WO1993007105A1 - Conversion of plastic waste to useful oils - Google Patents
Conversion of plastic waste to useful oils Download PDFInfo
- 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
Links
- 238000006243 chemical reaction Methods 0.000 title claims description 21
- 239000003921 oil Substances 0.000 title claims description 21
- 239000013502 plastic waste Substances 0.000 title description 10
- 238000000034 method Methods 0.000 claims description 35
- 239000001257 hydrogen Substances 0.000 claims description 22
- 229910052739 hydrogen Inorganic materials 0.000 claims description 22
- 239000002699 waste material Substances 0.000 claims description 22
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 18
- 239000000463 material Substances 0.000 claims description 17
- 229930195733 hydrocarbon Natural products 0.000 claims description 16
- 150000002430 hydrocarbons Chemical class 0.000 claims description 16
- 239000004215 Carbon black (E152) Substances 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 229920003023 plastic Polymers 0.000 claims description 14
- 239000004033 plastic Substances 0.000 claims description 14
- 239000004793 Polystyrene Substances 0.000 claims description 13
- -1 polypropylene Polymers 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 10
- 229920001179 medium density polyethylene Polymers 0.000 claims description 10
- 239000004701 medium-density polyethylene Substances 0.000 claims description 10
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 9
- 239000004743 Polypropylene Substances 0.000 claims description 9
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 9
- 229910052750 molybdenum Inorganic materials 0.000 claims description 9
- 239000011733 molybdenum Substances 0.000 claims description 9
- 238000009835 boiling Methods 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 8
- 229920001903 high density polyethylene Polymers 0.000 claims description 8
- 239000004700 high-density polyethylene Substances 0.000 claims description 8
- 239000002245 particle Substances 0.000 claims description 8
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 6
- 229920002223 polystyrene Polymers 0.000 claims description 6
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 6
- 239000010779 crude oil Substances 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 229920001577 copolymer Polymers 0.000 claims description 4
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 3
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 3
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical compound C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims description 2
- 239000004952 Polyamide Substances 0.000 claims description 2
- 229920002647 polyamide Polymers 0.000 claims description 2
- 229920001195 polyisoprene Polymers 0.000 claims description 2
- 239000011541 reaction mixture Substances 0.000 claims description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 229910052717 sulfur Inorganic materials 0.000 description 10
- 239000011593 sulfur Substances 0.000 description 10
- 239000000571 coke Substances 0.000 description 7
- 239000003502 gasoline Substances 0.000 description 7
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 239000002283 diesel fuel Substances 0.000 description 5
- 230000005484 gravity Effects 0.000 description 4
- 229920000098 polyolefin Polymers 0.000 description 4
- 239000002174 Styrene-butadiene Substances 0.000 description 3
- 239000008186 active pharmaceutical agent Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000000295 fuel oil Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 238000005194 fractionation Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000010813 municipal solid waste Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229920000573 polyethylene Polymers 0.000 description 2
- 229920000915 polyvinyl chloride Polymers 0.000 description 2
- 239000004800 polyvinyl chloride Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000012495 reaction gas Substances 0.000 description 2
- 238000005204 segregation Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000010802 sludge Substances 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 1
- 241000282326 Felis catus Species 0.000 description 1
- 229920002292 Nylon 6 Polymers 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011344 liquid material Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 239000010812 mixed waste Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- 235000005985 organic acids Nutrition 0.000 description 1
- 239000003208 petroleum Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000012958 reprocessing Methods 0.000 description 1
- 229920003051 synthetic elastomer Polymers 0.000 description 1
- 239000005061 synthetic rubber 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
- C10G1/02—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
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
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
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
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.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US771,504 | 1985-08-30 | ||
US77150491A | 1991-10-04 | 1991-10-04 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1993007105A1 true WO1993007105A1 (en) | 1993-04-15 |
Family
ID=25092035
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1992/008388 WO1993007105A1 (en) | 1991-10-04 | 1992-10-02 | Conversion of plastic waste to useful oils |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU2764792A (en) |
WO (1) | WO1993007105A1 (en) |
Cited By (15)
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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 |
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US11453716B2 (en) | 2016-05-20 | 2022-09-27 | Harpoon Therapeutics, Inc. | Single domain serum albumin binding protein |
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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 |
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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 |
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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 |
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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 |
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