WO2023100139A1 - Methods for removal of silicon and chloride contaminants from mixed plastic waste based pyrolysis oil - Google Patents
Methods for removal of silicon and chloride contaminants from mixed plastic waste based pyrolysis oil Download PDFInfo
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- WO2023100139A1 WO2023100139A1 PCT/IB2022/061668 IB2022061668W WO2023100139A1 WO 2023100139 A1 WO2023100139 A1 WO 2023100139A1 IB 2022061668 W IB2022061668 W IB 2022061668W WO 2023100139 A1 WO2023100139 A1 WO 2023100139A1
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- Prior art keywords
- pyrolysis oil
- fraction
- alkaline hydroxide
- upgraded
- hydroxide solution
- Prior art date
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- 239000003921 oil Substances 0.000 title claims abstract description 262
- 238000000197 pyrolysis Methods 0.000 title claims abstract description 256
- 238000000034 method Methods 0.000 title claims abstract description 57
- 239000013502 plastic waste Substances 0.000 title claims abstract description 39
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title abstract description 25
- 229910052710 silicon Inorganic materials 0.000 title abstract description 24
- 239000010703 silicon Substances 0.000 title abstract description 24
- 239000000356 contaminant Substances 0.000 title abstract description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims abstract description 129
- 150000001805 chlorine compounds Chemical class 0.000 claims abstract description 62
- 150000003377 silicon compounds Chemical class 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims description 69
- 239000012223 aqueous fraction Substances 0.000 claims description 43
- 239000000203 mixture Substances 0.000 claims description 33
- 239000007788 liquid Substances 0.000 claims description 20
- 239000012530 fluid Substances 0.000 claims description 9
- 238000004064 recycling Methods 0.000 claims description 9
- 238000004891 communication Methods 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 238000000926 separation method Methods 0.000 claims description 4
- 238000004581 coalescence Methods 0.000 claims description 3
- 239000000243 solution Substances 0.000 description 83
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 30
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 22
- 229930195733 hydrocarbon Natural products 0.000 description 9
- 150000002430 hydrocarbons Chemical class 0.000 description 9
- 238000009835 boiling Methods 0.000 description 8
- 230000003247 decreasing effect Effects 0.000 description 8
- 239000002699 waste material Substances 0.000 description 6
- 239000004215 Carbon black (E152) Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004231 fluid catalytic cracking Methods 0.000 description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 238000004517 catalytic hydrocracking Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005235 decoking Methods 0.000 description 2
- 239000003925 fat Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011368 organic material Substances 0.000 description 2
- 238000004230 steam cracking Methods 0.000 description 2
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 description 2
- KJESGYZFVCIMDE-UHFFFAOYSA-N 1-chloroethanol Chemical compound CC(O)Cl KJESGYZFVCIMDE-UHFFFAOYSA-N 0.000 description 1
- NHWQMJMIYICNBP-UHFFFAOYSA-N 2-chlorobenzonitrile Chemical compound ClC1=CC=CC=C1C#N NHWQMJMIYICNBP-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000003637 basic solution Substances 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000003518 caustics Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- 150000008280 chlorinated hydrocarbons Chemical class 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- -1 cyclic siloxanes Chemical class 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000011143 downstream manufacturing Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229910017464 nitrogen compound Inorganic materials 0.000 description 1
- 150000002830 nitrogen compounds Chemical class 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
- C10G19/00—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment
- C10G19/02—Refining hydrocarbon oils in the absence of hydrogen, by alkaline treatment with aqueous alkaline solutions
-
- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/04—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step
- C10G53/06—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one extraction step including only extraction steps, e.g. deasphalting by solvent treatment followed by extraction of aromatics
-
- 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
- C10G53/00—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes
- C10G53/02—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only
- C10G53/12—Treatment of hydrocarbon oils, in the absence of hydrogen, by two or more refining processes plural serial stages only including at least one alkaline treatment step
-
- 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
- C10G67/04—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 solvent extraction 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
- 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
- C10G67/10—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 alkaline treatment as the refining step in the absence of hydrogen
Definitions
- the present disclosure generally relates to systems and methods for processing mixed plastic waste pyrolysis oil to remove silicon and chloride contaminants. More specifically, the present disclosure relates to systems and methods for processing mixed plastic waste pyrolysis oil to produce a feedstock that is usable for a refinery unit, such as a hydrotreater, or a hydrocracker, or a combination thereof.
