastics mostly constituted of polyolefm and/or polystyrene are preferred.
  • plastics such as polyvinyl chloride, polyvinylidene chloride, polyethylene terephthalate, polyurethane (PU), acrylonitrile-butadiene-styrene (ABS), ethylene vinyl alcohol polymer (EVA), polyvinylacetate, polycarbonate, polyacrylate, polymethylmetacrylate (PMMA), nylon and fluorinated polymers are less desirable. If present in the plastic, they are preferably present in a minor amount of less than 50 % by weight, preferably less than 30 % by weight, more preferably less than 20 % by weight, even more preferably less than 10 % by weight of the total weight of the dry weight plastic.
  • the plastic comprises one or more thermoplastic polymers and is essentially free of thermosetting polymers.
  • Essentially free in this regard is intended to denote a content of thermosetting polymers of less than 15, preferably less than 10 and even more preferably less than 5 % by weight of the plastic starting material.
  • the plastic used in the process of the present invention can be selected among :
  • single waste plastic, single virgin plastic on spec or off spec, mixed waste plastic, rubber waste, organic waste, biomass or a mixture thereof Single plastic waste, single virgin plastic off spec, mixed waste plastic, rubber waste or a mixture thereof are preferred. Single virgin plastic off-spec, mixed waste plastic or a mixture thereof particularly preferred. Mixed plastic waste gives usually good results.
  • the mixture can be pretreated by a physico-chemical process including one or more operations as size reduction, grinding, shredding, screening, chipping, melt removal, foreign material removal, dust removal, drying, degassing, melting, solidifying and
  • waste plastic contains other non-desired components, namely foreign materials such as glass, stone, metal, etc. Limited quantities of such unpyrolizable components as contaminant of the inlet raw material are acceptable.
  • the mixture used in the process of the present invention may contain less than 50 % by weight, preferably less than 20 % by weight, more preferably less than 10 % by weight of the total weight of the dry mixture unpyrolizable components.
  • waste plastic very often contains other non-desired components, mainly cellulosic base materials, such as wood, cardboard, paper, tissue, etc.
  • These pyrolizable components are mostly oxygenated compounds, such as oxygenated hydrocarbons, which during cracking of plastic result in an undesired increase in oxygen content of the obtained gases, liquid fuels and waxes.
  • Oxygenated compounds in the sense of the present invention are, however, not limited to organic compounds but may also include inorganic compounds which comprise oxygen atoms being bound to other atoms but which are chemically not stable under the cracking conditions. H 2 0 is not considered as an oxygenated compound in the sense of the present invention.
  • oxygenated compounds are difficult to remove because pyrolysis of oxygenated compounds, such as cellulosic materials, as suggested in US 4,308,411 requires high temperatures at which cracking of the plastic may occur.
  • the present inventors now surprisingly found that in a mixture comprising plastic and at least one oxygenated compound the temperature required for converting the oxygenated compound into gases is rather low. There remained, however, the problem that under specific conditions also plastics can be cracked at low temperatures. It was therefore necessary to determine a parameter suitable for distinguishing between the deoxygenation process during which the oxygenated compounds are removed from the mixture and the cracking process during which the plastic is converted into the desired products. Upon further investigation, the present inventors found that the density of the condensate of the gas stream obtained from the heated mixture is a suitable parameter to distinguish between the deoxygenation step and the cracking step.
  • the measurement of the density of the condensate of the gas stream obtained from the heated mixture allows for an optimization not only of the quality of the obtained gases, liquid fuels and waxes but also of their yield.
  • the deoxygenation step is conducted until the condensate of the gas stream obtained from the heated mixture has a density in the range of 0.90 g/cm 3 to 0.93 g/cm 3 , preferably in the range of 0.91 g/cm 3 to 0.93 g/cm 3 , more preferably in the range of 0.920 g/cm 3 to 0.928 g/cm 3 , even more preferably in the range of 0.923 g/cm 3 to 0.927 g/cm 3 , and most preferably about 0.925 g/cm 3 .
  • the "condensate of the gas stream obtained from the heated mixture” is to be understood as the fraction of gaseous products obtained from the mixture being heated to at least 200°C which is obtained when cooling the hot gas stream to 40°C. Those components of the gas stream which do not condense at 40°C are discharged.
  • the condensate is then further cooled to a temperature of 25°C. At this temperature the density of the condensate is measured. Possibly, the condensate may split into an aqueous fraction and an oil fraction. Therefore, the density of the condensate is defined as the ratio of the weight of the sample to the volume of the sample without taking into account any possible liquid phase split. This measurement can be conducted by simply using the apparent weight and apparent volume of the "mixed" condensate.
