BE1026831A1 - Process for upgrading waste oil - Google Patents

Abstract

The present invention relates to a method comprising subjecting a feedstock having an oxygen content of at most 5.0% by weight (on a dry basis) to heat treatment, separating solids from the heat-treated material to produce a metal-depleted feed the metal-depleted feedstock, optionally together with an additional feedstock, hydrocracking and recovering at least one hydrocarbon fraction boiling in the liquid fuel area from the hydrocracked material.

Description

Process for upgrading waste oil

DESCRIPTION

Technical field

The present invention relates to a method for producing fuel components from waste oil, a fuel component obtainable by the method, and the use of the fuel component.

Technical background

Mobility and logistics are essential parts of life, the economy and today's society. In order to meet the increasing energy needs of traffic and transportation, it is important to strive for sustainable fuel solutions. Decarbonizing the transportation sector (or avoiding carbon-based technologies in the transportation sector) is an overwhelming task and fossil fuels should slowly be replaced by more sustainable fuels. A liquid fuel has advantages over gases and electricity in traffic solutions due to the existing infrastructure and fuel logistics. The energy content of liquid fuels is also superior, which is essential since the energy must be carried in the vehicles.

In addition to biofuels, there is growing interest in the use of recycled (recycled) fossil-based materials, such as used lubricant oils (ULO) or other waste oils for the production of transport fuels. Unlike most biomass-derived liquids, ULO and others exhibit

BE2019 / 5916 fossil waste oils have a distinguished advantage in that they contain very little oxygen. In contrast, ULO and other waste oils contain a variety of other contaminants (metals, phosphorus, silicon, chlorine), which mainly result from additives that have been used in the production process. However, the hydrocarbons contained in the recycled fossil-based materials, such as ULO and other waste oils, are largely paraffinic and fall within a boiling point range that is suitable for catalytic cracking. Waste oils like this therefore offer an alternative to conventional crack raw materials, such as vacuum gas oil (VGO).

In addition, as of 2020, the new renewable energy directive (RED II) in the European Union may include certain types of incentives for transport fuels made from fossil-based recycled feedstocks. Thus, even though ULO and other waste oils are a highly challenging raw material for purification, they are seen as an alternative refinery raw material with good potential. One method of purifying waste oils is distillation; it simultaneously separates most of the metallic impurities / phosphorus and the heaviest hydrocarbons into the distillation bottoms, resulting in distillates that take a more usable form.

An alternative approach to upgrading used oils, such as ULO, is to re-refine the hydrocarbons to their base oil components, for example by hydrotreating (hydrogenation treatment), and then use them in the formulation of new lubricants. With this approach, it is essential to avoid cracking the base oil hydrocarbon chains during purification and hydrotreating. Therefore, distillation techniques, which are particularly suitable for thermal

BE2019 / 5916 unstable materials are suitable, often used for fractionating ULO.

Furthermore, US 4,512,878 A discloses a method for recycling waste oils, which comprises a heat impregnation step, a distillation step and a hydrorefining step.

US 4411774 A discloses heat treating ULO in the presence of a pretreatment chemical to remove contaminants, followed by filtration and reuse of the liquids thus treated as lubricating oils.

US 3980551 A discloses the demetallization of ULO in an ebullated bed reactor followed by vacuum distillation to produce a clean fraction and heavy fractions containing slag and metals.

Summary of the invention

It is an object of the present invention to provide an improved method for treating waste oils.

The inventors of the present invention surprisingly found that a heat treatment step is suitable for reducing the metal content of a waste oil material to such an extent that the heat treated material, after removal of solid substance which is formed during the heat treatment, undergoes a metal-tolerant hydrocracking process without any further purification, such as distillation, can be subjected. More specifically, the inventors found that a heat-treated raw material (or a heat-treated raw material) has suitable properties that

BE2019 / 5916 would allow its direct transfer to hydrocracking without further need for distillation in order to significantly improve the yield of the purification process before cracking as well as the overall yield.

That is, a particular disadvantage of distillation is the significant loss of hydrocarbon material in the distillation bottoms, even though it provides fairly pure material. In addition, although the majority of the metals are fractionated into the distillation bottoms, the resulting distillates do not necessarily meet the stringent contamination specifications of fixed bed hydrotreating / hydrocracking units (hydrogenation treatment / hydrocracks). In practice, this means that a secondary cleaning agent must be used in order to further reduce the contamination concentrations of the used oil distillates. Depending on the distillation characteristics of the waste oil sample and the distillation methodology, the hydrocarbons separated into the distillation sumps can, for example, correspond to a vacuum residue (VR) material that has a boiling point of> 550 ° C and contains significant amounts of metal impurities.

Thus, since an adequate level of metal removal can be achieved without distillation, the present invention provides a process that achieves extremely high yields compared to conventional techniques that use distillation to provide a feedstock suitable for hydrotreating.

The present invention is defined in the independent claims. Further preferred embodiments are set out in the dependent claims. Specifically, the present invention relates to one or more of the following:

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1. A method comprising the following steps: subjecting a starting material (or feed or

Raw material) of a heat treatment (heat treatment step) to produce a heat-treated material containing liquid components and solid components,

Separating solids from the heat treated material to produce a metal depleted feed,

Subjecting the metal-depleted feed, optionally together with an additional feed, to hydrocracking (hydrocracking step) to form a hydrocracked material,

Recovering at least one hydrocarbon fraction boiling in the area of liquid fuel from the hydrocracked material; the starting material having an oxygen content of at most 5.0% by weight on a dry basis.

