EP4677047A1

EP4677047A1 - A process for storing one or more pyrolysis oils

Info

Publication number: EP4677047A1
Application number: EP24708851.1A
Authority: EP
Inventors: Michael Bachtler; Harald Becker; Steffen Wagloehner; Felix HUELSMANN; Monica Haag
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2023-03-08
Filing date: 2024-03-07
Publication date: 2026-01-14
Also published as: WO2024184464A1; CN120813668A; KR20250156780A

Abstract

The present invention relates to a process for storing one or more pyrolysis oils as well as a storage unit for storing one or more pyrolysis oils. The present invention further relates to a use of one or more stored pyrolysis oils obtained by said process as a feedstock for a cracker.

Description

A process for storing one or more pyrolysis oils

Pyrolysis oils obtained from different solid material such as mixed waste plastics, rubber materials, textiles and bio waste are corrosive towards containers, such as means for storing, transporting, directing, handling a pyrolysis, made of steel, especially containers made of carbon- steels and low-alloyed steels. The reasons for the undesired corrosiveness of pyrolysis oils are manifold. In comparison with oils from fossil sources such as crude oil, pyrolysis oils have a higher content of components such as water, halogen(s), sulfur and organic acids. In addition, the total acid number (TAN) of pyrolysis oils is higher than in oils from fossil sources such as crude oil. Said differences in composition lead to an increased corrosion of pyrolysis oils towards containments such as vessels, pipes, reactors and heat exchangers, made of steel, especially containments made of carbon-steels and low-alloyed steels during storage, transport and handling of the pyrolysis oils. Such corrosion is detrimental for such containment units as well as for the pyrolysis oils.

Therefore, there is a constant need to provide improved process for handling the pyrolysis oils and in particular the storage of such pyrolysis oils.

Therefore, it was an object of the present invention to provide an improve process for storing one or more pyrolysis oils which prevents corrosion in tanks and pipes and which is cost effective. It has been surprisingly found that, according to the process of the present invention, lower corrosion occurs, notably in view of the prevention of phase separation in the pyrolysis oils. This is possible as the pyrolysis oils are stored with a recirculation and the tank has a sloped bottom surface.

Therefore, the present invention relates to a process for storing one or more pyrolysis oils, the process comprising

(i) providing one or more pyrolysis oils OP;

(ii) passing at least a portion P1 of the one or more pyrolysis oils OP provided according to (i), P1 comprising the one or more pyrolysis oils, into a storage tank S(T) comprised in a storing unit S, for a period of time At1 , the storing unit S further comprising a pump S(P);

(iii) storing P1 in the storage tank S(T) of S for a period of time At2; wherein, during the period of time At2, (iii) further comprises removing a portion P2 of P1 from the storage tank S(T) and reintroducing a portion P3 of P2 into the storage tank S(T), P2 and P3 comprising the one or more pyrolysis oils, wherein removing P2 and reintroducing P3 are performed with the pump S(P), for a period of time At3, with At2 > At3; wherein the storage tank S(T) comprises a top portion T1 , an intermediate portion T2 and a bottom portion T3, wherein T1 is adjacent to T2 and T2 is adjacent to T3, wherein, in T3, the bottom of S(T) is a sloped surface.

In the context of the present invention, it was found that the sloped bottom surface of the storage tank in the storing unit S as well as the recirculation of the pyrolysis oil via the pump in the storage unit S permits to avoid the corrosion of the walls of the tank.

Preferably, the one or more pyrolysis oils OP provided according to (i) are obtainable or obtained by pyrolyzing a waste material, the waste material being one or more of plastics, tires and textiles.

Alternatively, the one or more pyrolysis oils OP provided according to (i) are obtainable or obtained by pyrolyzing a waste material of biogenic nature, the waste material of biogenic nature being one or more of plants, woods, straw, and algae.

According to a second alternative, the one or more pyrolysis oils OP provided according to (i) are obtainable or obtained by pyrolyzing a biomass, the biomass being one or more of plants, woods, straw, and algae.

In the context of the present invention, the one or more pyrolysis oils to be stored can have any water content. Preferably, the one or more pyrolysis oils OP provided according to (i) have a water content of at most 10 weight-%, more preferably of at most 5 weight-%, more preferably of at most 1 weight-%, based on the weight of the pyrolysis oil, determined as described in Reference Example 1.

In the context of the present invention, the one or more pyrolysis oils to be stored can have any halogen content. It is however preferred that the one or more pyrolysis oils OP provided according to (i) have a halogen content in the range of from 10 to 20,000 wppm (ppm by weight), more preferably from 50 to 5,000 wppm, more preferably from 50 to 2,000 wppm, determined as described in Reference Example 2.

In the context of the present invention, the one or more pyrolysis oils to be stored can have any sulfur content. It is however preferred that the one or more pyrolysis oils OP provided according to (i) have a sulfur content in the range of from 50 to 30,000 ppm by weight (wppm), more preferably from 50 to 15,000 wppm, determined as described in Reference Example 3.

In the context of the present invention, the one or more pyrolysis oils to be stored can have any TAN number. It is however preferred that the one or more pyrolysis oils OP provided according to (i) have a TAN number in the range of from 0 to 25 mg(KOH) per gram of pyrolysis oil (mg(KOH)/g(oil)), more preferably in the range of from 0.5 to 15 mg(KOH)/g(oil), more preferably in the range of from 1 to 10 mg(KOH)/g(oil), determined as described in Reference Example 4. Preferably, (i) comprises

(1.1 ) preparing the one or more pyrolysis oils OP;

(1.2) introducing OP prepared according to (i.1 ) in one or more trucks and transporting OP in said one or more trucks to a storage site, comprising the storage unit S.

Preferably, (i.1 ) comprises pyrolysing solid waste material, more preferably one or more of tire waste material, mixed plastic waste material and textile waste material.