  • the density of the condensate can be measured continuously or at least semi-continuously. It can, however, be preferred to collect a certain volume of the condensate before measuring its density.
  • a suitable volume can be selected relative to the amount of plastic in the starting mixture being introduced into the reactor. In this case, the volume can be in the range of 0.1 to 250 cm 3 /kg of the plastic, preferably 0.15 to 100 cm 3 /kg of the plastic, more preferably 0.2 to 20 cm 3 /kg of the plastic. In another embodiment a suitable volume can be in the range of for example 0.5 to 10 cm 3 , preferably 0.5 to 5 cm 3 , more preferably from 0.5 to 4 cm 3 .
  • the condensate can be collected for a certain time before the density of the condensate collected during this time is measured.
  • the time interval during which the condensate is collected depends for example on the composition and amount of the mixture comprising the plastic and the oxygenated compound, the size of the reactor, the catalyst, the heating powder, the flow of the condensate, etc. and can be in the range of for example 1 to 120 minutes, preferably 1 to 90 minutes, more preferably 1 to 60 minutes, such as in the range of 2 to 30 minutes.
  • the shorter the time interval during which the condensate is collected for the measurement of its density the higher is the precision in determining the end of the deoxygenation step and the beginning of the cracking step.
  • the obtained condensate is collected either for a certain period of time or until a certain volume is obtained.
  • the density of the thus obtained condensate is measured and, if the density is above about 0.94 g/cm 3 , the deoxygenation step is continued and a further sample of the condensate is collected for the next density measurement. Each sample is collected for a certain period of time or until a certain volume is obtained.
  • the process of the invention can also be conducted continuously for example by using a reactor, like a rotating drum reactor or a screw reactor wherein the mixture comprising plastic and at least one oxygenated compound is continuously moved from one reaction zone to the next. From each reaction zone, a gas stream is collected and the density of the condensate of the gas stream is measured as described above. As long as the gas stream obtained from a given reaction zone has a density of above about 0.94 g/cm 3 , the reaction zone is operated under deoxygenation conditions.
  • this and the subsequent reaction zones are operated under cracking conditions for obtaining product streams containing the desired gases, liquid fuels and waxes.
  • the gas stream obtained during the deoxygenation step contains gaseous products to which the oxygenated compounds are converted.
  • the oxygenated compounds are removed and a residue mainly consisting of the plastic (and optionally the above described unpyrolyzable components and small amounts of plastic pyrolysis products) is obtained. This residue is subsequently subjected to cracking conditions.
  • the temperature at which oxygenated compounds are converted into gaseous products depends on the plastic in the mixture.
  • oxygenated compounds are converted into gases at a temperature slightly lower than 350°C if the plastic is polyethylene and at a temperature slightly lower than 300°C if the plastic is polypropylene. This demonstrates that the plastic in the mixture comprising plastic and the at least one oxygenated compound influences the temperature at which the oxygenated compound is converted into gases.
  • the gases produced during the deoxygenation step are removed as a fist gas stream.
  • This gas stream contains the products of the undesired oxygen-containing compounds which are thereby removed before the plastic is cracked.
  • Removing of the first gas stream can for example be conducted by purging the space above the heated mixture with a gas, such as air, preferably an inert gas, such as nitrogen.
  • the first gas stream can be removed by applying a reduced pressure.
  • the gas stream obtained during the deoxygenation step is removed for a time sufficient to remove at least 50 % by weight of the at least one oxygenated compound from the mixture, based on the total weight of the at least one oxygenated compound being present in the mixture prior to the deoxygenation step. More preferably, at least 70 % by weight, even more preferably at least 80 % by weight and most preferably substantially all of the at least one oxygenated compound is removed from the mixture prior to the cracking step.
  • substantially all of the at least one oxygenated compound is understood such that at least 90 % by weight, preferably at least 95 % by weight and even more preferably at least 97 % by weight based on the total weight of the at least one oxygenated compound being present in the mixture prior to the deoxygenation step is removed prior to the cracking step.
  • This residue comprises the plastic which was not depolymerized at the first temperature, optionally remaining amounts of oxygenated compounds, and optionally the above described unpyrolizable components. If the heating of the mixture at the first temperature has been conducted in the presence of the catalyst, this catalyst is also comprised within the residue.
  • the residue is submitted to cracking conditions. At these conditions, cracking of the plastic occurs thereby producing a product stream containing the desired gases, liquid fuels and waxes. This product stream is removed from the heated residue.