2. The method according to item 1, wherein the starting material has an oxygen content, on a dry basis, in the range from 0.1% by weight to 5.0% by weight, preferably at most 4.0% by weight, at most 3.5 % By weight or at most 3.0% by weight, and / or at least 0.2% by weight, at least 0.3% by weight, at least 0.4% by weight or at least 0.5% by weight. -% having.

3. The method according to item 1 or 2, wherein the total content of hydrogen (H) and carbon (C) in the base material, on a dry basis, is at least 80% by weight, preferably at least 85% by weight, at least 90% by weight. %, at least 92% by weight, at least 94% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight or at least 99% by weight .

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4. The method according to any one of the preceding items, further comprising a pretreatment step of dewatering a raw feedstock to produce the starting material.

5. The method according to one of the preceding points, wherein the metal-depleted feed material (or the metal-depleted feed) is subjected to hydrocracking together with an additional feed material (or an additional feed).

6. The method according to any one of the preceding points, wherein the additional feed is a fossil-based feed, a renewable feed, or a combination of both.

7. The method of item 6, wherein the fossil-based feed is a fraction of crude oil and / or the renewable feed is a material derived from deoxygenation of a renewable material.

8. The method according to any one of the preceding points, wherein the metal content of the metal-depleted feedstock is less than the metal content of the starting material.

9. The method according to any one of the preceding points, wherein the metal content of the metal-depleted feedstock is at most 60% by weight of the metal content of the starting material, preferably at most 50% by weight, at most 40% by weight, at most 30% by weight, at most 20 wt%, at most 15 wt%, at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, at most 4 wt % or at most 3% by weight of the metal content of the starting material.

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10. The method according to any one of the preceding points, wherein the heat treatment is carried out at a temperature of at least 290 ° C., preferably at least 300 ° C. or at least 310 ° C.

11. The method according to any one of the preceding points, wherein the heat treatment is carried out at a temperature of at least 320 ° C or at least 330 ° C.

12. The method according to any one of the preceding points, wherein the heat treatment is carried out at a temperature of at most 450 ° C, preferably at most 400 ° C, at most 380 ° C, at most 370 ° C, at most 360 ° C, at most 350 ° C, at most 340 ° C or at most 335 ° C.

13. The method according to one of the preceding points, wherein the heat treatment is carried out for at least 1 minute, preferably at least 2 minutes, at least 5 minutes, at least 10 minutes, at least 20 minutes, at least 30 minutes, at least 40 minutes, at least 50 minutes, at least 60 Minutes, at least 80 minutes or at least 100 minutes.

14. The method according to any one of the preceding points, wherein the heat treatment is carried out at a pressure of 1.0 bar or more, preferably 1.2 bar or more, 1.5 bar or more, 2.0 bar or more or 3.0 cash or more.

15. The method according to one of the preceding points, wherein the starting material contains at most 20.0% by weight of water, preferably at most 15.0% by weight, at most 12.0% by weight, at most 10.0% by weight, at most 8.0 wt%, at most 7.0 wt%, at most 6.0 wt%, at most 5.0 wt%, at most 4.0 wt%, at most 3.0 wt.

BE2019 / 5916%, at most 2.0% by weight, at most 1.5% by weight, at most 1.0% by weight, at most 0.7% by weight or at most 0.5% by weight of water .

16. The method according to any one of the preceding points, wherein the hydrocracking step is carried out at a temperature in the range from 300 ° C to 500 ° C.

17. The method according to any one of the preceding points, wherein the hydrocracking step is carried out at a temperature of at least 310 ° C, at least 320 ° C, at least 330 ° C, at least 340 ° C, or at least 350 ° C, and / or at most 490 ° C, maximum 480 ° C, maximum 470 ° C, maximum 460 ° C, maximum 450 ° C, maximum 440 ° C or maximum 430 ° C.

18. The method according to any one of the preceding points, wherein the metal-depleted feedstock is subjected to hydrocracking in the presence of a solid catalyst.

19. The method of item 18, wherein the solid catalyst contains at least one Group VIII base metal and at least one Group VIB metal and a support.

20. The method according to item 19, wherein the carrier contains silicon oxide, aluminum oxide or clay.

21. The method according to items 18 or 19, wherein the carrier comprises a Bronsted acid component.

22. The method according to item 21, wherein the Bronsted acid component is zeolite or amorphous silicon oxide-aluminum oxide.

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23. The method of item 22, wherein the zeolite is Y zeolite, beta zeolite, or any other 12-membered ring zeolite.

24. The method according to items 19 to 23, wherein the base metal of group VIII is Co or Ni and the metal of group VIB is Mo or W.

25. The method according to any one of the preceding points, wherein the hydrogen partial pressure in the hydrocracking step is in the range from 70 to 200 bar.

26. The method according to any one of the preceding points, wherein the hydrocracking step is carried out in a fluidized bed reactor (ebullated bed reactor), a slurry reactor (suspension reactor) or a fixed bed reactor.