- a refinery unit such as a hydrotreater, or a hydrocracker, or a combination thereof.
- Pyrolysis oil (pyoil) from the mixed plastic waste is emerging as an alternative feedstock via chemical recycling.
- Pyoil contains several contaminants such as silicon, chlorides, nitrogen, oxygenates and other heavy species. These contaminants result in several detrimental effects, such as fouling and downstream catalyst poisoning.
- products derived from the processing of pyoil are subjected to strict elemental requirements to be used as a replacement for the fossil-based feedstock, such as naphtha or fuels. Presence of silicon and chloride contaminants limit further downstream applications.
- One way of processing the pyoil is to send it to a hydrotreater unit to remove the hetero-atom impurities, such as the silicon, oxygen compounds, nitrogen compounds, and chloride compounds along with saturating the unsaturated species.
- a drawback of this process is that the hydrotreater catalyst tends to coke rapidly due to heavy components. Another drawback is that such a process requires a large quantity of hydrogen and a large reactor due to the high level of contamination present in the raw pyoil. Moreover, the hydrotreatment of pyoils with such contaminants requires expensive and special metallurgical equipment to address the corrosion issues.
- Applicant has developed systems and methods for pretreating raw mixed plastic waste pyrolysis oil to remove silicon and chloride contaminants. Products formed from the hydrotreating of the pretreated mixed plastic waste pyrolysis oil can also be subject to further hydrocracking and distillation.
- the pyrolysis oil can be a raw mixed plastic waste pyrolysis oil or can be certain specific fractions.
- the pyrolysis oil obtained from processing of raw mixed plastic waste can be fractionated to provide multiple fractions, such as a light liquid fraction with a boiling point less than about 170 degrees centigrade (°C), a middle liquid fraction with a boiling point ranging from about 170 °C to about 370 °C, and a heavy end fraction with a boiling point greater than about 370 °C. In certain instances, this heavy end fraction has a boiling point greater than about 400 °C.
- a mixture of all the three fractions is called a full range pyrolysis oil.
- An embodiment of a method of treating a pyrolysis oil includes the step of supplying, to a reaction vessel, a pyrolysis oil containing a plurality of silicon compounds and a plurality of chloride compounds, mixing the pyrolysis oil with an aqueous alkaline hydroxide solution in the reaction vessel operated at a temperature ranging from about 15 °C to about 225 °C, allowing the mixture of the pyrolysis oil and the aqueous alkaline hydroxide solution to separate into an upgraded pyrolysis oil fraction and an aqueous fraction, extracting the upgraded pyrolysis oil fraction and optionally supplying it to a hydroprocessing unit.
- the pyrolysis oil is mixed with the aqueous alkaline hydroxide solution in the reaction vessel operated at a temperature ranging from about 15 °C to about 100 °C, or from about 15 °C to about 50 °C, or at room temperature.
- the alkaline hydroxide solution contains less than about 50 weight percent of the alkaline hydroxide.
- the aqueous alkaline hydroxide solution can contain less than about 20 weight percent of the alkaline hydroxide.
- the aqueous alkaline hydroxide solution can contain less than about 10 weight percent of the alkaline hydroxide.
- the alkaline hydroxide solution contains an amount of alkaline hydroxide ranging from about 1 weight percent to about 20 weight percent.
