Method for inhibiting catalyst poisoning caused by contact of pyrolytic oil with steel vessel system

Abstract

The present invention relates to pyrolysis oils, mixtures and blends of pyrolysis oils comprising at least one catalyst poisoning inhibitor, the catalyst poisoning inhibitor being selected from amphiphilic compounds comprising at least one non-polar residue selected from C6 to C26 alkyl and / or alkylene and at least one polar residue, the at least one polar residue comprises at least one nitrogen atom. The invention further relates to a method for inhibiting catalyst poisoning and / or fouling during thermal processes and to the use of a catalyst poisoning inhibitor selected from amphiphilic compounds comprising at least one non-polar residue selected from C6 to C26 alkyl groups and / or alkylene groups and at least one polar residue, the at least one polar residue comprises at least one nitrogen or oxygen atom. Heterogeneous catalyst poisoning and / or fouling is reduced during thermal processes used in the purification, upgrading and / or conversion of pyrolytic oils derived from plastic waste, rubber materials and mixtures / blends of such pyrolytic oils in the presence of at least one inhibitor of catalyst poisoning.

Description

Technical Field

[0001] The present invention relates to pyrolysis oil comprising at least one catalyst poisoning inhibitor, a method for reducing catalyst poisoning and / or fouling during a thermal process in the purification, blending, upgrading and / or conversion of pyrolysis oil, and the use of a catalyst poisoning inhibitor in pyrolysis oil for reducing heterogeneous catalyst poisoning and / or fouling during a thermal process. Background Art

[0002] A liquid (referred to as pyrolysis oil) obtained from raw materials such as mixed waste plastics, rubber materials and textiles by a pyrolysis reaction is highly corrosive to a containment system made of steel, especially a containment system made of carbon steel and low alloy steel.

[0003] The reasons for the undesired corrosivity of pyrolysis oil are manifold. Compared with oils from fossil sources (such as crude oil), pyrolysis oil has a higher content of components such as water, oxygenates, one or more halogens and sulfur (for example, combined in organic compounds). In addition, the total acid number (TAN) of pyrolysis oil is higher than that of oils from fossil sources (such as crude oil). These compositional differences result in an increased corrosion of pyrolysis oil to a containment system made of steel (such as containers, pipes, reactors, heat exchangers, etc.), especially a containment system made of carbon steel and low alloy steel, during the storage, transportation, handling and conversion of pyrolysis oil.

[0004] For economic reasons, cheaper steel materials and less corrosion-resistant steels such as carbon steel (including construction steel) and low alloy steel are preferred materials for the containment system. Therefore, the increased corrosivity of pyrolysis oil to such materials compared with oils from fossil sources is a major problem.

[0005] One negative aspect of this increased corrosion behavior results in the enrichment of metal ions and metal compounds in pyrolysis oil during storage, transportation, handling and / or conversion in a containment system (such as storage containers, mixing containers and pipes). Metal ions and metal compounds transferred from the containment system material to pyrolysis oil include Fe 2+ 、Fe 3+ and Ni 2+ ions and soluble and insoluble compounds of such metal ions, such as the corresponding metal hydroxides, oxides and hydroxyoxides.

[0006] The pyrolysis oil needs to be subjected to specified purification and / or upgrading steps before being further used, for example, in steam cracking units, catalytic cracking units, fluid catalytic cracking units, partial oxidation units, and other downstream unit operations to obtain chemical products from such pyrolysis oil. Such purification and / or upgrading steps are needed, for example, to remove all kinds of unwanted components such as water, oxygenates, one or more halogens, and sulfur.

[0007] Catalyst poisons such as sulfur (e.g., incorporated in organic compounds and chloride compounds present in the pyrolysis oil) can be removed or their concentration reduced by conventional methods such as extraction, hydrotreating, adsorption, and dechlorination, which are disclosed, for example, in EP 3907267A1.

[0008] Some of the purification / upgrading methods applied use one or more catalysts that have active sites and / or pores that can be poisoned and / or fouled by Fe 2+ 、Fe 3+ and Ni 2+ ions and soluble and insoluble compounds of such metal ions (such as the corresponding metal hydroxides, oxides, and oxyhydroxides).

[0009] Metal ions transferred from the container system material to the pyrolysis oil and soluble and insoluble compounds of such metal ions are not significantly removed from the pyrolysis oil during the purification and / or upgrading steps because neither the purification nor the upgrading step is specifically directed at the removal of these metal ions and / or the corresponding metal compounds.

[0010] Thus, the metal ions and metal compounds remain in the pyrolysis oil and act as catalyst poisons for heterogeneous catalysts, and thereby reduce the activity and lifespan of the catalysts used in subsequent process steps. Catalyst poisons deactivate heterogeneous catalysts partially or completely, for example, by reducing the total number of active sites.

[0011] Metal ions (such as Fe 2+ 、Fe 3+ and Ni 2+ ) and compounds of such metal ions (such as hydroxides, oxides, and oxyhydroxides) are permanent poisons for noble and base metal catalysts applied in the purification and upgrading of pyrolysis oil, which is necessary before further using the pyrolysis oil as a feedstock for, for example, steam cracking, fluid catalytic cracking, catalytic cracking, partial oxidation, and other downstream processes.

[0012] The metal ions also tend to be adsorbed onto the walls of the vessel system (such as vessels, pipes, reactors), from which they may be slowly released again, thus also poisoning future catalyst charges.

[0013] For example, Ni 2+ ions are poisons when deposited on the catalyst surface because these ions can act as strong dehydrogenation catalysts, thus promoting undesired carbon deposition. Ni 2+ ions' effects in units used for fluid catalytic cracking are well documented, where Ni 2+ ions also increase the production of unwanted "light end" gases.

[0014] Another example is iron oxide (formed from Fe 2+ / Fe 3+ ions and oxygen present in, for example, the "aqueous impurity fraction" of pyrolysis oil and / or oxygen bound to organic residues (such as Fe-carboxylates)), which is a known poison for several types of hydrocarbon processing catalysts and which increases the unwanted deposition of carbon on the surface of such heterogeneous catalysts.

[0015] The finely dispersed iron oxide reacts with catalyst components containing sodium and / or silicon and thus accumulates on the catalyst surface and can form new low-temperature phases. Such new low-temperature phases can grow and cause masking of the existing active sites of the catalyst and / or pore blockage, both of which reduce the activity of the catalyst.

[0016] Fe 2+ 、Fe 3+ and Ni 2+ ions and their compounds being adsorbed onto the catalyst surface also reduce the activity of catalysts used in HDS (hydrodesulfurization) processes, which are common purification steps carried out before using pyrolysis oil as a cracker feedstock.

[0017] Several methods for preventing corrosion of the materials of the vessel system and the undesired transfer of Fe 2+ 、Fe 3+ and Ni 2+ ions and their compounds into pyrolysis oil are known in the art.