Optionally, prior to (ii), the process further comprises admixing the one or more pyrolysis oils OP provided according to (i) with an additive, obtaining one or more pyrolysis oils comprising an additive; said additive being one or more amphiphilic compounds. The one or more amphiphilic compounds comprise at least one nonpolar residue selected from Ce to C26 alkyl and/or alkylene and at least one polar residue comprising at least one heteroatom selected from the group consisting of N and O. Preferably, the additive comprises one or more of

- C6-C26 fatty acids, such fatty acids being saturated, mono-unsaturated or poly-unsaturated;

- dimerized fatty acids;

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

- alkenylsuccinic acid and alkenylsuccinic acid anhydride wherein the alkenyl-residue is selected from C6-C26 alkenyl having one or more C=C bonds;

- C6-C26 fatty acids, saturated, mono-unsaturated and poly-unsaturated coupled by a C-C bond to a N-heterocyclic compound;

- nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydro- carbyl-substituted polycarboxylic acid.

Suitable saturated Ce to C26 fatty acids comprise caprylic acid, capric acid, lauric acid, arachidic acid, behenic acid, lignoceric acid and cerotic acid.

Suitable mono- and poly-unsaturated Ce to C26 fatty acids comprise myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, vaccenic acid, linoleic acid, linoelaidic acid, a-lino- lenic acid, arachidonic acid, eicosapentaenoic acid, erucic acid and docosahexaenoic acid.

Suitable dimerized fatty acids comprise dimerized oleic acid (CAS-No. 61788-89-4), which can for example be obtained by dimerizing unsaturated fatty acids obtained from tall oil, oleic acid, canola oil or cottonseed oil, usually on clay catalysts.

Suitable copolymers of at least one ethylenically unsaturated, polymerizable polycarboxylic anhydride with at least one polymerizable alkene comprise C4 to Ce dicarboxylic anhydride, especially maleic acid anhydride and least one a-alkene, especially a C2oto C26 a-alkene. The synthesis of such copolymers is disclosed in WO 2015/113681 A1 which is incorporated by reference. Suitable alkenylsuccinic acids and alkenylsuccinic acid anhydrides wherein the alkenyl-residue is selected from Ce to C26 alkenyl and the C=C bond may be terminal (a-position) and/or internal (P-position, y-position, etc.) comprising 2-octenylsuccinic acid, 2-dodecenylsuccinic acid, 7- dodecenylsuccinic acid, 8-eicosenylsuccinc acid, 2-octenylsuccinic acid anhydride, 2- dodecenylsuccinic acid anhydride, 7- dodecenylsuccinic acid anhydride, 8-eicosenylsuccinc acid anhydride. The synthesis of such alkenylsuccinic acids is disclosed in WO 82/00467 A1 , the synthesis of alkylensuccinic acid anhydrides is disclosed in US 2008/0108836 A1 which are both incorporated by reference.

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

Suitable nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid comprise Ciealkyl-N(CH3)2 quaternized with propyleneoxide in the presence of polyisobythylene succinic acid. Other suitable nitrogen-compounds quaternized with a hydrocarbyl epoxide in combination with a free hydrocarbyl-substituted polycarboxylic acid and the synthesis methods for obtaining such quaternized compounds are disclosed in WO 2014/195464 A1 and WO 2015/113681 A1 which are both incorporated by reference.

Preferably, the concentration of the additive in the one or more pyrolysis oils is in the range of 1 to 20000 wppm (ppm by weight).

More preferably from 1 to 1000 wppm (ppm by weight), more preferably from 5 to 500 wppm, more preferably from 10 to 250 wppm, more preferably from 20 to 150 wppm.

Alternatively, more preferably from 5000 to 20000 wppm.

Preferably, the admixing of one or more pyrolysis oils with said additive is performed by forced agitation such as by stirring or any other suitable means to obtain a homogeneous contribution of the additive (i.e. a catalyst poisoning suppressant) in the one or more pyrolysis oils. Alternatively, the admixing is performed without forced agitation.

In the context of the present invention, it is noted that the aforementioned term “additive” preferably refers to “corrosion inhibitor” or “catalyst poisoning suppressant”.

Preferably, in the one or more trucks in (i .2), the liquid phase of OP is at a temperature in the range of from -10 to 100 °C, more preferably in the range of from -10 to 60 °C. Preferably, At1 is in the range of from 0.5 to 150 h, more preferably in the range of from 0.5 to 50 h, more preferably in the range of from 1 to 20 h, more preferably in the range of from 1 to 5 h.

Preferably, (ii) is performed at a filing rate in the range of from 0.5 to 120 m³/h, more preferably in the range of from 1 to 100 m³/h, more preferably in the range of from 2 to 90 m³/h.

In the context of the present invention, the filling rate is preferably measured using a mass flow controller. Said mass flow controller as known in the art is able to measure the filing rate, the fluid density and detect density difference in the liquid entering the tank. For example, waterphase presence in the oils can be detected by such mass flow controller. When an oil with higher water content passes through the controller it leads to an abrupt increase in the liquid density.

Preferably, (ii) is performed via one or more pipes. Preferably, the one or more pipes are made of one or more of carbon steel, such as ASTM 1045 (EN 1.1191 ), 1.0425, 1.0037 and 1.0345, and stainless steel, more preferably one or more of Cr-Ni steel, such as 1 .4541 , 1 .4301 , 1 .4306 and 1.4307, and Cr-Ni-Mo stainless steel, such as 1.4571 , 1.4401 and 1.4404.

Preferably, the storage tank S(T) is ventilated with a gas atmosphere, more preferably the gas atmosphere being an inert gas, more preferably nitrogen.

Preferably, in T1 , the storage tank S(T) comprises an inlet means for introducing N2, the inlet means being located, in the top portion T 1 , between the top of S(T) and the bottom of the top portion.

Preferably, in T1 , the storage tank S(T) comprises an outlet means for removing O2 from the storage tank, the outlet means being located, in the top portion T1 , at the top of S(T).

Preferably, in T2, the storage tank S(T) comprises an inlet means for passing P1 of OP into the tank, said inlet means being located, in T2, at a height H(i) in the range of from 30 to 70 %, more preferably of from 40 to 60 %, more preferably of from 45 to 55 %, H(T2), H(T2) being the maximal axial distance between the bottom of the top portion T1 and the top of the bottom portion T3 and H(i) being the axial distance between the bottom of T2 and the inlet means for passing P1.

