Method for inhibiting catalyst poisoning caused by contact of bio-oil with steel container systems

Abstract

The present invention relates to bio-oils, mixtures and blends of bio-oils comprising at least one catalyst poisoning inhibitor, wherein the catalyst poisoning inhibitor is selected from amphiphilic compounds comprising at least one non-polar residue selected from C6 to C 26 alkyl and / or alkylene and at least one polar residue comprising at least one nitrogen atom. The present invention further relates to a process for inhibiting catalyst poisoning and / or fouling during a thermal process and the use of a catalyst poisoning inhibitor selected from amphiphilic compounds comprising at least one non-polar residue selected from C6 to C 26 alkyl and / or alkylene and at least one polar residue comprising at least one nitrogen or oxygen atom. In the presence of at least one catalyst poisoning inhibitor, heterogeneous catalyst poisoning and / or fouling is reduced during a thermal process used in the purification, upgrading and / or conversion of bio-oils and mixtures / blends of such bio-oils.

Description

Technical Field

[0001] This invention relates to bio-oils containing at least one catalyst poisoning inhibitor, a method for reducing catalyst poisoning and / or scaling during thermal processes of purifying, blending, upgrading and / or converting bio-oils, and the use of the catalyst poisoning inhibitor in bio-oils for reducing heterogeneous catalyst poisoning and / or scaling during thermal processes. Background Technology

[0002] Liquids derived from different types of biomass through pyrolysis or other processes (called bio-oils) can be highly corrosive to container systems made of steel, especially carbon steel and low-alloy steel.

[0003] The undesirable corrosiveness of bio-oils stems from several factors. Compared to oils derived from fossil sources such as crude oil, bio-oils contain higher levels of components such as water, oxygen, one or more halogens, and sulfur (e.g., bound in organic compounds). Additionally, bio-oils have a higher total acid number (TAN) than oils derived from fossil sources such as crude oil. These compositional differences lead to increased corrosion of bio-oils on steel container systems (e.g., containers, pipes, reactors, heat exchangers, etc.), particularly those made of carbon steel and low-alloy steel, during storage, transportation, processing, and conversion.

[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 container systems. Therefore, the increased corrosivity of bio-oils to such materials compared to oils from fossil sources is a major concern.

[0005] One negative aspect of this increased corrosion behavior is the accumulation of metal ions and metal compounds in bio-oil during storage, transportation, handling, and / or conversion within container systems (such as storage containers, mixing containers, and pipelines). Metal ions and metal compounds transferred from container system materials into the bio-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 hydroxy oxides.

[0006] Bio-oils require specific purification and / or upgrading steps before further use in downstream operations such as steam cracking, catalytic cracking, fluidized bed catalytic cracking, partial oxidation, and other units to obtain chemical products. These purification and / or upgrading steps are necessary to remove, for example, various unwanted components such as water, oxygen, one or more halogens, and sulfur.

[0007] For pyrolysis oil from plastic waste, catalyst poisons such as sulfur (e.g., bound in organic compounds) and chloride compounds can be removed or their concentrations reduced by conventional methods such as extraction, hydrotreating, adsorption and dechlorination, which are disclosed, for example, in EP 3907267 A1.

[0008] Some of the purification / upgrading methods used employ one or more catalysts, which may react with Fe... 2+ Fe 3+ and Ni 2+ Ions and soluble and insoluble compounds of such metal ions (such as corresponding metal hydroxides, oxides and hydroxyl oxides) are poisoned and / or subjected to scaling active sites and / or pores.

[0009] Metal ions transferred from the container system material into the bio-oil, as well as soluble and insoluble compounds of such metal ions, are not significantly removed from the bio-oil during the purification and / or upgrading steps, because neither the purification nor upgrading steps are specifically designed for the removal of these metal ions and / or the corresponding metal compounds.

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

[0011] Metal ions (such as Fe) 2+ Fe 3+ and Ni 2+ The compounds of the metal ions (such as hydroxides, oxides, and hydroxyoxides) are permanent poisons to the noble and base metal catalysts used in the purification and upgrading of bio-oils, which are necessary before they can be used as feedstocks for downstream processes such as steam cracking, fluidized bed catalytic cracking, catalytic cracking, partial oxidation, and others.

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

[0013] For example, Ni 2+ Ions are poisons when deposited on the catalyst surface because they can act as strong dehydrogenation catalysts, thus promoting undesirable carbon deposition. 2+ The effects of ions in units used for fluid catalytic cracking are well documented, among which Ni 2+ Ions also increase the generation of unwanted "light fraction" gases.

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

[0015] Finely dispersed iron oxide reacts with catalyst components containing sodium and / or silicon, thereby accumulating on the catalyst surface and forming a new low-temperature phase. This new low-temperature phase can grow and cause masking of existing active sites and / or pore blockage of the catalyst, both of which reduce catalyst activity.

[0016] Fe 2+ Fe 3+ and Ni 2+ The adsorption of ions and their compounds onto the catalyst surface also reduces the activity of catalysts used in HDO (hydrodeoxygenation) processes, which are common purification steps performed before using bio-oil as a feedstock for crackers.

[0017] Several methods for preventing corrosion of container system materials and Fe are known in the art. 2+ Fe 3+ and Ni 2+ Methods for the undesirable transfer of ions and their compounds into bio-oils.

[0018] Therefore, a more feasible way is needed to suppress Fe from reacting with container system materials such as steel, and more particularly carbon steel and low-alloy steel. 2+ Fe 3+ and Ni 2+ Ions and their compounds are released into the bio-oil, thereby inhibiting or reducing catalyst poisoning and / or scaling during thermal processes. Summary of the Invention

[0019] The first objective of this invention is to reduce the poisoning and / or scaling of heterogeneous catalysts 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 through pyrolysis). Preferably, the purification, upgrading, and / or conversion is a hydrotreating method carried out in the presence of hydrogen and at least one heterogeneous catalyst.

[0020] A second object of the present invention is to provide a method for inhibiting scaling during thermal processes used to convert bio-oil, mixtures of bio-oil, and at least one bio-oil with other hydrocarbon liquids such as naphtha or pyrolysis oil (i.e., liquids derived from mixed waste plastics, rubber materials, or textiles via pyrolysis). Preferably, the conversion is a thermal process selected from the group consisting of steam cracking and partial oxidation. Most preferably, scaling is reduced during steam cracking and partial oxidation.