27. The method according to any one of the preceding points, wherein the total content of metals and phosphorus in the starting material is in the range from 500 mg / kg to 10000 mg / kg, preferably 1000 mg / kg to 8000 mg / kg.

28. Method according to one of the preceding points, the starting material being liquid at 25 ° C.

29. The method according to any one of the preceding points, wherein the temperature during dewatering is lower than the (highest) temperature in the heat treatment step.

30. The method according to any one of the preceding points, wherein the step of removing insoluble constituents from the heat-treated material (the step of removing solids)

BE2019 / 5916 comprises at least one of centrifugation, filtration and sedimentation, preferably at least centrifugation.

31. The method according to any one of the preceding points, wherein the heat treatment step is carried out for 100 hours or less, preferably 50 hours or less, 40 hours or less, 30 hours or less, 20 hours or less, 10 hours or less or 5 hours or less .

32. The method according to any one of the preceding points, wherein a metal removal additive is admixed to the starting material before or during the heat treatment step, the metal removal additive preferably being at least one selected from the group consisting of ammonium sulfate, ammonium bisulfate, diammonium phosphate, ammonium dihydrogen phosphate

Calcium hydrogen phosphate, phosphoric acid, magnesium sulfate, calcium sulfate, aluminum sulfate and sodium sulfate.

33. Fuel component obtainable by the method according to one of the preceding points.

34. Fuel component according to item 33, comprising the hydrocarbon fraction obtained, the fraction being preferably a fraction which boils in the gasoline range or a fraction which boils in the middle distillate range.

35. Use of the hydrocarbon fraction obtained, which is obtained by the method according to any one of items 1 to 32, for producing a fuel or a fuel component.

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The oxygen content in the starting material can be determined by elemental analysis. In the present invention, the oxygen content is determined on a dry basis of the starting material (excluding water if it is present in the starting material).

Brief description of the drawing

1 is a schematic illustration of the process according to the present invention.

Detailed description of the invention

The invention will now be described in detail with reference to specific embodiments. It should be noted that any feature of the embodiments can be combined with any feature of another embodiment, provided that such a combination does not result in a contradiction.

The present invention relates to a method comprising a heat treatment step, a solid separation step, a hydrocracking step and a recovery step. The heat treatment step is a step of subjecting a raw material to heat treatment to produce a heat-treated material comprising liquid components and solid components. The starting material has an oxygen content of at most 5.0% by weight on a dry basis (i.e. excluding water). The solids separation step is a step of separating solids from the heat treated material to produce a metal depleted feed. The hydrocracking step is a step of subjecting the metal-depleted feed, optionally together

BE2019 / 5916 with an additional feed, hydrocracking, to form a hydrocracked material. The recovery step is a step of recovering at least one hydrocarbon fraction boiling in the liquid fuel area from the hydrocracked material.

The inventors of the present invention surprisingly found that heat treatment of the feedstock and subsequent removal of solids is sufficient to provide a feedstock suitable for metal tolerant hydrocracking units, such as residue hydrocracking (RHC) units. In particular, the inventors found that distillation of the heat-treated material is not necessary, and thus the significant loss of valuable hydrocarbon material in the distillation bottoms can be avoided.

Furthermore, the heat treatment can decrease the tendency to fouling of the cracking catalyst and thus increase the catalyst life. Although not wishing to be bound by theory, it is believed that the heat treatment causes reactive components in the starting material to undergo a reaction and thus end up as a solid material that can be removed, for example, by filtration or centrifugation . It is believed that such reactive components are responsible for coke formation (slagging or fouling) in the hydrocracking step.

The starting material of the present invention includes any material from fossils or renewable (biomass-based) origin with an oxygen content of at most 5% by weight on a dry basis. In a preferred embodiment, this is

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The starting material is a waste oil or a drained waste oil. The use of waste materials (materials already used) in the present invention provides a sustainable process of reintroducing fossil or renewable carbon materials into the value chain, thus reducing the need to exploit natural resources. Since the raw material has an oxygen content of at most 5% by weight, non-processed bio-based oils such as raw vegetable oil, fats and the like are not included because these materials have a high oxygen content. Rather, the invention relates to a material that mainly contains hydrocarbons as well as contaminants, for example contaminants that are included as a result of the manufacturing process of the material or as a result of the first use of the material.

In the present invention, the total content of metals (not including metalloids such as Si) and phosphorus in the starting material is preferably in the range of 500 mg / kg to 10000 mg / kg, preferably 1000 mg / kg to 8000 mg / kg. In other words, the starting material of the present invention is preferably a contaminated material such as a waste material. The content of metals in the starting material can be determined, for example, using inductively coupled plasma atomic emission spectrometry based on the ASTM D5185 standard. For the purpose of the present invention, the total content of metals preferably refers to the total content (total content) of Al, Cr, Cu, Fe, Na, Ni, Pb, Sn, V, Ba, Ca, Mg, Mn and Zn.

