Process for purifying pyrolysis oil

Abstract

The invention relates to a method for purifying pyrolysis oil, comprising an extraction step prior to a heat treatment step, a production unit for carrying out said method and a purified pyrolysis oil obtained or obtainable by said method.

Description

[0001] The present invention relates to a method for purifying pyrolysis oil, comprising an extraction step prior to a heat treatment step, a production unit for carrying out the method, and a purified pyrolysis oil obtained or available by the method.

[0002] Currently, plastic waste is primarily landfilled or incinerated to generate heat. Chemical recycling is an attractive way to transform waste plastic materials into useful chemicals. A key technology for the chemical recycling of plastic waste is pyrolysis. Pyrolysis involves the thermal degradation of plastic waste in an inert atmosphere, producing value-added byproducts such as pyrolysis gas, liquid pyrolysis oil, and char (residue), with pyrolysis oil being the primary product. Pyrolysis gas and char can be used as fuel to generate heat, for example, for reactor heating purposes. Pyrolysis oil can be used as a source for syngas production and / or processed, for example, in (steam) crackers into chemical feedstocks such as ethylene, propylene, C4 fractions, etc.

[0003] Typically, plastic waste is a mixture of different types of polymers. Polymers are usually composed of carbon and hydrogen combined with other elements such as chlorine, bromine, fluorine, sulfur, oxygen, and nitrogen, which complicates recycling efforts. Elements other than carbon and hydrogen can be harmful during further processing of crude pyrolysis oil, as they can deactivate or poison catalysts used in this process. During (steam) cracking, halogenated compounds, as well as acids and oxygen-containing compounds, can damage the cracker, for example, through corrosion, as they release hydrogen halides. Sulfur-containing compounds can deactivate or poison catalysts used in the cracker or can contaminate cracker products. Nitrogenous impurities can also poison downstream catalysts. Additionally, when heated, they can pose safety problems by forming explosive NOx. When mixed plastics containing polyvinyl chloride (PVC) undergo thermal degradation, compounds with carbon double bonds and hydrogen chloride are formed. The hydrogen chloride released from PVC attacks compounds with carbon-carbon double bonds, leading to the formation of chlorinated organic compounds. Plastic waste typically contains heteroatom-containing additives, such as stabilizers and plasticizers, which are incorporated to improve polymer properties. These additives often also include nitrogen-, halogenated, and sulfur-containing compounds and heavy metals. For example, waste engine oil, transformer oil, hydraulic oil, and machine oil may contain heavy metal abrasives. Heavy metals are generally toxic, and their presence degrades the quality of pyrolysis oil. Furthermore, plastic waste is often uncleaned plastic, potentially containing residues of elements other than carbon and hydrogen. Therefore, high-quality pyrolysis oil rich in carbon and hydrogen but low in other elements is preferred as a feedstock to prevent catalyst deactivation and corrosion problems in downstream refining processes.

[0004] WO 2017 / 083018 A1 discloses a method for reducing the chloride content of a hydrocarbon feed stream. WO 2014 / 165859 A1 discloses a method for purifying pyrolysis oil, which includes one or two extraction steps. Furthermore, WO 2020 / 178597 A1 discloses a method for upgrading pyrolysis oil, which includes treating the pyrolysis oil with an aqueous solution (preferably composed of water) and alkanes, and treating the resulting organic phase with an upgrading solution containing a polar organic solvent.

[0005] However, there remains a need for improved methods for purifying pyrolysis oil obtained from plastic waste. In particular, there is a need for improved methods that exhibit longer run times, lower pressure drops, and avoid scaling. This has not been addressed using existing technologies.

[0006] Therefore, there is a need for a method to purify pyrolysis oil (preferably pyrolysis oil obtained from waste), particularly by reducing the total acid value and the content of chlorine, oxygen, and nitrogen. In practice, there is a need to provide high-value purified pyrolysis oil while using economical methods.

[0007] Surprisingly, the method of the present invention allows for a reduction in total acid value, as well as chlorine, oxygen, and nitrogen content, with reductions particularly suitable for subsequent storage and / or steam cracking. Furthermore, it has been unexpectedly found that the method of the present invention provides an economical method for purifying high-value pyrolysis oils.

[0008] Therefore, the present invention relates to a method for purifying pyrolysis oil, the method comprising:

[0009] (i) Providing a stream F0 containing pyrolysis oil, the pyrolysis oil containing one or more halogenated organic compounds and one or more organic compounds containing conjugated double bonds;

[0010] (ii) Ensure that the flow F0 provided in (i) is in at least one extraction zone Z E The medium undergoes extraction to obtain a stream F1 containing the extracted pyrolysis oil, wherein (ii) includes:

[0011] (ii.1) Introduce F0 into Z E middle;

[0012] (ii.2) In Z E F0 is contacted with water and alkali B at temperatures ranging from 10°C to 200°C to obtain P containing an aqueous phase. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7.5 to 11;

[0013] (ii.3) PA With P O Separate to obtain P A flow F A and P, which is extracted as pyrolysis oil O Flow F1;

[0014] (iii) Ensure that the flow F1 obtained according to (ii) is in at least one heat treatment zone Z P After undergoing heat treatment, Z P Located in Z E Downstream, a stream F2 is obtained that is depleted from one or more of the organic compounds containing conjugated double bonds and one or more of the halogenated organic compounds compared to F1.

[0015] Preferably, the heat treatment according to (iii) is carried out at a temperature in the range of 80°C to 400°C.

[0016] Typically, 1 to 100 wt% or 5 to 100 wt% or 10 to 100 wt% or 20 to 100 wt% or 30 to 100 wt% or 40 to 100 wt% or 50 to 100 wt% or 60 to 100 wt% or 70 to 100 wt% or 80 to 100 wt% or 90 to 100 wt% of F0 can be composed of pyrolysis oil.

[0017] The FO is preferably composed of pyrolysis oil at a weight of 95 to 100%, more preferably 98 to 100%, and even more preferably 99 to 100% by weight.

[0018] It is possible that 99.5 to 100 wt%, 99.8 to 100 wt%, or 99.9 wt% of F0 consists of pyrolysis oil.

[0019] The pyrolysis oil (oil to be purified) according to (i) may have any total acid value (TAN). Preferably, the pyrolysis oil according to (i) has a total acid value (TAN) in the range of 0.5 to 60 mg KOH / g (F0), more preferably in the range of 1 to 40 mg KOH / g (F0), and even more preferably in the range of 3 to 20 mg KOH / g (F0), as determined in Reference Example 1.

[0020] The pyrolysis oil (oil to be purified) according to (i) can have any oxygen content. Preferably, the pyrolysis oil according to (i) has an oxygen content in the range of 0.1 to 15 g(O) / 100 g(F0), more preferably in the range of 0.5 to 10 g(O) / 100 g(F0), and even more preferably in the range of 0.1 to 5 g(O) / 100 g(F0), as determined in Reference Example 5.

[0021] Preferably, the one or more halogenated organic compounds contained in the pyrolysis oil according to (i) comprise one or more of mono-, oligo- or polyhalogenated aromatic compounds, alkyl halides and alkenyl halides.

[0022] The pyrolysis oil (oil to be purified) according to (i) may have any total chlorine content. Preferably, the pyrolysis oil according to (i) has a total chlorine content in the range of 30 to 3,000 wppm (ppm by weight), more preferably 30 to 500 wppm, and even more preferably 30 to 100 wppm, as determined in Reference Example 3.1.

[0023] The pyrolysis oil (oil to be purified) according to (i) may have any nitrogen content. Preferably, the pyrolysis oil according to (i) has a nitrogen content in the range of 10 to 20,000 wppm (ppm by weight), more preferably 50 to 5,000 wppm, and even more preferably 100 to 4,000 wppm, as determined in Reference Example 2.

[0024] The pyrolysis oil (oil to be purified) according to (i) may have any sulfur content. Preferably, the pyrolysis oil according to (i) has a sulfur content in the range of 10 to 30,000 ppm (wppm), more preferably 20 to 5,000 wppm, more preferably 50 to 3,000 wppm by weight, as determined in Reference Example 6.

[0025] The pyrolysis oil (oil to be purified) according to (i) may contain any amount of one or more organic compounds containing conjugated double bonds. Preferably, the pyrolysis oil according to (i) contains one or more organic compounds containing conjugated double bonds in a total amount ranging from 0.1 to 75 g (I2) / 100 g, more preferably from 0.4 to 60 g (I2) / 100 g, and even more preferably from 1 to 30 g (I2) / 100 g of pyrolysis oil, as determined in Reference Example 4.

[0026] The pyrolysis oil (oil to be purified) according to (i) may have any styrene content. Preferably, the pyrolysis oil according to (i) has a styrene content in the range of 0.2 to 30 area % and more preferably in the range of 1 to 20 area % as determined in Reference Example 7.

[0027] Preferably, the one or more organic compounds containing conjugated double bonds comprise one or more organic compounds according to formula (I).

[0028] R 1 R 2 C 1 =C 2 R3 -C 3 R 4 =X(I)

[0029] Where =X represents =O, =S, =NR 5 、or =C 4 R 6 R 7 Preferred = C 4 R 6 R 7 ;

[0030] More preferably, wherein R 1 R 2 R 3 R 4 R 5 Independently, they are H, alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 1 to 6 carbon atoms, or aryl groups having 5 to 10 carbon atoms, more preferably H;

[0031] More preferably, wherein R 6 and R 7 Independently, R is H, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 10 carbon atoms, more preferably H; or more preferably, wherein R 4 and R 6 or R 4 and R 7 Connected together, thus with C 3 =C 4 Together they form a more preferred aromatic ring with 5 or 6 members.

[0032] Preferably, the one or more organic compounds containing conjugated double bonds include one or more of butadiene, isoprene, diene having 5 or 6 carbon atoms, styrene, methylstyrene, indene, substituted styrene, substituted indene, and 3-methyl-2-butenal, more preferably one or more of butadiene, isoprene, diene having 5 or 6 carbon atoms, styrene, methylstyrene, indene, and 3-methyl-2-butenal.

[0033] Preferably, the one or more organic compounds containing conjugated double bonds include styrene.

[0034] Preferably, the pyrolysis oil contained in F0 is obtained from waste.

[0035] In the context of this invention, the pyrolysis oil contained in F0 is preferably obtained from pyrolysis waste, which is one or more of plastics and tires.

[0036] Preferably, the flow F0 is a liquid flow.

[0037] In the context of this invention, for example, in order to maintain F0 in a liquid state, the pyrolysis oil can be heated as is known to those skilled in the art.

[0038] Step (ii)

[0039] Preferably, no organic solvent is used in the extraction according to (ii).

[0040] Preferably, there is no washing with hydrocarbon streams such as alkanes in (ii) or between (ii) and (iii).

[0041] Preferably, the extraction according to (ii) is performed at a pressure p in the range of 0.8 to 1.2 bar (absolute pressure), more preferably in the range of 0.9 to 1.1 bar (absolute pressure). E The following will proceed.

[0042] Alternatively, the extraction according to (ii) is performed at a pressure p in the range of 0.5 to 5 bar (absolute pressure), more preferably in the range of 0.7 to 3 bar (absolute pressure), and even more preferably in the range of 0.9 to 2 bar (absolute pressure). E The following will proceed.

[0043] Preferably, the extraction according to (ii) is carried out at a temperature in the range of 10°C to 95°C, more preferably in the range of 15°C to 90°C, more preferably in the range of 20°C to 85°C, and even more preferably in the range of 25°C to 80°C.

[0044] Preferably, when the temperature of extraction (ii) is ≤ 95°C, the extraction of (ii) is carried out at a pressure of 0.8 to 1.2 bar (absolute pressure), more preferably in the range of 0.9 to 1.1 bar (absolute pressure), and even more preferably at a pressure of about 1 bar (absolute pressure).

[0045] In the context of this invention, alternatively, when the temperature of extraction (ii) is > 95°C, the pressure is preferably in the range of 1 to 16 bar (absolute pressure).

[0046] In the context of this invention, it should be noted that the pH of the aqueous phase of the mixture of water and pyrolysis oil provided in (i) is preferably in the range of 0 to 6, more preferably in the range of 1 to 5.5.

[0047] Preferably, base B is one or more of an alkali metal compound, an alkaline earth metal compound (such as alkaline earth metal oxides and / or hydroxides (e.g., calcium hydroxide)), and ammonia. More preferably, B is an alkali metal compound, which is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate; more preferably, one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; more preferably, one or more of potassium hydroxide and sodium hydroxide; more preferably, potassium hydroxide or sodium hydroxide; and even more preferably, potassium hydroxide.

[0048] Preferably, the water used in (ii) is demineralized water.

[0049] Preferably, for extraction according to (ii), Z E The weight ratio of water to F0 is in the range of 0.05:1 to 2:1, more preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, more preferably in the range of 0.1:1 to 0.7:1, more preferably in the range of 0.2:1 to 0.5:1, and more preferably in the range of 0.3:1 to 0.5:1.

[0050] In the context of this invention, it is preferable to determine the amount of base B used in (ii) to obtain the aqueous phase P of M. A The pH is in the range of 7 to 11, more preferably 7 to 10. Alternatively, it is preferable to determine the amount of alkali B used in (ii) to obtain the aqueous phase P of M. A The pH ranges from 7.5 to 11. This can be achieved by a technician based on their common sense.

[0051] Preferably, the aqueous phase P of M obtained according to (ii.2) A The pH ranges from 7 to 10.

[0052] Alternatively, the aqueous phase P of M obtained according to (ii.2) A The pH ranges from 7.5 to 11.

[0053] Preferably, via the location Z E One or more pH sensors in the system measure the aqueous phase pH of M obtained according to (ii.2). A pH.

[0054] Regarding (ii.2), according to an alternative, preferably (ii.2) includes

[0055] (ii.2.1) Introduce water and B, preferably a mixture of water and B, into Z. E middle;

[0056] (ii.2.2) In Z E F0 is brought into contact with water and B, more preferably a mixture of water and B, and more preferably mixed to obtain a mixture containing an aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7 to 10.

[0057] Regarding (ii.2), according to another alternative, preferably (ii.2) includes

[0058] (ii.2.1') ​​Introduce water into Z E middle;

[0059] (ii.2.2') in Z E The FO is brought into contact with water, or more preferably mixed, to obtain a mixture containing water and pyrolysis oil;

[0060] (ii.2.3') Introduce B into Z E In and in Z E B is brought into contact with, or more preferably mixed with, the mixture obtained in (ii.2.2') to obtain a mixture containing the aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7 to 10.

[0061] Regarding (ii.2), according to the second alternative, preferably (ii.2) includes

[0062] (ii.2.1) Introduce water and B, preferably a mixture of water and B, into Z. E middle;

[0063] (ii.2.2) In Z E F0 is brought into contact with water and B, more preferably a mixture of water and B, and more preferably mixed to obtain a mixture containing an aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7.5 to 11.

[0064] Regarding (ii.2), according to the third alternative, preferably (ii.2) includes

[0065] (ii.2.1') ​​Introduce water into Z E middle;

[0066] (ii.2.2') in Z EThe FO is brought into contact with water, or more preferably mixed, to obtain a mixture containing water and pyrolysis oil;

[0067] (ii.2.3') Introduce B into Z E In and in Z E B is brought into contact with, or more preferably mixed with, the mixture obtained in (ii.2.2') to obtain a mixture containing the aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7.5 to 11.

[0068] Preferably, (ii.2) includes

[0069] (ii.2.1') ​​Introduce water into Z E middle;

[0070] (ii.2.2') in Z E F0 is brought into contact with water, more preferably mixed, to obtain a mixture M1 containing water and pyrolysis oil, wherein the pH of the aqueous phase of M1 has a more preferably Z-value. E pH measured by the pH sensor in the device;

[0071] (ii.2.3') By ​​introducing B into Z E To adjust the pH of the aqueous phase of M1 and in Z E B is brought into contact with, or more preferably mixed with, M1 obtained in (ii.2.2') to obtain a mixture containing the aqueous phase P. A and organic phase P O A mixture M, wherein the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7.5 to 11, and the aqueous phase P of M is... A The pH of M1 is greater than the pH of the aqueous phase.

