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WO1993007105A1 - Conversion of plastic waste to useful oils - Google Patents

Conversion of plastic waste to useful oils 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
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WO
WIPO (PCT)
Prior art keywords
accordance
reaction vessel
hydrogen
waste
polymeric
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Application number
PCT/US1992/008388
Other languages
French (fr)
Inventor
Paul R. Stapp
Original Assignee
Iit Research Institute
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Filing date
Publication date
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Publication of WO1993007105A1 publication Critical patent/WO1993007105A1/en

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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G1/00Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
    • C10G1/02Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal by distillation
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F02COMBUSTION ENGINES; HOT-GAS OR COMBUSTION-PRODUCT ENGINE PLANTS
    • F02BINTERNAL-COMBUSTION PISTON ENGINES; COMBUSTION ENGINES IN GENERAL
    • F02B3/00Engines characterised by air compression and subsequent fuel addition
    • F02B3/06Engines 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.

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  • 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

The present invention is directed to a process for converting waste plastics 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.

Description

CONVERSION OF PLASTIC WASTE TO USEFUL OILS
Field of the Invention
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.
Background of the Invention Polymeric materials, referred to hereinafter by the generic term "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. Although 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. As used herein, the term "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. In accordance with the process, an upgrading process is provided 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 APIgQ gravity and having a lower content of hydrocarbons boiling above 1000° F. than the feed stream.
In accordance with the process of the Stapp patent, 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. Detailed Description of the Invention The present invention is directed to a process for converting polymeric waste to an oil feedstock. In the method, 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.
The polymeric waste materials may be comminuted to provide particles of polymeric waste prior to introduction into the reaction vessel. Alternatively, the plastic waste may be melted prior to introduction into the reaction vessel. After polymeric waste particles or melted polymeric waste is charged into the reaction vessel, the reaction vessel is closed, stirring is initiated and the reaction vessel is pressurized with 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. For some applications, it is desirable to include from about 15% to about 75% of crude oil or used lubricating oil in the charge. 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.
For 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
Oil Yield API
Experiment Feedstock
Composition* t % Gravit
Remarks
A560-81 49.0% PS, 42.6% PP, 8.4% MDPE
415° C, lh Hr
A560-95 46.5% PS, 44.9% PP, 8.6% MDPE
400° C, 2 Hr A560-97 47.5% Ps, 42.1% PP, 10.5% MDPE
385° C, 2 Hr
A560-99 51.1% PS, 48.9% MDPE
24.8 400° C, 2 Hr
A560-107 75.0% PS, 25.0% MDPE 97.2
Figure imgf000007_0001
Hr - 6 -
A560-109 33.9% PS,
66.1% SBR 98.3 17.5400° C. , 2
Hr
A560-111 100 SBR 96.4 17.8 400° C. , 2 Hr
A560-117 75.6% PS,
24.4% HDPE 97.4 21.5415° C. , 2
Hr
A560-119 SEB Copolymer 98.0 21.0 400° C, 2 Hr
* PS = Polystyrene PP = Polypropylene MDPE = Medium density polyethylene SBR = Styrene-butadiene rubber HDPE = High density polyethylene
SEB = Styrene-ethylene-butylene copolymer
Analysis of the product oils produced by the above treatment of the plastic scrap materials provided the composition shown in Table 2. Table 2
Resid
F650-
932 866
949
Figure imgf000008_0001
Polyethylene terephthalate and nylon 6/6 were also converted in the stirred autoclave in admixture with polystyrene. The product oils can be used, but they are contaminated with the corresponding organic acids, terephthalic acid and adipic acid and either filtration or some additional processing would be required. Results of comparison experiments involving liquification of mixtures of polystyrene (50%) , polypropylene (30%) and medium density polyethylene (20%) with hydrogen sulfide-hydrogen combinations and hydrogen alone are shown in Tables 3 and 4. These experiments were conducted at 415° C. for 1.25 hours at an identical initial total pressure of 1400/1500 psig.
Table 3
Oil Yield Coke Yield API Sulfur
Experiment Gas Used Wt % Wt % Gravity Content
A560-77 H2S-H2 90.1 3.4 31.9 1.4 A560-81 H2 92.9 0.5 32.0 The liquid product distributions (by simulated distillation) are shown in Table 4.
Table 4
Gasoline Diesel Gas Oil End
Experiment IBP-400° F 400-650° F650- 1000° F Point ° F
A560-77 68.0% 16.0 16.0 861 A560-81 58.5% 22.5 19.0 932
Both experiments provided very high quality oils from a refinery viewpoint. There is no liquid material boiling above 1000° F. and the major constituents are hydrocarbons boiling in the gasoline range. The runs with hydrogen sulfide-hydrogen mixtures provided a lighter oil containing more gasoline, but also produced significantly more coke and contained enough sulfur so that catalytic hydrotreating would be required before the oil product could be used. The hydrocarbon products produced using hydrogen alone are of extremely high quality, contain no sulfur and essentially no coke is produced.
It is also within the scope of this invention to recycle any gas oils (b.p. 650-1000° F.) and resids (b.p. > 1000° F.) back into the reaction vessel and reprocess them with additional polymeric waste to provide gasoline and diesel range hydrocarbon materials.
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. If, for example, 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. Similarly, 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.

