EP4688242A2 - Déchloration de flux de liquide et de gaz à partir de processus de pyrolyse de matières plastiques - Google Patents

Déchloration de flux de liquide et de gaz à partir de processus de pyrolyse de matières plastiques

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Publication number
EP4688242A2
EP4688242A2 EP24782041.8A EP24782041A EP4688242A2 EP 4688242 A2 EP4688242 A2 EP 4688242A2 EP 24782041 A EP24782041 A EP 24782041A EP 4688242 A2 EP4688242 A2 EP 4688242A2
Authority
EP
European Patent Office
Prior art keywords
adsorbent
ppmw
alumina
stream
chloride concentration
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP24782041.8A
Other languages
German (de)
English (en)
Inventor
Armin Lange De Oliveira
Dana Rehms MOONEY
Garrett Dylan REHMS
Bernard Reesink
Gisela Hieber
Artem D. VITYUK
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
Original Assignee
BASF Corp
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Filing date
Publication date
Application filed by BASF Corp filed Critical BASF Corp
Publication of EP4688242A2 publication Critical patent/EP4688242A2/fr
Pending legal-status Critical Current

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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
    • C10G1/002—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
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/12—Recovery of used adsorbent
    • 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

Definitions

  • hydroprocessing The only commercial solution accessible at scale that allows reduction of these impurities to 1-5 ppmw levels making these liquids drop-in substitute into naphtha crackers is hydroprocessing.
  • Hydroprocessing has been standardized in refining and does not require major process tune ups if to be used for plastics pyrolysis liquids. The only major exception is chlorides/halogens.
  • Hydroprocessing catalysts perform hydrogenation of -N, -O, -S, and -Cl compounds which results in production of respective NH3, H2O, H2S, and HC1.
  • there are issues with higher levels of chlorides in such units i.e.
  • One aspect of the present disclosure relates to a method of removing chlorides from a plastics pyrolysis stream comprising an initial chloride concentration of greater than about 10 ppmw.
  • the method comprises: contacting the stream with an alumina adsorbent, the alumina adsorbent comprising a promoter comprising sodium.
  • a final chloride concentration of the treated stream is less than about 10 ppmw.
  • the initial chloride concentration is from about 10 ppmw to about 45 ppmw. In at least one embodiment, the initial chloride concentration is from about 45 ppmw to about 250 ppmw.
  • the promoter is present from about 2 wt% to about 10 wt% based on the total weight of the adsorbent.
  • the promoter comprises the sodium in the form of Na2O.
  • the alumina adsorbent has a BET surface area of about 150 m 2 /g to about 300 m 2 /g.
  • the alumina adsorbent has a total pore volume from about 0.2 mL/g to about 6 rnL/g.
  • the alumina adsorbent exhibits a bimodal pore size distribution.
  • the alumina adsorbent has a density of about 0.5 g/mL to about 1.0 g/mL.
  • the alumina adsorbent is in the form of spherical particles.
  • the spherical particles have an average diameter of from about 2 mm to about 4 mm.
  • the particles exh i bi t a side crush strength of greater than about 40 N.
  • a chlorides removal ratio is at least about 80%, at least about 85%, or at least about 90% for a temperature of the pyrolysis stream from 200°C to 350°C.
  • the alumina adsorbent is regenerative.
  • the method further comprises: subsequently contacting the alumina adsorbent with a regeneration stream to regenerate the alumina adsorbent, at least one embodiment, the regeneration stream comprises hydrogen gas at a temperature of about 450°C to about 600°C.
  • the regeneration stream comprises oxygen gas at a temperature of about 250°C to about 350°C .
  • a further aspect of the present disclosure relates to a method of removing chlorides from a plastics pyrolysis stream comprising an initial chloride concentration of greater than about 10 ppmw.
  • the method comprises: contacting the stream with an adsorbent, the adsorbent comprising copper oxide, zinc oxide, and alumina.
