CN118251479A - Method for treating waste plastics - Google Patents
Method for treating waste plastics Download PDFInfo
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- CN118251479A CN118251479A CN202280072540.3A CN202280072540A CN118251479A CN 118251479 A CN118251479 A CN 118251479A CN 202280072540 A CN202280072540 A CN 202280072540A CN 118251479 A CN118251479 A CN 118251479A
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- lwp
- hydrotreating
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- 238000000034 method Methods 0.000 title claims abstract description 64
- 239000004033 plastic Substances 0.000 title claims abstract description 47
- 229920003023 plastic Polymers 0.000 title claims abstract description 47
- 239000002699 waste material Substances 0.000 title claims abstract description 43
- 239000003054 catalyst Substances 0.000 claims abstract description 65
- 229930195733 hydrocarbon Natural products 0.000 claims abstract description 41
- 150000002430 hydrocarbons Chemical class 0.000 claims abstract description 41
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 22
- 238000002156 mixing Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000001257 hydrogen Substances 0.000 claims abstract description 11
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 11
- 239000003921 oil Substances 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 12
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 10
- 238000009835 boiling Methods 0.000 claims description 10
- 229910003294 NiMo Inorganic materials 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 150000001993 dienes Chemical class 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 239000010779 crude oil Substances 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 claims description 4
- 229910052710 silicon Inorganic materials 0.000 claims description 4
- 239000010703 silicon Substances 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- 239000008346 aqueous phase Substances 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 3
- 238000000605 extraction Methods 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000005194 fractionation Methods 0.000 claims description 3
- 229910052736 halogen Inorganic materials 0.000 claims description 3
- 150000002367 halogens Chemical class 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 230000003647 oxidation Effects 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000000737 periodic effect Effects 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 238000006722 reduction reaction Methods 0.000 claims description 3
- 238000000638 solvent extraction Methods 0.000 claims description 3
- 238000001179 sorption measurement Methods 0.000 claims description 3
- 229910052723 transition metal Inorganic materials 0.000 claims description 3
- 150000003624 transition metals Chemical class 0.000 claims description 3
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 2
- 239000003925 fat Substances 0.000 claims description 2
- 239000000194 fatty acid Substances 0.000 claims description 2
- 229930195729 fatty acid Natural products 0.000 claims description 2
- 150000004665 fatty acids Chemical class 0.000 claims description 2
- 239000003350 kerosene Substances 0.000 claims description 2
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 claims description 2
- 238000010791 quenching Methods 0.000 claims 1
- 239000000047 product Substances 0.000 description 17
- 239000012535 impurity Substances 0.000 description 15
- 229920000642 polymer Polymers 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 7
- 239000011593 sulfur Substances 0.000 description 7
- 229910052717 sulfur Inorganic materials 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000003915 liquefied petroleum gas Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 238000000197 pyrolysis Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 230000001627 detrimental effect Effects 0.000 description 5
- 125000005842 heteroatom Chemical group 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000002184 metal Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 239000000654 additive Substances 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 230000002939 deleterious effect Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- -1 polyethylene Polymers 0.000 description 3
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910003296 Ni-Mo Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000000945 filler Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052945 inorganic sulfide Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- DDTIGTPWGISMKL-UHFFFAOYSA-N molybdenum nickel Chemical compound [Ni].[Mo] DDTIGTPWGISMKL-UHFFFAOYSA-N 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 238000007353 oxidative pyrolysis Methods 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000005020 polyethylene terephthalate Substances 0.000 description 1
- 229920000139 polyethylene terephthalate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920000915 polyvinyl chloride Polymers 0.000 description 1
- 239000004800 polyvinyl chloride Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002910 solid waste Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000004230 steam cracking Methods 0.000 description 1
- 238000004227 thermal cracking Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc 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
- C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
- C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
- C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J11/00—Recovery or working-up of waste materials
- C08J11/04—Recovery or working-up of waste materials of polymers
-
- 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
- C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G, C10K; LIQUEFIED PETROLEUM GAS; ADDING MATERIALS TO FUELS OR FIRES TO REDUCE SMOKE OR UNDESIRABLE DEPOSITS OR TO FACILITATE SOOT REMOVAL; FIRELIGHTERS
- C10L1/00—Liquid carbonaceous fuels
- C10L1/10—Liquid carbonaceous fuels containing additives
- C10L1/14—Organic compounds
- C10L1/143—Organic compounds mixtures of organic macromolecular compounds with organic non-macromolecular compounds
Landscapes
- Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Sustainable Development (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Separation, Recovery Or Treatment Of Waste Materials Containing Plastics (AREA)
Abstract
The present invention provides a method of treating Liquefied Waste Plastics (LWP). The method comprises the steps of a) hydrotreating a Liquefied Waste Plastic (LWP) stream in a first hydrotreating step in the presence of hydrogen and a catalyst in a reactor system comprising at least one reactor each comprising at least one catalyst bed under mild hydrotreating conditions to form a hydrotreated LWP stream, and b) blending the hydrotreated LWP stream with a stream comprising hydrocarbons to form a hydrotreated LWP and hydrocarbon mixed stream. The invention also provides a purified hydrocarbon product.
