EP4174150A1 - Method of treating waste plastic - Google Patents
Method of treating waste plastic Download PDFInfo
- Publication number
- EP4174150A1 EP4174150A1 EP21205587.5A EP21205587A EP4174150A1 EP 4174150 A1 EP4174150 A1 EP 4174150A1 EP 21205587 A EP21205587 A EP 21205587A EP 4174150 A1 EP4174150 A1 EP 4174150A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- lwp
- stream
- hydrotreatment
- catalyst
- fraction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims abstract description 62
- 239000004033 plastic Substances 0.000 title claims abstract description 46
- 229920003023 plastic Polymers 0.000 title claims abstract description 46
- 239000002699 waste material Substances 0.000 title claims abstract description 42
- 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
- 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
- 239000004215 Carbon black (E152) Substances 0.000 claims abstract description 6
- 239000003921 oil Substances 0.000 claims description 17
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 16
- 239000007789 gas Substances 0.000 claims description 12
- 238000009835 boiling Methods 0.000 claims description 11
- 229910003294 NiMo Inorganic materials 0.000 claims description 10
- 238000004230 steam cracking Methods 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- 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
- 238000002203 pretreatment Methods 0.000 claims description 8
- 229910052593 corundum Inorganic materials 0.000 claims description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 claims description 6
- 150000001336 alkenes Chemical class 0.000 claims description 5
- 239000010779 crude oil Substances 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
- 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
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 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
- 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
- 239000005864 Sulphur Substances 0.000 description 7
- 230000009931 harmful effect Effects 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
- 125000005842 heteroatom Chemical group 0.000 description 5
- 238000004519 manufacturing process Methods 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
- 238000006243 chemical reaction Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 239000000356 contaminant Substances 0.000 description 4
- 230000001627 detrimental effect Effects 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
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-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
- 230000007613 environmental effect Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 150000002739 metals Chemical class 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
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 2
- 239000001273 butane Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000005984 hydrogenation reaction Methods 0.000 description 2
- 239000000463 material Substances 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
- 230000001590 oxidative effect Effects 0.000 description 2
- 239000001294 propane Substances 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 239000004411 aluminium Substances 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
- 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
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 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
- 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
- 150000002894 organic compounds Chemical class 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
- 239000002994 raw material Substances 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
- 238000004227 thermal cracking Methods 0.000 description 1
- 238000001149 thermolysis 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
Images
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
- C10G1/10—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal from rubber or rubber waste
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G1/00—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal
- C10G1/002—Production of liquid hydrocarbon mixtures from oil-shale, oil-sand, or non-melting solid carbonaceous or similar materials, e.g. wood, coal in combination with oil conversion- or refining processes
-
- C—CHEMISTRY; METALLURGY
- C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
- C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
- C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
- C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
- C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
- C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
- C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof
-
- 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
-
- 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
- C10G9/00—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
- C10G9/34—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts
- C10G9/36—Thermal non-catalytic cracking, in the absence of hydrogen, of hydrocarbon oils by direct contact with inert preheated fluids, e.g. with molten metals or salts with heated gases or vapours
-
- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/20—Characteristics of the feedstock or the products
- C10G2300/201—Impurities
- C10G2300/202—Heteroatoms content, i.e. S, N, O, P
Definitions
- the present invention relates to a method of treating waste plastic, especially liquified waste plastic treatment by hydrotreatment.
- the method includes removal of impurities and hydrogenation of the LWP.
- the method comprises two separate hydrotreatments of the LWP, where the second hydrotreatment is performed on a blend of hydrocarbons and already hydrotreated LWP.
- Waste plastic is a growing environmental concern, since many of the polymers constituting the plastics are very stable and do not degrade in nature. Incineration of waste plastic increases greenhouse gases and also leads to other environmental concerns in the form of air and land pollution. Incineration of waste plastic is largely considered a waste of valuable raw material, even if the energy in form of heat is collected.
- Plastics or polymers mainly constitute carbon, hydrogen and heteroatoms such as oxygen and/or nitrogen.
- waste plastics also contain many impurities, such as metal and chlorine impurities.
- impurities such as metal and chlorine impurities.
- Fuels are mixtures of hydrocarbons, but production of liquid fuels from waste plastic is generally not considered useful.
- Direct incineration of waste plastic also produces energy, which can be captured and used for heating and/or production of electricity etc. Therefore, there is a need to upgrade waste plastic to high end hydrocarbon components, which can be utilized in the production of new plastics, chemicals or other materials.
- Waste plastics have been treated by pyrolysis to produce liquefied waste plastic (LWP), but the LWP feed still contains large amounts of various impurities and contaminants.
- the LWP feed therefore needs to undergo various purification and pre-treatment steps before it can be used as feedstock for various upgrading processes.
- Document WO2021/110395 describes a process for treating a feed comprising waste plastic pyrolysis oil, the process includes a hydrogenation step at a temperature of 100 °C to 250 °C, followed by a hydrotreatment step at a temperature of 250 °C to 430 °C.
- the product thus obtained is further separated into a gaseous effluent, an aqueous effluent and a hydrocarbon effluent.
- the current invention provides an improved process of treating and purifying LWP obtained e.g. through pyrolysis of waste plastic.
- the present invention aims to provide an optimised solution for chemical recycling of waste plastics.
- the invention strives to make chemical recycling a viable and economical and thereby a complementary solution to recycled waste plastic streams that are not suitable for mechanical recycling.
- the chemical processes needed are devised in such a way that they can handle the complexities of chemical components in the waste products.
- Waste plastics are, on a general level, very heterogeneous materials. Depending on the polymer type and in what application it has been used, different plastic products will contain different types of additives such as pigments, fillers, flame retardants and so forth. When the waste plastic is converted into LWP via e.g. pyrolysis, the polymers and the various additives etc.
- LWP low-density polyethylene
- Conversion of LWP into higher quality value-added products entails the use of catalytic processes, and catalysts that are typically employed in such processes are sensitive to different impurities, i.e. the activity of the catalysts can be deactivated due to deposition of various catalyst poisons.