[0072] Preferably, according to (ii.3), P A With P O Separation is carried out by decantation or centrifugation, preferably by decantation.

[0073] Preferably, (ii) includes

[0074] (ii.1) Introduce F0 into Z E It includes the hybrid unit UM1;

[0075] (ii.2) In UM1, F0 is mixed with water and alkali B at a temperature ranging from 10°C to 200°C, more preferably from 10°C to 95°C, to obtain a mixture containing an aqueous phase P. A and organic phase P OThe mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7.5 to 11;

[0076] Remove M from UM1;

[0077] (ii.3) P A With P O Separation, of which (ii.3) includes

[0078] (ii.3.1) Make M enter Z E In the liquid-liquid separation unit US1, which is located downstream of UM1, P is obtained. A flow F A and P, which is extracted as pyrolysis oil O Flow F1;

[0079] From Z E Move F1 out of the middle.

[0080] Preferably, the extraction unit UM1 is one or more of a stirring container, a mixing pump, and a static mixer, more preferably a stirring container.

[0081] Preferably, the liquid-liquid separation unit US1 is one or more of a hydrocyclone, a settling tank, and a centrifuge, more preferably a decanter, a hydrocyclone, a settling tank, or a centrifuge, and even more preferably a settling tank.

[0082] Preferably, UM1 and US1 are different units. It is also conceivable that UM1 and US1 form a mixer-settler.

[0083] Alternatively, preferably, (ii) includes

[0084] (ii.1) Introduce F0 into Z E It includes the hybrid unit UM1;

[0085] (ii.2) In UM1, F0 is mixed with water and alkali B at a temperature ranging from 10°C to 200°C, preferably from 10°C to 95°C, to obtain a mixture containing an aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7.5 to 11;

[0086] Remove M from UM1;

[0087] (ii.3) P A With P O Separation, of which (ii.3) includes

[0088] (ii.3.1') Make M enter Z E In the liquid-liquid separation unit US1, which is downstream of UM1, P is obtained. A flow F A and P, which is extracted as pyrolysis oil O The flow F1”;

[0089] Remove F1 from US1;

[0090] (ii.3.2') subjecting the stream F1” provided in (ii.3.1') to washing to obtain stream F1 containing the purified extracted pyrolysis oil, wherein (iii.3.2') includes:

[0091] (A)

[0092] - Introducing F1" into Z E The included hybrid unit UM2 is located in Z. E Downstream of US1;

[0093] - Mix F1” with water in UM2 at a temperature T2 ranging from 10°C to 95°C to obtain a mixture containing the aqueous phase P. A (2) and organic phase P O (2) mixture, the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A pH;

[0094] - The obtained mixture enters Z E In the liquid-liquid separation unit US2, which is located downstream of UM2, the extracted pyrolysis oil P containing purified extract is obtained. O (2) flow F1; or

[0095] (B)

[0096] - Introducing F1" into Z E The extraction tower UM+US is included;

[0097] - Introduce water into UM+US;

[0098] - Contact F1” with water in UM+US at a temperature T2' ranging from 10°C to 95°C to obtain P containing the aqueous phase. A (2) flow F A (2), the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P AThe pH was determined, and the purified extract containing P was obtained. O (2) Flow F1.

[0099] In the context of this invention, preferably, the weight ratio of water to F1” is in the range of 0.05:1 to 2:1, more preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, and even more preferably in the range of 0.1:1 to 0.7:1.

[0100] Preferably, T2 according to (A) or T2' according to (B) is in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C.

[0101] Preferably, at least one extraction zone Z E It includes one or more mixing units and one or more liquid-liquid separation units. More preferably, according to (A), at least one extraction zone Z E It includes a mixing unit UM1, a mixing unit UM2, a liquid-liquid separation unit US1, and a liquid-liquid separation unit US1. More preferably, UM1 is located upstream of US1, US1 is located downstream of UM1 and upstream of UM2, UM2 is located upstream of US2 and downstream of US1, and US2 is located downstream of UM2.

[0102] Preferably, the extraction unit UM1 is one or more of a stirring container, a mixing pump, and a static mixer, more preferably a stirring container.

[0103] Preferably, the liquid-liquid separation unit US1 is one or more of a hydrocyclone, a settling tank, and a centrifuge, more preferably a decanter, a hydrocyclone, a settling tank, or a centrifuge, and even more preferably a settling tank.

[0104] Preferably, the extraction unit UM2 is one or more of a stirring container, a mixing pump, and a static mixer, more preferably a stirring container.

[0105] Preferably, the liquid-liquid separation unit US2 is one or more of a hydrocyclone, a settling tank, and a centrifuge, more preferably a decanter, a hydrocyclone, a settling tank, or a centrifuge, and even more preferably a settling tank.

[0106] In the context of this invention, UM2 and US2 are different units.

[0107] Alternatively, more preferably, according to (B), at least one extraction zone Z E It includes a first mixing unit UM1, a liquid-liquid separation unit US1, and an extraction tower UM+US. More preferably, UM1 is located upstream of US1, US1 is located downstream of UM1, and UM+US is located downstream of UM+US.

[0108] In the context of this invention, optionally, at least one extraction zone Z E Further comprising one or more filtration units, which are preferably filters. The use of filters typically implies discontinuous solid-liquid separation, where the pressure differential increases with increasing filtration time. After a certain pressure differential or filtration time, solids must be removed from the filter by a fluid or gas, or a mixture of both, via backwashing (e.g., disposal filter, backwash filter) or by an automatic system (e.g., automatic cleaning filter) or by rotation or vibration (e.g., pressure vane filter, candle filter, filter press). During solid removal, a second parallel filter begins operation until a certain pressure differential or filtration time is reached, at which point the filter with the solids emptied will operate again.

[0109] Filtration can be carried out using disposable filters (such as bag filters, filters with filter discs or membranes), where solids are removed by backwashing or remain on the filter cloth, which leads to filter replacement after a certain pressure differential or operating time.

[0110] Filtration can be enhanced by using filter aids to improve filtration behavior. This may lead to the potential use of continuous filters, such as belt filters and drum filters.

[0111] Depending on the type of centrifuge, centrifuges can be used for discontinuous or continuous solid-liquid separation. Centrifuges (e.g., decanter centrifuges, separator centrifuges) can be used in two-phase (solid-liquid) or three-phase systems with two liquid phases and a solid phase to separate solids from one or more liquids and to separate liquids from liquids. In contrast to decanter centrifuges (where solids are continuously separated and removed), in separator centrifuges, solids must be released after the centrifuge has been loaded to its maximum solid content (discontinuous). Centrifugation can be supported by the use of flocculants to improve centrifugal behavior.

[0112] Preferably, (ii) consists of (ii.1), (ii.2) and (ii.3).

[0113] Preferably, (ii.3) consists of (ii.3.1) or consists of (ii.3.1') and (ii.3.2').

[0114] Preferably, the stream F1 containing the extracted pyrolysis oil obtained according to (ii) has a TAN lower than the total acid number (TAN) of the pyrolysis oil provided in (i) before undergoing (iii) or (iv). More preferably, the extracted pyrolysis oil has a TAN in the range of 0 to 20 mg KOH / g (F1), more preferably in the range of 0 to 4.5 mg KOH / g (F1), as determined as described in Reference Example 1.

[0115] Preferably, the stream F1 containing the extracted pyrolysis oil obtained according to (ii) has an oxygen content equal to or less than, more preferably less than, the oxygen content of the pyrolysis oil provided in (i) before undergoing (iii) or (iv). More preferably, the extracted pyrolysis oil obtained according to (ii) has an oxygen content in the range of 0 to 2 g (O) / 100 g (F1) before undergoing (iii) or (iv), as determined as described in Reference Example 5.

[0116] Preferably, the stream F1 containing the extracted pyrolysis oil obtained according to (ii) has a nitrogen content equal to or less than, more preferably less than, the nitrogen content of the pyrolysis oil provided in (i) before undergoing (iii) or (iv). More preferably, the extracted pyrolysis oil obtained according to (ii) has a nitrogen content in the range of 10 to 20,000 wppm (ppm by weight), more preferably 50 to 5,000 wppm, more preferably 100 to 4,000 wppm, as determined as described in Reference Example 2, before undergoing (iii) or (iv).

[0117] Preferably, 95 to 100% by weight, more preferably 98 to 100% by weight, even more preferably 99 to 100% by weight, and even more preferably 99.5 to 100% by weight of F1 is composed of pyrolysis oil.

[0118] Step (iii)

[0119] Preferably, the heat treatment according to (iii) is one or more of dehalogenation, hydrogenation, hydrogenation treatment, dehalogenation heating, hydrogenation heating, hydrogenation treatment heating, and distillation.

[0120] - Dehalogenation and hydrogenation

[0121] Preferably, (iii) includes

[0122] (iii.1) Optionally, the stream F1 obtained according to (ii) is placed in at least one reaction zone Z containing a heterogeneous hydrogenation catalyst. H Z undergoes hydrogenation H Included in Z P In this process, a stream F containing one or more organic compounds comprising conjugated double bonds is obtained that is depleted compared to F1. H ;

[0123] (iii.2) Make the stream F1 obtained according to (ii) or the stream F obtained according to (iii.1) H Included in Z P In and located in Z H —If present—at least one downstream dehalogenation zone Z DThe medium undergoes dehalogenation to obtain F1 or F when (iii.1) is performed. H Compared to F2 containing one or more halogenated organic compounds.

[0124] Dehalogenation

[0125] As used in the context of this invention, the term "dehalogenation" generally includes "dechlorination," "debromination," and "defluorination." According to the invention, the term "dehalogenation" preferably includes "dechlorination." For example, if the pyrolysis oil to be subjected to the method according to the invention does not contain brominated and fluorinated organic compounds, but only chlorinated compounds as halogenated organic compounds, then the term "dehalogenation" will refer to "dechlorination," and the method of the invention will be a method for purifying pyrolysis oil, comprising...

[0126] (i) Providing a stream F0 containing pyrolysis oil, the pyrolysis oil containing one or more chlorinated organic compounds and one or more organic compounds containing conjugated double bonds;

[0127] (ii) Ensure that the flow F0 provided in (i) is in at least one extraction zone Z E The medium undergoes extraction to obtain a stream F1 containing the extracted pyrolysis oil, wherein (ii) includes:

[0128] (ii.1) Introduce F0 into Z E middle;

[0129] (ii.2) In Z E F0 is contacted with water and alkali B at temperatures ranging from 10°C to 200°C to obtain P containing an aqueous phase. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7.5 to 11;

[0130] (ii.3) P A With P O Separate to obtain P A flow F A and P, which is extracted as pyrolysis oil O Flow F1;

[0131] (iii) Ensure that the flow F1 obtained according to (ii) is in at least one heat treatment zone Z P After undergoing heat treatment, Z P Located in Z E Downstream, a stream F2 is obtained that is depleted of one or more of the organic compounds containing conjugated double bonds and one or more of the chlorinated organic compounds compared to F1;

[0132] Among them, (iii) includes

[0133] (iii.1) Optionally, the stream F1 obtained according to (ii) is placed in at least one reaction zone Z containing a heterogeneous hydrogenation catalyst. H Z undergoes hydrogenation H Included in Z P In this process, a stream F containing one or more organic compounds comprising conjugated double bonds is obtained that is depleted compared to F1. H ;

[0134] (iii.2) Make the stream F1 obtained according to (ii) or the stream F obtained according to (iii.1) H Included in Z P In and located in Z H —If present—at least one downstream dechlorination zone Z D After undergoing dechlorination, F1 is obtained, or F is obtained when (iii.1) is performed. H Compared to F2 containing one or more chlorinated organic compounds.

[0135] Preferably, according to an alternative, the dehalogenation zone Z according to (iii.2) D It includes an adsorption region, more preferably an adsorption region, and more preferably contains a heterogeneous adsorption material suitable for adsorbing at least one of the one or more halogenated organic compounds, more preferably all of the halides contained in the one or more halogenated organic compounds.

[0136] Preferably, the heterogeneous adsorbent according to (iii.2) comprises one or more of carbon-containing adsorbents and aluminum-containing adsorbents, more preferably aluminum-containing adsorbents. Preferably, the carbon-containing adsorbent is a carbon molecular sieve, more preferably activated carbon.

[0137] Preferably, the aluminum-containing adsorbent is alumina, aluminum-containing molecular sieve, aluminosilicate, silica-alumina hydrate, or hydrotalcite;

[0138] The aluminum-containing molecular sieve is more preferably alumina or aluminosilicate, and more preferably has a Si:Al molar ratio calculated as SiO2:Al2O3 in the range of 2:1 to 10:1, and more preferably 2:1 to 4:1.

[0139] The silica-alumina hydrate preferably has a weight ratio of Al2O3 to SiO2 in the range of 1:1 to 10:1, more preferably 1:1 to 2:1.

[0140] The hydrotalcite is more preferably an aluminum and magnesium-containing hydrotalcite, more preferably magnesium aluminum hydroxycarbonate, and more preferably has a MgO:Al2O3 weight ratio in the range of 63:37 to 70:30. More preferably, the heterogeneous adsorbent material further comprises hydrotalcite.

[0141] Preferably, the heterogeneous adsorbent material according to (iii.2) comprises elements of groups 1, 2, 11 and 12.

[0142] Preferably, the heterogeneous adsorbent material according to (iii.2) comprises particles characterized by a D50 value in the range of 1 to 6,500 micrometers, more preferably 2 to 2,000 micrometers, more preferably 8 to 500 micrometers, more preferably 10 to 50 micrometers or 3 to 9 micrometers, the D50 particle size being determined as described in Reference Example 10.

[0143] Preferably, the heterogeneous adsorbent material according to (iii.2) has an average pore volume in the range of 0.1 to 5 ml / g, more preferably in the range of 0.15 to 2 ml / g, the average pore volume being determined as described in Reference Example 11.

[0144] Preferably, the heterogeneous adsorbent material according to (iii.2) has a BET specific surface area in the range of 50 to 1,000 m² / g, more preferably in the range of 100 to 900 m² / g, and even more preferably in the range of 150 to 600 m² / g, the BET specific surface area being determined as described in Reference Example 12.

[0145] Preferably, (iii.2) includes

[0146] (iii.2.1) Introduce gas flow G1 into Z D —More preferably, in the adsorption zone—the gas stream G1 preferably contains one or more of hydrogen and nitrogen, more preferably hydrogen;

[0147] (iii.2.2) The stream F1 obtained from (ii) or F obtained from (iii.1) H Introducing Z D middle;

[0148] (iii.2.3) Make F1 or F H With Z D The G1 contained therein comes into contact with an optional heterogeneous adsorbent material to obtain an adsorption of F1 or F1. H Compared to F2 containing one or more halogenated organic compounds;

[0149] (iii.2.4) From Z D Move F2 out of the middle.

[0150] Preferably, the gas flow G1 has a temperature in the range of 100°C to 500°C, more preferably in the range of 150°C to 500°C, and even more preferably in the range of 300°C to 400°C.

[0151] Preferably, the gas flow G1 is introduced at a pressure in the range of 1 to 100 bar (absolute pressure), more preferably in the range of 5 to 80 bar (absolute pressure), and even more preferably in the range of 10 to 50 bar (absolute pressure).

[0152] Preferably, in Z D In the meantime, the liquid hourly space velocity (LHSV) ranged from 0.2 to 10 h. -1 Within the range, more preferably within 0.3 to 5 h -1 Within the range, more preferably within 0.5 to 2 h -1 Within the range.

[0153] Preferably, 90 to 100 wt%, more preferably 95 to 100 wt%, and even more preferably 98 to 100 wt%, of the gas stream G1 is composed of H2. Alternatively, preferably, 90 to 100 wt%, more preferably 95 to 100 wt%, and even more preferably 98 to 100 wt%, of the gas stream G1 is composed of nitrogen. Alternatively, preferably, 98 to 100 wt%, of G1 is composed of nitrogen and hydrogen, wherein 90 to 100 wt%, of G1 is composed of nitrogen and 0 to 10 wt%, of G1 is composed of hydrogen.