[0021] A third object of the present invention is to provide a bio-oil wherein, upon physical and / or chemical contact with container system materials, metal ions (such as Fe) 2+ Fe 3+ and Ni 2+ Compounds of such metal ions are not enriched or are at least less enriched in bio-oils, bio-oil mixtures, and blends of at least one bio-oil with other hydrocarbon liquids such as naphtha or pyrolysis oil (i.e., liquids derived from mixed waste plastics, rubber materials, or textiles through pyrolysis).

[0022] A fourth object of the present invention is to provide a method for use in blends of bio-oil, bio-oil mixtures, and at least one bio-oil with other hydrocarbon liquids such as naphtha or pyrolysis oil (i.e., liquids derived from mixed waste plastics, rubber materials, or textiles through pyrolysis) to suppress Fe. 2+ Fe 3+ and Ni 2+ Additives that release ions and their compounds from container system materials such as steel, especially carbon steel and low alloy steel.

[0023] These objectives are achieved by bio-oils containing at least one catalyst poisoning inhibitor selected from amphiphilic compounds, mixtures of at least two bio-oils, or blends containing at least one bio-oil, wherein the amphiphilic compounds contain at least one selected from C6 to C4. 26 The nonpolar residues of alkyl and / or alkylene groups and at least one polar residue, wherein the at least one polar residue contains at least one nitrogen atom.

[0024] These objectives are further addressed by a method for inhibiting catalyst poisoning and / or scaling during thermal processes for upgrading and / or converting bio-oils, mixtures of at least two bio-oils, and blends containing at least one bio-oil, the method comprising the following steps:

[0025] (i) Providing a bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil in a steel container system, wherein the bio-oil, the mixture of at least two bio-oils, or the blend containing at least one bio-oil is in physical and / or chemical contact with the steel container system.

[0026] (ii) Adding at least one catalyst poisoning inhibitor to the bio-oil, a mixture of the at least two bio-oils, or a blend containing at least one bio-oil, wherein the at least one catalyst poisoning inhibitor is selected from the group consisting of amphiphilic compounds, which contain at least one compound selected from C6 to C6. 26 The nonpolar residues of 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.

[0027] (iii) Contacting the bio-oil containing at least one catalyst poisoning inhibitor, a mixture of at least two bio-oils, or a blend containing at least one bio-oil with at least one heterogeneous catalyst, or

[0028] The bio-oil containing at least one catalyst poisoning inhibitor, a mixture of at least two bio-oils, or a blend containing at least one bio-oil is subjected to a heating process.

[0029] These objectives are further achieved by using at least one additive as a catalyst poisoning inhibitor in bio-oils, mixtures of at least two bio-oils, or blends containing at least one bio-oil, to inhibit the use of an additive selected from Fe... 2+ Ions, Fe 3+ Ions, Ni 2+ Catalytic poisons of the group consisting of ions and compounds of the metal ions are enriched in the bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil, wherein the at least one additive is selected from amphiphilic compounds containing at least one compound selected from C6 to C4. 26 The nonpolar residues of alkyl and / or alkylene groups and at least one polar residue containing at least one heteroatom selected from the group consisting of nitrogen and oxygen.

[0030] This reduces poisoning of heterogeneous catalysts and / or fouling of adsorbents and / or membranes, and extends the lifespan of heterogeneous catalysts and / or adsorbents and / or membranes used in subsequent process steps, and maintains their activity for a longer time and / or at higher throughput. Detailed Implementation

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

[0032] In this paper, a “catalyst” is defined as a heterogeneous catalyst, which is a solid material that includes a surface and has active sites necessary for the desired catalytic properties of such a catalyst.

[0033] "ppm" is defined in this paper as a fraction of mass in parts per million.

[0034] In the context of this specification and the appended claims, the term “about” preferably means a deviation of ±15% from the value described herein.

[0035] In the context of this invention, the term "combination thereof" includes one or more of the listed elements.

[0036] In the context of this invention, the term "mixture thereof" includes one or more of the listed elements.

[0037] Pyrolysis oil can be produced from raw materials such as plastic waste, mixed plastic waste, rubber waste, textiles, or mixtures thereof through a pyrolysis reaction. Pyrolysis oil can also be produced from mixtures of the above-mentioned raw materials with other types of waste and impurities.

[0038] Examples of waste plastics include pure plastic waste, mixed plastic waste, membrane waste (containing filth, adhesive materials, fillers, residues, etc.), industrial plastic waste, and municipal plastic waste. Mixed plastic waste consists of different types of polymers.

[0039] Examples of rubber waste include end-of-life tires, rubber waste generated during the manufacturing process, and discarded rubber-containing products such as latex inspection gloves. End-of-life tires contain additional components, such as textiles and organic and inorganic additives, which can be separated from the rubber portion of the tire before pyrolysis.

[0040] Bio-oil is obtained or acquired from biomass through mechanical and physical operations as well as chemical methods. The mechanical and physical operations may include harvesting and collecting, as well as crushing, breaking, cutting, shredding, grinding, stripping, milling, extrusion, irradiation, pressing, filtration, sieving, adsorption, and thermal treatment such as drying and roasting. The chemical methods may include extraction, distillation, thermochemical conversions such as pyrolysis or hydrothermal liquefaction, hydrolysis, saponification, neutralization, ketation, and hydrogenation.

[0041] The term biomass includes any material of plant or animal origin, such as plants or parts thereof like crops, wood or their residues, marine organisms like algae, and biological waste such as green waste, food waste such as slaughterhouse waste, meat processing waste, fish processing waste or used cooking oil, human waste, feces, sewage, and sewage sludge.

[0042] According to one embodiment, the biomass is plant-derived, preferably comprising or derived from algae, oil crops, oil palm, soybean, rapeseed, mustard, flax, cottonseed, sunflower, corn, hemp, wild iris, water jatropha, jatropha, macaba, mahua, camellia, 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 comprising or derived from algae, oil crops, oil palm, soybean, rapeseed, water jatropha, jatropha, camellia, and carinata, and most preferably comprising or derived from oil palm, soybean, rapeseed, jatropha, and macaba.

[0043] According to another embodiment, the biomass is of animal origin, preferably comprising or derived from animal fat, livestock-related products (such as beef tallow, fish fat, or food waste).

[0044] Bio-oils are mixtures of liquid compounds that primarily consist of highly oxidized compounds (e.g., glycerides, esters, carboxylic acids, phenols, alcohols, ketones, aldehydes, furans, and sugars) and water, with their exact composition depending on the biomass feedstock and the processing steps applied. The term bio-oils specifically includes vegetable oils (like rapeseed oil, sunflower oil, soybean oil, corn oil, palm oil, jatropha oil, and macaba oil), used cooking oils, tall oils, animal fats, and oils obtained through the thermochemical conversion of biomass, such as biomass-derived pyrolysis oils or hydrothermal liquefaction oils.