[0018] JP 2002060541 A discloses a pyrolysis reactor bed made of ceramics for preventing corrosion. Such a ceramic bed, although it can inhibit the release of Fe 2+ 、Fe 3+ and Ni 2+ ions and their compounds into pyrolysis oil, is very expensive and prone to mechanical damage, for example during temperature cycling (such as between filling the reactor and the pyrolysis reaction at temperatures in the hundreds of degrees Celsius).

[0019] US 2015 / 0135583 A1 discloses adding an adsorbent to plastic waste prior to the pyrolysis reaction. Such an adsorbent, although capable of removing some impurities present in the pyrolysis oil, is not suitable for inhibiting the release of Fe 2+ 、Fe 3+ and Ni 2+ ions and their compounds from the container system materials into the pyrolysis oil.

[0020] JP 2002179837 A discloses adding an alkaline substance to waste plastics containing PVC prior to the pyrolysis reaction. Acids (such as benzoic acid) formed during the pyrolysis reaction are neutralized, and thereby corrosion of equipment made of metal is reduced. The acids and the resulting low pH value of the pyrolysis oil are only one of the reasons for the release of Fe 2+ 、Fe 3+ and Ni 2+ ions and their compounds into the pyrolysis oil. Other reasons for the release of Fe 2+ 、Fe 3+ and Ni 2+ ions and their compounds into the pyrolysis oil, such as higher water content (compared to oils from fossil sources) and high oxygen content, are not solved by this method.

[0021] Document WO 2013 / 188021 A1 discloses a method that includes blending the pyrolysis oil with an alcohol having 8 carbon atoms, crude jatropha oil, and castor oil (both containing oleic fatty acid). Then the composition is filtered.

[0022] Document WO 2020 / 178599 A1 discloses a method that includes blending the pyrolysis oil with a upgrading solution, which can be a C10 alcohol, a C10 carbonate, or a C10 amide. Then the composition is separated from the pyrolysis oil.

[0023] Therefore, a more feasible way is needed to inhibit the release of Fe 2+ 、Fe 3+ and Ni 2+ ions and their compounds into the pyrolysis oil when in contact with container system materials (such as steel, more particularly carbon steel and low alloy steel), in order to inhibit or reduce catalyst poisoning and / or fouling during the thermal process. SUMMARY OF THE INVENTION

[0024] The first object of the present invention is to reduce heterogeneous catalyst poisoning and / or fouling during the thermal process used in the purification and / or upgrading of pyrolysis oil, pyrolysis oil mixtures, and blends of at least one pyrolysis oil with other hydrocarbon liquids (such as naphtha) derived from plastic waste and rubber materials. Preferably, the purification, upgrading, and / or conversion is a hydrotreating method carried out in the presence of hydrogen and at least one heterogeneous catalyst.

[0025] A second object of the present invention is to provide a method for suppressing fouling during a thermal process used in the conversion of pyrolysis oil, pyrolysis oil mixtures, and blends of at least one pyrolysis oil with other hydrocarbon liquids (such as naphtha) derived from plastic waste and rubber materials. Preferably, the conversion is a thermal process selected from the group consisting of steam cracking and partial oxidation. Most preferably, fouling during steam cracking and partial oxidation is reduced.

[0026] A third object of the present invention is to provide a pyrolysis oil in which metal ions (such as Fe 2+ 、Fe 3+ and Ni 2+ ) and compounds of such metal ions are not enriched or at least less enriched in the pyrolysis oil, pyrolysis oil mixtures, and blends of at least one pyrolysis oil with other hydrocarbon liquids (such as naphtha).

[0027] A fourth object of the present invention is to provide additives for use in pyrolysis oil, pyrolysis oil mixtures, and blends of at least one pyrolysis oil with other hydrocarbon liquids (such as naphtha) to inhibit the release of Fe 2+ 、Fe 3+ and Ni 2+ ions and their compounds from container system materials (such as steel, especially carbon steel and low alloy steel).

[0028] These objects are solved by a pyrolysis oil, a mixture of at least two pyrolysis oils, or a blend comprising at least one pyrolysis oil containing at least one catalyst poisoning inhibitor selected from amphiphilic compounds, the amphiphilic compounds comprising at least one non-polar residue selected from C6 to C26 alkyl and / or alkylene groups and at least one polar residue, the at least one polar residue comprising at least one nitrogen atom.

[0029] These objects are further solved by a method for suppressing catalyst poisoning and / or fouling during a thermal process for upgrading and / or converting pyrolysis oil, a mixture of at least two pyrolysis oils, and a blend comprising at least one pyrolysis oil, the method comprising the following steps:

[0030] (i) Providing a pyrolysis oil, a mixture of at least two pyrolysis oils, or a blend comprising at least one pyrolysis oil in a steel container system, wherein the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil is in physical and / or chemical contact with the steel container system,

[0031] (ii) Add at least one catalyst poisoning inhibitor to the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil, wherein the at least one catalyst poisoning inhibitor is selected from the group consisting of amphiphilic compounds, these amphiphilic compounds comprising at least one nonpolar residue selected from C6 to C26 alkyl and / or alkylene groups and at least one polar residue, the at least one polar residue comprising at least one heteroatom selected from the group consisting of nitrogen and oxygen,

[0032] (iii) Contact the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil comprising the at least one catalyst poisoning inhibitor with at least one heterogeneous catalyst, or subject the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil comprising the at least one catalyst poisoning inhibitor to a thermal process.

[0033] These objects are further solved by using at least one additive as a catalyst poisoning inhibitor in the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil to inhibit the enrichment of catalyst poisons selected from the group consisting of Fe 2+ ions, Fe 3+ ions, Ni 2+ ions and compounds of said metal ions in the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil, the at least one additive being selected from amphiphilic compounds, these amphiphilic compounds comprising at least one nonpolar residue selected from C6 to C26 alkyl and / or alkylene groups and at least one polar residue comprising at least one heteroatom selected from the group consisting of nitrogen and oxygen.

[0034] Thereby, the poisoning of the heterogeneous catalyst and / or the fouling of the adsorbent and / or the membrane are reduced, and the lifetime of the heterogeneous catalyst and / or the adsorbent and / or the membrane used in subsequent process steps is prolonged, and their activity is maintained for a longer time and / or throughput. Detailed Description

[0035] "Blend" is defined herein as a blend comprising at least one pyrolysis oil blended (mixed) with at least one other hydrocarbon liquid such as naphtha or high vacuum residue (also referred to as "HVR", "vacuum residue" and "residue", which is the heaviest of the distillation fractions and can be obtained from the bottom fraction of the vacuum distillation column of an oil refinery). Blending is used, for example, to change physical properties such as reducing viscosity, and / or to change chemical properties such as reducing the concentration of certain components (e.g., sulfur) by diluting the one or more pyrolysis oils with at least one other hydrocarbon liquid.