In the present invention, the oxygen content "on a dry basis" means that the oxygen content is determined on the assumption that

BE2019 / 5916 that all water has been removed before determining the content. The oxygen content on a dry basis can be determined by drying the starting material and determining the oxygen content (for example by elemental analysis). Alternatively, the oxygen content can be determined on a dry basis from a wet starting material as follows:

Oxygen content (dry basis) = 100% * {(total oxygen content of the wet starting material, for example by elemental analysis) - (oxygen content contained in the wet starting material in the form of water)} / {(mass of the moist starting material) - (mass of the water in the moist starting material)}

The content (mass) of the water contained in the moist starting material can be determined by suitable means (for example Karl Fisher titration according to ASTM D6304, or distillation according to ASTM D95).

The source material may include waste oil, such as used lubricant oil (ULO). Specifically, waste oils according to the present invention may include any fossil (mineral oil-based) or renewable (biomass-based) lubricating or industrial oils which have become unsuitable for the originally intended use, and in particular used engine oils and gear oils and also mineral lubricating oils, turbine oils and hydraulic oils.

The starting material is preferably liquid at 25 ° C. Thus, the starting material can be handled easily and does not require excessive heating during storage and / or during transportation.

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In the process of the present invention, the starting material preferably has an oxygen content, on a dry basis, in the range of 0.1 wt% to 5.0 wt%, more preferably at most 4.0 wt%, at most 3 , 5% by weight or at most 3.0% by weight, and / or at least 0.2% by weight, at least 0.3% by weight, at least 0.4% by weight or at least 0.5 % By weight.

In other words, it is preferred that the starting material be a material that contains only small amounts of oxygen.

It is further preferred that the total content of hydrogen (H) and carbon (C) in the starting material, on a dry basis, is at least 80% by weight, preferably at least 85% by weight, at least 90% by weight, at least 92 wt%, at least 94 wt%, at least 95 wt%, at least 96 wt%, at least 97 wt%, at least 98 wt%, or at least 99 wt%. It is preferred that the total content of hydrogen (H) and carbon (C) in the starting material, on a dry basis, be at least 90% by weight. The levels of hydrogen and carbon in the starting material can be determined by elemental analysis using, for example, ASTM D5291.

That is, the starting material of the present invention is preferably mainly composed of hydrocarbon material (consisting of C and H) with low contents of heteroatoms, which can be contained as inorganic impurities and / or in the form of organic non-hydrocarbon material.

The method of the present invention may further include a pretreatment step of dewatering a raw feed to provide the starting material. In terms of

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Dewatering does not have to be carried out efficiently if the material to be processed already contains small amounts of water, and thus the material can be used directly as the starting material.

Dewatering can be accomplished by any suitable chemical and / or physical method. For example, an absorbent or an adsorbent for water can be brought into contact with the raw feed material or water can be removed thermally by evaporation (distillation). The temperature during dewatering is usually lower than in the heat treatment step. The water removal step is preferably carried out at a temperature of less than 150 ° C., preferably 130 ° C. or less. It is further preferred that the dewatering is carried out at ambient pressure in order to keep the process equipment simple.

Dewatering the raw feedstock enables better performance in the subsequent steps, particularly the heat treatment step. In particular, stable pressure conditions can be achieved by removing water (and optionally other light components) before the heat treatment step.

In contrast, some amount of water may be present in the starting material of the present invention. Depending on the circumstances, it may be advantageous to use a water-containing starting material without subjecting it to a water removal step. In any event, the starting material of the present invention preferably contains at most 20.0% by weight of water, more preferably at most 15.0% by weight, at most 12.0% by weight, at most 10.0% by weight, or at most 8.0% by weight. Yet

BE2019 / 5916 smaller amounts of water are desirable, but may involve additional effort to remove water. Nevertheless, the starting material can have a water content of at most 7.0% by weight, at most 6.0% by weight, at most 5.0% by weight, at most 4.0% by weight, at most 3.0%. -%, at most 2.0% by weight, at most 1.5% by weight, at most 1.0% by weight, at most 0.7% by weight or at most 0.5% by weight of water.

The method of the present invention includes a step of removing solids (insolubles) before performing hydrocracking. The insoluble components include everything that is insoluble in the liquid phase that has been subjected to the heat treatment step. In particular, the insoluble ingredients include particulate solids, precipitates, slag, including (highly) viscous liquids, which are immiscible with the liquid phase (which becomes the metal-depleted feed). By reducing the content of insoluble matter (or by completely removing solids) before hydrocracking, the slagging tendency can be reduced and handling properties can be improved. Suitable methods for removing solids include, but are not limited to, centrifuging, filtering, and sedimentation, and it is preferred that the process of the present invention include at least centrifugation as the single solids removal step or as one or more solids removal steps.

In the present invention, the metal content of the metal-depleted feedstock is less than the metal content of the feedstock. In other words, metals in the raw material accumulate in the solids and are separated after the heat treatment. As a result, the metal content is reduced. In the following invention

BE2019 / 5916 does not include "metal content" in the content of metalloids (e.g. Si, B). The content of other contaminants (such as metalloids, phosphorus, sulfur and chlorine) may also be reduced.

