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WO1993007105A1 - Conversion de dechets en plastique en petroles utiles - Google Patents

Conversion de dechets en plastique en petroles utiles Download PDF

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Publication number
WO1993007105A1
WO1993007105A1 PCT/US1992/008388 US9208388W WO9307105A1 WO 1993007105 A1 WO1993007105 A1 WO 1993007105A1 US 9208388 W US9208388 W US 9208388W WO 9307105 A1 WO9307105 A1 WO 9307105A1
Authority
WO
WIPO (PCT)
Prior art keywords
accordance
reaction vessel
hydrogen
waste
polymeric
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.)
Ceased
Application number
PCT/US1992/008388
Other languages
English (en)
Inventor
Paul R. Stapp
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.)
IIT Research Institute
Original Assignee
IIT Research Institute
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by IIT Research Institute filed Critical IIT Research Institute
Publication of WO1993007105A1 publication Critical patent/WO1993007105A1/fr
Anticipated expiration legal-status Critical
Ceased 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
    • C10G1/02—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02—COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02B—INTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00—Engines characterised by air compression and subsequent fuel addition
    • F02B3/06—Engines characterised by air compression and subsequent fuel addition with compression ignition

Definitions

  • the present invention is directed to a process for converting polymeric waste to an oil feedstock. More particularly, the present invention is directed to a process for treating polymeric waste wherein the polymeric scrap is broken down into liquid hydrocarbon materials having a boiling point below about 1,000° F.
  • Plastics account for about 7% of municipal solid waste and up to about 20% of the waste by volume. This amounts to about 10 to about 12 million tons per year in the United States.
  • plastics recycling is increasing, reprocessing and recycling generally requires segregation by type of plastic. Consumers, in general, and reprocessors often have no idea as to the composition of individual plastic articles. Consequently, processes for utilization of mixed plastic waste, particularly polystyrene, polypropylene and polyethylene, are urgently needed.
  • the present invention provides a process for conversion of mixed plastic waste materials to a high quality synthetic crude oil which can be separated by fractionation into gasoline, diesel fuel and gas-oil components suitable as a feedstock to a catalytic cracker without additional treatment.
  • plastic waste includes all forms of polymeric materials which require or will benefit from recycling, including processing scrap, municipal waste and recovered or recycled polymeric materials.
  • United States Patent No. 4,724,068 to Stapp describes a process for hydrotreating hydrocarbon- containing feed streams, especially heavy oils.
  • the process of the Stapp patent utilizes a polymeric treating agent for upgrading the composition of heavy oils.
  • an upgrading process comprising the step of contacting (a) a substantially liquid hydrocarbon-containing feed stream substantially simultaneously with (b) free hydrogen, (c) hydrogen sulfide and (d) at least one polymer selected from the group consisting of homopolymers and copolymers of olefinic monomers, in the substantial absence of a solid, inorganic cracking catalyst and a solid inorganic hydroconversion catalyst.
  • the process is performed under conditions so as to obtain a product stream having higher API gQ gravity and having a lower content of hydrocarbons boiling above 1000° F. than the feed stream.
  • impurities contained in the hydrocarbon- containing feed stream are at least partially converted to a "sludge", i.e., a precipitate of metals and coke, which is dispersed in the liquid portion of the hydrocarbon-containing product stream.
  • the sludge and the dispersed olefin polymers are then separated from the liquid portion of the hydrocarbon-containing product stream by any suitable separation means, such as distillation, filtration, centrifugation or settling and subsequent draining of the liquid phase.
  • the hydrocarbon-containing product stream has an increased AP gg gravity and lower content of heavy fractions.
  • the weight ratio of olefin polymer to hydrocarbon-containing feed is described as being generally in the range of from about 0.01:1 to about 5:1, preferably from about 0.02:1 to about 1:1 and more preferably from about 0.05:1 to about 0.5:1.
  • the Stapp patent generally describes a procedure for hydrovisbreaking a heavy oil with a mixture of hydrogen and hydrogen sulfide in the presence of olefin polymers followed by recovery of an improved hydrocarbon oil product after separation from the olefin polymers. Summary of the Invention It has now been found that waste plastics can be directly converted to a high quality synthetic crude oil which can be separated by fractionation into gasoline, diesel fuel and gas oils suitable as a feedstock to a catalytic cracker.