[0154] In the context of this invention, preferably, according to (iii.2.1), G1 introduces Z continuously or semi-continuously, more preferably continuously. D In, and preferably, according to (iii.2.2), F1 or F H Z is introduced continuously or semi-continuously, more preferably continuously. D middle.

[0155] Preferably, the adsorption region Z D It is included in a continuous stirred tank reactor (CSTR), a fluidized bed or a fixed bed reactor, more preferably in a fixed bed reactor, which more preferably includes an adsorption bed containing heterogeneous adsorbent material.

[0156] Preferably, according to (iii.2), two or more reaction zones Z are arranged in series and / or parallel. D More preferably, according to (iii.2), a single reaction zone Z is adopted. D .

[0157] Preferably, the F2 obtained from (iii.2) has a total acid value (TAN) in the range of 0 to 20 mg KOH / g, more preferably in the range of 0 to 4.5 mg KOH / g, as determined in Reference Example 1.

[0158] Preferably, the F2 obtained from (iii.2) has an oxygen content in the range of 0 to 2 g (O2) / 100 g of the F2, as determined in Reference Example 5.

[0159] Preferably, the F2 obtained from (iii.2) has a total chlorine content in the range of 0 to 200 wppm (ppm by weight), more preferably 0 to 160 wppm, more preferably 0 to 130 wppm, and more preferably 0 to 120 wppm, as determined in Reference Example 3.1.

[0160] Preferably, the F2 obtained from (iii.2) has a chloride content of up to 40 wppm (ppm by weight), more preferably 0 to 30 wppm, more preferably 0 to 20 wppm, and more preferably 0 to 1 wppm, as determined in Reference Example 3.2.

[0161] Preferably, the stream F2 obtained from (iii.2) comprises one or more organic compounds containing conjugated double bonds, the total amount of which is in the range of 0 to 3 g (I2) / 100 g, preferably 0 to 2 g (I2) / 100 g, more preferably 0 to 1 g (I2) / 100 g, more preferably 0 to 0.25 g (I2) / 100 g, more preferably 0 to 0.1 g (I2) / 100 g of the stream F2, as determined in Reference Example 4.

[0162] Preferably, the F2 obtained from (iii.2) has a nitrogen content in the range of 50 to 20,000 ppm (wppm), more preferably 50 to 5,000 wppm, and even more preferably 100 to 4,000 wppm by weight, as determined in Reference Example 2.

[0163] Preferably, the F2 obtained from (iii.2) has a sulfur content in the range of 50 to 30,000 ppm (wppm), more preferably 50 to 5,000 wppm, and even more preferably 100 to 3,000 wppm by weight, as determined in Reference Example 6.

[0164] Preferably, 95 to 100% by weight, more preferably 98 to 100% by weight, even more preferably 99 to 100% by weight, and even more preferably 99.5 to 100% by weight of F2 is composed of pyrolysis oil.

[0165] Preferably, according to another alternative, the dehalogenation zone Z according to (iii.2) D It includes a catalytic region, more preferably a catalytic region, which more preferably contains a heterogeneous dehalogenation catalyst, said catalyst containing one or more catalytically active elements from groups 8 to 12 of the periodic table.

[0166] Preferably, according to the alternative, (iii.2) includes Z D F1 or F obtained according to (iii.1) H The process involves contacting a heterogeneous dehalogenation catalyst, wherein the catalyst comprises one or more catalytically active elements from groups 8 to 12 of the periodic table, and F1 or FH is reacted with the catalyst to obtain a product that reacts with F1 or FH. H Compared to F2 containing one or more halogenated organic compounds.

[0167] Preferably, according to another alternative, the dehalogenation according to (iii.2) includes

[0168] (iii.2.1') ​​Optionally, gas flow G11 can be introduced into Z. D In a reactor that contains no adsorbent material and no catalyst, the gas stream G11 preferably contains one or more of hydrogen and nitrogen, more preferably hydrogen;

[0169] (iii.2.2') will be obtained from the stream F1 obtained in (ii) or F obtained in (iii.1). H Introducing Z D (It is a reactor that contains no adsorbent material and no catalyst);

[0170] (iii.2.3') Heating F1 or F in the reactor H And if (iii.2.1') ​​is performed, then F1 or F H Contact G11 to obtain access to F1 or F H Compared to F2 containing one or more halogenated organic compounds;

[0171] (iii.2.4') From Z D Move F2 out of the middle.

[0172] According to the alternative used for dehalogenation, preferably dechlorination, it is not even necessary to include it in F1 or F2. H The extracted pyrolysis oil comes into contact with a catalyst or adsorbent material. Dechlorination preferably consists of heat treatment, preferably at a temperature in the range of 200°C to 400°C.

[0173] Preferably, the gas flow G11 has a temperature in the range of 150°C to 500°C, more preferably in the range of 200°C to 400°C.

[0174] Preferably, the gas flow G11 is introduced at a pressure in the range of 1 to 100 bar (absolute pressure), more preferably in the range of 5 to 80 bar (absolute pressure), and even more preferably in the range of 10 to 50 bar (absolute pressure).

[0175] hydrogenation

[0176] Preferably, the stream F1 subjected to hydrogenation in (iii.1) has a temperature in the range of 80°C to 250°C, more preferably 90°C to 220°C, and even more preferably 100°C to 200°C.

[0177] Preferably, the heterogeneous hydrogenation catalyst according to (iii.1) comprises elements from groups 8 to 12 of the periodic table, more preferably from groups 8 to 10, more preferably from groups 9 and 10, preferably elements selected from the group consisting of Ni, Pd and Co, and more preferably elements selected from the group consisting of Ni and Pd.

[0178] Preferably, the heterogeneous hydrogenation catalyst according to (iii.1) further comprises a support material of an element from Groups 8 to 12 of the periodic table, wherein the support material is more preferably selected from the group consisting of an oxidizing material and carbon, wherein the oxidizing material is more preferably one or more of alumina, silica, magnesium oxide, zirconium oxide, titanium dioxide, zeolite, aluminosilicate phosphate (SAPO), zinc oxide, sodium oxide, mixed silica-alumina, zeolite and calcium oxide, and more preferably alumina.

[0179] Preferably, the heterogeneous hydrogenation catalyst according to (iii.1) contains, more preferably, an amount of Ni calculated as NiO in the range of 0.5 to 70 wt% based on the total weight of the hydrogenation catalyst, more preferably 0.75 to 45 wt%, and more preferably 1 to 20 wt%.

[0180] Preferably, the heterogeneous hydrogenation catalyst used in (iii.1) further comprises an element of Group 6 of the periodic table, wherein the element of Group 6 is preferably one or more of Mo and W, more preferably Mo.

[0181] Preferably, the hydrogenation catalyst comprises 1 to 40 wt% of the total weight of the hydrogenation catalyst, more preferably 2 to 35 wt%, and even more preferably 3 to 30 wt% of the group 6 element.

[0182] Preferably, the heterogeneous hydrogenation catalyst according to (iii.1) comprises Ni and Mo supported on a support material (more preferably a support material as defined above), wherein the hydrogenation catalyst preferably comprises Ni and Mo supported on alumina.

[0183] Alternatively, the heterogeneous hydrogenation catalyst according to (iii.1) comprises, more preferably, an amount of Pd calculated as elemental Pd in ​​the range of 0.01 to 5 wt% based on the total weight of the catalyst, more preferably 0.1 to 1 wt%, more preferably 0.15 to 0.8 wt%. More preferably, the heterogeneous hydrogenation catalyst according to (iii.1) further comprises a promoter, which is more preferably one or more elements of Groups 10 and 11 of the periodic table, more preferably one or more of Cu, Au, Ag, and Pt, more preferably one or more of Ag and Pt, more preferably Ag.

[0184] Preferably, the atomic ratio of the elements in groups 8 to 12 of the periodic table, more preferably Pd, to the promoter is in the range of 0.1:1 to 10:1, more preferably 2:1 to 7:1, and more preferably 2.5:1 to 6:1.

[0185] Preferably, the heterogeneous hydrogenation catalyst according to (iii.1) comprises Pd supported on a support material (more preferably a support material as defined above), wherein the support material is more preferably alumina or carbon, more preferably alumina.

[0186] In the context of this invention, preferably, the heterogeneous hydrogenation catalyst according to (iii.1) is in the form of an extrusion, granules, rings, spherical particles or spheres, more preferably in the form of spherical particles or extrusions.

[0187] Preferably, (iii.1) includes

[0188] (iii.1.1) Introduce gas flow G0 into Z H In this gas stream, H2 is present.

[0189] (iii.1.2) Introduce the flow F1 into Z H middle;

[0190] (iii.1.3) Make F1 and Z H The G0 contained therein is contacted with the heterogeneous hydrogenation catalyst to obtain a stream F1 that is depleted of one or more organic compounds containing conjugated double bonds compared to F1. H ;

[0191] (iii.1.4) From Z H Move out of F H .

[0192] (iii.1.5) Optionally from Z H Gas stream G1 is removed from the middle, and G1 contains H2.

[0193] Preferably, the gas flow G0 has a temperature in the range of 100°C to 250°C, more preferably 120°C to 220°C, and even more preferably 140°C to 200°C.

[0194] Preferably, the gas flow G0 is introduced at a pressure of 10 to 100 bar (absolute pressure), more preferably 15 to 90 bar (absolute pressure), more preferably 20 to 80 bar (absolute pressure), and even more preferably 20 to 55 bar (absolute pressure).

[0195] Preferably, 70 to 100% by volume, more preferably 80 to 100% by volume, and even more preferably 90 to 100% by volume, of the gas stream G0 is composed of H2.

[0196] Preferably, according to (iii.1.1), G0 is introduced Z continuously or semi-continuously, more preferably continuously. H In particular, and preferably, according to (iii.1.2), F1 introduces Z semi-continuously or continuously, more preferably continuously. H middle.

[0197] Preferably, G0 is introduced into Z1 according to (iii.1.1) before F1 is introduced into Z1 according to (iii.1.2). H The duration Δt is in the middle.

[0198] More preferably, during the period Δt, G0 and Z H The heterogeneous hydrogenation catalyst contact contained therein, wherein G0 has a temperature in the range of 50°C to 250°C, more preferably 120°C to 220°C, and even more preferably 140°C to 200°C.

[0199] Preferably, in Z H In this context, the liquid hourly space velocity (LHSV) is in the range of 0.2 to 10 m³ / (m³h), more preferably in the range of 0.3 to 5 m³ / (m³h), and even more preferably in the range of 0.5 to 2 m³ / (m³h), wherein the LHSV is defined as Z m³ / (m³h) per volume. H The heterogeneous hydrogenation catalyst contained therein (in m³) is processed through Z H The volumetric flow rate of F1 (in m³ / h).

[0200] Preferably, the reaction zone Z H It is contained in a continuous stirred tank reactor (CSTR) or a fixed bed reactor, more preferably in a fixed bed reactor, wherein the fixed bed reactor is more preferably a trickle bed reactor.

[0201] Preferably, according to (iii.1), two or more reaction zones Z are arranged in series and / or parallel. H , or in which, according to (iii.1), a single reaction zone Z is adopted. H .

[0202] Preferably, the stream F obtained from (iii.1) and subjected to dehalogenation in (iii.2) H The stream F contains one or more organic compounds comprising conjugated double bonds, wherein the total amount is 0 to 3 g (I2) / 100 g, more preferably 0 to 2 g (I2) / 100 g, more preferably 0 to 1 g (I2) / 100 g, more preferably 0 to 0.25 g (I2) / 100 g, more preferably 0 to 0.1 g (I2) / 100 g. H Within the range, as measured in Reference Example 4.

[0203] Preferably, the stream F obtained from (iii.1) and subjected to dehalogenation in (iii.2) H It contains a styrene content that is 50% to 100%, more preferably 70% to 100%, and even more preferably 75% to 100% lower than that of F0. The styrene content is determined as described in Reference Example 7.

[0204] Preferably, the stream F obtained from (iii.1) and subjected to dehalogenation in (iii.2) H It has a styrene content in the range of 0 to 1.5 area %, more preferably in the range of 0 to 0.1 area %, as determined as described in Reference Example 7.

[0205] Preferably, the stream F undergoes dehalogenation in (iii.2) H It has a temperature range of 150°C to 450°C, more preferably 200°C to 400°C, and even more preferably 250°C to 350°C.

[0206] Preferably, (iii) includes

[0207] (iii.1') Ensure that the stream F1 obtained according to (ii) is in at least one distillation zone Z L After distillation, Z L Included in Z P In this process, a stream F2, which is poor in the presence of one or more organic compounds compared to F1, and a stream F3, which is rich in the presence of one or more organic compounds compared to F1, are obtained.

[0208] Preferably, the heat treatment according to (iii.1') is carried out in a distillation column, wherein the stream F1 obtained according to (ii) is split into two streams F2 and F3. One of F2 and F3 contains low-boiling and / or medium-boiling components obtained from the top of the column, and the other of F2 and F3 contains high-boiling components obtained from the bottom of the column. Additionally, a side stream can be drawn from the distillation column to obtain a medium-boiling component conforming to predetermined specifications.

[0209] Preferably, the distillation according to (iii.1') is carried out at a temperature ranging from 0°C to 400°C, more preferably from 60°C to 400°C, and even more preferably from 80°C to 250°C. The corresponding operating pressure of the distillation column according to (iii.1') is preferably in the range of 0.001 bar to 4 bar (absolute pressure), more preferably from 0.001 bar to 0.98 bar (absolute pressure), and even more preferably from 0.01 bar to 0.05 bar (absolute pressure).

[0210] Preferably, the predetermined specifications and yield of the overhead product are obtained in one or a series of distillation columns, wherein the first distillation column is operated at a pressure of ≥ 0.98 bar (absolute pressure) to recover low-boiling components, which may otherwise be difficult to recover at lower pressures.

[0211] Step (iv)

[0212] -store

[0213] Preferably, the method of the present invention further includes

[0214] (iv) Prior to one or more purification steps, allow the stream F2 to enter a storage tank and store the pyrolysis oil contained in F2 for a duration ΔT.

[0215] - Hydrogenation treatment

[0216] Alternatively, preferably, the method of the present invention further includes

[0217] (iv) Make the flow F2 obtained from (iii) in Z D Downstream at least one reaction zone Z HP Z undergoes hydrogenation treatment HP Including a heterogeneous hydrogenation catalyst; to obtain stream F3;

[0218] The flow F2 subjected to (iv) has a temperature in the range of 150°C to 400°C, more preferably in the range of 200°C to 375°C, and even more preferably in the range of 250°C to 350°C.

[0219] Preferably, the heterogeneous hydrogenation catalyst used in (iv) comprises elements from groups 8 to 10 of the periodic table, preferably groups 9 and 10, preferably elements selected from the group consisting of Ni and Co, wherein the hydrogenation catalyst more preferably comprises Ni;

[0220] The heterogeneous hydrogenation catalyst according to (iv) more preferably contains an amount of Ni calculated as NiO based on the weight of the hydrogenation catalyst in the range of 0.5 to 10 wt%, more preferably in the range of 1 to 6 wt%.

[0221] Preferably, the heterogeneous hydrogenation catalyst according to (iv) further comprises a support of elements from groups 8 to 10 of the periodic table, wherein the support is more preferably an oxidizing material. More preferably, the oxidizing material is one or more of alumina, silica, magnesium oxide, zirconium oxide, zinc oxide, calcium oxide, mixed silica-alumina, zeolite, Mo-doped alumina, and titanium dioxide, more preferably alumina, zeolite, and silica-alumina, and even more preferably alumina.

[0222] Preferably, the heterogeneous hydrogenation catalyst according to (iv) further comprises an element of Group 6 of the periodic table, wherein the Group 6 element is preferably one or more of Mo and W. More preferably, the hydrogenation catalyst comprises an oxide of the Group 6 element, preferably Mo oxide or W oxide, in an amount ranging from 1 to 40 wt% based on the weight of the hydrogenation catalyst, more preferably 3 to 30 wt%.

[0223] Preferably, the heterogeneous hydrogenation catalyst according to (iv) comprises Ni and Mo on a support (more preferably, a support as defined above), and more preferably, the support is one or more of alumina, zeolite, and silica-alumina. More preferably, the hydrogenation catalyst according to (iv) comprises Ni and Mo on alumina.

