CA3229309A1 - Method for purifying hydrocarbon feedstock in an aqueous medium and use thereof - Google Patents

Abstract

Disclosed is a method for purifying a composition containing a plastic liquefaction oil, the method comprising treating with a strong base in the presence of water, followed by washing with water. The method is useful for reducing the concentration of heteroelements and, in particular, alkali metal and alkali earth cations in said composition, with a view to making it compatible for introduction as feedstock in conversion methods such as steam cracking, fluid-bed catalytic cracking, catalytic hydrogenation or hydrocracking, without deactivating catalysts used in these methods.

Description

TITLE: PROCESS FOR PURIFYING HYDROCARBON FEED IN AN ENVIRONMENT
AQUEOUS AND USE
Technical field of the invention The present invention relates to a charge purification method hydrocarbon and its subsequent use in refining and petrochemical processes. THE
process according to the invention makes it possible to purify charges containing pyrolysis oils of plastic and/or hydrothermal liquefaction oils of plastic, particularly with a view to of their use in a steam cracking process.
Technology background Patent JP3776335 discloses a dechlorination and denitrogenation process of an oil resulting from the catalytic or thermal cracking of plastic waste which is treated at different temperatures up to 425 C for 30 minutes in the presence of a solution aqueous solution of an alkaline compound of an alkali or alkaline earth metal at a pH
higher or equal to 7. All natural alkali or alkaline earth metal hydroxides non-radioactive are tested. The reaction product is then separated from the solution aqueous alkaline by liquid-liquid separation with ethyl ether.
Patent application W02012/069467 claims a process for eliminating siloxanes contained in a plastic pyrolysis oil by heat treatment between 200 and 350 C in the presence of an alkali metal hydroxide in the solid state or in solution. Use of calcium hydroxide at 5% by weight at 225 C does not make it possible to obtain reduction of siloxane content (table 5, p.12 and lines 9 to 11, p.13). At the end of the reaction, oil pyrolysis is separated by distillation under reduced pressure.
Patent FI128848 describes a process sequence comprising a treatment thermal of a plastic pyrolysis oil at at least 200 C in the presence of a aqueous solution alkaline. At the end of the reaction, the pyrolysis oil is separated from the aqueous phase alkaline. A final hydrotreatment makes it possible to obtain a steam cracker feed who is possibly washed with an acid solution before introduction into the steam cracker.
Patent application W02020/020769 claims a sequence of processes for purification of a composition comprising at least 20 ppm of chlorine. Of many Recyclable liquid waste can be treated, including pyrolysis oils of plastic.
The process sequence includes a heat treatment of the load in presence of an alkali metal hydroxide in order to obtain a reduction of at least 50% of the contained in chlorine in relation to the load, followed by hydrotreatment in order to obtain a new reduction at least 50% of the chlorine content.

WO 2023/037059

2 Patent application W02021/105326 claims a process for valorizing waste liquefied plastics including a waste pretreatment step liquefied plastics by bringing into contact with an aqueous medium having a pH of at least 7 at a temperature of 200 C or more, followed by liquid-liquid separation in which the phase aqueous is separated from the organic phase, to produce a waste plastic material liquefied pretreated. The proposed solution includes the use of a NaOH solution in water. There separation of the aqueous and organic phases is implemented by methods physical (centrifugation) or chemical (addition of additives to aid the separation, for example non-aqueous solvents, addition of additional quantity of aqueous medium used for the brought into contact or with an aqueous medium having a substance concentration alkaline different), or by gravity.
Patent application US20140303421A1 describes a process for treating oils raw synthetics making it possible to lower the acid content and/or the presence of particles and contaminants containing heteroatoms. Synthetic crude oil is washed with a basic aqueous solution having a pH not higher than 10 in order to avoid a saponification. The synthetic crude oil is then separated from the solution watery. In a embodiment illustrated in Figure 3, the synthetic crude oil is washed with a first solution to eliminate particles, contaminants containing metals or metalloids or alkali metals. For this purpose, the first solution is acid for neutralize alkaline species and absorb acids or metals, metalloids of organic polar molecules or other impurities and/or the first solution contains chelating agents to remove metals. Synthetic crude oil as well washed is then separated then washed with a second basic aqueous solution having a pH
no more raised to 10 before being separated again.
Patent application W02020239729 describes a process for purifying oils pyrolysis of plastic which includes a purification step in which the oil is subject to a hydrothermal treatment at 150-450 C with water or water at pH>7. Oil is then separated from the aqueous phase then sent without any other intermediate treatment in hydrotreatment, alone or in a mixture, in the presence of a catalyst and hydrogen in order to carry out one or more hydrogenation, hydrodeoxygenation reactions, hydrodesulfurization, hydrodenitrogenation, hydrodechlorination, hydrodearomatization or hydroisomerization.
These documents do not present ways to lower the metal content alkaline/alkaline earth present in plastic pyrolysis oil and/or in oil hydrothermal liquefaction of plastic after pretreatment with a base strong. But, he is known that the presence of alkali/alkaline earth metals can cause deactivation of WO 2023/037059

3 catalysts used in catalytic oil processing processes plastic pretreated.
Summary of the invention The invention aims to propose a process for purifying liquefaction oil plastic making it easier to purify by limiting the quantity of strong base used while now high abatement performance, including for abatement of the alkali and/or alkaline earth metal content resulting from the treatment of the oil of liquefaction of plastic by a strong base.
For this purpose, the invention relates to a process for reducing the concentration in heteroatoms of a composition comprising a liquefaction oil of plastic containing at least 20 ppm by mass of chlorine as measured according to the standard ASTM
D7359-18, including:
(has). bringing said composition into contact with 0.1-50% by mass of a strong base comprising an alkali or alkaline earth metal cation in the presence of water, for 1 minute to 20 minutes at a temperature of not more than 450 C, (b). washing with water at neutral or acidic pH of the product resulting from step (a).
The plastic liquefaction oil can be a pyrolysis oil of plastic, oil hydrothermal liquefaction of plastic or a mixture of both, for example an oil of plastic pyrolysis.
In particular, step (a) is carried out without adding any solvent other than water or a solvent possibly already present in the composition.
During step (a), the composition is brought into contact with 0.1 to 50% in mass of a base strong compared to the mass of the composition introduced.
Advantageously, during step (a), the composition is brought into contact with 0.1 to 15% in mass of a strong base in the presence of water, more preferably with 1 to 15%
in mass of a strong base, more preferably with 1 to 10% by mass of a base strong.
Advantageously, the strong base added in step (a) is in solution in the water. Thus, at during step (a), the composition can be brought into contact with a aqueous solution a strong base comprising an alkali or alkaline earth metal cation.
The man of WO 2023/037059