  • the process generally includes the steps of heating the plastic waste in a hydrogen atmosphere at moderate temperatures and pressures. It has also been discovered that it is important to the process of the invention that under certain conditions of operation that the proportion of high density polyethylene in the plastic scrap feed mixture be kept below a minimum level of about 25% by weight to achieve complete conversion of the mixture to liquid hydrocarbon materials boiling below 1000° F.
  • the present invention is directed to a process for converting polymeric waste to an oil feedstock.
  • a reaction mixture of polymeric scrap particles is provided in a pressurized reaction vessel provided with stirring means, such as a stirred, pressurized autoclave.
  • the polymeric scrap particles are contacted in the reaction vessel with a gas atmosphere selected from hydrogen and mixtures of hydrogen and hydrogen sulfide.
  • the polymeric scrap particles are heated in the reaction vessel to a temperature in the range of from about 350" C. to about 450° C. at a pressure of from about 500 psig to about 5,000 psig, preferably from about 750 psig to about 3,000 psig. for a time sufficient to convert the plastic scrap to liquid hydrocarbon materials having a boiling point below about 1000" F. , which time is generally in the range of from about 15 minutes to about 8 hours, preferably from about 30 minutes to about 4 hours.
  • the process of the present invention is suitable for conversion of a wide range of plastic waste feedstocks.
  • Suitable plastic materials include polystyrene, polypropylene, medium density polyethylene, high density polyethylene, polyisoprene, styrene- butadiene copolymer, styrene-ethylene-butylene copolymer, polyethylene terephthalate, polyvinyl chloride and polyamides with the proviso that the high density polyethylene content should be limited to no more than about 25% by weight of the mixture of plastic waste materials at operating temperatures of less than about 400° C. and operating times of less than about 2 hours. It is estimated that municipal waste contains about 8% halogenated polymers on average. Accordingly, if it is known that the polymeric waste includes a halogenated polymer, such as polyvinyl chloride, it is desirable to include a basic material, such as calcium carbonate to neutralize any halogen acids that are formed.
  • a basic material such as calcium carbonate
  • the polymeric waste materials may be comminuted to provide particles of polymeric waste prior to introduction into the reaction vessel.
  • the plastic waste may be melted prior to introduction into the reaction vessel.
  • a reaction gas selected from hydrogen and mixtures of hydrogen and hydrogen sulfide.
  • the ratio of hydrogen sulfide to hydrogen for the reaction gas of the present invention is from 0:1 to about 1:1, based on pressure.
  • the oil serves as a carrier for the polymeric waste, particularly melted polymeric waste.
  • the oil is also substantially upgraded in the reaction vessel to provide an oil stock having a boiling point of less than about 1000" F.
  • a soluble catalyst can also be added to polymeric waste in the reaction vessel. Suitable catalysts include molybdenum octoate, molybdenum acetyl acetonate, molybdenum hexacarbonyl and molybdenum napthenate. When used, the catalyst is preferably added at a level sufficient to provide from about 10 ppm to about 5,000 ppm of molybdenum.
  • oxygenated polymers it is preferred to use a catalyst and a hydrogen/hydrogen sulfide atmosphere. While not wishing to be bound by any theory, it is believed that sulfur replaces the oxygen in the oxygenated polymers and that the sulfur is hydrogenated to form the hydrocarbon.
  • a range of plastic waste material feedstocks were tested utilizing temperatures in the range of 385° C. to 415° C.
  • the plastic scrap materials were first converted to particles by use of suitable comminuting apparatus.
  • the polymeric scrap particles were introduced into a stirred autoclave, the autoclave was sealed and hydrogen pressures were developed in the range of 1400/1500 psig.
  • Table 1 summarizes the results of heating the various combinations of plastic scrap materials and synthetic rubber materials under hydrogen atmospheres in the stirred autoclave. Table 1
  • the present invention describes a simple process to convert mixed waste scrap plastics and to a synthetic crude oil which would be highly useful as a feedstock for a refinery. Only a small amount of coke is produced and the coke produced contains no heteroatoms. The coke could therefore be used as a fuel to supply process heat.
  • the hydrocarbon products contain no sulfur, oxygen, nitrogen or metals and would be suitable refinery feedstocks, when hydrogen alone is used. Sulfur is introduced when mixtures of hydrogen and hydrogen sulfide are used. The presence of sulfur poses no problem to refiners and existing refinery equipment can be used to handle sulfur containing feedstocks.
  • the octane number of the gasoline is too low, it could be reformed or isomerized without the hydrotreating that is normally required for petroleum napthas.
  • diesel oil obtained from the process would be expected to have a high cetane number, particularly diesel oil produced from polyethylene. Such diesel oil would not require hydrotreating for sulfur removal.
  • Gas oils and residues contain no heteroatoms and would be suitable cat cracker feedstocks without prior hydrotreating or demetalization.
  • the process of the present invention could readily use a mixed plastic separated by gravity segregation from municipal solid waste.