- LWP contains various impurities that are detrimental to catalysts, and consequently its further catalytic processing is technically more challenging e.g. when compared to conventional crude oil. This has led to the present invention, where these problems have been resolved by the process steps as claimed. Claimed process allows the processing of waste plastics to be made continuous and economical without having to worry about the damage and detrimental effects caused to the assets carrying out those processing.
- an object of the current invention is to provide a method of processing liquefied waste plastic (LWP), wherein the method comprises step a) hydrotreating a stream of liquified waste plastic (LWP) in presence of hydrogen and a catalyst in a first hydrotreatment step in mild hydrotreatment conditions, to form a stream of hydrotreated LWP, in a reactor system comprising at least one reactor each containing at least one catalyst bed, step b) blending said stream of hydrotreated LWP with a stream comprising hydrocarbons to form a mixed stream of hydrotreated LWP and hydrocarbons.
- LWP liquefied waste plastic
- Figure 1 is a schematic view of a specific embodiment of the current invention.
- the current invention relates to a method of processing liquefied waste plastic, wherein the method comprises a first hydrotreatment of the LWP in mild conditions followed by blending the hydrotreated LWP with a stream comprising hydrocarbons.
- liquefied waste plastic is hereby meant a liquid product produced from any waste plastic through a non-oxidative thermolysis process.
- liquefied waste plastic is produced by pyrolysis of waste plastic.
- Other processes to produce LWP include but are not limited to hydrothermal liquefaction processes.
- the LWP is a mixture of hydrocarbonaceous organic components with a wide range of carbon chain lengths. Provided the large variations of carbon chain lengths and chemical structures and the properties of the LWP varies depending on the types of plastics (polymers) used in the production of LWP, the type of liquefaction process and conditions of the liquefaction process.
- Typical waste plastic feedstock used in the liquefaction method includes mainly polyethylene with varying amounts of polypropylene, polystyrene and other minor components such as polyamides, polyethylene terephthalate and polyvinyl chloride.
- the liquefied waste plastic can be obtained by pyrolyzing waste plastic and subsequently collecting a liquid fraction from the pyrolyzed waste plastic.
- the solid waste plastic is heated to a temperature of 400-600 °C under non-oxidative conditions.
- the polymers thermally decompose and consequently release vapours and gases that exit the reactor in the gas phase.
- This vapor/gas stream is subsequently cooled down to condense the LWP product and to separate the gases.
- the LWP typically has a boiling range of about 40 °C - 550 °C, which corresponds approximately to carbon chain lengths of C5 to C55. Depending on the conversion technology, the final boiling point of the LWP can go up to 750 °C.
- LWP is a thermal cracking product of various polymers and is a complex mixture of mainly paraffins, olefins, naphthenes and aromatic hydrocarbons.
- the total amount of olefins is typically high, from 40 wt.% to 60 wt.%, whereas the amount of aromatic hydrocarbons is typically lower than 20 wt.%.
- LWP also contains heteroatoms, including oxygen, nitrogen, chlorine and sulphur, in the form of organic compounds with heteroatom substituents. The amounts of heteroatoms vary depending on the polymers used in production of LWP. Water is usually removed from the LWP product, but some dissolved water may still be present in the LWP.
- the liquefied waste plastic can also undergo pre-treatment processes before the hydrotreatments according to the present invention.
- the LWP undergoes a pre-treatment step before hydrotreatment step a) and the pre-treatment step comprises reactive extraction, solvent extraction, adsorption, filtration, centrifugation, oxidation, reduction or any combination thereof.
- hydrotreatment step a) is defined as the first hydrotreatment step to be performed on the LWP in mild conditions.
- a stream of liquefied waste plastic (LWP) is subjected to a hydrotreatment step a) in the presence of hydrogen and a catalyst in mild conditions to form a stream of hydrotreated LWP.
- the mild conditions in the hydrotreatment step a) can be at a temperature from 100 °C to 350 °C, preferably 170 °C to 340 °C.
- all temperatures of any hydrotreatment step are to be defined as the weighted average temperature of the reactor in which the hydrotreatment is performed, if nothing else is mentioned.
- the catalyst may, for example, comprise at least one component selected from IUPAC group 6, 8 or 10 of the Periodic Table of Elements.
- the catalyst preferably contains Mo and at least one further transition metal on a support. Examples of such a supported catalyst are a supported NiMo catalyst or a supported CoMo catalyst, or a mixture of both.
- the support preferably comprises alumina and/or silica. These catalysts are usually employed as sulphided catalysts to ensure that the catalysts are in their active (sulphided) form. Turning the catalysts into their active (sulphided) form may be achieved by sulphiding them in advance (i.e.
- the hydrotreating employs a catalyst and the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/Al 2 O 3 ) and/or the catalyst is a supported CoMo catalyst and the support comprises alumina (CoMo/Al 2 O 3 ).
- the catalyst of the hydrotreatment step a) is preferably supported NiMo, wherein the support preferably comprises alumina and/or silica.
- the conditions of the hydrotreatment step a) are preferably selected from the following:
- the hydrotreatment step a) is repeated before the subsequent blending step.
- the hydrotreatment step a) can be repeated to ensure sufficient hydrotreatment of LWP in the stream.
- the possible need for repeating the hydrotreatment step a) depends on among others, on the hydrotreatment conditions, the hydrotreatment catalyst and reactor design, such as number of reactors, type of catalyst beds and number of catalyst beds in the reactors and so forth.
- the stream of LWP consists only of LWP and the hydrotreatment in step a) is performed only on LWP.
- the hydrotreatment a) in mild hydrotreatment conditions is performed solely on a stream containing only LWP and no other streams are directed to the first hydrotreatment step (step a) in claims).
- the hydrotreatment step a) in this embodiment is a step where only components of the stream of LWP originating from waste plastic are hydrotreated in the mild hydrotreatment conditions.
- the hydrotreatment step a) includes a step where a part of the formed stream of hydrotreated LWP from the hydrotreatment step a) is recycled back to the reactor carrying out the hydrotreatment step a).
- the amount of recycling depends among others on the hydrotreatment conditions, the hydrotreatment catalyst and reactor design, such as number of reactors, type of catalyst bed and number of catalyst beds in the reactors.
- a stream of first hydrotreated LWP is formed.