[0036] "Catalyst" is defined herein as a heterogeneous catalyst, which is a solid material including a surface and having active sites necessary for the desired catalytic properties of such a catalyst.

[0037] "ppm" is defined herein as parts per million notation with respect to mass fraction.

[0038] In the context of this specification and the appended claims, the term "about" preferably means a deviation of ±15% of the value so described.

[0039] In the context of the present invention, the term "in combination therewith" includes one or more of the recited elements.

[0040] In the context of the present invention, the term "in mixture therewith" includes one or more of the recited elements.

[0041] Pyrolysis oil can be produced by pyrolysis reaction from raw materials such as plastic waste, mixed plastic waste, rubber waste, textiles, mixtures thereof, etc. Pyrolysis oil can also be produced from mixtures of the above raw materials with other types of waste and impurities.

[0042] Examples of waste plastics include pure plastic waste, mixed plastic waste, film waste (including dirt, adhesive materials, fillers, residues, etc.), industrial plastic waste, and municipal plastic waste. Mixed plastic waste is composed of different types of polymers.

[0043] Examples of rubber waste include scrap tires, rubber waste generated during manufacturing processes, and discarded rubber-containing products such as latex examination gloves. Scrap tires contain additional components such as textiles and organic and inorganic additives, which can be separated from the rubber part of the scrap tires before pyrolysis.

[0044] Preferably, pyrolysis oil to which at least one catalyst poisoning inhibitor is added is produced by pyrolysis from a raw material containing rubber waste.

[0045] Preferably, at least one of the pyrolysis oils in a mixture containing two pyrolysis oils to which the at least one catalyst poisoning inhibitor is added is produced by pyrolysis from a raw material containing rubber waste.

[0046] Preferably, at least one of the pyrolysis oils in a blend containing at least one pyrolysis oil to which the at least one catalyst poisoning inhibitor is added is produced by pyrolysis from a raw material containing rubber waste.

[0047] Most preferably, pyrolysis oil to which at least one catalyst poisoning inhibitor is added is produced by pyrolysis from a raw material containing scrap tires or parts thereof (such as rubber components).

[0048] Pyrolysis is the thermal decomposition or degradation of such feedstocks under inert conditions and results in the formation of a gas fraction, a liquid fraction and a solid carbon fraction. During pyrolysis, the feedstock is converted into a variety of chemical substances, including a) gases such as H2, C1-C4-alkanes, C2-C4-olefins, acetylene, propyne, 1-butyne, b) pyrolysis oil having a boiling temperature in the range from 25 °C to 500 °C, and c) carbon.

[0049] The pyrolysis processes themselves are known. They are described, for example, in EP 0713906 A1 and WO 95 / 03375 A1. Suitable pyrolysis oils are also commercially available. Pyrolysis oil is typically liquid at 15 °C. "Liquid at 15 °C" in the context of the present invention means that the pyrolysis oil has a density of at most 1.3 g / ml at 15 °C and 1013 mbar, as determined according to DIN EN ISO 12185, for example in the range from 0.65 to 0.98 g / ml.

[0050] The pyrolysis oil obtained from the pyrolysis reaction contains:

[0051] - at least 30 mg / l of sulfur, preferably from 100 to 5000 mg / l of sulfur, more preferably from 200 to 4000 mg / l of sulfur (determined according to ASTM D5453);

[0052] - at least 30 mg / l of nitrogen, preferably from 100 to 4000 mg / l of nitrogen, more preferably from 200 to 4000 mg / l of nitrogen (determined according to ASTM D6069);

[0053] - at least 5 mg / l of halogens, preferably from 10 to 1000 mg / l of halogens, more preferably from 20 to 800 mg / l of halogens (determined according to ASTM D 5808);

[0054] - at least 0.01 wt.-% of water, preferably from 0.1 to 5 wt.-% of water, more preferably from 0.2 to 3 wt.-% of water (determined according to ASTM E 1064);

[0055] - at least 100 ppm of oxygenates; preferably from 200 to 5000 ppm of oxygenates, more preferably from 300 to 1800 ppm of oxygenates (determined according to ASTM 5291);

[0056] - at least 2 wt.-% of olefins, preferably from 2.1 to 15 wt.-% of olefins, more preferably from 2.3 to 10 wt.-% of olefins (determined by gas chromatography);

[0057] - a total acid number (TAN) of from 0.1 to 18 (determined by titration with a KOH solution and given as the amount of KOH (in mg) required to neutralize the acids in one gram of pyrolysis oil).

[0058] - A pH value in the range of about 2 to about 5.

[0059] Examples of sulfur-containing compounds include thiols, sulfides, disulfides, sulfoxides, sulfones, sulfinic acids, sulfonic acids, sulfonamides, sulfonates, sulfates, thiones, thiocarboxylic acids, thioesters, dithiocarboxylic acids, thiocyanates, sulfonamides, etc.

[0060] Examples of nitrogen-containing compounds include amines, imines, amides, imides, azides, azo compounds, oximes, hydrazones, hydrazines, cyanates, nitrates, nitriles, nitrites, nitro compounds, nitroso compounds, oximes, N-containing heteroaromates, carbamates, sulfonamides, thiocyanates, sulfonamides.

[0061] Examples of halogens are halogen-containing compounds, including aliphatic halides, (hetero)aromatic halides, aliphatic-aromatic halides, acyl halides, etc. Halogens can also be present as anions (such as F - , Cl - , Br - and I - ) in the pyrolysis oil.

[0062] Examples of oxygen-containing compounds are compounds containing oxygen as part of their chemical structure. Oxygen-containing compounds include, for example, compounds such as alcohols, ethers, aldehydes, ketones, and carboxylates / carboxylic acids.

[0063] Examples of carboxylic acids include formic acid, acetic acid, higher carboxylic acids, carboxylic acids having at least two carboxylic acid residues, benzoic acid, and its salts.

[0064] The pyrolysis oil obtained by the pyrolysis reaction preferably further has a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g (determined by ASTM 1159) and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-% (determined by ASTM D5134) and / or a naphthalene content of about 0.5 wt.-% to about 18.4 wt.-% (determined by ASTM D 5134) and / or a styrene content of about 0.02 wt.-% to about 29.5 wt.-% (determined by ASTM D 5134) and / or a toluene content of about 4.3 wt.-% to about 71.5 wt.-% (determined by ASTM D 5134). Such pyrolysis oil is particularly suitable as one or more pyrolysis oils for the methods and uses according to the present invention.

[0065] A mixture of pyrolysis oils can be obtained by mixing two or more pyrolysis oils made from different feedstocks and / or made under different pyrolysis reaction conditions and / or made in different batches from the same feedstock and pyrolysis reaction conditions.