Preferably, removing a portion P2 of P1 from the storage tank S(T) according to (iii) is performed at an outlet means for removing P2, with the pump S(P), said outlet means being located at the bottom of the sloped surface in T3. This is illustrated by Figure 1 .

In the context of the present invention, it was found that the sloped bottom surface of the storage tank in the storing unit S as well as the recirculation of the pyrolysis oil from the bottom of the sloped surface via the pump in the storage unit S permits to avoid the corrosion of the walls of the tank.

Preferably, wherein the storage tank S(T) comprises no outlet means at the top portion T1 .

Preferably, removing a portion P2 of P1 from the storage tank S(T) according to (iii) is performed periodically or constantly, more preferably constantly.

Alternatively as to the removal of P2, it is preferred that removing a portion P2 of P1 from the storage tank S(T) is performed with the pump S(P) at an outlet means for removing P2, said outlet means being located, in T2, at a height H(o) in the range of from 0.4 to 1.25 m, preferably in the range of from 0.5 to 1 m, H(o) being the axial distance between the bottom of S(T) and the outlet means for removing P2. This is illustrated by Figure 2.

Preferably, according to said alternative, removing a portion P2 of P1 from the storage tank S(T) according to (iii) is performed periodically or constantly, more preferably constantly.

Preferably, according to said alternative, during the period of time At2, (iii) further comprises removing a portion P4 of P1 , P4 comprising water, from S(T), wherein the removal is performed at the bottom of the sloped surface in the bottom portion T3.

The removal of P4 from S(T) is performed periodically or punctually.

More preferably, when the removal of P4 is performed punctually, (iii) further comprises determining a maximum acceptable water content (W_max) in P1 , measuring the water content in P1 during At2 by one or more of a mass flow controller measuring liquid density and a water sensor, and triggering the removal (purge) of P4 from S(T) when W_max is reached. A mass flow controller, as known in the art, is able to measure the liquid density and detect density difference in the liquid entering the tank. For example, water-phase presence in the oil can be detected by such mass flow controller. When an oil with higher water content passes through the controller it leads to an abrupt increase in the liquid density, e.g. from about 0.9 to 1.0 kg/L.

In the context of the present invention, it was found that the sloped bottom surface of the tank as well as the removal of water at the bottom of said sloped surface of the tank together with a recirculation of the oils in the tank permit to avoid the corrosion of the walls of the tank.

Preferably, the water content in the portion P4 of P1 is of at least 25 weight-%, more preferably of at least 35 weight-%, more preferably in the range of from 35 to 100 weight-%, more preferably in the range of from 45 to 100 weight-%, more preferably in the range of from 48 to 100 weight-%, more preferably in the range of 50 to 95 weight-%, based on the weight of P4. In the context of the present invention, preferably, introducing P3 of P2 into the storage tank S(T) is performed with the pump S(P) at an inlet means for introducing P3, said inlet means being located, in the top portion T 1 of S(T), more preferably between the top of S(T) and the bottom of the top portion T 1 .

Preferably, in T3 of S(T), the sloped surface is a surface titled at an angle in the range of from 0.5 to 20 °, more preferably in the range of from 0.75 to 10 °, more preferably in the range of from 0.80 to 5 °, more preferably in the range of from 0.85 to 2 °, more preferably in the range of from 0.90 to 1.5 °.

Preferably, the maximum slope height is in the range of from 0.364 x tank diameter (m) to 0.01 x tank diameter (m), more preferably in the range of from 0.017 x tank diameter (m) to 0.035 x tank diameter (m).

Preferably, in S(T), the maximum temperature of the liquid phase of P1 , T_max(P1), in °C, is 80 °C, more preferably 60 °C, more preferably 40 °C; wherein, in S(T), the minimum temperature of the liquid phase of P1 , T_min(P1 ), in °C, is -10 °C, more preferably 0 °C, more preferably 5 °C.

Preferably, the temperature T(P1 ) in S(T) is not constant during At2. More preferably, T(P1) varies during At2 (storage duration) from 5 to 40 °C, more preferably from 10 to 35 °C. Alternatively, preferably, T(P1) is constant and is more preferably in the range of from 5 to 40 °C, more preferably in the range of from 10 to 35 °C.

Preferably, in S(T), the pressure is in the range of from 100 to 1 mbar, more preferably in the range of from 50 to 5 mbar , more preferably in the range of from 20 to 10 mbar.

Preferably, the storage tank S(T) is made of one or more of carbon steel and stainless steel.

Preferably, the storage tank S(T) is made of carbon steel, such as ASTM 1045 (EN 1 .1191), 1.0425, 1.0037 and 1.0345.

Alternatively, preferably, the storage tank S(T) is made of stainless steel, more preferably one or more of Cr-Ni steel, such as 1 .4541 , 1 .4301 , 1 .4306 and 1 .4307, and Cr-Ni-Mo stainless steel, such as 1.4571 , 1.4401 and 1.4404.

Preferably, the volume of the storage tank S(T) is in the range of from 100 to 10 000 m³, more preferably in the range of from 150 to 5000 m³. More preferably, the volume of the storage tank S(T) is in the range of from 150 to 500 m³. Alternatively, preferably, the volume of the storage tank S(T) is in the range of from 1500 to 5000 m³.

Preferably, the storing unit S further comprises one or more storage tanks and one or more pumps, the one or more storage tanks and the one or more pumps being more preferably as defined in the foregoing. Preferably, storing P1 in S(T) according to (iii) is performed in the dark.

Preferably, At2 is in the range of from 1 day to 180 days, more preferably in the range of from 4 to 60 days.

Preferably, At3 is in the range of from 50 to 100% of At2, preferably in the range of from 75 to 99% of At2.

Preferably, during At2, the process further comprises periodically determining the corrosion state of the storage tank S(T) by means of visual testing and/or of measuring the mean linear corrosion rate vl(mm/year) as determined in Example 1.