  • a final chloride concentration of the treated stream is less than about 10 ppmw.
  • the initial chloride concentration is from about 10 ppmw to about 45 ppmw. In at least one embodiment, the initial chloride concentration is from about 45 ppmw to about 250 ppmw.
  • the copper oxide is present from about 50 wt% to about 80 wt% based on the total weight of the adsorbent.
  • the zinc oxide is present from about 20 wt% to about 30 wt% based on the total weight of the adsorbent.
  • the alumina is present from about 3 wt% to about 10 wt% based on the total weight of the adsorbent.
  • the copper oxide is present from about 50 wt% to about 80 wt%; the zinc oxide is present from about 10 wt% to about 40 wt%; and the alumina is present as the balance of the weight of the adsorbent.
  • the adsorbent is formed by co-precipitation of copper oxide and zinc oxide on alumina.
  • the adsorbent has a BET surface area of about 25 m 2 /g to about 150 m 2 /g.
  • the adsorbent has a total pore volume from about 0. 15 mL/g to about 2 mL/g.
  • the adsorbent has a density' of about 1.0 g/mL to about 3.0 g/mL.
  • the adsorbent is in the form of tablets.
  • the tablets have an average length of about 3 mm to about 6 mm, and an average width of about 2 mm to about 4 mm.
  • the tablets exhibit a side crush strength of greater than about 60 N.
  • a chlorides removal ratio is at least about 80%, at least about 85%, or at least about 90% for a temperature of the pyrolysis stream from 200°C to 350°C.
  • the adsorbent is regenerative.
  • the method further comprises: subsequently contacting the adsorbent with a regeneration stream to regenerate the adsorbent.
  • the regeneration stream comprises hydrogen gas at a temperature of about 450°C to about 600°C.
  • the regeneration stream comprises oxygen gas at a temperature of about 250°C to about 350°C .
  • FIG. 1 is a plot of pore volume distribution for a sample prepared in accordance with the embodiments described herein compared to a reference sample.
  • FIG. 2 is a plot showing chlorides removal versus temperature for samples prepared in accordance with the embodiments described herein compared to a reference sample.
  • FIG. 2 is a plot showing chlorides removal versus temperature for a sample prepared in accordance with the embodiments described herein compared to two reference samples.
  • Embodiments of the present disclosure relate to processes and compositions for the efficient removal of chlorides from plastics pyrolysis streams (which may be liquid or gas streams).
  • adsorbent comprising a promoter (e.g., sodium) for removing chlorides from a plastics pyrolysis stream (e.g., having an initial chloride concentration of greater than about 10 ppmw).
  • a promoter e.g., sodium
  • formulations comprising sodium on a high- pore volume support e.g., copper- or sodi um-promoted high-pore volume alumina
  • Other embodiments relate to adsorbents comprising precipitated copper oxide onto a support (e.g., which may be coprecipitated with zinc oxide).
  • the adsorbents described may utilize a porous support and one or more active metal components supported thereon.
  • Exemplary supports include metal oxides, metalloid oxides, activated carbons, and molecular sieves.
  • the support may include titanium oxide, ceria, alumina, silica, zirconia, magnesium oxide, zeolites, or combinations thereof.
  • supports include silica.
  • the support may include high surface area metal oxides.
  • the support may comprise aluminum oxide.
  • the support may comprise a mixture of titanium dioxide and aluminum oxide.
  • Metal oxide mixtures for example a mixture of titanium dioxide and aluminum oxide, may contain metal oxides in a weight/weight ratio of titanium dioxide to aluminum oxide of from any of about 9/1, about 8/1, about 7/1. about 6/1, about 5/1, about 4/1, about 3/1, about 2/1 or about 1/1 to any of about 1/2, about 1/3, about 1/4, about 1/5, about 1/6, about 1/7, about 1/8, or about 1/9.
  • the adsorbent comprises a high-pore volume support, such as high-pore volume alumina.
  • the promoter is dispersed on the support, for example, by impregnation.
