Process for purifying biooil

Abstract

The invention relates to a method for purifying bio-oil and a unit for carrying out said method. The invention further relates to a purified bio-oil obtainable or obtained by said process.

Description

[0001] This invention relates to a method for purifying bio-oils and units for carrying out said method. The invention further relates to purified bio-oils obtainable or acquired by said method.

[0002] Bio-oils obtained from different types of biomass are becoming increasingly important as renewable feedstocks for industrial and fuel applications. A key technology for producing bio-oils is the pyrolysis of biomass, which involves thermal degradation in an inert atmosphere.

[0003] Bio-oils obtained from pyrolysis or other methods, if not purified, can corrode and damage steel containers, especially those made of carbon steel and low-alloy steel, used for storing, transporting, guiding, or handling bio-oils. Therefore, purified, high-quality bio-oils are preferred as feedstock to prevent corrosion problems during storage and downstream refining processes.

[0004] US 2021 / 0277324 A1 discloses a method for purifying pyrolysis oil by treating it with sodium hydroxide at a temperature of 240°C. WO 2014 / 165859 A1 discloses a method for purifying pyrolysis oil by reducing the content of contaminants such as acids and metals. Furthermore, WO 2020 / 178599 A1 discloses a method for upgrading pyrolysis oil, which includes washing the pyrolysis oil with water, subsequently washing it with alkanes, and treating the resulting organic phase with an upgrading solution containing a polar organic solvent.

[0005] However, there remains a need to provide improved methods for purifying bio-oils obtained from biomass. In particular, there remains a need to provide improved methods that allow for reduced corrosion during downstream processes and / or storage.

[0006] Therefore, there is a need for a method to purify bio-oils (particularly by reducing total acid value and oxygen content). In practice, there is a need to provide high-value purified bio-oils using economical methods.

[0007] Therefore, the present invention relates to a method for purifying bio-oil, the method comprising:

[0008] (i) Provide a flow F0 containing bio-oil;

[0009] (ii) Ensure that the flow F0 provided in (i) is in at least one extraction zone Z E The medium undergoes extraction to obtain a stream F1 containing the extracted bio-oil, wherein (ii) includes:

[0010] (ii.1) Introduce F0 into Z E The extraction unit UM1 is included;

[0011] (ii.2) In UM1, F0 is contacted with water and alkali B at a temperature T1 ranging from 10°C to 200°C to obtain P containing an aqueous phase. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) The pH ranges from 7.5 to 11;

[0012] (ii.3) Allow the mixture M1 obtained according to (ii.2) to enter Z. E The liquid-liquid separation unit US1, located downstream of UM1, contains P. A (1) flow F A (1) and P contained in the bio-oil extracted from it. O (1) Flow F1;

[0013] (ii.4) From Z E Move F1 out of the middle;

[0014] (iii) Ensure that the flow F1 provided in (ii) is in at least one washing zone Z W The middle undergoes a cleansing—Z W Located in Z E Downstream, to obtain a stream F2 containing purified bio-oil; and optionally...

[0015] (v) The F2 containing the bio-oil obtained according to (iii) is introduced into at least one storage unit SU and the bio-oil is stored in the SU.

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

[0017] Preferably, 95 to 100 wt%, more preferably 98 to 100 wt%, and even more preferably 99 to 100 wt% of F0 is composed of bio-oil. It is possible that 99.5 to 100 wt%, 99.8 to 100 wt%, or 99.9 wt% of F0 is composed of bio-oil.

[0018] Preferably, the total acid value (TAN) of the bio-oil according to (i) is in the range of 0 to 200 mg (KOH) / g F0 (mg (KOH) / g (F0)), for example 50 to 200 mg (KOH) / g (F0) or 100 to 200 mg (KOH) / g (F0).

[0019] 0 to 150 mg (KOH) / g (F0), for example 50 to 150 mg (KOH) / g (F0) or 100 to 150 mg (KOH) / g (F0).

[0020] 0 to 100 mg (KOH) / g (F0), for example 50 to 100 mg (KOH) / g (F0) or 70 to 100 mg (KOH) / g (F0).

[0021] Preferably 0 to 70 mg (KOH) / g (F0), for example greater than 60 mg (KOH) / g (F0) and not greater than 70 mg (KOH) / g (F0).

[0022] Preferably, the concentration is 0.5 to 60 mg KOH / g (F0), more preferably 1 to 40 mg KOH / g (F0), and most preferably in the range of 3 to 20 mg KOH / g (F0), as determined in Reference Example 3.

[0023] In the context of this invention, the bio-oil to be purified can have any oxygen content.

[0024] Preferably, the bio-oil according to (i) has an oxygen content in the range of 0.5 to 70 g(O) / 100 g(F0), for example, greater than 25 to not greater than 70 g(O) / 100 g(F0).

[0025] Preferably 0.5 to 50 g(O) / 100 g(F0), for example greater than 15 to no greater than 50 g(O) / 100 g(F0), preferably 25 to 50 g(O) / 100 g(F0), or

[0026] The concentration is 0.5 to 15 g(O) / 100 g(F0), more preferably in the range of 0.5 to 10 g(O) / 100 g(F0), more preferably in the range of 0.5 to 5 g(O) / 100 g(F0), and even more preferably in the range of 0.5 to 2 g(O) / 100 g(F0), as determined in Reference Example 4.

[0027] Preferably, the bio-oil according to (i) has a total chlorine content in the range of 30 to 3,000 wppm (ppm by weight), more preferably 30 to 500 wppm, and even more preferably 30 to 300 wppm, as determined in Reference Example 1.1.

[0028] Preferably, the bio-oil according to (i) has a chloride content of up to 40 wppm, more preferably in the range of 0 to 30 wppm, as determined in Reference Example 1.2.

[0029] Preferably, the bio-oil according to (i) has a nitrogen content in the range of 50 to 20,000 wppm (ppm by weight), more preferably 50 to 5,000 wppm, and even more preferably 100 to 4,000 wppm, as determined in Reference Example 2.

[0030] Preferably, the bio-oil according to (i) has a sulfur content of not more than 5,000 wppm (ppm by weight), preferably not more than 3,000 wppm, more preferably not more than 800 wppm, as determined in Reference Example 5.

[0031] (i) The bio-oil is available or obtained from biomass through mechanical and physical processes as well as chemical methods. Bio-oil is a mixture of liquid compounds, primarily consisting of highly oxidized compounds (e.g., glycerides, esters, carboxylic acids, phenols, alcohols, ketones, aldehydes, furans, and sugars) and water, and its exact composition depends on the biomass feedstock and the processing steps applied. The term bio-oil specifically includes vegetable oils such as rapeseed oil, sunflower oil, soybean oil, corn oil, castor oil, jatropha oil, palm oil, and makkapa palm (kernel or pulp) oil and their processing residues (such as palm fatty acid distillates), waste cooking oils, tall oils, animal fats, and oils obtained through the thermochemical conversion of biomass (e.g., biomass-derived pyrolysis or hydrothermal liquefaction oils), and mixtures thereof. Vegetable oils are primarily composed of glycerides, particularly triglycerides, i.e., esters formed from glycerol and fatty acids.

[0032] 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 organic food waste, such as meat processing waste, fish processing waste, or waste cooking oil.

[0033] The mechanical and physical operations may include harvesting and collecting, as well as crushing, cracking, cutting, shredding, grinding, peeling, milling, extrusion, irradiation, compression, pressing, filtering, sieving, adsorption, and heat treatment such as drying and roasting.

[0034] The chemical methods may include extraction, distillation, thermochemical transformations such as pyrolysis or hydrothermal liquefaction, hydrolysis, saponification, neutralization, ketation, and hydrogenation.

[0035] Preferably, (i) includes

[0036] (i.1) Removing bio-oil from storage tanks, trucks or tankers.

[0037] Preferably, (ii.2) includes

[0038] (ii.2.1) Introduce water into Z E Included in UM1;

[0039] (ii.2.2) In UM1, F0 is brought into contact with water, or more preferably mixed, to obtain a mixture PM1 containing water and the bio-oil;

[0040] (ii.2.3) Introduce B into UM1 and contact B with the mixture PM1 obtained in (ii.2.2) in UM1, more preferably mix them, to obtain a mixture containing the aqueous phase P. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) The pH is in the range of 7.5 to 11, more preferably in the range of 8 to 10.

[0041] Preferably, (ii.2) includes

[0042] (ii.2.1) Introduce water into Z E Included in UM1;

[0043] (ii.2.2) In Z E F0 is brought into contact with water, and more preferably mixed, to obtain a mixture PM1 containing water and the bio-oil, wherein the aqueous phase of PM1 has a pH value pH (PM1), which is more preferably measured by a pH sensor in UM1.

[0044] (ii.2.3) By introducing B into UM1 and adjusting the pH of the aqueous phase of PM1 by contacting, or more preferably mixing, B with M1 obtained in (ii.2.2) in UM1, an aqueous phase P is obtained. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) pH > pH(PM1), P A (1) The pH is in the range of 7.5 to 11, more preferably in the range of 8 to 10.

[0045] Alternatively, preferably, (ii.2) includes

[0046] (ii.2.1') ​​Mix water and B to obtain a mixture M0 of water and B having a pH (M0) in the range of 12 to 14;

[0047] (ii.2.2') The M0 obtained according to (ii.2.1') ​​is introduced into UM1 and F0 is brought into contact with M0, more preferably mixed, to obtain a mixture containing the aqueous phase P. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) The pH is in the range of 7.5 to 11, more preferably in the range of 8 to 10.

[0048] In the context of this invention, preferably, the extraction unit UM1 is one or more of a stirring container, a mixing pump, and a static mixer, more preferably a stirring container.

[0049] In the context of this invention, those skilled in the art, based on their common sense and the properties / type of the bio-oil, will know how much temperature to apply to bring the flow FO, water, and alkali B into contact in the liquid phase.

[0050] Preferably, the contact and mixing according to (ii.2) are carried out at a temperature T1 in the range of 10°C to 95°C, more preferably in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0051] Preferably, the contact and mixing are carried out according to (ii.2) at a pressure p1 in the range of 0.8 to 1.2 bar (absolute pressure), more preferably in the range of 0.9 to 1.1 bar (absolute pressure). More preferably, when T1 ≤ 95°C, the contact and mixing are carried out according to (ii.2) at a pressure p1 in the range of 0.8 to 1.2 bar (absolute pressure), more preferably in the range of 0.9 to 1.1 bar (absolute pressure), more preferably in the range of about 1 bar (absolute pressure).

[0052] In the context of this invention, when T1 > 95°C, the pressure p1 is in the range of 1 to 16 bar (absolute pressure).

[0053] Preferably, the base B is one or more of an alkali metal compound, an alkaline earth metal compound (e.g., alkaline earth metal oxides and / or hydroxides such as calcium hydroxide), and ammonia. More preferably, B is an alkali metal compound, which is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate; more preferably, one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate; more preferably, one or more of potassium hydroxide and sodium hydroxide; and more preferably, potassium hydroxide or sodium hydroxide.