- the formed hydrotreated LWP stream contains lower amounts of impurities, contaminants and harmful components compared to the before hydrotreated LWP feed.
- impurities, contaminants and harmful components is herein meant any substance, compound or composition which have detrimental properties to any component, equipment or catalyst downstream of the hydrotreatment.
- Especially harmful components are compounds containing hetero atoms, metals and metalloids.
- Especially harmful hetero atoms include halogens such as chlorine.
- Especially harmful metals include but are not limited to mercury, lead, sodium, arsenic, vanadium, iron, zinc and aluminium.
- conjugated diolefins and olefins are considered agents causing coking or fouling which have to be minimised from the LWP in order for the treated LWP to be used downstream as a feedstock for steam cracking for example.
- the purpose of hydrotreating a stream of liquified waste plastic (LWP) according to the invention is to reduce the risk of harmful and/or detrimental properties of any of the impurities, contaminants and harmful components, which might be present in the LWP.
- the hydrotreating step reduces the amount of these components and therefore reduces the risks and harms they would otherwise pose on any component, equipment or catalyst downstream of the hydrotreatment.
- the conjugated diolefin content in the LWP is reduced to below 0.2 wt.%.
- the method of the current invention further comprises blending the stream of hydrotreated LWP obtained from mild hydrotreatment step a), with a stream comprising hydrocarbons to form a mixed stream comprising hydrotreated LWP and hydrocarbons.
- the stream comprising hydrocarbons would have a different impurities profile than the LWP feed being subjected to the hydrotreatment step a), since said hydrocarbons is of any origins other than LWP thus "hydrocarbons" and “hydrocarbons of other origins" are to mean synonymously.
- hydrocarbons of other origins in the form of stream is selected from vacuum gas oil (VGO) fraction, gas oil (GO) fraction, heavy gas oil (HGO) fraction, kerosene fraction, light gas oil fraction, atmospheric residue (AR) fraction, vacuum residue (VR) fraction and deasphalted oil (DAO) fraction.
- VGO vacuum gas oil
- GO gas oil
- HGO heavy gas oil
- kerosene fraction light gas oil fraction
- AR atmospheric residue
- VR vacuum residue
- DAO deasphalted oil
- the other suitable hydrocarbon streams to be used for blending include a crude oil-derived feedstock comprising at least one crude oil-fraction, or a bio-based fats or oils or fatty acids, or lignocellulosic based hydrocarbons, or Fischer Tropsch or other synthetic hydrocarbons.
- the mixed stream of hydrotreated LWP and hydrocarbons is kept at a temperature of at least 140 °C before subjecting the mixed stream to the subsequent hydrotreatment step c), preferably said mixed stream comprising hydrotreated LWP and hydrocarbons is kept at a temperature of from 140 °C to 370 °C, more preferably from 200 °C to 350 °C. Keeping the mixed stream at an elevated temperature to ensure sufficient mixing of the two streams. Mixing at an elevated temperature also ensures no or minimal precipitation of impurities.
- the stream of hydrocarbons to be blended with the hydrotreated LWP will typically have a higher temperature compared to the stream of hydrotreated LWP.
- the mixed stream of hydrotreated LWP and hydrocarbons contains up to 70 wt.% LWP based on total weight of stream, preferably the content of LWP in said stream is from 5 wt.% to 70 wt.%, more preferably from 10 wt.% to 50 wt.% and even more preferably from 15 wt.% to 30 wt.%.
- the method further comprises c) hydrotreating said mixed stream of hydrotreated LWP and hydrocarbons in the presence of hydrogen and a catalyst in severe hydrotreatment conditions to provide a refined stream.
- the hydrotreatment step c) is defined by its severe conditions which can be carried out at a temperature of 355 °C to 400 °C, preferably 360°C to 390°C.
- hydrotreatment step c) is referred to as the hydrotreatment step subsequent to hydrotreatment step a) after the hydrotreated stream of step a) has been blended with a stream of hydrocarbons of other origins.
- the catalyst of the hydrotreatment step a) and c) is a supported catalyst, and the catalyst preferably comprises at least one component selected from IUPAC group 6, 8 or 10 of the Periodic Table of Elements.
- the supported catalyst can contain Mo and at least one further transition metal on a support, such as a supported NiMo catalyst or a supported CoMo catalyst, wherein the support preferably comprises alumina and/or silica.
- the catalyst is a supported CoMo catalyst and the support comprises alumina (CoMo/Al 2 O 3 ) and/or the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/Al 2 O 3 ).
- the conditions of the hydrotreatment step c) are preferably selected from the following:
- hydrotreatment steps a) and c) can be carried out respectively in a single reactor unit comprising at least one catalyst bed.
- hydrotreatment step a) and c) can be carried out respectively in a reactor system comprising at least two reactor units, wherein each reactor unit contains at least one catalyst bed.
- hydrogen is being mixed with the LWP before carrying out hydrotreatment step a) and/or step c).
- the LWP undergoes a pre-treatment step before hydrotreatment step a) and the pre-treatment step comprises reactive extraction, solvent extraction, adsorption, filtration, centrifugation, oxidation, reduction or any combination thereof.
- the method further comprises a step of adding water to said process and/or removal of an aqueous phase from said process after said hydrotreatment step a) and/or after said hydrotreatment c).
- water is added to the process after any of the hydrotreatment steps in order to remove impurities.
- the impurities are or become water soluble in the hydrotreatment and can thus be removed by washing the hydrotreated LWP stream with water.
- the water soluble impurities are dissolved in the water stream and the aqueous phase containing the impurities is then decanted from the hydrotreated LWP stream.
- the method further comprises a step of subjecting the refined stream after the hydrotreatment step c), to one or more fractionation step(s) to form two or more product streams.
- the fractionated product streams include a naphtha fraction having a 5-95 wt.% boiling point range of 30-200 °C, preferably from about 30 °C to about 180 °C, more preferably from about 30 °C to about 110 °C, and a middle distillate fraction having a 5-95 wt.% having a boiling point from about 150 °C to about 400 °C, preferably from about 160 °C to about 360 °C, and more preferably from about 160 °C to about 330 °C, and a liquefied petroleum gas (LPG) fraction comprising one or more of ethane, propane or butane.