[0045] According to one embodiment, the bio-oil according to the invention is a vegetable oil, used cooking oil, pyrolyzed bio-oil, or hydrothermal liquefaction bio-oil. According to another embodiment, the bio-oil according to the invention is not produced by the pyrolysis of biological waste.

[0046] Preferably, the bio-oil to which at least one catalyst poisoning inhibitor is added is a vegetable oil, used cooking oil, pyrolyzed bio-oil, or hydrothermal liquefaction bio-oil. In one embodiment, the bio-oil is not produced by the pyrolysis of biological waste.

[0047] Preferably, at least one of the bio-oils in the mixture comprising at least two bio-oils (with at least one catalyst poisoning inhibitor added thereto) is vegetable oil, used cooking oil, pyrolyzed bio-oil, or hydrothermal liquefaction bio-oil. In one embodiment, the bio-oil is not produced by the pyrolysis of biological waste.

[0048] Preferably, the bio-oil in the blend containing at least one bio-oil (with at least one catalyst poisoning inhibitor added thereto) is vegetable oil, used cooking oil, pyrolyzed bio-oil, or hydrothermal liquefaction bio-oil. In one embodiment, the bio-oil is not produced by the pyrolysis of biological waste.

[0049] Pyrolysis is the thermal decomposition or degradation of such feedstocks under inert conditions, producing gaseous, liquid, and solid carbon fractions. During pyrolysis, the feedstock is converted into a variety of chemical substances, including a) gases such as H2, C1-C4 alkanes, C2-C4 alkenes, acetylene, propyne, and 1-butyne; b) pyrolysis oil with a boiling temperature ranging from 25°C to 500°C; and c) carbon.

[0050] Pyrolysis methods are known in themselves. They are described, for example, in EP 0713906 A1 and WO 95 / 03375 A1.

[0051] Bio-oil contains:

[0052] - Sulfur concentration not exceeding 5,000 mg / L, preferably not exceeding 3,000 mg / L, more preferably not exceeding 800 mg / L (as determined according to ASTM D 5453);

[0053] - At least 10 mg / L of nitrogen, preferably not more than 20,000 mg / L of nitrogen, more preferably not more than 10,000 mg / L of nitrogen, and most preferably 30 to 5,000 mg / L of nitrogen (as determined according to ASTM D 6069).

[0054] - At least 1 mg / L of halogen, preferably 1 to 20,000 mg / L of halogen, more preferably 5 to 5,000 mg / L of halogen, and most preferably 5 to 200 mg / L of halogen (as determined according to ASTM D 5808).

[0055] -Based on the weight of bio-oil, up to 50 wt% (e.g., 15 to 50 wt%) or up to 40 wt% (e.g., 15 to 40 wt%), preferably up to 30 wt% (e.g., 15 to 30 wt%), more preferably up to 20% (e.g., more than 10 wt% and not more than 20 wt%), more preferably up to 10 wt%, more preferably up to 5 wt%, more preferably up to 1 wt% water (as determined according to DIN 51777);

[0056] -Oxygen (as determined according to ASTM 5291) in the range of 0.5 to 70 g(O) / 100 g(oil) (e.g., more than 25 to no more than 70 g(O) / 100 g(oil)), preferably 0.5 to 50 g(O) / 100 g(oil) (e.g., more than 15 to no more than 50 g(O) / 100 g(oil)), preferably 25 to 50 g(O) / 100 g(oil), or 0.5 to 15 g(O) / 100 g(oil); and / or

[0057] - In the range of 0 to 200 mg (KOH) / g bio-oil (mg (KOH) / g (oil)) (e.g., 10 to 200 mg (KOH) / g (oil) or 50 to 200 mg (KOH) / g (oil)), 0 to 150 mg (KOH) / g (oil) (e.g., 10 to 150 mg (KOH) / g (oil) or 50 to 150 mg (KOH) / g (oil)), preferably 0 to 100 mg (KOH) / g (KOH) / g (e.g., 10 to 100 mg (KOH) / g (oil) or 50 to 100 mg (KOH) / g (oil)), preferably 0 to 70 mg (KOH) / g (KOH) / g (e.g., more than 10 mg (KOH) / g (oil) and not more than 70 mg (KOH) / g (oil)), preferably 0 to 25 mg (KOH) / g (oil) Total acid number (TAN) in the range of mg (KOH) / g (oil) (determined by titration with KOH solution and given in milligrams of KOH required to neutralize the acid in one gram of bio-oil).

[0058] Examples of sulfur-containing compounds include thiols, sulfides, disulfides, sulfoxides, sulfones, sulfinic acids, sulfonic acids, sulfonamides, sulfonates, sulfates, thioketones, thiocarboxylic acids, thioesters, dithiocarboxylic acids, thiocyanates, sulfonamides, etc.

[0059] 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 heteroaromatic compounds, carbamates, sulfonamides, thiocyanates, and sulfonamides.

[0060] Examples of halogen-containing compounds include aliphatic halides, (hetero)aromatic halides, aliphatic-aromatic halides, acyl halides, etc. Halogens can also act as anions (such as F). - Cl - ,Br - and I - It exists in bio-oils.

[0061] Examples of oxygen-containing compounds include oxygenated compounds, glycerides, esters, carboxylic acids, phenols, alcohols, ethers, ketones, aldehydes, furans, and sugars.

[0062] 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 its salts.

[0063] The bio-oil preferably further has a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g (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). Such bio-oils are particularly suitable for the methods and uses according to the invention.

[0064] A mixture of bio-oils can be obtained by mixing two or more bio-oils made from different raw materials and / or under different pyrolysis conditions and / or made from the same raw materials and pyrolysis conditions in different batches.

[0065] Blends containing 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 residue (HVR), or pyrolysis oil). Other hydrocarbon liquids suitable for blending with at least one bio-oil are known to those skilled in the art.

[0066] In one embodiment of the invention, at least one bio-oil is blended with one or more other hydrocarbon liquids (such as naphtha and / or high-vacuum residue oil and / or pyrolysis oil). 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 additionally contain water. The resulting blend comprises, 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.

[0067] Bio-oil and / or mixtures and / or blends of at least two different bio-oils come into physical and / or chemical contact with the container system during pyrolysis, storage, transportation, processing, purification, upgrading, blending with other bio-oils, and blending at least one bio-oil with at least one other hydrocarbon liquid (such as naphtha or pyrolysis oil).