Preferably, the process of the present invention further comprises

(iv) after storing in S(T) for At2, removing at least a portion PP of P2 from S(T) via the pump S(P), PP comprising the one or more pyrolysis oils.

The present invention further relates to a use of one or more stored pyrolysis oils obtained according to the process of the present invention as a feedstock for a cracker, preferably a thermal cracker or a catalytic cracker.

The present invention further relates to a process for purifying one or more pyrolysis oils, the process comprising

(a) a process for storing one or more pyrolysis oils according to the present invention;

(b) after storing in S(T) for At2 according to (a), removing at least a portion PP of P2 from S(T) via the pump S(P), PP comprising the one or more pyrolysis oils;

(c) passing PP obtained according to (b) through a cracker unit C, obtaining a stream SP comprising one or more purified pyrolysis oils.

In the context of the present invention, any cracker unit known in the art can be used for step (c), such as a thermal cracker or a catalytic cracker.

The present invention further relates to a storage unit for storing one or more pyrolysis oils OP, preferably according to the process of the present invention, the storage unit comprising

- a storage tank S(T), wherein the storage tank S(T) comprises a top portion T1 , an intermediate portion T2 and a bottom portion T3, wherein T1 is adjacent to T2 and T2 is adjacent to T3, wherein, in T3, the bottom of S(T) is a sloped surface;

- a pump S(P);

- an inlet means for passing at least a portion P1 of OP into S(T);

- an outlet means for removing a portion P2 of P1 from S(T);

- an inlet means for introducing a portion P3 of P2 into S(T). In the context of the present invention, it is believed that the sloped bottom surface of the storage tank in the storing unit as well as the recirculation of the pyrolysis oil via the pump in the storage unit permits to avoid the corrosion of the walls of the tank.

Preferably, the inlet means for passing at least a portion P1 of OP into S(T) comprises one or more pipes, the one or more pipes being more preferably made of carbon steel and stainless steel.

Preferably, the outlet means for removing a portion P2 of P1 from S(T) comprises one or more pipes, the one or more pipes being more preferably made of carbon steel and stainless steel.

Preferably, the means for introducing P3 of P2 into S(T) comprises one or more pipes, the one or more pipes being more preferably made of carbon steel and stainless steel.

Preferably, the inlet means for passing P1 of OP into the tank is located, in T2, at a height H(i) in the range of from 30 to 70 %, more preferably of from 40 to 60 %, more preferably of from 45 to 55 %, H(T2), H(T2) being the maximal axial distance between the bottom of the top portion T1 and the top of the bottom portion T3 and H(i) being the axial distance between the bottom of T2 and the inlet means for passing P1 .

Preferably, the outlet means for removing P2 is located, in T3, at the bottom of the sloped surface in T3.

Alternatively, preferably, the outlet means for removing P2 is located, in T2, at a height H(o) in the range of from 0.4 to 1.25 m, more preferably in the range of from 0.5 to 1 m, H(o) being the axial distance between the bottom of S(T) and the outlet means for removing P2.

Preferably, according to said alternative, the storage unit further comprises a means for removing P4 from S(T), said means being located, in T3, at the bottom of the sloped surface.

In the context of the present invention, it is believed that the sloped bottom surface of the tank as well as the removal of water at the bottom of said sloped surface of the tank permits to avoid the corrosion of the walls of the tank.

Preferably, the inlet means for introducing P3 is located, in the top portion T1 of S(T), more preferably between the top of S(T) and the bottom of the top portion T 1 . Preferably, in T3 of S(T), the sloped surface is a surface titled at an angle in the range of from 0.5 to 20 °, more preferably in the range of from 0.75 to 10 °, more preferably in the range of from 0.80 to 5 °, more preferably in the range of from 0.85 to 2 °, more preferably in the range of from 0.90 to 1.5 °.

In the context of the present invention, it is alternatively conceivable that the bottom portion of S(T) has a substantially conical shape, the tip of the cone being located at the lowest point of the tank (bottom of the tank).

Preferably, the storage S(T) comprises a means for measuring the density of the liquid entering the tank, more preferably a mass flow controller. Such means preferably permits to monitor the water content in the oil based on the density measurement of the oil.

Preferably, the storage S(T) comprises a means for measuring the density of the liquid exiting the tank, more preferably a mass flow controller. Such means preferably permits to monitor the water content in the oils based on the density measurement of the oils.

Preferably, the storage S(T) comprises a means for measuring the water content of the liquid in the tank, more preferably a water sensor. A water sensor - capacitance determination in the high-frequency stray field - permits to determine the presence of water in a liquid and its content.

Alternatively, preferably, the storage tank S(T) is made of stainless steel, more preferably one or more of Cr-Ni steel, such as 1 .4541 , 1.4301 , 1.4306 and 1.4307, and Cr-Ni-Mo stainless steel, such as 1.4571 , 1.4401 and 1.4404.

Preferably, the storing unit further comprises one or more storage tanks and one or more pumps, the one or more storage tanks and the one or more pumps being more preferably as defined in the foregoing. Preferably, the storage unit further comprises a means for measuring the corrosion level in the storage tank S(T).

The present invention is further illustrated by the following set of embodiments and combinations of embodiments resulting from the dependencies and back-references as indicated. In particular, it is noted that in each instance where a range of embodiments is mentioned, for example in the context of a term such as "The process of any one of embodiments 1 to 3", every embodiment in this range is meant to be explicitly disclosed for the skilled person, i.e. the wording of this term is to be understood by the skilled person as being synonymous to "The process of any one of embodiments 1 , 2 and 3". Further, it is explicitly noted that the following set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.

1 . A process for storing one or more pyrolysis oils, the process comprising

(i) providing one or more pyrolysis oils OP;

2. The process of embodiment 1 , wherein the one or more pyrolysis oils OP provided according to (i) are obtainable or obtained by pyrolyzing a waste material, the waste material being one or more of plastics, tires and textiles.