Description
Technical Field
The present invention relates to a method for treating waste plastics, in particular liquefied waste plastics by means of a hydrotreatment. The method includes removing impurities and hydrogenating the LWP. In detail, the method comprises two separate hydrotreatments of LWP, wherein the second hydrotreatment is performed on a blend of hydrocarbon and LWP that has been hydrotreated.
Background
Environmental problems and the desire to limit the use of fossil-based raw materials have led to the need to develop the possibility of using waste plastics. Waste plastics are an increasing environmental problem because many of the polymers that make up plastics are very stable and do not degrade in nature. Incineration of waste plastics increases greenhouse gases and also causes other environmental problems in the form of air and land pollution. Incineration of waste plastics is considered to a large extent to waste valuable raw materials, even if energy is collected in the form of heat.
The plastic or polymer is predominantly composed of carbon, hydrogen and heteroatoms such as oxygen and/or nitrogen. However, waste plastics also contain many impurities, such as metal and chlorine impurities. There is increasing interest in using waste plastics to produce various hydrocarbon components. Fuels are mixtures of hydrocarbons, but the production of liquid fuels from waste plastics is not generally considered useful. Direct incineration of waste plastics also generates energy that can be captured and used for heating and/or producing electricity, etc. Thus, there is a need to upgrade waste plastics to higher hydrocarbon components that can be used to produce new plastics, chemicals, or other materials.
Waste plastics have been treated by pyrolysis to produce Liquefied Waste Plastics (LWP), but LWP feeds still contain significant amounts of various impurities and contaminants. Thus, the LWP feed needs to undergo various purification and pretreatment steps before it can be used as a feedstock for various upgrading processes.
Document WO 2021/110395 discloses a process for treating a feed comprising waste plastic pyrolysis oil, comprising a hydrogenation step at a temperature of 100 ℃ to 250 ℃ followed by a hydrogenation treatment step at a temperature of 250 ℃ to 430 ℃. The product thus obtained is further separated into a gaseous effluent, an aqueous effluent and a hydrocarbon effluent.
The present invention provides an improved method of treating and purifying LWP obtained, for example, by pyrolysis of waste plastics.
Disclosure of Invention
The object of the present invention is to provide an optimized solution for chemical recycling of waste plastics. The present invention strives to make chemical recycling viable and economical, thereby becoming a complementary solution to recycling waste plastic streams unsuitable for mechanical recycling. The required chemical processes are designed in such a way that they can handle the complexity of the chemical components in the waste product. At a general level, waste plastics are very heterogeneous materials. Depending on the type of polymer and the application for which it is used, different plastic products will contain different types of additives, such as pigments, fillers, flame retardants, etc. When waste plastics are converted to LWP via, for example, pyrolysis, the polymer and various additives etc. will react/decompose in some way and thus a number of different compounds will be transferred into the product LWP. The conversion of LWP to higher quality value-added products requires the use of catalytic processes, and the catalysts commonly employed in such processes are sensitive to different impurities, i.e., the activity of the catalyst may be deactivated due to the deposition of various catalyst poisons. LWP has been observed to contain various impurities that are detrimental to the catalyst, and thus its further catalytic treatment is more technically challenging, for example when compared to conventional crude oil. This has led to the present invention in which these problems have been solved by the claimed method steps. The claimed method allows for the treatment of waste plastics to be continuous and economical without fear of damage and deleterious effects to the assets where such treatments are performed.