[0054] Preferably, the water used in (ii) is demineralized water.

[0055] Preferably, according to (ii.2), the weight ratio of water to FO is in the range of 0.05:1 to 2:1, more preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, and even more preferably in the range of 0.1:1 to 0.5:1.

[0056] Preferably, the liquid-liquid separation unit US1 is one or more of a hydrocyclone, a settling tank, and a centrifuge, more preferably a decanter, a hydrocyclone, a settling tank, or a centrifuge, and even more preferably a settling tank.

[0057] In the context of this invention, UM1 and US1 are two different units.

[0058] Preferably, the separation in US1 according to (ii.3) is carried out at a temperature in the range of 10°C to 95°C, more preferably in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0059] Preferably, before introducing M1 into US1 according to (ii.3), the method further includes

[0060] M1 is introduced into the solid-liquid separation unit SLS1 to remove solids (if any) from M1.

[0061] Preferably, the solid-liquid separation unit SLS1 is one or more of a filter and a centrifuge.

[0062] Solid-liquid separation can be performed using filters that use differential pressure as the driving force or centrifuges that work by centrifugal force to separate liquids and solids.

[0063] The use of filters typically implies discontinuous solid-liquid separation, where the pressure differential increases with filtration time. After a certain pressure differential or filtration time, solids must be removed from the filter by a fluid or gas, or a mixture of both, via backwashing (e.g., disposal filters, backwash filters) or by an automatic system (e.g., automatic cleaning filters) or by rotation or vibration (e.g., pressure vane filters, candle filters, filter presses). During solid removal, a second parallel filter begins operation until a certain pressure differential or filtration time is reached, at which point the filter with the solids emptied will operate again.

[0064] Filtration can be carried out using disposable filters (e.g., bag filters, filters with filter discs or membranes), where solids are removed by backwashing or remain on the filter cloth, which necessitates filter replacement after a certain pressure differential or operating time.

[0065] Filtration can be enhanced by using filter aids to improve filtration behavior. This may lead to the potential use of continuous filters (e.g., belt filters, drum filters).

[0066] Depending on the type of centrifuge, centrifuges can be used for discontinuous or continuous solid-liquid separation. Centrifuges (e.g., decanter centrifuges, separator centrifuges) can be used in two-phase (solid-liquid) or three-phase systems with two liquid phases and a solid to separate solids from one or more liquids and to separate liquids from liquids. In contrast to decanter centrifuges (where solids are continuously separated and removed), in separator centrifuges, solids must be released after the centrifuge has been loaded to its maximum solid content (discontinuous). Centrifugation can be supported by the use of flocculants to improve centrifugal behavior.

[0067] Alternatively, preferably, no separation unit is provided between UM1 and US1. In this respect, M1 removed from UM1 directly enters US1.

[0068] It is conceivable that these units UM1 and US1 are placed side by side, for example, to form a mixer-settler.

[0069] Preferably, the method further includes

[0070] Make the inclusion of P obtained according to (ii.3) A (1) flow F A (1) Enter the separation unit USA1, preferably the settling tank, to obtain the water-containing aqueous flow SA1.

[0071] Preferably, the method further includes one or more purification steps for purifying SA1.

[0072] Preferably, the method further includes recycling SA1, more preferably purified SA1 (water), in UM1.

[0073] Preferably, 80 to 100 wt% of F, more preferably 85 to 100 wt% A (1) It is composed of water.

[0074] Alternatively, preferably, the method further includes

[0075] The F obtained according to (ii.3) A At least a portion of the water contained in (1) is recycled into UM1.

[0076] In the context of this invention, preferably, no organic solvent is used in (ii).

[0077] It is conceivable that the method further includes an acid treatment following (ii) and preceding (iii). In particular, the acid treatment may include the addition of one or more acidic components to F1.

[0078] It is conceivable that the method of the present invention (ii) further includes ZE One or more subsequent extractions in the process.

[0079] Preferably, the method further includes, when in US1 in P A (1) and P O When dirt forms at the interface of (1), the dirt is cleaned from US1.

[0080] Preferably, US1 includes a method for cleaning in P A (1) and P O (1) A device for the formation of optional dirt at the interface.

[0081] Preferably, the cleaned dirt undergoes one or more purification treatments. For example, the dirt can be treated with a filter and / or a centrifuge.

[0082] Regarding (iii), according to the first alternative, (iii) preferably includes

[0083] (iii.1) Introduce F1 into Z W It includes the washing unit UM2;

[0084] (iii.2) In UM2, F1 is brought into contact with water at a temperature T2 ranging from 10°C to 95°C to obtain P containing the aqueous phase. A (2) and organic phase P O (2) The mixture M2, the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A (1) pH;

[0085] (iii.3) Allow the mixture M2 obtained according to (iii.2) to enter Z. W The liquid-liquid separation unit US2, located downstream of UM2, contains P. A (2) flow F A (2) and P contained in the purified bio-oil O (2) Flow F2.

[0086] Preferably, the present invention relates to a method for purifying bio-oil, the method comprising:

[0087] (i) Provide a flow F0 containing bio-oil;

[0088] (ii) Ensure that the flow F0 provided in (i) is in at least one extraction zone Z E The medium undergoes extraction to obtain a stream F1 containing the extracted bio-oil, wherein (ii) includes:

[0089] (ii.1) Introduce F0 into Z E The extraction unit UM1 is included;

[0090] (ii.2) In UM1, F0 is contacted with water and alkali B at a temperature T1 ranging from 10°C to 200°C to obtain P containing an aqueous phase. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) The pH ranges from 7.5 to 11;

[0091] (ii.3) Allow the mixture M1 obtained according to (ii.2) to enter Z. E The liquid-liquid separation unit US1, located downstream of UM1, contains P. A (1) flow F A (1) and P contained in the bio-oil extracted from it. O (1) Flow F1;

[0092] (ii.4) From Z E Move F1 out of the middle;

[0093] (iii) Ensure that the flow F1 provided in (ii) is in at least one washing zone Z W The middle undergoes a cleansing—Z W Located in Z E Downstream, a stream F2 containing purified bio-oil is obtained, wherein (iii) includes

[0094] (iii.1) Introduce F1 into Z W It includes the washing unit UM2;

[0095] (iii.2) In UM2, F1 is brought into contact with water at a temperature T2 ranging from 10°C to 95°C to obtain P containing the aqueous phase. A (2) and organic phase P O (2) The mixture M2, the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A (1) pH;

[0096] (iii.3) Allow the mixture M2 obtained according to (iii.2) to enter Z. W The liquid-liquid separation unit US2, located downstream of UM2, contains P. A (2) flow F A (2) and P contained in the purified bio-oil O (2) flow F2; and optionally

[0097] (v) The F2 containing the bio-oil obtained according to (iii) is introduced into at least one storage unit SU and the bio-oil is stored in the SU.

[0098] Figure 1 , Figure 2 and Figure 4 This alternative solution was demonstrated.

[0099] Preferably, the washing unit UM2 is one or more of a stirring container, a mixing pump, and a static mixer, more preferably a stirring container.

[0100] Preferably, according to (iii.2), the weight ratio of water to F1 is in the range of 0.05:1 to 2:1, more preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, and even more preferably in the range of 0.1:1 to 0.5:1.

[0101] Preferably, when B is KOH or NaOH, the weight ratio of water to F1 is in the range of 0.05:1 to 2:1, more preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, and even more preferably in the range of 0.1:1 to 0.5:1.

[0102] Preferably, T2 is in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0103] Preferably, 0.75 T1 ≤ T2 ≤ 1.25 T1, more preferably, 0.90 T1 ≤ T2 ≤ 1.1 T1.

[0104] Preferably, the water used in (iii) is demineralized water.

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

[0106] Preferably, UM2 and US2 are two different units.

[0107] Preferably, the separation in US2 according to (iii.3) is carried out at a temperature in the range of 10°C to 85°C, more preferably in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0108] Optionally, before introducing M2 into US2 according to (iii.3), the method further includes

[0109] M2 is introduced into the solid-liquid separation unit SLS2 to remove any solids (if any) from M2.

[0110] Preferably, the solid-liquid separation unit SLS2 is one or more of a filter and a centrifuge.

[0111] Solid-liquid separation can be performed using filters that use differential pressure as the driving force or centrifuges that work by centrifugal force to separate liquids and solids.

[0112] The use of filters typically implies discontinuous solid-liquid separation, where the pressure differential increases with filtration time. After a certain pressure differential or filtration time, solids must be removed from the filter by a fluid or gas, or a mixture of both, via backwashing (e.g., disposal filters, backwash filters) or by an automatic system (e.g., automatic cleaning filters) or by rotation or vibration (e.g., pressure vane filters, candle filters, filter presses). During solid removal, a second parallel filter begins operation until a certain pressure differential or filtration time is reached, at which point the filter with the solids emptied will operate again.

[0113] Filtration can be carried out using disposable filters (e.g., bag filters, filters with filter discs or membranes), where solids are removed by backwashing or remain on the filter cloth, which necessitates filter replacement after a certain pressure differential or operating time.

[0114] Filtration can be enhanced by using filter aids to improve filtration behavior. This may lead to the potential use of continuous filters (e.g., belt filters, drum filters).

[0115] Depending on the type of centrifuge, centrifuges can be used for discontinuous or continuous solid-liquid separation. Centrifuges (e.g., decanter centrifuges, separator centrifuges) can be used in two-phase (solid-liquid) or three-phase systems with two liquid phases and a solid to separate solids from one or more liquids and to separate liquids from liquids. In contrast to decanter centrifuges (where solids are continuously separated and removed), in separator centrifuges, solids must be released after the centrifuge has been loaded to its maximum solid content (discontinuous). Centrifugation can be supported by the use of flocculants to improve centrifugal behavior.

[0116] Alternatively, preferably, no separation unit is provided between UM2 and US2. In this respect, M2, which is removed from UM2, directly enters US2.

[0117] It is conceivable that these units UM2 and US2 are placed side by side, for example, to form a mixer-settler.

[0118] Preferably, the method further includes, when in US2 in P A (2) and P O When dirt forms at the interface of (2), the dirt is cleaned from US2.

[0119] Regarding (iii), according to the second alternative, (iii) preferably includes

[0120] (iii.1') Introduce F1 into Z W The extraction tower UM+US is included;

[0121] (iii.2') Introduce water into UM+US;

[0122] (iii.3') In UM+US, F1 is brought into contact with water at a temperature T2' ranging from 10°C to 95°C to obtain P containing the aqueous phase. A (2) flow F A (2), the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A (1) pH, and obtain a stream F2 containing the purified bio-oil.

[0123] Figure 3 This alternative solution was demonstrated.