3. The process of embodiment 1 or 2, wherein the one or more pyrolysis oils OP provided according to (i) have a water content of at most 10 weight-%, preferably of at most 5 weight- %, more preferable of at most 1 weight-%, based on the weight of the pyrolysis oil, determined as described in Reference Example 1 .

4. The process of any one of embodiments 1 to 3, further comprises, prior to (ii), admixing the one or more pyrolysis oils OP provided according to (i) with an additive being one or more amphiphilic compounds, the one or more amphiphilic compounds comprise at least one nonpolar residue selected from Ce to C26 alkyl and/or alkylene and at least one polar residue comprising at least one heteroatom selected from the group consisting of N and O.

5. The process of any one of embodiments 1 to 4, wherein At1 is in the range of from 0.5 to 150 h, preferably in the range of from 0.5 to 50 h, more preferably in the range of from 1 to 20 h, more preferably in the range of from 1 to 5 h.

6. The process of any one of embodiments 1 to 5, wherein the storage tank S(T) is ventilated with a gas atmosphere, preferably the gas atmosphere being an inert gas, more preferably nitrogen.

7. The process of any one of embodiments 1 to 6, wherein, in T1 , the storage tank S(T) comprises an inlet means for introducing N2, the inlet means being located, in the top portion

T 1 , between the top of S(T) and the bottom of the top portion.

8. The process of any one of embodiments 1 to 7, wherein, in T1 , the storage tank S(T) comprises an outlet means for removing O2 from the storage tank, the outlet means being located, in the top portion T1 , at the top of S(T).

9. The process of any one of embodiments 1 to 8, wherein, in T2, the storage tank S(T) comprises an inlet means for passing P1 of OP into the tank, said inlet means being located, in T2, at a height H(i) in the range of from 30 to 70 %, preferably of from 40 to 60 %, more preferably of from 45 to 55 %, H(T2), H(T2) being the maximal axial distance between the bottom of the top portion T1 and the top of the bottom portion T3 and H(i) being the axial distance between the bottom of T2 and the inlet means for passing P1 .

10. The process of any one of embodiments 1 to 9, wherein removing a portion P2 of P1 from the storage tank S(T) according to (iii) is performed with the pump S(P) at an outlet means for removing P2, said outlet means being located at the bottom of the sloped surface in T3.

11 . The process of embodiment 10, wherein removing a portion P2 of P1 from the storage tank S(T) according to (iii) is performed periodically or constantly, preferably constantly.

12. The process of any one of embodiments 1 to 9, wherein removing a portion P2 of P1 from the storage tank S(T) is performed with the pump S(P) at an outlet means for removing P2, said outlet means being located, in T2, at a height H(o) in the range of from 0.4 to

1 .25 m, preferably in the range of from 0.5 to 1 m, H(o) being the axial distance between the bottom of S(T) and the outlet means for removing P2.

13. The process of embodiment 12, wherein, during the period of time At2, (iii) further comprises removing a portion P4 of P1 , P4 comprising water, from S(T), wherein the removal is performed at the bottom of the sloped surface in the bottom portion T3.

14. The process of any one of embodiments 1 to 13, wherein introducing P3 of P2 into the storage tank S(T) is performed with the pump S(P) at an inlet means for introducing P3, said inlet means being located, in the top portion T1 of S(T), preferably between the top of S(T) and the bottom of the top portion T1 .

15. The process of any one of embodiments 1 to 14, wherein, in T3 of S(T), the sloped surface is a surface titled at an angle in the range of from 0.5 to 20 °, preferably in the range of from 0.75 to 10 °, more preferably in the range of from 0.80 to 5 °, more preferably in the range of from 0.85 to 2 °, more preferably in the range of from 0.90 to 1.5 °.

16. The process of any one of embodiments 1 to 15, wherein, in S(T), the maximum temperature of the liquid phase of P1 , T_max(P1), in °C, is 80 °C, preferably 60 °C, more preferably 40 °C; wherein, in S(T), the minimum temperature of the liquid phase of P1 , T_min(P1), in ° C, is -10 °C, preferably 0 °C, more preferably 5 °C.

17. The process of any one of embodiments 1 to 16, wherein, in S(T), the pressure is in the range of from 100 to 1 mbar, preferably in the range of from 50 to 5 mbar , more preferably in the range of from 20 to 10 mbar.

18. The process of any one of embodiments 1 to 17, wherein the storage tank S(T) is made of one or more of carbon steel and stainless steel.

19. The process of any one of embodiments 1 to 18, wherein storing P1 in S(T) according to

(iii) is performed in the dark.

20. The process of any one of embodiments 1 to 19, wherein At2 is in the range of from 1 day to 180 days, preferably in the range of from 4 to 60 days.

21 . The process of any one of embodiments 1 to 20, wherein At3 is in the range of from 50 to 100% of At2, preferably in the range of from 75 to 99% of At2.

22. The process of any one of embodiments 1 to 21 , wherein, during At2, the process further comprises periodically determining the corrosion state of the storage tank S(T) by means of visual testing and/or of measuring the mean linear corrosion rate vl(mm/year) as determined in Example 1.

23. The process of any one of embodiments 1 to 22, further comprising

(iv) after storing in S(T) for At2, removing at least a portion PP of P2 from S(T) via the pump S(P), PP comprising the one or more pyrolysis oils. 24. Use of one or more stored pyrolysis oils obtained according to a process of any one of embodiments 1 to 23 as a feedstock for a cracker, preferably a thermal cracker or a catalytic cracker.

25. A process for purifying one or more pyrolysis oils, the process comprising

(a) a process for storing one or more pyrolysis oils according to any one of embodiments 1 to 22;

26. A storage unit for storing one or more pyrolysis oils OP, preferably according to the process of any one of embodiments 1 to 23, the storage unit comprising

- a pump S(P);

- an inlet means for passing at least a portion P1 of OP into S(T);

- an outlet means for removing a portion P2 of P1 from S(T);

- an inlet means for introducing a portion P3 of P2 into S(T).

27. The storage unit of embodiment 26, wherein the inlet means for passing at least a portion P1 of OP into S(T) comprises one or more pipes, the one or more pipes being preferably made of carbon steel and stainless steel.