The object of the invention is achieved by a method characterized by what is stated in the independent claims. Preferred embodiments of the invention are disclosed in the dependent claims.
It is therefore an object of the present invention to provide a method of treating Liquefied Waste Plastics (LWP), wherein the method comprises the steps of a) hydrotreating a Liquefied Waste Plastics (LWP) stream in the presence of hydrogen and a catalyst in a first hydrotreating step under mild hydrotreating conditions to form a hydrotreated LWP stream in a reactor system comprising at least one reactor each comprising at least one catalyst bed, step b) mixing said hydrotreated LWP stream with a stream comprising hydrocarbons to form a hydrotreated LWP and hydrocarbon mixed stream.
Drawings
Hereinafter, the present invention will be described in more detail by preferred embodiments with reference to the accompanying drawings, in which
FIG. 1 is a schematic diagram of an embodiment of the present invention. In fig. 1, a dashed box = optional step; p1=product 1; p2=product 2; a1/a2=hydrotreating step a); b = blending step B); c=hydrotreating step C); CF = hydrocarbon stream.
Detailed Description
The present invention relates to a method of treating liquefied waste plastics, wherein the method comprises a first hydrotreatment of LWP under mild conditions, followed by blending the hydrotreated LWP with a stream comprising hydrocarbons.
The term "liquefied waste plastics" herein refers to liquid products produced from any waste plastics by non-oxidative pyrolysis processes. Typically, the liquefied waste plastics are produced by pyrolysis of the waste plastics. Other methods for producing LWP include, but are not limited to, hydrothermal liquefaction methods. LWP is a mixture of hydrocarbon organic components having a wide range of carbon chain lengths. Provided that the carbon chain length and chemical structure and properties of the LWP variants vary greatly depending on the type of plastic (polymer) used in the production of the LWP, the type of liquefaction process and the conditions of the liquefaction process. Typical waste plastic materials used in liquefaction processes mainly comprise polyethylene with varying amounts of polypropylene, polystyrene and other minor components such as polyamide, polyethylene terephthalate and polyvinyl chloride.
The liquefied waste plastics may be obtained by pyrolyzing the waste plastics and then collecting a liquid fraction from the pyrolyzed waste plastics. In a typical pyrolysis process, solid waste plastics are heated to a temperature of 400-600 ℃ under non-oxidizing conditions. These polymers thermally decompose and thus release vapors and gases leaving the reactor in the gas phase. The vapor/gas stream is then cooled to condense the LWP product and separate the gases. LWP typically has a boiling range of about 40 ℃ -550 ℃, which approximately corresponds to a carbon chain length of C5 to C55. Depending on the conversion technique, the final boiling point of LWP can rise to 750 ℃.
LWP is a thermal cracking product of various polymers and is a complex mixture of mainly paraffins, olefins, naphthenes and aromatics. The total amount of olefins is typically higher, from 40wt.% to 60wt.%, while the amount of aromatics is typically less than 20wt.%. LWP also contains heteroatoms in the form of organic compounds having heteroatom substituents, including oxygen, nitrogen, chlorine, and sulfur. The amount of heteroatoms varies depending on the polymer used in the production of LWP. Water is typically removed from the LWP product, but some dissolved water may still be present in the LWP.
The liquefied waste plastic may also undergo a pretreatment process prior to the hydrotreatment according to the invention. The LWP is subjected to a pretreatment step prior to the hydrotreating step a), and the pretreatment step comprises reactive extraction, solvent extraction, adsorption, filtration, centrifugation, oxidation, reduction, or any combination thereof.
According to the invention, the hydrotreating step a) is defined as the first hydrotreating step carried out under mild conditions on LWP. The Liquefied Waste Plastics (LWP) stream is subjected to a hydrotreating step a) under mild conditions in the presence of hydrogen and a catalyst to form a hydrotreated LWP stream. The mild conditions in the hydrotreating step a) may be at a temperature of from 100 ℃ to 350 ℃, preferably from 170 ℃ to 340 ℃. All temperatures of any hydrotreating step are defined herein as the weighted average temperature of the reactor in which hydrotreating is performed, if not otherwise mentioned.