  • the term “dispersed form” may be synonymous with “dispersed thereon”, “impregnated in”, “supported by /on”, and the like.
  • the promoter material or a precursor of the promoter material is combined with the support to facilitate incipient wetness impregnation, and the impregnated support is subsequently dried and calcined.
  • the adsorbents described herein may be prepared by a variety of methods. For instance, a metal may be dispersed onto a support via an incipient-wetness technique. “Impregnated,” in general, means that the materials are “in” pores of the support. In at least one embodiment, the metal is precipitated onto the support. In at least one embodiment, the metal may be reduced after being dispersed or precipitated onto the support.
  • the adsorbent comprises a promoter (e.g., Na2O), which may be present from about 0.5 wt% to about 20 wt% based on the total weight of the adsorbent.
  • the promoter e.g., NaO
  • the promoter may be present at about 0.5 wt%.
  • the adsorbent comprises copper oxide (e.g., precipitated copper oxide), which may be present from about 50 wt% to about 80 wt% based on the total weight of the adsorbent.
  • the copper oxide may be present at about 50 wt%, about 51 wt%, about 52 wt%, about 53 wt%, about 54 wt%, about 55 wt%, about 56 wt%, about 57 wt%, about 58 wt%, about 59 wt%, about 60 wt%, about 61 wt%, about 62 wt%, about 63 wt%, about 64 wt%, about 65 wt%, about 66 wt%, about 67 wt%, about 68 wt%, about 69 wt%, about 70 wt%, about 71 wt%, about 72 wt%, about 73 wt%,
  • the adsorbent comprises a zinc oxide (e.g., precipitated zinc oxide), which may be present from about 10 wt% to about 40 wt% based on the total weight of the adsorbent.
  • a zinc oxide e.g., precipitated zinc oxide
  • the zinc oxide may be present at about 10 wt%, about 11 wt%, about 12 wt%, about 13 wt%, about 14 wt%, about 15 wt%, about 16 wt%, about 17 wt%, about 18 wt%, about 19 wt%, about 20 wt%, about 21 wt%, about 22 wt%, about 23 wt%, about 24 wt%, about 25 wt%, about 26 wt%, about 27 wt%, about 28 ⁇ t%.
  • BET surface area is determined by the Brunauer-Emmett-Teller (BET) method according to DIN ISO 9277:2003-05 (which is a revised version of DIN 66131), which may be referred to as “BET surface area.”
  • the specific surface area is determined by a multipoint BET measurement in the relative pressure range from 0.05-0.3 p/po.
  • the adsorbent has a BET surface area of about 100 m 2 /g, about 110 m 2 /g, about 120 m 2 /g, about 130 m 2 /g, about 140 m 2 /g, about 150 m 2 /g, about 160 m 2 /g, about 170 m 2 /g, about 180 m 2 /g, about 190 m 2 /g, about 200 m 2 /g, about 210 m 2 /g, about 220 m 2 /g, about 230 m 2 /g, about 240 m 2 /g, about 250 m 2 /g, greater than 250 m 2 /g, or in any range defined by and inclusive of these points (e.g., from about 150 m 2 /g to about 200 m 2 /g).
  • the BET surface area is at least about 25 m 2 /g, at least about 50 m 2 /g, or at least about 75 m 2 /g to about 150 m 2 /g to greater.
  • Pore volume and average pore radius are determined by the Barret-Joyner-Halenda (BJH) method.
  • BJH Barret-Joyner-Halenda
  • Mercury porosimetry analysis can be used to characterize porosity. Mercury porosimetry applies controlled pressure to a sample immersed in mercury. External pressure is applied for the mercury to penetrate into the voids/pores of the material. The amount of pressure required to intrude into the voids/pores is inversely proportional to the size of the voids/pores.
  • porous silica microspheres containing voids/pores with an average size of about 165 nm can have an average porosity of about 0.8.
  • the alumina adsorbent has a total volume of about 0.1 mL/g, about 0.15 mL/g, about 0.2 mL/g, about 0.3 mL/g, about 0.4 mL/g, about 0.5 mL/g, about 0.6 mL/g, about 0.7 mL/g, about 0.8 mL/g, about 0.9 mL/g, about 1.0 mL/g, about 1.5 mL/g, 2.0 mL/g, about 2.5 mL/g, 3.0 mL/g, about 3.5 mL/g, 4.0 mL/g, about 4.5 mL/g, 5.0 mL/g, about 5.5 mL/g, about 6.0 mL/g, greater than about 6.0 mL/g, or in any range defined by and inclusive of these points (e.g., from about 0.3 mL/g to about 6 mL/g).
  • the adsorbent has a density of about 0.5 g/mL. about 0.6 g/mL, about 0.7 g/mL, about 0.8 g/mL, about 0.9 g/mL, about 1 .0 g/mL, about 1 .1 g/mL, about 1.2 g/mL, about 1.3 g/mL, about 1.4 g/mL, about 1.5 g/mL, about 1.6 g/mL, about 1.7 g/mL, about 1.8 g/mL, about 1.9 g/mL, about 2.0 g/mL, about 2.