28. The storage unit of embodiment 26 or 27, wherein the outlet means for removing a portion P2 of P1 from S(T) comprises one or more pipes, the one or more pipes being preferably made of carbon steel and stainless steel.

29. The storage unit of any one of embodiments 26 to 28, wherein the means for introducing P3 of P2 into S(T) comprises one or more pipes, the one or more pipes being preferably made of carbon steel and stainless steel.

30. The storage unit of any one of embodiments 26 to 29, wherein, in T1 , the storage tank S(T) comprises an inlet means for introducing N2, the inlet means being located, in the top portion T 1 , between the top of S(T) and the bottom of the top portion.

31 . The storage unit of any one of embodiments 26 to 30, wherein, in T1 , the storage tank S(T) comprises an outlet means for removing O2 from the storage tank, the outlet means being located, in the top portion T1 , at the top of S(T). 32. The storage unit of any one of embodiments 26 to 31 , wherein the inlet means for passing P1 of OP into the tank is located, in T2, at a height H(i) in the range of from 30 to 70 %, preferably of from 40 to 60 %, more preferably of from 45 to 55 %, H(T2), H(T2) being the maximal axial distance between the bottom of the top portion T1 and the top of the bottom portion T3 and H(i) being the axial distance between the bottom of T2 and the inlet means for passing P1 .

33. The storage unit of any one of embodiments 26 to 32, wherein the outlet means for removing P2 is located, in T3, at the bottom of the sloped surface in T3.

34. The storage unit of any one of embodiments 26 to 32, wherein the outlet means for removing P2 is located, in T2, at a height H(o) in the range of from 0.4 to 1.25 m, preferably in the range of from 0.5 to 1 m, H(o) being the axial distance between the bottom of S(T) and the outlet means for removing P2; wherein preferably the storage unit further comprises a means for removing P4 from S(T), said means being located , in T3, at the bottom of the sloped surface in T3.

35. The storage unit of any one of embodiments 25 to 34, wherein the inlet means for introducing P3 is located, in the top portion T1 of S(T), preferably between the top of S(T) and the bottom of the top portion T 1 .

36. The storage unit of any one of embodiments 25 to 35, wherein, in T3 of S(T), the sloped surface is a surface titled at an angle in the range of from 0.5 to 20 °, preferably in the range of from 0.75 to 10 °, more preferably in the range of from 0.80 to 5 °, more preferably in the range of from 0.85 to 2 °, more preferably in the range of from 0.90 to 1.5 °.

37. The storage unit of any one of embodiments 25 to 36, wherein the storage tank S(T) is made of one or more of carbon steel and stainless steel.

38. The storage unit of any one of embodiments 25 to 37, further comprising a means for measuring the corrosion level in the storage tank S(T).

In the context of the present invention, the sloped surface in T3 preferably refers to an inclined surface, more preferably to an inclined plane.

It is explicitly noted that the above set of embodiments represents a suitably structured part of the general description directed to preferred aspects of the present invention, and, thus, suitably supports, but does not represent the claims of the present invention.

In the context of the present invention, it is noted that “alkylene” and “alkanediyl” can be used interchangeably. In the context of the present invention, a term “X is one or more of A, B and C”, wherein X is a given feature and each of A, B and C stands for specific realization of said feature, is to be understood as disclosing that X is either 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 regard, it is noted that the skilled person is capable of transfer to above abstract term to a concrete example, e.g. where X is a chemical element and A, B and C are concrete elements such as Li, Na, and K, or X is a temperature and A, B and C are concrete temperatures such as 10 °C, 20 °C, and 30 °C. In this regard, it is further noted that the skilled person is capable of extending the above term to less specific realizations of said feature, e.g. “X is one or more of A and B” disclosing that X is either A, or B, or A and B, or to more specific realizations of said feature, e.g. “X is one or more of A, B, C and D”, disclosing that X is either 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.

The present invention is further illustrated by the following examples.

Examples

Reference Example 1 : Measurement of water content in a pyrolysis oil

The water content in a given pyrolysis oil is measured according to DIN 51777.

Reference Example 2: Measurement of halogen content in a pyrolysis oil (wppm)

The halogen content in a given pyrolysis oil is measured according to ASTM D5808.

Reference Example 3: Measurement of sulfur content in a pyrolysis oil (wppm)

The sulfur content in a given pyrolysis oil is measured according to ASTM D5453.

Reference Example 4: Measurement of the Determination of the total acid number (TAN)

The total acid number was determined by titration with KOH according to ASTM E1064 or ASTM D95.

Comparative Example 1 : Pyrolysis oil storage not according to the present invention

The present experiment simulate the tank conditions without circulation and without bottom sloped surface. Said experiments were made according of the Laboratory immersion corrosion tests according to DIN 509051 ASTM G31-72 carried out in ISO 9001 certified corrosion laboratory with a pyrolysis oil, having a sulfur content of 1.1 wt.-% based on the weight of the oil, a halogen content of 15 wppm (ppm by weight of the oil), a water content of 0.1 wt.-% based on the weight of the oil and a TAN of 8.7 mg(KOH)/g(oil), for 4 x 7 days, without medium exchange (the pyrolysis oil was not changed during the testing experiments), at T = 60 °C, atmospheric pressure (1 bar). Standard corrosion coupons with welding seam (50 x 20 x 2 mm) were used, coupons were made of carbon steel 1 .0425 (P265GH/ HI I), coupons were made of austenitic stainless steel 1.4541 (X6CrNiTi 18-10), that were installed in a glass flask in the vapor phase, in the liquid phase and in the phase boundary liquid-vapor. To consider a susceptibility to stress corrosion cracking, the coupons made of 1 .4541 were roughly ground on one side. The flask volume was blanketed with N2 and the medium was not agitated.

The metal coupons were analyzed by weight loss measurements and visually inspected in the binocular microscope for local corrosion (shallow pit corrosion, pitting, crevice corrosion, stress corrosion cracking, etc.). To detect stress corrosion cracking (SCC) the rough-ground coupons were bent at an angle of approximately 45 degrees after the corrosion test which makes cracks visible in the microscope if SCC actually occurs. These results were used to establish the linear corrosion rate (vl). The results are shown below.