[0124] Preferably, the present invention relates to a method for purifying bio-oil, the method comprising:

[0125] (i) Provide a flow F0 containing bio-oil;

[0126] (ii) Ensure that the flow F0 provided in (i) is in at least one extraction zone Z E The medium undergoes extraction to obtain a stream F1 containing the extracted bio-oil, wherein (ii) includes:

[0127] (ii.1) Introduce F0 into Z E The extraction unit UM1 is included;

[0128] (ii.2) In UM1, F0 is contacted with water and alkali B at a temperature T1 ranging from 10°C to 200°C to obtain P containing an aqueous phase. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) The pH ranges from 7.5 to 11;

[0129] (ii.3) Allow the mixture M1 obtained according to (ii.2) to enter Z. EThe liquid-liquid separation unit US1, located downstream of UM1, contains P. A (1) flow F A (1) and P contained in the bio-oil extracted from it. O (1) Flow F1;

[0130] (ii.4) From Z E Move F1 out of the middle;

[0131] (iii) Ensure that the flow F1 provided in (ii) is in at least one washing zone Z W The middle undergoes a cleansing—Z W Located in Z E Downstream, a stream F2 containing purified bio-oil is obtained, wherein (iii) includes

[0132] (iii.1') Introduce F1 into Z W The extraction tower UM+US is included;

[0133] (iii.2') Introduce water into UM+US;

[0134] (iii.3') In UM+US, F1 is brought into contact with water at a temperature T2' ranging from 10°C to 95°C to obtain P containing the aqueous phase. A (2) flow F A (2), the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A (1) pH, and obtain stream F2 containing the purified bio-oil; and optionally

[0135] (v) The F2 containing the bio-oil obtained according to (iii) is introduced into at least one storage unit SU and the bio-oil is stored in the SU.

[0136] Preferably, according to (iii.3'), the weight ratio of water to F1 is in the range of 0.05:1 to 2:1, more preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, and even more preferably in the range of 0.1:1 to 0.5:1.

[0137] Preferably, T2' is in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0138] Preferably, 0.75 T1 ≤ T2' ≤ 1.25 T1, more preferably, 0.90 T1 ≤ T2' ≤ 1.1 T1.

[0139] Preferably, (iii) the process is carried out at a pressure p2 of about 1 bar (absolute pressure) in the range of 0.75 to 1.25 bar (absolute pressure), more preferably in the range of 0.9 to 1.1 bar (absolute pressure).

[0140] Preferably, 90 to 100 wt% of F, more preferably 95 to 100 wt% A (2) It is composed of water.

[0141] In the context of this invention, it is preferred that the method further includes

[0142] Recycle F obtained from (iii.3) and / or (iii.2) in (ii.2). A (2) Contains at least a portion of the water; or

[0143] Recycle based on (iii.3') and / or (iii.2') obtained in (ii.2) F A (2) contains at least a portion of the water.

[0144] Preferably, the F obtained according to (iii.3) and / or (iii.2) in (ii.2) is recycled. A (2) contains at least a portion of the water that makes the F obtained according to (iii.3) A (2) At least a portion of the water contained therein enters UM1 and / or UM2.

[0145] Preferably, the F obtained according to (iii.3') and / or (iii.2') in (ii.2) is recycled. A (2) contains at least a portion of the water that makes F obtained according to (iii.3') A (2) At least a portion of the water contained therein enters UM1 and / or UM+US.

[0146] Preferably, the water used in (iii) is demineralized water.

[0147] Preferably, no organic solvent is used in (iii).

[0148] Preferably, no base is added in (iii), the base being one or more of an alkali metal compound (such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate, more preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate), an alkaline earth metal compound and ammonia.

[0149] Preferably, the stream F2 containing purified bio-oil obtained according to (iii) has a lower total acid value (TAN) than the TAN of the bio-oil provided in (i).

[0150] Preferably, the stream F2 containing purified bio-oil obtained according to (iii) has a TAN in the range of 0 to 40 mg KOH / g (F2), preferably in the range of 0 to 20 mg KOH / g (F2), more preferably in the range of 0 to 10 mg KOH / g (F2), and even more preferably in the range of 0 to 4 mg KOH / g (F2), as determined in Reference Example 3.

[0151] Preferably, the stream F2 containing purified bio-oil obtained according to (iii) has an oxygen content equal to or lower than, more preferably lower than, the oxygen content of the bio-oil provided in (i).

[0152] Preferably, the stream F2 containing purified bio-oil has an oxygen content in the range of 0 to 20 g(O) / 100 g(F2), preferably 0 to 10 g(O) / 100 g(F2), more preferably 0 to 5 g(O) / 100 g(F2), and most preferably 0 to 2 g(O) / 100 g(F2), as determined in Reference Example 4.

[0153] According to the present invention, it is conceivable that the stream F2 containing purified bio-oil obtained according to (iii) has a reduced total chlorine content and / or chloride content compared to the bio-oil provided in (i). For example, the reduction in total chlorine content and / or chloride content in F2 compared to the bio-oil provided in (i) may be in the range of 1% to 100%, or in the range of 1% to 80%, or in the range of 10% to 50%.

[0154] According to the invention, it is conceivable that the stream F2 containing purified bio-oil obtained according to (iii) has a lower nitrogen content than the bio-oil provided in (i).

[0155] According to the invention, it is conceivable that the stream F2 containing purified bio-oil obtained according to (iii) has a lower sulfur content than the bio-oil provided in (i).

[0156] Optionally, the method of the present invention further includes Z W One or more subsequent washes are performed. According to this option, the method further includes...

[0157] (iv) In Z W The process involves at least a portion of the stream F2 obtained according to (iii) undergoing one or more subsequent washes, wherein (iv) includes:

[0158] (iv.1) Optionally, at least a portion, preferably F2, of the F2 obtained according to (iii) is introduced into Z. W The washing unit UM3 contained therein is located downstream of US2;

[0159] In UM3, at least a portion, preferably F2, of the F2 is brought into contact with water at a temperature T3 in the range of 10°C to 95°C to obtain a P-phase containing water. A (3) and organic phase P O (3) The mixture M3, M3 is in the range of 7.5 to 11, P A (3) pH < P A (1) pH;

[0160] Let the mixture M3 enter Z W The liquid-liquid separation unit US3, located downstream of UM3, contains P. A (3) flow F A (3) and P contained in the purified bio-oil O (3) Flow F3;

[0161] (iv.2) Introduce at least a portion, preferably F2, of F2 obtained according to (iii) or at least a portion, preferably F3, of F3 obtained according to (iv.1) into Z. W The washing unit UM4 is located downstream of US3.

[0162] (iv.3) In UM4, at least a portion of F2, preferably F2, or at least a portion of F3, preferably F3, is brought into contact with water at a temperature T4 in the range of 10°C to 95°C to obtain a solution containing an aqueous phase P. A (4) and organic phase P O (4) The mixture M4, the aqueous phase P of M4 A (4) pH ranges from 7.5 to 11, P A (4) pH < P A (1) pH;

[0163] (iv.4) Allow the mixture M4 obtained according to (iv.3) to enter Z. W The liquid-liquid separation unit US4, located downstream of UM4, contains P. A (4) flow F A (4) and P contained in the purified bio-oil O (4) flow F4.

[0164] The options are, for example, provided by Figure 4 exhibit.

[0165] Preferably, P A (3) pH < P A (2) pH.

[0166] Preferably, P A (4) pH < P A (2) pH.

[0167] Preferably, P A (4) pH < P A (3) pH. More preferably, P A (4) pH < P A (3) pH < P A (2) pH < P A (1) pH.

[0168] Preferably, according to the option, the method further includes

[0169] At least a portion of F A (4) Recycle into UM2 and / or UM3 (if they exist).

[0170] Preferably, 90 to 100 wt% of F, more preferably 95 to 100 wt% A (4) It is composed of water.

[0171] Preferably, UM4 (if present) is one or more of a stirring vessel, a mixing pump, and a static mixer, more preferably a stirring vessel.

[0172] Preferably, according to (iv.3), the weight ratio of water to at least a portion of F2, more preferably F2 or at least a portion of F3, more preferably F3 is in the range of 0.05:1 to 2:1, more preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, and more preferably in the range of 0.1:1 to 0.5:1.

[0173] Preferably, T4 is in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0174] Preferably, 0.75 T1 ≤ T4 ≤ 1.25 T1, more preferably, 0.90 T1 ≤ T4 ≤ 1.1 T1.

[0175] Preferably, the liquid-liquid separation unit US4 is one or more of a hydrocyclone, a settling tank, and a centrifuge, more preferably a hydrocyclone, a settling tank, or a centrifuge, and even more preferably a settling tank or a centrifuge.

[0176] Preferably, UM4 and US4 are two different units.

[0177] Preferably, the separation in US4 according to (iv.4) is carried out at a temperature in the range of 10°C to 85°C, more preferably in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0178] Preferably, before introducing M4 into US4 according to (iv.4), the method further includes

[0179] M4 is introduced into the solid-liquid separation unit SLS4 to remove any solids (if any) from M4.

[0180] Preferably, the solid-liquid separation unit SLS4 is one or more of a filter and a centrifuge.

[0181] Solid-liquid separation can be performed using filters that utilize differential pressure as the driving force or centrifuges that operate using centrifugal force to separate liquids and solids. The use of filters typically implies discontinuous solid-liquid separation, where the pressure differential increases with filtration time. After a certain pressure differential or filtration time, solids must be removed from the filter by passing through a fluid or gas, or a mixture of both, via backwashing (e.g., disposal filters, backwash filters) or by an automatic system (e.g., automatic cleaning filters) or by rotation or vibration (e.g., pressure vane filters, candle filters, filter presses). During solid removal, a second parallel filter begins operation until a certain pressure differential or filtration time is reached, at which point the filter with the solids emptied will run again.

[0182] Filtration can be carried out using disposable filters (e.g., bag filters, filters with filter discs or membranes), where solids are removed by backwashing or remain on the filter cloth, which necessitates filter replacement after a certain pressure differential or operating time.

[0183] Filtration can be enhanced by using filter aids to improve filtration behavior. This may lead to the potential use of continuous filters (e.g., belt filters, drum filters).

[0184] Depending on the type of centrifuge, centrifuges can be used for discontinuous or continuous solid-liquid separation. Centrifuges (e.g., decanter centrifuges, separator centrifuges) can be used in two-phase (solid-liquid) or three-phase systems with two liquid phases and a solid to separate solids from one or more liquids and to separate liquids from liquids. In contrast to decanter centrifuges (where solids are continuously separated and removed), in separator centrifuges, solids must be released after the centrifuge has been loaded to its maximum solid content (discontinuous). Centrifugation can be supported by the use of flocculants to improve centrifugal behavior.

[0185] Alternatively, preferably, no separation unit is provided between UM4 and US4. In this respect, M4 removed from UM4 directly enters US4.

[0186] Preferably, when performing (iv.1), the method further includes

[0187] At least a portion of F A (3) Recycle back into UM2.

[0188] Preferably, 90 to 100 wt% of F, more preferably 95 to 100 wt% A (3) It is composed of water.

[0189] Preferably, UM3 (if present) is one or more of a stirring vessel, a mixing pump, and a static mixer, more preferably a stirring vessel.

[0190] Preferably, according to (iv.1), the weight ratio of water to at least a portion of the F2, more preferably the weight ratio of F2, is in the range of 0.05:1 to 2:1, more preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, and more preferably in the range of 0.1:1 to 0.5:1.