[0224] Preferably, (iv) includes

[0225] (iv.1) Introduce gas flow G2 into Z HP In G2, H2 is contained within G2;

[0226] (iv.2) The stream F2 obtained from (iii) will be introduced into Z. HP middle;

[0227] (iv.3) Make F2 and Z HP The G2 contained in the catalyst is contacted with a heterogeneous hydrogenation treatment to obtain flow F3;

[0228] (iv.4) From Z HPRemove F3 obtained in (iv.3).

[0229] Preferably, the gas flow G2 has a temperature in the range of 250°C to 550°C, more preferably in the range of 300°C to 450°C, and even more preferably in the range of 325°C to 400°C.

[0230] Preferably, the gas flow G2 is introduced at a pressure of 20 to 150 bar (absolute pressure), more preferably in the range of 30 to 90 bar (absolute pressure), even more preferably in the range of 40 to 80 bar (absolute pressure), and even more preferably in the range of 45 to 60 bar (absolute pressure).

[0231] Preferably, in Z HP In the meantime, the liquid hourly space velocity (LHSV) ranged from 0.1 to 10 h. -1 Within the range, more preferably within 0.1 to 5 h -1 Within the range, more preferably within 0.2 to 2 h -1 Within the range.

[0232] Preferably, 50 to 100 wt% of the gas stream G2 is composed of H2, more preferably 70 to 100 wt% and even more preferably 90 to 100 wt%.

[0233] Preferably, according to (iv.1), G2 is introduced into Z continuously or semi-continuously, preferably continuously. HP middle.

[0234] Preferably, according to (iv.2), F2 is introduced into Z continuously or semi-continuously, more preferably continuously. HP middle.

[0235] Preferably, the reaction zone Z HP The reactor contains, more preferably, n catalyst beds B(i) connected in series, i = 1, ..., n, n ≥ 2, wherein the catalyst bed B(i) contains a heterogeneous hydrogenation catalyst, more preferably 2 ≤ n ≤ 10, more preferably 2 ≤ n ≤ 5; wherein B(i) is the upstream catalyst bed and B(n) is the downstream catalyst bed.

[0236] Preferably, (iv) includes

[0237] (iv.1') Introduce gas flow G2 into Z HP In G2, H2 is contained within G2;

[0238] (iv.2') The stream F2 obtained from (iii) will be introduced into Z. HP middle;

[0239] (iv.3') n consecutive processing stages P(i), i = 1…n,

[0240] In P(1)

[0241] - Introduce the gas stream G2 into catalyst bed B(1) and contact it with the heterogeneous hydrogenation catalyst obtained from (iv) and B(1) to obtain stream S. P (1);

[0242] In each P(i), when i = 2…n-1,

[0243] - Introduce a gas stream X(i-1) containing H2 into the catalyst bed B(i) and allow it to react with the S in B(i). P (i-1) Heterogeneous hydrogenation treatment of catalyst contact to obtain flow S P (i);

[0244] - Remove S from B(i) P (i); and

[0245] In P(n),

[0246] - Introduce the gas stream X(n-1) into the catalyst bed B(n) and make it react with the S in B(n). P (n-1) The catalyst is contacted with heterogeneous hydrogenation treatment to obtain gas stream F3;

[0247] (iv.4') From Z HP Remove F3 obtained in (iv.3').

[0248] Preferably, the gas flow G2 has a temperature in the range of 250°C to 550°C, more preferably in the range of 300°C to 450°C, and even more preferably in the range of 325°C to 400°C.

[0249] Preferably, the gas flow G2 is introduced at a pressure of 20 to 150 bar (absolute pressure), more preferably in the range of 30 to 90 bar (absolute pressure), even more preferably in the range of 40 to 80 bar (absolute pressure), and even more preferably in the range of 45 to 60 bar (absolute pressure).

[0250] Preferably, 50 to 100 wt% of the gas stream G2 is composed of H2, more preferably 70 to 100 wt% and even more preferably 90 to 100 wt%.

[0251] Preferably, in Z HP In the meantime, the liquid hourly space velocity (LHSV) ranged from 0.1 to 10 h. -1 Within the range, more preferably within 0.1 to 5 h -1 Within the range, more preferably within 0.2 to 2 h -1 Within the range.

[0252] Preferably, according to (iv.1'), G2 is introduced into Z continuously or semi-continuously, more preferably continuously. HP middle.

[0253] Preferably, according to (iv.2'), F2 is introduced into Z continuously or semi-continuously, more preferably continuously. HP middle.

[0254] Preferably, 50 to 100 wt% of the gas stream X(i), more preferably 70 to 100 wt%, and even more preferably 90 to 100 wt%, is composed of H2.

[0255] Preferably, the gas flow X(i) is introduced at a pressure of 20 to 150 bar (absolute pressure), more preferably in the range of 30 to 90 bar (absolute pressure), more preferably in the range of 40 to 80 bar (absolute pressure), and even more preferably in the range of 45 to 60 bar (absolute pressure).

[0256] Preferably, the n catalyst beds B(i) connected in series are fixed catalyst beds.

[0257] Preferably, the reaction zone Z HP It is included in a continuous stirred tank reactor (CSTR) or a fixed bed reactor, more preferably in a fixed bed reactor, and even more preferably in a trickle bed reactor.

[0258] Preferably, the F3 obtained from (iv) has a total acid value (TAN) in the range of 0 to 10 mg KOH / g (F3), more preferably in the range of 0 to 4.5 mg KOH / g (F3), as determined in Reference Example 1.

[0259] Preferably, the F3 obtained from (iv) has an oxygen content in the range of 0 to 2 g (O) / 100 g (F3), as determined in Reference Example 5.

[0260] Preferably, the stream F3 obtained from (iv) has a total chlorine content in the range of 0 to 50 wppm (ppm by weight), more preferably 0 to 30 wppm, more preferably 0 to 20 wppm, more preferably 0 to 10 wppm, more preferably 0 to 5 wppm, and more preferably 0 to less than 2 wppm, as determined in Reference Example 3.1.

[0261] Preferably, the F3 obtained from (iv) has, more preferably, a nitrogen content in the range of 0 to 200 ppm (wppm) by weight, more preferably 0 to 100 wppm, more preferably 0 to 50 wppm, and more preferably 0 to 10 wppm, as determined in Reference Example 2, after the removal of dissolved NH3.

[0262] Preferably, the F3 obtained from (iv), more preferably after the removal of dissolved H2S, has a sulfur content in the range of 0 to 200 ppm (wppm) by weight, more preferably 0 to 100 wppm, more preferably 0 to 50 wppm, as determined in Reference Example 6.

[0263] Preferably, the stream F3 obtained from (iv) comprises one or more organic compounds containing conjugated double bonds, the total amount of which is in the range of 0 to 3 g (I2) / 100 g, more preferably 0 to 2 g (I2) / 100 g, more preferably 0 to 1 g (I2) / 100 g, more preferably 0 to 0.25 g (I2) / 100 g, more preferably 0 to 0.1 g (I2) / 100 g from the stream F3 obtained from (iv), as determined in Reference Example 4.

[0264] Other steps

[0265] Preferably, the method further includes, after (iii)

[0266] One or more of the following steps: steam cracking, hydrocracking, hydrotreatment, distillation, stripping, storage, and aqueous extraction.

[0267] Preferably, the method of the present invention is a continuous or semi-continuous method.

[0268] Preferably, the method according to the invention comprises (i), (ii) and (iii), more preferably (i), (ii), (iii) and (iv).

[0269] The present invention further relates to a production unit for carrying out the method for purifying pyrolysis oil according to the present invention, the unit comprising:

[0270] - Used to introduce F0 into Z E The inlet device;

[0271] - Used from Z E Remove the F1 outlet device from the middle;

[0272] -At least one extraction zone Z E ,

[0273] -At least one heat treatment zone Z P Z P Located in Z E Downstream;

[0274] - Used to introduce F1 into Z P The inlet device;

[0275] - Used from ZD The F2 outlet device is moved out of the middle.

[0276] Preferably, the unit includes

[0277] - Optionally, at least one reaction zone Z containing a heterogeneous hydrogenation catalyst H Z H Included in Z P middle,

[0278] -Optionally used to introduce F1 into Z H The inlet device;

[0279] -Optionally used from Z H Move out of F H The outlet device;

[0280] - Included in Z P In and in Z H —If present—at least one downstream dehalogenation zone Z D Among them, Z D Preferably, it contains heterogeneous adsorbent material or heterogeneous dehalogenation catalyst, or contains no catalyst and no adsorbent material;

[0281] - Used to switch between F1 and Z H When F exists H Introducing Z D The inlet device in the middle, preferably Z P = Z D + Optional Z H .

[0282] Preferably, the unit further includes

[0283] -At least one distillation zone Z L Z L Included in Z P middle;

[0284] - Used to introduce F1 into Z L The inlet device in the middle, preferably Z L = Z P .

[0285] Preferably, the unit further includes

[0286] -At least one reaction zone Z HP Z HP Includes heterogeneous hydrogenation catalysts;

[0287] - Used to introduce F2 into Z HP The inlet device;

[0288] - Used from Z HPRemove the F3 outlet device from the middle;

[0289] Among them, Z P Located in Z HP Upstream.

[0290] The present invention further relates to a purified pyrolysis oil, which can be obtained or acquired by the method according to the present invention.

[0291] Preferably, the purified pyrolysis oil of the present invention has a total acid value (TAN) in the range of 0 to 10 mg KOH / g (oil), more preferably in the range of 0 to 4.5 mg KOH / g (oil), as determined in Reference Example 1.

[0292] Preferably, the purified pyrolysis oil of the present invention has an oxygen content in the range of 0 to 2 g (O) / 100 g (oil), as determined in Reference Example 5.

[0293] Preferably, the purified pyrolysis oil of the present invention has a nitrogen content in the range of 10 to 20,000 wppm (ppm by weight), more preferably 50 to 5,000 wppm, and even more preferably 100 to 4,000 wppm, as determined in Reference Example 2.

[0294] The invention is further illustrated by the following set of embodiments and combinations of embodiments derived from the dependent relationships and reverse references shown. In particular, it should be noted that in each instance of reference to a series of embodiments, such as in the context of the term "method as described in any one of Embodiments 1 to 4," each embodiment in this series is intended to clearly disclose to those skilled in the art that the wording of this term should be understood by those skilled in the art to be synonymous with "method as described in any one of Embodiments 1, 2, 3, and 4." Furthermore, it should be clearly noted that the following set of embodiments represents appropriate structural portions of the general description of preferred aspects of the invention and therefore appropriately supports, but does not represent, the claims of the invention.

[0295] 1. A method for purifying pyrolysis oil, the method comprising:

[0296] (i) Providing a stream F0 containing pyrolysis oil, the pyrolysis oil containing one or more halogenated organic compounds and one or more organic compounds containing conjugated double bonds;

[0297] (ii) Ensure that the flow F0 provided in (i) is in at least one extraction zone Z E The medium undergoes extraction to obtain a stream F1 containing the extracted pyrolysis oil, wherein (ii) includes:

[0298] (ii.1) Introduce F0 into Z E middle;

[0299] (ii.2) In Z E F0 is contacted with water and alkali B at temperatures ranging from 10°C to 200°C to obtain P containing an aqueous phase. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7.5 to 11;

[0300] (ii.3) P A With P O Separate to obtain P A flow F A and P, which is extracted as pyrolysis oil O Flow F1;

[0301] (iii) Ensure that the flow F1 obtained according to (ii) is in at least one heat treatment zone Z P After undergoing heat treatment, Z P Located in Z E Downstream, a stream F2 is obtained that is depleted from one or more of the organic compounds containing conjugated double bonds and one or more of the halogenated organic compounds compared to F1.

[0302] 2. The method as described in Example 1, wherein the heat treatment according to (iii) is performed at a temperature in the range of 80°C to 400°C.

[0303] 3. The method as described in Example 1 or 2, wherein the pyrolysis oil according to (i) has an oxygen content in the range of 0.1 to 15 g(O) / 100 g(F0), preferably in the range of 0.5 to 10 g(O) / 100 g(F0), more preferably in the range of 0.1 to 5 g(O) / 100 g(F0), as determined in Reference Example 5.

[0304] 4. The method as described in any one of Examples 1 to 3, wherein the pyrolysis oil according to (i) has a total acid value (TAN) in the range of 0.5 to 60 mg KOH / g (F0), preferably in the range of 1 to 40 mg KOH / g (F0), more preferably in the range of 3 to 20 mg KOH / g (F0), as determined in Reference Example 1.

[0305] 5. The method as described in any one of Examples 1 to 4, wherein the one or more halogenated organic compounds contained in the pyrolysis oil according to (i) comprise one or more of mono-, oligo- or polyhalogenated aromatic compounds, alkyl halides and alkenyl halides.

[0306] 6. The method as described in any one of Examples 1 to 5, wherein the pyrolysis oil according to (i) has a total chlorine content in the range of 30 to 3,000 wppm (ppm by weight), preferably 30 to 500 wppm, more preferably 30 to 100 wppm, as determined in Reference Example 3.1.

[0307] 7. The method as described in any one of Examples 1 to 6, wherein the pyrolysis oil according to (i) has a nitrogen content in the range of 10 to 20,000 wppm (ppm by weight), preferably 50 to 5,000 wppm, more preferably 100 to 4,000 wppm, as determined in Reference Example 2.

[0308] 8. The method of any one of Examples 1 to 7, wherein the pyrolysis oil according to (i) has a sulfur content in the range of 10 to 30,000 ppm (wppm), preferably 20 to 5,000 wppm, more preferably 50 to 3,000 wppm by weight, as determined as described in Reference Example 6.

[0309] 9. The method as described in any one of Examples 1 to 8, wherein the pyrolysis oil according to (i) comprises one or more organic compounds containing conjugated double bonds, the total amount of which is in the range of 0.1 to 75 g (I2) / 100 g, preferably 0.4 to 60 g (I2) / 100 g, more preferably 1 to 30 g (I2) / 100 g of the pyrolysis oil, as determined as described in Reference Example 4; and / or

[0310] The pyrolysis oil according to (i) has a styrene content in the range of 0.2 to 30 area % and more preferably in the range of 1 to 20 area % as determined in Reference Example 7.

[0311] 10. The method as described in any one of Examples 1 to 9, wherein the one or more organic compounds comprising conjugated double bonds comprise one or more organic compounds according to formula (I).

[0312] R 1 R 2 C 1 =C 2 R 3 -C 3 R 4 =X(I)

[0313] Where =X represents =O, =S, =NR 5 、or =C 4 R 6 R 7 Preferred = C 4 R 6R 7 ;

[0314] Preferably, R 1 R 2 R 3 R 4 R 5 Independently, they are H, alkyl groups having 1 to 6 carbon atoms, alkenyl groups having 1 to 6 carbon atoms, or aryl groups having 5 to 10 carbon atoms, more preferably H;

[0315] Preferably, R 6 and R 7 Independently, R is H, an alkyl group having 1 to 6 carbon atoms, an alkenyl group having 1 to 6 carbon atoms, or an aryl group having 5 to 10 carbon atoms, more preferably H; or preferably, wherein R 4 and R 6 or R 4 and R 7 Connected together, thus with C 3 =C 4 Together they form an aromatic ring with preferably 5 or 6 members.

[0316] 11. The method of any one of Examples 1 to 10, wherein the pyrolysis oil is obtained from waste.

[0317] 12. The method as described in any one of Examples 1 to 11, wherein the flow F0 is a liquid flow.

[0318] 13. The method as described in any one of Examples 1 to 12, wherein no organic solvent is used in the extraction according to (ii).

[0319] 14. The method as described in any one of Examples 1 to 13, wherein the extraction according to (ii) is performed at a pressure p in the range of 0.8 to 1.2 bar (absolute pressure), more preferably in the range of 0.9 to 1.1 bar (absolute pressure). E The following will proceed.