4 profession will then choose a sufficient quantity of water to dissolve/solubilize the strong base, of preferably the lowest possible quantity of water, or just enough to saturate the water strong base.
Advantageously, the strong base added in step (a) is in solution in water, and the content in strong base of water is 0.1 to 50% by mass, preferably 25% to 50%
in mass more preferably 40 to 50% by mass, even more preferably, the water is saturated with strong base, in particular water contains a just sufficient quantity strong base to obtain a saturated solution.
During step (a), the volume ratio of the strong base in solution in water / composition, ie the volume ratio of the mixture (strong base + water)/composition, can be from 0.1/99.9 to 80/20, from 1/99 to 80/20, from 1/99 to 70/30, from 1/99 to 65/35, from 1/99 to 60/40, from 1/99 to 50/50, or in any interval defined by any two of the limits aforementioned.
The composition may further comprise a pyrolysis oil or liquefaction hydrothermal biomass, in particular a pyrolysis or liquefaction oil hydrothermal biomass such as Panicum virgatum, tall oil, an oil used food, animal fat, vegetable oil such as oil rapeseed, canola, castor oil, palm oil, soybean oil, an oil extracted from algae, an oil taken from a fermentation of oleaginous microorganisms such as oleaginous yeasts, an oil pyrolysis or hydrothermal liquefaction of biomass such as biomass lignocellulosic such as a pyrolysis oil of wood, paper and/or cardboard, oil obtained by pyrolysis or hydrothermal liquefaction of crushed used furniture, an oil of pyrolysis or hydrothermal liquefaction of elastomers, for example latex possibly vulcanized or tires, as well as their mixtures.
The composition may comprise at least 2% by mass of a plastic oil, even at less 1% by mass of plastic oil. The remainder can then be composed of at over 98% in mass, or at most 99% by mass of a diluent or solvent such as a hydrocarbon and/or one or more of the components listed above. In a mode of realization, the composition may comprise at least 5%m, preferably at least 10%m, more of preferably at least 25% by mass of plastic oil, preferably at least 50% in mass, more preferably 75 ')/0 in mass, even more preferably at minus 90 ')/0 in mass of plastic oil. The composition may include at most 80% m or 90%m or 95%m or 100%m plastic liquefaction oil It is also possible to use only plastic oil.

WO 2023/037059

5 Contacting is preferably carried out for a period of 1 minute to 20 minutes, preferably from 1 minute to 16 minutes, at a temperature of 50 to 450 C, from preference of 50 to 350 C or 90 to 350 C, more preferably 150 to 350 C, again more preferably from 50 to 250 C, from 50 to 225 C or from 50 to 200 C, and at a pressure absolute from 0.1 to 100 bars, preferably from 1 to 50 bars. Note that the duration of implementation contact can be longer (for example from 30 minutes to 1 hour, or even no more, but does not make it possible to improve the quality of the products obtained.
In a particularly preferred embodiment, contacting is carried out during a duration of 1 minute to 20 minutes, preferably 1 minute to 16 minutes, a temperature of at most 250 C, more preferably at most 225 C, of way again most preferred of at most 200 C. In this embodiment particularly preferred, the setting in contact can be carried out at a temperature of at least 50 C, preferably at least 90 C, more preferably at least 150 C. In this embodiment particularly preferred, contacting can be carried out at a pressure absolute of 0.1 at 100 bars, preferably from 1 to 50 bars.
In this particularly preferred embodiment, the composition can advantageously be put in contact with:
- 0.1 to 15% by mass of a strong base comprising an alkali metal cation or alkaline-earthy in the presence of water, preferably with 1 to 15% by mass of a base strong, more preferably with 1 to 10% by weight of a strong base (percentages strong base masses relative to the composition), and/or - with water containing 25 to 50% by weight of strong base, preferably 25% to 50% by mass, more preferably 40 to 50% by mass (percentages mass strong base compared to water), even more preferably with water saturated in strong base.
A preferred strong base can be chosen from Li0H, NaOH, CsOH, Ba(OH)2, Na2O, KOH, K20, CaO, Ca(OH)2, MgO, Mg(OH)2 and their mixtures. A strong base more favorite can be chosen from NaOH, KOH and their mixtures, in particular for the implementation artwork of the particularly preferred embodiment.
The water used in step (b) can have an acidic pH (PH<7) or neutral (pH=7). In particular, the water used does not contain a base and in particular does not contain no strong base comprising an alkali or alkaline earth metal cation. An acidic pH can be obtained by addition of one or more organic or inorganic acids. Examples of acids WO 2023/037059

6 Usable organics include citric acid (C6H807), formic acid (CH202), acetic acid (CH3COOH). Examples of inorganic acids are the acid hydrochloric (HCI), nitric acid (HNO3), sulfuric acid (H2SO4), acid phosphoric (H3PO4), sulfamic acid (H3NS03).
Step (b) can be carried out at a temperature of 0 to 80 C, for example 0 to 60 C, from preferably from 00 to 40 C, more preferably from 0 to 30 C, in particular without external heating. Step (b) is typically carried out under pressure atmospheric.
During step (b), the water/composition volume ratio with the strong base could be 10/90 to 90/10, from 20/80 to 80/20, from 30/70 to 70/30, from 35/65 to 65/35, from 35/65 at 60/40, from 40/60 to 60/40, or in any interval defined by any two of the terminals aforementioned.
Step (b) may include, or consist of, bringing the product into contact from the stage (a) with water by any means known in the prior art.
For example, the product from step (a) and water can be introduced in tanks, reactors or mixers commonly used in the profession and two components can be mixed. The contact may include a hustle vigorously of the two components by a mixing device. For example, the two Components can be mixed together by stirring or shaking.
Alternatively, contact can be made in an enclosure in which the two components circulate in countercurrent. This contact can be produce more once, particularly under the conditions presented above.
Step (b) can be implemented on the product directly resulting from step (a) (including the strong base in solution in water and the product resulting from the in contact with the composition), without intermediate step, or on the product resulting from step (a) having suffered a separation stage.
Thus, in one embodiment, the method according to the invention comprises, between step (a) and (b), a step of separation between the strong base comprising the cation of alkali metal or alkaline earth in solution in water and the product resulting from the implementation contact of said composition. The product resulting from bringing said composition into contact corresponds to a composition comprising a plastic pyrolysis oil having a concentration in heteroatoms weaker than the initial composition. It is thus a purified composition.