[0191] Preferably, T3 is in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0192] Preferably, 0.75 T1 ≤ T3 ≤ 1.25 T1, more preferably, 0.90 T1 ≤ T3 ≤ 1.1 T1.

[0193] Preferably, the liquid-liquid separation unit US3 is one or more of a hydrocyclone, a settling tank, and a centrifuge, more preferably a hydrocyclone, a settling tank, or a centrifuge, and even more preferably a settling tank or a centrifuge.

[0194] Preferably, UM3 and US3 are two different units.

[0195] Preferably, the separation in US3 according to (iv.1) is carried out at a temperature in the range of 10°C to 85°C, more preferably in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0196] Preferably, before introducing M3 into US3 according to (iv.1), the method further includes

[0197] M3 is introduced into the solid-liquid separation unit SLS3 to remove solids (if any) from M3.

[0198] Preferably, the solid-liquid separation unit SLS3 is one or more of a filter and a centrifuge.

[0199] Alternatively, preferably, no separation unit is provided between UM3 and US3. In this respect, M3 removed from UM3 directly enters US3.

[0200] Preferably, the water used in (iv) is demineralized water.

[0201] Preferably, no organic solvent is used in (iv).

[0202] Preferably, no base is added in (iv), the base being one or more of an alkali metal compound (such as potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate and sodium bicarbonate, more preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate and sodium carbonate), an alkaline earth metal compound and ammonia.

[0203] Preferably, (iv) the test is carried out at a pressure p3 of about 1 bar (absolute pressure) in the range of 0.75 to 1.25 bar (absolute pressure), more preferably in the range of 0.9 to 1.1 bar (absolute pressure).

[0204] In the context of this invention, the method further includes

[0205] (v) The F2 containing the bio-oil obtained according to (iii), and optionally the F4 obtained according to (iv), are introduced into at least one storage unit SU and the bio-oil is stored in the SU.

[0206] Preferably, the storage unit SU is a storage tank, more preferably a storage tank made of one or more of steel and stainless steel, and even more preferably carbon steel and stainless steel.

[0207] Preferably, the method of the present invention further includes

[0208] One or more of the following steps: dechlorination, hydrogenation, hydrotreating, steam cracking, hydrocracking, fluid catalytic cracking, adsorption, distillation, stripping, and aqueous extraction.

[0209] Preferably, the method of the present invention is a continuous or semi-continuous method.

[0210] Preferably, the method of the present invention consists of (i), (ii), (iii), and optionally (iv) and optionally (v).

[0211] The present invention further relates to a unit for performing a method for purifying bio-oil according to the present invention, the unit comprising:

[0212] - At least one extraction zone Z comprising extraction unit UM1 and liquid-liquid separation unit US1 E UM1 is located upstream of US1;

[0213] - Used to introduce F0 into Z E The inlet device;

[0214] - Used from Z E Remove the F1 outlet device from the middle;

[0215] - An entry device used to introduce F0 into UM1;

[0216] - An exit device for removing M1 from UM1;

[0217] - An inlet device for introducing M1 into US1;

[0218] - An exit device for removing F1 from US1;

[0219] -At least one washing area Z W It is located in Z E Downstream,

[0220] - Used to introduce F1 into Z W The inlet device;

[0221] - Used from Z W The outlet device of F2 is removed from the middle; and optionally

[0222] - Storage tank.

[0223] Preferably, US1 includes a method for cleaning in P A (1) and P O (1) A device for the formation of optional dirt at the interface.

[0224] Preferably, according to the first alternative, Z W Include

[0225] -Washing unit UM2;

[0226] -Liquid-liquid separation unit US2, UM2 is located upstream of US2;

[0227] - An entry device used to introduce F1 into UM2;

[0228] - An inlet device for introducing water into UM2;

[0229] - An exit device for removing M2 from UM2;

[0230] - An inlet device for introducing M2 into US2;

[0231] - An exit device for removing F2 from US2.

[0232] Optionally, Z W It further includes a washing unit UM4 (preferably a mixing unit) and a liquid-liquid separation unit US4, UM4 being downstream of US2 and US4 being downstream of UM4.

[0233] Optionally, Z W It further includes a washing unit UM3 (preferably a mixing unit) and a liquid-liquid separation unit US3, UM3 being located downstream of US2 and upstream of UM4, and US3 being located downstream of UM3 and upstream of UM4.

[0234] Preferably, according to the second alternative, Z W Include

[0235] -Extraction tower UM+US;

[0236] - An entry device used to introduce F1 into UM+US;

[0237] - An inlet device for introducing water into UM+US;

[0238] - An exit device for removing F2 from UM+US.

[0239] In the context of this invention, preferably, the unit further comprises

[0240] One or more of the following: storage tank, cracking zone, dechlorination zone, hydrogenation zone, hydrotreating zone, stripping zone, and distillation zone.

[0241] The present invention further relates to a purified bio-oil, which can be obtained or acquired by the method according to the invention.

[0242] Preferably, the purified bio-oil of the present invention has a total acid value (TAN) in the range of 0 to 40 mg KOH / g bio-oil (KOH / g (oil)), preferably 0 to 20 mg KOH / g (oil), more preferably 0 to 10 mg KOH / g (oil), more preferably 0 to 4 mg KOH / g (oil), more preferably 0 to 1 mg KOH / g (oil), and even more preferably 0 to less than 1 mg KOH / g (oil), as determined in Reference Example 3.

[0243] Preferably, the purified bio-oil of the present invention has an oxygen content in the range of 0 to 20 g(O) / 100 g(F2), preferably 0 to 10 g(O) / 100 g(F2), more preferably 0 to 5 g(O) / 100 g(F2), and most preferably 0 to 2 g(O) / 100 g(oil), as determined in Reference Example 4.

[0244] The invention is further illustrated by the following set of embodiments and combinations of embodiments derived from the dependent relationships and reverse references shown. In particular, it should be noted that in each instance of reference to a series of embodiments, such as in the context of the term "method as described in any one of Embodiments 1 to 4," each embodiment in this series is intended to clearly disclose to those skilled in the art that the wording of this term should be understood by those skilled in the art to be synonymous with "method as described in any one of Embodiments 1, 2, 3, and 4." Furthermore, it should be clearly noted that the following set of embodiments represents appropriate structural portions of the general description of preferred aspects of the invention and therefore appropriately supports, but does not represent, the claims of the invention.

[0245] 1. A method for purifying bio-oil, the method comprising:

[0246] (i) Providing a stream F0 containing the bio-oil, wherein preferably, the bio-oil is available or obtained from biomass by mechanical and physical operations and chemical methods;

[0247] (ii) Ensure that the flow F0 provided in (i) is in at least one extraction zone Z E The medium undergoes extraction to obtain a stream F1 containing the extracted bio-oil, wherein (ii) includes:

[0248] (ii.1) Introduce F0 into Z E The extraction unit UM1 is included;

[0249] (ii.2) In UM1, F0 is contacted with water and alkali B at a temperature T1 ranging from 10°C to 200°C to obtain P containing an aqueous phase. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1A (1) The pH ranges from 7.5 to 11;

[0250] (ii.3) Allow the mixture M1 obtained according to (ii.2) to enter Z. E The liquid-liquid separation unit US1, located downstream of UM1, contains P. A (1) flow F A (1) and P contained in the bio-oil extracted from it. O (1) Flow F1;

[0251] (ii.4) From Z E Move F1 out of the middle;

[0252] (iii) Ensure that the flow F1 provided in (ii) is in at least one washing zone Z W The middle undergoes a cleansing—Z W Located in Z E Downstream, to obtain a stream F2 containing purified bio-oil; and optionally...

[0253] (v) The F2 containing the bio-oil obtained according to (iii) is introduced into at least one storage unit SU and the bio-oil is stored in the SU.

[0254] 2. The method as described in Example 1, wherein 95 to 100% by weight, preferably 98 to 100% by weight, more preferably 99 to 100% by weight, of F0 is composed of bio-oil.

[0255] 3. The method as described in Example 1 or 2, wherein the bio-oil according to (i) has an oxygen content in the range of 0.5 to 70 g(O) / 100 g(F0), for example, greater than 15 to no more than 50 g(O) / 100 g(F0), or 0.5 to 15 g(O) / 100 g(F0), preferably in the range of 0.5 to 10 g(O) / 100 g(F0), more preferably in the range of 0.5 to 5 g(O) / 100 g(F0), and even more preferably in the range of 0.5 to 2 g(O) / 100 g(F0), as determined in Reference Example 4.

[0256] 4. The method as described in any one of Examples 1 to 3, wherein the bio-oil according to (i) has a total acid value (TAN) in the range of 0 to 200 mg (KOH) / g (F0), for example 50 to 200 mg (KOH) / g (F0) or 100 to 200 mg (KOH) / g (F0), preferably 0 to 100 mg (KOH) / g (F0), for example 50 to 100 mg (KOH) / g (F0) or 70 to 100 mg (KOH) / g (F0), preferably 0.5 to 60 mg (KOH) / g (F0), preferably 1 to 40 mg KOH / g (F0), preferably in the range of 3 to 20 mg KOH / g (F0), as determined in Reference Example 3.

[0257] 5. The method as described in any one of Examples 1 to 4, wherein the bio-oil according to (i) has a total chlorine content in the range of 30 to 3,000 wppm (ppm by weight), preferably 30 to 500 wppm, more preferably 30 to 300 wppm, as determined in Reference Example 1.1;

[0258] The bio-oil according to (i) has a chloride content of up to 40 wppm, more preferably in the range of 0 to 30 wppm, as determined in Reference Example 1.2.

[0259] 6. The method as described in any one of Examples 1 to 5, wherein the bio-oil according to (i) has a nitrogen content in the range of 50 to 20,000 wppm (ppm by weight), preferably 50 to 5,000 wppm, more preferably 100 to 4,000 wppm, as determined in Reference Example 2.

[0260] 7. The method as described in any one of Examples 1 to 6, wherein (ii.2) includes

[0261] (ii.2.1) Introduce water into Z E Included in UM1;

[0262] (ii.2.2) In UM1, F0 is brought into contact with water, preferably mixed, to obtain a mixture PM1 containing water and the bio-oil;

[0263] (ii.2.3) Introduce B into UM1 and contact B with the mixture PM1 obtained in (ii.2.2) in UM1, preferably mix them, to obtain a mixture containing the aqueous phase P. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) The pH is in the range of 7.5 to 11, preferably in the range of 8 to 10;

[0264] Preferably, (ii.2) includes

[0265] (ii.2.1) Introduce water into Z E Included in UM1;

[0266] (ii.2.2) In Z E F0 is brought into contact with water, preferably mixed, to obtain a mixture PM1 containing water and the bio-oil, wherein the aqueous phase of PM1 has a pH value pH (PM1), which is preferably measured by a pH sensor in UM1.

