Method for suppressing catalyst poisoning by bio-oils in contact with steel containments

Abstract

The present invention concerns bio-oils, mixtures, and blends of bio-oils comprising at least one catalyst poisoning suppressant, wherein the catalyst poisoning suppressant is selected from amphiphilic compounds, the amphiphilic compounds comprising at least one nonpolar residue selected from C6 to C26 alkyl and / or alkylene and at least one polar residue, the at least one polar residue comprising at least one nitrogen atom. The invention further concerns a method for suppressing catalyst poisoning and / or fouling during thermal processes and the use of catalyst poisoning suppressants selected from amphiphilic compounds, the amphiphilic compounds comprising at least one nonpolar residue selected from C6 to C26 alkyl and / or alkylene and at least one polar residue, the at least one polar residue comprising at least one nitrogen or oxygen atom. The poisoning of heterogeneous catalysts and / or fouling during thermal processes used in the purification, upgrading, and / or conversion of bio-oils and mixtures / blends of such bio-oils is reduced in the presence of at least one catalyst poisoning suppressant.

Description

[0001] Method for suppressing catalyst poisoning by bio-oils in contact with steel containments

[0002] Technical Area

[0003] The present invention relates to bio-oils comprising at least one catalyst poisoning suppressant, a method for reducing catalyst poisoning and / or fouling during thermal processes in purification, blending, upgrading, and / or conversion of bio-oils and the use of catalyst poisoning suppressants in bio-oils to reduce poisoning of heterogeneous catalysts and / or fouling during thermal processes.

[0004] Background of the Invention

[0005] Liquids derived from different types of biomass by a pyrolysis reaction or other processes (denoted bio-oils) may be highly corrosive towards containments made of steel, especially containments made of carbon-steels and low-alloyed steels.

[0006] The reasons for the undesired corrosiveness of bio-oils are manifold. In comparison with oils from fossil sources such as crude oil, bio-oils have a higher content of components such as water, oxygen, halogen(s), and sulfur e.g., bound in organic compounds. In addition, the total acid number (TAN) of bio-oils is higher than in oils from fossil sources such as crude oil. Said differences in composition lead to an increased corrosion of bio-oils towards containments (e.g., vessels, pipes, reactors, heat exchangers and the like) made of steel, especially containments made of carbon-steels and low-alloyed steels during storage, transport, handling, and conversion of the bio-oils.

[0007] For economic reasons cheaper steel materials and less corrosion-resistant steels such as carbon-steel (including construction steel) and low-alloyed steels are preferred containment materials. Hence, the increased corrosiveness of biooils towards such materials in comparison to oils from fossil sources is a major problem.

[0008] One negative aspect of said increased corrosive behavior leads to an enrichment of metal ions and metal compounds in the bio-oil during storage, transportation, handling, and / or conversion in containments such as storage vessels, mixing vessels, and pipes. The metal ions and metal compounds transferred from the containment material into the bio-oil comprise Fe2+, Fe3+, and Ni2+ions as well as soluble and insoluble compounds of such metal ions such as the respective metal hydroxides, oxides, and hydroxy-oxides.

[0009] Bio-oils require designated purification and / or upgrading steps prior to further use in e.g., a steam cracking unit, a catalytic cracking unit, a fluid catalytic cracking unit, a partial oxidation unit, and further downstream unit operations to obtain chemical products from such bio-oils. Such purification and / or upgrading steps are required for example to remove all the various unwanted components such as water, oxygen, halogen(s), and sulfur.

[0010] For pyrolysis oils from plastic waste, catalyst poisons such as sulfur e.g., bound in organic compounds and chloride compounds can be removed or their concentration reduced with conventional methods such as extraction, hydrotreatment, adsorption, and de-chlorination which are for example disclosed in EP 3907267 A1.

[0011] Some of the purification / upgrading methods applied use one or more catalysts having active sites and / or pores which can be poisoned and / or subjected to fouling by Fe2+, Fe3+, and Ni2+ions as well as soluble and insoluble compounds of such metal ions such as the respective metal hydroxides, oxides and hydroxy-oxides. The metal ions transferred from the containment material into the bio-oil as well as soluble and insoluble compounds of such metal ions are not substantially removed from the bio-oil during said purification and / or upgrading steps because none of the purification and / or upgrading steps is particularly directed to the removal of these metal ions and / or respective metal compounds.

[0012] Accordingly, the metal ions and metal compounds remain in the bio-oil and act as catalyst poisons towards heterogeneous catalysts and thereby reduce the activity and lifetime of the catalysts used in later process steps. The catalyst poisons partially or totally deactivate a heterogeneous catalyst by e.g., decreasing the total number of active sites. Metal ions such as Fe2+, Fe3+, and Ni2+and compounds of said metal ions such as hydroxides, oxides, and hydroxyoxides are permanent poisons for precious metal and base metal catalysts applied for purification and upgrading of bio-oils which is necessary before further use of a bio-oil as e.g. a feedstock for steam cracking, fluid catalytic cracking, catalytic cracking, partial oxidation, and other downstream processes.

[0013] Said metal ions also tend to be adsorbed onto the walls of the containment (such as vessels, pipes, reactors) from where they may be slowly re-released to poison also future charges of catalysts.

[0014] For example, Ni2+ions are a poison when deposited on a catalyst surface as they can act as a strong dehydrogenation catalyst which contributes to undesired carbon deposition. The effect of Ni2+ions is well documented in units for fluid catalytic cracking where Ni2+ions also increase the unwanted "light ends” gas production.

[0015] Another example is iron oxide (formed from Fe2+ / Fe3+ions and oxygen present e.g., in the "water impurity part” of the bio-oil and / or oxygen bound to organic residues such as Fe-carboxylates) which is a known poison for several types of hydrocarbon processing catalysts which increases undesired deposition of carbon on the surface of such heterogeneous catalysts.

[0016] Finely divided iron oxide is reactive with catalyst components containing sodium and / or silicon and thereby 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 plugging pores which both reduce the activity of the catalyst.

[0017] Adsorption of Fe2+, Fe3+, and Ni2+ions and compounds thereof onto the surface of catalysts also decreases the activity of catalysts used for HDO (hydrodeoxygenation) processes which are a common purification steps before utilizing biooils as a cracker feedstock.

[0018] Several approaches to prevent corrosion of a containment material and undesired transfer of Fe2+, Fe3+, and Ni2+ions and compounds thereof into the bio-oil are known in the art.

[0019] Accordingly, a more feasible way to suppress the release of Fe2+, Fe3+, and Ni2+ions and compounds thereof into the bio-oil while in contact with containment materials such as steel, more particularly carbon-steels and low-alloy steels is needed to suppress or reduce the poisoning of catalysts and / or fouling during thermal processes.

[0020] Summary of the Invention

[0021] It is a first objective of the present invention to reduce the poisoning of heterogeneous catalysts and / or fouling during thermal processes used in the purification and / or upgrading of bio-oils, mixtures of bio-oils, and blends of at least one bio-oil with other hydrocarbon liquids such as naphtha or pyrolysis oils (i.e., liquids derived from mixed waste plastics, rubber materials, or textiles by a pyrolysis reaction). Preferably said purification, upgrading and / or conversion is a hydrotreatment method in the presence of hydrogen and at least one heterogeneous catalyst.