All hydrotreating described herein is carried out in the presence of at least one catalyst. The catalyst may for example comprise at least one component selected from IUPAC groups 6, 8 or 10 of the periodic table of the elements. When a supported catalyst is used, the catalyst preferably contains Mo and at least one other transition metal on a support. Examples of such supported catalysts are supported NiMo catalysts or supported CoMo catalysts, or mixtures of both. In the supported catalyst, the support preferably comprises alumina and/or silica. These catalysts are typically used as sulfiding catalysts to ensure that the catalyst is in its active (sulfided) form. The conversion of the catalysts into their active (sulfided) form can be achieved by the following steps: they are sulfided beforehand (i.e. before starting the hydrotreating reaction) and/or by adding a sulfur-containing feed (sulfur, for example as organic or inorganic sulfide). The feed may contain sulfur from the starter, or sulfur additives may be mixed into the feed. In a preferred embodiment, the hydrotreating uses a catalyst and the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/Al 2O3) and/or the catalyst is a supported CoMo catalyst and the support comprises alumina (CoMo/Al 2O3).
The catalyst of the hydrotreating step a) is preferably supported Ni-Mo, wherein the support preferably comprises alumina and/or silica.
The conditions of the hydrotreating step a) are preferably selected from the following:
The ratio of H 2 to oil is 200-450Nm 3/stdm3, preferably 220-400Nm 3/stdm3;
LHSV of 0.1-2.0h -1, preferably 0.2-0.5h -1
-A temperature of 100-350 ℃, preferably 170-340 DEG C
Pressures of 4000 to 6000kPa (a), preferably 4800 to 5500kPa (a),
In one embodiment of the invention, the hydrotreating step a) is repeated prior to the subsequent blending step. The hydrotreating step a) may be repeated to ensure adequate hydrotreating of the LWP in the stream. The possible need to repeat the hydrotreating step a) depends inter alia on the hydrotreating conditions, the hydrotreating catalyst and the reactor design, such as the number of reactors, the type of catalyst bed in the reactor, the number of catalyst beds, etc.
In one embodiment of the invention, the LWP stream consists of LWP only, and the hydrotreating in step a) is performed on LWP only. In this embodiment, the hydrotreating a) under mild hydrotreating conditions is carried out only on a stream containing only LWP, and no other stream is introduced into the first hydrotreating step (step a) in the claims). The hydrotreating step a) in this embodiment is a step in which only the components of the LWP stream derived from waste plastics are hydrotreated under mild hydrotreating conditions.
In one embodiment of the invention, the hydrotreating step a) comprises a step in which the hydrotreated LWP stream formed from a portion of hydrotreating step a) is recycled back to the reactor in which hydrotreating step a) is performed. The amount of recycle, if present, depends inter alia on the hydrotreating conditions, the hydrotreating catalyst and the reactor design, such as the number of reactors, the type of catalyst beds in the reactor, and the number of catalyst beds.
As a result of the hydrotreating step a), a first hydrotreated LWP stream is formed. The resulting hydrotreated LWP stream contains lower amounts of impurities, contaminants, and harmful components than the LWP feed prior to hydrotreating. Impurities, contaminants and detrimental components refer herein to any substance, compound or composition having detrimental properties to any component, equipment or catalyst downstream of the hydrotreating. Particularly detrimental components are compounds containing heteroatoms, metals and metalloids. Particularly deleterious heteroatoms include halogens such as chlorine. Particularly deleterious metals include, but are not limited to, mercury, lead, sodium, arsenic, vanadium, iron, zinc, and aluminum. If not removed, compounds containing silicon, phosphorus, oxygen, nitrogen and sulfur may also be problematic downstream of the hydrotreating process. Further, conjugated dienes and olefins are considered agents that cause coking or fouling, which must be minimized from the LWP in order to use the treated LWP downstream as a feedstock for, for example, steam cracking.