- the mixture of the pyrolysis oil and the aqueous alkaline hydroxide solution is separated into the upgraded pyrolysis oil fraction and the aqueous fraction by settling or coalescence.
- the upgraded pyrolysis oil fraction contains at least about 30 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 50 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil.
- the upgraded pyrolysis oil fraction contains at least about 50 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 90 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil.
- An embodiment of a method of treating a pyrolysis oil includes the step of supplying, to a reaction vessel, a pyrolysis oil containing a plurality of silicon compounds and a plurality of chloride compounds, mixing the pyrolysis oil with a first aqueous alkaline hydroxide solution in the reaction vessel operated at a temperature ranging from about 15 °C to about 30 °C, allowing the mixture of the pyrolysis oil and the first aqueous alkaline hydroxide solution to separate into a first upgraded pyrolysis oil fraction and a first aqueous fraction, removing the first aqueous fraction from the reaction vessel, mixing the first upgraded pyrolysis oil fraction and a second aqueous alkaline hydroxide solution in the reaction vessel operated at a temperature ranging from about 15 °C to 30 °C, allowing the mixture of the first upgraded pyrolysis oil fraction and the second aqueous alkaline hydroxide solution to separate into a second upgraded pyrolysis oil fraction
- Each of the first aqueous alkaline hydroxide solution, the second aqueous alkaline hydroxide solution, and the third aqueous alkaline hydroxide solution has a pH of about 10 or greater.
- the third upgraded pyrolysis oil fraction contains at least about 30 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 50 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil.
- the third upgraded pyrolysis oil fraction contains at least about 30 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 80 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil. In certain embodiments, the third upgraded pyrolysis oil fraction contains at least about 50 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 80 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil.
- the third upgraded pyrolysis oil fraction contains at least about 50 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 90 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil.
- Methods disclosed herein can be used to treat a pyrolysis oil that is a light liquid fraction obtained from processing of raw mixed plastic waste pyrolysis oil at less than about 170 °C, defining a naphtha fraction. Methods disclosed herein can be used to treat a pyrolysis oil that is a medium liquid fraction obtained from processing of raw mixed plastic waste pyrolysis oil from about 170 °C to about 370 °C, defining a diesel fraction. Methods disclosed herein can be used to treat a pyrolysis oil that is a full range pyrolysis oil.
- Embodiments include systems for treating a pyrolysis oil.
- One such system includes the following: (i) a reaction vessel operated at a temperature ranging from about 15 °C to about 30 °C and containing (a) a pyrolysis oil inlet configured to receive and supply to the reaction vessel a pyrolysis oil containing a plurality of silicon compounds and a plurality of chloride compounds,
- an alkaline hydroxide inlet configured to receive and supply to the reaction vessel an aqueous alkaline hydroxide solution containing less than about 20 weight percent of the alkaline hydroxide
- the reaction vessel can also include a jacket heater operatively connected to an external wall of the reaction vessel.
- the system includes a hydrotreater unit connected to and
- FIG. 1 is an illustration of a system for processing mixed plastic waste pyrolysis oil, according to an embodiment.
- FIG. 2 is a schematic flowchart for a method of processing mixed plastic waste pyrolysis oil, according to an embodiment.
- FIG. 3 is a schematic flowchart for a method of processing mixed plastic waste pyrolysis oil using multiple treatments with the alkaline hydroxide solution, according to an embodiment.
- the present disclosure describes various embodiments related to processes, devices, and systems for pretreating the raw mixed plastic waste pyrolysis oil. Also, provided here are systems and methods for processing the pretreated raw mixed plastic waste pyrolysis oil by subjecting it to further hydrotreating processes. Further embodiments may be described and disclosed.
- Embodiments of the present disclosure include systems and methods for processing mixed plastic waste pyrolysis oil to remove silicon and chloride contaminants. More specifically, the present disclosure relates to systems and methods for processing mixed plastic waste pyrolysis oil to produce a feedstock that is usable for a refinery unit, such as a hydrotreater, or a hydrocracker, or a combination thereof. [0024] Embodiments include systems for treating a pyrolysis oil.