[0320] 15. The method as described in any one of Examples 1 to 14, wherein the extraction according to (ii) is carried out at a temperature in the range of 10°C to 95°C, preferably in the range of 15°C to 90°C, more preferably in the range of 20°C to 85°C, more preferably in the range of 25°C to 80°C, more preferably in the range of 30°C to 70°C, more preferably in the range of 33°C to 65°C, and more preferably in the range of 35°C to 60°C.

[0321] 16. The method as described in any one of Examples 1 to 15, wherein the base B is one or more of an alkali metal compound, an alkaline earth metal compound, and ammonia, preferably B is an alkali metal compound, which is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate, more preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate, more preferably one or more of potassium hydroxide and sodium hydroxide, more preferably potassium hydroxide or sodium hydroxide, and even more preferably potassium hydroxide.

[0322] 17. The method as described in any one of Examples 1 to 16, wherein, for the extraction according to (ii), Z E The weight ratio of water to F0 is in the range of 0.05:1 to 2:1, preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, more preferably in the range of 0.1:1 to 0.7:1, more preferably in the range of 0.2:1 to 0.5:1, and even more preferably in the range of 0.3:1 to 0.5:1.

[0323] 18. The method as described in any one of Examples 1 to 17, wherein the aqueous phase P of M obtained according to (ii.2) A The pH ranges from 7 to 10.

[0324] 19. The method as described in any one of Examples 1 to 18, wherein (ii.2) includes

[0325] (ii.2.1) Introduce water and B, preferably a mixture of water and B, into Z. E middle;

[0326] (ii.2.2) In Z E F0 is brought into contact with water and B, preferably a mixture of water and B, and preferably mixed to obtain a solution containing an aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, preferably in the range of 7 to 10.

[0327] 20. The method as described in any one of Examples 1 to 18, wherein (ii.2) includes

[0328] (ii.2.1') ​​Introduce water into Z E middle;

[0329] (ii.2.2') in Z E In the process of contacting and preferably mixing FO with water, a mixture containing water and pyrolysis oil is obtained;

[0330] (ii.2.3') Introduce B into Z E In and in Z E B is brought into contact with, preferably mixed with, the mixture obtained in (ii.2.2') to obtain a mixture containing the aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, preferably in the range of 7 to 10.

[0331] 21. The method as described in Example 20, wherein (ii.2) includes

[0332] (ii.2.1') ​​Introduce water into Z E middle;

[0333] (ii.2.2') in Z E F0 is brought into contact with water, preferably mixed, to obtain a mixture M1 containing water and pyrolysis oil, wherein the pH of the aqueous phase of M1 preferably has a pH value that is obtained by means of Z. E pH measured by the pH sensor in the device;

[0334] (ii.2.3') By ​​introducing B into Z E To adjust the pH of the aqueous phase of M1 and in Z E B is brought into contact with and preferably mixed with M1 obtained in (ii.2.2') to obtain a mixture containing the aqueous phase P. A and organic phase P O A mixture M, wherein the aqueous phase P of M A The pH is in the range of 7 to 11, and the pH of the aqueous phase of M is P. A The pH of M1 is greater than the pH of the aqueous phase.

[0335] 22. The method as described in any one of Examples 1 to 21, wherein (ii) includes

[0336] (ii.1) Introduce F0 into Z E It includes the hybrid unit UM1;

[0337] (ii.2) In UM1, F0 is mixed with water and alkali B at a temperature ranging from 10°C to 200°C, preferably from 10°C to 95°C, to obtain a mixture containing an aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH range is 7 to 11;

[0338] Remove M from UM1;

[0339] (ii.3) P A With P OSeparation, of which (ii.3) includes

[0340] (ii.3.1) Make M enter Z E In the liquid-liquid separation unit US1, which is located downstream of UM1, P is obtained. A flow F A and P, which is extracted as pyrolysis oil O Flow F1;

[0341] From Z E Move F1 out of the middle.

[0342] 23. The method as described in any one of Examples 1 to 21, wherein (ii) includes

[0343] (ii.1) Introduce F0 into Z E It includes the hybrid unit UM1;

[0344] (ii.2) In UM1, F0 is mixed with water and alkali B at a temperature ranging from 10°C to 200°C, preferably from 10°C to 95°C, to obtain a mixture containing an aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, more preferably in the range of 7.5 to 11;

[0345] Remove M from UM1;

[0346] (ii.3) P A With P O Separation, of which (ii.3) includes

[0347] (ii.3.1') Make M enter Z E In the liquid-liquid separation unit US1, which is downstream of UM1, P is obtained. A flow F A and P, which is extracted as pyrolysis oil O The flow F1”;

[0348] Remove F1 from US1;

[0349] (ii.3.2') subjecting the stream F1” provided in (ii.3.1') to washing to obtain stream F1 containing the purified extracted pyrolysis oil, wherein (iii.3.2') includes:

[0350] (A)

[0351] - Introducing F1" into Z E The included hybrid unit UM2 is located in Z. E Downstream of US1;

[0352] - Mix F1” with water in UM2 at a temperature T2 ranging from 10°C to 95°C to obtain a mixture containing the aqueous phase P. A (2) and organic phase P O (2) mixture, the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A pH;

[0353] - The obtained mixture enters Z E In the liquid-liquid separation unit US2, which is located downstream of UM2, the extracted pyrolysis oil P containing purified extract is obtained. O (2) flow F1; or

[0354] (B)

[0355] - Introducing F1" into Z E The extraction tower UM+US is included;

[0356] - Introduce water into UM+US;

[0357] - Contact F1” with water in UM+US at a temperature T2' ranging from 10°C to 95°C to obtain P containing the aqueous phase. A (2) flow F A (2), the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A The pH was determined, and the purified extract containing P was obtained. O (2) Flow F1.

[0358] 24. The method of any one of Examples 1 to 23, wherein the heat treatment according to (iii) is one or more of dehalogenation, hydrogenation, hydrogenation treatment, dehalogenation heating, hydrogenation heating, hydrogenation treatment heating, and distillation.

[0359] 25. The method as described in any one of Examples 1 to 24, wherein (iii) includes

[0360] (iii.1) Optionally, the stream F1 obtained according to (ii) is placed in at least one reaction zone Z containing a heterogeneous hydrogenation catalyst. H Z undergoes hydrogenation H Included in Z P In this process, a stream F containing one or more organic compounds comprising conjugated double bonds is obtained that is depleted compared to F1. H ;

[0361] (iii.2) Make the stream F1 obtained according to (ii) or the stream F obtained according to (iii.1) H Included in Z P In and located in Z H —If present—at least one downstream dehalogenation zone Z D The medium undergoes dehalogenation to obtain F1 or F when (iii.1) is performed. H Compared to F2 containing one or more halogenated organic compounds.

[0362] 26. The method as described in Example 25, wherein the dehalogenation zone Z according to (iii.2) D It includes an adsorption region, preferably an adsorption region, and preferably contains a heterogeneous adsorption material suitable for adsorbing at least one, preferably all, of the halides contained in the one or more halogenated organic compounds.

[0363] 27. The method as described in Example 26, wherein the heterogeneous adsorbent according to (iii.2) comprises one or more of a carbon-containing adsorbent and an aluminum-containing adsorbent, preferably an aluminum-containing adsorbent;

[0364] The carbon-containing adsorbent material is preferably a carbon-containing molecular sieve, and more preferably activated carbon;

[0365] The aluminum-containing adsorbent material is preferably alumina, aluminum-containing molecular sieve, silica-alumina phosphate, silica-alumina hydrate, or hydrotalcite.

[0366] The aluminum-containing molecular sieve is preferably alumina or aluminosilicate, and preferably has a Si:Al molar ratio calculated as SiO2:Al2O3 in the range of 2:1 to 10:1, more preferably 2:1 to 4:1.

[0367] The silica-alumina hydrate preferably has a weight ratio of Al2O3 to SiO2 in the range of 1:1 to 10:1, more preferably 1:1 to 2:1.

[0368] The hydrotalcite is preferably an aluminum and magnesium-containing hydrotalcite, more preferably magnesium aluminum hydroxycarbonate, and preferably has a MgO:Al2O3 weight ratio in the range of 63:37 to 70:30.

[0369] The heterogeneous adsorption material preferably includes hydrotalcite;

[0370] The heterogeneous adsorbent material according to (iii.2) preferably contains elements of groups 1, 2, 11 and 12.

[0371] 28. The method of any one of Examples 25 to 27, wherein the heterogeneous adsorbent material according to (iii.2) comprises particles characterized by a D50 value of particle size distribution in the range of 1 to 6,500 micrometers, preferably 2 to 2,000 micrometers, more preferably 8 to 500 micrometers, more preferably 10 to 50 micrometers or 3 to 9 micrometers, the D50 particle size being determined as described in Reference Example 10.

[0372] 29. The method of any one of Examples 25 to 27, wherein the heterogeneous adsorbent material according to (iii.2) has an average pore volume in the range of 0.1 to 5 ml / g, preferably in the range of 0.15 to 2 ml / g, which is determined as described in Reference Example 11.

[0373] 30. The method of any one of Examples 25 to 28, wherein the heterogeneous adsorbent material according to (iii.2) has a BET specific surface area in the range of 50 to 1,000 m² / g, preferably in the range of 100 to 900 m² / g, more preferably in the range of 150 to 600 m² / g, as determined as described in Reference Example 12.

[0374] 31. The method as described in any one of Examples 25 to 30, wherein (iii.2) includes

[0375] (iii.2.1) Introduce gas flow G1 into Z D —Preferredly in the adsorption zone—, the gas stream G1 preferably contains one or more of hydrogen and nitrogen, more preferably hydrogen;

[0376] (iii.2.2) The stream F1 obtained from (ii) or F obtained from (iii.1) H Introducing Z D middle;

[0377] (iii.2.3) Make F1 or F H With Z D The G1 contained therein comes into contact with an optional heterogeneous adsorbent material to obtain an adsorption of F1 or F1. H Compared to F2 containing one or more halogenated organic compounds;

[0378] (iii.2.4) From Z D Move F2 out of the middle.

[0379] 32. The method as described in Example 31, wherein the gas stream G1 has a temperature in the range of 150°C to 500°C, preferably in the range of 300°C to 400°C.

[0380] 33. The method as described in Example 31 or 32, wherein the gas flow G1 is introduced at a pressure in the range of 1 to 100 bar (absolute pressure), preferably in the range of 5 to 80 bar (absolute pressure), and more preferably in the range of 10 to 50 bar (absolute pressure).

[0381] 34. The method as described in any one of Examples 29 to 33, wherein, in Z D In the meantime, the liquid hourly space velocity (LHSV) ranged from 0.2 to 10 h. -1 Within the range, preferably within 0.3 to 5 hours. -1 Within the range, more preferably within 0.5 to 2 h -1 Within the range.

[0382] 35. The method as described in any one of Examples 31 to 34, wherein 90 to 100 wt%, preferably 95 to 100 wt%, more preferably 98 to 100 wt%, of the gas stream G1 is composed of H2; or

[0383] Of which, 90 to 100 wt%, preferably 95 to 100 wt%, and more preferably 98 to 100 wt%, of the gas stream G1 is composed of nitrogen; or

[0384] Of which, 98 to 100 wt% of G1 is composed of nitrogen and hydrogen, of which 90 to 100 wt% of G1 is composed of nitrogen and 0 to 10 wt% of G1 is composed of hydrogen.

[0385] 36. The method as described in any one of Examples 31 to 35, wherein, according to (iii.2.1), G1 is introduced into Z continuously or semi-continuously, preferably continuously. D In, and among which, according to (iii.2.2), F1 or F H Z is introduced continuously or semi-continuously, preferably continuously. D middle;

[0386] Among them, the adsorption region Z D Preferably contained in a continuous stirred tank reactor (CSTR), a fluidized bed or a fixed bed reactor, preferably in a fixed bed reactor, which preferably includes an adsorption bed containing heterogeneous adsorbent material.

[0387] 37. The method as described in any one of Examples 25 to 36, wherein, according to (iii.2), two or more reaction zones Z are arranged in series and / or parallel. D , or in which, according to (iii.2), a single reaction zone Z is adopted. D .

[0388] 38. The method as described in Example 25, wherein the dehalogenation zone Z according to (iii.2) DIt includes a catalytic region, preferably a catalytic region, which preferably contains a heterogeneous dehalogenation catalyst, said catalyst containing one or more catalytically active elements from groups 8 to 12 of the periodic table.

[0389] 39. The method as described in Example 25, wherein the dehalogenation according to (iii.2) includes

[0390] (iii.2.1') ​​Optionally, gas flow G11 can be introduced into Z. D In a reactor that contains no adsorbent material and no catalyst, the gas stream G11 preferably contains one or more of hydrogen and nitrogen, more preferably hydrogen;

[0391] (iii.2.2') will be obtained from the stream F1 obtained in (ii) or F obtained in (iii.1). H Introducing Z D middle;

[0392] (iii.2.3') Heating F1 or F in the reactor H And if (iii.2.1') ​​is performed, then F1 or F H Contact G11 to obtain access to F1 or F H Compared to F2 containing one or more halogenated organic compounds;

[0393] (iii.2.4') From Z D Move F2 out of the middle.

[0394] 40. The method as described in any one of Examples 25 to 39, wherein the stream F1 subjected to hydrogenation in (iii.1) has a temperature in the range of 80°C to 250°C, preferably 90°C to 220°C, more preferably 100°C to 200°C.

[0395] 41. The method of any one of Examples 25 to 40, wherein the heterogeneous hydrogenation catalyst according to (iii.1) comprises elements of Groups 8 to 12 of the periodic table, preferably Groups 8 to 10, more preferably Groups 9 and 10, preferably elements selected from the group consisting of Ni, Pd and Co, more preferably elements selected from the group consisting of Ni and Pd.

[0396] 42. The method as described in Example 41, wherein the heterogeneous hydrogenation catalyst according to (iii.1) further comprises a support material of an element from Groups 8 to 12 of the periodic table, wherein the support material is preferably selected from the group consisting of an oxidizing material and carbon, wherein the oxidizing material is preferably one or more of alumina, silica, magnesium oxide, zirconium oxide, titanium dioxide, zeolite, aluminosilicate phosphate (SAPO), zinc oxide, sodium oxide, mixed silica-alumina, zeolite, and calcium oxide, more preferably alumina.

[0397] 43. The method as described in Examples 41 or 42, wherein the heterogeneous hydrogenation catalyst according to (iii.1) comprises an amount of Ni calculated as NiO, preferably in the range of 0.5 to 70 wt% based on the total weight of the hydrogenation catalyst, more preferably 0.75 to 45 wt%, and even more preferably 1 to 20 wt%.

[0398] 44. The method of any one of Examples 41 to 43, wherein the heterogeneous hydrogenation catalyst used in (iii.1) further comprises an element of Group 6 of the periodic table, wherein the element of Group 6 is preferably one or more of Mo and W, more preferably Mo;

[0399] Preferably, the heterogeneous hydrogenation catalyst according to (iii.1) comprises Ni and Mo supported on a support material (preferably the support material defined in Example 16), wherein the hydrogenation catalyst preferably comprises Ni and Mo supported on alumina;

[0400] The hydrogenation catalyst preferably contains 1 to 40 wt% of the total weight of the hydrogenation catalyst, more preferably 2 to 35 wt%, and more preferably 3 to 30 wt% of the elements of Group 6.

[0401] 45. The method as described in Examples 41 or 42, wherein the heterogeneous hydrogenation catalyst according to (iii.1) comprises an amount of Pd calculated in terms of elemental Pd, preferably in the range of 0.01 to 5 wt% based on the total weight of the catalyst, preferably 0.1 to 1 wt%, more preferably 0.15 to 0.8 wt%.

[0402] Preferably, the heterogeneous hydrogenation catalyst according to (iii.1) further comprises a promoter, which is more preferably one or more elements of groups 10 and 11 of the periodic table, more preferably one or more of Cu, Au, Ag and Pt, more preferably one or more of Ag and Pt, and more preferably Ag;

[0403] More preferably, the atomic ratio of elements in groups 8 to 12 of the periodic table, preferably Pd, to the promoter is in the range of 0.1:1 to 10:1, more preferably 2:1 to 7:1, and more preferably 2.5:1 to 6:1.