[0068] When bio-oil, a mixture of two or more bio-oils, or a blend containing at least one bio-oil comes into physical and / or chemical contact with the container system, the temperature range is low (e.g., room temperature) or the temperature outside the building where the bio-oil can be stored and / or transported, up to several hundred °C applied during the pyrolysis reaction. The temperature of the bio-oil, a mixture of two or more bio-oils, or a blend containing at least one bio-oil can be raised to, for example, 50 °C or 70 °C during pipeline transport or other processing operations to obtain reduced viscosity and thus more favorable fluid properties. During storage, transport, and / or processing, the temperature range of the bio-oil, a mixture of two or more bio-oils, or a blend containing at least one bio-oil is from about -10 °C to about 100 °C. The temperature of the bio-oil, a mixture of two or more bio-oils, or a blend containing at least one bio-oil can be raised to approximately 270°C or even higher, such as 300°C, 400°C, or 500°C, in a thermal process (e.g., preheating), and then the bio-oil is fed, for example, into a steam cracking reactor or a partial oxidation reactor for steam cracking or partial oxidation. During all said temperatures, the bio-oil, a mixture of two or more bio-oils, or a blend containing at least one bio-oil is preferably in contact with a steel container system.

[0069] The thermal process in step (iii) is preferably selected from the group consisting of: preheating for steam cracking, steam cracking, preheating for partial oxidation, and partial oxidation.

[0070] Therefore, the temperature range is from about 10°C to about 300°C. This temperature range also applies to blends containing at least one bio-oil and bio-oil mixtures containing at least two bio-oils.

[0071] "Container system" is defined herein as an apparatus for the storage, transport, directing, processing, and thermal processing of bio-oils, mixtures comprising at least two bio-oils, or blends comprising at least one bio-oil. A container system can also be a reactor, wherein a) the bio-oil is produced by a pyrolysis reaction and / or b) the bio-oil or a portion thereof is chemically and / or physically transformed, for example, during a thermal process. "Container system" includes, but is not limited to, stationary containers, movable containers, piping, reactors, heat exchangers, valves, etc.

[0072] The container system according to the invention is made of or contains steel. The steel is in physical and / or chemical contact with bio-oil, a mixture containing at least two bio-oils, or a blend containing at least one bio-oil.

[0073] In principle, steel materials can be any type of material called steel, such as stainless steel, high-alloy steel, low-alloy steel, carbon steel, etc. For economic reasons, carbon steel or low-alloy steel is preferred. Carbon steel and low-alloy steel are cheaper than, for example, stainless steel, but are less resistant to corrosion caused by bio-oils.

[0074] “Carbon steel” is defined herein as steel containing C in the range of about 0.05 to about 2.0 wt.% . ...

[0075] 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.%

[0076] "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. The 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.

[0077] Compared to oils from fossil sources (such as crude oil), the specific composition of bio-oils, with higher levels of components (such as sulfur, nitrogen, halogens, water, and oxygen) and a higher total acid number (TAN), leads to (more) severe corrosion of the steel in container systems, especially when these 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 bio-oil, causing poisoning of the heterogeneous catalysts to which the bio-oil comes into contact during subsequent process steps, such as purification and / or upgrading, as well as scaling of the adsorbents and / or membranes.

[0078] To prevent such heterogeneous catalyst poisoning and / or fouling of adsorbents and / or membranes in subsequent process steps, at least one catalyst poisoning inhibitor is added to the bio-oil, a mixture containing at least two bio-oils, or a blend containing at least one bio-oil.

[0079] 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 inhibitor selected from amphiphilic compounds, wherein the amphiphilic compounds contain at least one C6 to C6 compound. 26 The nonpolar residues of alkyl and / or alkylene groups and at least one polar residue, wherein the at least one polar residue contains at least one nitrogen atom.

[0080] "Amphiphilic" is defined in this paper as a molecule and / or ion that simultaneously possesses hydrophilic (polar) and lipophilic (nonpolar) properties.

[0081] The at least one catalyst poisoning inhibitor is preferably selected from the group consisting of:

[0082] - Coupled to the saturated, monounsaturated, and polyunsaturated C6 to C6 of N-heterocyclic compounds via C-C bonds. 26 fatty acid;

[0083] - Nitrogen compounds quaternized with polycarboxylic acids by combining free hydrocarbon groups with hydrocarbon epoxides; and

[0084] - Its mixture.

[0085] Saturated, monounsaturated, and polyunsaturated C6 to C 26 Suitable adducts of fatty acids coupled to N-heterocyclic compounds via C-C bonds include 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 to 270°C for five hours and removing the water formed by azeotropic distillation with xylene.

[0086] Suitable nitrogen compounds quaternized with free hydrocarbon groups by combining hydrocarbon epoxides with free hydrocarbon groups specifically include C4 ... 16 -alkyl-N(CH3)2. Other suitable nitrogen compounds quaternized with free hydrocarbon-substituted polycarboxylic acids by alkyl epoxides 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 herein by reference. In particular, suitable nitrogen compounds quaternized with free hydrocarbon-substituted polycarboxylic acids by alkyl epoxides comprise a cation having formula (1a) or (1b) and an anion having formula (2).

[0087]

[0088] And can be obtained by reacting compounds having formulas (3), (4) and (5).

[0089]

[0090] in

[0091] -R1 is a long-chain hydrocarbon group, preferably having a number average molecular weight of 350 to 20,000 or 350 to 5,000; and

[0092] - At least one of the groups R2, R3 and R4 is a straight-chain or branched, saturated or unsaturated C8-C40-hydrocarbon group, and the other groups are the same or different straight-chain or branched, saturated or unsaturated C1-C6-hydrocarbon groups;

[0093] or

[0094] All R2, R3, and R4 groups are the same or different straight-chain or branched, saturated or unsaturated long-chain C8-C40 hydrocarbon groups;

[0095] or

[0096] All R2, R3, and R4 groups are the same or different short-chain C1-C7 alkyl groups;

[0097] -R5 is an H or hydrocarbon group, wherein the hydrocarbon group is an aliphatic or aromatic group having 1 to 10 carbon atoms; and

[0098] -- R is H or a group produced by esterification with an epoxide.

[0099] Preferably, at least two of the R2, R3 and R4 groups are the same or different and each is a straight-chain or branched C10-C20-alkyl group, and the other group is a C1-C4-alkyl group.