WO 2023/037059

7 The separation between the strong base in solution in water and the product resulting from step (a) is advantageously carried out by (i) centrifugation, (ii) decantation, or (iii) by the combination of these two stages.
Typically, this separation step makes it possible to separate an organic phase, corresponding to the product resulting from the contacting of step (a), and a aqueous phase containing the strong base comprising the alkali or alkaline metal cation earthy. She can be preceded by a solids separation step by (i) filtration, (ii) centrifugation or (iii) a combination of the two steps. This solids separation step can allows to facilitate the separation of the organic and subsequent aqueous phases by eliminating all or part solids present in the product resulting from step (a).
Also, advantageously, the strong base in solution in water separated during of this separation step can be returned (recycled), partially or in part whole, in step (has).
The separation step makes it possible to reduce part of the content of the resulting product from step (a) in alkaline or alkaline earth cation. The remaining alkaline cation content or alkaline earth (or all or almost all of the alkaline or alkaline cation content earthy when this separation step is absent) is eliminated during washing step (b).
The composition thus processed can be used without causing deactivation of catalysts used in subsequent catalytic treatment processes.
Washing step (b) can make it possible to obtain a product having a cation content alkaline or alkaline earth less than or equal to 2 ppm (by mass).
The invention may also include an additional step prior to step (a) of bringing into contact, in which said composition is subjected, in particular immediately before step (a), (i) filtration, (ii) washing with a solvent polar, (iii) distillation, (iv) decantation, or (v) the combination of two, three or four of the steps (i) to (iv).
This preliminary step can help remove some of the impurities contained in the composition such as oxygen, nitrogen, chlorine, sulfur or others heteroatoms.
In particular, reducing the quantity of oxygen can help avoid training of solid and/or gels during step (b).

WO 2023/037059

8 During the additional prior washing step (ii), the volume ratio solvent fleece/composition can be from 10/90 to 90/10, from 20/80 to 80/20, from 30/70 to 70/30, from 35/65 at 65/35, from 35/65 to 60/40, from 40/60 to 60/40.
The polar solvent may have a density greater or less than the density of the composition comprising a plastic oil, in particular a pyrolysis oil of plastic.
In particular, the density of the polar solvent can be greater or 3 to 50% lower than that of composition.
The polar solvent is also an immiscible solvent in the composition including a pyrolysis oil to purify.
In the present invention, it can be considered that the polar solvent (or than a mixture of polar solvents where applicable) is immiscible when its rate of recovery is greater than or equal to 0.95. This recovery rate is defined as the ratio volume of extract on the volume of initial solvent, this extract being a phase containing the solvent, not miscible with the composition containing a pyrolysis oil, recovered after agitation then decanting a mixture of one part by volume of solvent with twenty five parts by volume of the composition containing a pyrolysis oil to be purified, pressure atmospheric and at a temperature of 20 C.
We can in particular determine this recovery rate by following the procedure next :
= Introduction of 50 mL of composition containing a pyrolysis oil into a ball flat bottom with a volume of 100mL, using a precision pipette of +/-0.5mL, = Introduce 2 mL of solvent into the flask, using a pipette precision +/-0.1mL, = Insert a magnetic bar, close the balloon with a cork polypropylene, - Stir the mixture on a mechanical stirring plate at speed 500 rpm for 5min, - At the end of 5 minutes, stop stirring, remove the magnetic bar using a rod magnetic, - Transfer the contents of the flask into a graduated tube with a accuracy of +/-0.05 mL for a volume less than or equal to 2mL and an accuracy of +/-0.1 mL
For a volume greater than 2mL. Wait for complete demixing by decantation and measure the volume of the 2 phases using the graduations. We consider that the Complete demixing is achieved when the volumes of the two phases do not vary more.
The expression polar solvent within the meaning of this patent application covers all chemical species, alone or in mixture, capable of solvating a composition comprising a plastic oil, in particular a pyrolysis oil of plastic, and comprising at least one carbon-hydrogen, carbon-halogen covalent bond, carbon-chalcogen or carbon-nitrogen and having a non-zero dipole moment. The solvent polar can WO 2023/037059

9 thus contain one or more heteroatoms, in particular chosen from oxygen, sulfur and nitrogen, preferably oxygen. Polar solvents acceptable, no miscible with the composition comprising a plastic oil to be purified, include compositions comprising hydrocarbon compounds which contain heteroatoms in their molecular structure, for example (i) alcohols such as methanol and ethanol, and mixtures of alcohols resulting from fermentation, for example a mixture of isomers of butanol or a mixture of pentanol isomers such as fusel oil (ii) ethers, for example cyclopentylmethylether or 1,4-dioxane, (iii) sulfur compounds, for example example the thiophene or dimethyl sulfoxide, (iv) nitrogen compounds, for example N,N-dimethylformamide, (y) halogenated compounds, for example dichloromethane where the chloroform, or:
- water with an acidic, basic or neutral pH. An acidic pH can be obtained by addition of one or more organic or inorganic acids. Examples organic acids which can be used include citric acid (C6I-1807), acid formic (CH202), acetic acid (CH3000H), sulfamic acid (H3NS03). Of the Examples of inorganic acids are hydrochloric acid (HCI), acid nitric (H NO3), sulfuric acid (H2SO4), phosphoric acid (H3PO4). A pH
basic can be obtained by addition of alkali and alkaline earth metal oxides, alkaline and alkaline earth hydroxides (e.g. NaOH, KOH, Ca(OH)2) and of the amines (e.g. triethylamine, ethylenediamine, ammonia).
- glycol ethers, including in particular polyethylene glycol chemical formula HO-(CH2-CH2-0),-H with a mass average molar mass of 90 to 800g/mol, per example diethylene glycol and tetraethylene glycol, polypropylene glycol of chemical formula H[OCH(CH3)CH2]OH of mass average molar mass from 130 to 800g/mol, for example dipropylene glycol and tetrapropylene glycol, - dialkyl formamides, in which the alkyl group may comprise 1 to 8 or 1 to 3 carbon atoms, in particular dimethyl formamide (DMF), - dialkyl sulfoxides, in which the alkyl group may comprise 1 to 8 or 1 to 3 carbon atoms, in particular dimethyl sulfoxide (DMSO) and sulfolane - compounds comprising a furan ring, - cyclic carbonate esters, comprising in particular from 3 to 8 or from 3 at 4 carbon atoms, notably propylene carbonate and carbonate of ethylene.
One or more of the aforementioned solvents may be used. However, advantageously, only one of the aforementioned solvents can be used provided that it is immiscible with the composition containing a plastic oil, in particular a pyrolysis oil of plastic, to be purified.
Preferably, the polar solvent may be a glycol ether, in particular polyethylene glycol of chemical formula HO-(CH2-CH2-0),-H of mass average molar mass of 90 WO 2023/037059