[0404] 46. ​​The method as described in Example 45, wherein the heterogeneous hydrogenation catalyst according to (iii.1) comprises Pd supported on a support material (preferably the support material defined in Example 16), wherein the support material is preferably alumina or carbon, more preferably alumina.

[0405] 47. The method of any one of Examples 25 to 46, wherein the heterogeneous hydrogenation catalyst according to (iii.1) is in the form of an extrusion, granules, rings, spherical particles or spheres, preferably in the form of spherical particles or extrusions.

[0406] 48. The method as described in any one of Examples 25 to 47, wherein (iii.1) comprises

[0407] (iii.1.1) Introduce gas flow G0 into Z H In this gas stream, H2 is present.

[0408] (iii.1.2) Introduce the flow F1 into Z H middle;

[0409] (iii.1.3) Make F1 and Z H The G0 contained therein is contacted with the heterogeneous hydrogenation catalyst to obtain a stream F1 that is depleted of one or more organic compounds containing conjugated double bonds compared to F1. H ;

[0410] (iii.1.4) From Z H Move out of F H .

[0411] (iii.1.5) Optionally from Z H Gas stream G1 is removed from the middle, and G1 contains H2.

[0412] 49. The method as described in Example 48, wherein the gas stream G0 has a temperature in the range of 100°C to 250°C, preferably 120°C to 220°C, more preferably 140°C to 200°C.

[0413] 50. The method as described in Examples 48 or 49, wherein the gas flow G0 is introduced at a pressure of 10 to 100 bar (absolute pressure), preferably 15 to 90 bar (absolute pressure), more preferably 20 to 80 bar (absolute pressure), and even more preferably 20 to 55 bar (absolute pressure).

[0414] 51. The method as described in any one of Examples 48 to 50, wherein 70 to 100 volume-%, preferably 80 to 100 volume-%, more preferably 90 to 100 volume-%, of the gas stream G0 is composed of H2.

[0415] 52. The method as described in any one of Examples 48 to 51, wherein, according to (iii.1.1), G0 is introduced Z continuously or semi-continuously, preferably continuously. H In, and wherein, according to (iii.1.2), F1 is introduced into Z semi-continuously or continuously, preferably continuously. H middle.

[0416] 53. The method as described in Example 52, wherein G0 is introduced into Z1 according to (iii.1.1) before F1 is introduced into Z1 according to (iii.1.2). H The duration Δt is in the middle.

[0417] Preferably, during the period Δt, G0 and Z H The heterogeneous hydrogenation catalyst contact contained therein, wherein G0 has a temperature in the range of 50°C to 250°C, more preferably 120°C to 220°C, and even more preferably 140°C to 200°C.

[0418] 54. The method as described in any one of Examples 48 to 53, wherein, in Z H In this context, the liquid hourly space velocity (LHSV) is in the range of 0.2 to 10 m³ / (m³h), preferably in the range of 0.3 to 5 m³ / (m³h), and more preferably in the range of 0.5 to 2 m³ / (m³h), wherein the LHSV is defined as the liquid hourly space velocity per volume Z. H The heterogeneous hydrogenation catalyst contained therein (in m³) is processed through Z H The volumetric flow rate of F1 (in m³ / h).

[0419] 55. The method as described in any one of Examples 25 to 54, wherein the reaction zone Z H It is contained in a continuous stirred tank reactor (CSTR) or a fixed bed reactor, preferably in a fixed bed reactor, wherein the fixed bed reactor is preferably a trickle bed reactor.

[0420] 56. The method as described in any one of Examples 25 to 55, wherein, according to (iii.1), two or more reaction zones Z are arranged in series and / or parallel. H , or in which, according to (iii.1), a single reaction zone Z is adopted. H .

[0421] 57. The method as described in any one of Examples 25 to 56, wherein the stream F undergoing dehalogenation in (iii.2) H It has a temperature range of 150°C to 450°C, preferably 200°C to 400°C, and more preferably 250°C to 350°C.

[0422] 58. The method as described in any one of Examples 1 to 24, wherein (iii) includes

[0423] (iii.1') Ensure that the stream F1 obtained according to (ii) is in at least one distillation zone Z L After distillation, Z L Included in Z P In this process, a stream F2, which is poor in the presence of one or more organic compounds compared to F1, and a stream F3, which is rich in the presence of one or more organic compounds compared to F1, are obtained.

[0424] 59. The method as described in any one of Examples 1 to 58, further comprising, after (iii)

[0425] One or more of the following steps: steam cracking, hydrocracking, hydrotreatment, distillation, stripping, storage, and aqueous extraction.

[0426] 60. The method as described in any one of Examples 1 to 59, wherein it is a continuous or semi-continuous method.

[0427] 61. A production unit for carrying out a method for purifying pyrolysis oil as described in any one of Examples 1 to 60, the unit comprising:

[0428] - Used to introduce F0 into Z E The inlet device;

[0429] - Used from Z E Remove the F1 outlet device from the middle;

[0430] -At least one extraction zone Z E ,

[0431] -At least one heat treatment zone Z P Z P Located in Z E Downstream;

[0432] - Used to introduce F1 into Z P The inlet device;

[0433] - Used from Z D The F2 outlet device is moved out of the middle.

[0434] 62. The production unit as described in Example 61, further comprising:

[0435] - Optionally, at least one reaction zone Z containing a heterogeneous hydrogenation catalyst H Z H Included in Z P middle,

[0436] -Optionally used to introduce F1 into Z H The inlet device;

[0437] -Optionally used from Z H Move out of F H The outlet device;

[0438] - Included in Z P In and in Z H —If present—at least one downstream dehalogenation zone Z D Among them, Z D Preferably, it contains heterogeneous adsorbent material or heterogeneous dehalogenation catalyst, or contains no catalyst and no adsorbent material;

[0439] - Used to switch between F1 and Z H When F exists H Introducing Z D The inlet device in the middle, preferably Z P = Z D + Optional Z H .

[0440] 63. The production unit as described in Example 61, further comprising:

[0441] -At least one distillation zone Z L Z L Included in Z P middle;

[0442] - Used to introduce F1 into Z L The inlet device in the middle, preferably Z L = Z P .

[0443] 64. The production unit as described in any one of Examples 61 to 63, further comprising:

[0444] -At least one reaction zone Z HP Z HP Includes heterogeneous hydrogenation catalysts;

[0445] - Used to introduce F2 into Z HP The inlet device;

[0446] - Used from Z HP Remove the F3 outlet device from the middle;

[0447] Among them, Z P Located in Z HP Upstream.

[0448] 65. A method comprising the following steps:

[0449] - Use the production unit according to any one of Examples 61 to 64 to obtain purified pyrolysis oil, monomer, polymer or polymer product.

[0450] 66. A method, preferably comprising the steps according to any one of Examples 1 to 60, the method further comprising the following steps:

[0451] - The conversion of a stream of F2 obtained or acquired by the method according to any one of Examples 1 to 60, or a chemical material obtained or acquired by the method according to any one of Examples 1 to 60, into a monomer, polymer, or polymer product.

[0452] 67. The method as described in any one of Examples 1 to 60 and / or 65 to 66,

[0453] The polymer or polymer product is granules, strands, rods, plates, tubes, foils, layers, films, sheets, fibers, filaments, coatings, extruded articles and / or molded articles, flexible foams, semi-rigid foams and / or rigid foams.

[0454] 68. The method as described in any one of Examples 1 to 60 and / or 65 to 67,

[0455] Wherein, the monomer is a diol or polyol; preferably butanediol; aldehyde; preferably formaldehyde; diisocyanate or polyisocyanate; preferably methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (pMDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI); amide; preferably caprolactam; olefin; preferably styrene, ethylene and norbornene; alkyne, (di) ester; preferably methyl methacrylate; monoacid or diacid; preferably adipic acid or terephthalic acid; diamine; preferably hexamethylene diamine, nonadiamine; or sulfone; preferably 4,4'-dichlorodiphenyl sulfone.

[0456] 69. The method as described in any one of Examples 1 to 60 and / or 65 to 68,

[0457] The polymer and / or the polymer product contains polyamide (PA); preferably PA 6 and PA 66; a polyisocyanate addition polymer; preferably polyurethane (PU), thermoplastic polyurethane (TPU), polyurea or polyisocyanurate (PIR); low-density polyethylene (LDPE), high-density polyethylene (HDPE), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinyl acetate (PVA), polystyrene (PS), polyacrylonitrile-butadiene-styrene (ABS), polystyrene-acrylonitrile (SAN), polyacrylate-styrene-acrylonitrile (ASA), polytetrafluoroethylene (Teflon), thermoplastic polyurethane (TPU), poly(methyl acrylate) (PMA), poly(methyl methacrylate) (PMMA), polybutadiene (BR, PBD), poly(cis-1,4-isoprene), poly(trans-) Poly(1,4-isoprene), polyoxymethylene (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene adipate terephthalate (PBAT), polyester (PES), polyethersulfone (PESU), polyhydroxyalkanoate (PHA), poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), polyhydroxyvalerate (PHV), polyhydroxyhexanoate (PHH), polyhydroxyoctanoate (PHO), polylactic acid (PLA), polysulfone (PSU), polyphenylene sulfone (PPSU), polycarbonate (PC), polyetheretherketone (PEEK), poly(p-phenylene oxide) (PPO), poly(p-phenylene ether) (PPE); and copolymers and mixtures thereof.

[0458] 70. The method as described in any one of Examples 1 to 60 and / or 65 to 69,

[0459] The polymer and / or the polymer product is one or more of the following:

[0460] - Automotive parts, preferably cylinder head covers, engine hoods, turbocharger housings, turbocharger baffles, intake pipes, intake manifolds, connectors, gears, fan wheels, coolant tanks, heat exchanger housings or housing parts, coolant coolers, turbocharger coolers, thermostats, water pumps, radiators, fasteners or parts for electric vehicle battery systems, dashboards, steering column switches, seats, headrests, center consoles, transmission components, door modules, A, B, C or D pillar covers for automotive exteriors, spoilers, door handles, exterior mirrors, windshield wipers, windshield wiper protective housings, decorative grilles, cover strips, roof rails, window frames, sunroof frames, antenna panels, headlights and taillights, engine hoods, cylinder head covers, intake manifolds, airbags or buffer pads;

[0461] - Fabrics, preferably shirts, trousers, sweaters, boots, shoes, shoe soles, bodysuits or jackets;

[0462] - Electrical components, preferably electrical or electronic passive or active components, printed circuit boards, printed circuit boards, housing components, foil, wire, switches, plugs, sockets, distributors, relays, resistors, capacitors, inductors, spools, lamps, diodes, LEDs, transistors, connectors, voltage regulators, integrated circuits (ICs), processors, controllers, memory, sensors, connectors, microswitches, micro buttons, semiconductors, reflector housings for light-emitting diodes (LEDs), fasteners, gaskets, bolts, strips, slide-in guides, screws, nuts, membrane hinges, spring hooks (snap-in type) or spring tongues;

[0463] - Consumer goods and / or pharmaceutical products, preferably tennis strings, climbing ropes, bristles, brushes, artificial turf, 3D printed filaments, lawnmowers, zippers, hook and loop fasteners, paper machine fabrics, extrusion coatings, fishing lines, fishing nets, offshore lines and ropes, vials, syringes, ampoules, bottles, sliding elements, spindle nuts, chain conveyors, sliding bearings, rollers, wheels, gears, ring gears, screws and spring dampers, hoses, pipes, cable sheaths, sockets, switches, cable ties, fan wheels, carpets, cosmetic boxes or bottles, mattresses, cushions or insulating materials; and / or

[0464] Packaging for the food industry; preferred materials include single-layer or multi-layer blown film, cast film (single-layer or multi-layer), biaxial stretch film, and laminated film.

[0465] 71. The method as described in any one of Examples 1 to 60 and / or 65 to 70,

[0466] The purified pyrolysis oil, monomers, polymers, and / or polymer products contain pyrolysis oil in stream F0 at a content of 1 wt% or more, preferably 2 wt% or more, more preferably 5 wt% or more, more preferably 15 wt% or more, more preferably 30 wt% or more, more preferably 40 wt% or more, more preferably 60 wt% or more, more preferably 80 wt% or more, more preferably 90 wt% or more, more preferably 95 wt% or more; and / or

[0467] The purified pyrolysis oil, monomers, polymers, and / or polymer products contain pyrolysis oil in stream F0 at a content of 100% by weight or less, preferably 95% by weight or less, more preferably 90% by weight or less, more preferably 50% by weight or less, more preferably 25% by weight or less, and more preferably 10% by weight or less; and

[0468] Preferably, the content is determined based on an identity preservation and / or segregation and / or quality balance and / or book and claims custody model, preferably based on quality balance, and preferably based on the International Sustainability and Carbon Certification (ISCC) standard.

[0469] 72. A purified pyrolysis oil, which can be obtained or acquired by the method according to any one of Examples 1 to 60.

[0470] It should be clearly noted that the above set of embodiments represents appropriate structural portions of the general description of preferred aspects of the invention, and therefore appropriately supports but does not represent the claims of the invention.

[0471] In the context of this invention, the term "X is one or more of A, B, and C" (where X is a given feature and each of A, B, and C represents a specific implementation of said feature) should be understood to disclose that X is A, or B, or C, or A and B, or A and C, or B and C, or A and B and C. In this respect, it should be noted that those skilled in the art can translate the above abstract terms into concrete examples, for example, where X is a chemical element and A, B, and C are specific elements such as Li, Na, and K, or X is a temperature and A, B, and C are specific temperatures such as 10°C, 20°C, and 30°C. In this regard, it should be further noted that those skilled in the art can extend the above terms to less specific implementations of the feature, such as "X is one or more of A and B," which discloses that X is A, or B, or A and B, or extend them to more specific implementations of the feature, such as "X is one or more of A, B, C, and D," which discloses that X is A, or B, or C, or D, or A and B, or A and C, or A and D, or B and C, or B and D, or C and D, or A and B and C, or A and B and D, or B and C and D, or A and B and C and D.

[0472] The conversion steps to obtain monomers, polymers, or polymer products may include one or more synthetic steps and can be performed by conventional synthesis and techniques well known to those skilled in the art. Those skilled in the art who perform the conversion steps, regardless of their ability to evaluate the novelty and inventive step of the independent claim, come from the technical field of pyrolysis, vaporization, remonomerization, depolymerization, and / or synthesis and / or production of monomers, polymers, and polymer compounds, and their further processing (e.g., extrusion, injection molding). Examples of the conversion steps are described in the following titles: “Industrial Organic Chemistry”, Volume 3, Wiley-VCH, 1997; ISBN: 978-3-527-28838-0; “Kunststoffhandbuch”, Volume 11, Subvolume 17, Carl Hanser Verlag, especially Volume 6, “Polyamide”, 1st edition, 1966; Volume 7, “Polyurethane”, 3rd edition, 1993; and Volume 8, “Polyester”, 1st edition, 1973; “Industrial Organic Chemistry”, Volume 3, Wiley-VCH, 1997; ISBN: 978-3-527-28838-0; "Injection Molding Reference Guide", 4th Edition, CreateSpace Independent Publishing Platform, 2011, ISBN: 978-1466407824, EP 0989146 (A1), EP 1460094 (A1), WO 2006034800 (A1), EP 1529792 (A1), WO 2006042674 (A1), EP 0364854 (A2), US5506275 (A), EP 0897402 (A1), WO 2015082316 (A1), WO 2021021855 (A1), WO2021126938 (A1), WO 2021021902 (A1), WO 2021092311 (A1), WO 2008155271 (A1), WO2013139827 (A1), each of which is incorporated herein by reference.

[0473] The invention is further illustrated by the following examples. Example

[0474] Reference Example 1: Determination of Total Acid Number (TAN)

[0475] According to ASTM D3242, the total acid value is determined by titration with KOH.

[0476] Reference Example 2: Measurement of N content (wppm)

[0477] Through

[0478] Nitrogen content was determined by burning each sample at 1000°C. The NO in the resulting combustion gases reacted with ozone to form NO2*. Relaxation of excited-state nitrogen species was detected using a chemiluminescence detector according to ASTM D4629 (N). The calibration range was 0.5 wppm to 50 wppm. Samples with higher concentrations were diluted with xylene to bring them within the calibration range.