Landscapes

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

Abstract

L'invention concerne un procédé de conversion de matières plastiques résiduelles en un pétrole brut synthétique de haute qualité que l'on peut séparer par fractionnement en essence, en carburant pour moteur diesel et en mazout pouvant constituer une charge d'alimentation pour une unité de craquage catalytique. Le procédé comprend les étapes consistant à chauffer les déchets en matière plastique dans une atmosphère d'hydrogène à des températures et des pressions modérées. On a également découvert qu'il est important pour le procédé de l'invention que dans certaines conditions de fonctionnement les proportions de polyéthylène à haute densité dans le mélange d'alimentation de déchets en matière plastique soit maintenu au-dessous d'un niveau minimum d'environ 25 % en poids, afin d'obtenir une conversion totale du mélange en hydrocarbures liquides dont le point d'ébullition est inférieur à 1000 ° F.
PCT/US1992/008388 1991-10-04 1992-10-02 Conversion de dechets en plastique en petroles utiles Ceased WO1993007105A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US77150491A 1991-10-04 1991-10-04
US771,504 1991-10-04

Publications (1)

Publication Number Publication Date
WO1993007105A1 true WO1993007105A1 (fr) 1993-04-15

Family

ID=25092035

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/US1992/008388 Ceased WO1993007105A1 (fr) 1991-10-04 1992-10-02 Conversion de dechets en plastique en petroles utiles

Country Status (2)

Country Link
AU (1) AU2764792A (fr)
WO (1) WO1993007105A1 (fr)

Cited By (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU658288B2 (en) * 1992-04-22 1995-04-06 Bp Chemicals Limited Polymer cracking
US10730954B2 (en) 2017-05-12 2020-08-04 Harpoon Therapeutics, Inc. MSLN targeting trispecific proteins and methods of use
US10815311B2 (en) 2018-09-25 2020-10-27 Harpoon Therapeutics, Inc. DLL3 binding proteins and methods of use
US10844134B2 (en) 2016-11-23 2020-11-24 Harpoon Therapeutics, Inc. PSMA targeting trispecific proteins and methods of use
US10849973B2 (en) 2016-11-23 2020-12-01 Harpoon Therapeutics, Inc. Prostate specific membrane antigen binding protein
US10927180B2 (en) 2017-10-13 2021-02-23 Harpoon Therapeutics, Inc. B cell maturation antigen binding proteins
US10954311B2 (en) 2015-05-21 2021-03-23 Harpoon Therapeutics, Inc. Trispecific binding proteins and methods of use
US11136403B2 (en) 2017-10-13 2021-10-05 Harpoon Therapeutics, Inc. Trispecific proteins and methods of use
US11180563B2 (en) 2020-02-21 2021-11-23 Harpoon Therapeutics, Inc. FLT3 binding proteins and methods of use
US11453716B2 (en) 2016-05-20 2022-09-27 Harpoon Therapeutics, Inc. Single domain serum albumin binding protein
US11535668B2 (en) 2017-02-28 2022-12-27 Harpoon Therapeutics, Inc. Inducible monovalent antigen binding protein
US11607453B2 (en) 2017-05-12 2023-03-21 Harpoon Therapeutics, Inc. Mesothelin binding proteins
US11623958B2 (en) 2016-05-20 2023-04-11 Harpoon Therapeutics, Inc. Single chain variable fragment CD3 binding proteins
WO2024256281A1 (fr) 2023-06-14 2024-12-19 IFP Energies Nouvelles Hydroconversion en lit bouillonnant ou hybride promue par de l'h2s d'une charge comportant une fraction plastique
US12195544B2 (en) 2018-09-21 2025-01-14 Harpoon Therapeutics, Inc. EGFR binding proteins and methods of use
US12415860B2 (en) 2018-05-14 2025-09-16 Harpoon Therapeutics, Inc. Binding moiety for conditional activation of immunoglobulin molecules