The metal content of the metal-depleted feed material is preferably at most 60% by weight of the metal content of the starting material, preferably at most 50% by weight, at most 40% by weight, at most 30% by weight, at most 20% by weight, at most 15% .-%, at most 10 wt.%, at most 8 wt.%, at most 7 wt.%, at most 6 wt.%, at most 5 wt.%, at most 4 wt.% or at most 3 wt. % of the metal content of the starting material. The metal content can be determined by any suitable means, such as atomic spectroscopy (e.g. AAS, AES, AFS, ICP-MS), for example inductively coupled plasma atomic emission spectroscopy based on the ASTM D5185 standard.

The more the metal content is reduced by the heat treatment and subsequent solids removal, the more metal-depleted feed can be used in the subsequent hydrocracking step without worrying about catalyst poisoning or other adverse effects of the metal contaminants.

In the present invention, the heating temperature during the heat treatment step is preferably at least 290 ° C. In this regard, the balance between heating temperature and heating time (residence time) affects the efficiency of the method of the present invention. In general, the lower the heat treatment temperature, the longer the heat treatment time should be to get the best results.

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The heat treatment temperature is preferably at least 300 ° C or at least 310 ° C and can be at least 320 ° C or at least 330 ° C.

It is particularly preferred that the heat treatment temperature be the highest temperature among all temperatures of the process of the present invention preceding the hydrocracking step.

In the present invention, the heat treatment temperature refers to the temperature of the material to be treated (i.e. the starting material).

If the heat treatment temperature is at least 290 ° C, remarkable metal depletion can be achieved. In this regard, although a reduction in the metal content can be achieved even at lower temperatures, this takes long heating times, which is therefore not preferred. In contrast, heat treatment temperatures of much higher than 440 ° C are usually not necessary to achieve the object of the present invention, so that the heat treatment temperature is preferably 450 ° C or lower, more preferably 440 ° C or lower. The heat treatment temperature may also be 430 ° C or lower, 420 ° C or lower, 410 ° C or lower, 400 ° C or lower, 390 ° C or lower, 380 ° C or lower, 370 ° C or lower, 360 ° C or lower, 350 ° C or lower, 340 ° C or lower or 335 ° C or lower.

The heat treatment time (heat treatment time / residence time) also affects the efficiency of the method of the present invention. In general, it is preferred that the heat treatment step be carried out for at least 1 minute

BE2019 / 5916 to achieve sufficient metal reduction (solid formation) and also to enable good process control. The heat treatment time is preferably at least 2 minutes, at least 5 minutes, at least 10 minutes, at least 20 minutes, at least 30 minutes or at least 40 minutes. The heat treatment time may also be at least 50 minutes, at least 60 minutes, at least 80 minutes or at least 100 minutes. In general, there is no upper limit on the heat treatment time. In terms of process efficiency, the heat treatment time, although preferably without an upper limit, is 100 hours or less, more preferably 50 hours or less, 40 hours or less, 30 hours or less, 20 hours or less, 10 hours or less or 5 hours or fewer.

If the heat treatment is carried out in a batch reactor, the heat treatment time corresponds to the temperature holding time. In a continuous reactor, the heat treatment time corresponds to the residence time.

The heat treatment step is preferably at a pressure of 0.5 bar or more, more preferably 0.8 bar or more, 1.0 bar or more, 1.2 bar or more, 1.5 bar or more, 2.0 bar or more, 3.0 bar or more, 4.0 bar or more, 5.0 bar or more, 6.0 bar or more, 8.0 bar or more, 10.0 bar or more, 12.0 bar or more or 14.0 bar or more. Increased pressure during the heat treatment step can reduce the tendency to evaporate and thus ensure efficient heat treatment. The pressure should be 200 bar or less, preferably 100 bar or less, more preferably 50 bar or less, in order to keep the technical equipment simple.

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Unless otherwise stated, a pressure indicated in the present invention means an absolute pressure. The pressure values above relate to the highest pressure that occurs in the heat treatment step, that is, measured at the point / time of the highest pressure. In particular, it is preferred that the heat treatment is not carried out under reduced pressure (negative pressure), but rather under ambient pressure or increased pressure. In particular, higher pressure reduces the tendency to evaporate and thus possible product loss or boiling effects (e.g. in continuous processes).

A metal removal additive may be present during the heat treatment step. The metal removal additive can be added before the start of the heat treatment and / or during the heat treatment. Suitable metal removal additives are those mentioned in US 4411774 A, but they are not limited to these. Specifically, the metal removal additive of the present invention may be one or more selected from the group consisting of ammonium sulfate, ammonium bisulfate, diammonium phosphate, ammonium dihydrogen phosphate,

Calcium hydrogen phosphate, phosphoric acid and magnesium sulfate and / or one or more selected from the group consisting of calcium sulfate, aluminum sulfate and sodium sulfate. The total addition amount of the metal removal additive is preferably at least 0.1% by weight, more preferably at least 0.5% by weight or at least 1.0% by weight, relative to the dry weight of the starting material (total weight on a dry basis). The total addition amount refers to the total amount of all metal removal additives added (but not including solvents, insofar as these are added together with the metal removal additives). If the metal removal additive is one or more selected from the

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Group consisting of calcium sulfate, aluminum sulfate and sodium sulfate, the addition amount is preferably at least 2.0% by weight, more preferably at least 3.0% by weight and further preferably at least 4.0% by weight, so as to improve the filterability . However, metal removal efficiency is improved with any (even small) amount of metal removal additive compared to a process that does not use any additive at all.