[0267] (ii.2.3) By introducing B into UM1 and adjusting the pH of the aqueous phase of PM1 by contacting and preferably mixing B with M1 obtained in (ii.2.2) in UM1, an aqueous phase P is obtained. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) pH > pH(PM1), P A (1) The pH is in the range of 7.5 to 11, preferably in the range of 8 to 10.

[0268] 8. The method as described in any one of Examples 1 to 6, wherein (ii.2) includes

[0269] (ii.2.1') ​​Mix water and B to obtain a mixture M0 of water and B having a pH (M0) in the range of 12 to 14;

[0270] (ii.2.2') The M0 obtained according to (ii.2.1') ​​is introduced into UM1 and F0 is brought into contact with M0, more preferably mixed, to obtain a mixture containing the aqueous phase P. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) The pH is in the range of 7.5 to 11, preferably in the range of 8 to 10.

[0271] 9. The method as described in any one of Examples 1 to 8, wherein the extraction unit UM1 is one or more of a stirred container, a mixing pump, and a static mixer, preferably a stirred container.

[0272] 10. The method as described in any one of Examples 1 to 9, wherein the contact and mixing according to (ii.2) are carried out at a temperature T1 in the range of 10°C to 95°C, more preferably in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0273] 11. The method as described in any one of Examples 1 to 10, wherein the base B is one or more of an alkali metal compound, an alkaline earth metal compound, and ammonia, preferably B is an alkali metal compound, which is one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, sodium carbonate, potassium bicarbonate, and sodium bicarbonate, more preferably one or more of potassium hydroxide, sodium hydroxide, potassium carbonate, and sodium carbonate, more preferably one or more of potassium hydroxide and sodium hydroxide, and more preferably potassium hydroxide or sodium hydroxide.

[0274] 12. The method as described in any one of Examples 1 to 11, wherein the water used in (ii) is demineralized water.

[0275] 13. The method as described in any one of Examples 1 to 12, wherein the liquid-liquid separation unit US1 is one or more of a hydrocyclone, a settling tank, and a centrifuge, preferably a decanter, a hydrocyclone, a settling tank, or a centrifuge, more preferably a settling tank.

[0276] 14. The method as described in any one of Examples 1 to 13, wherein the separation in US1 according to (ii.3) is carried out at a temperature in the range of 10°C to 95°C, preferably in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

[0277] 15. The method as described in any one of Examples 1 to 14, wherein, before introducing M1 into US1 according to (ii.3), the method further comprises

[0278] M1 is introduced into the solid-liquid separation unit SLS1 to remove solids (if any) from M1.

[0279] 16. The method as described in Example 15, wherein the solid-liquid separation unit SLS1 is one or more of a filter and a centrifuge.

[0280] 17. The method as described in any one of Examples 1 to 16, further comprising:

[0281] Make the inclusion of P obtained according to (ii.3) A (1) flow F A (1) Enter the separation unit USA1, preferably the settling tank, to obtain the water-containing aqueous flow SA1.

[0282] 18. The method as described in any one of Examples 1 to 17, wherein no organic solvent is used in (ii).

[0283] 19. The method as described in any one of Examples 1 to 18, further comprising, when in US1 at P A(1) and P O When dirt forms at the interface of (1), the dirt is cleaned from US1.

[0284] 20. The method as described in any one of Examples 1 to 19, wherein (iii) includes

[0285] (iii.1) Introduce F1 into Z W It includes the washing unit UM2;

[0286] (iii.2) In UM2, F1 is brought into contact with water at a temperature T2 ranging from 10°C to 95°C to obtain P containing the aqueous phase. A (2) and organic phase P O (2) The mixture M2, the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A (1) pH;

[0287] (iii.3) Allow the mixture M2 obtained according to (iii.2) to enter Z. W The liquid-liquid separation unit US2, located downstream of UM2, contains P. A (2) flow F A (2) and P contained in the purified bio-oil O (2) Flow F2.

[0288] 21. The method as described in Example 20, wherein the washing unit UM2 is one or more of a stirring container, a mixing pump, and a static mixer, preferably a stirring container.

[0289] 22. The method as described in Example 20 or 21, wherein, according to (iii.2), the weight ratio of water to F1 is in the range of 0.05:1 to 2:1, preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, even more preferably in the range of 0.1:1 to 0.5:1, or even more preferably in the range of 0.8:1 to 1.2:1.

[0290] 23. The method of any one of Examples 20 to 22, wherein the liquid-liquid separation unit US2 is one or more of a hydrocyclone, a settling tank, and a centrifuge, preferably a hydrocyclone, a settling tank, or a centrifuge, more preferably a settling tank or a centrifuge.

[0291] 24. The method as described in any one of Examples 20 to 23, wherein the separation in US2 according to (iii.3) is carried out at a temperature ranging from 10°C to 85°C, preferably from 15°C to 85°C, more preferably from 20°C to 80°C, and even more preferably from 20°C to 50°C.

[0292] 25. The method as described in any one of Examples 20 to 24, wherein, before introducing M2 into US2 according to (iii.3), the method further comprises

[0293] M2 is introduced into the solid-liquid separation unit SLS2 to remove any solids (if any) from M2.

[0294] 26. The method as described in Example 25, wherein the solid-liquid separation unit SLS2 is one or more of a filter and a centrifuge.

[0295] 27. The method as described in any one of Examples 20 to 24, wherein no separation unit is provided between UM2 and US2.

[0296] 28. The method as described in any one of Examples 1 to 19, wherein (iii) includes

[0297] (iii.1') Introduce F1 into Z W The extraction tower UM+US is included;

[0298] (iii.2') Introduce water into UM+US;

[0299] (iii.3') In UM+US, F1 is brought into contact with water at a temperature T2' ranging from 10°C to 95°C to obtain P containing the aqueous phase. A (2) flow F A (2), the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A (1) pH, and obtain a stream F2 containing the purified bio-oil.

[0300] 29. The method as described in Example 28, wherein, according to (iii.3'), the weight ratio of water to F1 is in the range of 0.05:1 to 2:1, preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, even more preferably in the range of 0.1:1 to 0.5:1, or even more preferably in the range of 0.8:1 to 1.2:1.

[0301] 30. The method as described in any one of Examples 20 to 29, further comprising:

[0302] Recycle F obtained from (iii.3) and / or (iii.2) in (ii.2). A (2) Contains at least a portion of the water; or

[0303] Recycle based on (iii.3') and / or (iii.2') obtained in (ii.2) F A (2) Contains at least a portion of the water; and / or

[0304] Recycle F obtained from (ii.3) in (ii.2). A (1) contains at least a portion of the water.

[0305] 31. The method as described in any one of Examples 1 to 30, wherein no organic solvent is used in (iii).

[0306] 32. The method of any one of Examples 1 to 31, wherein the stream F2 containing the purified bio-oil obtained according to (iii) has a total acid value (TAN) lower than that of the bio-oil provided in (i).

[0307] 33. The method as described in Example 32, wherein the stream F2 containing the purified bio-oil obtained according to (iii) has a TAN in the range of 0 to 40 mg KOH / g (F2), preferably 0 to 20 mg KOH / g (F2), more preferably 0 to 10 mg KOH / g (F2), and even more preferably 0 to 4 mg KOH / g (F2), as determined in Reference Example 3.

[0308] 34. The method of any one of Examples 1 to 33, wherein the stream F2 containing the purified bio-oil obtained according to (iii) has an oxygen content equal to or less than, more preferably less than, the oxygen content of the bio-oil provided in (i).

[0309] 35. The method as described in Example 34, wherein the stream F2 containing the purified bio-oil has an oxygen content in the range of 0 to 20 g(O) / 100 g(F2), preferably 0 to 10 g(O) / 100 g(F2), more preferably 0 to 5 g(O) / 100 g(F2), and most preferably 0 to 2 g(O) / 100 g(F2), as determined in Reference Example 4.

[0310] 36. The method of any one of Examples 1 to 35, wherein, with respect to Example 36 being subordinate to any one of Examples 20 to 27, the method further comprises

[0311] (iv) In Z W The process involves at least a portion of the stream F2 obtained according to (iii) undergoing one or more subsequent washes, wherein (iv) includes:

[0312] (iv.1) Optionally, at least a portion, preferably F2, of the F2 obtained according to (iii) is introduced into Z. W The washing unit UM3 contained therein is located downstream of US2;

[0313] In UM3, at least a portion, preferably F2, of the F2 is brought into contact with water at a temperature T3 in the range of 10°C to 95°C to obtain a P-phase containing water. A (3) and organic phase P O (3) The mixture M3, M3 is in the range of 7.5 to 11, P A (3) pH < P A (1) pH;

[0314] Let the mixture M3 enter Z W The liquid-liquid separation unit US3, located downstream of UM3, contains P. A (3) flow F A (3) and P contained in the purified bio-oil O (3) Flow F3;

[0315] (iv.2) Introduce at least a portion, preferably F2, of F2 obtained according to (iii) or at least a portion, preferably F3, of F3 obtained according to (iv.1) into Z. W The washing unit UM4 is located downstream of US3.

[0316] (iv.3) In UM4, at least a portion of F2, preferably F2, or at least a portion of F3, preferably F3, is brought into contact with water at a temperature T4 in the range of 10°C to 95°C to obtain a solution containing an aqueous phase P. A (4) and organic phase P O (4) The mixture M4, the aqueous phase P of M4 A (4) pH ranges from 7.5 to 11, P A (4) pH < P A (1) pH;

[0317] (iv.4) Allow the mixture M4 obtained according to (iv.3) to enter Z. WThe liquid-liquid separation unit US4, located downstream of UM4, contains P. A (4) flow F A (4) and P contained in the purified bio-oil O (4) flow F4.

[0318] 37. The method as described in any one of Examples 1 to 36, further comprising:

[0319] (v) The F2 containing the bio-oil obtained according to (iii), and optionally the F4 obtained according to (iv), are introduced into at least one storage unit SU and the bio-oil is stored in the SU.

[0320] 38. The method as described in Example 37, wherein the storage unit SU is a storage tank, preferably made of one or more of steel and stainless steel, more preferably carbon steel and stainless steel.

[0321] 39. The method as described in any one of Examples 1 to 38, further comprising one or more of the following steps: dechlorination, hydrogenation, hydrotreating, steam cracking, hydrocracking, fluid catalytic cracking, distillation, stripping, and aqueous extraction.

[0322] 40. The method as described in any one of Examples 1 to 39, wherein it is a continuous or semi-continuous method.

[0323] 41. A unit for performing the method for purifying bio-oil as described in any one of Examples 1 to 40, the unit comprising:

[0324] - At least one extraction zone Z comprising extraction unit UM1 and liquid-liquid separation unit US1 E UM1 is located upstream of US1;

[0325] - Used to introduce F0 into Z E The inlet device;

[0326] - Used from Z E Remove the F1 outlet device from the middle;

[0327] - An entry device used to introduce F0 into UM1;

[0328] - An exit device for removing M1 from UM1;

[0329] - An inlet device for introducing M1 into US1;

[0330] - An exit device for removing F1 from US1;

[0331] -At least one washing area Z WIt is located in Z E Downstream,

[0332] - Used to introduce F1 into Z W The inlet device;

[0333] - Used from Z W The outlet device of F2 is removed from the middle; and optionally

[0334] - Storage tank.