Table 1

1 ) The limit value of technical corrosion resistance is vl = 0.1 mm/year without the presence of local corrosion.

2) The highest corrosion rates (up to 0.086 mm/year in the liquid phase) occurred in the first test period and decreased steadily.

3) The maximum measured corrosion depth (shallow pit corrosion) is approx. 20 pm, which corresponds to a local corrosion velocity rate of approx. 0.26 mm/year

Comparative Example 2: Pyrolysis oil storage not according to the present invention

The present experiment simulate the tank conditions without circulation and without bottom sloped surface. Said experiments were made according of the Laboratory immersion corrosion tests according to DIN 509051 ASTM G31-72 carried out in ISO 9001 certified corrosion laboratory with a pyrolysis oil, having a sulfur content of 1.1 wt.-% based on the weight of the oil, a halogen content of 15 wppm (ppm by weight of the oil), a water content of 0.1 wt.-% based on the weight of the oil and a TAN of 8.7 mg(KOH)/g(oil), for 4 x 7 days, without medium exchange (the pyrolysis oil was not changed during the testing experiments), at T = 80 °C, atmospheric pressure (1 bar). Per test period, approx. 5000 ppm of demineralized water was added to the medium, increasing the water content in the oil to about 0.6 wt.-%. Standard corrosion coupons with welding seam (50 x 20 x 2 mm) were used, coupons were made of carbon steel 1 .0425 (P265GH/ HI I), that were installed in a glass flask in the vapor phase, in the liquid phase and in the phase boundary liquid-vapor. The flask volume was blanketed with N2 and the medium was not agitated.

The metal coupons were analyzed by weight loss measurements and visually inspected in the binocular microscope for local corrosion (shallow pit corrosion, pitting, crevice corrosion, stress corrosion cracking). These results were used to establish the linear corrosion rate (vl). The results are shown below.

Table 2

1) The limit value of the technical corrosion resistance is vl = 0.1 mm/year without the presence of local corrosion.

2) The highest corrosion rates (up to 0.112 mm/year) have occurred in the first test period (7 days) and have steadily decreased.

3) The maximum measured corrosion depth (shallow pit corrosion) is approx. 25 pm, which corresponds to a local corrosion rate of approx. 0.33 mm/year.

4) The maximum measured corrosion depth (crevice corrosion) is approx. 10 pm, which corresponds to a local corrosion rate of approx. 0.13 mm/year.

Thus, as may be taken from Comparative Examples 1 and 2, corrosion appears on carbon steel as well as slightly on the stainless steel if standard process are used for storing the pyrolysis oil. It is also shown that the presence of water is clearly detrimental and increase the corrosion. Remark: Due to the safety reasons, to avoid corrosion in the production tanks being used, the comparative experiments were realized in the lab and using glass reactors according to the ASTM G31-72.

Example 1 : Pyrolysis oil storage according to the present invention

Pyrolysis oils are placed in the storage tanks, the pyrolysis oils have a sulfur content of about 1 .1 wt.-% (+/- 0.1 wt.-%) based on the weight of the pyrolysis oil mixture, an halogen content of about 18 wppm (+/- 5 wppm), a water content of about 0.1 wt.-% (+/- 0.05 wt.-%) based on the weight of the pyrolysis oil mixture.

Pyrolysis oils were placed in storage tanks comprising a top portion T1 , an intermediate portion T2 and a bottom portion T3, wherein T1 is adjacent to T2 and T2 is adjacent to T3, wherein, in T3, the bottom of the storage tanks is a sloped surface. The recirculation of the oils was done from the bottom of the slope as illustrated in Figure 1 .

The samples used are standard corrosion coupons with weld seam (50 x 20 x 2 mm) installed in the vapor and liquid phases of the tank containing the pyrolysis oils, coupons were made of carbon steel and coupons were made of austenitic stainless steel 1 .4541 and 1 .4571 (Table 3 below). To consider a susceptibility to stress corrosion cracking, the coupons made of 1 .4541 and 1.4571 were roughly ground on one side. Interim evaluation was done after 180 days of continuous exposure time. The storage tank had an operating temperature of approx. 15-35 °C and an operating pressure of 15 mbar under nitrogen atmosphere. Tank containing the pyrolysis oils had the volume of 150 m³. The (re-)circulation of the oil was done with a pump (Figure 1) and the circulation rate in the tank was 6m³/h.

Table 3

1 ) The limit value of the technical corrosion resistance is vl = 0.1 mm/year without the presence of local corrosion.

2) The maximum measured corrosion depth (shallow pit corrosion) is approx. 40 pm, which corresponds to a local corrosion rate of approx. 0.08 mm/year.

3) The maximum measured corrosion depth (crevice corrosion) is approx. 70 pm, which corresponds to a local corrosion rate of approx. 0.14 mm/year.

Thus, as may be taken from Example 1 , the corrosion rate was drastically reduced when recirculating the pyrolysis oil in a tank with a bottom sloped surface compared to Comparative Example 1 and 2. Without wanting to be bound to any theory, the sloped surface in combination with the recirculation permits to prevent phase separation in the pyrolysis oil and thus the corrosion of the tank is reduced.

Description of the figures

Figure 1 represents a storage unit according to embodiments of the present invention.

The storage unit comprises a storage tank S(T) and a pump S(P). S(T) comprises a top portion T1 , an intermediate portion T2 and a bottom portion T3, wherein T1 is adjacent to T2 and T2 is adjacent to T3, wherein, in T3, the bottom of S(T) is a sloped surface. A portion P1 of one or more pyrolysis oils which is transported in one or more trucks X is introduced in to S(T), preferably at about half of the height of T2. During storage, N2 is introduced in S(T) via an inlet means located, in the top portion T 1 , between the top of S(T) and the bottom of the top portion T 1 . Further, during storage, O2 is removed from S(T) via an outlet means, the outlet means being located, in the top portion T1 , at the top of S(T). The top portion T 1 of S(T) is substantially conical. S(T) also comprises an outlet means for removing a portion P2 of P1 from S(T), said means is located, in T3, at the bottom of the sloped surface in T3. S(T) further comprises an inlet means for introducing a portion P3 of P2 into S(T), said means being located, in the top portion T1 of S(T), between the top of S(T) and the bottom of the top portion T1 . After the storage in S(T), a stream PP comprising the one or more pyrolysis oils is removed via the pump S(P). Figure 2 represents a storage unit according to embodiments of the present invention.