In the present invention, the type of hydrocracking is not particularly limited as long as it can tolerate the metal content of the metal-depleted feed (optionally mixed with an additional feed). A conventional hydrocracking process can be used and types of hydrocracking that can be used include fixed bed hydrocracking, fluidized bed hydrocracking and suspension hydrocracking.

The hydrocracking can be carried out in the presence of a solid catalyst (or solid catalyst). The solid catalyst can be a bifunctional catalyst. If a catalyst is used, the cracking effect can be achieved at a lower cracking temperature.

The solid catalyst preferably contains at least one Group VIII non-noble metal, at least one Group VIB metal and a carrier. Both the Group VIII non-noble metal and the at least one Group VIB metal are preferably supported on the carrier. A suitable carrier can be used, and a carrier comprising silicon oxide, aluminum oxide or clay is preferred. Furthermore, a carrier containing a Bronsted acid component can preferably be used. The Bronsted acid component can preferably be a zeolite or amorphous silicon oxide-aluminum oxide. A suitable zeolite is Y zeolite, beta zeolite or any other 12-membered

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Ring zeolite. The Group VIII base metal is preferably Co or Ni. The Group VIB metal is preferably Mo or W. Specifically, the following types of catalysts are preferred, especially when supported on a support as mentioned above: Co-Mo, Co-W, Ni-Mo, NiW.

The cracking temperature is not particularly limited and any suitable temperature can be used. In particular, a temperature in a range from 300 ° C to 500 ° C can be used. The cracking temperature is preferably at least 310 ° C, at least 320 ° C, at least 330 ° C, at least 340 ° C, or at least 350 ° C. The cracking temperature may be at most 490 ° C, at most 480 ° C, at most 470 ° C, at most 460 ° C, at most 450 ° C, at most 440 ° C or at most 430 ° C.

In the hydrocracking step, the hydrogen partial pressure in the hydrocracking step is preferably in the range from 70 to 200 bar.

The hydrocracking step can be carried out in any suitable reactor and preferred is a fluidized bed reactor, a slurry reactor (suspension reactor) or a fixed bed reactor.

The feed of the hydrocracking step may include one or more additional feeds in addition to the metal-depleted feed of the present invention. The additional feed (or the additional feed) may be a fossil-based feed, a renewable feed, or a combination of both.

The feedstock of the hydrocracking step preferably comprises a renewable feedstock component (biomass-based

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Feed ingredient) as an additional feed in addition to the metal-depleted feed (ingredient). By combining the metal-depleted feed with a biomass-based feed, the method of the following invention can become even more sustainable. The feedstock, and much more the metal-depleted feedstock made from it, primarily comprises hydrocarbons (compounds consisting of carbon atoms and hydrogen atoms), and thus the oxygen content and other properties can be fine-tuned by combining the biomass-based feedstock and the metal-depleted feedstock.

The renewable feedstock may be a material derived from deoxygenation of a renewable material.

Furthermore, the feed of the hydrocracking step may contain a fossil feed component in addition to the metal-depleted feed. The fossil feed may be a suitable feed different from the metal-depleted feed and may be a fraction of crude oil (e.g. a fraction from crude oil distillation or a fraction obtained by processing crude oil). In particular, the fossil feed may be a conventional cracking feed, such as vacuum gas oil (VGO) or vacuum residue (VR).

By combining the metal-depleted feed material with another feed material (additional feed material or additional feed), the hydrocracking properties can be fine-tuned and the desired product distribution can be set more easily. The content of the metal-depleted feed material in the (total) feed material of the hydrocracking step is preferably 50% by weight or

BE2019 / 5916 less, more preferably 40% by weight or less, 30% by weight or less or 20% by weight or less. In order to efficiently increase the use of waste oil components, the content of the metal-depleted feed in the feed of the hydrocracking step is preferably 1% by weight or more, more preferably 2% by weight or more, 5% by weight or more or 8% by weight. -% or more. By limiting the content of the metal-depleted feed in the (total) hydrocracking feed, the metal content can be limited while still achieving a sustainable effect. Limiting the metal content allows selection of less metal tolerant catalysts and / or can improve catalyst life.

The method of the present invention further includes a step of recovering at least one hydrocarbon fraction from the hydrocracked material (the product of the hydrocracking step / product). This step can be accomplished by fractionating the hydrocracked material and recovering the at least one fraction. Fractionation can be carried out by any known means and preferably results in the production of a fraction in the gasoline range and / or a fraction in the middle distillate range.

The procedure of the present invention is shown schematically in FIG. 1. As illustrated in FIG. 1, water can be removed in a dewatering step (optional), insoluble constituents (precipitates) are removed, for example, in a centrifugation step. The resulting metal-depleted feedstock is then subjected to hydrocracking.

BE2019 / 5916

The present invention further relates to a fuel component obtainable by the method of the present invention.

As can be seen from the results of the examples, the method of the present invention makes it possible to produce fuel components, in particular in the gasoline range and in the middle distillate range, in high yield.

The present invention further relates to the use of the recovered hydrocarbon fraction to produce a fuel or a fuel component.