[0479] Refer to Example 3.1 for the measurement of total chlorine content (wppm).

[0480] Samples were filtered using a 0.45 µm syringe filter prior to analysis. Chlorine content was determined by burning each sample at 1050°C. The resulting combustion gas, hydrogen chloride, was introduced into the coulometric titration cell.

[0481] Refer to Example 3.2 for the measurement of chloride content (wppm).

[0482] Samples were filtered using a 0.45 µm syringe filter prior to analysis. Chloride content was determined by ion chromatography. Apparatus: Ion chromatograph 850 Professional (Metrohm) (pre-column: Metrosep A Supp4 / 5 S-Guard and analytical column: Metrosep A Supp5 250 / 4; flow rate: 0.7 mL / min; column temperature: 30°C; detector temperature: 40°C; injection volume: 25 µL; inhibitor: MSM HC Rotor A). Eluents: 3.2 mmol / L Na₂CO₃; 1.0 mmol / L NaHCO₃; and regenerator: 50 mmol / L sulfuric acid.

[0483] Sample preparation: Weigh 0.2 g–0.4 g of sample and dissolve it in 10 mL of toluene. For analyte extraction, add 10 mL of deionized water. After centrifugation, extract the aqueous phase and analyze it. For samples with concentrations below the method limit, add 20 µg / L chloride standard solution (corresponding to the limit of 1 mg / kg chloride in the sample) to check the recovery.

[0484] Reference Example 4: Measurement of the total amount of one or more organic compounds containing conjugated double bonds

[0485] Diene content is determined using UOP326-17. In this procedure, the diene reacts with maleic anhydride (MA) and the amount of MA consumed is determined (by titrating the remaining MA). It can be expressed as g(I2) / 100 g (sample) or alternatively g(MA) / 100 g (sample). This unit can be converted to each other by multiplying the MA value (MAV) by a factor of 2.59 to obtain a value expressed as g(I2) / 100 g (sample), corresponding to the molar weights of I2 and MA. Therefore, 1 wt% styrene or 0.52 wt.% butadiene corresponds to 0.94 g(MA) / 100 g or 2.43 g(I2) / 100 g.

[0486] Refer to Example 5 for the measurement of oxygen content.

[0487] The oxygen content was determined according to ASTM D5622. The sample was pyrolyzed upon contact with soot in a reducing gas atmosphere, thereby converting oxygen into carbon monoxide (CO). Carbon monoxide was detected and quantified by IR spectroscopy.

[0488] Reference Example 6: Measurement of S content (wppm)

[0489] Sulfur content was determined by burning individual samples at 1000°C. The sulfur dioxide contained in the resulting combustion gases was excited by UV (ultraviolet) light. The light emitted during relaxation was detected using a UV fluorescence detector according to ASTM D5453(S). The calibration range was 0.5 wppm to 50 wppm. Samples with higher concentrations were diluted with xylene to bring them within the calibration range.

[0490] Refer to Example 7 for the determination of styrene content.

[0491] The GC method was used with a nonpolar, 100% dimethylpolysiloxane phase column and an FID detector. The final column temperature and inlet temperature were 330°C and 320°C, respectively. The area percentage (%) is the ratio of the integral area signal of styrene to the ratio of all integral peaks multiplied by 100%. The area percentage is approximately correlated with wt.%.

[0492] Refer to Example 8: Reactor Loading and Testing Apparatus

[0493] All reaction steps in the example (except extraction) were carried out in a reactor with an inner diameter of 10 mm and operated in trickle bed mode (downflow). The reactor (80 cm long) was loaded with corundum (WSK F46; commercial corundum) from the bottom, such that the lower 25 cm was filled with inert corundum (cooling zone). Above this, a 30 cm long adsorbent bed was placed from 25 to 55 cm, and the reaction temperature was maintained in this zone. In the absence of a catalyst or adsorbent, this zone was filled only with corundum (WSK F46; commercial corundum). Corundum (WSK F46; commercial corundum) was filled from 55 to 80 cm above the catalyst and adsorbent bed, respectively. In this corundum zone, the feed was preheated to the reaction temperature, while in the lower corundum-filled zone, the product stream was cooled from the reactor temperature to the tracing temperature.

[0494] Example 1: Method for purifying pyrolysis oil according to the present invention

[0495] A feed stream F0 containing pyrolysis oil with a total acid value (TAN) of 20.4 mg (KOH) / g (feed), a total chlorine content of 590 wppm, a chloride content of 1 wppm, a nitrogen content of approximately 3260 wppm, an oxygen content of approximately 0.82 g (O) / 100 g (feed), and a density of 0.8653 g / ml was subjected to extraction with NaOH. Specifically, F0 (5 L of pyrolysis oil) was introduced into a stirred 12 L steel vessel and mixed with 1.5 L of demineralized water. Next, while stirring, the feed stream F0 containing 0.3 M NaOH solution (3.5 L of 0.3 M NaOH solution) was introduced... N The solution was pumped into the mixing unit (12 L steel container) for a period of 50 minutes. Once 3.5 L of NaOH solution (F) was added... N The resulting mixture was stirred for another 30 minutes. Mixing was then stopped, allowing the two-phase mixture to settle overnight in the mixing apparatus. The pH of the aqueous mixture was measured and found to be approximately 8. The entire procedure (i.e., mixing and settling) was carried out at 40°C to dissolve the contained wax. The oil phase was then mixed with the aqueous phase (F... W The process involves separating the aqueous phase from the mixing / sedimentation unit for wastewater treatment and removing the oil phase (stream F1) from the mixing / sedimentation unit for subsequent dechlorination. Compared to F0, the resulting oil phase (stream F1) contains pyrolysis oil with a reduced total acid number (TAN) of approximately 4 mg (KOH) / g (feed), while the N, O, and Cl contents remain largely unchanged.

[0496] Stream F1 was then subjected to dechlorination in a reactor containing a Cl adsorbent (hydroxyaluminum magnesium carbonate powder with a weight ratio of hydrotalcite:MgO:Al2O3 of 70:30) at 350°C and 50 bar in the presence of H2. Prior to use, the adsorbent was compacted, then crushed and sieved to an average particle size of 500–1000 micrometers. It was also calcined in air at 450°C for 5 h and equilibrated overnight in ambient air. Before introducing F1 into the reactor, the obtained Cl adsorbent was dried separately at 100°C and 200°C at ambient pressure in nitrogen at 2000 h / h with a gas hourly space velocity (GHSV) of 2000 / h, while simultaneously increasing the temperature at a ramp rate of 1 K / min. At 200°C, the gas was switched from N2 to H2, and the pressure was increased to 50 bar over 1 hour. After reaching this pressure, the GHSV was reduced to 475 / h, and the reactor was heated to 350°C at 1 K / min. Once 350°C was reached, S1 was introduced into the reactor at a liquid hourly space velocity (LHSV) of 0.95 / h. The resulting product stream was analyzed as shown in Table 2.1 and showed a reduced total chlorine content (approximately 90% reduction at the start of operation).

[0497] Table 1. Chlorine and chloride content of F1 and dechlorination product streams at different operating times (TOS).

[0498]

[0499] The intermediate products (F2) from the reaction process were combined to form feed F2. The resulting feed stream F2 had an average total chlorine content of 260 wppm and a chloride content of 1 wppm. Compared with F1, the N and O contents remained unchanged.

[0500] Comparative Example 1: A method for purifying pyrolysis oil not according to the present invention

[0501] Unlike Example 1, this method begins with a dechlorination step without extraction. A feed stream F0 containing pyrolysis oil (such as in Example 1) (i.e., having a total acid number (TAN) of approximately 20 mg (KOH) / g (feed), a total chlorine content of 560 wppm, a chloride content of 1 wppm, a nitrogen content of approximately 3260 wppm, an oxygen content of approximately 0.82 g (O) / 100 g (feed), and a density of 0.8653 g / ml) is subjected to dechlorination in a reactor containing a Cl adsorbent (hydrotalcite:MgO:Al2O3 powder in a weight ratio of 70:30, consisting of magnesium aluminum hydroxycarbonate) at 350°C and 50 bar in the presence of H2. Prior to use, the adsorbent is compacted, then crushed and sieved to an average particle size of 500–1000 micrometers. Furthermore, it is calcined in air at 450°C for 5 h and equilibrated overnight in ambient air. Before introducing FO into the reactor, the obtained Cl adsorbent was dried in nitrogen at ambient pressure for 1 hour at 100°C and 200°C with a gas hourly space velocity (GHSV) of 2000 / h, while the temperature was increased at a ramp rate of 1 K / min. At 200°C, the gas was switched from N2 to H2 and the pressure was increased to 50 bar over 1 hour. After reaching this pressure, the GHSV was reduced to 475 / h and the reactor was heated to 350°C at 1 K / min. Once 350°C was reached, FO was introduced into the reactor with a liquid hourly space velocity (LHSV) of 0.95 / h.

[0502] After 12.5 h TOS, the pressure drop in the reactor system increased by more than 10 bar, necessitating the cessation of feed feeding and the cooling, purging with toluene, and drying with nitrogen. The reactor pressure drop, measured externally at 100 mln (N2) / min at ambient outlet pressure, was 535 mbar, compared to 28 mbar measured before the test. The testing period was too short, causing the test setup to shut down due to excessive pressure before the first scheduled sampling 30 h later.

[0503] Table 2 Comparative pressure drop after dechlorination alone or after extraction + dechlorination / TAN

[0504]

[0505] Reference Example 9: Extraction - according to step (ii) of the invention

[0506] A feed stream F0 containing pyrolysis oil with a total acid number (TAN) of approximately 8.5 mg KOH / g, a total chlorine content of 24 wppm, a chloride content of < 5 wppm, a nitrogen content of 0.5 wt.-% (based on weight of the pyrolysis oil) and an oxygen content of 1 wt.-% (based on weight of the pyrolysis oil), a density of 916 kg / m³, and a viscosity of 6.4 mPas was subjected to extraction with KOH at T = 50°C and pH 7. For this purpose, F0 was introduced into a 1.3 L stirred glass vessel. Demineralized water was then added to the vessel (relative to v(water / pyrolysis oil) = 0.5 kg / kg) to form a mixture. The pH of the aqueous phase of the mixture was adjusted to 7.2 with 25 wt.-% KOH. The resulting mixture was mixed for 15 min. After settling (lasting 2 min), the resulting aqueous phase was separated from the organic phase. The organic phase was analyzed.

[0507] Next, a washing step was performed. Demineralized water was added to the organic phase at a ratio v(demineralized water / organic phase) = 0.5 kg / kg to remove salt and caustic alkali entrainments from the pyrolysis oil. The results are listed in Table 5 below.

[0508] Table 3

[0509]

[0510] pH of the aqueous phase

[0511] **The pH of the aqueous phase of F0 after washing F0 with demineralized water only.

[0512] As can be seen from Table 3, the contents of TAN, O, and N can be reduced at pH 7 and in the presence of KOH. Therefore, this type of extraction (conditions, etc.) can also be used prior to dechlorination as in Example 1. In practice, this will allow for the avoidance of scaling in the production unit, increase of TOS, and reduction of pressure drop, as demonstrated by the comparison between Example 1 and Comparative Example 1.

[0513] Example 2: Testing of the extracted pyrolysis oil obtained according to step (ii)

[0514] In this example, the extracted pyrolysis oil obtained according to (ii) of the invention (i.e., by extraction as described in Example 1) is subjected to heat treatment only and compared with the unextracted pyrolysis oil.

[0515] A feed stream F1 (extracted pyrolysis oil) with approximately 4 mg (KOH) / g (feed), approximately 3260 wppm nitrogen content, approximately 0.82 g (O) / 100 g (feed) oxygen content, 9.01 g (I2) / 100 g MAV, 6.1 area % styrene content as determined by GC, 560 wppm total chlorine content, 1 wppm chloride content, and 0.8653 g / ml density was obtained. This was then compared with a feed stream F1 (extracted pyrolysis oil) with approximately 20 mg (KOH) / g (feed), approximately 3260 wppm nitrogen content, approximately 0.82 g (O) / 100 g (feed) oxygen content, 9.01 g (I2) / 100 g MAV, 6.1 area % styrene content as determined by GC, 560 wppm total chlorine content, 1 wppm chloride content, and 0.8653 g / ml density. The density of the feed stream F11 (unextracted pyrolysis oil) was compared with that of g / ml.

[0516] F1 and F11 were subjected to different heat treatments. The feed was added at a rate of 20 ml / h to a reactor filled with inert material (such as corundum as shown in Reference Example 8), corresponding to an LHSV of 0.85 / h if the inert volume in the reaction zone is considered the reaction volume. Pressure and temperature were varied equally in both experiments, and samples were collected near the end of each condition. The degree of polymerization of styrene was determined under different conditions, and each sample was compared. The degree of polymerization was calculated from the area % value of the feed and the samples collected during the experiment. The total loss of styrene is equal to 100% of the degree of polymerization of styrene.

[0517] Table 4

[0518] Extraction feed (F1)

[0519]

[0520] Table 5

[0521] Unextracted feed (F11)

[0522]

[0523] Therefore, this example demonstrates that extraction prior to subsequent heat treatment not only allows for a reduction in the total acid number (TAN) of the obtained pyrolysis oil but also significantly reduces solid formation, particularly due to styrene polymerization—a reduction that is evident as can be seen from Tables 4 and 5 above. This allows for better subsequent purification of the pyrolysis oil and / or subsequent heating steps (lower pressure drop, longer expected TOS). Without wishing to be bound by any theory, this example shows that extraction of the pyrolysis oil prior to subsequent heat treatment according to the method of the invention prevents further polymerization of styrene monomers contained in the pyrolysis oil and thus reduces the amount of impurities in the pyrolysis oil that hinder further purification.

[0524] Reference Example 10: Particle Size (D50)

[0525] D50 particle size is determined by optical methods or by air sieves, for example by various instruments, namely the Cilas Particle Size Analyzer 1064 supplied by Quantachrome, the Malvern Mastersizer, or the Luftstrahlsieb (air sieve) supplied by Alpine.

[0526] Reference Example 11: Determination of Average Pore Volume

[0527] Pore ​​volume can be obtained by BET measurement (for micropores and mesopores) or, alternatively, by Hg porosity determination (for macropores). The Determination of Pore Volume and Area Distributions in Porous Substances. I. Computations from Nitrogen Isotherms. JACS 1951 (73) 373-380 EP Barret, LG Joyner, PP Halenda.

[0528] Reference Example 12: Determination of BET Specific Surface Area

[0529] The BET surface area of ​​the adsorbent material was measured using instruments supplied by either Konta (Nova series) or Micromeritics (Gemini series). This method requires low-temperature adsorption of nitrogen in the BET region of the adsorption isotherm.

[0530] Comparative Example 2: A method for purifying pyrolysis oil not according to the present invention

[0531] A feed stream F0 containing pyrolysis oil with a total acid number (TAN) of 7 mg KOH / g was subjected to a first washing step with demineralized water in a 250 ml glass bottle, wherein the ratio v(demineralized water / pyrolysis oil (F0)) = 1 kg / kg. The mixture was shaken. The pH of the aqueous phase of the mixture was pH 4.3. The resulting mixture of water / organic phase (oil) was introduced into a centrifuge. Thus, the aqueous phase and the organic (oil) phase were separated.

[0532] After separating the aqueous and organic phases, demineralized water was further added to the organic phase for a second washing step. Demineralized water was added at a ratio v(demineralized water / organic phase) = 1 kg / kg. The resulting water / organic phase (oil) mixture was introduced into a centrifuge. The aqueous and organic phases were separated. Finally, a third washing step was performed, and the aqueous and organic phases were separated by centrifugation. The washed organic phase was analyzed. The results are listed in Table 3 below.

[0533] Table 6

[0534]

[0535] pH of the aqueous phase

[0536] **The pH of the aqueous phase of F0 after washing F0 with demineralized water only.

[0537] As can be seen from Table 6, the washing step is insufficient to reduce the TAN value.