  • the suitable components may be present in the adsorbent compositions in a bulk form, meaning in a continuous form in general not interrupted by other materials.
  • a bulk form may contain substantially no other materials.
  • the adsorbent compositions may be in any suitable final form, for instance, spheres, tablets, extrudates, pellets, rods, moldings or monoliths, etc., in various shapes and sizes.
  • an adsorbent e.g. an alumina adsorbent having precipitated or impregnated copper
  • an extruded material such as extruded particles.
  • the extruded particles are elongated and may have an average extrudate length (i.e., an average largest dimension) of about 1 mm, about 2 mm, about 3 mm, about 4 mm. about 5 mm. about 6 mm, or in any range defined by and inclusive of these points (e.g., from about 3 mm to about 5 mm).
  • the adsorbent particles exhibit a side crush strength of greater than about 10 N, greater than about 20 N, greater than about 30 N, greater than about 40 N, greater than about 50 N, greater than about 60 N, greater than about 70 N. greater than about 80 N, greater than about 90 N, or greater than about 100 N.
  • the adsorbents described herein may be suitable for removing chlorides and/or other components from feed streams, such as plastics pyrolysis streams.
  • chlorides refers to chlorine-containing compounds that may include, but not limited to, chloroalkanes, chloroalkenes, chlorooxygenates, chloronaphthenes, and chloroaromatics.
  • Streams suitable for treatment by the adsorbents described herein may include a chlorides content of greater than about 10 ppmw, up to about 500 ppmw (e.g., about 10 ppmw to about 45 ppmw, or about 100 ppmw to about 250 ppmw), or greater.
  • the adsorbent exhibits a chlorides removal ratio of at least about 90%. at least about 91%, at least about 92%, at least about 93%, at least about 94%, at least about 95%, at least about 96%, at least about 97%, at least about 98%, or at least about 99% when contacted with a pyrolysis liquid stream (e.g., having a chlorides content of greater than about 80 ppmw) at a temperature from about 200°C to 350°C.
  • a pyrolysis liquid stream e.g., having a chlorides content of greater than about 80 ppmw
  • the adsorbent is regenerative (i.e., the adsorbent is capable of being regenerated to restore its activity to or near its activity prior to use).
  • the adsorbent can be regenerated by treating the adsorbent with a regeneration stream.
  • the regeneration stream is at a temperature of about 450°C to about 600°C and comprises hydrogen gas.
  • the regeneration stream is at a temperature of about 250°C to about 350°C and comprises oxygen gas.
  • Embodiment 1 A method of removing chlorides from a plastics pyrolysis stream comprising an initial chloride concentration of greater than about 10 ppmw, the method comprising: contacting the stream with an alumina adsorbent, the alumina adsorbent comprising a promoter comprising sodium, wherein a final chloride concentration of the treated stream is less than about 10 ppmw.
  • Embodiment 2 The method of Embodiment 1, wherein the initial chloride concentration is from about 10 ppmw to about 45 ppmw.
  • Embodiment 3 The method of Embodiment 1, wherein the initial chloride concentration is from about 45 ppmw to about 250 ppmw.
  • Embodiment 4 The method of any of the preceding Embodiments, wherein the promoter is present from 2 wt% to about 10 wt% based on the total weight of the adsorbent.
  • Embodiment 5 The method of Embodiment 4, wherein the promoter comprises the sodium in the form of Na2O.
  • Embodiment 6 The method of any of the preceding Embodiments, wherein the alumina adsorbent has a BET surface area of about 150 m 2 /g to about 300 m 2 /g.
  • Embodiment 7 The method of any of the preceding Embodiments, wherein the alumina adsorbent has a total pore volume from about 0.2 mL/g to about 6 mL/g.
  • Embodiment 8 The method of any of the preceding Embodiments, wherein the alumina adsorbent exhibits a bimodal pore size distribution.
  • Embodiment 9 The method of any of the preceding Embodiments, wherein the alumina adsorbent has a density of about 0.5 g/mL to about 1.0 g/mL.