The purpose of the hydrotreated Liquefied Waste Plastic (LWP) stream according to the invention is to reduce the risk of detrimental and/or adverse properties of any impurities, contaminants and harmful components that may be present in the LWP. The hydrotreating step reduces the amount of these components and thus reduces the risk and hazard they would otherwise pose to any components, equipment or catalysts downstream of the hydrotreating. After said hydrotreating step a) under mild hydrotreating conditions, the conjugated diene content in the LWP is reduced to less than 0.2wt.%.
The method of the invention further comprises blending the hydrotreated LWP stream obtained from the mild hydrotreating step a) with a stream comprising hydrocarbons to form a mixed stream comprising hydrotreated LWP and hydrocarbons. The stream comprising hydrocarbons will have a different impurity profile than the LWP feed subjected to the hydrotreating step a) because the hydrocarbons have any source other than LWP, and thus "hydrocarbons" and "hydrocarbons of other sources" are intended to be synonymously denoted.
In one embodiment of the invention, the hydrocarbon of other origin in the form of a stream is selected from the group consisting of Vacuum Gas Oil (VGO) fraction, gas Oil (GO) fraction, heavy Gas Oil (HGO) fraction, kerosene fraction, light gas oil fraction, atmospheric Residuum (AR) fraction, vacuum Residuum (VR) fraction and deasphalted oil (DAO) fraction. Other suitable hydrocarbon streams to be used for blending include crude oil derived feeds comprising at least one crude oil fraction, or biological fats or oils or fatty acids, or lignocellulosic hydrocarbons, or fischer-tropsch or other synthetic hydrocarbons.
In one embodiment, the hydrocarbon-containing stream has one or more of the following properties:
depending on the boiling point range, a boiling point range of 60 ℃ to 700 ℃, most preferably 100 ℃ to 600 ℃ can be measured according to ASTM D2887, or EN 15199-2;
A molecular weight of 250-400g/mol, most preferably 280-350g/mol, measured according to ASTM D2887;
-an aromatic content of >10wt.%, most preferably >35wt.% measured according to astm d 2549;
-a density measured according to ENIS012185 from 870kg/m 3-940 kg/m3, most preferably 890kg/m 3-920 kg/m3;
-a sulfur content of < 5wt.%, preferably < 1.8 wt.%;
-bromine number according to ISO3839M, < 10g Br/100g, preferably < 4g Br/100 g;
-an asphaltene content according to TOTAL642 of < 300mg/kg, preferably 250 mg/kg; and
-A silicon content of < 2.5mg/kg, preferably < 1mg/kg according to astm d 5185.
According to one embodiment of the invention, the mixed stream comprising hydrotreated LWP and hydrocarbon is maintained at a temperature of at least 140 ℃, preferably at a temperature of 140 ℃ to 370 ℃, more preferably 200 ℃ to 350 ℃, before subjecting the hydrotreated LWP and hydrocarbon mixed stream to a subsequent hydrotreating step c). The mixed streams are maintained at an elevated temperature to ensure thorough mixing of the two streams. Mixing at elevated temperature also ensures that no or minimal precipitation of impurities occurs. The hydrocarbon stream to be blended with the hydrotreated LWP will typically have a higher temperature than the hydrotreated LWP stream.
According to one embodiment of the invention, the mixed stream of hydrotreated LWP and hydrocarbons comprises up to 70wt.% LWP, based on the total weight of the stream, preferably the content of LWP in the stream is from 5wt.% to 70wt.%, more preferably from 10wt.% to 50wt.% and even more preferably from 15wt.% to 30wt.%.
According to one embodiment of the invention, the method further comprises:
c) Hydrotreating the hydrotreated LWP and hydrocarbon mixed stream in the presence of hydrogen and a catalyst under stringent hydrotreating conditions to provide a refined stream.
The hydrotreating step c) is defined by the stringent conditions under which it can be carried out at a temperature of 355 ℃ to 400 ℃, preferably 360 ℃ to 390 ℃. Furthermore, the hydrotreating step c) refers to a hydrotreating step after hydrotreating step a) after the hydrotreated stream of step a) has been blended with a hydrocarbon stream of other origin.