[0022] It is a second objective of the present invention to provide a method for suppressing fouling during thermal processes used in the conversion of bio-oils, mixtures of bio-oils, and blends of at least one bio-oil with other hydrocarbon liquids such as naphtha or pyrolysis oils (i.e., liquids derived from mixed waste plastics, rubber materials, or textiles by a pyrolysis reaction). Preferably said conversion is a thermal process selected from the group consisting of steam cracking and partial oxidation. Most preferably, the fouling during steam cracking and partial oxidation is reduced.

[0023] It is a third objective of the present invention to provide a bio-oil in which upon physical and / or chemical contact with a containment material metal ions such as Fe2+, Fe3+, and Ni2+and compounds of such metal ions are not enriched or at least less enriched in the bio-oil, mixtures of bio-oils, and blends of at least one bio-oil with other hydrocarbon liquids such as naphtha or pyrolysis oils (i.e., liquids derived from mixed waste plastics, rubber materials, or textiles by a pyrolysis reaction).

[0024] It is a fourth objective of the present invention to provide additives for the use in bio-oils, mixtures of bio-oils, and blends of at least one bio-oil with other hydrocarbon liquids such as naphtha or pyrolysis oils (i.e., liquids derived from mixed waste plastics, rubber materials, or textiles by a pyrolysis reaction) to suppress the release of Fe2+, Fe3+, and Ni2+ions and compounds thereof from containment materials such as steel, particularly carbon-steels and low-alloy steels.

[0025] These objectives are solved by a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil containing at least one catalyst poisoning suppressant selected from amphiphilic compounds, the amphiphilic compounds comprising at least one nonpolar residue selected from Ce to C26 alkyl and / or alkylene and at least one polar residue, the at least one polar residue comprising at least one nitrogen atom.

[0026] These objectives are further solved by a method for suppressing catalyst poisoning for upgrading and / or fouling during thermal processes for converting a bio-oil, a mixture of at least two bio-oils, and a blend comprising at least one biooil, comprising the steps

[0027] (i) providing a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil in a steel containment, wherein the bio-oil, the mixture of at least two bio-oils, or the blend comprising at least one bio-oil is in physical and / or chemical contact with said steel containment,

[0028] (ii) adding at least one catalyst poisoning suppressant to said bio-oil, the mixture of at least two bio-oils, or the blend comprising at least one bio-oil, wherein the at least one catalyst poisoning suppressant is selected from the group consisting of amphiphilic compounds, the amphiphilic compounds comprising at least one nonpolar residue selected from Ce to C26 alkyl and / or alkylene 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,

[0029] (iii) contacting said bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil, comprising said at least one catalyst poisoning suppressant with at least one heterogeneous catalyst or subjecting said bio-oil, mixture of at least two bio-oils or blend comprising at least one bio-oil, comprising said at least one catalyst poisoning suppressant to a thermal process. These objectives are further solved by the use of at least one additive, said at least one additive selected from amphiphilic compounds comprising at least one nonpolar residue selected from Ce to C26 alkyl and / or alkylene and at least one polar residue comprising at least one hetero-atom selected from the group consisting of nitrogen and oxygen as a catalyst poisoning suppressant in a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil to suppress enrichment of a catalyst poison selected from the group comprising Fe2+ions, Fe3+ions, Ni2+ions, and compounds of said metal ions in said bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil. Thereby, the poisoning of heterogeneous catalysts and / or fouling of adsorbents and / or membranes is reduced and the lifetime of heterogeneous catalysts and / or adsorbents and / or membranes used in later process steps is increased and their activity is maintained for a longer time and / or throughput.

[0030] Detailed Description of the Invention

[0031] "Blend” is defined herein as a blend comprising at least one bio-oil blended (mixed) with at least one other hydrocarbon liquid such as naphtha, high vacuum residue (also known as "HVR”, "vac resid” and "residuum” which is the heaviest of the distillation cuts and can be obtained from the bottom cut of a vacuum distillation tower of a refinery), or pyrolysis oils. Blending is for example used to alter physical properties such as reducing the viscosity and / or chemical properties such as reducing the concentration of certain ingredients e.g., sulfur by diluting the one or more bio-oils with at least one other hydrocarbon liquid.

[0032] "Catalyst” is defined herein as a heterogeneous catalyst which is a solid material comprising a surface and having active sites mandatory for the desired catalytic properties of such a catalyst.

[0033] "ppm” is defined herein as a parts-per-million notation referring to a mass fraction.

[0034] In the context of the present description and the accompanying claims, the term "about” preferably means a deviation of the thus described value of ±15%.

[0035] In the context of the present invention, the term "combinations thereof' is inclusive of one or more of the recited elements.

[0036] In the context of the present invention, the term "mixture thereof' is inclusive of one or more of the recited elements.

[0037] Pyrolysis oil can be manufactured by a pyrolysis reaction from feedstocks such as plastic waste, mixed plastic waste, rubber waste, textiles, or mixtures thereof. Pyrolysis oils can also be manufactured from mixtures of the aforementioned feedstocks with other kinds of waste and impurities.

[0038] Examples of waste plastics include pure plastic waste, mixed plastic waste, film waste, including soiling, adhesive materials, fillers, residues etc., industrial plastic waste, and municipal plastic waste. Mixed plastic waste is composed of different types of polymers.

[0039] Examples of rubber waste include end-of-life tires, rubber waste produced during manufacturing processes, and discarded rubber containing products such as latex examining gloves. End-of-life tires comprise further ingredients such as textiles and organic and inorganic additives which may be separated from the rubber portion of end-of-life tires prior to pyrolysis. Bio-oils are obtainable or obtained from biomass by performing mechanical and physical operations as well as chemical processes. Said mechanical and physical operations may include harvesting and collecting as well as crushing, cracking, cutting, shredding, grinding, chipping, milling, extrusion, irradiation, squeezing, pressing, filtering, sieving, adsorption, and thermal treatments such as drying and torrefaction. Said chemical processes may include extraction, distillation, thermochemical conversions like pyrolysis or hydrothermal liquefaction, hydrolysis, saponification, neutralization, ketonization, and hydrogenation.

[0040] The term biomass comprises any material of vegetable or animal origin, such as plants or parts thereof like crops, wood, or residues thereof, marine organisms like algae, and bio-waste such as green waste, food waste, e.g., slaughterhouse waste, meat industry waste, fish processing waste, or used cooking oil, human waste, manure, sewage, and sewage sludge.

[0041] According to one embodiment, the biomass is of vegetable origin, preferably it comprises or is derived from algae, oil crops, oil palms, soybeans, rapeseed, mustard, flax, cottonseed, sunflower, corn, hemp, field pennycress, pongamia, jatropha, macauba, mahua, camelina, salicornia, carinata, lignocellulose, wood, forestry residues, agricultural residues, crop residues, residues from vegetable oil production, green waste, food waste, and used vegetable cooking oil, more preferably it comprises or is derived from algae, oil crops, oil palms, soybeans, rapeseed, pongamia, jatropha, camelina, and carinata, most preferably it comprises or is derived from oil palms, soybeans, rapeseed, jatropha, and macauba.