- One such system includes the following: (i) a reaction vessel operated at a temperature ranging from about 15 °C to about 225 °C and containing (a) a pyrolysis oil inlet configured to receive and supply to the reaction vessel a pyrolysis oil containing a plurality of silicon compounds and a plurality of chloride compounds,
- an alkaline hydroxide inlet configured to receive and supply to the reaction vessel an aqueous alkaline hydroxide solution containing less than about 20 weight percent of the alkaline hydroxide
- the reaction vessel can also include a jacket heater operatively connected to an external wall of the reaction vessel.
- the system includes a hydrotreater unit connected to and
- the higher temperatures result in greater removal of silicon and chloride impurities, but can affect the amount of pyoil that is recovered in the liquid phase.
- the effect of increased temperatures on the recovery of the pyoil depends on the nature and hydrocarbon profile of the pyoil.
- These systems and methods for processing the pyrolysis oil reduce the level of silicon compounds and chloride compounds in the pyrolysis oil before being supplied to the downstream processing units in the hydrotreater feed. For example, this treatment step facilitates the reduction of hydrogen consumption in the hydrotreater.
- the pyrolysis oil can be obtained from recycled or renewable organic material. These organic materials can contain fossil waste-based oils, waste oils, algal oils and microbial oils, plant based fats and oils, animal based fats and oils, or combinations thereof.
- the fossil waste-based pyrolysis oil can include waste plastic pyrolysis oil (WPPO), end-life-tire pyrolysis oil (ELTPO), used lubricating oil (ULO), or combinations thereof.
- WPPO waste plastic pyrolysis oil
- ELTPO end-life-tire pyrolysis oil
- UEO used lubricating oil
- the pyrolysis oil can be a raw mixed plastic waste pyrolysis oil or can be certain specific fractions.
- the raw mixed plastic waste can be processed to provide multiple fractions, such as a light liquid fraction with a boiling point less than about 170 °C, a middle liquid fraction with a boiling point ranging from about 170 °C to about 370 °C, and a heavy end fraction with a boiling point greater than about 370 °C. In certain instances, this heavy end fraction has a boiling point greater than about 400 °C.
- a mixture of all the three fractions constitutes a full range pyrolysis oil.
- FIG. 1 is a schematic representation of the caustic wash arrangement to remove the silicon and chlorides from the pyoil stream.
- the system 100 includes a reaction vessel 102 that can be operated at a temperature ranging from about 15 °C to about 225 °C.
- the reaction vessel 102 can also include a jacket heater 104 operatively connected to an external wall of the reaction vessel 102.
- the reaction vessel can be one or more of a fixed bed, a moving bed, a fixed stirred unit, or a fluidized bed unit, either placed as a single unit, or as multiple units in series or in parallel to pretreat the raw mixed plastic waste pyrolysis oil stream.
- the fluidized bed unit can be an ebullated bed unit.
- the reaction vessel is a microwave heated reaction vessel.
- the reaction vessel can be equipped with a microwave heating system, including several components such as a microwave source, a receiver, a transmitter, and a shield.
- a pyoil stream 106 is fed from the bottom through a pyrolysis oil inlet 108 configured to receive and supply to the reaction vessel.
- the aqueous alkaline hydroxide solution 110 is supplied to the reaction vessel 102 via an alkaline hydroxide inlet 112.
- a mixing element 114 is located inside the reaction vessel 102 to facilitate mixing of the pyrolysis oil and the aqueous alkaline hydroxide solution.
- the mixing element is one or more of an agitator, an impeller, a baffle, or a draft tube configured within the reactor to provide effective mixing of the first dehalogenated pyrolysis oil and water.
- the impeller is one of three types such as a propeller, paddle, or turbine, which generate either axial or radial flow of the fluids within the reactor.