In one embodiment of the invention, the catalyst of the hydrotreating steps a) and c) is a supported catalyst and the catalyst preferably comprises at least one component selected from IUPAC groups 6, 8 or 10 of the periodic table of the elements. In addition, the supported catalyst may contain Mo and at least one other transition metal, such as a supported NiMo catalyst or a supported CoMo catalyst, on a support, wherein the support preferably comprises alumina and/or silica. Specifically, the catalyst is a supported CoMo catalyst and the support comprises alumina (CoMo/Al 2O3) and/or the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/Al 2O3).
The conditions of the hydrotreating step c) are preferably selected from the following:
The ratio of H 2 to oil is 150-400Nm 3/stdm3, preferably 180-250Nm 3/stdm3;
-LHSV of 0.5-2.0h -1, preferably 1.1-1.5h -1;
-355-400 ℃, preferably 360-390 DEG C
Pressures of 4000-6000kPa (a), preferably 4800-5500kPa (a).
In one embodiment, the hydrotreating steps a) and c) may each be carried out in a single reactor unit containing at least one catalyst bed. In another embodiment, the hydrotreating steps a) and c) may be carried out separately in a reactor system comprising at least two reactor units, wherein each reactor unit contains at least one catalyst bed.
In one embodiment of the invention, hydrogen is mixed with LWP before the hydrotreating step a) and/or step c) is performed.
In one embodiment of the invention, the LWP is subjected to a pretreatment step prior to the hydrotreating step a), and the pretreatment step comprises reactive extraction, solvent extraction, adsorption, filtration, centrifugation, oxidation, reduction, or any combination thereof.
In one embodiment, the method further comprises the step of adding water to the process and/or removing an aqueous phase from the process after the hydrotreating step a) and/or after the hydrotreating step c). In one embodiment of the invention, water is added to the process after any hydrotreating step to remove impurities. The impurities are or become water soluble in the hydrotreatment and can therefore be removed by washing the hydrotreated LWP stream with water. The water-soluble impurities are dissolved in the aqueous stream and then the aqueous phase containing the impurities is decanted from the hydrotreated LWP stream.
In one embodiment of the invention, the process further comprises the step of subjecting the refined stream to one or more fractionation steps after the hydrotreating step c) to form two or more product streams. Preferably, the fractionated product stream comprises a naphtha fraction having a boiling point range of from 5 to 95wt.% of from 30 to 200 ℃, preferably from about 30 ℃ to about 180 ℃, more preferably from about 30 ℃ to about 110 ℃, and a middle distillate fraction having a boiling point of from 5 to 95wt.% of from about 150 ℃ to about 400 ℃, preferably from about 160 ℃ to about 360 ℃, and more preferably from about 160 ℃ to about 330 ℃, and a Liquefied Petroleum Gas (LPG) fraction comprising one or more of ethane, propane or butane. The naphtha fraction may be further steam cracked and/or the middle distillate may be further steam cracked and/or the LPG fraction may be further steam cracked.
In a further embodiment of the invention, the hydrotreating step a) and the hydrotreating step c) are carried out in a reactor system comprising one or more reactors, each reactor having one or more catalyst beds and at least one reactor being fed to the reactor by direct hydrogen. The reactors designated for the hydrotreating steps a) and c) may also be carried out in separate reactors, each having multiple independent catalyst beds and independent reaction temperatures, or any combination thereof.
In one embodiment of the invention, it further relates to an LWP product P1 obtainable by hydrotreating LWP according to step a) of hydrotreating and blending according to step b), and wherein said product comprises
A silicon reduction of less than 6mg/kg, more preferably < 1mg/kg, and/or a phosphorus reduction of less than 5mg/kg, more preferably less than 1mg/kg, measured by ICP-MS/MS,
A low ratio of diolefins to total olefin content of less than 0.01, more preferably less than 0.001, measured by astm d8071,
A low ratio of conjugated diene to non-conjugated diene measured by astm d8071 of less than 2, more preferably less than 1,
Halogen content below 5mg/kg, preferably below 1mg/kg
Metal measurements by ICP-MS/MS were made on the samples, which were warmed to liquid prior to weighing if necessary. It was digested with acid in a microwave oven to a clean water/acid matrix, diluted to a known amount and analyzed for acid-based calibration using ICP-MS/MS. The low element content results were measured in ppb (μg/kg).