[0100] The term "and mixtures thereof" in relation to at least one catalyst poisoning inhibitor should be understood to mean that the inhibitor contains, for example, one or more saturated, monounsaturated, and polyunsaturated C6 to C6 groups coupled to N-heterocyclic compounds via C-C bonds. 26 Fatty acids, or, for example, one or more saturated, monounsaturated, and polyunsaturated C6 to C6 nucleotides coupled to N-heterocyclic compounds via C-C bonds. 26 A combination of fatty acids with, for example, one or more quaternized nitrogen compounds of polycarboxylic acids that are substituted with free hydrocarbon groups by hydrocarbon epoxides.

[0101] The mass fraction of the at least one catalyst poisoning inhibitor in the bio-oil ranges from 5 to 25,000 ppm, preferably from 10 to 20,000 ppm, and more preferably from 20 to 10,000 ppm.

[0102] The at least one catalyst poisoning inhibitor can also be used in mixtures of at least two bio-oils and blends containing at least one bio-oil.

[0103] The mass fraction of the at least one catalyst poisoning inhibitor in a mixture of at least two bio-oils ranges from 5 to 25,000 ppm, preferably from 10 to 20,000 ppm, and more preferably from 20 to 10,000 ppm.

[0104] The mass fraction of the at least one catalyst poisoning inhibitor in the blend containing at least one bio-oil ranges from 5 to 25,000 ppm, preferably from 10 to 20,000 ppm, and more preferably from 20 to 10,000 ppm.

[0105] The at least one catalyst poisoning inhibitor can also be used in a method for inhibiting catalyst poisoning and / or scaling during a thermal process for upgrading and / or converting bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil, the method comprising the following steps:

[0106] (i) Providing a bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil in a steel container system, wherein the bio-oil, the mixture of at least two bio-oils, or the blend containing at least one bio-oil is in physical and / or chemical contact with the steel container system.

[0107] (ii) Adding at least one catalyst poisoning inhibitor to the bio-oil, a mixture of the at least two bio-oils, or a blend containing at least one bio-oil, wherein the at least one catalyst poisoning inhibitor is selected from the group consisting of amphiphilic compounds, which contain at least one compound selected from C6 to C6. 26 The nonpolar residues of 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.

[0108] (iii) Contacting the bio-oil containing at least one catalyst poisoning inhibitor, a mixture of at least two bio-oils, or a blend containing at least one bio-oil with at least one heterogeneous catalyst, or

[0109] The bio-oil containing at least one catalyst poisoning inhibitor, a mixture of at least two bio-oils, or a blend containing at least one bio-oil is subjected to a heating process.

[0110] Preferably, the at least one catalyst poisoning inhibitor in the method is selected from the group consisting of:

[0111] - Saturated, monounsaturated, and polyunsaturated C6 to C6 26 fatty acid;

[0112] -Dimeric fatty acids;

[0113] - A copolymer of at least one olefinically unsaturated polymerizable polycarboxylic anhydride and at least one polymerizable olefin;

[0114] -Alkenyl succinic acid and alkenyl succinic anhydride, wherein the alkenyl residue is selected from C6 to C6 having one or more C=C bonds. 26 alkenyl;

[0115] - Coupled to the saturated, monounsaturated, and polyunsaturated C6 to C6 of N-heterocyclic compounds via C-C bonds. 26 fatty acid;

[0116] - Nitrogen compounds quaternized with polycarboxylic acids by combining free hydrocarbon groups with hydrocarbon epoxides; and

[0117] - Its mixture.

[0118] Preferably, the bio-oil provided according to the present invention and in step (i) contains not more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil).

[0119] More preferably, the bio-oil provided according to the present invention and in step (i) contains not more than 800 mg / L of sulfur, not more than 10,000 mg / L of nitrogen, 5 to 200 mg / L of halogen, and oxygen in the range of 0.5 to 50 g (O) / 100 g (oil).

[0120] Preferably, the mixture of at least two bio-oils provided according to the present invention and in step (i) contains no more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil).

[0121] More preferably, according to the present invention and the mixture of at least two bio-oils provided in step (i) contains no more than 800 mg / L of sulfur, no more than 10,000 mg / L of nitrogen, 5 to 200 mg / L of halogen, and oxygen in the range of 0.5 to 50 g (O) / 100 g (oil).

[0122] Preferably, according to the invention and in the blend provided in step (i) at least one bio-oil contains not more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil).

[0123] More preferably, according to the present invention, at least one bio-oil in the blend provided in step (i) contains not more than 800 mg / L of sulfur, not more than 10,000 mg / L of nitrogen, 5 to 200 mg / L of halogen, and oxygen in the range of 0.5 to 50 g (O) / 100 g (oil).

[0124] Preferably, the steel container system comprises one or more materials selected from the group consisting of carbon steel and low alloy steel.

[0125] Preferably, steel containers are used for steps (i) and (ii), for example for the storage and / or transport of bio-oils, mixtures of at least two bio-oils, or blends containing at least one bio-oil, and for the addition of said at least one catalyst poisoning inhibitor. Optionally, step (iii) is carried out in a reaction vessel different from the steel container system used for steps (i) and (ii).

[0126] Preferably, the mass fraction of the at least one catalyst poisoning inhibitor in the bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil ranges from 5 to 25,000 ppm, more preferably from 10 to 20,000 ppm, and most preferably from 20 to 10,000 ppm.

[0127] After separating the gaseous and solid products formed by the pyrolysis reaction, the at least one catalyst poisoning inhibitor can be added to the bio-oil. The at least one catalyst poisoning inhibitor can also be added to the bio-oil in subsequent process steps, such as when or after filling the bio-oil into a storage container, or when or after filling the bio-oil into a transport container, and after filtration of the bio-oil. The at least one catalyst poisoning inhibitor can also be added to the bio-oil before, during, and / or after purifying the pyrolysis oil through 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 bio-oil is not limited to specific process steps or times.

[0128] The at least one catalyst poisoning inhibitor may be added to a mixture of at least two bio-oils before, during, and / or after the individual bio-oils are mixed.

[0129] The at least one catalyst poisoning inhibitor may be added to a blend containing at least one bio-oil before, during, and / or after blending.

[0130] In one embodiment of the invention, the mixture of at least one catalyst poisoning inhibitor and bio-oil is formed by forced agitation (e.g., by stirring) or any other suitable means to obtain a uniform contribution of the at least one catalyst poisoning inhibitor in the bio-oil.

[0131] In another embodiment of the invention, the at least one catalyst poisoning inhibitor is added to the bio-oil without forced agitation.

[0132] When at least one catalyst poisoning inhibitor is added, both forced agitation and non-forced agitation can be applied to mixtures of at least two bio-oils and blends containing at least one bio-oil.