The storage unit comprises a storage tank S(T) and a pump S(P). S(T) comprises a top portion T1 , an intermediate portion T2 and a bottom portion T3, wherein T1 is adjacent to T2 and T2 is adjacent to T3, wherein, in T3, the bottom of S(T) is a sloped surface. A portion P1 of one or more pyrolysis oils which is transported in one or more trucks X is introduced in to S(T), preferably at about half of the height of T2. During storage, N2 is introduced in S(T) via an inlet means located, in the top portion T 1 , between the top of S(T) and the bottom of the top portion T 1 . Further, during storage, O2 is removed from S(T) via an outlet means, the outlet means being located, in the top portion T1 , at the top of S(T). The top portion T 1 of S(T) is substantially conical. S(T) also comprises an outlet means for removing a portion P2 of P1 from S(T), said means is located, in T2, at a height H(o) in the range of from 0.4 to 1 .25 m, preferably in the range of from 0.5 to 1 m. S(T) further comprises a purge for removing P4 comprising water, the purge is located, in T3, at the bottom of the sloped surface in T3. S(T) further comprises an inlet means for introducing a portion P3 of P2 into S(T), said means being located, in the top portion T1 of S(T), between the top of S(T) and the bottom of the top portion T 1 . After the storage in S(T), a stream PP comprising the one or more pyrolysis oils is removed via the pump S(P).

Cited literature

- WO 2015/113681 A1

- WO 82/00467 A1

- US 2008/0108836 A1

- WO 2014/195464 A1

- WO 2015/113681 A1

Claims

1 . A process for storing one or more pyrolysis oils, the process comprising

(i) providing one or more pyrolysis oils OP;

(ii) passing at least a portion P1 of the one or more pyrolysis oils OP, P1 comprising the one or more pyrolysis oils, into a storage tank S(T) comprised in a storing unit S, for a period of time At1 , the storing unit S further comprising a pump S(P);

2. The process of claim 1 , wherein the one or more pyrolysis oils OP provided in (i) are obtainable or obtained by pyrolyzing a waste material, the waste material being one or more of plastics and tires.

3. The process of claim 1 or 2, wherein the one or more pyrolysis oils OP provided in (i) have a water content of at most 10 weight-%, more preferably of at most 5 weight-%, more preferable of at most 1 weight-%, based on the weight of the pyrolysis oil.

4. The process of any one of claims 1 to 3, further comprises, prior to (ii), admixing the one or more pyrolysis oils OP provided in (i) with an additive being one or more amphiphilic compounds, the one or more amphiphilic compounds comprise at least one nonpolar residue selected from Ce to C26 alkyl and/or alkylene and at least one polar residue comprising at least one heteroatom selected from the group consisting of N and O.

5. The process of any one of claims 1 to 4, wherein the storage tank S(T) is ventilated with a gas atmosphere, more preferably the gas atmosphere being an inert gas, more preferably nitrogen.

6. The process of any one of claims 1 to 5, wherein removing a portion P2 of P1 from the storage tank S(T) according to (iii) is performed with the pump S(P) at an outlet means for removing P2, said outlet means being located at the bottom of the sloped surface in T3.

7. The process of claim 6, wherein removing a portion P2 of P1 from the storage tank S(T) according to (iii) is performed periodically or constantly, preferably constantly.

8. The process of any one of claims 1 to 5, wherein removing a portion P2 of P1 from the storage tank S(T) is performed with the pump S(P) at an outlet means for removing P2, said outlet means being located, in T2, at a height H(o) in the range of from 0.4 to 1 .25 m, preferably in the range of from 0.5 to 1 m, H(o) being the axial distance between the bottom of S(T) and the outlet means for removing P2.

9. The process of claim 8, wherein, during the period of time At2, (iii) further comprises removing a portion P4 of P1 , P4 comprising water, from S(T), wherein the removal is performed at the bottom of the sloped surface in the bottom portion T3.

10. The process of any one of claims 1 to 9, wherein, in T3 of S(T), the sloped surface is a surface titled at an angle in the range of from 0.5 to 20 °, preferably in the range of from 0.75 to 10 °, more preferably in the range of from 0.80 to 5 °, more preferably in the range of from 0.85 to 2 °, more preferably in the range of from 0.90 to 1.5 °.

11 . The process of any one of claims 1 to 10, wherein, in S(T), the maximum temperature of the liquid phase of P1 , Tmax(P1), in °C, is 80 °C, preferably 60 °C, more preferably 40 °C; wherein, in S(T), the minimum temperature of the liquid phase of P1 , Tmin(P1), in °C, is -10 °C, preferably 0 °C, more preferably 5 °C.

12. The process of any one of claims 1 to 11 , wherein, in S(T), the pressure is in the range of from 100 to 1 mbar, more preferably in the range of from 50 to 5 mbar, more preferably in the range of from 20 to 10 mbar.

13. The process of any one of claims 1 to 12, wherein the storage tank S(T) is made of one or more of carbon steel and stainless steel.

14. Use of one or more stored pyrolysis oils obtained according to a process of any one of claims 1 to 13 as a feedstock for a cracker, preferably a thermal cracker or a catalytic cracker.

15. A storage unit for storing one or more pyrolysis oils OP, preferably according to the process of any one of claims 1 to 13, the storage unit comprising

- a pump S(P);

- an inlet means for passing at least a portion P1 of OP into S(T);

- an outlet means for removing a portion P2 of P1 from S(T);

- an inlet means for introducing a portion P3 of P2 into S(T).