  • Embodiment 10 The method of any of the preceding Embodiments, wherein the alumina adsorbent is in the form of spherical particles.
  • Embodiment 11 The method of Embodiment 10, wherein the spherical particles have an average diameter of from about 2 mm to about 4 mm.
  • Embodiment 12 The method of either Embodiment 10 or Embodiment 11 , wherein the spherical particles exhibit a side crush strength of greater than about 40 N.
  • Embodiment 13 The method of any of the preceding Embodiments, wherein a chlorides removal ratio is at least about 80%, at least about 85%, or at least about 90% for a temperature of the pyrolysis stream from 200°C to 350°C.
  • Embodiment 14 The method of any of the preceding Embodiments, wherein the alumina adsorbent is regenerative.
  • Embodiment 15 The method of any of the preceding Embodiments, further comprising: subsequently contacting the alumina adsorbent with a regeneration stream to regenerate the alumina adsorbent.
  • Embodiment 16 The method of Embodiment 15, wherein the regeneration stream comprises hydrogen gas at a temperature of about 450°C to about 600°C.
  • Embodiment 17 The method of Embodiment 15, wherein the regeneration stream comprises oxygen gas at a temperature of about 250°C to about 350°C .
  • Embodiment 18 A method of removing chlorides from a plastics pyrolysis stream comprising an initial chloride concentration of greater than about 10 ppmw, the method comprising: contacting the stream with an adsorbent, the adsorbent comprising copper oxide, zinc oxide, and alumina, wherein a final chloride concentration of the treated stream is less than about 10 ppmw.
  • Embodiment 19 The method of Embodiment 18, wherein the initial chloride concentration is from about 10 ppmw to about 45 ppmw.
  • Embodiment 20 The method of Embodiment 18, wherein the initial chloride concentration is from about 45 ppmw to about 250 ppmw.
  • Embodiment 21 The method of any of Embodiments 18-20, wherein the copper oxide is present from about 50 wt% to about 80 wt% based on the total weight of the adsorbent.
  • Embodiment 22 The method of any of Embodiments 18-21, wherein the zinc oxide is present from about 20 wt% to about 30 wt% based on the total weight of the adsorbent.
  • Embodiment 23 The method of any of Embodiments 18-22, wherein the alumina is present from about 3 wt% to about 10 wt% based on the total weight of the adsorbent.
  • Embodiment 24 The method of any of Embodiments 18-23, wherein: the copper oxide is present from about 50 wt% to about 80 wt%; the zinc oxide is present from about 10 wt% to about 40 wt%; and the alumina is present as the balance of the weight of the adsorbent.
  • Embodiment 25 The method of any of Embodiments 18-24, wherein the adsorbent is formed by co-precipitation of copper oxide and zinc oxide on alumina.
  • Embodiment 26 The method of any of Embodiments 18-25, wherein the adsorbent has a BET surface area of about 25 m 2 /g to about 150 m 2 /g.
  • Embodiment 27 The method of any of Embodiments 18-26, wherein the adsorbent has a total pore volume from about 0.15 mL/g to about 2 mL/g.
  • Embodiment 28 The method of any of Embodiments 18-27, wherein the adsorbent has a density of about 1.0 g/mL to about 3.0 g/mL.
  • Embodiment 29 The method of any of Embodiments 18-28, wherein the adsorbent is in the form of tablets.
  • Embodiment 30 The method of Embodiment 29, wherein the tablets have an average length of about 3 mm to about 6 mm, and an average width of about 2 mm to about 4 mm.
  • Embodiment 31 The method of either Embodiment 29 or Embodiment 30, wherein the tablets exhibit a side crush strength of greater than about 60 N.
  • Embodiment 32 The method of any of Embodiments 18-20, wherein a chlorides removal ratio is at least about 80%, at least about 85%, or at least about 90% for a temperature of the pyrolysis stream from 200°C to 350°C.
  • Embodiment 33 The method of any of Embodiments 18-20, wherein the adsorbent is regenerative.
  • Embodiment 34 The method of any of Embodiments 18-20, further comprising: subsequently contacting the adsorbent with a regeneration stream to regenerate the adsorbent.