[0133] At least one additive can be used as a catalyst poisoning inhibitor in bio-oils, mixtures containing at least two bio-oils, or blends containing at least one bio-oil to inhibit the formation of catalysts selected from Fe. 2+ Ions, Fe 3+ Ions, Ni 2+ Catalytic poisons of the group consisting of ions and compounds of the metal ions are enriched in the bio-oil, a mixture comprising at least two bio-oils, or a blend comprising at least one bio-oil, wherein the at least one additive is selected from amphiphilic compounds containing at least one compound selected from C6 to C4. 26 The nonpolar residues of alkyl and / or alkylene groups and at least one polar residue, the at least one polar residue containing at least one heteroatom selected from the group consisting of oxygen and nitrogen.

[0134] Preferably, for the stated use, the at least one additive is selected from the group consisting of:

[0135] - Saturated, monounsaturated, and polyunsaturated C6 to C6 26 fatty acid;

[0136] -Dimeric fatty acids;

[0137] - A copolymer of at least one olefinically unsaturated polymerizable polycarboxylic anhydride and at least one polymerizable olefin;

[0138] -Alkenyl succinic acid and alkenyl succinic anhydride, wherein the alkenyl residue is selected from C6 to C6 having one or more C=C bonds. 26 alkenyl;

[0139] - Coupled to the saturated, monounsaturated, and polyunsaturated C6 to C6 of N-heterocyclic compounds via C-C bonds. 26 fatty acid;

[0140] - Nitrogen compounds quaternized with polycarboxylic acids by combining free hydrocarbon groups with hydrocarbon epoxides; and

[0141] - Its mixture.

[0142] Preferably, for the stated use, the mass fraction of the at least one additive in the bio-oil, a mixture comprising at least two bio-oils, or a blend comprising at least one bio-oil ranges from 5 to 25,000 ppm, more preferably from 10 to 20,000 ppm, and most preferably from 20 to 10,000 ppm.

[0143] Preferably, for the stated use, the bio-oil contains no more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g(O) / 100 g(oil).

[0144] More preferably, for the stated use, the bio-oil contains not more than 800 mg / L of sulfur, not more than 10,000 mg / L of nitrogen, 5 to 200 mg / L of halogen, and oxygen in the range of 0.5 to 50 g (O) / 100 g (oil).

[0145] Preferably, for the stated use, the bio-oil mixture comprising at least two bio-oils contains no more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil).

[0146] More preferably, for the stated use, the bio-oil mixture comprising at least two bio-oils contains no more than 800 mg / L of sulfur, no more than 10,000 mg / L of nitrogen, 5 to 200 mg / L of halogen, and oxygen in the range of 0.5 to 50 g (O) / 100 g (oil).

[0147] Preferably, for the stated use, the at least one bio-oil in the blend containing at least one bio-oil contains no more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil).

[0148] More preferably, for the stated use, the at least one bio-oil in the blend containing at least one bio-oil contains not more than 800 mg / L of sulfur, not more than 10,000 mg / L of nitrogen, 5 to 200 mg / L of halogen, and oxygen in the range of 0.5 to 50 g (O) / 100 g (oil).

[0149] Preferably, for the stated use, the bio-oil, a bio-oil mixture comprising at least two bio-oils, or a blend comprising at least one bio-oil is in physical and / or chemical contact with a steel container system comprising one or more materials selected from carbon steel and low alloy steel.

[0150] Assume that the at least one catalyst poisoning inhibitor can form a film on the surface of the container system by adsorption, the adsorption including the interaction between the at least one catalyst poisoning inhibitor and the surface of the container system through physical adsorption and / or chemical adsorption.

[0151] Bio-oils containing at least one catalyst poisoning inhibitor, bio-oil mixtures containing at least two bio-oils, or blends containing at least one bio-oil, and methods using such bio-oil compositions reduce undesirable poisoning of heterogeneous catalysts used in or after the purification, upgrading, and / or blending of bio-oils.

[0152] Examples of purification processes involving heterogeneous catalysts are hydrotreatment or hydroprocessing technologies used to remove oxygen compounds (hydrodeoxygenation, HDO), sulfur compounds (hydrodesulfurization, HDS), and nitrogen compounds (hydronitrogenation, HDN) from bio-oils. Such catalysts typically comprise at least one Group 6 metal component and at least one Group 8, 9, or 10 metal component complexed with a support. The catalysts used in such purification methods are typically composed of, for example, Fe... 2+ Ions, Fe 3+ Ions, Ni 2+ Poisoning caused by ions and compounds of the metal ions is highly sensitive. When using the bio-oil compositions and methods according to the invention, the lifetime of the catalysts is increased and their activity is maintained for a longer period of time.

[0153] Furthermore, Fe adsorbed on the steel surface 2+ and / or Fe 3+ In the presence of ions, undesirable coking may occur at elevated temperatures in parts such as pipes made of steel, preferably carbon steel or low-alloy steel. Such undesirable coking may cause blockages in parts such as pipes.

[0154] Bio-oils containing at least one catalyst poisoning inhibitor, bio-oil mixtures containing at least two bio-oils, or blends containing at least one bio-oil, and methods of using such bio-oil compositions also reduce undesirable scaling during or after thermal processes in the purification, upgrading, blending, and / or conversion of bio-oils.

[0155] A small amount of at least one catalyst poisoning inhibitor in bio-oil, a mixture of bio-oils containing at least two bio-oils, or a blend containing at least one bio-oil has no negative impact during purification, upgrading, blending, and / or conversion processes. This is achieved by using 5 to 25,000 ppm, preferably 10 to 20,000 ppm, and more preferably 20 to 10,000 ppm. Preferred embodiment

[0156] 1. A bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil, wherein the bio-oil contains at least one catalyst poisoning inhibitor selected from amphiphilic compounds, the amphiphilic compounds comprising at least one C6 to C6 compound. 26 The nonpolar residues of 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, preferably comprising at least one nitrogen atom.

[0157] 2. The bio-oil, mixture, or blend according to Example 1, wherein the at least one catalyst poisoning inhibitor is selected from the group consisting of:

[0158] - Coupled to the saturated, monounsaturated, and polyunsaturated C6 to C6 of N-heterocyclic compounds via C-C bonds. 26 fatty acid;

[0159] - Nitrogen compounds quaternized with polycarboxylic acids by combining free hydrocarbon groups with hydrocarbon epoxides; and

[0160] - Its mixture.

[0161] 3. The bio-oil, mixture or blend according to any one of Examples 1 and 2, wherein the mass fraction of the at least one catalyst poisoning inhibitor ranges from 5 to 25,000 ppm.