10 at 800g/mol or polypropylene glycol of chemical formula H[OCH(CH3)CH2],0H of mass average molar mass of 130 to 800g/mol, or a compound comprising a ring furan, or a cyclic carbonate ester, in particular propylene carbonate or ethylene, alone or in a mixture, preferably alone.
In a preferred embodiment, the polar solvent is chosen from carbonate of propylene, ethylene carbonate and polyethylene glycol of formula chemical HO-(CH2-CH2-0)nH with a mass average molar mass of 90 to 800g/mol, alone or in blend, preferably alone.
The invention may also include an additional step in which:
(vs). the product resulting from the washing of step (b) undergoes a catalytic hydrogenation in one or two step.
In the case where the catalytic hydrogenation is carried out in two stages, the stage (c) is carried out in a first step (c-1) in which the product resulting from the implementation contact is hydrogenated at a temperature between 20 and 200 C, preferably between 30 and 90 C
in the presence of hydrogen at an absolute pressure of between 5 and 60 bars, preference between 20 and 30 bars and in the presence of a hydrogenation catalyst comprising Pd (0.1-10 % by weight) and/or Ni (0.1-60% by weight) and/or NiMo (0.1-60% by weight), and in a second step (c-2) in which the effluent from step (c-1) is hydrogenated to a temperature between 200 and 450 C, preferably between 200 and 340 C in presence of hydrogen at an absolute pressure of between 20 and 140 bars, of preferably between 30 and 60 bars and in the presence of a hydrogenation catalyst comprising NiMo (0.1-60% in weight) and/or CoMo (0.1-60 (1/0 by weight).
The product from step (b) or the effluent from step (c) is (d) preferably purified by passage over a solid adsorbent in order to reduce the content of at least one element among F, Cl, Br, I, 0, N, S, Se, Si, P, As, Fe, Ca, Na, K, Mg and Hg and/or the content of water.
The adsorbent can be operated in regenerative or non-regenerative mode, at a temperature less than 400 C, preferably less than 100 C, more preferably lower than 60 C, chosen from: (i) a silica gel, (ii) a clay, (iii) a clay crushed, (iv) apatite, (y) hydroxyapatite and their combinations, (vi) an alumina for example an alumina obtained by precipitation of boehmite, a calcined alumina such as Ceralox 0 from Sasol, (vii) boehmite, (viii) bayerite, (ix) hydrotalcite, (x) a spinel such as Pural 0 or Puralox from Sasol, (xi) a promoted alumina, for example Selexsorb 0 from BASF, a acid-promoted alumina, an alumina promoted by a zeolite and/or by a metal such as Ni, Co, Mo or a combination of two or more of them, (xii) a clay acid treated WO 2023/037059

11 PCs such as Tonsil 0 from Clariant, (xiii) a molecular sieve in the form of a aluminosilicate containing an alkaline or alkaline earth cation, for example sieves 3A, 4A, 5A, 13X, par example marketed under the brand Siliporite 0 from Ceca, (xiv) a zeolite, (xv) a activated carbon, or the combination of at least two adsorbents, the adsorbent or at least two adsorbents retaining at least 20% by weight, preferably at least 50% by weight of at least one element from F, Cl, Br, I, 0, N, S, Se, Si, P, As, Fe, Ca, Na, K, Mg and Hg and/or water.
According to a preferred embodiment, the adsorbent is regenerable, has a specific surface of at least 200 m2/g and is operated in a fixed bed reactor at less than 100 C
with VVH
from 0.1 to 10h-1.
According to an additional embodiment, at least part of the product from the stage (b) or the effluent from step (c) or (d) can be:
(e). treated in a steam cracker, and/or (f). treated in a fluidized bed catalytic cracker, and/or (g). treated in a hydrocracker, and/or (h). treated in a catalytic hydrogenation unit, and/or (i). used as is or separated into streams usable for preparation fuels and fuels such as LPG, gasoline, diesel, heavy fuel oil and/or for preparation of lubricants.
The steps previously described of the process according to the invention can be implementations work one after the other without any intermediate step apart from the steps additional options described.
Definitions The Hourly Volume Velocity (VVH) is defined as the hourly volume of flow dump per unit of catalytic volume and is expressed here in h-1.
The terms including)) and includes)) as used herein are synonymous with including, includes'> or contains, containing, and are inclusive or without limits and do not exclude additional features, elements or steps of methods no specified.
Specifying a numeric domain without decimal places includes all numbers whole and, where appropriate, fractions of these (e.g., 1 to 5 can include 1, 2, 3, 4 and 5 when reference is made to a number of elements, and can also include 1.5, 2, 2.75 and 3.80, when reference is made to, for example, a measurement.).