[0042] According to another embodiment, the biomass is of animal origin, preferably it comprises or is derived from animal fat, livestock-related products like tallow, fish fat, or food waste.

[0043] Bio-oils are liquid compound mixtures, mainly comprising highly oxygenated compounds (e.g., glycerides, esters, carboxylic acids, phenols, alcohols, ketones, aldehydes, furans, and sugars) and water, while their exact compositions depend on the biomass feedstocks and the processing steps applied. The term bio-oil includes in particular vegetable oils like rapeseed oil, sunflower oil, soybean oil, corn oil, palm oil, jatropha oil, and macauba oil, used cooking oil, tall oil, animal fats, and oils obtained by thermochemical conversion of biomass, e.g., biomass-derived pyrolysis or hydro- thermal liquefaction oils.

[0044] According to one embodiment, the bio-oil according to the invention is a vegetable oil, used cooking oil, a pyrolysis bio-oil, or a hydrothermal liquefaction bio-oil. According to another embodiment, the bio-oil according to the invention is not manufactured by pyrolysis of bio waste.

[0045] Preferably, the bio-oil, to which at least one catalyst poisoning suppressant is added, is a vegetable oil, used cooking oil, a pyrolysis bio-oil, or a hydrothermal liquefaction bio-oil. In one embodiment, said bio-oil is not manufactured by pyrolysis of bio waste.

[0046] Preferably, at least one of the bio-oils in the mixture comprising at least two bio-oils, to which the at least one catalyst poisoning suppressant is added, is a vegetable oil, used cooking oil, a pyrolysis bio-oil, or a hydrothermal liquefaction bio-oil. In one embodiment, said bio-oil is not manufactured by pyrolysis of bio waste.

[0047] Preferably, at least one of the bio-oils in the blend comprising at least one bio-oil, to which the at least one catalyst poisoning suppressant is added, is a vegetable oil, used cooking oil, a pyrolysis bio-oil, or a hydrothermal liquefaction bio-oil. In one embodiment, said bio-oil is not manufactured by pyrolysis of bio waste. The pyrolysis reaction is a thermal decomposition or degradation of such feedstocks under inert conditions and results in a gaseous fraction, a liquid fraction, and a solid char fraction. During the pyrolysis, the feedstocks are converted into a great variety of chemicals including a) gases such a H2, Ci-C4-alkanes, C2-C4-alkenes, ethyne, propyne, 1 -butyne, b) pyrolysis oil having a boiling temperature in the range of 25 to 500 °C and c) char.

[0048] Pyrolysis processes as such are known. They are described, e.g., in EP 0713906 A1 and WO 95 / 03375 A1.

[0049] The bio-oils comprise:

[0050] - not more than 5,000 mg / L sulfur, preferably not more than 3,000 mg / L sulfur, more preferably not more than 800 mg / L (determined in accordance with ASTM D 5453);

[0051] - at least 10 mg / L nitrogen, preferably not more than 20,000 mg / L nitrogen, more preferably not more than 10,000 mg / L nitrogen, most preferably from 30 to 5,000 mg / L nitrogen (determined in accordance with ASTM D 6069);

[0052] - at least 1 mg / L halogen, preferably 1 to 20,000 mg / L halogen, more preferably 5 to 5,000 mg / L halogen, most preferably 5 to 200 mg / L halogen (determined in accordance with ASTM D 5808);

[0053] - at most 50 weight-% water, e.g., of from 15 to 50 weight-%, or of at most 40 weight-%, e.g., of from 15 to 40 weight- %, preferably of at most 30 weight-%, e.g., of from 15 to 30 weight-%, more preferably of at most 20%, e.g., of more than 10 weight-% and not more than 20 weight-%, more preferably of at most 10 weight-%, more preferably of at most 5 weight-%, more preferably of at most 1 weight-%, based on the weight of the bio-oil, (determined in accordance with DIN 51777);

[0054] - oxygen in the range of from 0.5 to 70 g(O) / 100 g(oil), e.g., of from more than 25 to not more than 70 g(O) / 100 g(oil), preferably of from 0.5 to 50 g(O) / 100 g(oil), e.g., of from more than 15 to not more than 50 g(O) / 100 g(oil), preferably of from 25 to 50 g(O) / 100 g(oil), or of from 0.5 to 15 g(O) / 100 g(oil), (determined in accordance with ASTM 5291); and / or

[0055] - a total acid number (TAN) in the range of from 0 to 200 mg (KOH) per gram of bio-oil (mg(KOH) / g(oil)), e.g., of from 10 to 200 mg(KOH) / g(oil) or from 50 to 200 mg(KOH) / g(oil), of from 0 to 150 mg(KOH) / g(oil), e.g., of from 10 to 150 mg(KOH) / g(oil) or from 50 to 150 mg(KOH) / g(oil), preferably of from 0 to 100 mg (KOH) / g(oil), e.g., of from 10 to 100 mg(KOH) / g(oil) or from 50 to 100 mg(KOH) / g(oil), preferably of from 0 to 70 mg(KOH) / g(oil), e.g., of more than 10 mg(KOH) / g(oil) and not more than 70 mg(KOH) / g(oil), preferably of from 0 to 25 mg(KOH) / g(oil)(deter- mined by titration with a KOH solution and given as amount of KOH in milligrams that is needed to neutralize the acids in one gram of bio-oil).

[0056] Examples of sulfur-containing compounds include thiols, sulfides, disulfides, sulfoxides, sulfones, sulfinic acids, sulfonic acid, sulfonic acid amides, sulfonate ester, ester of sulfuric acid, thioketones, thiocarboxylic acids, thioesters, dithiocarboxylic acids, thiocyanates, sulfonic acid amides etc.

[0057] Examples of nitrogen-containing compounds include amines, imines, amides, imides, azides, azo compounds, oximes, hydrazones, hydrazines, cyanates, nitrates, nitriles, nitrite, nitro compounds, nitroso compounds, oximes, N-containing heteroaromats, carbamate ester, sulfonic acid amides, thiocyanates, sulfonic acid amides. Examples of halogen-containing compounds include aliphatic halides, (hetero)aromatic halides, aliphatic- aromatic halides, acyl halides, etc. Halogens may also be present in the bio-oils as anions such as F Cl Br, and |-.

[0058] Examples of oxygen-containing compounds include oxygenates, glycerides, esters, carboxylic acids, phenols, alcohols, ethers ketones, aldehydes, furans, and sugars.

[0059] Examples of carboxylic acids include formic acid, acetic acid, higher carboxylic acids, fatty acids, carboxylic acids having at least two carboxylic acid residues, benzoic acid, and salts thereof.