[0066] A blend comprising at least one pyrolysis oil can be obtained by blending at least one pyrolysis oil with at least one other hydrocarbon liquid (such as naphtha, high vacuum residue (HVR), etc.). Other hydrocarbon liquids suitable for blending with at least one pyrolysis oil are known to those skilled in the art.

[0067] In one embodiment of the present invention, at least one pyrolysis oil is blended with one or more other hydrocarbon liquids (such as naphtha and / or high vacuum residue). Such blends comprise, for example, about 30 wt.-% of one or more pyrolysis oils and about 70 wt.-% of one or more other hydrocarbon liquids; about 50 wt.-% of one or more pyrolysis oils and about 50 wt.-% of one or more other hydrocarbon liquids; or about 70 wt.-% of one or more pyrolysis oils and about 30 wt.-% of one or more other hydrocarbon liquids. Such blends can additionally contain water. The resulting blends comprise, for example, about 30 wt.-% of one or more pyrolysis oils, 30 wt.-% of one or more other hydrocarbon liquids, and about 30 wt.-% of water.

[0068] The pyrolysis oil and / or a mixture and / or blend of at least two different pyrolysis oils are in physical and / or chemical contact with the container system during pyrolysis reactions, storage, transportation, handling, purification, upgrading, mixing with other pyrolysis oils, and blending of at least one pyrolysis oil with at least one other hydrocarbon liquid (such as naphtha, etc.).

[0069] When in physical and / or chemical contact with a container system, the temperature of the pyrolysis oil, a mixture of two or more pyrolysis oils, or a blend containing at least one pyrolysis oil ranges from a low temperature (such as room temperature or the temperature outside a building where the pyrolysis oil can be stored and / or transported) to several hundred degrees Celsius applied during the pyrolysis reaction. During transportation in a pipeline or other processing operations, the temperature of the pyrolysis oil, a mixture of two or more pyrolysis oils, or a blend containing at least one pyrolysis oil can be raised to, for example, 50 °C or 70 °C to obtain a reduced viscosity and thus more favorable fluid properties. During storage, transportation, and / or processing, the temperature of the pyrolysis oil, a mixture of two or more pyrolysis oils, or a blend containing at least one pyrolysis oil ranges from about -10 °C to about 100 °C. The temperature of the pyrolysis oil, a mixture of two or more pyrolysis oils, or a blend containing at least one pyrolysis oil can be raised to about 270 °C or even higher, such as 300 °C, 400 °C, 500 °C, in a thermal process (such as preheating), and then the pyrolysis oil is fed, for example, into a steam cracking reactor or a partial oxidation reactor for steam cracking or partial oxidation. During all of the aforementioned temperatures, the pyrolysis oil, a mixture of two or more pyrolysis oils, or a blend containing at least one pyrolysis oil is preferably in contact with a steel container system.

[0070] The thermal process in step (iii) is most preferably selected from the group consisting of: preheating for steam cracking, steam cracking, preheating for partial oxidation, and partial oxidation.

[0071] Therefore, the temperature range is from about 10 °C to about 300 °C. This temperature range also applies to blends containing at least one pyrolysis oil and pyrolysis oil mixtures containing at least two pyrolysis oils.

[0072] "Container system" is defined herein as a device for storing, transporting, guiding, processing, and subjecting pyrolysis oil, a mixture containing at least two pyrolysis oils, or a blend containing at least one pyrolysis oil to a thermal process. The container system can also be a reactor in which a) the pyrolysis oil is made by a pyrolysis reaction and / or b) the pyrolysis oil or a portion thereof is chemically and / or physically transformed, for example, in / during a thermal process. "Container system" includes, but is not limited to, fixed containers, movable containers, pipelines, reactors, heat exchangers, valves, etc.

[0073] The container system according to the present invention is made of or contains steel material. The steel material is in physical and / or chemical contact with the pyrolysis oil, a mixture containing at least two pyrolysis oils, or a blend containing at least one pyrolysis oil.

[0074] The steel material can in principle be any type of material known as steel, such as stainless steel, high-alloy steel, low-alloy steel, carbon steel, etc. For economic reasons, the steel material is preferably selected from carbon steel or low-alloy steel. Carbon steel and low-alloy steel are cheaper than, for example, stainless steel, but are less resistant to corrosion caused by pyrolysis oil.

[0075] "Carbon steel" is defined herein as steel containing C in the range of about 0.05 to about 2.0 wt.-%.

[0076] "Carbon steel" also includes steel that, in addition to a C content in the range of about 0.05 to about 2.0 wt.-%, also has. There is no stipulation or requirement for a minimum content for Cr, Co, Mo, Ni, Nb, Ti, V, W, Zr or any other element to be added to obtain the desired alloying effect; the stipulated minimum value for Cu does not exceed 0.4 wt.-%; or the maximum content of any of the following elements does not exceed the marked percentage: 1.65 wt.-% Mn; 0.6 wt.-% Si; 0.6 wt.-% Cu.

[0077] More preferably, the carbon steel is low-carbon steel having a C content of about 0.05 to about 0.15 wt.-% and / or medium-carbon steel having a C content of about 0.3 to about 0.5 wt.-%.

[0078] "Low-alloy steel" is defined herein as steel containing about 1 to about 5 wt.-% of a single alloying element and less than 10.5 wt.-% of all alloying elements together. Alloying elements include, but are not limited to, one or more of the following chemical elements: Co, Cr, Mo, Ni, Nb, Ti, V, W, Zr.

[0079] Compared with oil from fossil sources (such as crude oil), the specific composition of pyrolysis oil with higher contents of components (such as sulfur, nitrogen, halogens, water, oxygenates, olefins) and a higher total acid number TAN results in more severe corrosive attack on the steel of the container system, especially when these container systems are made of or contain carbon steel and low-alloy steel. Therefore, undesirable metal ions (such as Fe 2+ 、Fe 3+ and Ni 2+ ions) and / or their compounds are released from the container system material into the pyrolysis oil and cause poisoning of the heterogeneous catalyst with which the pyrolysis oil comes into contact and / or fouling of the adsorbent and / or membrane during subsequent process steps such as purification and / or upgrading.

[0080] To prevent such poisoning of the heterogeneous catalyst and / or fouling of the adsorbent and / or membrane from occurring in subsequent process steps, at least one catalyst poisoning inhibitor is added to the pyrolysis oil, a mixture containing at least two pyrolysis oils, or a blend containing at least one pyrolysis oil.

[0081] The pyrolysis oil according to the invention, a mixture of at least two pyrolysis oils or a blend comprising at least one pyrolysis oil contains at least one catalyst poisoning inhibitor selected from amphiphilic compounds, which amphiphilic compounds comprise at least one nonpolar residue selected from C6 to C26 alkyl and / or alkylene groups and at least one polar residue, the at least one polar residue comprising at least one nitrogen atom.