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901951A (en) * 1972-03-27 1975-08-26 Agency Ind Science Techn Method for treating waste plastics
US4724068A (en) * 1986-07-17 1988-02-09 Phillips Petroleum Company Hydrofining of oils
US5158982A (en) * 1991-10-04 1992-10-27 Iit Research Institute Conversion of municipal waste to useful oils
US5158983A (en) * 1991-10-04 1992-10-27 Iit Research Institute Conversion of automotive tire scrap to useful oils

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3901951A (en) * 1972-03-27 1975-08-26 Agency Ind Science Techn Method for treating waste plastics
US4724068A (en) * 1986-07-17 1988-02-09 Phillips Petroleum Company Hydrofining of oils
US5158982A (en) * 1991-10-04 1992-10-27 Iit Research Institute Conversion of municipal waste to useful oils
US5158983A (en) * 1991-10-04 1992-10-27 Iit Research Institute Conversion of automotive tire scrap to useful oils

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5481052A (en) * 1992-04-22 1996-01-02 Bp Chemicals Limited Polymer cracking
AU658288B2 (en) * 1992-04-22 1995-04-06 Bp Chemicals Limited Polymer cracking
US10954311B2 (en) 2015-05-21 2021-03-23 Harpoon Therapeutics, Inc. Trispecific binding proteins and methods of use
US12084518B2 (en) 2015-05-21 2024-09-10 Harpoon Therapeutics, Inc. Trispecific binding proteins and methods of use
US11623958B2 (en) 2016-05-20 2023-04-11 Harpoon Therapeutics, Inc. Single chain variable fragment CD3 binding proteins
US11453716B2 (en) 2016-05-20 2022-09-27 Harpoon Therapeutics, Inc. Single domain serum albumin binding protein
US10849973B2 (en) 2016-11-23 2020-12-01 Harpoon Therapeutics, Inc. Prostate specific membrane antigen binding protein
US10844134B2 (en) 2016-11-23 2020-11-24 Harpoon Therapeutics, Inc. PSMA targeting trispecific proteins and methods of use
US11535668B2 (en) 2017-02-28 2022-12-27 Harpoon Therapeutics, Inc. Inducible monovalent antigen binding protein
US10730954B2 (en) 2017-05-12 2020-08-04 Harpoon Therapeutics, Inc. MSLN targeting trispecific proteins and methods of use
US11607453B2 (en) 2017-05-12 2023-03-21 Harpoon Therapeutics, Inc. Mesothelin binding proteins
US11136403B2 (en) 2017-10-13 2021-10-05 Harpoon Therapeutics, Inc. Trispecific proteins and methods of use
US11976125B2 (en) 2017-10-13 2024-05-07 Harpoon Therapeutics, Inc. B cell maturation antigen binding proteins
US10927180B2 (en) 2017-10-13 2021-02-23 Harpoon Therapeutics, Inc. B cell maturation antigen binding proteins
US12371504B2 (en) 2017-10-13 2025-07-29 Harpoon Therapeutics, Inc. Trispecific proteins and methods of use
US12415860B2 (en) 2018-05-14 2025-09-16 Harpoon Therapeutics, Inc. Binding moiety for conditional activation of immunoglobulin molecules
US12195544B2 (en) 2018-09-21 2025-01-14 Harpoon Therapeutics, Inc. EGFR binding proteins and methods of use
US10815311B2 (en) 2018-09-25 2020-10-27 Harpoon Therapeutics, Inc. DLL3 binding proteins and methods of use
US11807692B2 (en) 2018-09-25 2023-11-07 Harpoon Therapeutics, Inc. DLL3 binding proteins and methods of use
US11180563B2 (en) 2020-02-21 2021-11-23 Harpoon Therapeutics, Inc. FLT3 binding proteins and methods of use
WO2024256281A1 (fr) 2023-06-14 2024-12-19 IFP Energies Nouvelles Hydroconversion en lit bouillonnant ou hybride promue par de l'h2s d'une charge comportant une fraction plastique
FR3149900A1 (fr) 2023-06-14 2024-12-20 IFP Energies Nouvelles Hydroconversion en lit bouillonnant ou hybride promue par de l’h2s d’une charge comportant une fraction plastique

Also Published As

Publication number Publication date
AU2764792A (en) 1993-05-03

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