[0538] Reference Example 13: Testing for Different Bases

[0539] In this example, the pyrolysis oils (each having a total acid number (TAN) of approximately 8.5 mg KOH / g, a total chlorine content of 24 wppm, a chloride content of < 5 wppm, a nitrogen content of 0.5 wt.% based on the weight of the pyrolysis oil, an oxygen content of 1 wt.% based on the weight of the pyrolysis oil, a density of 916 kg / m³, and a viscosity of 6.4 mPas) were extracted in centrifuge glasses with NaOH or KOH under the conditions detailed in Table 9. Phase separation of these oils was observed after extraction (see Table 9).

[0540] Table 9

[0541]

[0542] As can be seen from Table 9, extraction of pyrolysis oil using NaOH at a pH of approximately 10 results in the formation of solids, making phase separation invisible in the gravitational field between the aqueous and oil phases. Further centrifugation is required to separate the solids, aqueous phase, and oil phase after extraction. When the pH decreases during extraction, less solids are formed, and phase separation between the aqueous and oil phases is clearly visible—making separation of the aqueous and oil phases easier after extraction. Furthermore, when using KOH to extract pyrolysis oil at a pH of approximately 10, less solids are formed. Without being bound by any theory, extraction of pyrolysis oil using NaOH may lead to the formation of sodium soaps (sodium salts of fatty acids), which are mostly solids and thus hinder phase separation of the aqueous and oil phases after extraction. In contrast, potassium soaps (potassium salts of fatty acids) are mostly liquids and therefore do not hinder phase separation of the aqueous and oil phases after extraction. Therefore, KOH can be chosen over NaOH to avoid these disadvantages. References

[0543] - WO 2017 / 083018 A1

[0544] - WO 2020 / 178597 A1

[0545] - WO 2014 / 165859 A1.

Claims

1. A method for purifying pyrolysis oil, the method comprising: (i) Providing a stream F0 containing pyrolysis oil, the pyrolysis oil containing one or more halogenated organic compounds and one or more organic compounds containing conjugated double bonds; (ii) Ensure that the flow F0 provided in (i) is in at least one extraction zone Z E The medium undergoes extraction to obtain a stream F1 containing the extracted pyrolysis oil, wherein (ii) includes: (ii.1) Introduce F0 into Z E middle; (ii.2) In Z E F0 is contacted with water and alkali B at temperatures ranging from 10°C to 200°C to obtain P containing an aqueous phase. A and organic phase P O The mixture M, the aqueous phase P of M A The pH range is 7 to 11; (ii.3) P A With P O Separate to obtain P A flow F A and P, which is extracted as pyrolysis oil O Flow F1; (iii) Ensure that the flow F1 obtained according to (ii) is in at least one heat treatment zone Z P After undergoing heat treatment, Z P Located in Z E Downstream, a stream F2 is obtained that is depleted from one or more of the organic compounds containing conjugated double bonds and one or more of the halogenated organic compounds compared to F1.

2. The method as described in claim 1, wherein, No organic solvents are used in the extraction according to (ii).

3. The method as described in claim 1 or 2, wherein, The extraction according to (ii) is carried out at a temperature in the range of 10°C to 95°C, preferably in the range of 15°C to 90°C, more preferably in the range of 20°C to 85°C, and even more preferably in the range of 25°C to 80°C. Wherein, the extraction according to (ii) is preferably performed at a pressure p in the range of 0.8 to 1.2 bar (absolute pressure), more preferably in the range of 0.9 to 1.1 bar (absolute pressure). E The following will proceed.

4. The method according to any one of claims 1 to 3, wherein, The base B is one or more of an alkali metal compound, an alkaline earth metal compound, and ammonia. Preferably, B is an alkali metal compound, which is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate. More preferably, it is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate. More preferably, it is one or more of potassium hydroxide and sodium hydroxide. More preferably, it is potassium hydroxide or sodium hydroxide. More preferably, it is potassium hydroxide.

5. The method according to any one of claims 1 to 4, wherein, For the extraction according to (ii), Z E The weight ratio of water to F0 is in the range of 0.05:1 to 2:1, preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, more preferably in the range of 0.1:1 to 0.7:1, more preferably in the range of 0.2:1 to 0.5:1, and even more preferably in the range of 0.3:1 to 0.5:

1.

6. The method according to any one of claims 1 to 5, wherein, (ii.2) Includes (ii.2.1) Introduce water and B, preferably a mixture of water and B, into Z. E middle; (ii.2.2) In Z E F0 is brought into contact with water and B, preferably a mixture of water and B, and then mixed to obtain a solution containing an aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, preferably in the range of 7 to 10; or (ii.2) includes (ii.2.1') ​​Introduce water into Z E middle; (ii.2.2') in Z E The FO is brought into contact with water and preferably mixed to obtain a mixture containing water and pyrolysis oil; (ii.2.3') Introduce B into Z E In and in Z E B is brought into contact with, preferably mixed with, the mixture obtained in (ii.2.2') to obtain a mixture containing the aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH is in the range of 7 to 11, preferably in the range of 7 to 10.

7. The method according to any one of claims 1 to 6, wherein, (ii) Includes (ii.1) Introduce F0 into Z E It includes the hybrid unit UM1; (ii.2) In UM1, F0 is mixed with water and alkali B at a temperature ranging from 10°C to 200°C, preferably from 10°C to 95°C, to obtain a mixture containing an aqueous phase P. A and organic phase P O The mixture M, the aqueous phase P of M A The pH range is 7 to 11; Remove M from UM1; (ii.3) P A With P O Separation, of which (ii.3) includes (ii.3.1) Make M enter Z E In the liquid-liquid separation unit US1, which is located downstream of UM1, P is obtained. A flow F A and P, which is extracted as pyrolysis oil O Flow F1; From Z E Move F1 out of the middle; Preferably, according to (ii.3), P is... A With P O Separation is carried out by decantation or centrifugation, more preferably by decantation.

8. The method according to any one of claims 1 to 7, wherein, According to (iii), the heat treatment is one or more of the following: dehalogenation, hydrogenation, hydrogenation treatment, dehalogenation heating, hydrogenation heating, hydrogenation treatment heating, and distillation.

9. The method according to any one of claims 1 to 8, wherein, (iii) Includes (iii.1) Optionally, the stream F1 obtained according to (ii) is placed in at least one reaction zone Z containing a heterogeneous hydrogenation catalyst. H Z undergoes hydrogenation H Included in Z P In this process, a stream F containing one or more organic compounds comprising conjugated double bonds is obtained that is depleted compared to F1. H ; (iii.2) Make the stream F1 obtained according to (ii) or the stream F obtained according to (iii.1) H Included in Z P In and located in Z H —If present—at least one downstream dehalogenation zone Z D The medium undergoes dehalogenation to obtain F1 or F when (iii.1) is performed. H Compared to F2 containing one or more halogenated organic compounds.

10. The method of claim 9, wherein, According to (iii.2), the dehalogenation zone Z D It includes an adsorption region, preferably an adsorption region, and preferably contains a heterogeneous adsorption material suitable for adsorbing at least one, preferably all, of the halides contained in the one or more halogenated organic compounds.

11. The method of any one of claims 9 or 10, wherein, (iii.2) Includes (iii.2.1) Introduce gas flow G1 into Z D —Preferredly in the adsorption zone—, the gas stream G1 preferably contains one or more of hydrogen and nitrogen, more preferably hydrogen; (iii.2.2) The stream F1 obtained from (ii) or F obtained from (iii.1) H Introducing Z D middle; (iii.2.3) Make F1 or F H With Z D The G1 contained therein comes into contact with an optional heterogeneous adsorbent material to obtain an adsorption of F1 or F1. H Compared to F2 containing one or more halogenated organic compounds; (iii.2.4) From Z D Move F2 out of the middle.

12. The method of claim 11, wherein, The gas flow G1 has a temperature in the range of 150°C to 500°C, preferably in the range of 300°C to 400°C; Preferably, the gas flow G1 is introduced at a pressure in the range of 1 to 100 bar (absolute pressure), more preferably in the range of 5 to 80 bar (absolute pressure), and even more preferably in the range of 10 to 50 bar (absolute pressure).

13. The method of claim 9, wherein, According to (iii.2), dehalogenation includes (iii.2.1') ​​Optionally, gas flow G11 can be introduced into Z. D In a reactor that contains no adsorbent material and no catalyst, the gas stream G11 preferably contains one or more of hydrogen and nitrogen, more preferably hydrogen; (iii.2.2') will be obtained from the stream F1 obtained in (ii) or F obtained in (iii.1). H Introducing Z D middle; (iii.2.3') The F1 or F in the reactor H Heating to a temperature in the range of 80°C to 400°C, preferably in the range of 200°C to 400°C, and if (iii.2.1') ​​is performed, then F1 or F H Contact G11 to obtain access to F1 or F H Compared to F2 containing one or more halogenated organic compounds; (iii.2.4') From Z D Move F2 out of the middle.

14. The method according to any one of claims 1 to 8, wherein, (iii) Includes (iii.1') Ensure that the stream F1 obtained according to (ii) is in at least one distillation zone Z L After distillation, Z L Included in Z P In this process, a stream F2, which is poor in the presence of one or more organic compounds compared to F1, and a stream F3, which is rich in the presence of one or more organic compounds compared to F1, are obtained.

15. The method according to any one of claims 1 to 14, further comprising, after (iii), one or more of a steam cracking step, a hydrocracking step, a hydrotreatment step, a distillation step, a stripping step, a storage step, and an aqueous extraction step.

16. A production unit for carrying out the method for purifying pyrolysis oil according to any one of claims 1 to 15, the unit comprising: - Used to introduce F0 into Z E The inlet device; - Used from Z E Remove the F1 outlet device from the middle; -At least one extraction zone Z E , -At least one heat treatment zone Z P Z P Located in Z E Downstream; - Used to introduce F1 into Z P The inlet device; - Used from Z D The F2 outlet device is moved out of the middle.

17. A method comprising the steps of: - Use the production unit according to claim 16 to obtain purified pyrolysis oil, monomer, polymer or polymer product.

18. A method, preferably comprising the steps of any one of claims 1 to 15, the method further comprising the following steps: - Convert the stream F2 that can be obtained or acquired by the method according to any one of claims 1 to 14 or the chemical material that can be obtained or acquired by the method according to claim 15 to obtain a monomer, polymer or polymer product.

19. The method as described in claim 17 or 18, in, The polymer or polymer product is granules, strands, rods, plates, tubes, foils, layers, films, sheets, fibers, filaments, coatings, extruded and / or molded articles, flexible foams, semi-rigid foams and / or rigid foams.

20. The method as described in any one of claims 17 to 19, in, The monomer is a diol or polyol; preferably butanediol; an aldehyde; preferably formaldehyde; a diisocyanate or polyisocyanate; preferably methylene diphenyl diisocyanate (MDI), polymeric methylene diphenyl diisocyanate (pMDI), toluene diisocyanate (TDI), hexamethylene diisocyanate (HDI) or isophorone diisocyanate (IPDI); an amide; preferably caprolactam; an olefin; preferably styrene, ethylene and norbornene; an alkyne, (di) ester; preferably methyl methacrylate; a monoacid or diacid; preferably adipic acid or terephthalic acid; a diamine; preferably hexamethylenediamine, nonadiamine; or a sulfone; preferably 4,4'-dichlorodiphenyl sulfone.

21. The method as described in any one of claims 17 to 20, in, The polymer and / or the polymer product contains polyamide (PA); preferably PA 6 and PA 66; a polyisocyanate addition polymer; preferably polyurethane (PU), thermoplastic polyurethane (TPU), polyurea or polyisocyanurate (PIR); low-density polyethylene (LDPE), high-density polyethylene (HDPE), polyethylene (PE), polypropylene (PP), polyvinyl chloride (PVC), polyvinyl acetate (PVA), polystyrene (PS), polyacrylonitrile-butadiene-styrene (ABS), polystyrene-acrylonitrile (SAN), polyacrylate-styrene-acrylonitrile (ASA), polytetrafluoroethylene (Teflon), thermoplastic polyurethane (TPU), poly(methyl acrylate) (PMA), poly(methyl methacrylate) (PMMA), polybutadiene (BR, PBD), poly(cis-1,4-isoprene), poly(trans-) Poly(1,4-isoprene), polyoxymethylene (POM), polyethylene terephthalate (PET), polybutylene terephthalate (PBT), polybutylene adipate terephthalate (PBAT), polyester (PES), polyethersulfone (PESU), polyhydroxyalkanoate (PHA), poly-3-hydroxybutyrate (P3HB), poly-4-hydroxybutyrate (P4HB), polyhydroxyvalerate (PHV), polyhydroxyhexanoate (PHH), polyhydroxyoctanoate (PHO), polylactic acid (PLA), polysulfone (PSU), polyphenylene sulfone (PPSU), polycarbonate (PC), polyetheretherketone (PEEK), poly(p-phenylene oxide) (PPO), poly(p-phenylene ether) (PPE); and copolymers and mixtures thereof.

22. The method as described in any one of claims 17 to 21, in, The polymer and / or the polymer product is one or more of the following: - Automotive parts, preferably cylinder head covers, engine hoods, turbocharger housings, turbocharger baffles, intake pipes, intake manifolds, connectors, gears, fan wheels, coolant tanks, heat exchanger housings or housing parts, coolant coolers, turbocharger coolers, thermostats, water pumps, radiators, fasteners or parts for electric vehicle battery systems, dashboards, steering column switches, seats, headrests, center consoles, transmission components, door modules, A, B, C or D pillar covers for automotive exteriors, spoilers, door handles, exterior mirrors, windshield wipers, windshield wiper protective housings, decorative grilles, cover strips, roof rails, window frames, sunroof frames, antenna panels, headlights and taillights, engine hoods, cylinder head covers, intake manifolds, airbags or buffer pads; - Fabrics, preferably shirts, trousers, sweaters, boots, shoes, shoe soles, bodysuits or jackets; - Electrical components, preferably electrical or electronic passive or active components, printed circuit boards, printed circuit boards, housing components, foil, wire, switches, plugs, sockets, distributors, relays, resistors, capacitors, inductors, spools, lamps, diodes, LEDs, transistors, connectors, voltage regulators, integrated circuits (ICs), processors, controllers, memory, sensors, connectors, microswitches, micro buttons, semiconductors, reflector housings for light-emitting diodes (LEDs), fasteners, gaskets, bolts, strips, slide-in guides, screws, nuts, membrane hinges, spring hooks (snap-in type) or spring tongues; - Consumer goods and / or pharmaceutical products, preferably tennis strings, climbing ropes, bristles, brushes, artificial turf, 3D printed filaments, lawnmowers, zippers, hook and loop fasteners, paper machine fabrics, extrusion coatings, fishing lines, fishing nets, offshore lines and ropes, vials, syringes, ampoules, bottles, sliding elements, spindle nuts, chain conveyors, sliding bearings, rollers, wheels, gears, ring gears, screws and spring dampers, hoses, pipes, cable sheaths, sockets, switches, cable ties, fan wheels, carpets, cosmetic boxes or bottles, mattresses, cushions or insulating materials; and / or Packaging for the food industry; preferred materials include single-layer or multi-layer blown film, cast film (single-layer or multi-layer), biaxial stretch film, and laminated film.

23. The method as described in any one of claims 17 to 22, in, The purified pyrolysis oil, monomers, polymers, and / or polymer products contain pyrolysis oil in stream F0 at a content of 1 wt% or more, preferably 2 wt% or more, more preferably 5 wt% or more, more preferably 15 wt% or more, more preferably 30 wt% or more, more preferably 40 wt% or more, more preferably 60 wt% or more, more preferably 80 wt% or more, more preferably 90 wt% or more, more preferably 95 wt% or more; and / or The content of the pyrolysis oil in the purified pyrolysis oil, monomer, polymer and / or polymer product in the stream F0 is 100% by weight or less, preferably 95% by weight or less, more preferably 90% by weight or less, more preferably 50% by weight or less, more preferably 25% by weight or less, more preferably 10% by weight or less; and Preferably, the content is determined based on an identity preservation and / or segregation and / or quality balance and / or book and claims custody model, preferably based on quality balance, and preferably based on the International Sustainability and Carbon Certification (ISCC) standard.

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