[0335] 42. The unit as described in Example 41, wherein US1 includes components for cleaning in P A (1) and P O (1) A device for the formation of optional dirt at the interface.

[0336] 43. The unit as described in embodiment 41 or 42, wherein Z W Include

[0337] -Washing unit UM2;

[0338] -Liquid-liquid separation unit US2, UM2 is located upstream of US2;

[0339] - An entry device used to introduce F1 into UM2;

[0340] - An inlet device for introducing water into UM2;

[0341] - An exit device for removing M2 from UM2;

[0342] - An inlet device for introducing M2 into US2;

[0343] - An exit device for removing F2 from US2.

[0344] 44. The unit as described in Example 43, wherein Z W It further includes a washing unit UM4 (preferably a mixing unit) and a liquid-liquid separation unit US4, UM4 being located downstream of US2 and US4 being located downstream of UM4;

[0345] Optionally, Z W It further includes a washing unit UM3 (preferably a mixing unit) and a liquid-liquid separation unit US3, UM3 being located downstream of US2 and upstream of UM4, and US3 being located downstream of UM3 and upstream of UM4.

[0346] 45. The unit as described in embodiment 41 or 42, wherein Z W Include

[0347] -Extraction tower UM+US;

[0348] - An entry device used to introduce F1 into UM+US;

[0349] - An inlet device for introducing water into UM+US;

[0350] - An exit device for removing F2 from UM+US.

[0351] 46. ​​The unit as described in any one of Examples 41 to 45, further comprising one or more of a storage tank, a cracking zone, an adsorption zone, a dechlorination zone, a hydrogenation zone, a hydrotreating zone, a stripping zone, and a distillation zone.

[0352] 47. A purified bio-oil, which can be obtained or acquired by any one of Examples 1 to 40.

[0353] In the context of this invention, the term "fouling" refers to an electrostatic, solid, or surface-active stabilized layer containing an aqueous and an organic phase, which most commonly accumulates at the water / organic interface in settlers of solvent extraction methods well known in the art.

[0354] In the context of this invention, the term "X is one or more of A, B, and C" (where X is a given feature and each of A, B, and C represents a specific implementation of said feature) should be understood to disclose that X is A, or B, or C, or A and B, or A and C, or B and C, or A and B and C. In this respect, it should be noted that those skilled in the art can translate the above abstract terms into concrete examples, for example, where X is a chemical element and A, B, and C are specific elements such as Li, Na, and K, or X is a temperature and A, B, and C are specific temperatures such as 10°C, 20°C, and 30°C. In this regard, it should be further noted that those skilled in the art can extend the above terms to less specific implementations of the feature, such as "X is one or more of A and B," which discloses that X is A, or B, or A and B, or extend them to more specific implementations of the feature, such as "X is one or more of A, B, C, and D," which discloses that X is A, or B, or C, or D, or A and B, or A and C, or A and D, or B and C, or B and D, or C and D, or A and B and C, or A and B and D, or B and C and D, or A and B and C and D.

[0355] The invention is further illustrated by the following examples. Example

[0356] Reference Example 1.1 Measurement of Total Chlorine Content (wppm)

[0357] Samples were filtered using a 0.45 µm syringe filter prior to analysis. The chlorine content was determined by burning the sample at 1050°C. The resulting combustion gas, hydrogen chloride, was introduced into the coulometric titration cell.

[0358] Refer to Example 1.2 for the measurement of chloride content (wppm).

[0359] Samples were filtered using a 0.45 µm syringe filter prior to analysis. Chloride content was determined by ion chromatography. Apparatus: Ion chromatograph 850 Professional (Metrohm) (pre-column: Metrosep A Supp4 / 5 S-Guard and analytical column: Metrosep A Supp5 250 / 4; flow rate: 0.7 mL / min; column temperature: 30°C; detector temperature: 40°C; injection volume: 25 µL; suppressor: MSM HC Rotor A). Eluents: 3.2 mmol / L Na₂CO₃; 1.0 mmol / L NaHCO₃; and regenerator: 50 mmol / L sulfuric acid.

[0360] Sample preparation: Weigh 0.2 g–0.4 g of sample and dissolve it in 10 mL of toluene. For analyte extraction, add 10 mL of deionized water. After centrifugation, extract the aqueous phase and analyze it. For samples with concentrations below the method limit, add 20 µg / L chloride standard solution (corresponding to the limit of 1 mg / kg chloride in the sample) to check the recovery.

[0361] Reference Example 2: Measurement of N content (wppm)

[0362] The nitrogen content was determined by burning the sample at 1000°C. The NO in the resulting combustion gases reacted with ozone to form NO2. Relaxation of excited-state nitrogen species was detected using a chemiluminescence detector according to ASTM D4629 (N). The calibration range was 0.5 wppm to 50 wppm. Samples with higher concentrations were diluted with xylene to bring them within the calibration range.

[0363] Determination of Total Acid Number (TAN) as per Example 3

[0364] According to ASTM D3242, the total acid number is determined by titration with KOH.

[0365] Refer to Example 4 for the measurement of oxygen content (O content) (weight - %)

[0366] Samples (1-10 mg) were pyrolyzed / reduced in a reducing gas atmosphere upon contact with soot, thereby converting oxygen into carbon monoxide (CO). Carbon monoxide was detected and quantified by IR spectroscopy. The analyzer used was a rapidOXY cube® elemental analyzer.

[0367] Reference Example 5: Measurement of sulfur content (wppm) in bio-oils

[0368] The sulfur content in a given bio-oil is measured according to ASTM D5453.

[0369] Reference Example 6 Corrosion Test

[0370] Two corrosion samples of steel 1.0425 (DIN EN 10028-2) were stored in the test pyrolysis oil at 60°C under a nitrogen atmosphere. Every 7 days, the samples were washed again with water, xylene, and water, dried, and weighed. The medium was then replaced with fresh pyrolysis oil, and the samples were returned to the tank. After 4 cycles (28 days), the average linear corrosion rate was calculated. The specimens are then examined. According to DIN 50905, the surface of the corroded specimens is examined using a binocular microscope at 10-20x magnification to detect various corrosion phenomena, the frequency, extent, and distribution of localized corrosion, as well as discoloration, scaling, or corrosion products on the specimen surface. The depth of localized corrosion (e.g., pitting corrosion) is measured by optical focusing using an optical microscope.

[0371] v l Average linear corrosion rate [mm / year]

[0372] Dm: Weight loss [g]

[0373] F: Sample surface [cm] 2 ]

[0374] r: Material density [g / cm³] 3 ]

[0375] T: Test duration [days]

[0376] The following examples, reference examples, and comparative examples are based on experiments conducted using oils obtained through 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, for instance, from Eschenbacher et al. (Energy Fuels 2021, 35, 18333-18369; and the corresponding references cited therein), that biomass-derived pyrolysis oils typically exhibit high oxygen content and high total acid value.

[0377] Example 1: Method for purifying pyrolysis oil according to the present invention

[0378] The product contains a total acid number (TAN) of approximately 8.5 mg KOH / g, a total chlorine content of 24 wppm, a chloride content of < 5 wppm, a nitrogen content of 0.5 wt.% based on the weight of the pyrolysis oil, and an oxygen content of 1 wt.% based on the weight of the pyrolysis oil, with a concentration of 916 kg / m³.3 The feed stream F0 of pyrolysis oil with a density of 6.4 mPas and a viscosity of 30°C was subjected to extraction with NaOH (1.1) or with KOH (1.2) and (1.3) at pH 10. For this purpose, F0 was introduced into a 1.3 L stirred glass vessel. Demineralized water was then added to the vessel (relative to v(demineralized water / pyrolysis oil) = 0.3 kg / kg) to form a mixture. The pH of the aqueous phase of the mixture was adjusted to 10 with 10% NaOH (1.1) or KOH (1.2 and 1.3). The resulting mixture was mixed for 15 min. For the mixture with NaOH, the mixture was transferred to a centrifuge. For the mixture with KOH, the mixture was settled in a 1.3 L glass vessel for 5 (1.2) and 7 (1.3) min. Thus, the aqueous phase was separated from the organic (oil) phase after settling. The organic phase was analyzed.

[0379] Following the separation and neutralization of the aqueous phase, demineralized water was further added to the organic phase to remove residual salts / caustic alkalis (entrainment). Demineralized water was added at a ratio v(demineralized water / organic phase) = 1 kg / kg. The resulting mixture of aqueous / organic (oil) phase was introduced into a settler (liquid / liquid separation unit). After settling, the aqueous phase was separated from the organic phase, and the washed organic phase was analyzed. Depending on the sample, different settling durations were applied: 8 min for 1.1, 6 min for 1.2, and 2.5 min for 1.3. The results are listed in Table 1 below.

[0380] Table 1. Composition of pyrolysis oil before extraction, after extraction, and after washing.

[0381]

[0382] pH of the aqueous phase

[0383] pH of the aqueous phase of F0 after washing with demineralized water only

[0384] "-" indicates not measured / determined.

[0385] As can be seen from Table 1, extraction + washing allows for the purification of pyrolysis oil by reducing its TAN, oxygen content, and N- and Cl- content.

[0386] Corrosion test: Corrosion tests were performed using pyrolysis oil F0 and purified pyrolysis oils obtained after washing with samples 1.1, 1.2, and 1.3, as described in Reference Example 6. The results are detailed in Tables 2 through 4 below.

[0387] Table 2 shows the corrosion test results of two steel samples of 1.0425 (DIN EN 10028-2) using pyrolysis oil F0.

[0388]

[0389] As can be seen from Table 2, the pyrolysis oil prior to the purification treatment according to the present invention is corrosive. Localized corrosion and pitting are unacceptable.

[0390] Table 3 shows the corrosion tests performed on two samples of steel 1.0425 (DIN EN 10028-2) using purified pyrolysis oil (washed sample 1.1) with reduced TAN and O content.

[0391]

[0392] As can be seen from Table 3, the pyrolysis oil purified with NaOH according to the present invention significantly reduces corrosion: the average linear corrosion (vl) is reduced by more than 99% and only sporadic rust spots (on the surface) are observed. Therefore, unlike the comparative examples, there is no pitting or localized corrosion, demonstrating a significant improvement. The purified pyrolysis oil does not affect the technical stability of the steel (vl less than 0.1 mm / y, combined with the absence of pitting or localized corrosion).

[0393] Table 4 shows the corrosion tests performed on two steel samples 1.0425 (DIN EN 10028-2) using purified pyrolysis oil (washed sample 1.2) with reduced TAN and O content.

[0394]

[0395] As can be seen from Table 4, the pyrolysis oil purified with KOH according to the present invention significantly reduces corrosion: the average linear corrosion rate (vl) is reduced by approximately 80%, and only sporadic rust spots (on the surface) are observed. Therefore, unlike the comparative examples, there is no pitting or localized corrosion, demonstrating a significant improvement. The purified pyrolysis oil does not affect the technical stability of the steel.