WO 2023/037059

12 Specifying a decimal also includes the decimal itself (e.g.
example, 1.0 to 5.0 includes 1.0 and 5.0). Any range of numeric values recited here also includes any subrange of numerical values mentioned above above.
The expressions A in weight and A in mass have an equivalent meaning and refer to the proportion of the mass of a product compared to 100g of a composition including.
Unless otherwise noted, measurements given in parts per million (ppm) are expressed in weight.
The expression "plastic liquefaction oil" or "plastic oil liquefied" or oil plastic designates the liquid products resulting from the pyrolysis of plastic and/or hydrothermal liquefaction of plastic, alone or in mixture and generally in the form of plastic waste, possibly mixed with at least one other waste such as biomass, for example chosen from lignocellulosic biomass, paper and the cardboard and/or elastomers, for example possibly vulcanized latex or tires.
Biomass can be defined as an organic plant or animal product, including including the residues and organic waste. Biomass thus includes (i) biomass produced by the surplus of agricultural land, not used for human food or animal:
dedicated crops, called energy crops; (ii) the biomass produced speak deforestation (forest maintenance) or cleaning of agricultural land; (iii) the residue agricultural products from cereal crops, vines, orchards, olive trees, fruits and vegetables, residues agri-food,...; (iv) forest residues from forestry and wood processing; (y) agricultural residues from livestock (manure, slurry, litter, droppings,...); (vi) organic household waste (paper, cardboard, green waste, etc.);
(vii) ordinary industrial organic waste (paper, cardboard, wood, waste putrescible,...). The liquefaction oil treated by the invention can be derived from the liquefaction of waste containing at least 1 /om/m, possibly 1-50 /0m/m, 2-30%m/m, or in a range defined by two of these limits, of one or more of biomasses, residues and organic waste mentioned above, and the remainder consisting of waste plastics, optionally mixed with elastomers, particularly in the form of waste.
Elastomers are linear or branched polymers transformed by vulcanization in an infusible and insoluble three-dimensional weakly cross-linked network. They include the natural or synthetic rubbers. They can be part of waste tire type or any other household or industrial waste containing elastomers, rubber natural and/or synthetic, mixed or not with other components, such as than plastics, plasticizers, fillers, vulcanizing agent, vulcanization accelerators, additives, etc. Of the Examples of elastomeric polymers include ethylene-propylene copolymers, THE
ethylene-propylene-diene terpolymer (EPDM), polyisoprene (natural or synthetic), the WO 2023/037059

13 polybutadiene, styrene-butadiene copolymers, polymers based isobutene, isobutylene isoprene copolymers, chlorinated or brominated, copolymers of butadiene acrylonitrile (NBR), and polychloroprenes (CR), polyurethanes, elastomers of silicone, etc. The plastic liquefaction oil treated by the invention can come from the liquefaction of waste containing at least 1%m/rn, optionally from 1 to 50%
m/m, of 2 at 30%m/m or in an interval defined by any two of these limits, of one or several of the aforementioned elastomers, in particular in the form of waste, the remainder being constituted plastic waste, optionally mixed with biomass, residues and waste organic.
The expression plastic pyrolysis oil)> or oil resulting from pyrolysis of plastic refers to liquid products obtained after a pyrolysis of polymers thermoplastics, thermosetting or elastomers, alone or in mixture and usually in the form of waste. The pyrolysis process must be understood as a thermal cracking process, typically carried out at a temperature of 300 to 1000 C or from 400 to 700 C, used in the presence or absence of catalyst (for example pyrolysis rapid catalytic or not, etc...).
The term "hydrothermal plastic oil" or "oil resulting from liquefaction hydrothermal process of plastic" designates the liquid products obtained after liquefaction hydrothermal process of plastic or plastic waste. The process of liquefaction hydrothermal heat is typically carried out at a temperature of 250 to 500 C and at of the pressures from 10 to 25-40 MPa in the presence of water.
Pyrolyzed plastic or resulting from hydrothermal liquefaction can be of any what type. For example, the plastic can be polyethylene, polypropylene, polystyrene, polyester, polyamide, polycarbonate, etc. These oils liquefaction of plastic contain paraffins, i-paraffins (iso-paraffins), dienes, alkynes, olefins, naphthenes and aromatics. Plastic liquefaction oils contain also impurities such as chlorinated, oxygenated and/or organic compounds silylated, metals, salts, phosphorus compounds, sulfur, and nitrogen.
The composition of plastic pyrolysis oil or plastic oil hydrothermal liquefaction of plastic is dependent on the nature of the plastic pyrolyzed or treated by liquefaction hydrothermal and is essentially (in particular at more than 80% m/m, the most often more of 90%m/m) consisting of hydrocarbons having 1 to 150 carbon atoms and impurities.
A plastic liquefaction oil typically comprises 5 to 80% m/m of paraffins (including cyclo-paraffins), from 10 to 95% m/m of unsaturated compounds (including WO 2023/037059

14 olefins, dienes and acetylenes), from 5 to 70% m/m aromatics. These contents can be determined by gas chromatography.
A plastic liquefaction oil may in particular comprise one or more several of the following heteroatom contents: from 0 to 8% rn/m of oxygen (measured according to the standard ASTM D5622), 1 to 13,000 ppm nitrogen (measured according to ASTM D4629), 2 has 10000ppm of sulfur (measured according to ISO 20846), from 1 to 10000ppm of metals (measured by ICP), 50 to 6000ppm chlorine (measured according to ASTM D7359-18), of 0 to 200ppm bromine (measured according to ASTM D7359-18), 1 to 40ppm fluorine (measured according to ASTM D7359-18), 1 to 2000 ppm silicon (measured by XRF).
The expression MAV (acronym for Maleic Anhydric Value> for index anhydride maleic) refers to method U0P326-82 which is expressed in mg anhydride maleic which react with 1 g of sample to be measured.
The expression Number of bromine> corresponds to the quantity of bromine in grams having reacted on 100 g of sample and can be measured according to the ASTM D1159 method-07.
The expression Bromine Index)) is the number of milligrams of bromine which react with 100 g of sample and can be measured according to ASTM D2710 or ASTM
D5776.
Boiling points as mentioned here are measured at pressure atmospheric, except otherwise indicated. An initial boiling point is defined as the value temperature at from which a first vapor bubble is formed. A point final boiling point is highest temperature attainable during distillation. At this temperature, no more Steam cannot be transported to a condenser. The determination of initial points and final uses techniques known in the trade and several methods adapted in depending on the range of distillation temperatures are applicable, for example example NF EN
15199-1 (2020 version) or ASTM D2887 for measuring boiling points of fractions petroleum by gas chromatography, ASTM D7169 for hydrocarbons heavy, ASTM D7500, D86 or D1160 for distillates.
The concentration of metals in hydrocarbon matrices can be determined by any known method. Acceptable methods include X-ray fluorescence (XRF) and inductively coupled plasma atomic emission spectrometry (ICP-AES). THE
specialists in analytical sciences know how to identify the method most suited to the measurement of each metal and each heteroelement depending on the hydrocarbon matrix considered.
The particular characteristics, structures, properties, modes of realization of the invention can be freely combined in one or more embodiments not specifically described herein, as may be apparent to those skilled in of treatment plastic pyrolysis oils using their knowledge general.