  • the temperature during cracking of the plastic usually is above 350°C, preferably above 400°C, more preferably at least 425°C, such as in the range of above 400°C to 650°C, even more preferably in the range of 425°C to 550°C.
  • the cracking may be conducted in an air depleted atmosphere.
  • An air depleted atmosphere can for examples contain or consist of one or more inert gases, such as nitrogen, or can be at reduced pressure.
  • the cracking may be conducted in the presence of a catalyst. It is, however, also possible that a catalyst is present also during the deoxygenation step. In this case, it is preferred that the deoxygenation step and the cracking step are conducted in the presence of a catalyst, preferably the same catalyst. It is, however, also possible that the two steps are conducted in the presence of two different catalysts or that a further, different catalyst is added to the cracking step. Finally, it is possible, but less desired, that only the deoxygenation step is conducted in the presence of a catalyst, which, however, must then be removed prior to the cracking of the residue.
  • the catalyst used in the process of the present invention can be any suitable catalyst.
  • Preferred catalysts are those used in FCC operations such as fresh FCC catalyst, spent FCC catalyst, equilibrated FCC catalyst, BCA (bottom cracking additives) or any mixture thereof.
  • the catalyst can comprise a zeolite-type catalyst.
  • zeolite-type catalyst Such catalysts may be selected from crystalline microporous zeolites which are known to the person skilled in the art and which are commercially available. Preferred examples for zeolite-type catalysts are described in WO 2010/135273, the content of which is incorporated herein by reference.
  • zeolite-type catalysts include but are not limited to ZSM-5, ZSM-11, ZSM-22, ZSM-23, ZSM-35, ZSM-48, ZSM-50, TS-1, TS-2, SSZ-46, MCM-22, MCM-49, FU-9, PSH-3, ITQ-1, EU-1, NU-10, silicalite-1, silicalite-2, boralite- C, boralite-D, BCA, and mixtures thereof.
  • the catalyst may comprise an amorphous-type catalyst which may comprise for example silica, alumina, kaolin, or any mixture thereof.
  • Silica in particular in the form of sand, is well known for FCC catalyst applications.
  • reactor types are fluidized bed, entrained bed, spouted bed, downcomer, fixed bed, rotating drum, rotating cone, screw cone, screw auger, extruder, molecular distillation, thin film evaporator, kneader, cyclone and the like.
  • Fluidized bed, entrained bed, spouted bed, screw auger and rotating drum are preferred.
  • Screw auger and rotating drum are particularly preferred.
  • the deoxygenation step and the cracking step are conducted in two different reactors.
  • the deoxygenation step and the cracking step are conducted in the same reactor. This can be done subsequently in the same section of a reactor or in two or more different sections of the same reactor, for example in a rotary drum or an auger where different sections are operated at different temperatures.
  • the process according to the invention can be conducted batchwise, semi- batchwise or continuously.
  • any feed stream and any product stream can be continuous but at least one feed stream or one product stream is discontinuous and/or at least one feed stream or one product stream is continuous.
  • the present invention furthermore relates to a process for removing oxygenated compounds from a mixture comprising plastic and at least one oxygenated compound, the process comprises : heating the mixture to a temperature of at least 200°C for a period until the condensate of the gas stream obtained from the heated mixture has a density of about 0.94 g/cm 3 or lower.
  • the preferred embodiments are those as described above.
  • temperature was increased to less than 425°C at a heating rate of 10°C/min. During this time the collection of gases and nitrogen was done in another gas sampling bag. Thereafter, the temperature was further increased to the cracking temperature of 425°C. When the internal temperature reached the cracking temperature, the catalyst was introduced inside the reactor, and the circulation of the gaseous products was commuted to another pair of glass traps and corresponding gas sampling bag.
  • liquid and gaseous products were collected in a pair of glass traps and their associated gas sampling bag, respectively.
  • the reactor was cooled to room temperature. During this cooling step, liquids and gases were also collected.
  • reaction products were classified into 3 groups : i) gases, ii) liquid hydrocarbons and iii) residue (waxy compounds, ashes and coke accumulated on the catalyst). Quantification of the gases was done by gas chromatography (GC) using nitrogen as the internal standard, while quantification of liquids and residue was done by weight. Glass traps (along with their corresponding caps) were weighed before and after the collection of liquids, while the reactor vessel was weighed before and after each run.
  • HCO heavy cycle oil which is considered as hydrocarbon molecules with at least 22 carbon atoms (+C22).
  • Waxes refer to hydrocarbon molecules with at least 20 carbon atoms (+C20).
  • Gasolines contains C5s and C6s in gases + liquids with bp (boiling point) ⁇ 150°C (ca. C5-C9)
  • Kerosene liquids with boiling point 150 ⁇ bp ⁇ 250°C (ca. C10-C14)
  • Determination of the different fractions is done by gas chromatography by the simulated distillation method and according to the ASTM-D-2887 standard.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Processing Of Solid Wastes (AREA)
  • Catalysts (AREA)