- the naphtha fraction can further be subjected to steam cracking, and/or the middle distillate can further be subjected to steam cracking, and/or the LPG fraction can
- hydrotreatment step a) and hydrotreatment 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 with a direct hydrogen feed to the reactor.
- the reactor designated for the hydrotreatment step a) and c) can also be carried out respectively in separate reactors, each having a plurality of independent catalyst beds and independent reaction temperatures, or any combination thereof.
- a LWP product, P1 obtainable by hydrotreating LWP according to hydrotreatment step a) and blending according to step b) and wherein the product comprises
- ICP-MS/MS Metals measurement by ICP-MS/MS is performed on a sample that is warmed to liquid if needed prior to weighing. It is digested with acids in the microwave oven to a clear water/acid matrix, diluted to a known amount and analysed against the acid based calibration using ICP-MS/MS. Low elemental results are determined as ppb ( ⁇ g/kg).
- the method further comprises a step of subjecting the refined stream after the hydrotreatment step a), and blending step b), i.e., product PI, to one or more fractionation step(s) to form two or more product streams.
- the fractionated product streams include a naphtha fraction having a 5-95 wt.% boiling point range of 30-200 °C, preferably from about 30 °C to about 180 °C, more preferably from about 30 °C to about 110 °C, and a middle distillate fraction having a 5-95 wt.% having a boiling point from about 150 °C to about 400 °C, preferably from about 160 °C to about 360 °C, and more preferably from about 160 °C to about 330 °C, and a liquefied petroleum gas (LPG) fraction comprising one or more of ethane, propane or butane.
- LPG liquefied petroleum gas
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Abstract
Description
- The present invention relates to a method of treating waste plastic, especially liquified waste plastic treatment by hydrotreatment. The method includes removal of impurities and hydrogenation of the LWP. In detail, the method comprises two separate hydrotreatments of the LWP, where the second hydrotreatment is performed on a blend of hydrocarbons and already hydrotreated LWP.
- Environmental concerns and a wish to limit the use of fossil based feedstock leads to a need to develop possibilities to use waste plastic. Waste plastic is a growing environmental concern, since many of the polymers constituting the plastics are very stable and do not degrade in nature. Incineration of waste plastic increases greenhouse gases and also leads to other environmental concerns in the form of air and land pollution. Incineration of waste plastic is largely considered a waste of valuable raw material, even if the energy in form of heat is collected.
- Plastics or polymers mainly constitute 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 a growing interest in making use of waste plastic for producing various hydrocarbon components. Fuels are mixtures of hydrocarbons, but production of liquid fuels from waste plastic is generally not considered useful. Direct incineration of waste plastic also produces energy, which can be captured and used for heating and/or production of electricity etc. Therefore, there is a need to upgrade waste plastic to high end hydrocarbon components, which can be utilized in the production of new plastics, chemicals or other materials.
- Waste plastics have been treated by pyrolysis to produce liquefied waste plastic (LWP), but the LWP feed still contains large amounts of various impurities and contaminants. The LWP feed therefore needs to undergo various purification and pre-treatment steps before it can be used as feedstock for various upgrading processes.
- Document
WO2021/110395 describes a process for treating a feed comprising waste plastic pyrolysis oil, the process includes a hydrogenation step at a temperature of 100 °C to 250 °C, followed by a hydrotreatment step at a temperature of 250 °C to 430 °C. The product thus obtained is further separated into a gaseous effluent, an aqueous effluent and a hydrocarbon effluent. - The current invention provides an improved process of treating and purifying LWP obtained e.g. through pyrolysis of waste plastic.
- The present invention aims to provide an optimised solution for chemical recycling of waste plastics. The invention strives to make chemical recycling a viable and economical and thereby a complementary solution to recycled waste plastic streams that are not suitable for mechanical recycling. The chemical processes needed are devised in such a way that they can handle the complexities of chemical components in the waste products. Waste plastics are, on a general level, very heterogeneous materials. Depending on the polymer type and in what application it has been used, different plastic products will contain different types of additives such as pigments, fillers, flame retardants and so forth. When the waste plastic is converted into LWP via e.g. pyrolysis, the polymers and the various additives etc. will react/decompose in certain ways, and consequently a plurality of different compounds will be transferred into the product LWP. Conversion of LWP into higher quality value-added products entails the use of catalytic processes, and catalysts that are typically employed in such processes are sensitive to different impurities, i.e. the activity of the catalysts can be deactivated due to deposition of various catalyst poisons. It has been observed that LWP contains various impurities that are detrimental to catalysts, and consequently its further catalytic processing is technically more challenging e.g. when compared to conventional crude oil. This has led to the present invention, where these problems have been resolved by the process steps as claimed. Claimed process allows the processing of waste plastics to be made continuous and economical without having to worry about the damage and detrimental effects caused to the assets carrying out those processing.
- The objects of the invention are achieved by a method characterized by what is stated in the independent claim. The preferred embodiments of the invention are disclosed in the dependent claims.
- Therefore, an object of the current invention is to provide a method of processing liquefied waste plastic (LWP), wherein the method comprises step a) hydrotreating a stream of liquified waste plastic (LWP) in presence of hydrogen and a catalyst in a first hydrotreatment step in mild hydrotreatment conditions, to form a stream of hydrotreated LWP, in a reactor system comprising at least one reactor each containing at least one catalyst bed, step b) blending said stream of hydrotreated LWP with a stream comprising hydrocarbons to form a mixed stream of hydrotreated LWP and hydrocarbons.
- In the following the invention will be described in greater detail by means of preferred embodiments with reference to the attached drawings, in which
Figure 1 is a schematic view of a specific embodiment of the current invention. Infigure 1 the dotted box= optional step; P1= Product 1; P2=Product 2; A1/A2= hydrotreatment step a); B= blending step b); C=hydrotreatment step c); CF= hydrocarbons stream. - The current invention relates to a method of processing liquefied waste plastic, wherein the method comprises a first hydrotreatment of the LWP in mild conditions followed by blending the hydrotreated LWP with a stream comprising hydrocarbons.