[0082] "Amphiphilic" is defined herein as a molecule and / or ion that simultaneously comprises hydrophilic (polar) and lipophilic (nonpolar) properties.

[0083] The at least one catalyst poisoning inhibitor is preferably selected from the group consisting of:

[0084] -

[0085] - saturated, mono-unsaturated and poly-unsaturated C6 to C26 fatty acids coupled to an N-heterocyclic compound via a C-C bond;

[0086] - nitrogen compounds quaternized with a polycarboxylic acid substituted with a hydrocarbyl epoxide and a free hydrocarbyl group; and

[0087] - mixtures thereof.

[0088] Suitable adducts of saturated, mono-unsaturated and poly-unsaturated C6 to C26 fatty acids coupled to an N-heterocyclic compound via a C-C bond include 2-(2-heptadec-8-enyl-2-imidazolin-1-yl)ethanol (CAS-number 95-38-5), which can be obtained by heating oleic acid with 2-(2-aminoethylamino)ethanol to 270 °C for five hours and removing the water formed by azeotropic distillation with xylene.

[0089] Suitable nitrogen compounds quaternized with a polycarboxylic acid substituted with a hydrocarbyl epoxide and a free hydrocarbyl group include C16-alkyl-N(CH3)2 quaternized with propylene oxide in the presence of polyisobutylene succinic acid. Other suitable nitrogen compounds quaternized with a polycarboxylic acid substituted with a hydrocarbyl epoxide and a free hydrocarbyl group and synthetic methods for obtaining such quaternized compounds are disclosed in WO 2014 / 195464 A1 and WO 2015 / 113681 A1, both of which are incorporated by reference.

[0090] The term "and mixtures thereof" with respect to the at least one catalyst poisoning inhibitor is to be understood to mean that the inhibitor comprises, for example, one or more saturated, mono-unsaturated and poly-unsaturated C6 to C26 fatty acids coupled to an N-heterocyclic compound via a C-C bond, or, for example, a combination of one or more saturated, mono-unsaturated and poly-unsaturated C6 to C26 fatty acids coupled to an N-heterocyclic compound via a C-C bond and, for example, one or more nitrogen compounds quaternized with polycarboxylic acids in which the hydrocarbon radicals are substituted by hydrocarbon epoxides and liberated hydrocarbon radicals.

[0091] The concentration range of the at least one catalyst poisoning inhibitor in the pyrolysis oil is from 5 to 20,000 ppm, preferably from 10 to 15,000 ppm and more preferably from 20 to 10,000 ppm.

[0092] The at least one catalyst poisoning inhibitor can also be used in mixtures of at least two pyrolysis oils and blends comprising at least one pyrolysis oil.

[0093] The concentration range of the at least one catalyst poisoning inhibitor in a mixture of at least two pyrolysis oils is from 5 to 20,000 ppm, preferably from 10 to 15,000 ppm and more preferably from 20 to 10,000 ppm.

[0094] The concentration range of the at least one catalyst poisoning inhibitor in a blend comprising at least one pyrolysis oil is from 5 to 20,000 ppm, preferably from 10 to 15,000 ppm and more preferably from 20 to 10,000 ppm.

[0095] The at least one catalyst poisoning inhibitor can also be used in a method for inhibiting catalyst poisoning and / or fouling during a thermal process for upgrading and / or converting pyrolysis oil, a mixture of at least two pyrolysis oils and a blend comprising at least one pyrolysis oil, the method comprising the steps of:

[0096] (i) providing the pyrolysis oil, the mixture of at least two pyrolysis oils or the blend comprising at least one pyrolysis oil in a steel container system, wherein the pyrolysis oil, the mixture of at least two pyrolysis oils or the blend comprising at least one pyrolysis oil is in physical and / or chemical contact with the steel container system,

[0097] (ii) adding at least one catalyst poisoning inhibitor to the pyrolysis oil, the mixture of at least two pyrolysis oils or the blend comprising at least one pyrolysis oil, wherein the at least one catalyst poisoning inhibitor is selected from the group consisting of amphiphilic compounds comprising at least one non-polar residue selected from C6 to C26 alkyl and / or alkylene groups and at least one polar residue, the at least one polar residue comprising at least one heteroatom selected from the group consisting of nitrogen and oxygen,

[0098] (iii) contacting the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil and containing the at least one catalyst poisoning inhibitor with at least one heterogeneous catalyst, or subjecting the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil and containing the at least one catalyst poisoning inhibitor to a thermal process.

[0099] Preferably, the at least one catalyst poisoning inhibitor in the method is selected from the group consisting of:

[0100] - saturated, mono-unsaturated and poly-unsaturated C6 to C26 fatty acids;

[0101] - dimer fatty acids;

[0102] - copolymers of at least one ethylenically unsaturated polymerizable polycarboxylic anhydride and at least one polymerizable olefin;

[0103] - alkenyl succinic acids and alkenyl succinic anhydrides, wherein the alkenyl residue is selected from C6 to C26 alkenyls having one or more C═C bonds;

[0104] - saturated, mono-unsaturated and poly-unsaturated C6 to C26 fatty acids coupled to an N-heterocyclic compound via a C-C bond;

[0105] - nitrogen compounds quaternized with polycarboxylic acids substituted with a hydrocarbyl epoxide and a free hydrocarbyl group; and

[0106] - mixtures thereof.

[0107] Preferably, the pyrolysis oil provided in step (i) according to the present invention contains at least 30 mg / l of sulfur, at least 30 mg / l of nitrogen, at least 5 mg / l of halogen and at least 100 ppm of oxygenates.

[0108] More preferably, the pyrolysis oil provided in step (i) according to the present invention contains 100 to 5000 mg / l of sulfur, 100 to 5000 mg / l of nitrogen, 10 to 1000 mg / l of halogen and 200 to 5000 ppm of oxygenates.

[0109] Preferably, the mixture of at least two pyrolysis oils provided in step (i) according to the present invention contains at least 30 mg / l of sulfur, at least 30 mg / l of nitrogen, at least 5 mg / l of halogen and at least 100 ppm of oxygenates.

[0110] More preferably, the mixture of at least two pyrolysis oils provided in step (i) according to the present invention contains 100 to 5000 mg / l of sulfur, 100 to 5000 mg / l of nitrogen, 10 to 1000 mg / l of halogen, and 200 to 100000 ppm of oxygenates.

[0111] Preferably, the at least one pyrolysis oil in the blend (the blend comprising at least one pyrolysis oil) provided in step (i) according to the present invention contains at least 30 mg / l of sulfur, at least 30 mg / l of nitrogen, at least 5 mg / l of halogen, and at least 100 ppm of oxygenates.