  • Embodiment 35 The method of Embodiment 34, wherein the regeneration stream comprises hydrogen gas at a temperature of about 450°C to about 600°C.
  • Embodiment 36 The method of Embodiment 34, wherein the regeneration stream comprises oxygen gas at a temperature of about 250°C to about 350°C .
  • Standard dechlorination experiments w ere performed for various samples (described below ) in a flow' reactor loaded w ith about 1 mL of a given sample.
  • Dechlorination was performed using a commercial waste plastics pyrolysis oil (PyOil) sample containing about 80 ppmw of chlorides, which were organic chlorides. Prior to each experiment, the reactor was purged with dry nitrogen, and samples were dehydrated at 250 °Cfor one hour at a gas hourly space velocity (GEISV) of 1000 hr' 1 . After dehydration, a liquid PyOil feed was introduced into the reactor at a liquid hourly space velocity (LHSV) of 1 hr' 1 and a total pressure of 50 barg.
  • LHSV liquid hourly space velocity
  • the reactor temperature was increased to 200 °C at 50 barg to ensure liquid only flow. Measurements of chlorides in the effluent liquid stream were at performed in the 200 to 325 °C range with temperature increments of 25 °C. Each temperature increment was maintained for about 20 hr to allow system to equilibrate.
  • Sample A was a high macropore pore volume sodium promoted alumina formulation with bimodal pore size distribution in the form of a sphere. Without wishing to be bound by theory, it is believed that unique pore size distribution that features macropore volume of about 0.3 mL/g enables high performance of this product in removal of chlorides from waste plastics pyrolysis oils.
  • the sodium oxide content was about 5.5 wt% based on a total weight of the formulation.
  • Reference 1 was a conventional sodium promoted alumina that did not exhibit any appreciable macropore volume (below 0.05 mL/g) or a bimodal pore size distribution, in the form of a sphere. The sodium oxide level was about 4 wt%. It is observed that performance of this formulation in removal of chlorides from waste plastics pyrolysis oils was inferior to Sample A.
  • Reference 2 was a conventional unpromoted high surface area activated alumina guard, in the form of a sphere. It did not exhibit any appreciable macropore volume (below 0.05 mL/g) or a bimodal pore size distribution. It was observed that performance of this formulation in removal of chlorides from waste plastics pyrolysis oils was substantially inferior to Sample A.
  • Sample B was a precipitated copper oxide zinc oxide based formulation in the form of a tablet, with a copper oxide content of about 70 wt% and a zinc oxide content of about 24.5 wt% balanced by alumina. Without wishing to be bound by theory', it is believed that due to exceptionally high copper oxide surface area this formulation shows high performance in removal of chlorides from waste plastics pyrolysis oils.
  • FIG. 1 shows the mercury pore volume distributions for Sample A versus Reference 1, demonstrating a significant macropore volume peak
  • FIG. 2 shows performance of Samples A and B in removal of chlorides from a waste plastics pyrolysis feed.
  • the experimental conditions were: pressure of 50 barg argon, temperature 200-325 °C, and commercial PyOil feed at 80 ppmw of chlorides.
  • FIG. 3 shows performance of Sample A in removal of chlorides from a waste plastics pyrolysis feed.
  • the experimental conditions were: pressure 50 barg Argon, temperature 200- 325 °C, and commercial PyOil feed at 80 ppmw of chlorides.
  • Table 1 Typically observed properties of Sample A, References 1 and 2.
  • X includes A or B is intended to mean any of the natural inclusive permutations. That is, if X includes A; X includes B; or X includes both A and B, then “X includes A or B” is satisfied under any of the foregoing instances. [0101]
  • the use of the terms “a,” “an,” “the,” and similar referents in the context of describing the materials and methods discussed herein (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context.
  • adsorbent composition that is substantially free of lead may refer to an adsorbent composition for which lead is below a detectable limit, or its presence has a negligible effect on the performance of the adsorbent.