WO 2023/037059

15 Description of the invention Examples The embodiments of the present invention are illustrated by the non-examples following limitations.
Example 1: Purification of a plastic pyrolysis oil in the presence from a strong base and of water followed by washing with water The physicochemical characteristics of plastic pyrolysis oil used are described in Table 1, below:
Table 1 HPP2 pyrolysis oil Density (g/mL) 0.800 Kinematic viscosity (15 C, mm2/s) 2.1 Distillation, initial boiling point (C) 69 Distillation, 50% (C) 214 Distillation, final boiling point (C) 451 Silicon (mass ppm) 82 Chlorine (mass ppm) 96 Oxygen (% by mass) 0.87 Nitrogen (ppm weight) 206 Test protocol:
A 1.5 L grade AlS1-316L stainless steel autoclave equipped with a hustle mechanical is loaded with HPP2 pyrolysis oil, a strong base under the form of NaOH
and water, the strong base being solubilized in water before its introduction in the autoclave (table 2). The sum of the volume of pyrolysis oil and the volume of water introduced is of approximately 600 mL at room temperature, without taking into account the effects possible volume variation during their mixing. The autoclave is closed and the sky gaseous in the autoclave is flushed with nitrogen for 30 minutes. The autoclave is then heated under autogenous pressure with stirring at a speed of 400 to 1500 rpm at a temperature of 225 C for a duration of 1 minute, 10 minutes or 20 minutes according to tests, once the target temperature has been reached. Climb speed in temperature is set at 30 C/10 minutes.
Table 2 Test 1 2 3 HPP2 HPP2 HPP2 pyrolysis oil Water/load volume ratio 0.024 0.024 0.024 WO 2023/037059

16 Temperature (C) 225 225 225 Time (min) 1 10 20 Water volume (mL) 13.8 13.8 138.0 Mass of NaOH (g) 14.0 14.0 138.0 Mass of pyrolysis oil (g) 467.2 467.2 368.0 Initial volume of pyrolysis oil (mL) 584 584 460 NaOH concentration in oil of 3 3 3 pyrolysis (%m/m) NaOH concentration in water (%m/m) 50 50 50 Initial density (g/mL) 0.8 0.8 0.8 Final pressure in the autoclave (bars) 10 8 12 At the end of the reaction, the autoclave is cooled to room temperature then, for the tests 1 and 2, the mixture is discharged and washed three times with water with, at each wash, a water/load volume ratio = 40/60, to eliminate strong base residues and the impurities soluble in water. The resulting purified and washed pyrolysis oil is analyzed for measure the content of residual impurities (table 3). For test 3, the mixture discharged of the autoclave is divided into two parts. The first part is washed with water in the same conditions as for tests 1 and 2 and the purified pyrolysis oil and resulting washed is analyzed (test 3A in Table 3). The second part is decanted in order to recover the organic phase, which is then centrifuged. Pyrolysis oil decanted and The resulting centrifuge is analyzed (test 3B in Table 3).
Table 3 Test 1 2 3A 3B
Initial silicon (ppm weight) 80 80 80 80 Final silicon (ppm weight) <2 <2 <2 <2 Silicon reduction (%) >97 >97 >97 97 Initial chlorine (ppm weight) 115 115 115 115 Final chlorine (ppm weight) 32 24 23 23 Chlorine reduction (%) 72 79 80 80 Initial oxygen (% weight) 0.90 0.90 0.90 0.90 Final oxygen (1D/0 weight) 0.12 0.13 0.11 0.47 Oxygen reduction ( /0) 87 86 88 48 Initial nitrogen (ppm weight) 192 192 192 192 Final nitrogen (ppm weight) 31 29.8 30.0 43.6 Nitrogen reduction ( /0) 84 84 84 77 WO 2023/037059

17 Initial sodium (ppm weight) <2 <2 2.5 <2 Final sodium (ppm weight) <2 <2 <2 1536 The data in Table 3 show that the use of soda in the presence of water followed by a washing makes it possible to significantly reduce the impurities initially contained in the oil of pyrolysis as well as the sodium introduced by the soda treatment, even for a length short treatment with soda.
In particular, we observed that in the absence of washing, for example after a simple decantation/centrifugation, the sodium content of the pyrolysis oil is high, in particular greater than 1000ppm, which is not acceptable for a further processing catalytic.
The pyrolysis oil can either be used as is, or possibly dried on a adsorbent such as a molecular sieve or an anhydrous salt, for example Na2SO4, then is distilled under reduced pressure in order to eliminate any possible trace of solid, for example strong base, adsorbent residue, anhydrous/hydrated salt or gums.
Example 2: Purification of a plastic pyrolysis oil in the presence of a strong foundation and of water followed by washing with water Another HPP8 pyrolysis oil was brought into contact with soda following a test protocol similar to that of Example 1 under the conditions gathered in the table 4. 450g of HPP8 oil were thus placed in contact for 20 minutes at 180 C with 22.5g of NaOH dissolved in water.
Table 4 HPP8 pyrolysis oil Water/load volume ratio 0.05 Temperature (C) 180 Time (min) 20 Water volume (mL) 22.5 Mass of NaOH (g) 22.5 Mass of pyrolysis oil (g) 450 Initial volume of pyrolysis oil (mL) 563.2 NaOH concentration in pyrolysis oil ( /0m/m) 5 NaOH concentration in water (Yom/m) 50 Initial density (g/mL) 0.799 Final pressure in the autoclave (bars) 8 WO 2023/037059

18 At the end of the reaction, the autoclave is cooled to room temperature then, the mixture is unloaded and washed three times with water with, for each wash, a ratio in volume water/load = 40/60, to remove strong base residues and impurities soluble in the water.
The data in Table 5 show that the use of soda in the presence of water followed by a washing makes it possible to significantly reduce the impurities initially contained in the oil of pyrolysis as well as the sodium introduced by the soda treatment, even for a soda treatment temperature below 200 C.
Table 5 Test 4 Initial silicon (ppm weight) 93 Final silicon (ppm weight) <2 Silicon reduction (%) > 98%
Initial chlorine (ppm weight) 470 Final chlorine (ppm weight) 79 Chlorine reduction (`)/0) 83%
Initial oxygen (% weight) 1.49 Final oxygen (/0 weight) 0.22 Oxygen reduction (/0) 85%
Initial nitrogen (ppm weight) 1820 Final nitrogen (ppm weight) 157 Nitrogen reduction (%) 91%
Initial sodium (ppm weight) --Final sodium (ppm weight) --Example 3: Two-step hydrotreatment and steam cracking of the product example 1 One of the purified and washed pyrolysis oils of Example 1 (from the tests 1, 2 or 3A) or from Example 2 (test 4) can be hydrotreated in two stages according to the procedure next :
The purified and washed pyrolysis oil can be introduced into a first section hydrotreatment (HDT1) mainly to hydrogenate diolefins and is operated in liquid phase. This step may include a plurality of reactors in series and or parallel if guard reactors are used upstream or downstream of the first reactor hydrogenation. These guard reactors can help reduce the concentration in certain undesirable chemical species and/or elements such as chlorine, silicon and metals. Particularly undesirable metals include Na, Ca, Mg, Fe and Hg.