[0060] The bio-oils preferably further have a bromine number of about 2 g Br2 / 100g to about 150 g Br2 / 100g (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). Such bio-oils are particularly suited for the method and the use according to the present invention.

[0061] Mixtures of bio-oils can be obtained by mixing two or more bio-oils made from different feedstocks and / or made with different pyrolysis reaction conditions and / or made in different batches from the same feedstock and pyrolysis reaction conditions.

[0062] Blends comprising at least one bio-oil can be obtained by blending at least one bio-oil with at least one other hydrocarbon liquid such as naphtha, high vacuum residues (HVR) etc., or pyrolysis oils. Other hydrocarbon liquids suitable for blending with at least one bio-oil are known to the skilled person.

[0063] In one embodiment of the present invention at least one bio-oil is blended with one or more other hydrocarbon liquids such as naphtha and / or high vacuum residue and / or pyrolysis oils. Such blends comprise for example about 30 wt.-% of one or more bio-oils and about 70 wt.-% of one or more other hydrocarbon liquids; about 50 wt.-% of one or more bio-oils and about 50 wt.-% of one or more other hydrocarbon liquids; or about 70 wt.-% of one or more bio-oils and about 30 wt.-% of one or more other hydrocarbon liquids. Such blends may comprise in addition water. The resulting blends comprise for example about 30 wt.-% of one or more bio-oils, 30 wt.-% of one or more other hydrocarbon liquids and about 30 wt.-% of water.

[0064] The bio-oil and / or mixture of at least two different bio-oils and / or blend is in physical and / or chemical contact with containments during the pyrolysis reaction, storage, transport, handling, purification, upgrading, mixing with other biooils, and blending of at least one bio-oil with at least one other hydrocarbon liquid such as naphtha etc. or pyrolysis oils.

[0065] The temperature of the bio-oil, mixture of two or more bio-oils, or blend comprising at least one bio-oil when in physical and / or chemical contact with a containment ranges from low temperatures such as room temperature or the temperature outside of a building where the bio-oil may be stored and / or transported to the temperature applied during the pyrolysis reaction of several hundred °C. The temperature of the bio-oil, mixture of two or more bio-oils, or blend comprising at least one bio-oil may be elevated to e.g., 50 °C or 70 °C during transport in a pipe or other handling operations to obtain a reduced viscosity and thereby more favorable fluidic properties. The temperature of the bio-oil, mixture of two or more bio-oils, or blend comprising at least one bio-oil ranges from about -10 °C to about 100 °C during storage, transport, and / or handling. The temperature of the bio-oil, mixture of two or more bio-oils, or blend comprising at least one bio-oil may be elevated to about 270 °C or even higher such as 300 °C, 400 °C, 500 °C in thermal processes such as pre-heating before the bio-oil is, for example, fed into a steam cracking reactor or into a partial oxidation reactor, steam cracking or partial oxidation. During all said temperatures, the bio-oil, mixture of two or more bio-oils, or blend comprising at least one bio-oil is preferably in contact with a steel containment.

[0066] The thermal process in step (iii) is most preferably selected from the group consisting of pre-heating for steam cracking, steam cracking, pre-heating for partial oxidation and partial oxidation.

[0067] Accordingly, the temperature ranges from about 10 to about 300 °C. This temperature range also applies to blends comprising at least one bio-oil and mixtures of bio-oils comprising at least two bio-oils.

[0068] "Containment” is defined herein as a means for storing, transporting, directing, handling, and thermal processing of a bio-oil, a mixture comprising at least two bio-oils, or a blend comprising at least one bio-oil. A containment can also be a reactor wherein a) the bio-oil is made by a pyrolysis reaction and / or b) the bio-oil or parts thereof is / are chemically and / or physically converted, for example in / during a thermal process. "Containment” includes but is not limited to stationary vessels, movable vessels, pipes, reactors, heat exchangers, valves, and the like.

[0069] Containments according to the present invention are made of or comprise steel materials. Said steel materials are in physical and / or chemical contact with the bio-oil, a mixture comprising at least two bio-oils, or a blend comprising at least one bio-oil.

[0070] The steel materials can be in principle any kind of materials referred to as steel such as stainless steels, high-alloyed steels, low-alloyed steels, carbon-steels etc. For economic reasons, the steel material is preferably selected from carbon-steels or a low-alloy steels. Carbon-steels and low-alloyed steels are cheaper than e.g., stainless steels but are less resistant against corrosion caused by a bio-oil.

[0071] "Carbon-steel” is defined herein as a steel comprising C in the range of about 0.05 to about 2.0 wt.-%. No minimum content is specified or required for Cr, Co, Mo, Ni, Nb, Ti, V, W and Zr or any other element to be added to obtain a desired alloying effect; the specified minimum for Cu does not exceed 0.4 wt.-%; or a maximum content for any of the following elements does not exceed the percentages noted: 1.65 wt.-% Mn; 0.6 wt.-% Si; 0.6 wt.-% Cu.

[0072] More preferably, the carbon-steel is a low-carbon-steel having a C content of about 0.05 to about 0.15 wt.-% and / or a medium-carbon-steel having a C content of about 0.3 to about 0.5 wt.-%.

[0073] "Low-alloy steel” is defined herein as a steel containing from about 1 to about 5 wt.-% of individual alloying elements 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.

[0074] The specific composition of bio-oils with a higher content of components such as sulfur, nitrogen, halogens, water, oxygen, and a higher total acid number TAN compared to oils from fossil sources such as crude oil results in a (more) severe corrosive attack towards steel of containments, especially when made of or comprising carbon-steels and low- alloy steels. Thereby undesired metal ions such as Fe2+, Fe3+, and Ni2+ions and / or compounds thereof are released from the containment material into the bio-oil and cause poisoning of heterogeneous catalysts and / or fouling of adsorbents and / or membranes with which the bio-oil is contacted in later process steps during e.g., purification and / or upgrading. To prevent such poisoning of heterogeneous catalyst and / or fouling of adsorbents and / or membranes in later process steps, at least one catalyst poisoning suppressant is added to the bio-oil, a mixture comprising at least two bio-oils, or a blend comprising at least one bio-oils.

[0075] The bio-oil, mixture of at least two bio-oils or blend comprising at least one bio-oil according to the present invention contains at least one catalyst poisoning suppressant selected from amphiphilic compounds, the amphiphilic compounds comprising at least one nonpolar residue selected from Ce to C26 alkyl and / or alkylene and at least one polar residue, the at least one polar residue comprising at least one nitrogen atom.

[0076] "Amphiphilic” is defined herein as molecules and / or ions comprising both hydrophilic (polar) and lipophilic (nonpolar) properties.

[0077] The at least one catalyst poisoning suppressant is preferably selected from the group comprising

[0078] - Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated coupled by a C-C bond to a N-hetero- cyclic compound;

[0079] - nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid; and

[0080] - mixtures thereof.

[0081] Suitable adducts of a Ce to C26 fatty acid, saturated, mono-unsaturated and poly-unsaturated coupled by a C-C bond with a N-heterocyclic compound comprise 2-(2-heptadec-8-enyl-2-imidazolin-1-yl)ethanol (CAS-No. 95-38-5) which can be obtained by heating oleic acid with 2-(2-aminoethylamino)ethanol up to 270 °C for five hours and removal of the water formed by azeotropic distillation with xylol.