- the pyrolysis oil is mixed with the aqueous alkaline hydroxide solution in the reaction vessel operated at a temperature ranging from about 15 °C to about 150 °C, from about 15 °C to about 100 °C, or from about 15 °C to about 50 °C, or at room temperature.
- the alkaline hydroxide solution contains less than about 50 weight percent of the alkaline hydroxide.
- the aqueous alkaline hydroxide solution can contain less than about 20 weight percent of the alkaline hydroxide.
- the aqueous alkaline hydroxide solution can contain less than about 10 weight percent of the alkaline hydroxide.
- the alkaline hydroxide solution contains an amount of alkaline hydroxide ranging from about 1 weight percent to about 20 weight percent.
- the reaction vessel 102 also includes an upgraded pyrolysis oil outlet 116 configured to discharge an upgraded pyrolysis oil fraction 118 that is produced by separation of the mixture of the pyrolysis oil and the aqueous alkaline hydroxide solution into the upgraded pyrolysis oil fraction and an aqueous fraction.
- the reaction vessel 102 also includes an effluent outlet 120 configured to supply the aqueous fraction 122 to an alkaline hydroxide recycling unit 124 and to discharge any solids formed during production of the upgraded pyrolysis oil fraction and the aqueous fraction.
- the waxy solid or deposits are recovered at the bottom and discharged as a waste stream 130 through a waste outlet 128.
- the system 100 includes an alkaline hydroxide recycling unit connected to and in fluid communication with the effluent outlet.
- the aqueous fraction is processed here to remove any contaminants and appropriate alkaline hydroxide is added to the processed aqueous fraction to align with the specification of the fresh aqueous alkaline hydroxide solution that is supplied to the reaction vessel.
- This processed aqueous fraction 126 is then recycled to the reaction vessel as a separate stream or in combination with the fresh aqueous alkaline hydroxide solution 110 via an alkaline hydroxide inlet 112.
- the system includes a hydrocarbon processing unit connected to and in fluid communication with the upgraded pyrolysis oil outlet of the reaction vessel.
- the hydrocarbon processing unit is one or more of a fluid catalytic cracking (FCC) unit, a hydrocracking unit, a decoking unit, a naphtha hydrotreatment unit, a hydrotreating unit, and a steam cracking unit.
- FCC fluid catalytic cracking
- the pyoil feed rate is controlled to provide the optimum residence time required for the removal of silicon and chloride compounds. Further, the vessel is provided with the heating jacket to supply heat and temperature (if required). The reaction mixture is left to react for a predetermined period of time and predetermined temperature preferably with mixing.
- Embodiments of the methods described herein are used to remove silicon compounds, chloride compounds, or combinations thereof from the pyrolysis oil by treating the pyrolysis oil with an aqueous basic solution under specific operating conditions.
- Silicon compounds include linear and cyclic siloxanes and derivatives.
- Chloride compounds include chloride salts and organic chloride compounds, such as chlorinated hydrocarbons, like chlorethanol or chlorobenzonitrile.
- the pyrolysis oil obtained from these treatment methods can further be processed in the steam cracker or hydrotreater units.
- FIG. 2 is a schematic flowchart for a method 200 for processing mixed plastic waste pyrolysis oil, according to an embodiment.
- This method 200 includes the step 202 of supplying, to a reaction vessel, a pyrolysis oil containing a plurality of silicon compounds and a plurality of chloride compounds.
- This method 200 includes the step 204 of mixing the pyrolysis oil with an aqueous alkaline hydroxide solution in the reaction vessel operated at a temperature ranging from about 15 °C to about 225 °C, and the step 206 of allowing the mixture of the pyrolysis oil and the aqueous alkaline hydroxide solution to separate into an upgraded pyrolysis oil fraction and an aqueous fraction.
- This method 200 further includes the step 208 of extracting the upgraded pyrolysis oil fraction and the step 210 of optionally supplying it to a hydroprocessing unit.