In one embodiment of the invention, the process further comprises the step of subjecting the refined stream (i.e. product P1) to one or more fractionation steps after the hydrotreating step a) and the blending step b) to form two or more product streams. Preferably, the fractionated product stream comprises a naphtha fraction having a boiling point range of from about 5 to 95wt.% of from 30 to 200 ℃, preferably from about 30 ℃ to about 180 ℃, more preferably from about 30 ℃ to about 110 ℃, and a middle distillate fraction having a boiling point of from about 150 ℃ to about 400 ℃, preferably from about 160 ℃ to about 360 ℃, and more preferably from about 160 ℃ to about 330 ℃, and a Liquefied Petroleum Gas (LPG) fraction comprising one or more of ethane, propane or butane. The naphtha fraction may be further steam cracked and/or the middle distillate may be further steam cracked and/or the LPG fraction may be further steam cracked.
It is obvious to a person skilled in the art that as technology advances, the inventive concept can be implemented in various ways. The invention and its embodiments are not limited to the examples described above but may vary within the scope of the claims.
Claims (22)
1. A method of treating Liquefied Waste Plastic (LWP), wherein the method comprises:
step a) hydrotreating a Liquefied Waste Plastic (LWP) stream in a first hydrotreating step under mild hydrotreating conditions in the presence of hydrogen and a catalyst in a reactor system comprising at least one reactor each containing at least one catalyst bed to form a hydrotreated LWP stream,
Step b) blending the hydrotreated LWP stream with a stream comprising hydrocarbons to form a mixed stream of hydrotreated LWP and hydrocarbons.
2. The method of claim 1, wherein the method further comprises:
step c) hydrotreating the hydrotreated LWP and hydrocarbon mixed stream under stringent hydrotreating conditions in the presence of hydrogen and a catalyst to provide a refined stream.
3. The process according to claim 1 or 2, wherein the mild hydrotreating conditions of hydrotreating step a) comprise a temperature of 100 ℃ to 350 ℃.
4. A process according to any one of claims 2 or 3, wherein the stringent hydrotreating conditions of hydrotreating step c) comprise a temperature of 355 ℃ to 400 ℃.
5. The method according to any one of the preceding claims, wherein the LWP stream is subjected to a pretreatment step prior to the hydrotreating step a), and the pretreatment step comprises reactive extraction, solvent extraction, adsorption, filtration, centrifugation, oxidation, reduction, or any combination thereof.
6. The method of any of the preceding claims, wherein the hydrocarbon-containing stream is a crude oil-derived feedstock comprising at least one crude oil fraction, or a biological fat or oil or fatty acid, or a lignocellulosic hydrocarbon, or a fischer-tropsch hydrocarbon, wherein the crude oil fraction is selected from the group consisting of a Vacuum Gas Oil (VGO) fraction, a Gas Oil (GO) fraction, a Heavy Gas Oil (HGO) fraction, a kerosene fraction, a light gas oil fraction, an Atmospheric Resid (AR) fraction, a Vacuum Resid (VR) fraction, and a deasphalted oil (DAO) fraction.
7. The method according to any of claims 2-6, wherein the mixed stream comprising hydrotreated LWP and hydrocarbons is maintained at a temperature of 140 ℃ to 370 ℃, preferably at a temperature of 200 ℃ to 350 ℃, prior to subjecting the mixed stream to the hydrotreating step c).
8. The method according to any of the preceding claims, wherein the mixed stream of hydrotreated LWP and hydrocarbons comprises up to 70wt.% LWP, based on the total weight of the stream, preferably the content of LWP in the stream is from 5wt.% to 70wt.%, more preferably from 10wt.% to 50wt.% and even more preferably from 15wt.% to 30wt.%.
9. The process according to any of the preceding claims, wherein the catalyst in the hydrotreating step a) is a supported catalyst and the catalyst preferably comprises at least one component selected from IUPAC groups 6, 8 or 10 of the periodic table of elements.