[0082] Suitable nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid specifically comprise Ci6-alkyl-N(CH3)2 quaternized with propylene oxide in the presence of polyisobutylene succinic acid. Other suitable nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid and the synthesis methods for obtaining such quaternized compounds are disclosed in WO 2014 / 195464 A1 and WO 2015 / 113681 A1 which are both incorporated by reference. In particular, suitable nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid comprise a cation of the formula (1 a) or (1 b) and an anion of the formula (2)

[0083] (1 a) (1b) (2) and is obtainable by reaction of compounds of the formulae (3), (4), and (5) in which

[0084] R1 is long-chain hydrocarbyl, preferably having a number-average molecular weight of 350 to 20000 or 350 to 5000; and at least one of the radicals R2, R3, and R4 is a straight-chain or branched, saturated or unsaturated C8-C40- hydrocarbyl radical and the other radicals are identical or different, straight-chain or branched, saturated or unsaturated C1-C6-hydrocarbyl radicals; or all the R2, R3 and R4 radicals are identical or different, straight-chain or branched, saturated or unsaturated long-chain C8-C40-hydrocarbyl radicals; or all the R2, R3 and R4 radicals are identical or different short-chain C1 -C7-alkyl radicals;

[0085] R5 is H or a hydrocarbyl radical, where the hydrocarbyl radical is an aliphatic or aromatic radical having 1 to 10 carbon atoms; and

[0086] - R is H or a radical produced by esterification with the epoxide.

[0087] Preferably, at least two of the R2, R3 and R4 radicals are identical or different and are each a straight-chain or branched C10-C20-alkyl radical and the other radical is C1-C4-alkyl.

[0088] The term "and mixtures thereof' in respect to the at least one catalyst poisoning suppressant is to be understood that said suppressant contains for example one or more Ce to C26 fatty acids, saturated, mono-unsaturated and poly-un- saturated coupled by a C-C bond to a N-heterocyclic compound or for example a combination of one or more Ce to C26 fatty acids, saturated, mono-unsaturated and poly-unsaturated coupled by a C-C bond to a N-heterocyclic compound with for example one or more nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid.

[0089] The mass fraction of the at least one catalyst poisoning suppressant in the bio-oil ranges from 5 to 25000 ppm, preferably from 10 to 20000 ppm and more preferably from 20 to 10000 ppm.

[0090] The at least one catalyst poisoning suppressant can also be used in mixtures of at least two bio-oils and blends comprising at least one bio-oil.

[0091] The mass fraction of the at least one catalyst poisoning suppressant in a mixture of at least two bio-oils ranges from 5 to 25000 ppm, preferably from 10 to 20000 ppm and more preferably from 20 to 10000 ppm. The mass fraction of the at least one catalyst poisoning suppressant in a blend comprising at least one bio-oil ranges from 5 to 25000 ppm, preferably from 10 to 20000 ppm and more preferably from 20 to 10000 ppm.

[0092] The at least one catalyst poisoning suppressant can also be used in a method for suppressing catalyst poisoning for upgrading of and / or fouling during a thermal process for converting of a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil, the method comprising the steps

[0093] (I) providing a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil in a steel containment, wherein the bio-oil, the mixture of at least two bio-oils, or the blend comprising at least one bio-oil is in physical and / or chemical contact with said steel containment,

[0094] (II) adding at least one catalyst poisoning suppressant to said bio-oil, the mixture of at least two bio-oils or the blend comprising at least one bio-oil, wherein the at least one catalyst poisoning suppressant is selected from the group consisting of amphiphilic compounds, the amphiphilic compounds comprising at least one nonpolar residue selected from Ce to C26 alkyl and / or alkylene 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,

[0095] (ill) contacting said bio-oil, mixture of at least two bio-oils or blend comprising at least one bio-oil comprising said at least one catalyst poisoning suppressant with at least one heterogeneous catalyst or subjecting said bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil, comprising said at least one catalyst poisoning suppressant to a thermal process.

[0096] Preferably, the at least one catalyst poisoning suppressant in this method is selected from the group comprising

[0097] - Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated;

[0098] - dimerized fatty acids;

[0099] - copolymers of at least one ethylenically unsaturated, polymerizable polycarboxylic anhydride with at least one polymerizable alkene;

[0100] - alkenylsuccinic acid and alkenylsuccinic acid anhydride wherein the alkenyl-residue is selected from Ce to C26 alkenyl having one or more C=C bonds;

[0101] - Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated coupled by a C-C bond to a N-heterocyclic compound;

[0102] - nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid; and

[0103] - mixtures thereof.

[0104] Preferably the bio-oil according to the present invention and provided in step (I) contains not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(C) / 100 g(oil).

[0105] More preferably, the bio-oil according to the present invention and provided in step (I) contains not more than 800 mg / L sulfur, not more than 10,000 mg / L nitrogen, 5 to 200 mg / L halogen, and oxygen in the range of from 0.5 to 50 g(O) / 100 g(oii). Preferably, the mixture of at least two bio-oils according to the present invention and provided in step (i) contains not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(O) / 100 g(oil).

[0106] More preferably, the mixture of at least two bio-oils according to the present invention and provided in step (i) contains not more than 800 mg / L sulfur, not more than 10,000 mg / L nitrogen, 5 to 200 mg / L halogen, and oxygen in the range of from 0.5 to 50 g(O) / 100 g(oil).

[0107] Preferably, the at least one bio-oil in a blend according to the present invention and provided in step (i), the blend comprising at least one bio-oil, contains not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(O) / 100 g(oil).

[0108] More preferably, the at least one bio-oil in a blend according to the present invention and provided in step (i), the blend comprising at least one bio-oil, contains not more than 800 mg / L sulfur, not more than 10,000 mg / L nitrogen, 5 to 200 mg / L halogen, and oxygen in the range of from 0.5 to 50 g(O) / 100 g(oil).

[0109] Preferably, the steel containment comprises one or more materials selected from the group comprising carbon-steel and low-alloy steel.

[0110] Preferably, the steel containment is used for steps (i) and (ii), e.g., for storage and / or transport of the bio-oil, the mixture of at least two bio-oils, or the blend comprising at least one bio-oil as well as for the addition of said at least one catalyst poisoning suppressant. Optionally, step (iii) is carried out in a reaction vessel that is different from the steel containment used for steps (i) and (ii).

[0111] Preferably, the mass fraction of the at least one catalyst poisoning suppressant in the bio-oil, the mixture of at least two bio-oils, or the blend comprising at least one bio-oil ranges from 5 to 25000 ppm, more preferably from 10 to 20000 ppm, and most preferably from 20 to 10000 ppm.