[0396] Therefore, it has been demonstrated that the pyrolysis oil prior to the purification treatment according to the present invention is corrosive, while the purified pyrolysis oil (TAN < 1) allows for a significant reduction in corrosion without affecting the technical stability of the steel.

[0397] Reference Example 7: A method for purifying pyrolysis oil not according to the invention - corrosion test

[0398] To determine the optimal purification conditions, an additional method for purifying the pyrolysis oil was employed. A feed stream F0 containing pyrolysis oil, as in Example 1, was subjected to extraction with KOH at T = 50°C and pH 7. For this purpose, F0 was introduced into a 1.3 L stirred glass vessel. Demineralized water was then added to the vessel (relative to v(water / pyrolysis oil) = 0.5 kg / kg) to form a mixture. The pH of the aqueous phase of the mixture was adjusted to 7.2 with 25 wt.-% KOH. The resulting mixture was mixed for 15 min. After settling (lasting 2 min), the resulting aqueous phase was separated from the organic phase. The organic phase was analyzed.

[0399] Next, a washing step was performed. Demineralized water was added to the organic phase at a ratio v(demineralized water / organic phase) = 0.5 kg / kg to remove salt and caustic alkali entrainments from the pyrolysis oil. The results are listed in Table 5 below.

[0400] Table 5

[0401]

[0402] pH of the aqueous phase

[0403] pH of the aqueous phase of F0 after washing F0 with demineralized water only.

[0404] As can be seen from Table 5, the decrease in TAN is much smaller at pH 7.

[0405] Corrosion test: Corrosion tests were performed using pyrolysis oil F0 (see Table 2 above) and purified pyrolysis oil (different pH values) not obtained according to the present invention, as described in Reference Example 6. The results are detailed in Table 6 below.

[0406] Table 6 shows the corrosion tests performed on two samples of steel 1.0425 (DIN EN 10028-2) using purified pyrolysis oil not obtained according to this invention.

[0407]

[0408] As can be seen from Table 6, the pyrolysis oil purified with KOH at pH 7 without the present invention reduced the average linear corrosion value (vl). However, this pyrolysis oil was more corrosive than the purified pyrolysis oil obtained by the method according to the present invention (see Tables 3 and 4 above). Even though vl was reduced, the presence of localized corrosion and pitting was unacceptable.

[0409] Example 2: Method for purifying pyrolysis oil according to the present invention

[0410] This results in a total acid value (TAN) of 15.9 mg KOH / g and a total acid value (TAN) of 863 kg / m³. 3 The feed stream F0 of pyrolysis oil with a density of 1.7 mPas and a viscosity of 1.7 mPas was subjected to extraction with NaOH at T = 25°C and pH 10. For this purpose, F0 was introduced into a 1.3 L stirred glass vessel. Demineralized water was then added to the vessel (relative to v(demineralized water / pyrolysis oil) = 0.5 kg / kg) to form a mixture. The pH of the aqueous phase of the mixture was adjusted to 10 with 25% NaOH. The resulting mixture was mixed for 15 min. For the mixture containing NaOH, the mixture was transferred to a centrifuge. Thus, the aqueous phase was separated from the organic (oil) phase after sedimentation. The organic phase was analyzed.

[0411] Following the separation and neutralization of the aqueous phase, demineralized water is further added to the organic phase to remove residual salts / caustic alkalis (entrainment). Demineralized water is added at a ratio v(demineralized water / organic phase) = 1 kg / kg. The resulting mixture of aqueous / organic (oil) phase is introduced into a settler (liquid / liquid separation unit). After settling, the aqueous phase is separated from the organic phase, and the washed organic phase is analyzed. The results are listed in Table 7 below.

[0412] Table 7 Composition of pyrolysis oil before and after extraction.

[0413]

[0414] pH of the aqueous phase

[0415] pH of the aqueous phase of F0 after washing F0 with demineralized water only.

[0416] As can be seen from Table 7, extraction (neutralization) allows for the purification of pyrolysis oil by reducing the TAN of the pyrolysis oil.

[0417] Comparative Example 1: A method for purifying pyrolysis oil not according to the present invention

[0418] A feed stream F0 containing pyrolysis oil with a total acid number (TAN) of 7 mg KOH / g was subjected to a first washing step with demineralized water in a 250 ml glass bottle, where the ratio v(demineralized water / pyrolysis oil (F0)) = 1 kg / kg. The mixture was shaken. The pH of the aqueous phase of the mixture was pH 4.3. The resulting mixture of water / organic phase (oil) was introduced into a centrifuge. Thus, the aqueous phase and the organic (oil) phase were separated.

[0419] After separating the aqueous and organic phases, demineralized water was further added to the organic phase for a second washing step. Demineralized water was added at a ratio v(demineralized water / organic phase) = 1 kg / kg. The resulting water / organic phase (oil) mixture was introduced into a centrifuge. The aqueous and organic phases were separated. Finally, a third washing step was performed, and the aqueous and organic phases were separated by centrifugation. The washed organic phase was analyzed. The results are listed in Table 3 below.

[0420] Table 8

[0421]

[0422] pH of the aqueous phase

[0423] pH of the aqueous phase of F0 after washing F0 with demineralized water only.

[0424] As can be seen from Table 8, the washing step is insufficient to reduce the TAN value. Attached Figure Description

[0425] Figure 1 This is a schematic diagram of a unit for performing a method for purifying bio-oil according to an embodiment of the present invention. The unit includes: an extraction zone Z. E The extraction zone includes an extraction unit UM1 and a liquid-liquid separation unit US1, with US1 located downstream of UM1; and in Z... E Downstream washing zone Z W The washing zone includes a washing unit UM2 and a liquid-liquid separation unit US2, located downstream of UM2. A stream F0 containing bio-oil is introduced into UM1 along with water and alkali B. In UM1, F0, water, and B are contacted at a temperature ranging from 10°C to 200°C, preferably from 10°C to 95°C. A mixture M1 containing an aqueous phase P is then removed from UM1. A (1) and organic phase P O (1), the aqueous phase P of M1 A (1) The pH ranges from 7.5 to 11. M1 is introduced into US1. A product containing P is obtained. A (1) flow F A (1) and bio-oils containing extracts (P) O (1)) flow F1 from US1 and Z E Remove from the middle. Furthermore, introduce F1 along with water into UM2. Contact F1 and water at a temperature ranging from 10°C to 95°C. Obtain mixture M2, which contains the aqueous phase P. A (2) and organic phase P O (2), the aqueous phase P of M2 A(2) The pH ranges from 7.5 to 11, P A (2) pH < P A (1) pH. Then M2 is introduced into US2. Stream F2 containing purified bio-oil is obtained. Also obtained is P A (2) The other flow F A (2). F2 can then be stored or transferred for further processing. Optionally, F can be recycled in UM1 and / or UM2. A (1) Water flow and / or F A (2) Aqueous flow (not shown). Optionally, if in P A (1) and P O If dirt forms at the interface of (1), the dirt is removed from US1 by cleaning (not shown).

[0426] Figure 2 This is a schematic diagram of a unit for performing a method for purifying bio-oil according to an embodiment of the present invention. The unit includes: an extraction zone Z. E The extraction zone includes an extraction unit UM1, a solid-liquid separation unit SLS1, and a liquid-liquid separation unit US1, with SLS1 located downstream of UM1 and US1 located downstream of SLS1; and in Z... E Downstream washing zone Z W The washing area includes a washing unit UM2, a solid-liquid separation unit SLS2, and a liquid-liquid separation unit US2. SLS2 is located downstream of UM2, and US2 is located downstream of SLS2. The method is as follows... Figure 1 As defined in the document, the difference is that M1 passes through SLS1 (if any) before being introduced into US1, and M2 passes through SLS2 (if any) before being introduced into US2.

[0427] Figure 3 This is a schematic diagram of a unit for performing a method for purifying bio-oil according to an embodiment of the present invention. The unit includes: an extraction zone Z. E The extraction zone includes an extraction unit UM1 and a liquid-liquid separation unit US1, with US1 located downstream of UM1; and in Z... E Downstream washing zone Z W The washing zone includes a washing unit UM2 incorporated into a liquid-liquid separation unit US2. ZE optionally includes a solid-liquid separation unit SLS1 located downstream of UM1 and upstream of US1. A stream F0 containing bio-oil is introduced into UM1 along with water and alkali B. In UM1, F0, water, and B are contacted at a temperature ranging from 10°C to 200°C, preferably from 10°C to 95°C. A mixture M1 containing an aqueous phase P is removed from UM1. A (1) and organic phase PO (1), the aqueous phase P of M1 A (1) The pH is in the range of 7.5 to 11. M1 is introduced into US1. If SLS1 is present, M1 passes through SLS1 before being introduced into US1. A product containing P is obtained. A (1) flow F A (1) and the stream F1 containing extracted bio-oil from US1 and Z E The mixture is removed from the middle. Furthermore, F1 is introduced into the combined UM2 / US2 as an extraction column. Water is also introduced into the column and contacted with F1 at a temperature ranging from 10°C to 95°C, in which the phases of M2 are separated, with the aqueous phase P of M2 being... A (2) The pH ranges from 7.5 to 11, P A (2) pH <P A (1) pH. Stream F2 containing purified bio-oil is obtained (removed at the top of the column). Also obtained is P... A (2) The other flow F A (2) (Remove from the opposite position of the tower, i.e., the bottom). F2 can then be stored or transferred for further processing. Optionally, in UM1 and / or Z W Recycle F A (2) Water flow (not shown).

[0428] Figure 4 This is a schematic diagram of a unit for performing a method for purifying bio-oil according to an embodiment of the present invention. The unit includes: an extraction zone Z. E The extraction zone includes an extraction unit UM1, an optional solid-liquid separation unit SLS1, and a liquid-liquid separation unit US1, with SLS1 located downstream of UM1 and US1 located downstream of SLS1; and in Z... E Downstream washing zone Z W The washing area includes a washing unit UM2, an optional solid-liquid separation unit SLS2, and a liquid-liquid separation unit US2, with SLS2 located downstream of UM2 and US2 located downstream of SLS2. The method is as follows... Figure 1 As defined in [reference needed], the difference lies in that M1 optionally passes through SLS1 to remove solids (if any) before being introduced into US1, and M2 optionally passes through SLS2 to remove solids (if any) before being introduced into US2. The Z [value] of this cell... W The system further includes a washing unit UM4, an optional solid-liquid separation unit SLS4, and a liquid-liquid separation unit US4, with SLS4 located downstream of UM4 and US4 downstream of SLS4. F2 is introduced into UM4 along with water. The F2 and water are brought into contact at a temperature ranging from 10°C to 95°C. A mixture M4 is obtained, which contains an aqueous phase P. A(4) and organic phase P O (4), the aqueous phase P of M4 A (4) pH ranges from 7.5 to 11, P A (4) pH < P A (1) pH. M4 is then introduced into US4, and optionally passed through USL4 before being introduced into US4. Stream F4 containing purified bio-oil is obtained. Also obtained is P... A (4) another flow F A (4). F4 can then be stored or transferred for further processing. Optionally, F can be recirculated in UM2. A (4) Water flow (not shown).