- With the term "liquefied waste plastic" is hereby meant a liquid product produced from any waste plastic through a non-oxidative thermolysis process. Typically, liquefied waste plastic is produced by pyrolysis of waste plastic. Other processes to produce LWP include but are not limited to hydrothermal liquefaction processes. The LWP is a mixture of hydrocarbonaceous organic components with a wide range of carbon chain lengths. Provided the large variations of carbon chain lengths and chemical structures and the properties of the LWP varies depending on the types of plastics (polymers) used in the production of LWP, the type of liquefaction process and conditions of the liquefaction process. Typical waste plastic feedstock used in the liquefaction method includes mainly polyethylene with varying amounts of polypropylene, polystyrene and other minor components such as polyamides, polyethylene terephthalate and polyvinyl chloride.
- The liquefied waste plastic can be obtained by pyrolyzing waste plastic and subsequently collecting a liquid fraction from the pyrolyzed waste plastic. In a typical pyrolysis process, the solid waste plastic is heated to a temperature of 400-600 °C under non-oxidative conditions. The polymers thermally decompose and consequently release vapours and gases that exit the reactor in the gas phase. This vapor/gas stream is subsequently cooled down to condense the LWP product and to separate the gases. The LWP typically has a boiling range of about 40 °C - 550 °C, which corresponds approximately to carbon chain lengths of C5 to C55. Depending on the conversion technology, the final boiling point of the LWP can go up to 750 °C.
- LWP is a thermal cracking product of various polymers and is a complex mixture of mainly paraffins, olefins, naphthenes and aromatic hydrocarbons. The total amount of olefins is typically high, from 40 wt.% to 60 wt.%, whereas the amount of aromatic hydrocarbons is typically lower than 20 wt.%. LWP also contains heteroatoms, including oxygen, nitrogen, chlorine and sulphur, in the form of organic compounds with heteroatom substituents. The amounts of heteroatoms vary depending on the polymers used in production of LWP. Water is usually removed from the LWP product, but some dissolved water may still be present in the LWP.
- The liquefied waste plastic can also undergo pre-treatment processes before the hydrotreatments according to the present invention. The LWP undergoes a pre-treatment step before hydrotreatment step a) and the pre-treatment step comprises reactive extraction, solvent extraction, adsorption, filtration, centrifugation, oxidation, reduction or any combination thereof.
- According to the present invention, hydrotreatment step a) is defined as the first hydrotreatment step to be performed on the LWP in mild conditions. A stream of liquefied waste plastic (LWP) is subjected to a hydrotreatment step a) in the presence of hydrogen and a catalyst in mild conditions to form a stream of hydrotreated LWP. The mild conditions in the hydrotreatment step a) can be at a temperature from 100 °C to 350 °C, preferably 170 °C to 340 °C. Herein all temperatures of any hydrotreatment step are to be defined as the weighted average temperature of the reactor in which the hydrotreatment is performed, if nothing else is mentioned.
- All of the hydrotreatments stated herein are performed in the presence of at least one catalyst. The catalyst may, for example, comprise at least one component selected from IUPAC group 6, 8 or 10 of the Periodic Table of Elements. When employing a supported catalyst, the catalyst preferably contains Mo and at least one further transition metal on a support. Examples of such a supported catalyst are a supported NiMo catalyst or a supported CoMo catalyst, or a mixture of both. In a supported catalyst, the support preferably comprises alumina and/or silica. These catalysts are usually employed as sulphided catalysts to ensure that the catalysts are in their active (sulphided) form. Turning the catalysts into their active (sulphided) form may be achieved by sulphiding them in advance (i.e. before starting the hydrotreatment reaction) and/or by adding a sulphur-containing feed (containing sulphur e.g. as an organic or inorganic sulphide). The feed may contain the sulphur from the start, or a sulphur additive may be admixed to the feed. In a preferable embodiment, the hydrotreating employs a catalyst and the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/Al2O3) and/or the catalyst is a supported CoMo catalyst and the support comprises alumina (CoMo/Al2O3).
- The catalyst of the hydrotreatment step a) is preferably supported NiMo, wherein the support preferably comprises alumina and/or silica.
- The conditions of the hydrotreatment step a) are preferably selected from the following:
- a H2 to oil ratio is 200 - 450 Nm3/stdm3, preferably 220 - 400 Nm3/stdm3;
- a LHSV of 0.1 - 2.0 h-1, preferably 0.2 - 0.5 h-1
- a temperature of 100-350 °C, preferably 170-340 °C
- a pressure of 4000-6000 kPa(a), preferably 4800-5500 kPa(a)
- In one embodiment of the current invention the hydrotreatment step a) is repeated before the subsequent blending step. The hydrotreatment step a) can be repeated to ensure sufficient hydrotreatment of LWP in the stream. The possible need for repeating the hydrotreatment step a) depends on among others, on the hydrotreatment conditions, the hydrotreatment catalyst and reactor design, such as number of reactors, type of catalyst beds and number of catalyst beds in the reactors and so forth.
- In one embodiment of the current invention the stream of LWP consists only of LWP and the hydrotreatment in step a) is performed only on LWP. In this specific embodiment, the hydrotreatment a) in mild hydrotreatment conditions is performed solely on a stream containing only LWP and no other streams are directed to the first hydrotreatment step (step a) in claims). The hydrotreatment step a) in this embodiment is a step where only components of the stream of LWP originating from waste plastic are hydrotreated in the mild hydrotreatment conditions.
- In one embodiment of the current invention the hydrotreatment step a) includes a step where a part of the formed stream of hydrotreated LWP from the hydrotreatment step a) is recycled back to the reactor carrying out the hydrotreatment step a). The amount of recycling, if present, depends among others on the hydrotreatment conditions, the hydrotreatment catalyst and reactor design, such as number of reactors, type of catalyst bed and number of catalyst beds in the reactors.
- As a result of the hydrotreatment step a), a stream of first hydrotreated LWP is formed. The formed hydrotreated LWP stream contains lower amounts of impurities, contaminants and harmful components compared to the before hydrotreated LWP feed. With impurities, contaminants and harmful components is herein meant any substance, compound or composition which have detrimental properties to any component, equipment or catalyst downstream of the hydrotreatment. Especially harmful components are compounds containing hetero atoms, metals and metalloids. Especially harmful hetero atoms include halogens such as chlorine. Especially harmful metals include but are not limited to mercury, lead, sodium, arsenic, vanadium, iron, zinc and aluminium. Compounds containing silicon, phosphorous, oxygen, nitrogen and sulphur can also be problematic downstream from the hydrotreatment, if not removed. Furthermore, the conjugated diolefins and olefins are considered agents causing coking or fouling which have to be minimised from the LWP in order for the treated LWP to be used downstream as a feedstock for steam cracking for example.