[0112] More preferably, the at least one pyrolysis oil in the blend (the blend comprising at least one pyrolysis oil) provided in step (i) according to the present invention contains 100 to 5000 mg / l of sulfur, 100 to 5000 mg / l of nitrogen, 10 to 1000 mg / l of halogen, and 200 to 100000 ppm of oxygenates.

[0113] Preferably, the steel container system comprises one or more materials selected from the group consisting of carbon steel and low alloy steel.

[0114] Preferably, the concentration range of the at least one catalyst poisoning inhibitor in the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil is 5 to 20000 ppm, more preferably 10 to 15000 ppm, and most preferably 20 to 10000 ppm.

[0115] After separating the gaseous and solid products formed by the pyrolysis reaction, the at least one catalyst poisoning inhibitor can be added to the pyrolysis oil. The at least one catalyst poisoning inhibitor can also be added to the pyrolysis oil in subsequent process steps, for example, when or after filling the pyrolysis oil into a storage container or when or after filling the pyrolysis oil into a transport container and after filtration of the pyrolysis oil. The at least one catalyst poisoning inhibitor can also be added to the pyrolysis oil before, during, and / or after purification of the pyrolysis oil by one or more purification steps selected from extraction, distillation, hydrotreating, absorption, and adsorption. The addition of the at least one catalyst poisoning inhibitor to the pyrolysis oil is not limited to a specific process step or time.

[0116] The at least one catalyst poisoning inhibitor can be added to the mixture of at least two pyrolysis oils before, during, and / or after mixing the individual pyrolysis oils.

[0117] The at least one catalyst poisoning inhibitor can be added to a blend comprising at least one pyrolysis oil before blending into the at least one pyrolysis oil, during blending, and / or after blending.

[0118] In one embodiment of the present invention, a mixture of the at least one catalyst poisoning inhibitor and the pyrolysis oil is formed by forced agitation (such as by stirring) or any other suitable means to obtain a uniform contribution of the at least one catalyst poisoning inhibitor in the pyrolysis oil.

[0119] In another embodiment of the present invention, the at least one catalyst poisoning inhibitor is added to the pyrolysis oil without forced agitation.

[0120] When adding the at least one catalyst poisoning inhibitor, both forced agitation and non-forced agitation can also be applied to a mixture of at least two pyrolysis oils and a blend comprising at least one pyrolysis oil.

[0121] At least one additive can be used as a catalyst poisoning inhibitor in a pyrolysis oil, a mixture comprising at least two pyrolysis oils, or a blend comprising at least one pyrolysis oil to inhibit catalyst poisons selected from the group consisting of Fe 2+ ions, Fe 3+ ions, Ni 2+ ions, and compounds of said metal ions from enriching in the pyrolysis oil, the mixture comprising at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil, and the at least one additive is selected from amphiphilic compounds that comprise at least one nonpolar residue selected from C6 to C26 alkyl and / or alkylene groups and at least one polar residue that comprises at least one heteroatom selected from the group consisting of oxygen and nitrogen.

[0122] Preferably, for said use, the at least one additive is selected from the group consisting of:

[0123] - saturated, mono-unsaturated and poly-unsaturated C6 to C26 fatty acids;

[0124] - dimer fatty acids;

[0125] - copolymers of at least one ethylenically unsaturated polymerizable polycarboxylic anhydride and at least one polymerizable olefin;

[0126] - alkenyl succinic acids and alkenyl succinic anhydrides, wherein the alkenyl residue is selected from C6 to C26 alkenyl groups having one or more C═C bonds;

[0127] - saturated, mono-unsaturated and poly-unsaturated C6 to C26 fatty acids coupled via a C-C bond to an N-heterocyclic compound;

[0128] - Quaternary ammonium compounds of nitrogen substituted with a hydrocarbyl epoxide and a free hydrocarbyl;

[0129] - And mixtures thereof.

[0130] Preferably, for said use, the concentration range of the at least one additive in the pyrolysis oil, the mixture containing at least two pyrolysis oils or the blend containing at least one pyrolysis oil is 5 to 20,000 ppm, more preferably 10 to 15,000 ppm and most preferably 20 to 10,000 ppm.

[0131] Preferably, for said use, the pyrolysis oil contains at least 30 mg / l of sulfur, at least 30 mg / l of nitrogen, at least 5 mg / l of halogen and at least 100 ppm of oxygenated compounds.

[0132] More preferably, for said use, the pyrolysis oil contains 100 to 5000 mg / l of sulfur, 100 to 4000 mg / l of nitrogen, 10 to 1000 mg / l of halogen and 200 to 5000 ppm of oxygenated compounds.

[0133] Preferably, for said use, the pyrolysis oil mixture containing at least two pyrolysis oils contains at least 30 mg / l of sulfur, at least 30 mg / l of nitrogen, at least 5 mg / l of halogen and at least 100 ppm of oxygenated compounds.

[0134] More preferably, for said use, the pyrolysis oil mixture containing at least two pyrolysis oils contains 100 to 5000 mg / l of sulfur, 100 to 5000 mg / l of nitrogen, 10 to 1000 mg / l of halogen and 200 to 5000 ppm of oxygenated compounds.

[0135] Preferably, for said use, the at least one pyrolysis oil in the blend containing at least one pyrolysis oil contains at least 30 mg / l of sulfur, at least 30 mg / l of nitrogen, at least 5 mg / l of halogen and at least 100 ppm of oxygenated compounds.

[0136] More preferably, for said use, the at least one pyrolysis oil in the blend containing at least one pyrolysis oil contains 100 to 5000 mg / l of sulfur, 100 to 5000 mg / l of nitrogen, 10 to 1000 mg / l of halogen and 200 to 5000 ppm of oxygenated compounds.

[0137] Preferably, for said use, the pyrolysis oil, the pyrolysis oil mixture containing at least two pyrolysis oils or the blend containing at least one pyrolysis oil is in physical and / or chemical contact with a steel container system made of a material selected from carbon steel and low alloy steel.

[0138] It is assumed that the at least one catalyst poisoning inhibitor can form a film on the surface of the container system by adsorption, which adsorption includes the interaction of the at least one catalyst poisoning inhibitor with the surface of the container system through physical adsorption and / or chemical adsorption.

[0139] The pyrolysis oil containing at least one catalyst poisoning inhibitor, the pyrolysis oil mixture containing at least two pyrolysis oils or the blend containing at least one pyrolysis oil, and the method of using such a pyrolysis oil composition reduce the undesired poisoning of the heterogeneous catalyst used in or after the purification, upgrading and / or blending of pyrolysis oil.