- the aqueous alkaline hydroxide solution can be a hydroxide of any one or more of Group I or Group 2 elements.
- the aqueous alkaline hydroxide solution can be one or more of lithium hydroxide, sodium hydroxide, potassium hydroxide, calcium hydroxide, or magnesium hydroxide.
- the aqueous alkaline hydroxide solution can be tetrabutylammonium hydroxide.
- the pyrolysis oil is mixed with the aqueous alkaline hydroxide solution in the reaction vessel operated at a temperature ranging from about 15 °C to about 100 °C, or from about 15 °C to about 50 °C, or at room temperature.
- the alkaline hydroxide solution contains less than about 50 weight percent of the alkaline hydroxide.
- the aqueous alkaline hydroxide solution can contain less than about 20 weight percent of the alkaline hydroxide.
- the aqueous alkaline hydroxide solution can contain less than about 10 weight percent of the alkaline hydroxide.
- the alkaline hydroxide solution contains an amount of alkaline hydroxide ranging from about 1 weight percent to about 20 weight percent.
- the mixture of the pyrolysis oil and the aqueous alkaline hydroxide solution is separated into the upgraded pyrolysis oil fraction and the aqueous fraction by settling or coalescence.
- the upgraded pyrolysis oil fraction contains at least about 30 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 50 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil.
- the upgraded pyrolysis oil fraction contains at least about 50 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 90 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil.
- FIG. 3 is a schematic flowchart for a method 300 of processing mixed plastic waste pyrolysis oil using multiple treatments with the alkaline hydroxide solution, according to an embodiment.
- This method 300 includes the step 302 of supplying, to a reaction vessel, a pyrolysis oil containing a plurality of silicon compounds and a plurality of chloride compounds.
- This method 300 includes the step 304 of mixing the pyrolysis oil with a first aqueous alkaline hydroxide solution in the reaction vessel operated at a temperature ranging from about 15 °C to about 30 °C, and the step 306 of allowing the mixture of the pyrolysis oil and the first aqueous alkaline hydroxide solution to separate into a first upgraded pyrolysis oil fraction and a first aqueous fraction.
- step 308 the first aqueous fraction is removed from the reaction vessel.
- This method 300 further includes the step 310 of mixing the first upgraded pyrolysis oil fraction and a second aqueous alkaline hydroxide solution in the reaction vessel operated at a temperature ranging from about 15 °C to 30 °C, and the step 312 of allowing the mixture of the first upgraded pyrolysis oil fraction and the second aqueous alkaline hydroxide solution to separate into a second upgraded pyrolysis oil fraction and a second aqueous fraction.
- step 314 the second aqueous fraction is removed from the reaction vessel.
- This method 300 further includes the step 316 of mixing the second upgraded pyrolysis oil fraction with a third aqueous alkaline hydroxide solution in the reaction vessel operated at a temperature ranging from about 15 °C to 30 °C, and the step 318 of allowing the mixture of the second upgraded pyrolysis oil fraction and the third aqueous alkaline hydroxide solution to separate into a third upgraded pyrolysis oil fraction and a third aqueous fraction.
- step 320 the third upgraded pyrolysis oil fraction is extracted, and in step 322, it is optionally supplied to a hydrocarbon processing unit.
- the hydrocarbon processing unit is one or more of a fluid catalytic cracking (FCC) unit, a hydrocracking unit, a decoking unit, a naphtha hydrotreatment unit, a hydrotreating unit, and a steam cracking unit.
- FCC fluid catalytic cracking
- Each of the first aqueous alkaline hydroxide solution, the second aqueous alkaline hydroxide solution, and the third aqueous alkaline hydroxide solution has a pH of about 10 or greater.
- each of the first aqueous alkaline hydroxide solution, the second aqueous alkaline hydroxide solution, and the third aqueous alkaline hydroxide solution has a concentration of the alkali hydroxide equal to or greater than about 0.0 IM.