10. The process according to claim 9, wherein the supported catalyst contains Mo and at least one other transition metal, such as a supported NiMo catalyst or a supported CoMo catalyst, on a support, wherein the support preferably comprises alumina and/or silica.
11. The method of claim 10, wherein the catalyst is a supported CoMo catalyst and the support comprises alumina (CoMo/Al 2O3) and/or the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/Al 2O3).
12. The process according to any of the preceding claims, wherein the process further comprises the step of adding water to the process and/or removing an aqueous phase from the process after the hydrotreating step a) and/or after the hydrotreating step c).
13. The method of any one of the preceding claims, wherein hydrotreating step a) is repeated prior to the step of blending the hydrotreated LWP stream with a stream comprising hydrocarbons to form a mixed stream of hydrotreated LWP and hydrocarbons.
14. The method according to any of the preceding claims, wherein the LWP stream consists of LWP only and the hydrotreating step a) is performed on LWP only.
15. The process according to any of the preceding claims, wherein the hydrotreating step a) is performed under the following conditions:
the ratio of H 2 to oil is 200-450Nm 3/stdm3, preferably 220-400Nm 3/stdm3;
-LHSV of 0.1-2.0h -1, preferably 0.2-0.5h -1;
-a temperature of 100-350 ℃, preferably 170-340 ℃.
16. The process according to any one of claims 2-15, wherein the hydrotreating step c) is performed under the following conditions:
The ratio of H 2 to oil is 150-400Nm 3/stdm3, preferably 180-250Nm 3/stdm3;
-LHSV of 0.5-2.0h -1, preferably 1.0-1.5h -1;
Temperatures of 355-400℃and preferably 360-390 ℃.
17. The process of any one of claims 2-16, wherein the process further comprises the step of subjecting the refined stream to one or more fractionation steps to form two or more product streams, preferably the product stream comprises a naphtha fraction having a boiling point range of from 5-95wt.% of from 30-200 ℃, preferably from about 30 ℃ to about 180 ℃, more preferably from about 30 ℃ to about 110 ℃, and a middle distillate fraction having a boiling point of from 5-95wt.% of from about 150 ℃ to about 400 ℃, preferably from about 160 ℃ to about 360 ℃, and more preferably from about 160 ℃ to about 330 ℃.
18. The process of claim 17, wherein the naphtha fraction is further steam cracked and/or the middle distillate is further steam cracked and/or the LPG fraction is further steam cracked.
19. The process according to any one of claims 2-18, wherein the hydrotreating steps a) and c), respectively, are performed in a single reactor unit comprising at least one catalyst bed, or the hydrotreating steps a) and c), respectively, are performed in a reactor system comprising at least two reactor units, wherein each reactor unit comprises at least one catalyst bed, or any combination thereof.
20. The method of any one of the preceding claims, wherein the at least one reactor has a direct hydrogen quench to the reactor.
21. The method according to any one of claims 2-20, wherein hydrogen is mixed with the LWP stream before the hydrotreating steps a) and c) are performed.
22. Purified hydrocarbon product obtained by hydrotreating LWP according to claim 1 according to step a) of hydrotreating and blending according to step b), and wherein said product comprises
A silicon reduction of less than 6mg/kg, more preferably < 1mg/kg, and/or a phosphorus reduction of less than 5mg/kg, more preferably 1mg/kg, measured by ICP-MS/MS,
A low ratio of diolefins to total olefin content of less than 0.01, more preferably less than 0.001, measured by astm d8071,
-Low ratio of conjugated diene to non-conjugated diene measured by astm d8071 lower than 2, more preferably lower than 1
Halogen content below 5mg/kg, preferably 1 mg/kg.
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| Application Number | Priority Date | Filing Date | Title |
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| EP21205587.5 | 2021-10-29 | ||
| FI20216124 | 2021-10-29 | ||
| FI20216124A FI130219B (en) | 2021-10-29 | 2021-10-29 | Method of treating waste plastic |
| PCT/EP2022/080245 WO2023073194A1 (en) | 2021-10-29 | 2022-10-28 | Method of treating waste plastic |
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| CN118251479A true CN118251479A (en) | 2024-06-25 |
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| FI (1) | FI130219B (en) |
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