[0162] 4. At least one bio-oil from any of the bio-oils, mixtures, or blends according to any one of Examples 1 to 3, containing not more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil), and optionally having a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g 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.

[0163] 5. The bio-oil according to any one of Examples 1 to 4, wherein the bio-oil, at least one of the bio-oils in the mixture comprising at least two bio-oils, or at least one of the bio-oils in the blend comprising at least one bio-oil is a vegetable oil, a pyrolytic bio-oil, or a hydrothermal liquefaction bio-oil.

[0164] 6. A method for inhibiting catalyst poisoning and / or scaling during a thermal process for upgrading and / or converting bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil, the method comprising the following steps:

[0165] (i) Providing a bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil in a steel container system, wherein the bio-oil, the mixture of at least two bio-oils, or the blend containing at least one bio-oil is in physical and / or chemical contact with the steel container system.

[0166] (ii) Adding at least one catalyst poisoning inhibitor to the bio-oil, a mixture of the at least two bio-oils, or a blend containing at least one bio-oil, wherein the at least one catalyst poisoning inhibitor is selected from the group consisting of amphiphilic compounds, which contain at least one compound selected from C6 to C6. 26 The nonpolar residues of 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.

[0167] (iii) Contacting the bio-oil containing at least one catalyst poisoning inhibitor, a mixture of at least two bio-oils, or a blend containing at least one bio-oil with at least one heterogeneous catalyst, or

[0168] The bio-oil containing at least one catalyst poisoning inhibitor, a mixture of at least two bio-oils, or a blend containing at least one bio-oil is subjected to a heating process.

[0169] 7. The method according to Example 6, wherein the mass fraction of the at least one catalyst poisoning inhibitor ranges from 5 to 25,000 ppm.

[0170] 8. The method according to any one of Examples 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.

[0171] 9. The method according to any one of Examples 6 to 8, wherein the at least one catalyst poisoning inhibitor is selected from the group consisting of:

[0172] - Saturated, monounsaturated, and polyunsaturated C6 to C6 26 fatty acid;

[0173] -Dimeric fatty acids;

[0174] - A copolymer of at least one olefinically unsaturated polymerizable polycarboxylic anhydride and at least one polymerizable olefin;

[0175] -Alkenyl succinic acid and alkenyl succinic anhydride, wherein the alkenyl residue is selected from C6 to C6 having one or more C=C bonds. 26 alkenyl;

[0176] - Coupled to the saturated, monounsaturated, and polyunsaturated C6 to C6 of N-heterocyclic compounds via C-C bonds.26 fatty acid;

[0177] - Nitrogen compounds quaternized with polycarboxylic acids by combining free hydrocarbon groups with hydrocarbon epoxides; and

[0178] - Its mixture.

[0179] 10. The method according to any one of Examples 6 to 9, wherein the bio-oil provided in step (i), or a mixture of the at least two bio-oils, or a blend containing at least one bio-oil, contains not more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil), and optionally has a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g 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.

[0180] 11. The method according to any one of Examples 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.

[0181] 12. At least one additive as a catalyst poisoning inhibitor in bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil for inhibiting the use of a selection including Fe. 2+ Ions, Fe 3+ Ions, Ni 2+ The use of catalyst poisons of the group consisting of ions and compounds of the metal ions in the enrichment of bio-oils, mixtures of at least two bio-oils, or blends containing at least one bio-oil, wherein the at least one additive is selected from amphiphilic compounds containing at least one compound selected from C6 to C4. 26 The nonpolar residues of 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.

[0182] 13. The use according to Example 12, wherein the at least one additive is selected from the group consisting of:

[0183] - Saturated, monounsaturated, and polyunsaturated C6 to C6 26 fatty acid;

[0184] -Dimeric fatty acids;

[0185] - A copolymer of at least one olefinically unsaturated polymerizable polycarboxylic anhydride and at least one polymerizable olefin;

[0186] -Alkenyl succinic acid and alkenyl succinic anhydride, wherein the alkenyl residue is selected from C6 to C6 having one or more C=C bonds. 26 alkenyl;

[0187] - Coupled to the saturated, monounsaturated, and polyunsaturated C6 to C6 of N-heterocyclic compounds via C-C bonds. 26 fatty acid;

[0188] - Nitrogen compounds quaternized with polycarboxylic acids by combining free hydrocarbon groups with hydrocarbon epoxides; and

[0189] - Its mixture.

[0190] 14. The use according to any one of Examples 12 and 13, wherein the mass fraction of the at least one additive in the bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil ranges from 5 to 25,000 ppm.

[0191] 15. The use according to any one of Examples 12 to 14, wherein the bio-oil, or a mixture of at least two bio-oils, or a blend containing at least one bio-oil, contains not more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil), and optionally has a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g 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.

[0192] The present invention will be further explained by the following non-limiting examples, some of which are based on experiments using oils obtained from the pyrolysis of solid waste. However, those skilled in the art will understand that the conclusions drawn therefrom are equally applicable to the bio-oils described herein. For example, it is known, as from Eschenbacher et al. (Energy Fuels 2021, 35, 18333-18369; and corresponding references cited therein), that biomass-derived pyrolysis oils typically also exhibit high water content, high oxygen content, and high total acid value. Example

[0193] Metal ions (such as Fe) during storage in steel container systems 2+ Fe 3+ Ni 2+The enrichment of compounds containing these metal ions was tested using pyrolysis oil by evaluating the corrosion erosion of steel fingers made of carbon steel (BS970-070M20; also known as DIN 1.0402) after immersion in the pyrolysis oil at 60°C for 4 h. The tests were conducted with and without the addition of different amounts of the catalyst poisoning inhibitor according to the invention.

[0194] A pyrolysis oil was obtained from end-of-life tires (ELTs) containing 30 mg / L of halogen and 1.2 g / L of sulfur, with a TAN = 8.4. Corrosion observed on the steel fingers was then visually inspected and rated from 0 (no visible corrosion) to ++++ (severe corrosion).

[0195] Table 1: Results of corrosion tests on steel finger-shaped components immersed in pyrolysis oil at 60°C for 4 hours.

[0196]

[0197] 1-4 Available from BASF SE

[0198] The examples and results in Table 1 demonstrate 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 present invention. Therefore, in the presence of at least one catalyst poisoning inhibitor added to the pyrolysis oil, metal ions (such as Fe) are reduced or inhibited. 2+ Fe 3+ and Ni 2+ Compounds of such metal ions are not enriched or are less enriched, and catalyst poisoning and / or fouling of adsorbents and / or membranes are reduced.