- the third upgraded pyrolysis oil fraction contains at least about 30 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 50 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil. In certain embodiments, the third upgraded pyrolysis oil fraction contains at least about 30 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 80 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil.
- the third upgraded pyrolysis oil fraction contains at least about 50 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 80 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil. In certain embodiments, the third upgraded pyrolysis oil fraction contains at least about 50 weight percent less of the plurality of silicon compounds than the plurality of silicon compounds in the pyrolysis oil and at least about 90 weight percent less of the plurality of chloride compounds than the plurality of chloride compounds in the pyrolysis oil.
- Methods disclosed herein can be used to treat a pyrolysis oil that is a light liquid fraction obtained from processing of raw mixed plastic waste pyrolysis oil at less than about 170 °C, defining a naphtha fraction. Methods disclosed herein can be used to treat a pyrolysis oil that is a medium liquid fraction obtained from processing of raw mixed plastic waste pyrolysis oil from about 170 °C to about 370 °C, defining a diesel fraction. Methods disclosed herein can be used to treat a pyrolysis oil that is a full range pyrolysis oil.
- a pyrolysis oil sample was prepared that contained the light liquid fraction obtained from processing of raw mixed plastic waste pyrolysis oil at less than about 170 °C (naphtha) and the medium liquid fraction obtained from processing of raw mixed plastic waste pyrolysis oil from about 170 °C to about 370 °C (diesel).
- the naphtha and the diesel components were present in a 2:
- This sample had a silicon content of 550 ppm, an organic chloride content of 5450 ppm, and a total chloride content of 5560 ppm.
- Three alkaline hydroxide solutions were prepared containing approximately 10 wt.%, 30 wt.%, and 50 wt.% of sodium hydroxide in water. Each of the alkaline hydroxide solutions was added to the pyrolysis oil sample in a 1 :1 ratio, and each of the resulting mixtures was continuously mixed in the reaction vessel operated at 20 °C. After an hour, the mixture of the pyrolysis oil and the aqueous alkaline hydroxide solution was allowed to separate into an upgraded pyrolysis oil fraction and an aqueous fraction.
- the silicon and chloride content in the upgraded pyrolysis oil fraction were evaluated by inductively coupled plasma mass spectroscopy and the analytical method prescribed in UOP 779-08 for determining chloride in liquid hydrocarbons, respectively.
- the silicon content in each of the mixtures decreased by 50% to about 270 ppm and the chloride content decreased by 94% to about 312 ppm.
- the pyrolysis oil sample prepared in Example 1 was treated with two alkaline hydroxide solutions containing approximately 10 wt.% and 30 wt.% of sodium hydroxide in water. Each of the alkaline hydroxide solutions was added to the pyrolysis oil sample in a 1 :1 ratio, and each of the resulting mixtures was continuously mixed in the reaction vessel operated at 225 °C. After an hour, the mixture of the pyrolysis oil and the aqueous alkaline hydroxide solution was allowed to separate into an upgraded pyrolysis oil fraction and an aqueous fraction. About 30% of the pyrolysis oil sample was recovered as the upgraded pyrolysis oil fraction, in the instance when the 10 wt.% sodium hydroxide solution was used.
- the silicon and chloride content in the upgraded pyrolysis oil fraction were evaluated by inductively coupled plasma mass spectroscopy and the analytical method prescribed in UOP 779-08 for determining chloride in liquid hydrocarbons, respectively.
- the silicon content in each of the mixtures decreased by 50% and the chloride content decreased by about 97%.
- the first sample was undistilled pyrolysis oil, while the second sample was the naphtha fraction and the third sample was the diesel fraction.
- the first sample had a silicon content of 220 ppm and a total chloride content of 3331 ppm.
- the second sample had a silicon content of 370 ppm and a total chloride content of 9020 ppm.