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  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)

Abstract

L'invention concerne des procédés et des matériaux pour la déchloration de flux de liquide et de gaz. Dans au moins un mode de réalisation, un procédé consiste à mettre en contact un flux de pyrolyse de plastique avec un adsorbant d'alumine, l'adsorbant d'alumine comprenant un promoteur (par exemple, du sodium). Dans un autre mode de réalisation, un procédé consiste à mettre en contact un flux de pyrolyse de plastique avec un adsorbant comprenant de l'oxyde de cuivre, de l'oxyde de zinc et de l'alumine.
EP24782041.8A 2023-03-30 2024-03-29 Déchloration de flux de liquide et de gaz à partir de processus de pyrolyse de matières plastiques Pending EP4688242A2 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US202363455733P 2023-03-30 2023-03-30
PCT/US2024/022257 WO2024206840A2 (fr) 2023-03-30 2024-03-29 Déchloration de flux de liquide et de gaz à partir de processus de pyrolyse de matières plastiques

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EP4688242A2 true EP4688242A2 (fr) 2026-02-11

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EP24782041.8A Pending EP4688242A2 (fr) 2023-03-30 2024-03-29 Déchloration de flux de liquide et de gaz à partir de processus de pyrolyse de matières plastiques

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Country Link
EP (1) EP4688242A2 (fr)
JP (1) JP2026511893A (fr)
CN (1) CN120916835A (fr)
AU (1) AU2024248194A1 (fr)
WO (1) WO2024206840A2 (fr)

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4183823A (en) * 1977-09-14 1980-01-15 The Research Council Of Alberta Regeneration process for poisoned claus alumina catalyst
US6632765B1 (en) * 2000-06-23 2003-10-14 Chervon U.S.A. Inc. Catalyst regeneration via reduction with hydrogen
US6589908B1 (en) * 2000-11-28 2003-07-08 Shell Oil Company Method of making alumina having bimodal pore structure, and catalysts made therefrom
EP3491102B1 (fr) * 2016-08-01 2020-07-15 SABIC Global Technologies B.V. Déchloration d'huiles de pyrolyse de plastiques mélangées à l'aide d'une extrudeuse de dégazage et de pièges à chlorure

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WO2024206840A2 (fr) 2024-10-03
CN120916835A (zh) 2025-11-07
JP2026511893A (ja) 2026-04-14
AU2024248194A1 (en) 2025-10-09
WO2024206840A3 (fr) 2025-02-06

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