[0140] Examples of purification processes involving heterogeneous catalysts are hydrotreating or hydroprocessing techniques for removing sulfur compounds (hydrodesulfurization, HDS) and nitrogen compounds (hydrodenitrogenation, HDN) from pyrolysis oil. Such catalysts typically comprise at least one Group 6 metal component and at least one Group 8, 9, and 10 metal component in combination with a support. The catalysts used in such purification methods are highly sensitive to poisoning caused by, for example, Fe 2+ ions, Fe 3+ ions, Ni 2+ ions and compounds of said metal ions. When using the pyrolysis oil composition and method according to the invention, the lifetime of the catalysts is increased and their activity is maintained over a longer period of time.

[0141] Furthermore, in the presence of Fe 2+ and / or Fe 3+ ions adsorbed on the steel surface, at elevated temperatures, undesired coking may occur in parts such as pipes made of, for example, steel, preferably carbon steel or low alloy steel. Such undesired coking may lead to blockage of parts such as pipes.

[0142] The pyrolysis oil containing at least one catalyst poisoning inhibitor, the pyrolysis oil mixture containing at least two pyrolysis oils or the blend containing at least one pyrolysis oil, and the method of using such a pyrolysis oil composition also reduce the undesired fouling during the thermal processes in or after the purification, upgrading, blending and / or conversion of pyrolysis oil.

[0143] A small amount of the at least one catalyst poisoning inhibitor in the pyrolysis oil, the pyrolysis oil mixture containing at least two pyrolysis oils or the blend containing at least one pyrolysis oil in an amount of 5 to 20000 ppm, preferably 10 to 15000 ppm and more preferably 20 to 10000 ppm has no negative impact during the purification, upgrading, blending and / or conversion process.

[0144] The present invention will be further explained by the following non-limiting examples.

[0145] Example

[0146] During storage in the materials of a steel container system, the enrichment of metal ions (such as Fe 2+ , Fe 3+ and Ni 2+ ) and compounds of such metal ions is tested with pyrolysis oil by evaluating the corrosion attack on a steel finger made of carbon steel (BS970 - 070M20; also known as DIN 1.0402) after immersion in the pyrolysis oil at 60 °C for 4 hours. The tests are carried out without and with the addition of different amounts of the catalyst poisoning inhibitor according to the invention.

[0147] The pyrolysis oil is obtained from DRON Industries (manufactured from end - of - life tires (ELT) by DRON Industries using a proprietary pyrolysis method, the pyrolysis oil contains 30 mg / l of halogens and 1.2 g / l of sulfur, TAN = 8.4). Then the corrosion observed on the steel finger is visually inspected and rated from 0 (no visible corrosion) to ++++(severe corrosion).

[0148] Table 1: Results from the corrosion tests where the steel finger was immersed in the pyrolysis oil at 60 °C for 4 hours.

[0149] Catalyst Poisoning Inhibitor Corrosion Comparative Example 1 None ++++ Example 1 <![CDATA[30ppm Kerocom 3767 1 > ++ Example 2 <![CDATA[30ppm Kerocom 3800 2 > ++ Example 3 <![CDATA[30ppm Amine O 3 > ++ Example 4 <![CDATA[30ppm Kerocom 3650 4 > ++ Example 5 <![CDATA[60ppm Kerocom 3767 1 > 0 Example 6 <![CDATA[60ppm Kerocom 3800 2 > 0 Example 7 <![CDATA[60ppm Amine O 3 > 0 Example 8 <![CDATA[60ppm Kerocom 3650 4 > 0 Example 9 <![CDATA[100ppm Kerocom 3767 1 > + Example 10 <![CDATA[100ppm Kerocom 3800 2 > +

[0150] 1-4 Available from BASF SE

[0151] The examples and results in Table 1 show that the corrosion of carbon steel is reduced or inhibited by adding at least one catalyst poisoning inhibitor to the pyrolysis oil according to the invention. Thus, in the presence of at least one catalyst poisoning inhibitor added to the pyrolysis oil, metal ions (such as Fe 2+ , Fe 3+ and Ni 2+ ) and compounds of such metal ions are not enriched or less enriched, and catalyst poisoning and / or fouling of adsorbents and / or membranes is reduced.

[0152] The pyrolysis oil manufactured by BASF is used in the following examples and comparative examples. The pyrolysis oil is manufactured by pyrolysis reaction of plastic waste containing polyolefins. The pyrolysis oil is mixed with high vacuum residue (HVR) and water as follows: 166 g of pyrolysis oil + 192 g of HVR + 136 g of water. At T = 275 °C, the corrosion behavior of steel plates made of 1.4541 (X6CrNiTi18-10) and 1.4571 (X6CrNiMoTi17-12-2) was tested for 4×7 days in a sealed autoclave made of nickel alloy, and the mixture containing pyrolysis oil was replaced between each round of testing. The steel plates made of 1.4551 and 1.4571 steel respectively have dimensions of 50×20×2 mm (including welds) and are coarsely ground on one side. During the test, the steel plates were immersed in the mixture containing pyrolysis oil, and the remaining autoclave volume was filled with nitrogen. The mixture containing pyrolysis oil was not agitated during the test. The temperature of 275 °C was selected to simulate the preheating conditions for steam cracking and partial oxidation.

[0153] The average linear corrosion rate was determined and rated as x (failed) or o (passed).

[0154] Table 2: Results from the corrosion test at T = 275 °C.

[0155] Steel Type Catalyst Poisoning Inhibitor Corrosion Comparative Example 2 1.4541 None x Example 11 1.4541 5000ppm Amine O o Comparative Example 3 1.4571 None x Example 12 1.4571 5000ppm Amine O o

Claims

1. A pyrolysis oil, a mixture of at least two pyrolysis oils, or a blend comprising at least one pyrolysis oil, which contains at least one catalyst poisoning inhibitor selected from amphiphilic compounds, these amphiphilic compounds comprising at least one nonpolar residue selected from C6 to C26 alkyl and / or alkylene groups and at least one polar residue, the at least one polar residue comprising at least one nitrogen atom.

2. The pyrolysis oil, mixture of at least two pyrolysis oils, or blend comprising at least one pyrolysis oil according to claim 1, wherein, The at least one catalyst poisoning inhibitor is selected from the group consisting of - saturated, mono-unsaturated and poly-unsaturated C6 to C26 fatty acids coupled to an N-heterocyclic compound via a C-C bond; - nitrogen compounds quaternized with polycarboxylic acids in which the free hydrocarbon groups are replaced by hydrocarbon epoxides; and - mixtures thereof.

3. The pyrolysis oil, mixture of at least two pyrolysis oils, or blend comprising at least one pyrolysis oil according to any one of claims 1 and 2, wherein, The concentration range of the at least one catalyst poisoning inhibitor is from 5 to 20000 ppm.