- the third sample had a silicon content of 230 ppm and a total chloride content of 2310 ppm.
- An alkaline hydroxide solution containing approximately 5 wt.% of sodium hydroxide in water was prepared. This 5% alkaline hydroxide solution was added to the first sample in a 1 : 5 ratio.
- the 5% alkaline hydroxide solution was added to the second sample in a 1:20 ratio. This 5% alkaline hydroxide solution was added to the third sample in a 1 :5 ratio. Each of the resulting mixtures was maintained in the reaction vessel operated at 25 °C. After ten minutes, the mixture of the pyrolysis oil and the aqueous alkaline hydroxide solution was allowed to separate into an upgraded pyrolysis oil fraction and an aqueous fraction. The upgraded pyrolysis oil fraction was again mixed with the 5% alkaline hydroxide solution and the foregoing process was repeated twice for a total of three washes with the alkaline hydroxide solution. About 90% of the pyrolysis oil sample was recovered from each of the three samples.
- the silicon and chloride content in the upgraded pyrolysis oil fraction were evaluated by inductively coupled plasma mass spectroscopy and the analytical method prescribed in UOP 779-08 for determining chloride in liquid hydrocarbons, respectively.
- the silicon content in each of the samples decreased by about 30%.
- the total chloride content decreased in the first and second samples by about 88% and in the third sample by about 50%.
- a pyrolysis oil sample containing undistilled pyrolysis oil was prepared.
- An alkaline hydroxide solution containing approximately 5 wt.% of sodium hydroxide in water was prepared. This 5% alkaline hydroxide solution was added to this sample in a 1 : 5 ratio. The resulting mixtures was maintained in the reaction vessel operated at 20 °C. After ten minutes, the mixture of the pyrolysis oil and the aqueous alkaline hydroxide solution was allowed to separate into an upgraded pyrolysis oil fraction and an aqueous fraction. The upgraded pyrolysis oil fraction was again mixed with the 5% alkaline hydroxide solution and the foregoing process was repeated twice for a total of three washes with the alkaline hydroxide solution.
- the silicon and chloride content in the upgraded pyrolysis oil fraction were evaluated by inductively coupled plasma mass spectroscopy and the analytical method prescribed in UOP 779-08 for determining chloride in liquid hydrocarbons, respectively.
- the silicon content in each of the mixtures decreased by about 30% and the chloride content decreased by about 90%.
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Publication number | Priority date | Publication date | Assignee | Title |
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US4180456A (en) * | 1977-06-27 | 1979-12-25 | The Dow Chemical Company | Process for recovering a premium oil from a slurry produced by high temperature hydrogenation of a solid, hydrocarbonaceous fuel |
EP0187947A1 (en) * | 1984-12-12 | 1986-07-23 | Lummus Crest, Inc. | Solvent for refining of residues |
US20130232857A1 (en) * | 2010-11-22 | 2013-09-12 | Philippe Gerard Moniotte | Process for removing siloxane-based derivatives from a liquid organic phase |
WO2021105326A1 (en) * | 2019-11-29 | 2021-06-03 | Neste Oyj | Two-step process for converting liquefied waste plastics into steam cracker feed |
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Publication number | Priority date | Publication date | Assignee | Title |
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US4180456A (en) * | 1977-06-27 | 1979-12-25 | The Dow Chemical Company | Process for recovering a premium oil from a slurry produced by high temperature hydrogenation of a solid, hydrocarbonaceous fuel |
EP0187947A1 (en) * | 1984-12-12 | 1986-07-23 | Lummus Crest, Inc. | Solvent for refining of residues |
US20130232857A1 (en) * | 2010-11-22 | 2013-09-12 | Philippe Gerard Moniotte | Process for removing siloxane-based derivatives from a liquid organic phase |
WO2021105326A1 (en) * | 2019-11-29 | 2021-06-03 | Neste Oyj | Two-step process for converting liquefied waste plastics into steam cracker feed |
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