WO 2023/037059

19 A second hydrotreatment section (HDT2) is dedicated to the hydrogenation of olefins and demetallization (H DM), desulfurization (HDS), denitrogenation (HDN) and the deoxygenation (HDO). HDT2 is operated in the gas phase. This section consists in one or several reactors operated in series, in lead-lag or in parallel.
As the hydrotreatment reactions in sections HDT1 and HDT2 are exothermic, quenching with cold hydrogen can be used to moderate the increase in temperature and control the reaction.
Isolated guard reactors, lead-lag, in series and/or in parallel can be considered depending on the nature and quantity of the contaminant in the flow to be processed.
In the event that the treatment of example 1 would not make it possible to obtain a reduction sufficient in impurities, guard reactors to eliminate chlorine and silicon can be operated in the gas phase. Silicon can also be trapped on the bed higher than one reactor of the HDT2 section or separately, upstream or downstream by the gas treatment hot leaving the HDT2 section.
Chlorine and mercury can be separated by guard reactors in liquid phase or gaseous.
There may be intermediate dips between the beds or between the HDT1 and HDT2 reactors or no tempering. In the latter case, recycling of part of the flow leaving the HDT1 or HDT2 must be made to control the temperature. Strict control of temperature in HDT1 must be conducted, in order to avoid clogging of the reactor and degradation of catalytic hydrogenation conditions.
The operating pressure in each of the HDT1 and HDT2 hydrotreatments is 5-60 bars, preferably 20-30 bars for HDT1 and 20-140 bars, preferably 30-60 bars for HDT2, typically 30-40 bars for HDT2.
Typical temperature range at the HDT1 inlet at the start of the cycle (SUR: start of run):
150-200 C. The catalyst for HDT 1 usually includes Pd (0.1-10 wt%) and/or Neither (0.1-60% by weight) and/or NiMo (0.1-60% by weight).
Typical temperature range at the HDT2 inlet at the start of the cycle (SUR: start of run):
200-340 C. Typical HDT2 outlet temperature range (SOR): 300-380 C, until 450 C. The catalyst for H DT 2 usually includes a NiMo (any type of catalyst commercial for refining or petrochemical applications), potentially a CoMo in the very last beds at the bottom of the reactor (any type of commercial catalyst for application refining or petrochemicals).
The upper bed of the HDT2 should preferably be operated with a NiMo having a capacity hydrogenating as well as a silicon trapping capacity. A superior bed of this type can be considered as an adsorbent as well as a metal trap also having a activity HDN and hydrogenating capacity. An example of an acceptable upper bed for this WO 2023/037059

20 function includes commercially available NiMo catalyst adsorbents such as ACT971, ACT981 from Axens or equivalents from Haldor Topsoe, Axens, Criterion, etc. He is possible to have two separate beds in an HDT2 reactor, with quenching between the two beds or between the two reactors, if the two beds are in two reactors distinct, or not soaks at all. Ideally, intermediate quenching is carried out using cold effluent of HDT2 or by a supply of cold hydrogen, that is to say at a temperature going generally from 15 to 30 C, in order to control the exotherm of HDT2. A dilution by recycle of hydrocarbon flow to the upper bed of HDT2 is not recommended in reason of increased risk of bed clogging. The charge arriving on the catalyst of HDT2 should be completely vaporized at any time, including in variable regime such as it's the case during starts. Sending liquid hydrocarbons to the upper bed of an HDT2 reactor can generate clogging and an increase in the difference in pressure between the inlet and outlet of said HDT2 reactor and lead to premature shutdown.
Depending on the metals present in the pyrolysis oil to be hydrotreated, a catalyst hydrodemetallation, for example commercial, can be added to the bed superior of the HDT2 section to protect the catalytic beds from deactivation lower.
Hydrotreated pyrolysis oil leaving HDT2 section can be used as is or fractionated according to distillation temperature ranges, to supply a steam cracker, an FCC, hydrocracker, catalytic reformer or fuel pool or fuels such as LPG, gasoline, jet, diesel, fuel oil.
Alternatively, the treated pyrolysis oil leaving the HDT2 section undergoes a step of additional purification by passing over a capture mass such as a adsorbent, for example (i) silica gel, (ii) clay, (iii) crushed clay, (iv) apatite, (y) hydroxyapatite and their combinations, (vi) an alumina for example an alumina obtained by precipitation of boehmite, a calcined alumina such as Ceralox from Sasol, (vii) of the boehmite, (viii) bayerite, (ix) hydrotalcite, (x) spinel such than Pural or Puralox from Sasol, (xi) a promoted alumina, for example Selexsorb from BASF, a promoted acid, an alumina promoted by a zeolite and/or by a metal such as Ni, Co, Mo or one combination of at least two of them, (xii) an acid-treated clay such as Tonsil Clariant CD, (xiii) a molecular sieve in the form of an aluminosilicate containing a alkaline or alkaline earth cation for example 3A, 4A, 5A, 13X sieves, for example example marketed under the brand Siliporite de Ceca, (xiv) a zeolite, (xv) a charcoal, or the combination of at least two adsorbents, the adsorbent or the at least two adsorbents retaining at least 20% by weight, preferably at least 50% by weight from to least one element from F, Cl, Br, I, 0, N, S, Se, Si, P, As, Fe, Ca, Na, K, Mg and Hg and/or the water. Ideally, the adsorbent is regenerable, has a specific surface area of at less 200 m2/g and is operated in a fixed bed reactor at less than 100 C with a VVH of 0.1 at 10:01 a.m.