- The purpose of hydrotreating a stream of liquified waste plastic (LWP) according to the invention is to reduce the risk of harmful and/or detrimental properties of any of the impurities, contaminants and harmful components, which might be present in the LWP. The hydrotreating step reduces the amount of these components and therefore reduces the risks and harms they would otherwise pose on any component, equipment or catalyst downstream of the hydrotreatment. After the hydrotreatment step a) in mild hydrotreatment conditions as specified, the conjugated diolefin content in the LWP is reduced to below 0.2 wt.%.
- The method of the current invention further comprises blending the stream of hydrotreated LWP obtained from mild hydrotreatment step a), with a stream comprising hydrocarbons to form a mixed stream comprising hydrotreated LWP and hydrocarbons. The stream comprising hydrocarbons would have a different impurities profile than the LWP feed being subjected to the hydrotreatment step a), since said hydrocarbons is of any origins other than LWP thus "hydrocarbons" and "hydrocarbons of other origins" are to mean synonymously.
- In one embodiment of the current invention hydrocarbons of other origins in the form of stream is selected from vacuum gas oil (VGO) fraction, gas oil (GO) fraction, heavy gas oil (HGO) fraction, kerosene fraction, light gas oil fraction, atmospheric residue (AR) fraction, vacuum residue (VR) fraction and deasphalted oil (DAO) fraction. The other suitable hydrocarbon streams to be used for blending include a crude oil-derived feedstock comprising at least one crude oil-fraction, or a bio-based fats or oils or fatty acids, or lignocellulosic based hydrocarbons, or Fischer Tropsch or other synthetic hydrocarbons.
- In one embodiment the stream comprising hydrocarbons have one or more of the following properties:
- a boiling point range from 60 °C - 700 °C, most preferably from 100 °C - 600 °C, boiling point can be measured according to ASTMD2887, or EN15199-2 depending on the boiling point range;
- a molecular weight of 250 - 400 g/mol, most preferably 280 - 350 g/mol, as measured according to ASTMD2887;
- aromatics content >10 wt.%, most preferably >35 wt.%, as measured according to ASTMD2549;
- density from 870-940 kg/m3, most preferably 890-920kg/m3, as measured according to ENIS012185;
- a sulphur content of <5 wt.%, preferably <1.8 wt.%;
- bromine number <10 g Br/100g, preferably < 4g Br/100g according to ISO3839M;
- asphaltenes content of <300 mg/kg, preferably 250mg/kg according to TOTAL642; and
- a silicon content of < 2.5 mg/kg, preferably < 1 mg/kg according to ASTMD5185.
- According to one embodiment of the invention the mixed stream of hydrotreated LWP and hydrocarbons is kept at a temperature of at least 140 °C before subjecting the mixed stream to the subsequent hydrotreatment step c), preferably said mixed stream comprising hydrotreated LWP and hydrocarbons is kept at a temperature of from 140 °C to 370 °C, more preferably from 200 °C to 350 °C. Keeping the mixed stream at an elevated temperature to ensure sufficient mixing of the two streams. Mixing at an elevated temperature also ensures no or minimal precipitation of impurities. The stream of hydrocarbons to be blended with the hydrotreated LWP will typically have a higher temperature compared to the stream of hydrotreated LWP.
- According to one embodiment of the invention the mixed stream of hydrotreated LWP and hydrocarbons contains up to 70 wt.% LWP based on total weight of stream, preferably the content of LWP in said stream is from 5 wt.% to 70 wt.%, more preferably from 10 wt.% to 50 wt.% and even more preferably from 15 wt.% to 30 wt.%.
- According to one embodiment of the current invention the method further comprises
c) hydrotreating said mixed stream of hydrotreated LWP and hydrocarbons in the presence of hydrogen and a catalyst in severe hydrotreatment conditions to provide a refined stream. - The hydrotreatment step c) is defined by its severe conditions which can be carried out at a temperature of 355 °C to 400 °C, preferably 360°C to 390°C. In addition, hydrotreatment step c) is referred to as the hydrotreatment step subsequent to hydrotreatment step a) after the hydrotreated stream of step a) has been blended with a stream of hydrocarbons of other origins.
- In one embodiment of the present invention, the catalyst of the hydrotreatment step a) and c) is a supported catalyst, and the catalyst preferably comprises at least one component selected from IUPAC group 6, 8 or 10 of the Periodic Table of Elements. Furthermore, the supported catalyst can contain Mo and at least one further transition metal on a support, such as a supported NiMo catalyst or a supported CoMo catalyst, wherein the support preferably comprises alumina and/or silica. In particular, the catalyst is a supported CoMo catalyst and the support comprises alumina (CoMo/Al2O3) and/or the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/Al2O3).
- The conditions of the hydrotreatment step c) are preferably selected from the following:
- a H2 to oil ratio is 150 - 400 Nm3/stdm3, preferably 180 - 250 Nm3/stdm3;
- a LHSV of 0.5 - 2.0 h-1, preferably 1.1 - 1.5 h-1;
- a temperature of 355-400 °C, preferably 360-390 °C
- a pressure of 4000-6000 kPa(a), preferably 4800-5500 kPa(a).
- In one embodiment, hydrotreatment steps a) and c) can be carried out respectively in a single reactor unit comprising at least one catalyst bed. In another embodiment, hydrotreatment step a) and c), can be carried out respectively 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 present invention, hydrogen is being mixed with the LWP before carrying out hydrotreatment step a) and/or step c).
- In one embodiment of the invention, the LWP undergoes a pre-treatment step before hydrotreatment step a) and the pre-treatment step comprises reactive extraction, solvent extraction, adsorption, filtration, centrifugation, oxidation, reduction or any combination thereof.