Examples

The present invention is further illustrated by way of examples. However, it should be noted that the invention is not intended to be limited to the exemplary embodiments shown in the examples.

example 1

Used lubricating oil (ULO) was used as a raw material. The ULO contained 17.0% by weight of water and had a high amount of metal impurities (3181 mg / kg on a wet basis = 3833 mg / kg on a dry basis; detected metals: Al, Cr, Cu, Fe, Na, Ni , Pb, Sn, V, Ba, Ca, Mg, Mn, Zn). The Si content was also detected and was 84 mg / kg (wet) and thus 101 mg / kg (dry). The oxygen content (on a dry basis) was 1.0% by weight.

BE2019 / 5916

The ULO was dewatered in a rotary evaporator at 100 ° C and 80 mbar. As a result, water (and light components) were removed. The dewatered ULO was then subjected to a heat treatment in a batch reactor at 320 ° C for 1 hour. The pressure at the start of the heat treatment was 1 bar and the pressure increased to about 23 bar as a result of the heating in the closed vessel. The heat treated material was cooled to 50 ° C and centrifuged at 4300 rpm for 30 minutes and the liquid parts (excluding solids and slag) were recovered as a metal-depleted feed ready to be fed into a hydrocracking process.

The yield of the respective process steps (% by weight of the original ULO) and the metal contents of the starting material (ULO) and the metal-depleted feed (after centrifugation) are given in Table 1 below.

Table 1 :

Process step electricity yield wet Exhaust yield dry Output Metals mg / kg (dry basis) Si mg / kg (dry foundation) P mg / kg (dry basis} - ULO ISO - 3833 101 1795 Enhvässem Water + · Soft ingredients 18, p __ - __ - T rcckeies ULO ' SO. 2nd 96.6 - __ - Heat treatment + solids removal Fsststsffe (and Slag) 6.5 7.8 __ - poor gfickung 73 _f 4 88, 4 48 17th 20

BE2019 / 5916

As can be seen from Table 1, the process of the present invention achieves a significant reduction in metal (and metalloid) content, making it suitable as a feedstock in a metal tolerant hydrocracking process.

Comparative Example 1

The metal-depleted feed from Example 1 was further subjected to thin film evaporation at 0.1 mbar (270-281 ° C). As a result, the total metal content of the distillate (boiling point <560 ° C) was further reduced to 2 mg / kg, whereas the Si content and the P content remained almost unchanged. In contrast, a further 6% by weight of product (relative to the starting material on a dry basis) was lost as a distillate sump.

Example 2

Another batch of used lubricating oil (ULO-2) was used as a starting material. The ULO-2 contained 2.6% by weight of water and had a high content of metal impurities (2155 mg / kg on a wet basis; detected metals: Al, Cr, Cu, Fe, Na, Ni, Pb, Sn, V , Ba, Ca, Mg, Mn, Zn). The Si content was 278 mg / kg (wet) and the P content was 455 mg / kg (wet). The oxygen content (on a dry basis) was 1.0% by weight.

The ULO-2 was dewatered in a rotary evaporator at 100 ° C and 80 mbar. As a result, water (and light components) were removed. A portion of the dewatered ULO-2 was then mixed with 3000 ppm (relative to the dewatered ULO-2) of 85 wt% H3PO4 as a metal removal enhancer and then became one

BE2019 / 5916

Heat treated in a batch reactor at 320 ° C for 1 hour.

Another part of the dewatered ULO-2 was subjected to the heat treatment in a batch reactor at 320 ° C for 1 hour without an additive.

In each case, the pressure at the start of the heat treatment was 1 bar and the pressure increased to about 6-7 bar as a result of the heating in the closed vessel. The heat treated material was cooled to 50 ° C and solids were removed and the liquid parts (excluding solids and slag) were recovered as a metal-depleted feed ready for hydrocracking.

Solids removal was carried out using centrifugation at 4300 rpm for 30 minutes. In another experiment, solids removal was carried out by filtration rather than centrifugation.

The yield of the respective process steps (% by weight of the original ULO) and the metal contents of the starting material (ULO-2) and the metal-depleted feed material (after centrifugation) are shown in Table 2 below.

Table 2:

BE2019 / 5916

Process step electricity Yield (Cew.-W moist Starting msteriM} Yield (% by weight of dry starting Ää) installe mg / kg (dry basis) Si mg / kg {dry Grufidlag e) P mg / kg (dry grimdiag e) - ÜLO 100 - 2213 285 467 Drainage. water + Real Components 4.6 - - - Dry 95, .4 97.9 - - - Heat treatment) with additive + Zentiîi Era. Solids 73 73 __ - Metailvenimen sending 88.1 90 ... 5 111 133 69 Heat treatment) with additive + Filtration Solids Schl-scke) 7 _S 6 7.8 - __ - Metal mad feed 87 _f p 90.1 31 71 14

As can be seen from Table 2, the process of the present invention achieves a significant reduction in the metal (and metalloid) content so that they are suitable for being loaded in a metal tolerant hydrocracking process. It can also be seen that the metal removal efficiency is significantly improved when a metal removal additive is used in combination with filtration as the solid removal step (preferably at least as the first stage of the metal removal step or as the only metal removal step).