Claims

WHAT IS CLAIMED IS;
1. A method for converting polymeric scrap to an oil feedstock comprising
(a) charging a polymeric waste into a reaction vessel,
(b) contacting said polymeric waste in said reaction vessel with a gas atmosphere selected from hydrogen and mixtures of hydrogen and hydrogen sulfide, and (c) heating said reaction mixture to a temperature in the range of from about 350° C. to about 450° C. for a time sufficient to convert said plastic scrap to liquid hydrocarbon materials having a boiling point below about 1000° F.
2. A method in accordance with Claim 1 wherein said polymeric waste is fed to said reaction vessel in the form of particles.
3. A method in accordance with Claim 1 wherein said polymeric waste is fed to said reaction vessel in the form of melted polymer.
4. A method in accordance with Claim 1 wherein said polymeric waste is selected from the group consisting of polystyrene, polypropylene, medium density polyethylene, high density polyethylene, polyisoprene, styrene-butadiene copolymer, styrene-ethylene-butylene copolymer, polyethylene terephthalate and polyamides.
5. A method in accordance with Claim 1 wherein said gas atmosphere is maintained at a pressure of from about 500 psig to about 5,000 psig during said contacting step.
6. A method in accordance with Claim 1 wherein said gas atmosphere is maintained at a pressure of from about 750 psig to about 3,000 psig during said contacting step.
7. A method in accordance with Claim 1 wherein said contacting is for a period of from about 15 minutes to about 8 hours.
8. A method in accordance with Claim 1 wherein said contacting is for a period of from about 30 minutes to about 4 hours.
9. A method in accordance with Claim 1 wherein a catalyst is present during said contacting step.
10. A method in accordance with Claim 9 wherein said catalyst is selected from molybdenum octoate, molybdenum acetyl acetonate, molybdenum hexacarbonyl and molybdenum napthanate.
11. A method in accordance with Claim 1 wherein said gas atmosphere has a hydrogen sulfide to hydrogen ratio of from 0:1 to about 1:1, based on pressure.
12. A method in accordance with Claim 1 wherein high density polyethylene comprises less than about 25% of said polymeric waste charge.
13. A method in accordance with Claim 1 wherein said contacting step takes place on a batch basis.
14. A method in accordance with Claim 1 wherein said contacting step takes place on a continuous basis.
15. A method in accordance with Claim 1 wherein said charge to said reaction vessel also comprises crude oil.
PCT/US1992/008388 1991-10-04 1992-10-02 Conversion of plastic waste to useful oils WO1993007105A1 (en)

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US77150491A 1991-10-04 1991-10-04

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Cited By (15)

* 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 (en) 2023-06-14 2024-12-19 IFP Energies Nouvelles H2s-promoted, ebullated bed or hybrid bed hydroconversion of a feedstock comprising a plastic fraction
US12195544B2 (en) 2018-09-21 2025-01-14 Harpoon Therapeutics, Inc. EGFR binding proteins and methods of use

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 (20)

* 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
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 (en) 2023-06-14 2024-12-19 IFP Energies Nouvelles H2s-promoted, ebullated bed or hybrid bed hydroconversion of a feedstock comprising a plastic fraction
FR3149900A1 (en) 2023-06-14 2024-12-20 IFP Energies Nouvelles H2S-PROMOTED BOILING BED OR HYBRID HYDROCONVERSION OF A FEEDSTOCK COMPRISING A PLASTIC FRACTION

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