- In one embodiment the method further comprises a step of adding water to said process and/or removal of an aqueous phase from said process after said hydrotreatment step a) and/or after said hydrotreatment c). In one embodiment of the current invention, water is added to the process after any of the hydrotreatment steps in order to remove impurities. The impurities are or become water soluble in the hydrotreatment and can thus be removed by washing the hydrotreated LWP stream with water. The water soluble impurities are dissolved in the water stream and the aqueous phase containing the impurities is then decanted from the hydrotreated LWP stream.
- In one embodiment of the invention, the method further comprises a step of subjecting the refined stream after the hydrotreatment step c), to one or more fractionation step(s) to form two or more product streams. Preferably the fractionated product streams include a naphtha fraction having a 5-95 wt.% boiling point range of 30-200 °C, preferably from about 30 °C to about 180 °C, more preferably from about 30 °C to about 110 °C, and a middle distillate fraction having a 5-95 wt.% having a boiling point from about 150 °C to about 400 °C, preferably from about 160 °C to about 360 °C, and more preferably from about 160 °C to about 330 °C, and a liquefied petroleum gas (LPG) fraction comprising one or more of ethane, propane or butane. The naphtha fraction can further be subjected to steam cracking, and/or the middle distillate can further be subjected to steam cracking, and/or the LPG fraction can further be subjected to steam cracking.
- In one further embodiment of the current invention, hydrotreatment step a) and hydrotreatment 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 with a direct hydrogen feed to the reactor. The reactor designated for the hydrotreatment step a) and c) can also be carried out respectively in separate reactors, each having a plurality of independent catalyst beds and independent reaction temperatures, or any combination thereof.
- In one embodiment of the present invention, it further relates to a LWP product, P1, obtainable by hydrotreating LWP according to hydrotreatment step a) and blending according to step b) and wherein the product comprises
- a reduced amount of silicon to be below 6 mg/kg, more preferably < 1 mg / kg, and/or phosphorous to be below 5 mg/kg, more preferably 1 mg/kg, as measured by ICP-MS/MS,
- a low ratio of diolefin to total olefin content to be below 0.01, more preferably below 0.001, measured by ASTMD8071
- a low ratio of conjugated diolefin to non-conjugated diolefin to be below 2, more preferably below 1, measured by ASTMD8071
- a halogen content to be under 5 mg/kg, preferably 1 mg/kg
- Metals measurement by ICP-MS/MS is performed on a sample that is warmed to liquid if needed prior to weighing. It is digested with acids in the microwave oven to a clear water/acid matrix, diluted to a known amount and analysed against the acid based calibration using ICP-MS/MS. Low elemental results are determined as ppb (µg/kg).
- In one embodiment of the invention, the method further comprises a step of subjecting the refined stream after the hydrotreatment step a), and blending step b), i.e., product PI, to one or more fractionation step(s) to form two or more product streams. Preferably the fractionated product streams include a naphtha fraction having a 5-95 wt.% boiling point range of 30-200 °C, preferably from about 30 °C to about 180 °C, more preferably from about 30 °C to about 110 °C, and a middle distillate fraction having a 5-95 wt.% having a boiling point from about 150 °C to about 400 °C, preferably from about 160 °C to about 360 °C, and more preferably from about 160 °C to about 330 °C, and a liquefied petroleum gas (LPG) fraction comprising one or more of ethane, propane or butane. The naphtha fraction can further be subjected to steam cracking, and/or the middle distillate can further be subjected to steam cracking, and/or the LPG fraction can further be subjected to steam cracking.
- It will be obvious to a person skilled in the art that, as the 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)
- A method of processing liquefied waste plastic (LWP), wherein the method comprises:step a) hydrotreating a stream of liquified waste plastic (LWP) in presence of hydrogen and a catalyst in a first hydrotreatment step in mild hydrotreatment conditions, to form a stream of hydrotreated LWP, in a reactor system comprising at least one reactor each containing at least one catalyst bed,step b) blending said stream of hydrotreated LWP with a stream comprising hydrocarbons to form a mixed stream of hydrotreated LWP and hydrocarbons.
- The method according to claim 1, wherein the method further comprises
step c) hydrotreating said mixed stream of hydrotreated LWP and hydrocarbons in presence of hydrogen and a catalyst in severe hydrotreatment conditions to provide a refined stream. - The method according to claim 1 or 2, wherein the mild hydrotreatment conditions of said hydrotreatment step a) includes a temperature from 100 °C to 350 °C.
- The method according to any claim 2 or 3, wherein the severe hydrotreatment conditions of said hydrotreatment step c) includes a temperature of from 355 °C to 400 °C.
- The method according to any of the previous claims, wherein the stream of LWP undergoes a pre-treatment step before hydrotreatment step a) and the pre-treatment step comprises reactive extraction, solvent extraction, adsorption, filtration, centrifugation, oxidation, reduction or any combination thereof.
- The method according to any of the previous claims, wherein said stream comprising hydrocarbons is a crude oil-derived feedstock comprising at least one crude oil-fraction or a bio-based fats or oils or fatty acids, or lignocellulosic based hydrocarbons, or Fischer Tropsch hydrocarbons, wherein the crude oil fraction is selected from vacuum gas oil (VGO) fraction, gas oil (GO) fraction, heavy gas oil (HGO) fraction, kerosene fraction, light gas oil fraction, atmospheric residue (AR) fraction, vacuum residue (VR) fraction and deasphalted oil (DAO) fraction.
- The method according to any one of claims 2 - 6, wherein said mixed stream comprising hydrotreated LWP and hydrocarbons is kept at a temperature of 140 °C to 370 °C before subjecting it to said hydrotreatment step c), preferably said mixed stream of hydrotreated LWP and hydrocarbons is kept at a temperature of 200 to 350 °C.
- The method according to any of the previous claims, wherein said mixed stream of hydrotreated LWP and hydrocarbons contains up to 70 wt.% LWP based on total weight of stream, preferably the content of LWP in said stream is from 5 wt.% to 70 wt.%, more preferably from 10 wt.% to 50 wt.% and even more preferably from 15 wt.% to 30 wt.%.