[0199] Another pyrolysis oil manufactured by BASF was used in the following examples and comparative examples. The pyrolysis oil is produced from plastic waste containing polyolefins through a pyrolysis reaction. The pyrolysis oil was mixed with high-vacuum residue oil (HVR) and water as follows: 166 g pyrolysis oil + 192 g HVR + 136 g water. The corrosion behavior of steel plates made of 1.4541 (X6CrNiTi18-10) and 1.4571 (X6CrNiMoTi17-12-2) was tested for 4 × 7 days at T = 275°C in a sealed autoclave made of nickel alloy, with the mixture containing pyrolysis oil being replaced between each round of testing. The steel plates, made of 1.4551 and 1.4571 steel respectively, had dimensions of 50 × 20 × 2 mm (including welds) and were 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 stirred during the test. A temperature of 275°C was selected to simulate the preheating conditions used for steam cracking and for partial oxidation.

[0200] The average linear corrosion rate was determined and rated as x (fail) or o (pass).

[0201] Table 2: Results from corrosion tests at T = 275°C.

[0202] .

Claims

1. A bio-oil, a mixture of at least two bio-oils, or a blend comprising at least one bio-oil, wherein the bio-oil contains at least one catalyst poisoning inhibitor selected from the group consisting of: - Coupled to the saturated, monounsaturated, and polyunsaturated C6 to C6 of N-heterocyclic compounds via C-C bonds. 26 fatty acid; - Nitrogen compounds quaternized with polycarboxylic acids by combining free hydrocarbon groups with hydrocarbon epoxides; and - Its mixture.

2. The bio-oil, mixture, or blend according to claim 1, wherein, The at least one catalyst poisoning inhibitor is selected from the group consisting of: 2-(2-heptadec-8-enyl-2-imidazoline-1-yl)ethanol, and C4 ... 16 -alkyl-N(CH3)2.

3. The bio-oil, mixture, or blend according to any one of claims 1 and 2, wherein, The mass fraction of the at least one catalyst poisoning inhibitor ranges from 5 to 25,000 ppm.

4. At least one of the bio-oils, mixtures, or blends according to any one of claims 1 to 3, containing not more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil), and optionally having a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g 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 one of claims 1 to 4, wherein, The bio-oil, at least one of the bio-oils in the mixture comprising at least two bio-oils, or at least one of the bio-oils in the blend comprising at least one bio-oil is a vegetable oil.

6. A method for inhibiting catalyst poisoning and / or scaling during a thermal process for upgrading and / or converting bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil, the method comprising the following steps: (i) Providing a bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil in a steel container system, wherein the bio-oil, the mixture of at least two bio-oils, or the blend containing at least one bio-oil is in physical and / or chemical contact with the steel container system. (ii) Adding at least one catalyst poisoning inhibitor to the bio-oil, a mixture of the at least two bio-oils, or a blend containing at least one bio-oil, wherein the at least one catalyst poisoning inhibitor is selected from the group consisting of saturated, monounsaturated, and polyunsaturated C6 to C6 groups of N-heterocyclic compounds coupled to them via C-C bonds. 26 Fatty acids; nitrogen compounds quaternized with free hydrocarbon groups by combining hydrocarbon epoxides with free hydrocarbon groups; and mixtures thereof. (iii) Contacting the bio-oil containing at least one catalyst poisoning inhibitor, a mixture of at least two bio-oils, or a blend containing at least one bio-oil with at least one heterogeneous catalyst, or The bio-oil containing at least one catalyst poisoning inhibitor, a mixture of at least two bio-oils, or a blend containing at least one bio-oil is subjected to a heating process.

7. The method according to claim 6, wherein, The mass fraction of the at least one catalyst poisoning inhibitor ranges from 5 to 25,000 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, monounsaturated, and polyunsaturated C6 to C6 26 fatty acid; -Dimeric fatty acids; - A copolymer of at least one olefinically unsaturated polymerizable polycarboxylic anhydride and at least one polymerizable olefin; -Alkenyl succinic acid and alkenyl succinic anhydride, wherein the alkenyl residue is selected from C6 to C6 having one or more C=C bonds. 26 alkenyl; - Coupled to the saturated, monounsaturated, and polyunsaturated C6 to C6 of N-heterocyclic compounds via C-C bonds. 26 fatty acid; - Nitrogen compounds quaternized with polycarboxylic acids by combining free hydrocarbon groups with hydrocarbon epoxides; and - Its mixture.

10. The method according to any one of claims 6 to 9, wherein, The bio-oil provided in step (i), or a mixture of the at least two bio-oils, or a blend containing at least one bio-oil, contains not more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil), and optionally has a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g 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 (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 as a catalyst poisoning inhibitor in bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil for inhibiting the use of a selection including Fe. 2+ Ions, Fe 3+ Ions, Ni 2+ The use of catalyst poisons of the group consisting of ions and compounds of the metal ions in the enrichment of bio-oils, mixtures of at least two bio-oils, or blends containing at least one bio-oil, wherein the at least one additive is selected from amphiphilic compounds containing at least one compound selected from C6 to C4. 26 The nonpolar residues of 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. The use according to claim 12, wherein, The at least one additive is selected from the group consisting of: - Saturated, monounsaturated, and polyunsaturated C6 to C6 26 fatty acid; -Dimeric fatty acids; - A copolymer of at least one olefinically unsaturated polymerizable polycarboxylic anhydride and at least one polymerizable olefin; -Alkenyl succinic acid and alkenyl succinic anhydride, wherein the alkenyl residue is selected from C6 to C6 having one or more C=C bonds. 26 alkenyl; - Coupled to the saturated, monounsaturated, and polyunsaturated C6 to C6 of N-heterocyclic compounds via C-C bonds. 26 fatty acid; - Nitrogen compounds quaternized with polycarboxylic acids by combining free hydrocarbon groups with hydrocarbon epoxides; and - Its mixture.

14. The use according to any one of claims 12 and 13, wherein, The mass fraction of the at least one additive in the bio-oil, a mixture of at least two bio-oils, or a blend containing at least one bio-oil ranges from 5 to 25,000 ppm.

15. The use according to any one of claims 12 to 14, wherein, The bio-oil, or a mixture of at least two bio-oils, or a blend containing at least one bio-oil, contains not more than 5,000 mg / L of sulfur, at least 10 mg / L of nitrogen, at least 1 mg / L of halogen, and oxygen in the range of 0.5 to 70 g (O) / 100 g (oil), and optionally has a bromine value of about 2 g Br2 / 100 g to about 150 g Br2 / 100 g 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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