Claims (14)

Claims 1. Method for reducing the concentration of heteroatoms in a composition comprising a plastic liquefaction oil containing at least 20 ppm in mass of chlorine as measured according to ASTM D7359-18, including:
(has). bringing said composition into contact with 0.1-50% by mass of a base strong comprising an alkali or alkaline earth metal cation, in the presence of water, for 1 minute to 20 minutes at a temperature of not more than 450 C, (b). washing with water at neutral or acidic pH of the product resulting from step (a), (vs). THE
product resulting from the washing of step (b) undergoes catalytic hydrogenation in a or two steps. 2. Method according to claim 1, in which the composition comprises in besides a pyrolysis or hydrothermal liquefaction oil of biomass, in particular a oil of pyrolysis or hydrothermal liquefaction of biomass such as Panicum virgatum, tall oil, used cooking oil, animal fat, vegetable oil such as rapeseed, canola, castor, palm, soybean oil, taken from a algae, an oil extracted from a fermentation of oleaginous microorganisms such as oleaginous yeasts, a pyrolysis or hydrothermal liquefaction oil of biomass such as lignocellulosic biomass such as coconut oil wood pyrolysis, of paper and/or cardboard, an oil obtained by pyrolysis or liquefaction hydrothermal crushed used furniture, an elastomer pyrolysis oil, for example latex possibly vulcanized or tires, as well as their mixtures. 3. Method according to claim 1 or 2, comprising between step (a) and (b) a step of separation between the strong base comprising the alkali metal cation or alkaline earth in solution in water and the product resulting from the bringing into contact of said composition. 4. Method according to claim 3, in which the separation step is carried out by (i) centrifugation, (ii) decantation, or (iii) by the combination of these two steps. 5. Method according to claim 3 or 4, in which the strong base in solution in water separated during the separation step is returned, partially or in part totality, in step (a) of contacting. 6. Method according to one of claims 3 to 5, in which the step of separation is preceded by a solids separation step by (i) filtration, (ii) centrifugation or (iii) a combination of the two steps. 7. Method according to any one of claims 1 to 6, in which the put in contact is carried out for a duration of 1 minute to 20 minutes, preferably 1 minute at 16 minutes, at a temperature of 50 to 450 C, preferably 50 to 350 C or 90 has 350 C, more preferably from 150 to 350 C, even more preferably from 50 to 250 C or 50 to 225 C or 50 to 200 C, and at an absolute pressure of 0.1 to 100 bars, preferably from 1 to 50 bars. 8. Method according to any one of claims 1 to 7, in which the strong base is chosen from Li0H, Na0H, Cs0H, Ba(OH)2, Na20, KOH, K20, CaO, Ca(OH)2, Mg0, Mg(OH)2 and their mixtures. 9. Method according to any one of claims 1 to 8, in which, prior to the contacting of step (a), said composition is subjected to (i) a filtration, (ii) a washing with a polar solvent, (iii) distillation, (iv) decantation, or (v) to the combination of two, three or four of steps (i) to (iv). 10. Method according to one of claims 1 to 9, in which the hydrogenation catalytic step (c) is carried out in a first step (c-1) in which the product from the setting in contact is hydrogenated at a temperature between 20 and 200 C, preference between 30 and 90 C in the presence of hydrogen at an absolute pressure between 5 and 60 bars, preferably between 20 and 30 bars and in the presence of a catalyst hydrogenation comprising Pd (0.1-10% by weight) and/or Ni (0.1-60% by weight) and or NiMo (0.1-60% by weight), and in a second step (c-2) in which the effluent from step (c-1) is hydrogenated at a temperature between 200 and 450 C, preferably between 200 and 340 C in the presence of hydrogen at absolute pressure between 20 and 140 bars, preferably between 30 and 60 bars and in presence of a hydrogenation catalyst comprising NiMo (0.1-60% by weight) and/or CoMo (0.1-60%
in weight). 11. Method according to any one of claims 1 to 10, in which the product from step (b) or the effluent from step (c) is (d) purified by passing through an adsorbent solid in order to reduce the content of at least one element among F, Cl, Br, l, 0, N, S, Se, Si, P, As, Fe, Ca, Na, K, Mg and Hg and/or water content. 12. Method according to claim 11, in which the adsorbent is operated in regenerative mode or non-regenerative, at a temperature below 400 C, preferably lower than 100 C, more preferably less than 60 C chosen from: (i) a gel of silica, (ii) a clay, (iii) crushed clay, (iv) apatite, (v) hydroxyapatite and their combinations, (vi) an alumina, for example an alumina obtained by precipitation of boehmite, a calcined alumina such as Ceralox 0 from Sasol, (vii) boehmite, (viii) bayerite, (ix) hydrotalcite, (x) a spinel such as Pural 0 or Puralox from Sasol, (xi) an alumina promoted, for example Selexsorb 0 from BASF, an acid promoted alumina, an alumina promoted by a zeolite and/or by a metal such as Ni, Co, Mo or a combination of least two of them, (xii) an acid-treated clay such as Tonsil 0 of Clariant, (xiii) a molecular sieve in the form of an aluminosilicate containing a cation alkaline or alkaline earth, for example 3A, 4A, 5A, 13X sieves, for example marketed under the brand Siliporite 0 from Ceca, (xiv) a zeolite, (xv) a coal active, or the combination of at least two adsorbents, the adsorbent or less two adsorbents retaining at least 20% by weight, preferably at least 50% by weight from to least one element from F, Cl, Br, l, 0, N, S, Se, Si, P, As, Fe, Ca, Na, K, Mg and Hg and/or some water. 13. Method according to claim 12, in which the adsorbent is regenerable, has a specific surface area of at least 200 m2/g and is operated in a bed reactor fixed at less than 100 C with a VVH of 0.1 at 10 h-1. 14. Method according to any one of claims 1 to 13, in which at minus one part of the product from step (b) or the effluent from step (c) or (d) is:
(e) processed in a steam cracker, and/or (f) processed in a fluidized bed catalytic cracker, and/or (g) treated in a hydrocracker, and/or (h) treated in a catalytic hydrogenation unit, and/or (i) used as is or separated into usable streams for the preparation of fuels and fuels such as LPG, gasoline, diesel, heavy fuel oil and/or for preparation of lubricants.