BE2019 / 5916

Comparative Example 2

ULO-2 was subjected to the heat treatment in the same manner as in Example 2, but without a metal removal additive and subsequent centrifugation. The heat-treated sample was then subjected to distillation under the conditions used in Comparative Example 1. The results are shown in Table 3 below.

Table 3

Process step electricity Yield (% by weight of moist base stock) yield drier Basic stock) Metals mg / kg (dry basis) Si mg / kg (dry basis} P mg / kg (dry basis} ULO 100 __ 2213 285 467 Drain Water + light Components 4.6 - - - - dry ÜLO 95.4 97.9 __ - - Bath treatment without additive 4- Centugate Solids (and Sch-acke) 5..6 9.9 - - - impoverished Eirssötzmatehal 85..7 88.0 801 123 308 Heat treatment + · centrifugation + distillation Swamps 14.4 14.8 - - __ distillate 71.3 73.2 4th 116 10th

As can be seen from Table 3, the metal removal efficiency of the distillation is higher than in a case where only centrifugation or filtration is carried out after the heat treatment. However

BE2019 / 5916 the Si content is still higher (presumably because volatile Si compounds themselves evaporate from the slag) than for the technology of the present invention. In addition, a significant amount of the product is lost as still bottoms.

Claims (15)

PATENT CLAIMS 1. A method comprising the following steps: subjecting a starting material (or feed or Raw material) of a heat treatment (heat treatment step) to produce a heat-treated material containing liquid components and solid components, Separating solids from the heat treated material to produce a metal depleted feed, Subjecting the metal-depleted feed, optionally together with an additional feed, to hydrocracking (hydrocracking step) to form a hydrocracked material, Recovering at least one hydrocarbon fraction boiling in the area of liquid fuel from the hydrocracked material; the starting material having an oxygen content of at most 5.0% by weight on a dry basis. 2. The method according to claim 1, wherein the starting material has an oxygen content, on a dry basis, in the range from 0.1% by weight to 5.0% by weight, preferably at most 4.0% by weight, at most 3.5 % By weight or at most 3.0% by weight, and / or at least 0.2% by weight, at least 0.3% by weight, at least 0.4% by weight or at least 0.5% by weight. -% having. 3. The method according to claim 1 or 2, wherein the total content of hydrogen (H) and carbon (C) in the base material, on a dry basis, is at least 80% by weight, preferably at least 85% by weight, at least 90% by weight. %, at least 92% by weight, at least 94% by weight, at least 95% by weight, at least 96% by weight, at least 97% by weight, at least 98% by weight or at least 99% by weight . BE2019 / 5916 4. The method according to any one of the preceding claims, wherein the metal-depleted feed (or the metal-depleted feed) is subjected to hydrocracking together with an additional feed, the additional feed preferably being a fossil-based feed, a renewable feed or a combination of both. 5. The method according to any one of the preceding claims, wherein the metal content of the metal-depleted feed material is at most 60% by weight of the metal content of the starting material, preferably at most 50% by weight, at most 40% by weight, at most 30% by weight, at most 20 wt%, at most 15 wt%, at most 10 wt%, at most 8 wt%, at most 7 wt%, at most 6 wt%, at most 5 wt%, at most 4 wt .-% or at most 3 wt .-% of the metal content of the starting material. 6. The method according to any one of the preceding claims, wherein the heat treatment is carried out at a temperature of at least 290 ° C, preferably at least 300 ° C, at least 310 ° C, at least 320 ° C or at least 330 ° C. 7. The method according to any one of the preceding claims, wherein the heat treatment is carried out for at least 1 minute, preferably at least 2 minutes, at least 5 minutes, at least 10 minutes, at least 20 minutes, at least 30 minutes, at least 40 minutes, at least 50 minutes, at least 60 Minutes, at least 80 minutes or at least 100 minutes. 8. The method according to any one of the preceding claims, wherein the hydrocracking step is carried out at a temperature in the range from 300 ° C to 500 ° C. BE2019 / 5916 9. The method according to any one of the preceding claims, wherein the metal-depleted feedstock is subjected to hydrocracking in the presence of a solid catalyst and the solid catalyst preferably contains at least one Group VIII base metal and at least one Group VIB metal and a carrier. 10. The method of claim 9, wherein the carrier comprises silica, alumina or clay and / or wherein the carrier comprises a Bronsted acid component, wherein the Bronsted acid component is preferably zeolite or amorphous silicon oxide-aluminum oxide. 11. The method according to any one of the preceding claims, wherein the hydrocracking step is carried out in a fluidized bed reactor, a slurry reactor or a fixed bed reactor. 12. The method according to any one of the preceding claims, wherein the total content of metals and phosphorus in the starting material is in the range of 500 mg / kg to 10000 mg / kg, preferably 1000 mg / kg to 8000 mg / kg. 13. The method according to any one of the preceding claims, wherein the step of removing insoluble components from the heat-treated material (the step of removing solids) comprises at least one of centrifuging, filtering and sedimenting, preferably at least centrifuging. 14. Fuel component which is obtainable by the method according to any one of the preceding claims. BE2019 / 5916 36 15. Use of the hydrocarbon fraction obtained, which is obtained by the method according to any one of claims 1 to 13, for producing a fuel or a fuel component.