Abstract

La présente invention concerne un processus de conversion par craquage d'un mélange comprenant du plastique et au moins un composé oxygéné en gaz, combustibles liquides et cires. Le processus comprend une étape de désoxygénation suivie d'une étape de craquage au cours de laquelle le mélange est soumis à des conditions de craquage afin d'obtenir un flux de produit contenant lesdits gaz, combustibles liquides et cires.
PCT/EP2017/081731 2016-12-07 2017-12-06 Processus de conversion par craquage de plastique en gaz, combustibles liquides et cires WO2018104401A1 (fr)

Priority Applications (5)

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JP2019529859A JP2020513453A (ja) 2016-12-07 2017-12-06 プラスチックを分解によってガス、液体燃料およびワックスに変換するための方法
KR1020197019255A KR20190092487A (ko) 2016-12-07 2017-12-06 크래킹에 의해 플라스틱을 가스, 액체 연료 및 왁스로 전환시키는 방법
EP17817700.2A EP3551726A1 (fr) 2016-12-07 2017-12-06 Processus de conversion par craquage de plastique en gaz, combustibles liquides et cires
US16/466,788 US20190345393A1 (en) 2016-12-07 2017-12-06 Process for converting plastic into gases, liquid fuels and waxes by cracking
CN201780003036.7A CN108603122A (zh) 2016-12-07 2017-12-06 用于通过裂化将塑料转化为气体、液体燃料和蜡的方法

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EP16306634.3 2016-12-07

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EP3919587A1 (fr) 2020-06-03 2021-12-08 SK Innovation Co., Ltd. Procédé de production d'huile de naphte sélective par pyrolyse secondaire d'huile usée

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US5216149A (en) 1991-06-07 1993-06-01 Midwest Research Institute Controlled catalytic and thermal sequential pyrolysis and hydrolysis of mixed polymer waste streams to sequentially recover monomers or other high value products
US6011187A (en) * 1996-02-27 2000-01-04 Mitsubishi Heavy Industries, Ltd. Method and apparatus for reclaiming oil from waste plastic
WO2006010324A1 (fr) * 2004-07-26 2006-02-02 Hefei Lafa Environmental Protection Technology Development Co., Ltd. Procede de production de carburants a partir de dechets de plastiques par craquage catalytique sous pression atmospherique
WO2010135273A2 (fr) 2009-05-18 2010-11-25 Integrated & Proven Catalyst Technologies Corporation Séparation de catalyseurs d'équilibre de craquage catalytique fluide pour améliorer la valeur et réduire les déchets
US20130118885A1 (en) * 2011-11-10 2013-05-16 Moinuddin Sarker Methods and systems for converting plastic to fuel
US20150001061A1 (en) * 2011-07-28 2015-01-01 Jbi Inc. System and process for converting plastics to petroleum products

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US4308411A (en) 1980-08-28 1981-12-29 Occidental Research Corporation Process for converting oxygenated hydrocarbons into hydrocarbons
US5216149A (en) 1991-06-07 1993-06-01 Midwest Research Institute Controlled catalytic and thermal sequential pyrolysis and hydrolysis of mixed polymer waste streams to sequentially recover monomers or other high value products
US6011187A (en) * 1996-02-27 2000-01-04 Mitsubishi Heavy Industries, Ltd. Method and apparatus for reclaiming oil from waste plastic
WO2006010324A1 (fr) * 2004-07-26 2006-02-02 Hefei Lafa Environmental Protection Technology Development Co., Ltd. Procede de production de carburants a partir de dechets de plastiques par craquage catalytique sous pression atmospherique
WO2010135273A2 (fr) 2009-05-18 2010-11-25 Integrated & Proven Catalyst Technologies Corporation Séparation de catalyseurs d'équilibre de craquage catalytique fluide pour améliorer la valeur et réduire les déchets
US20150001061A1 (en) * 2011-07-28 2015-01-01 Jbi Inc. System and process for converting plastics to petroleum products
US20130118885A1 (en) * 2011-11-10 2013-05-16 Moinuddin Sarker Methods and systems for converting plastic to fuel

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JP2020513453A (ja) 2020-05-14
EP3551726A1 (fr) 2019-10-16
US20190345393A1 (en) 2019-11-14
KR20190092487A (ko) 2019-08-07

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