[0112] The at least one catalyst poisoning suppressant can be added to the bio-oil after separating the gaseous and solid products formed by the pyrolysis reaction. The at least one catalyst poisoning suppressant can also be added to the bio-oil at a later process step e.g., when or after filling the bio-oil into a storage vessel or when or after filling the biooil into a transport vessel and after filtration of the bio-oil. The at least one catalyst poisoning suppressant can also be added to the bio-oil before, during and / or after purifying the pyrolysis by one or more purification steps selected from extraction, distillation, hydrotreatment, absorption and adsorption. The addition of the at least one catalyst poisoning suppressant to the bio-oil is not limited to a particular process step or time.

[0113] The at least one catalyst poisoning suppressant can be added to a mixture of at least two bio-oils prior to mixing to the individual bio-oils, during mixing of the bio-oils, and / or after mixing of the bio-oils.

[0114] The at least one catalyst poisoning suppressant can be added to a blend comprising at least one bio-oil prior to blending into the at least one bio-oil, during blending, and / or after blending.

[0115] In one embodiment of the present invention the mixture of at least one catalyst poisoning suppressant and bio-oil is formed by forced agitation such as by stirring or any other suitable means to obtain a homogeneous contribution of the at least one catalyst poisoning suppressant in the bio-oil. In another embodiment of the present invention the at least one catalyst poisoning suppressant is added to the bio-oil without forced agitation.

[0116] Both forced agitation and no forced agitation can also be applied to mixtures of at least two bio-oils and blends comprising at least one bio-oil when at least one catalyst poisoning suppressant is added.

[0117] At least one additive selected from amphiphilic compounds, the amphiphilic compounds comprising at least one nonpolar residue selected from Ce to C26 alkyl and / or alkylene and at least one polar residue, the at least one polar residue comprising at least one heteroatom selected from the group consisting of oxygen and nitrogen can be used as a catalyst poisoning suppressant in a bio-oil, a mixture comprising at least two bio-oils, or a blend comprising at least one bio-oil to suppress enrichment of a catalyst poison selected from the group comprising Fe2+ions, Fe3+ions, Ni2+ions, and compounds of said metal ions in said bio-oil, a mixture comprising at least two bio-oils, or a blend comprising at least one bio-oil.

[0118] Preferably for said use, the at least one additive is selected from the group comprising

[0119] - Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated;

[0120] - dimerized fatty acids;

[0121] - copolymers of at least one ethylenically unsaturated, polymerizable polycarboxylic anhydride with at least one polymerizable alkene;

[0122] - alkenylsuccinic acid and alkenylsuccinic acid anhydride wherein the alkenyl-residue is selected from Ce to C26 alkenyl having one or more C=C bonds;

[0123] - Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated coupled by a C-C bond to a N-heterocyclic compound;

[0124] - nitrogen-compounds quaternized with a hydrocarbyl epoxide that is in combination with a free hydrocarbyl-substi- tuted polycarboxylic acid; and

[0125] - mixtures thereof.

[0126] Preferably for said use, the mass fraction of the at least one additive in the bio-oil, mixture comprising at least two biooils or blend comprising at least one bio-oil ranges from 5 to 25000 ppm, more preferably from 10 to 20000 ppm and most preferably from 20 to 10000 ppm.

[0127] Preferably for said use, said bio-oil contains not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(C) / 100 g(oil).

[0128] More preferably for said use, the bio-oil contains not more than 800 mg / L sulfur, not more than 10,000 mg / L nitrogen, 5 to 200 mg / L halogen, and oxygen in the range of from 0.5 to 50 g(C) / 100 g(oil).

[0129] Preferably for said use, the mixture of bio-oils comprising at least two bio-oil not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(C) / 100 g(oil).

[0130] More preferably for said use, the mixture of bio-oils comprising at least two bio-oils contains not more than 800 mg / L sulfur, not more than 10,000 mg / L nitrogen, 5 to 200 mg / L halogen, and oxygen in the range of from 0.5 to 50-g(C) / 100 g(oii). Preferably for said use, the at least one bio-oil in a blend comprising at least one bio-oil contains not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70-g(0) / 100 g(oil).

[0131] More preferably for said use, the at least one bio-oil in a blend comprising at least one bio-oil contains not more than 800 mg / L sulfur, not more than 10,000 mg / L nitrogen, 5 to 200 mg / L halogen, and oxygen in the range of from 0.5 to 50 g(O) / 100 g(oil).

[0132] Preferably for said use, the bio-oil, the mixture of bio-oils comprising at least two bio-oils, or the blend comprising at least one bio-oil is in physical and / or chemical contact with a steel containment comprising one or more materials selected from carbon-steels and low-alloy steels.

[0133] It is assumed that the at least one catalyst poisoning suppressant is capable to form a film on the surface of the containment by adsorption which includes interaction of the at least one catalyst poisoning suppressant and the surface of the containment by physisorption and / or chemisorption.

[0134] The bio-oils, mixtures of bio-oils comprising at least two bio-oils or blends comprising at least one bio-oil comprising at least one catalyst poisoning suppressant and the method for using such bio-oil compositions reduce the undesired poisoning of heterogeneous catalysts used in or after purification, upgrading and / or blending of bio-oils.

[0135] Examples of purification processes comprising heterogeneous catalysts are hydrotreating or hydroprocessing techniques for removing oxygen compounds (hydrodeoxygenation, HDO), sulfur compounds (hydrodesulfurization, HDS), and nitrogen compounds (hydrodenitrogenation, HDN) from bio-oils. Such catalysts typically comprise at least one group 6 metal component and at least one group 8, 9 and 10 metal component composited with a support. The catalysts employed in such purification methods are highly sensitive to poisoning by e.g., Fe2+ions, Fe3+ions, Ni2+ions, and compounds of said metal ions. The lifetime of said catalysts is increased and their activity is maintained over a longer time when using the bio-oil compositions and methods according to the present invention.

[0136] Furthermore, undesired coking can occur in parts such as pipes made of steel, preferably carbon-steel or low-alloy steel, at elevated temperatures in presence of Fe2+and / or Fe3+ions adsorbed to the steel surface. Such undesired coking can lead to blocking of parts such as pipes.

[0137] The bio-oils, mixtures of bio-oils comprising at least two bio-oils, or blends comprising at least one bio-oil comprising at least one catalyst poisoning suppressant and the method for using such bio-oil compositions also reduce the undesired fouling during thermal processes in or after purification, upgrading, blending, and / or conversion of bio-oils.

[0138] The small amount of the at least one catalyst poisoning suppressant in the bio-oil, mixtures of bio-oils comprising at least two bio-oils, or blends comprising at least one bio-oil of 5 to 25000 ppm, preferably of 10 to 20000 ppm, and more preferably of from 20 to 10000 ppm has no negative effects during purification, upgrading, blending, and / or conversion processes. Preferred embodiments

[0139] 1. Bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil, containing at least one catalyst poisoning suppressant selected from amphiphilic compounds, the amphiphilic compounds comprising at least one nonpolar residue selected from Ce to C26 alkyl and / or alkylene 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, preferably comprising at least one nitrogen atom.