4. The at least one pyrolysis oil in the pyrolysis oil or the mixture or blend of at least two pyrolysis oils according to any one of claims 1 to 3, which has a bromine value of from about 2 g Br2 / 100 g to about 150 g Br2 / 100 g (determined by ASTM 1159) and / or a C5 hydrocarbon content of from about 0.03 wt.-% to about 12.2 wt.-% (determined by ASTM D 5134) and / or a naphthalene content of from about 0.5 wt.-% to about 18.4 wt.-% (determined by ASTM D 5134) and / or a styrene content of from about 0.02 wt.-% to about 29.5 wt.-% (determined by ASTM D 5134) and / or a toluene content of from about 4.3 wt.-% to about 71.5 wt.-% (determined by ASTM D 5134).

5. The pyrolysis oil according to any one of claims 1 to 4, wherein, The pyrolysis oil, at least one pyrolysis oil in the mixture comprising at least two pyrolysis oils or at least one pyrolysis oil in the blend comprising at least one pyrolysis oil is obtained from rubber waste by a pyrolysis reaction.

6. A method for inhibiting catalyst poisoning and / or fouling during a thermal process for upgrading and / or converting a pyrolysis oil, a mixture of at least two pyrolysis oils and a blend comprising at least one pyrolysis oil, the method comprising the steps of: (i) providing a pyrolysis oil, a mixture of at least two pyrolysis oils or a blend comprising at least one pyrolysis oil in a steel container system, wherein the pyrolysis oil, the mixture of at least two pyrolysis oils or the blend comprising at least one pyrolysis oil is in physical and / or chemical contact with the steel container system, (ii) adding at least one catalyst poisoning inhibitor to the pyrolysis oil, the mixture of at least two pyrolysis oils or the blend comprising at least one pyrolysis oil, wherein the at least one catalyst poisoning inhibitor is selected from the group consisting of amphiphilic compounds, these amphiphilic compounds comprising at least one nonpolar residue selected from C6 to C26 alkyl and / or alkylene groups and at least one polar residue, the at least one polar residue comprising at least one heteroatom selected from the group consisting of nitrogen and oxygen. (iii) Contacting the pyrolysis oil comprising the at least one catalyst poisoning inhibitor, a mixture of at least two pyrolysis oils, or a blend comprising at least one pyrolysis oil with at least one heterogeneous catalyst, or subjecting the pyrolysis oil comprising the at least one catalyst poisoning inhibitor, a mixture of at least two pyrolysis oils, or a blend comprising at least one pyrolysis oil to a thermal process.

7. The method according to claim 6, wherein The concentration range of the at least one catalyst poisoning inhibitor is from 5 to 20,000 ppm.

8. The method according to any one of claims 6 and 7, wherein The steel container system comprises one or more materials selected from the group consisting of carbon steel and low alloy steel.

9. The method according to any one of claims 6 to 8, wherein The at least one catalyst poisoning inhibitor is selected from the group consisting of - saturated, mono-unsaturated, and poly-unsaturated C6 to C26 fatty acids; - dimer fatty acids; - a copolymer of at least one ethylenically unsaturated polymerizable polycarboxylic anhydride and at least one polymerizable olefin; - alkenyl succinic acids and alkenyl succinic anhydrides, wherein the alkenyl residue is selected from C6 to C26 alkenyls having one or more C═C bonds; - saturated, mono-unsaturated, and poly-unsaturated C6 to C26 fatty acids coupled to an N-heterocyclic compound via a C-C bond; - a nitrogen compound quaternized with a polycarboxylic acid substituted with a hydrocarbyl epoxide and a free hydrocarbyl group; - and mixtures thereof.

10. The method according to any one of claims 6 to 9, wherein, The at least one pyrolysis oil in the pyrolysis oil or the mixture of at least two pyrolysis oils or the blend comprising at least one pyrolysis oil provided in step (i) has a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g (determined by ASTM 1159) and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-% (determined by ASTM D 5134) and / or a naphthalene content of about 0.5 wt.-% to about 18.4 wt.-% (determined by ASTM D 5134) and / or a styrene content of about 0.02 wt.-% to about 29.5 wt.-% (determined by ASTM D5134) and / or a toluene content of about 4.3 wt.-% to about 71.5 wt.-% (determined by ASTM D 5134).

11. The method according to any one of claims 6 to 10, wherein The thermal process in step (iii) is selected from the group consisting of: preheating for steam cracking, steam cracking, preheating for partial oxidation, and partial oxidation.

12. At least one additive is used as a catalyst poisoning inhibitor in pyrolysis oil, a mixture of at least two pyrolysis oils, or a blend containing at least one pyrolysis oil to inhibit the enrichment of catalyst poisons selected from the group consisting of Fe 2+ ions, Fe 3+ ions, Ni 2+ ions, and compounds of said metal ions in the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend containing at least one pyrolysis oil, wherein the at least one additive is selected from amphiphilic compounds, and these amphiphilic compounds contain at least one non-polar residue selected from C6 to C26 alkyl and / or alkylene groups and at least one polar residue containing at least one heteroatom selected from the group consisting of oxygen and nitrogen.

13. According to the use described in claim 12, wherein The at least one additive is selected from the group comprising - saturated, mono-unsaturated, and poly-unsaturated C6 to C26 fatty acids; - dimer fatty acids; - a copolymer of at least one ethylenically unsaturated polymerizable polycarboxylic anhydride and at least one polymerizable olefin; - alkenyl succinic acids and alkenyl succinic anhydrides, wherein the alkenyl residue is selected from C6 to C26 alkenyls having one or more C═C bonds; - saturated, mono-unsaturated, and poly-unsaturated C6 to C26 fatty acids coupled to an N-heterocyclic compound via a C-C bond; - a nitrogen compound quaternized with a polycarboxylic acid substituted with a hydrocarbyl epoxide and a free hydrocarbyl group; - and mixtures thereof.

14. The use according to claim 12 or 13, wherein, The concentration range of the at least one additive in the pyrolysis oil, the mixture of at least two pyrolysis oils, or the blend comprising at least one pyrolysis oil is from 5 to 20,000 ppm.

15. Use according to any one of claims 12 to 14, wherein The at least one pyrolysis oil in the pyrolysis oil or a mixture of at least two pyrolysis oils or a blend comprising at least one pyrolysis oil has a bromine value of from about 2 g Br2 / 100 g to about 150 g Br2 / 100 g (determined by ASTM 1159) and / or a C5 hydrocarbon content of from about 0.03 wt.-% to about 12.2 wt.-% (determined by ASTM D 5134) and / or a naphthalene content of from about 0.5 wt.-% to about 18.4 wt.-% (determined by ASTM D 5134) and / or a styrene content of from about 0.02 wt.-% to about 29.5 wt.-% (determined by ASTM D 5134) and / or a toluene content of from about 4.3 wt.-% to about 71.5 wt.-% (determined by ASTM D 5134).