- The method according to any of the previous claims, wherein the catalyst in said hydrotreatment step a) is a supported catalyst, and the catalyst preferably comprises at least one component selected from IUPAC group 6, 8 or 10 of the Periodic Table of Elements.
- The method according to claim 9, wherein the supported catalyst contains Mo and at least one further transition metal on a support, such as a supported NiMo catalyst or a supported CoMo catalyst, wherein the support preferably comprises alumina and/or silica.
- The method according to claim 10, wherein the catalyst is a supported CoMo catalyst and the support comprises alumina (CoMo/Al2O3) and/or the catalyst is a supported NiMo catalyst and the support comprises alumina (NiMo/Al2O3).
- The method according to any of the previous claims, wherein the method further includes a step of adding water to said process and/or removal of an aqueous phase from said process after said hydrotreatment step a) and/or after said hydrotreatment step c).
- The method according to any of the previous claims, wherein said hydrotreatment step a) is repeated before the step of blending said stream of hydrotreated LWP with a stream comprising hydrocarbons to form a mixed stream of hydrotreated LWP and hydrocarbons.
- The method according to any of the previous claims, wherein the stream of LWP consists only of LWP and the hydrotreatment step a) is performed only on LWP.
- The method according to any of the previous claims, wherein said hydrotreatment step a) is performed in the following conditions- a H2 to oil ratio is 200 - 450 Nm3/stdm3, preferably 220 - 400 Nm3/stdm3;- a LHSV of 0.1 - 2.0 h-1, preferably 0.2 - 0.5 h-1;- a temperature of 100-350 °C, preferably 170-340 °C.
- The method according to any of claims 2 - 15, wherein said hydrotreatment step c) is performed in the following conditions- a H2 to oil ratio is 150 - 400 Nm3/stdm3, preferably 180 - 250 Nm3/stdm3;- a LHSV of 0.5 - 2.0 h-1, preferably 1.0 - 1.5 h-1;- a temperature of 355-400 °C, preferably 360-390 °C.
- The method according to any of claims 2 - 16, wherein the method further comprises a step of subjecting said refined stream to one or more fractionation step(s) to form two or more product streams, preferably the product streams include a naphtha fraction having a 5-95 wt.% boiling point range of 30-200 °C, preferably from about 30 °C to about 180 °C, more preferably from about 30 °C to about 110 °C, and a middle distillate fraction having a 5-95 wt.% having a boiling point from about 150 °C to about 400 °C, preferably from about 160 °C to about 360 °C, and more preferably from about 160 °C to about 330 °C.
- The method according to claim 17, wherein the naphtha fraction is further subjected to steam cracking, and/or the middle distillate is further subjected to steam cracking and/or LPG fraction is further subjected to steam cracking.
- The method according to any of claims 2 - 18, wherein hydrotreatment steps a) and c) is carried out respectively in a single reactor unit comprising at least one catalyst bed, or hydrotreatment step a) and c), are carried out respectively in a reactor system comprising at least two reactor units, wherein each reactor unit contains at least one catalyst bed, or any combination thereof.
- The method according to any one of the preceding claims, wherein the at least one reactor has a direct hydrogen quench to the reactor.
- The method according to any one of claims 2 - 20, wherein hydrogen is being mixed with the stream of LWP before carrying out hydrotreatment step a) and step c).
- A purified hydrocarbon product, obtainable by hydrotreating LWP according to hydrotreatment step a) and blending according to step b) according to claim 1 and wherein the product comprises- a reduced amount of silicon to be below 6 mg/kg, more preferably < 1 mg/kg, and/or phosphorous to be below 5 mg/kg, more preferably 1 mg/kg, as measured by ICP-MS/MS,- a low ratio of diolefin to total olefin content to be below 0.01, more preferably below 0.001, measured by ASTMD8071- a low ratio of conjugated diolefin to non-conjugated diolefin to be below 2, more preferably below 1, measured by ASTMD8071- a halogen content to be under 5 mg/kg, preferably 1 mg/kg.
Priority Applications (5)
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EP21205587.5A EP4174150B1 (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 |
KR1020247015111A KR20240073975A (en) | 2021-10-29 | 2022-10-28 | How to dispose of waste plastic |
CA3235790A CA3235790A1 (en) | 2021-10-29 | 2022-10-28 | Method of treating waste plastic |
MX2024004679A MX2024004679A (en) | 2021-10-29 | 2022-10-28 | Method of treating waste plastic. |
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EP21205587.5A EP4174150B1 (en) | 2021-10-29 | 2021-10-29 | Method of treating waste plastic |
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EP4174150B1 EP4174150B1 (en) | 2024-09-25 |
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Citations (4)
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WO2021105326A1 (en) * | 2019-11-29 | 2021-06-03 | Neste Oyj | Two-step process for converting liquefied waste plastics into steam cracker feed |
WO2021110395A1 (en) | 2019-12-02 | 2021-06-10 | IFP Energies Nouvelles | Method for processing plastic pyrolysis oils with a view to their use in a steam-cracking unit |
FR3107530A1 (en) * | 2020-02-21 | 2021-08-27 | IFP Energies Nouvelles | OPTIMIZED PROCESS FOR TREATING PLASTIC PYROLYSIS OILS FOR THEIR RECOVERY |
WO2021204819A1 (en) * | 2020-04-07 | 2021-10-14 | Total Research & Technology Feluy | Purification of waste plastic based oil with a first trap and a first hydrotreatment and a second trap and a second hydrotreatment |
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WO2021105326A1 (en) * | 2019-11-29 | 2021-06-03 | Neste Oyj | Two-step process for converting liquefied waste plastics into steam cracker feed |
WO2021110395A1 (en) | 2019-12-02 | 2021-06-10 | IFP Energies Nouvelles | Method for processing plastic pyrolysis oils with a view to their use in a steam-cracking unit |
FR3107530A1 (en) * | 2020-02-21 | 2021-08-27 | IFP Energies Nouvelles | OPTIMIZED PROCESS FOR TREATING PLASTIC PYROLYSIS OILS FOR THEIR RECOVERY |
WO2021204819A1 (en) * | 2020-04-07 | 2021-10-14 | Total Research & Technology Feluy | Purification of waste plastic based oil with a first trap and a first hydrotreatment and a second trap and a second hydrotreatment |
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