[0140] 2. The bio-oil, the mixture, or the blend according to embodiment 1 wherein the at least one catalyst poisoning suppressant is selected from the group consisting of

[0141] - Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated coupled by a C-C bond to a N-het- erocyclic compound;

[0142] - nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substi- tuted polycarboxylic acid; and

[0143] - mixtures thereof.

[0144] 3. The bio-oil, the mixture, or the blend according to any of embodiments 1 and 2 wherein the mass fraction of the at least one catalyst poisoning suppressant ranges from 5 to 25000 ppm.

[0145] 4. The bio-oil, the mixture, or the at least one bio-oil in the blend according to any of embodiments 1 to 3, containing not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(O) / 100 g(oil), and optionally having a bromine number of about 2 g Br2 / 100g to about 150 g Br2 / 100g, as determined by ASTM 1159, and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.- %, as determined by ASTM D 5134.

[0146] 5. The bio-oil according to any of embodiments 1 to 4 wherein the bio-oil, at least one bio-oil in the mixture comprising at least two bio-oils, or at least one bio-oil in the blend comprising at least one bio-oil is a vegetable oil, a pyrolysis bio-oil, or a hydrothermal liquefaction bio-oil.

[0147] 6. Method for suppressing catalyst poisoning for upgrading of and / or fouling during a thermal process for converting of a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil, comprising the steps

[0148] (I) providing a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil in a steel containment, wherein the bio-oil, the mixture of at least two bio-oils, or the blend comprising at least one bio-oil is in physical and / or chemical contact with said steel containment,

[0149] (II) adding at least one catalyst poisoning suppressant to said bio-oil, the mixture of at least two bio-oils, or the blend comprising at least one bio-oil, wherein the at least one catalyst poisoning suppressant is selected from the group consisting of amphiphilic compounds, the amphiphilic compounds comprising at least one nonpolar residue selected from Ce to C26 alkyl and / or alkylene 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,

[0150] (iii) contacting said bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil, comprising said at least one catalyst poisoning suppressant with at least one heterogeneous catalyst or subjecting said bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil, comprising said at least one catalyst poisoning suppressant to a thermal process. The method according to embodiment 6 wherein the mass fraction of the at least one catalyst poisoning suppressant ranges from 5 to 25000 ppm. The method according to any of embodiments 6 and 7 wherein said steel containment comprises one or more materials selected from the group comprising carbon-steels and low-alloy steels. The method according to any of embodiments 6 to 8 wherein the at least one catalyst poisoning suppressant is selected from the group consisting of

[0151] - Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated;

[0152] - dimerized fatty acids;

[0153] - copolymers of at least one ethy lenically unsaturated, polymerizable polycarboxylic anhydride with at least one polymerizable alkene;

[0154] - alkenylsuccinic acid and alkenylsuccinic acid anhydride wherein the alkenyl-residue is selected from Ce to C26 alkenyl having one or more C=C bonds;

[0155] - Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated coupled by a C-C bond to a N-heter- ocyclic compound;

[0156] - nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid; and

[0157] - mixtures thereof.

[0158] 10. The method according to any of embodiments 6 to 9 wherein the bio-oil or the mixture of at least two bio-oils, or the at least one bio-oil in a blend, comprising at least one bio-oil, provided in step (I) contains not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(O) / 100 g(oil), and optionally has a bromine number of about 2 g Br2 / 100g to about 150 g Br2 / 100g, as determined by ASTM 1159, and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-%, as determined by ASTM D 5134.

[0159] 11. The method according to any one of embodiments 6 to 10 wherein the thermal process in step (iii) is selected from the group consisting of pre-heating for steam cracking, steam cracking, pre-heating for partial oxidation, and partial oxidation. 12. Use of at least one additive selected from amphiphilic compounds comprising at least one nonpolar residue selected from Ce to C26 alkyl and / or alkylene and at least one polar residue comprising at least one heteroatom selected from the group consisting of oxygen and nitrogen as a catalyst poisoning suppressant in a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil to suppress enrichment of a catalyst poison selected from the group comprising Fe2+ions, Fe3+ions, Ni2+ions, and compounds of said metal ions in said bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil.

[0160] 13. The use according to embodiment 12 wherein the at least one additive is selected from the group comprising

[0161] - Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated;

[0162] - dimerized fatty acids;

[0163] - copolymers of at least one ethy lenically unsaturated, polymerizable polycarboxylic anhydride with at least one polymerizable alkene;

[0164] - alkenylsuccinic acid and alkenylsuccinic acid anhydride wherein the alkeny l-residue is selected from Ce to C26 alkenyl having one or more C=C bonds;

[0165] - Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated coupled by a C-C bond to a N- heterocyclic compound;

[0166] - nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substi- tuted polycarboxylic acid; and

[0167] - mixtures thereof.

[0168] 14. The use according to any of embodiments 12 and 13 wherein the mass fraction of the at least one additive in the bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil ranges from 5 to 25000 ppm.

[0169] 15. The use according to any of embodiments 12 to 14 wherein the bio-oil or mixture of at least two bio-oils or the at least one bio-oil in a blend, comprising at least one bio-oil, contains not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(C) / 100 g(oil), and optionally has a bromine number of about 2 g Br2 / 100g to about 150 g Br2 / 100g, as determined by ASTM 1159, and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-%, as determined by ASTM D 5134.

[0170] The invention will be further explained by the following non-limiting examples some of which are based on experiments performed with an oil obtained by pyrolysis of solid waste material. The one of skill in the art will appreciate, however, that the conclusions drawn therefrom are equally applicable to the bio-oils described herein. For instance, it is known, e.g., from Eschenbacher et al. (Energy Fuels 2021 , 35, 18333-18369; as well as respective reference documents cited therein) that biomass-derived pyrolysis oils often also exhibit high water contents, high oxygen contents, and high total acid numbers. Examples

[0171] The enrichment of metal ions such as Fe2+, Fe3+, Ni2+, and compounds of such metal ions during storage in a steel containment material was tested with a pyrolysis oil by assessing the corrosive attack on steel fingers made of a carbon-steel (BS970-070M20; also denoted DIN 1.0402) after 4 h of immersion in the pyrolysis oil at 60 °C. The tests were conducted without and with addition of different amounts of a catalyst poisoning suppressant according to the present invention.

[0172] One pyrolysis oil was obtained from end-of-life tires (ELT), the pyrolysis oil comprising 30 mg / L halogen and 1.2 g / L sulfur, TAN = 8.4. The corrosion observed on the steel fingers were then visually inspected and rated from 0 (no visible corrosion) to ++++ (severe corrosion).

[0173] Table 1 : Results from corrosion tests with steel fingers immersed for 4 h at 60 °C in the pyrolysis oil.

[0174] 1available from BASF SE

[0175] The examples and the results in Table 1 show that the corrosion of a carbon-steel is reduced or suppressed by adding at least one catalyst poisoning suppressant according to the present invention to the pyrolysis oil. Accordingly, metal ions such as Fe2+, Fe3+, and Ni2+, and compounds of such metal ions are not enriched or less enriched in the presence of at least one catalyst poisoning suppressant to the pyrolysis oil and catalyst poisoning and / or fouling of an adsorbent and / or a membrane are reduced.