[0429] Optionally, the Z of this unit W The system further includes a washing unit UM3 and a liquid-liquid separation unit US3, and may further include a solid-liquid separation unit SL3, SLS3 (if present) located downstream of UM3 and US3 located downstream of SLS3. Therefore, F2 is introduced into UM3 (not UM4) along with water. F2 and water are brought into contact at a temperature ranging from 10°C to 95°C. A mixture M3 is obtained, which contains an aqueous phase P. A (3) and organic phase P O (3), the aqueous phase P of M3 A (3) The pH ranges from 7.5 to 11, P A (3) pH < P A (1) pH. M3 is then introduced into US3, and optionally passed through USL3 before being introduced into US3. Stream F3 containing purified bio-oil is obtained. Also obtained is P... A (3) The other flow F A (3). Then F3 and water are introduced into UM4. F3 and water are brought into contact at a temperature ranging from 10°C to 95°C. Mixture M4 is obtained, which contains an aqueous phase P. A (4) and organic phase P O (4), the aqueous phase P of M4 A (4) pH ranges from 7.5 to 11, P A (4) pH < P A (1) pH. M4 is then introduced into US4, and optionally passed through USL4 before being introduced into US4. Stream F4 containing purified bio-oil is obtained. Also obtained is P... A (4) another flow F A (4). F4 can then be stored or transferred for further processing. Optionally, F can be recycled in UM2 and / or UM3. A(4) Aqueous flow (not shown). Optionally, F is recirculated in UM2. A (3) Aqueous flow (not shown). Optionally, F is recirculated in UM1. A (2) Water flow (not shown). References

[0430] -US 2021 / 0277324 A1

[0431] -WO 2014 / 165859 A1

[0432] -WO 2020 / 178599 A1.

Claims

1. A method for purifying bio-oil, the method comprising: (i) Providing a stream F0 containing the bio-oil, wherein preferably, the bio-oil is obtained from biomass by mechanical and physical operations and chemical methods; (ii) Ensure that the flow F0 provided in (i) is in at least one extraction zone Z E The medium undergoes extraction to obtain a stream F1 containing the extracted bio-oil, wherein (ii) includes: (ii.1) Introduce F0 into Z E The extraction unit UM1 is included; (ii.2) In UM1, F0 is contacted with water and alkali B at a temperature T1 ranging from 10°C to 200°C to obtain P containing an aqueous phase. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) The pH ranges from 7.5 to 11; (ii.3) Allow the mixture M1 obtained according to (ii.2) to enter Z. E The liquid-liquid separation unit US1, located downstream of UM1, contains P. A (1) flow F A (1) and P contained in the bio-oil extracted from it. O (1) Flow F1; (ii.4) From Z E Move F1 out of the middle; (iii) Ensure that the flow F1 provided in (ii) is in at least one washing zone Z W The middle undergoes a cleansing—Z W Located in Z E Downstream, a stream F2 containing purified bio-oil is obtained; and (v) The F2 containing the bio-oil obtained according to (iii) is introduced into at least one storage unit SU and the bio-oil is stored in the SU.

2. The method as described in claim 1, wherein, (ii.2) Includes (ii.2.1) Introduce water into Z E Included in UM1; (ii.2.2) In UM1, F0 is brought into contact with water, preferably mixed, to obtain a mixture PM1 containing water and the bio-oil; (ii.2.3) Introduce B into UM1 and contact B with the mixture PM1 obtained in (ii.2.2) in UM1, preferably mix them, to obtain a mixture containing the aqueous phase P. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) The pH is in the range of 7.5 to 11, preferably in the range of 8 to 10; Preferably, (ii.2) includes (ii.2.1) Introduce water into Z E Included in UM1; (ii.2.2) In UM1, F0 is brought into contact with water, more preferably mixed, to obtain a mixture PM1 containing water and the bio-oil, wherein the aqueous phase of PM1 has a pH value pH (PM1), which is more preferably measured by a pH sensor in UM1. (ii.2.3) By introducing B into UM1 and adjusting the pH of the aqueous phase of PM1 by contacting and preferably mixing B with M1 obtained in (ii.2.2) in UM1, an aqueous phase P is obtained. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) pH > pH(PM1), P A (1) The pH is in the range of 7.5 to 11, more preferably in the range of 8 to 10.

3. The method as described in claim 1, wherein, (ii.2) Includes (ii.2.1') ​​Mix water and B to obtain a mixture M0 of water and B having a pH (M0) in the range of 12 to 14; (ii.2.2') The M0 obtained according to (ii.2.1') ​​is introduced into UM1 and F0 is brought into contact with M0 in UM1, preferably mixed, to obtain a solution containing the aqueous phase P. A (1) and organic phase P O (1) The mixture M1, the aqueous phase P of M1 A (1) The pH is in the range of 7.5 to 11, preferably in the range of 8 to 10.

4. The method according to any one of claims 1 to 3, wherein, According to (ii.2), the contact and mixing are preferably carried out at a temperature T1 in the range of 10°C to 95°C, more preferably in the range of 15°C to 85°C, more preferably in the range of 20°C to 80°C, and even more preferably in the range of 20°C to 50°C.

5. The method according to any one of claims 1 to 4, wherein, No organic solvents are used in (ii).

6. The method according to any one of claims 1 to 5, wherein, (iii) Includes: (iii.1) Introduce F1 into Z W It includes the washing unit UM2; (iii.2) In UM2, F1 is brought into contact with water at a temperature T2 ranging from 10°C to 95°C to obtain P containing the aqueous phase. A (2) and organic phase P O (2) The mixture M2, the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A (1) pH; (iii.3) Allow the mixture M2 obtained according to (iii.2) to enter Z. W The liquid-liquid separation unit US2, located downstream of UM2, contains P. A (2) flow F A (2) and P contained in the purified bio-oil O (2) flow F2, Preferably, the washing unit UM2 is one or more of a stirring container, a mixing pump, and a static mixer; more preferably, it is a stirring container. Preferably, the liquid-liquid separation unit US2 is one or more of a hydrocyclone, a settling tank, a centrifuge, and an extraction tower, more preferably a hydrocyclone, a settling tank, or a centrifuge, and even more preferably a settling tank or a centrifuge.

7. The method according to any one of claims 1 to 5, wherein, (iii) Includes: (iii.1') Introduce F1 into Z W The extraction tower UM+US is included; (iii.2') Introduce water into UM+US; (iii.3') In UM+US, F1 is brought into contact with water at a temperature T2' ranging from 10°C to 95°C to obtain P containing the aqueous phase. A (2) flow F A (2), the aqueous phase P of M2 A (2) The pH ranges from 7.5 to 11, P A (2) pH < P A (1) pH, and obtain a stream F2 containing the purified bio-oil.

8. The method according to any one of claims 6 to 7, wherein, According to (iii.2) or (iii.3'), the weight ratio of water to F1 is in the range of 0.05:1 to 2:1, preferably in the range of 0.1:1 to 1.5:1, more preferably in the range of 0.1:1 to 1.2:1, and even more preferably in the range of 0.1:1 to 0.5:

1.

9. The method of any one of claims 6 to 8, further comprising: Recycle F obtained from (iii.3) and / or (iii.2) in (ii.2). A (2) Contains at least a portion of the water; or Recycle based on (iii.3') and / or (iii.2') obtained in (ii.2) F A (2) contains at least a portion of the water.

10. The method of any one of claims 1 to 9, further comprising, when in US1 in P A (1) and P O When dirt forms at the interface of (1), the dirt is cleaned from US1—preferably a settling tank.

11. The method according to any one of claims 1 to 10, wherein, The total acid number (TAN) of the stream F2 containing the purified bio-oil obtained according to (iii) is lower than that of the bio-oil provided in (i); Preferably, the stream F2 containing the purified bio-oil obtained according to (iii) has an oxygen content equal to or lower than, more preferably lower than, the oxygen content of the bio-oil provided in (i).

12. A method for purifying bio-oil, the method comprising: (i) according to any one of the preceding claims; (II) According to any one of the preceding claims; (III) According to any one of the preceding claims; (iv) In Z W The process involves at least a portion of the stream F2 obtained according to (iii) undergoing one or more subsequent washes, wherein (iv) includes: (iv.1) Optionally, at least a portion, preferably F2, of the F2 obtained according to (iii) is introduced into Z. W The washing unit UM3 contained therein is located downstream of US2; In UM3, at least a portion, preferably F2, of the F2 is brought into contact with water at a temperature T3 in the range of 10°C to 95°C to obtain a P-phase containing water. A (3) and organic phase P O (3) The mixture M3, M3 is in the range of 7.5 to 11, P A (3) pH < P A (1) pH; Let the mixture M3 enter Z W The liquid-liquid separation unit US3, located downstream of UM3, contains P. A (3) flow F A (3) and P contained in the purified bio-oil O (3) Flow F3; (iv.2) Introduce at least a portion of F2 obtained according to (iii), preferably F2, or at least a portion of F3 obtained according to (iv.1) into Z. W The washing unit UM4 is located downstream of US3. (iv.3) In UM4, at least a portion of F2 or at least a portion of F3 is brought into contact with water at a temperature T4 in the range of 10°C to 95°C to obtain a P containing an aqueous phase. A (4) and organic phase P O (4) The mixture M4, the aqueous phase P of M4 A (4) pH ranges from 7.5 to 11, P A (4) pH < P A (1) pH; (iv.4) Allow the mixture M4 obtained according to (iv.3) to enter Z. W The liquid-liquid separation unit US4, located downstream of UM4, contains P. A (4) flow F A (4) and P contained in the purified bio-oil O (4) flow F4; and (v) The F4 obtained according to (iv) is introduced into at least one storage unit SU and the bio-oil is stored in the SU.

13. The method as described in any one of claims 1 to 12, in, The storage unit SU is a storage tank, preferably made of one or more of steel and stainless steel, more preferably carbon steel and stainless steel.

14. A unit for performing the method for purifying bio-oil as described in any one of claims 1 to 13, the unit comprising: - At least one extraction zone Z comprising extraction unit UM1 and liquid-liquid separation unit US1 E UM1 is located upstream of US1; - Used to introduce F0 into Z E The inlet device; - Used from Z E Remove the F1 outlet device from the middle; - An entry device used to introduce F0 into UM1; - An exit device for removing M1 from UM1; - An inlet device for introducing M1 into US1; - An exit device for removing F1 from US1; -At least one washing area Z W It is located in Z E Downstream; - Used to introduce F1 into Z W The inlet device; - Used from Z W The exit device of F2 was removed from the middle; and - Storage tank.

15. A purified bio-oil, obtained by the method according to any one of claims 1 to 14, wherein, Preferably, the purified bio-oil of the present invention has a total acid value (TAN) in the range of 0 to 10 mg KOH / g (oil), more preferably in the range of 0 to 4 mg KOH / g (oil).

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