[0176] Another pyrolysis oil manufactured by BASF was used for the following examples and comparative examples. The pyrolysis oil was manufactured from plastic waste comprising polyolefins by a pyrolysis reaction. The pyrolysis oil was mixed with high vacuum residue (HVR) and water as follows: 166 g pyrolysis oil + 192 g HVR + 136 g water. The corrosion behavior of steel sheets made of 1.4541 (X6CrNiTi 18-10) and 1.4571 (X6CrNiMoTi 17-12-2) was tested 4 x 7 days with exchange of the mixture comprising the pyrolysis oil in between at T = 275 °C in sealed autoclaves made of a nickel alloy. The steel sheets made of 1.4551 and 1.4571 steel, respectively, had a size of 50 x 20 x 2 mm, comprised a welding seam and were coarsely sanded on one side. The steel sheets were immersed in the mixture comprising the pyrolysis oil during the test and the remaining autoclave volume was filled with nitrogen gas. The mixture comprising a pyrolysis oil was not agitated during the tests. The temperature of 275 °C is selected to simulate the conditions of pre-heating for steam cracking and pre-heating for partial oxidation. The average linear corrosion velocity was determined and rated x (failed) or o (passed).

[0177] Table 2: results from corrosion tests at T = 275 °C.

Claims

Claims1 . Bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil, containing at least one catalyst poisoning suppressant- selected from the group consisting of Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsatu- rated coupled by a C-C bond to a N-heterocyclic compound;- nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substi- tuted polycarboxylic acid; and- mixtures thereof.

2. The bio-oil, the mixture, or the blend according to claim 1 wherein the at least one catalyst poisoning suppressant is selected from the group consisting of2-(2-heptadec-8-enyl-2-imidazolin-1 -yl)ethanol and Ci6-alkyl-N(CH3)2 quaternized with propylene oxide in the presence of polyisobutylene succinic acid.

3. The bio-oil, the mixture, or the blend according to any of claims 1 and 2 wherein the mass fraction of the at least one catalyst poisoning suppressant ranges from 5 to 25000 ppm.

4. The bio-oil, the mixture, or the at least one bio-oil in the blend according to any of claims 1 to 3, containing not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(O) / 100 g(oil), and optionally having a bromine number of about 2 g Br2 / 100g to about 150 g Br2 / 100g, as determined by ASTM 1159, and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-%, as determined by ASTM D 5134.

5. The bio-oil according to any of claims 1 to 4 wherein the bio-oil, at least one bio-oil in the mixture comprising at least two bio-oils, or at least one bio-oil in the blend comprising at least one bio-oil is a vegetable oil.

6. Method for suppressing catalyst poisoning for upgrading and / or for suppressing fouling during a thermal process for converting of a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil, comprising the steps(I) providing a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil in a steel containment, wherein the bio-oil, the mixture of at least two bio-oils, or the blend comprising at least one bio-oil is in physical and / or chemical contact with said steel containment,(II) adding at least one catalyst poisoning suppressant to said bio-oil, the mixture of at least two bio-oils, or the blend comprising at least one bio-oil, wherein the at least one catalyst poisoning suppressant is selected from the group consisting of Ce to C26 fatty acids, saturated, mono-unsaturated and poly-unsaturatedcoupled by a C-C bond to a N-heterocyclic compound; of nitrogen-compounds quaternized with a hydro- carbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid; and of mixtures thereof,(iii) contacting said bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil, comprising said at least one catalyst poisoning suppressant with at least one heterogeneous catalyst or subjecting said bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil, comprising said at least one catalyst poisoning suppressant to a thermal process.

7. The method according to claim 6 wherein the mass fraction of the at least one catalyst poisoning suppressant ranges from 5 to 25000 ppm.

8. The method according to any of claims 6 and 7 wherein said steel containment comprises one or more materials selected from the group comprising carbon-steels and low-alloy steels.

9. The method according to any of claims 6 to 8 wherein the at least one catalyst poisoning suppressant is selected from the group consisting of- Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated;- dimerized fatty acids;- copolymers of at least one ethylenically unsaturated, polymerizable polycarboxylic anhydride with at least one polymerizable alkene;- alkenylsuccinic acid and alkenylsuccinic acid anhydride wherein the alkenyl-residue is selected from Ce to C26 alkenyl having one or more C=C bonds;- Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated coupled by a C-C bond to a N-het- erocyclic compound;- nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid; and- mixtures thereof.

10. The method according to any of claims 6 to 9 wherein the bio-oil or the mixture of at least two bio-oils, or the at least one bio-oil in a blend, comprising at least one bio-oil, provided in step (i) contains not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(O) / 100 g(oil), and optionally has a bromine number of about 2 g Br2 / 100g to about 150 g Br2 / 100g, as determined by ASTM 1159, and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-%, as determined by ASTM D 5134.11 . The method according to any one of claims 6 to 10 wherein the thermal process in step (ill) is selected from the group consisting of pre-heating for steam cracking, steam cracking, pre-heating for partial oxidation, and partial oxidation.

12. Use of at least one additive selected from amphiphilic compounds comprising at least one nonpolar residue selected from Ce to C26 alkyl and / or alkylene and at least one polar residue comprising at least one heteroatom selected from the group consisting of oxygen and nitrogen as a catalyst poisoning suppressant in a bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil to suppress enrichment of a catalyst poison selected from the group comprising Fe2+ions, Fe3+ions, Ni2+ions, and compounds of said metal ions in said bio-oil, mixture of at least two bio-oils, or blend comprising at least one bio-oil.

13. The use according to claim 12 wherein the at least one additive is selected from the group comprising- Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated;- dimerized fatty acids;- copolymers of at least one ethylenically unsaturated, polymerizable polycarboxylic anhydride with at least one polymerizable alkene;- alkenylsuccinic acid and alkenylsuccinic acid anhydride wherein the alkenyl-residue is selected from Ce to C26 alkenyl having one or more C=C bonds;- Ce to C26 fatty acids, saturated, mono-unsaturated, and poly-unsaturated coupled by a C-C bond to a N-het- erocyclic compound;- nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substi- tuted polycarboxylic acid; and- mixtures thereof.

14. The use according to any of claims 12 and 13 wherein the mass fraction of the at least one additive in the biooil, mixture of at least two bio-oils, or blend comprising at least one bio-oil ranges from 5 to 25000 ppm.

15. The use according to any of claims 12 to 14 wherein the bio-oil or mixture of at least two bio-oils or the at least one bio-oil in a blend, comprising at least one bio-oil, contains not more than 5,000 mg / L sulfur, at least 10 mg / L nitrogen, at least 1 mg / L halogen, and oxygen in the range of from 0.5 to 70 g(O) / 100 g(oil), and optionally has a bromine number of about 2 g Br2 / 100g to about 150 g Br2 / 100g, as determined by ASTM 1159, and / or a C5 hydrocarbon content of about 0.03 wt.-% to about 12.2 wt.-%, as determined by ASTM D 5134.

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